Modules / Lectures

• Introduction : Composition of petroleum, laboratory tests, refinery feedstocks and products

• Evaluation of crude oil properties and Design of crude oil distillation column
• Furnace design
• Thermal and Catalytic cracking
• Catalytic Reforming
• Hydrotreating and Hydrocracking
• Isomerization, Alkylation and Polymerization
• Lube Oil Manufacturing
• Environmental issues and New Trends in petroleum refinery operations

Uniform Engine Fuels, Petroleum Products,and

Automotive Lubricants Regulation
Section 1.Definitions

ASTM :- The American Society for Testing and Materials means the national
voluntary consensus standards organization formed for the development of
standards on characteristics and performance of materials, products, systems,
and services, and the promotion of related knowledge.[1]

Antiknock Index (AKI) :- It means the arithmetic average of the Research

Octane Number (RON) and Motor Octane Number (MON): AKI = (RON +
MON)/2. This value is called by a variety of names like: octane rating, posted
octane, (R + M)/2 octane etc.[2]

Automotive Fuel Rating :- It means the automotive fuel rating is required

to be under the amended Octane Certification and Posting Rule (or as
amended, the Fuel Rating Rule), 16 CFR Part 306. Under this Rule, sellers of
liquid automotive fuels, including alternative fuels, must determine, certify,
and post an appropriate automotive fuel rating.[2] The automotive fuel rating
for gasoline is the antiknock index (octane rating). The automotive fuel rating
for alternative liquid fuels consists of the common name of the fuel, along with
a disclosure of the amount, expressed as a minimum percentage by volume
of the principal component of the fuel. For alternative liquid automotive fuels,
a disclosure of other components, expressed as a minimum percentage by
volume, may be included, if desired.[3]

Automotive Gasoline, Automotive Gasoline-Oxygenate Blend :- It

means a type of fuel suitable for use in spark ignition automobile engines and
also commonly used in marine and non-automotive applications.[2,3]

1
Aviation Gasoline. :- It means a type of gasoline suitable to use as a fuel in
an aviation spark-ignition internal combustion engine.[4]

Aviation Turbine Fuel :- It means a refined middle distillate suitable for to

as a fuel in an aviation gas turbine internal combustion engine.[4]

Base Gasoline :- It means all components other than ethanol in a blend of

gasoline and ethanol.

Biodiesel :- It means a blend consisting of diesel fuel and a substantial

amount of esterified animal fats and/or vegetable oil(s).[5]

Cetane Index :- It means an approximation of the cetane number of distillate

diesel fuel, which does not contain a cetane improver additive, calculated from
the density and distillation measurements.

Cetane Number :- It means a numerical measure of the ignition performance

of a diesel fuel obtained by comparing it to reference fuels in a standardized
engine test[2]..

Compressed Natural Gas (CNG) :- It means natural gas which has

been[6] compressed and dispensed into fuel storage containers and is suitable
for use as an engine fuel.

Denatured Fuel Ethanol :- It means "ethanol" as defined in below.[2]

Denatured Fuel :- It means a refined middle distillate suitable for use as a

fuel in a compression-ignition (diesel) internal combustion engine.

Distillate :-It indicates any product obtained by condensing the vapors given
off by boiling petroleum or its products.[2]

EPA :- United States Environmental Protection Agency.[7]

E85 Fuel Ethanol :- It means a blend of ethanol and hydrocarbons of which

the ethanol portion is nominally 85 to 75 volume percent denatured fuel
ethanol.

Energy Content :-It means the gross energy content or the heating value of
diesel fuel as defined by its heat of combustion; the heat released when a
known quantity of fuel is burned completely under specific conditions as
determined by ASTM Standard Test Method D 240.[1]

2
Engine Fuel :- It means any liquid or gaseous matter used for the generation
of power in an internal combustion engine.[8]

Engine Fuels Designed for Special Use :- It means engine fuels designated
by the Director requiring registration. These fuels normally do not have ASTM
or other national consensus standards applying to their quality or usability;
common special fuels are racing fuels and those intended for agricultural and
other off-road applications.[8]

Ethanol :- It also known as "Denatured Fuel Ethanol," means nominally

anhydrous ethyl alcohol meeting ASTM D 4806 standards. It is intended to be
blended with gasoline for use as a fuel in a spark-ignition internal combustion
engine. The denatured fuel ethanol is first made unfit for drinking by the
addition of Bureau of Alcohol, Tobacco, and Firearms (BATF) approved
substances before blending with gasoline.[10]

Fuel Injector Cleanliness :- It means a characteristic of the fuel which

allows engine operation without fuel contribution to excessive injector
deposits.[8]

Fuel Oil :-It means a refined oil middle distillates, heavy distillates, or
residues of refining, or blends of these, suitable for use as a fuel for heating
or power generation, the classification of which shall be defined by ASTM D
396.[9]

Gasoline :- It means a volatile mixture of liquid hydrocarbons generally

containing small amounts of additives suitable for use as a fuel in a spark-
ignition internal combustion engine.[9]

Gasoline-Alcohol Blend :- It means a fuel consisting primarily of gasoline

and a substantial amount (more than 0.35 mass percent of oxygen, or more
than 0.15 mass percent of oxygen if methanol is the only oxygenate) of one
or more alcohols.[11]

Gasoline Gallon Equivalent (GGE) :- Gasoline gallon equivalent (GGE)

means 2.567 kilograms (5.660 lb) of natural gas.[11]

Gasoline Liter Equivalent (GLE):- Gasoline liter equivalent (GLE) means

0.678 kilogram (1.495 lb) of natural gas.[11]

Gasoline-Oxygenate Blend :- It means a fuel consisting primarily of

gasoline along with a substantial amount (more than 0.35 mass percent of

3
oxygen, or more than 0.15 mass percent of oxygen if methanol is the only
oxygenate) of one or more oxygenates.[9]

Kerosene :- It means a refined middle distillate suitable for use as a fuel for
heating or illuminating, the classification of which shall be defined by ASTM D
3699.[2]

Lead Substitute :- It means an EPA-registered gasoline additive suitable,

when added in small amounts to fuel, to reduce or prevent exhaust valve
recession (or seat wear) in automotive spark-ignition internal combustion
engines designed to operate on leaded fuel.

Lead Substitute Engine Fuel :- It means, for labeling purposes, a gasoline

or gasoline-oxygenate blend that contains a "lead substitute."[12]

Leaded :- It means, for labeling purposes, any gasoline or gasoline-

oxygenate blend which contains more than 0.013 gram of lead per liter (0.05
g lead per U.S. gal). NOTE: EPA defines leaded fuel as one which contains
more than 0.0013 gram of phosphorus per liter (0.005 g per U.S. gal), or any
fuel to which lead or phosphorus is intentionally added.

Liquefied Natural Gas (LNG) :-It means natural gas that has been liquefied
at -126.1 EC ( 259 EF) and stored in insulated cryogenic tanks for use as an
engine fuel.[6]

Liquefied Petroleum Gas (LPG) :- It means a mixture of normally gaseous

hydrocarbons, predominantly propane, or butane, or both, that has been
liquefied by compression or cooling, or both to facilitate storage, transport,
and handling.[6]

Low Sulfur:- It means low sulfur diesel fuel that meets ASTM D 975 (e.g.,
Grade Low Sulfur No. 1-D or Grade Low Sulfur No. 2-D) standards. Diesel fuel
containing higher amounts of sulfur for off-road use is defined by EPA
regulations.[11]

Low Temperature Operability: -It means a condition which allows the

uninterrupted operation of a diesel engine through the continuous flow of fuel
throughout its fuel delivery system at low temperatures. Fuels with adequate
low temperature operability characteristics have the ability to avoid wax
precipitation and clogging in fuel filters.[11]

4
M100 Fuel Methanol :- It means nominally anhydrous methyl alcohol,
generally containing small amounts of additives, suitable for use as a fuel in
a compression-ignition internal combustion engine.[10]

M85 Fuel Methanol :- It means a blend of methanol and hydrocarbons of

which the methanol portion is nominally 70 to 85 volume percent.[10]

Motor Octane Number :- It means a numerical indication of a spark-ignition

engine fuel's resistance to knock obtained by comparison with reference fuels
in a standardized ASTM D 2700 Motor Method engine test.[2]

Oxygen Content of Gasoline :- It means the percentage of oxygen by mass

contained in a gasoline.[2]

Oxygenate :- It means an oxygen-containing, ash less, organic compound,

such as an alcohol or ether, which can be used as a fuel or fuel supplement.[2,9]

Reformulated Gasoline :- It means a volatile mixture of liquid hydrocarbons

and oxygenates meeting the reformulated gasoline requirements of the Clean
Air Act Amendments of 1990 and suitable for use as a fuel in a spark-ignition
internal combustion engine.[11]

Research Octane Number :- It means a numerical indication of a spark-

ignition engine fuel's resistance to knock obtained by comparison with
reference fuels in a standardized ASTM D 2699 Research Method Engine
Test.[2]

SAE :- It means the Society of Automotive Engineers, a technical organization

for engineers, scientists, technicians, and others in positions that cooperate
closely in the engineering, design, manufacture, use, and maintainability of
self-propelled vehicles.[8]

Substantially Similar :- It means the EPA's "Substantially Similar" rule,

Section 211 (f) (1) of the Clean Air Act [42 U.S.C. 7545 (f) (1)].[8]

Thermal Stability :- It means the ability of a fuel to resist the thermal stress
which is experienced by the fuel when exposed to high temperatures in a fuel
delivery system. Such stress can lead to formation of insoluble gums or
organic particulates. Insoluble (e.g., gums or organic particulates) can clog
fuel filters and contribute to injector deposits.[7]

Total Alcohol :- It means the aggregate total in volume percent of all alcohol
contained in any fuel.[10]

5
Total Oxygenate :- It means the aggregate total in volume percent of all
oxygenates contained in any fuel.[2,9]

Unleaded :- In conjunction with "engine fuel" or "gasoline" means any

gasoline or gasoline-oxygenate blend to which no lead or phosphorus
compounds have been intentionally added and which contains not more than
0.013 gram of lead per liter (0.05 g lead per U.S. gal) and not more than
0.0013 gram of phosphorus per liter (0.005 g phosphorus per U.S. gal).

Section 2. Standard Fuel Specifications

Gasoline and Gasoline-Oxygenate Blends :- (as defined in this regulation)

shall meet the following requirements :-

The most recent version of ASTM D 4814, "Standard Specification for

Automotive Spark Ignition Engine Fuel," except that volatility standards for
unleaded gasoline blended with ethanol shall not be more restrictive than
those adopted under the rules, regulations, and Clean Air Act waivers of the
U.S. Environmental Protection Agency (which includes rules promulgated by
the State). Gasoline blended with ethanol shall be blended under any of the
following three options The base gasoline used in such blends shall meet the
requirements of ASTM D 4814,[1]

or

The base gasoline used in such blends shall meet all the requirements
of ASTM D 4814, except distillation, and the blend shall meet the distillation
requirements of the ASTM specification. Blends of gasoline and ethanol shall
not exceed the ASTM D 4814, vapor pressure standard by more than 1.0 psi.

Minimum Antiknock Index (AKI):- The AKI shall not be less than the AKI
posted on the product dispenser or as certified on the invoice, bill of lading,
shipping paper, or other documentation.[2]

Minimum Motor Octane Number :-The minimum motor octane number

shall not be less than 82 for gasoline with an AKI of 87 or greater.

Minimum Lead Content to Be Termed "Leaded":- Gasoline and gasoline

oxygenate blends sold as "leaded" shall contain a minimum of 0.013 gram of
lead per liter (0.05 g per U.S. gal).[12]

Lead Substitute Gasoline:- Gasoline and gasoline-oxygenate blends sold as

"lead substitute" gasoline shall contain a lead substitute which provides
6
protection against exhaust valve seat recession equivalent to at least 0.026
gram of lead per liter (0.10 g per U.S. gal).[4]

Documentation of Exhaust Valve Seat Protection :- Upon the request of

the director, the lead substitute additive manufacturer shall provide
documentation to the director that demonstrates that the treatment level
recommended by the additive manufacturer provides protection against
exhaust valve seat recession equivalent to or better than 0.026 gram per liter
(0.1 g/gal) lead. The director may review the documentation and approve the
lead substitute additive before such additive is blended into gasoline. This
documentation shall consist of: Test results as published in the Federal
Register by the EPA Administrator as required in Section 211(f)(2) of the Clean
Air Act;[7]

or

Until such time as the EPA Administrator develops and publishes a test
procedure to determine the additive's effectiveness in reducing valve seat
wear, test results and description of the test procedures used in comparing
the effectiveness of 0.026 gram per liter lead and the recommended treatment
level of the lead substitute additive shall be provided.

Blending :- Leaded, lead substitute, and unleaded gasoline-oxygenate blends

shall be blended according to the EPA "substantially similar" rule or an EPA
waiver for unleaded fuel.

Diesel Fuel shall meet the most recent version of ASTM D 975, "Standard
Specification for Diesel Fuel Oils."

Premium Diesel Fuel :- Effective January 1, 2000, all products identified on

retail dispensers, bills of lading, invoices, shipping papers, or other
documentation such as premium, super, supreme, plus, or premier must
conform to at least two of the following requirements

Energy Content :-A minimum energy content of 38.65 MJ/L, gross (138,700
BTU/gallon, gross) as measured by ASTM Standard Test Method D 240.

Cetane Number :- A minimum cetane number of 47.0 as determined by

ASTM Standard Test Method D 613.

Low Temperature Operability:- A cold flow performance measurement

which meets the ASTM D 975 tenth percentile minimum ambient air
temperature charts and maps by either ASTM Standard Test Method D 2500
(Cloud Point) or ASTM Standard Test Method D 4539 (Low Temperature Flow

7
Test, LTFT). Low temperature operability is only applicable October 1 March
31 of each year.[7]

Thermal Stability:- A minimum reflectance measurement of 80 percent

using a green filter in the Octel America's Test Method No. F21 61 (180
minutes, 150 °C).

Fuel Injector:- Cleanliness A Coordinating Research Council (CRC) rating of

10.0 or less and a flow loss of 6.0 percent or less as determined by the
Cummins L 10 Injector Depositing Test.

When a fuel uses a detergent additive to meet the requirement, upon the
request of the Director, the fuel marketer shall provide test data indicating the
additive being used has passed the Cummins L 10 Injector Depositing Test
requirements when combined with Caterpillar 1 K (CAT 1 K) reference fuel.
The Director may also request records or otherwise audit the amount of
additive being used to ensure proper treatment of fuels according to the
additive manufacturer's recommended treat rates[8]

Upon the request of the Director, the fuel marketer shall provide an official
"Certificate of Analysis" of the physical properties of the additive.

Upon the request of the Director, the fuel supplier shall provide a sample of
detergent additive in an amount sufficient to be tested with CAT 1 K reference
fuel in a Cummins L 10 Injector Depositing Test. The regulatory agency
requesting the sample shall be responsible for all costs of testing.

When a fuel marketer relies on the inherent cleanliness of the diesel fuel to
pass the Cummins L 10 Injector Depositing Test or if the fuel requires a lower
detergent additive level than the amount required when the additive is used
with the CAT 1 K reference fuel, the fuel marketer shall provide, upon the
request of the Director, annual test results from an independent laboratory
that confirms the fuel meets the requirements of 2.2.1.(e). The time of fuel
sampling and testing shall be at the Director’s discretion. The Director may
witness the sampling of the fuel and the sealing of the sample container's with
security seals. The Director may request confirmation from the testing
laboratory that the seals were intact upon receipt by the laboratory. The final
test results shall be provided to the Director. All costs for sampling,
transporting, and testing shall be the responsibility of the fuel supplier. If the
annual test complies, any additional testing at the request of t Director shall
be paid for by the regulatory agency.

Aviation Turbine Fuels shall meet the most recent version of ASTM D
1655, "Standard Specification for Aviation Turbine Fuels."[1]

8
Aviation Gasoline shall meet the most recent version of ASTM D
910, "Standard Specification for Aviation Gasoline."

Fuel Oils shall meet the most recent version of ASTM D 396, "Standard
Specification for Fuel Oils."

Kerosene (Kerosene) shall meet the most recent version of ASTM D

3699, "Standard Specification for Kerosene."

Ethanol intended for blending with gasoline shall meet the most recent version
of ASTM D 4806, "Standard Specification for Denatured Fuel Ethanol for
Blending with Gasoline for Use as Automotive Spark-Ignition Engine Fuel."[1]

Liquefied Petroleum (LP) Gases shall meetASTM D 1835, "Standard

Specification for Liquefied Petroleum (LP) Gases." Note: Also reference Gas
Processors Association 2140, "Liquefied Petroleum Gas Specification and Test
Methods."

Compressed Natural Gas (CNG) shall meet the most recent version of SAE J
1616, "Recommended Practice for Compressed Natural Gas Vehicle Fuel."

E85 Fuel Ethanol shall meet the most recent version of ASTM D
5798, "Standard Specification for Fuel Ethanol (Ed75-Ed85) for Automotive
Spark-Ignition Engines."

M85 Fuel Methanol shall meet the most recent version of ASTM D
5797, "Standard Specification for Fuel Methanol M70-M85 for Automotive
Spark Ignition Engines."[1]

Section 3. Classification and Method of Sale of Petroleum Products

General Considerations

Automotive Gasoline and Automotive Gasoline-Oxygenate Blends

Posting of Antiknock Index Required -- All automotive gasoline and automotive

gasoline-oxygenate blends shall post the antiknock index in accordance with
applicable regulations, 16 CFR Part 306 issued pursuant to the Petroleum
Marketing.

When the Term "Leaded" may be Used -- The term "leaded" shall only be used
when the fuel meets specification requirements.[13]

9
Use of Lead Substitute must be Disclosed -- Each dispensing device from which
gasoline or gasoline-oxygenate blends containing a lead substitute is
dispensed shall display the following legend: "Contains Lead Substitute." The
lettering of this legend shall not be less than 12 mm (1/2 in) in height and the
color of the lettering shall be in definite contrast to the background color to
which it is applied.

Nozzle Requirements for Leaded Fuel -- Each dispensing device from which
gasoline or gasoline-oxygenate blends that contain lead in amounts sufficient
to be considered "leaded" gasoline, or lead substitute engine fuel, is sold shall
be equipped with a nozzle spout having a terminal end with an outside
diameter of not less than 23.63 mm (0.930 in).[11]

of Terms -- It is prohibited to use specific terms to describe a grade of

gasoline or gasoline-oxygenate blend unless it meets the minimum antiknock
index requirement shown in Table 1

Method of Retail Sale -- Type of Oxygenate must be Disclosed. -- All

automotive gasoline or automotive gasoline-oxygenate blends kept, offered,
or exposed for sale, or sold at retail containing at least 1.5 mass percent
oxygen shall be identified as “with” or “containing” (or similar wording) the
predominant oxygenate in the engine fuel. For example, the label may read
“contains ethanol” or “with MTBE.” The oxygenate contributing the largest
mass percent oxygen to the blend shall be considered the predominant
oxygenate. Where mixtures of only ethers are present, the retailer may post
the predominant oxygenate followed by the phrase “or other ethers” or
alternatively post the phrase “contains MTBE or other ethers.” In addition,
gasoline-methanol blend fuels containing more than 0.15 mass percent
oxygen from methanol shall be identified as “with” or “containing” methanol.
This information shall be posted on the upper 50 percent of the dispenser front
panel in a position clear and conspicuous from the driver’s position in a type
at least 12.7 mm (½ in) in height, 1.5 mm (1/16 in) stroke (width of
type).(Amended 1996).[1]

Documentation for Dispenser Labeling Purposes -- The retailer shall be

provided, at the time of delivery of the fuel, on an invoice, bill of lading,
shipping paper, or other documentation, a declaration of the predominant
oxygenate or combination of oxygenates present in concentrations sufficient
to yield an oxygen content of at least 1.5 mass percent in the fuel. Where
mixtures of only ethers are present, the fuel supplier may identify either the
predominant oxygenate in the fuel (i.e., the oxygenate contributing the
largest mass percent oxygen) or, alternatively, use the phrase “contains MTBE
or other ethers.” In addition, any gasoline containing more than 0.15 mass
10
percent oxygen from methanol shall be identified as “with” or “containing”
methanol. This documentation is only for dispenser labeling purposes; it is the
responsibility of any potential blender to determine the total oxygen content
of the engine fuel before blending.[13]

Diesel Fuel

Labeling of Grade Required. -- Diesel Fuel shall be identified by grades No. 1-

D, No. 1-D (low sulfur), No. 2-D, No. 2-D (low sulfur), or No. 4-D. Each retail
dispenser of diesel fuel shall be labeled according to the grade being dispensed
except the words "low sulfur" are not required.[13]

Location of Label. -- These labels shall be located on the upper 50 percent of

the dispenser front panel in a position clear and conspicuous from the driver’s
position, in a type at least 12 mm (1/2 in) in height, 1.5 mm (1/16 in) stroke
(width of type).[1]

Labeling Properties of Premium Diesel -- All retail dispensers identified as

premium diesel must display either:

A label that includes all qualifying parameters as specified in Premium Diesel

Fuel affixed to each retail dispenser. The label shall include a series of check
boxes clearly associated with each parameter. The boxes for the parameters
qualifying the fuel must be checked. All other boxes shall remain unchecked.
The marketer may check as many boxes as apply, or

A label that includes only the parameters selected by a marketer to meet the
premium diesel requirements as specified in 2.2.1. Premium Diesel Fuel. In
either case, the label must display the following words:

X "Premium Diesel Fuel" in a type at least 12 mm (1/2 in) in height by 1.4

mm (1/16 in) stroke (width of type). When applicable, as determined by the
label option and qualifying parameters chosen by the marketer, the label must
also display the following information and letter type size:-

X The words "Energy Content," "Cetane Number," "Low Temperature

Operability," "Thermal Stability," and "Fuel Injector Cleanliness" in a type at
least 6 mm (1/4 in) in height by 0.75 mm (1/32 in) stroke (width of type).[11,13]

X A declaration of the minimum Energy Content (minimum 38.65 MJ/ L gross

[138,700 BTU/gallon]), if energy content is chosen as a qualifying parameter,
in type at least 3 mm (1/8 in) in height by 0.4 mm (1/64 in) stroke (width of
type).

11
X The minimum cetane number guaranteed (at least 47.0) if cetane number
is chosen as a qualifying parameter, in a type at least 3 mm (1/8 in) in height
by 0.4 mm (1/64 in) stroke (width of type).

X The date range of low temperature operability enhancement, (e.g., October

March,) along with the qualifying test method (ASTM D 4539 or ASTM D 2500),
if low temperature operability is chosen as a qualifying parameter, in a type
at least 3 mm (1/8 in) in height by 0.4 mm (1/64 in) stroke (width of type).

For Example :-

Premium Diesel Fuel

1. High Energy Content

2. Cetane Number, 47.0 min
3. Low Temperature Operability (Oct.-Mar.,LTFT)
4. Thermal Stability
5. Fuel Injector Cleanliness

or

Premium Diesel Fuel

Cetane Number, 47.0 min

Low Temperature Operability (Oct.-Mar., LTFT)

Thermal Stability

X The label must be conspicuously displayed on the upper half of the product
dispenser front panel in a position that is clear and conspicuous from the
driver’s position.(Added 1998) (Amended 1999)

Delivery Documentation - Before or at the time of delivery of premium diesel

fuel, the retailer or the wholesale purchaser consumer shall be provided on an
invoice, bill of landing, shipping paper, or other documentation a declaration
of all performance properties that qualifies the fuel as premium diesel fuel as
required in (Added 1998) (Amended 1999)

Table 1.1 Minimum Antiknock Index Requirements [13]

12
 Minimum Antiknock Index
Term ASTM D 4841 Altitude ALL other ASTM D 4814
Reduction Areas IV and V Areas
Premium,Super,Supreme,High Test 90 91
Midgrade,Plus 87 89
Regular Leaded 86 88
Regular,Unleaded(alone) 85 87
Economy - 86

*(Table Amended 1997)

Aviation Turbine Fuels

Labeling of Grade Required: Aviation turbine fuels shall be identified by Jet

A, Jet A 1, or Jet B.

NFPA Labeling Requirements also Apply Each dispenser or airport fuel

truck dispensing aviation turbine fuels shall be labeled in accordance with the
most recent edition of National Fire Protection Association NFPA 407,
"Standard for Aircraft Fuel Servicing." NFPA 407, 1990 Edition: Section 2 3.18
Product Identification Signs. Each aircraft fuel servicing vehicle shall have a
sign on each side and the rear to indicate the product. The sign shall have
letters at least 3 inches (75 mm) high of color sharply contrasting with its
background for visibility. It shall show the word "FLAMMABLE" and the name
of the product carried, such as "JET A," "JET B," "GASOLINE," or "AVGAS." [14]

Aviation Gasoline

Labeling of Grade Required: Aviation gasoline shall be identified by Grade

80, Grade 100, or Grade 100LL.

NFPA Labeling Requirements also Apply: Each dispenser or airport fuel

truck dispensing aviation gasoline shall be labeled in accordance with the most
recent edition of National Fire Protection Association (NFPA) 407, "Standard
for Aircraft Fuel Servicing." NFPA 407, 1990 Edition: Section 2 3.18 Product
Identification Signs. Each aircraft fuel servicing vehicle shall have a sign on
each side and the rear to indicate the product. The sign shall have letters at
least 3 inches (75 mm) high of color sharply contrasting with its background
for visibility. It shall show the word "FLAMMABLE" and the name of the product
carried, such as "JET A," "JET B," "GASOLINE," or "AVGAS."

13
Fuel Oils

Labeling of Grade Required Fuel Oil shall be identified by the grades of No.
1, No. 2, No. 4 (Light), No. 4, No. 5 (Light), No. 5 (Heavy), or No. 6.

Kerosene (Kerosine)

Labeling of Grade Required: Kerosene shall be identified by the grades No.

1-K or No. 2-K.

Additional Labeling Requirements: Each retail dispenser of kerosene shall

be labeled as 1-K Kerosene or 2-K. In addition, No. 2-K dispensers shall
display the following legend "Warning - Not Suitable for use in unvented
heaters requiring No. 1-K." The lettering of this legend shall not be less than
12 mm (1/16 in) in height by 1.5 mm (1/16 in) stroke; block style letters and
the color of lettering shall be in definite contrast to the background color to
which it is applied.[14]

Fuel Ethanol Fuel ethanol shall be identified by the capital letter E followed
by the numerical value volume percentage.

Retail Dispenser Labeling: Each retail dispenser of fuel ethanol shall be

labeled with the capital letter E followed by the numerical value of volume
percent denatured ethanol and ending with the word "ethanol."

Additional Labeling Requirements:Fuel ethanol shall be labeled with its

automotive fuel rating in accordance with 16 CFR Part 306.[14]

Fuel Methanol

How Fuel Methanol is to be Identified: Fuel methanol shall be identified

by the capital letter M followed by the numerical value volume percentage of
methanol.

Retail Dispenser Labeling Each retail dispenser of fuel methanol shall be

labeled by the capital letter M followed by the numerical value volume percent
and ending with the word "methanol."

Liquefied Petroleum (LP) Gas

How LPG is to be Identified: Liquefied petroleum gases shall be identified

by grades of commercial Propane, commercial Butane, commercial PB
Mixtures or Special-Duty Propane (HD5)[14]

14
Compressed Natural Gas

How Compressed Natural Gas is to be Identified: for the purposes of this

regulation, it can be identified by the term "Compressed Natural Gas" or
"CNG."

Retail Sales of Compressed Natural Gas Sold as a Vehicle Fuel.

Method of Retail Sale All compressed natural gas kept, offered, or exposed
for sale or sold at retail as a vehicle fuel shall be in terms of the gasoline liter
equivalent (GLE) or gasoline gallon equivalent (GGE).

Retail Dispenser Labeling [14]

Identification of Product. Each retail dispenser of compressed natural gas

shall be labeled as "Compressed Natural Gas."

Conversion Factor. All retail compressed natural gas dispensers shall be

labeled with the conversion factor in terms of kilograms or pounds. The label
shall be permanently and conspicuously displayed on the face of the dispenser
and shall have either the statement "1 Gasoline Liter Equivalent (GLE) is equal
to 0.678 kg of Natural Gas" or "1 Gasoline Gallon Equivalent (GGE) is equal
to 5.660 lb of Natural Gas" consistent with the method of sale used.

Pressure CNG is dispensed into vehicle fuel containers with working

pressures of 16 574 kPa, 20 684 kPa, or 24 821 kPa. The dispenser shall be
labeled 16 574 kPa, 20 684 kPa, or 24 821 kPa corresponding to the pressure
of the CNG dispensed by each fueling hose.

Liquefied Natural Gas[14]

How Liquefied Natural Gas is to be Identified: For the purposes of this

regulation, liquefied natural gas shall be identified by the term "Liquefied
Natural Gas" or "LNG."

Introduction :Composition of petroleum,laboratory

tests,refinery feedstocks and products

15
 Fig:1.1[15]

Fig.1.2 Distribution of world energy resources.

(From World Energy Outlook 2005, International Energy Agency.)[16,17]

Introduction to petroleum refinery

Petroleum refineries have goal to convert as much of the barrel of crude oil
into transportation fuels which is economically practical. Refineries produce

16
many profitable products however, the high-volume profitable products are
the transportation fuel gasoline, diesel and turbine (jet) fuels, and the light
heating oils. These transportation fuels have boiling points between 25 and
350oC. Although products such as lubricating oils, refrigeration and
transformer oils, and petrochemical feedstocks are profitable.They amount to
less than 5 percent of the total crude oil charged to refineries. The processing
equipment indicated is for processing crude oils of average gravities and sulfur
contents. Crude oils with low API gravities (high specific gravities) and high
sulfur contents require additional hydrotreating equipment. The quality of
crude oils processed by worldwide refineries is expected to worsen slowly in
the future with the sulfur contents and densities to increase. Therefore
refineries will require processing the entire barrel of crude rather than just the
material boiling below (550 oC).Sulfur restrictions on fuels, coke and heavy
fuel oils affects the bottom-of-the-barrel processing as well. These factors
requires extensive refinery additions modernization the shift in market
requirements among gasolines and reformulated fuels for transportation
challenges.[16]

Refinery Overview[15-20]

The crude oil is heated in a furnace and charged to an atmospheric distillation

tower, where it is separated into light gas (C1-C4), light naphtha, heavy
naphtha, kerosine, atmospheric gas oil, and reduced (topped) crude . The
reduced crude is sent to the vacuum distillation tower and separated into
vacuum gas oil stream and vacuum reduced crude bottoms (residua, resid).
The reduced crude bottoms from the vacuum distillation tower is thermally
cracked in a delayed coker to produce gas, coker gasoline, coker gas oil, and
coke. The atmospheric and vacuum crude unit gas oils and coker gas oil are
used as feedstocks for the catalytic cracking or hydrocracking units where
heavy molecules get converted into lower molecular weight compounds boiling
in the gasoline and distillate fuel ranges. The hydrocracked products are
saturated whereas catalytic cracker products are unsaturated and further need
improvement in quality by either hydrotreating or by reforming. The light
naphtha streams from the crude tower, coker and cracking units are sent to
an isomerization unit to convert straight-chain paraffins into isomers which
have higher octane numbers. The heavy naphtha streams from the crude
tower, coker, and cracking units are fed to the catalytic reformer to improve
octane numbers. The products from the catalytic reformer can be blended into
regular and premium gasolines for marketing. The wet gas streams from the
crude unit, coker, and cracking units are separated in the vapor recovery
section (gas plant) into fuel gas, liquefied petroleum gas (LPG), unsaturated
hydrocarbons (propylene, butylenes, and pentenes), normal butane, and
isobutane. The fuel gas is burned as a fuel in refinery furnaces and the normal
butane is blended into gasoline or LPG. The unsaturated hydrocarbons and

17
isobutane are sent to the alkylation unit to react olefins with isobutane to yield
isoparaffins. The alkylation is done at high pressure and low temperature in
the presence of sulfuric or hydrofluoric acid as catalyst. The product is called
alkylated gasoline, which is a high-octane product blended into premium
motor gasoline and aviation gasoline. The middle distillates from the crude
unit, coker, and cracking units are blended into diesel and jet fuels and furnace
oils. In some refineries, the heavy vacuum gas oil and reduced crude from
paraffinic or naphthenic base crude oils are processed into lubricating oils. The
asphaltenes are removed in a propane deasphalting unit, and the reduced
crude from bottoms are processed with the vacuum gas oils to produce lubeoil
base stocks (LOBS). The vacuum gas oils and deasphalted stocks are solvent-
extracted to remove the aromatic compounds followed by dewaxing to
improve the pour point. These LOBS are further treated with acid clays to
improve their color and stability before being blended into lubricating oils.
Each refinery has its own unique processing scheme which is determined by
the process equipment available, crude oil characteristics, operating costs,
and product demand.

Refinery Feed Stocks[19-20]

The basic raw material for refineries is petroleum or crude oil. The chemical
compositions of crude oils obtained from various sources are almost uniform
although their physical characteristics vary widely. The elementary
composition of crude oil usually falls within the following ranges: C 84-88; H
11-15; S up to 5%, N up to 0.5 %. Crude oils are classified as paraffin base,
naphthene base, asphalt base, or mixed base depending upon the composition
of the residue left after distillation. Crude oils which have up to 80% aromatic
content are known as aromatic-base oils. The U.S. Bureau of Mines has
developed a system which classifies the crude according to two key fractions
obtained in distillation: No. 1 from 250 to 275 oC at atmospheric pressure and
No. 2 from 275 to 300 oC at 40 mmHg pressure. The API gravity of these
fractions varies depending upon paraffinic and naphthenic grade of the
crude(Paraffin : API 40 for No. 1 and 30 for No. 2, Naphthene : API < 30 for
No. 1 oil and <=20 for No. 2 oil). The paraffinic and asphailtic classifications
in common use are based on the properties of the residuum left from
nondestructive distillation and are more descriptive to the refiner because they
convey the nature of the products to be expected and the processing
necessary.

Composition Of Petroleum[19-20]

Crude oils are composed of many members of homologous series of

hydrocarbons. Petroleum is essentially a mixture of hydrocarbons, and even
the non-hydrocarbon elements are generally present as components of

18
complex molecules predominantly hydrocarbon in character, but containing
small quantities of oxygen, sulfur, nitrogen, vanadium nickel, and chromium.
The composition of the total mixture, in terms of elementary composition,
does not vary a great deal, but small differences in composition can greatly
affect the physical properties and the processing required to production
marketable products. The hydrocarbons present in crude petroleum are
classified into three general types: paraffins, naphthenes, and aromatics.
Olefins are generally not present in crude oil, however these are formed during
processing by the dehydrogenation of paraffins and naphthenes. The paraffin
series of hydrocarbons is characterized by the rule that the carbon atoms are
connected by a single bond and the other bonds are saturated with hydrogen
atoms.The general formula for paraffins is CnH2n+2. Crude oil contains molecules
with up to 70 carbon atoms, and the number of possible paraffinic
hydrocarbons is very high .Olefins do not naturally occur in crude oils but are
formed during the processing. They are very similar in structure to paraffins
but at least two of the carbon atoms are joined by double bonds. The general
formula is CnH2n. Olefins are generally undesirable in finished products because
the double bonds are reactive and the compounds are more easily oxidized
and polymerized to form gums and varnishes. Olefins containing five carbon
atoms have high reaction rates with compounds in the atmosphere that form
pollutants and, even though they have high research octane numbers, are
considered generally undesirable. Some diolefins (containing two double
bonds) are also formed during processing, but they react very rapidly with
olefins to form high-molecular-weight polymers consisting of many simple
unsaturated molecules joined together. Diolefins are very undesirable in
products because they are so reactive they polymerize and form filter and
equipment plugging compounds. Cycloparaffin hydrocarbons in which all of
the available bonds of the carbon atoms are saturated with hydrogen are
called naphthenes. There are many types of naphthenes present in crude oil,
but except for the lower-molecular-weight such as cyclopentane and
cyclohexane, are generally not handled as individual compounds. They are
classified according to boiling range and their properties determined with the
help of correlation factors such as the characterization (Kw) factor or
correlation index ( CI) . The aromatic series of hydrocarbons is chemically and
physically very different from the paraffins and cycloparaffins (naphthenes).
The cyclic hydrocarbons, both naphthenic and aromatic, can add paraffin side
chains in place of some of the hydrogen attached to the ring carbons and form
a mixed structure.

Petroleum /crude oil[19]

• Petroleum (also called crude oil) is a mixture of gaseous, liquid , and

solid hydrocarbon compounds.

19
 • Petroleum occurs in sedimentary rock deposits throughout the world and
also contains small quantities of nitrogen oxygen and sulfur-containing
compounds as well as trace amounts of metallic constituents.

Petroleum[19]

• The fuels derived from Petroleum contribute approximately one-third to

one-half of the total world energy supply and are used for transportation
fuels (gasoline,diesel fuel,and aviation fuel,among others) and heating
buildings.
• Petroleum products have a wide variety of uses that vary from gaseous
and liquid fuels to near-solid machinery lubricants. Residue of many
refinery processes asphalt—is now a premium value product for highway
surfaces, roofing materials, and miscellaneous waterproofing uses.
• Crude petroleum is a mixture of compounds boiling at different
temperatures that can be separated into a variety of different generic
fractions by distillation and the terminology of these fractions has been
bound by utility and often bears little relationship to composition.

Major Processes:[19-20]

• Desalting
• Sweetening
• Hydrogen Generation Unit
• DHDS/DHDT
• Reformer
• Isomerisation
• Amine Treating
• Sulphur Recovery Unit
• Bitumen Blowing Unit
• Lube and wax
• Solvent Extraction
• Solvent dewaxing
• Solvent Deoiling
• Solvent deasphalting
• Lube isomerisation
• Hydrodesulfurisation

20
 Fig:1.3[15]A typical REFINERY PROCESS CHART

Typical Refinery Products

• LPG 2.1%
• NAPHTHA 5.0%
• MS 11.2%
• OTHERS 18.3%
• LIGHT DISTILLATE 36.6%
• ATF 9.0

Chemistry in Fuel refining

Key properties of Fuels

• MS: Octane number, Sulphur, distillation, Oxidation stability, Bz/
Aromatics/ Olefin content.
• HSD: Cetane number,Sulphur,distillation,lubricity.
• Kerosene: Smoke Point.

21
 • ATF: Freezing point.
• Furnace oil: Stability.
• Bitumen: Penetration, viscosity, Softening point.
• LOBS: Viscosity, Viscosity Index.

Definations and Terminology[19,20]

Petroleum is a mixture of gaseous, liquid, and solid hydrocarbon compounds

that occur in sedimentary rock deposits throughout the world and also
contains small quantities of nitrogen, oxygen, and sulfur-containing
compounds as well as trace amounts of metallic constituents.Petroleum is a
naturally occurring mixture of hydrocarbons, generally in a liquid state, which
may also include compounds of sulfur, nitrogen, oxygen, metals, other
elements .Any naturally occurring hydrocarbon, whether in a liquid, gaseous,
or solid state may found explorations.

Complexity of a refinery[19,20]

The combination of refining processes and operations employed (complexity)

varies from one refinery to another.Modern refinery is highly complex, energy
and capital intensive. Role of catalytic processes, secondary processing and
hydroprocessing is increasing .Factors deciding the complexity of a refinery.

• Nature/source of crude oils- flexibility to process variety of crudes.

• Demand pattern in the markets.
• Product quality - current/ future.
• Production of feedstocks for downstream units.
• Inter-fuel substitution.

Separation : Heavy on the bottom, light on the top

• The separation of crude oil by atmospheric and vacuum distillation into

groups of hydrocarbon compounds of different boiling point ranges
called “fractions” or “cuts”.
• The first step in crude oil processing, where the first separation takes
place is called Crude Distillation Unit (CDU) Atmospheric & Vacuum Unit
(AVU).
• This step is performed in all refineries :These units are called “Mother
Units”
• Typical products from CDU are : Gas, LPG, naphtha, SKO/ATF, HSD and
RCO.
• Vacuum Distillation of RCO produces VGO (or LOBS cuts) and VR
22
• All products need further treatment/processing.

Classification of crude

The hydrocarbons found in petroleum are classified into the

following types:[19,20]
• Paraffins(CnH2n+2)saturated hydrocarbons with straight or
branched chains, but without any ring structure.
• Cycloparaffins (CnH2n)(naphthenes),saturated hydrocarbons
containing one or more rings, each of which may have one or more
paraffin side-chains(also known as alicyclic hydrocarbons).
• Aromatics(CnH2n-6)i.e,hydrocarbons containing one or more
aromatic nuclei such as benzene, naphthalene, and phenanthrene
ring systems that may be linked up with (substituted) naphthalene
rings or paraffin side-chains.

Paraffins:
• Carbon atoms connected by single bond
• Other bonds saturated with hydrogen

Naphthenes:
• Ringed Paraffins (Cycloparaffins)
• All bonds saturated with hydrogen

Aromatics:
• Six Carbon Rings (Multiple Bonding)
• All bonds unsaturated

Olefins:
• Usually not in crude oil
• Formed During Processing
• At least two carbon atoms connected by double bond

23
 Fig:1.4 A typical example of n-butane, Cyclopentane, Decaline,
Benzene, Napthalene, and 1-butene.

Paraffin /naphthene/Asphaslt base crude (based on residue

after distillation)[21]
• Paraffin base:The presence of paraffin wax in residue is reflected
in the paraffin nature of the constituent.
• Asphaltic base:high asphaltic content corresponds with the
naphthene properties of the fractions.Asphalt-base(black
amorphous soild MW 600-30K)crude oils our mainly of highly
Aromatic (or naphthene) hydrocarbons.

Crude oil[19]

Color: Light brown to dark brown

Sp.gr: 0.81—0.985
Boiling range : 25 – 400oC
Hydrocarbons C1- C70 (4000 compounds)
Metals: V, Fe, Ni
S-( H2S,Thiols (mercaptans), sulfides, di sulfides, poly sulfides and
thiophenes).

24
 Cause corrosion of equipments, bad odour in products,catalyst
poisoning, Air pollution.
N –Indols, pyridines and quinolenes (Difficult to remove).
• Oxygen compounds: present as naphthenic acids and phenols
• Are corrosive in nature and cause odour.
• Metal: act as catalyst poisons

Crude composition
C: 84-87%,H: 11-14%,S: 0-5%,N: 0-1%,O: 0-2%.

Reservoirs/ sedimentary basin[19-22]

• Petroleum occurs underground, at various pressures depending on
the depth.
• Because of the pressure, it contains considerable natural gas in
solution. Petroleum underground is much more amount of fluid with
than the surface and is generally mobile under reservoir conditions
because of the elevated temperature phase(the geothermal
gradient) in subterranean formations decrease the viscosity.
• Petroleum is derived from aquatic plants and animals that lived and
died hundreds of millions of years ago.Their remains mixed with
mud and sand in layered deposits that, over the millennia, were
geologically transformed into sedimentary rock.

Reservoiur and Oil field

• Gradually the organic matter decomposed and eventually formed
petroleum (or a related precursor), which migrated from the
original source beds to more porous and permeable rocks, such as
sandstone and silt stone, where it finally became entrapped. Such
entrapped accumulations of petroleum are called reservoirs.
• A series of reservoirs within a common rock structure or a series of
reservoirs in separate but neighboring formations is commonly
referred to as an oil field.
• A group of fields is often found in a single geologic environment
known as a sedimentary basin or province.

Estimations of Reserves[22]

Estimation of HC Content :Done by material balance

Estimation of fresh finding:by physical condition of the reservoir.
Porous sedimentary rocks:porosity(e)
Maximum amount of HC that can present in rock=e * (vol. of reservoir)
WATER present in oil=SW connate water

25
Total volume of HC deposited=vol.of reservoir.*e*(1-SW)( volume
Deposited under reservoir condition)
Generally deposits are several meter deep where pressure >100atm.Lig/
gas volume expan-sion factor Bg at surface conditions For liquid
expansion factor is small but for gas it is high.
Thus Total vol.of deposit at surface condition=vol. of reservoir*e*(1-
Sw)* Bg.

Table:1.2

Subdivision of Petroleum and Similar

Materials into Various Subgroups[19-22]

Natural Derived Manufactured

Materials Materials Materials

Synthetic
Natural Gas Saturates
Crude Oil

Petroleum Aromatics Distillates

Lubricating
Heavy Oil Resins
Oils

Bitumena Asphaltenes Wax

Asphaltite Carbenesb Residuum

Asphaltoid Carboidsb Asphalt

Ozocerite(Natural
- Coke
Wax)

Kerogen - Tar

Coal - Pitch

Refinery Operation

• Crude oil is transported to refineries by pipelines, (more than

500,000 barrels per day), or by ocean-going tankers.
• The basic refinery process is distillation, which separates the crude
oil into fractions of differing volatility.

26
 • After the distillation,other physical methods are employed to
separate the mixtures including absorption adsorption solvent
extraction and crystallization.
• After physical separation into such constituents as light and heavy
naphtha, kerosene, light and heavy gas oils selected petroleum
fractions may be subjected to conversion processes such as
thermal cracking (i.e., coking;) and catalytic cracking.
• Cracking breaks the large molecules of heavier gas oils into the
smaller molecules that form the lighter, more valuable naphtha
fractions.
• Reforming changes the structure of straight-chain paraffin
molecules into branched-chain iso-paraffins and ring-shaped
aromatics. The process is widely used to raise the octane number
of gasoline obtained by distillation of paraffinic crude oils.

Table:1.3

Process Development Since The Commencement Of The

Modern Refining Era[19,20]

Year Process Name Purpose By Product

Atmospheric Naphtha,Cracked
1862 Produce Kerosene
Distillation Residuum

1870 Vacuum Distillation Lubricants Asphalt,Residua

Increase Gasoline
1913 Thermal Cracking Residua,Fuel Oil
Yield

1916 Sweetening Reduce Sulfur Sulfur

Improve Octane
1930 Thermal Reforming Residua
Number

1932 Hydrogenation Remove Sulfur Sulfur

1932 Coking Produce Gasoline Coke

Improve Lubricant
1933 Solvent Extraction Aromatics
Viscosity Index

1935 Solvent Dewaxing Improve Pour Point Wax

27
 Catalytic Improve Octane Petrochemical
1935
Polymerization Number Feedstocks

Higher Octane Petrochemical

1937 Catalytic Cracking
Gasoline Feedstocks

Increased
1939 Visbreaking Reduce Viscosity
distillate Yield

Increase Octane High-Octane

1940 Alkylation
Number aviation Fuel

Produce Alkylation
1940 Isomerization Naphtha
Feedstock

Fluid Catalytic Increase Gasoline Petrochemical

1942
Cracking Yield Feedstocks

Increase Cracker
1950 Deasphalting Asphalt
Feedstock

Convert Low-Quality
1952 Catalytic Reforming Aromatics
Naphtha

1954 Hydrodesulfurization Remove Sulfur Sulfur

Inhibitor Disulfides and

1956 Remove Mercaptans
Sweetening Sulfur

Catalytic Convert To High Alkylation

1957
Isomerization Octane Products Feedstocks

Improve Quality And Alkylation

1960 HydroCracking
Reduce Sulfur Feedstocks

1974 Catalytic Dewaxing Improve Pour Point Wax

Resid Increase Gasoline

1975 Cracked Residua
HydroCracking Yield

28
 Fig:1.5[15]A typical REFINERY PROCESS CHART with both
Atmospheric (ADU) and Vaccum distillation process (VDU).

Classification of Crude as a hydrocarbon resource:[19,20]

Fossil energy resources divide into two classes:

29
 • Naturally occurring hydrocarbons (petroleum, natural gas, and
natural waxes)
• Hydrocarbon sources (oil shale and coal) which may be made to
generate hydrocarbons by the application of conversion
processes.Oil Shale are argillaceous, laminated sediments of
generally high organic content that can be thermally decomposed
to yield appreciable amounts of oil.
• The classification of petroleum and natural gas as naturally
occurring mixtures of hydrocarbons occurs by virtue of the fact that
they can be separated into their original hydrocarbon constituents.
• The hydrocarbon constituents, separated from petroleum and
natural gas, are the hydrocarbon constituents that existed from the
reservoir.
• Naturally occurring hydrocarbons are major contributors to the
composition of petroleum and natural gas.
• Coal and kerogen do not enjoy this by means of separation and
methods of thermal decomposition and it must be applied before
hydrocarbons are produced.
• Kerogen is the complex carbonaceous (organic) material that
occurs in sedimentary rocks and shales.

Subdivision of the earth’s organic sediments[20]

30
 Fig:1.6

Classification of the earth’s organic sediments according to

hydrocarbon occurrence and production.[20]

Fig:1.7

Characterization of crude:

Crude Oil Properties

Crude of petroleum is very complex except for the low-

boiling components, no attempt is made by the refiner
to analyze for the pure components that contained in
the crude oil. Relatively simple analytical tests are run
on the crude and the results of these are used with
empirical correlations to evaluate the crude oils as
feedstocks for the particular refinery. Each crude is
compared with the other feedstocks available and,

31
based upon the operating cost and product realization,
is assigned a value. The useful properties are discussed.

API Gravity:The density of petroleum oils is expressed

in the United States in terms of API gravity rather than
specific gravity; it is related to specific gravity in such a
fashion that an increase in API gravity corresponds to a
decrease in specific gravity. The units of API gravity are
API and can be calculated from specific gravity (sp. Gr.)
by the following:
API=141.5/Sp.Gr-131.5
Sp. Gr. of rude oil may vary from less than 10oAPI to
over 50oAPI but most crudes fall in the 20 to 45o API
range. API gravity always refers to the liquid sample at
60 oF (15.6 oC). API gravities are not linear and,
therefore, cannot be averaged. For example, a gallon of
20o API gravity hydrocarbons when mixed with a gallon
of 30oAPI hydrocarbons will not yield two gallons of
25o API hydrocarbons, but will give two gallons of
hydrocarbons with an API gravity different from 250 API.
On the other hand Specific gravities of different oils can
be averaged.

Sulfur Content, wt%[20]

Sulfur content and API gravity are two properties which

have the greatest influence on the value of crude oil,
although nitrogen and metals contents are increasing in
importance. The sulfur content is expressed as percent
of sulfur by weight and varies from less than 0.1% to
greater than 5%. Crudes with greater than 0.5% sulfur
generally require more extensive processing than those
with lower sulfur content.

Pour Point[20]

The pour point of the crude oil, in oF or oC, is a rough

indicator of the relative paraffinicity and aromaticity of
the crude. The lower the pour point, the lower the
paraffin content and the greater the content of
aromatics.

Carbon Residue[20]

32
Carbon residue is determined by distillation to a coke
residue in the absence of air. The carbon residue is
roughly related to the asphalt content of the crude and
to the quantity of the lubricating oil fraction that can be
recovered. In most cases the lower the carbon residue,
the more valuable the crude. This is expressed in terms
of the weight percent carbon residue by either the
Ramsbottom (RCR) or Conradson (CCR) .

Salt Content[20]

If the salt content of the crude, when expressed as NaCl,

is greater than 10 lb/ 1000 bbl, it is generally necessary
to desalt the crude before processing. If the salt is not
removed, severe corrosion problems may be
encountered. If residua are processed catalytically,
desalting is desirable at even lower salt contents of the
crude. Although it is not possible to have an accurate
conversion unit between lb/1000 bbl and ppm by weight
because of the different densities of crude oils, 1
lb/1000 bbl is approximately 3 ppm.

Characterization Factors[20]

There are several correlations between yield and the

aromaticity and paraffinicity of crude oils, but the two
most widely used are the UOP or Watson
‘‘characterization factor’’ (KW) and the U.S. Bureau of
Mines ‘‘correlation index’’ (CI).
KW= TB1/3/ G , Where,TB is the mean average boiling
point, R and G is the specific gravity at 60 oF.
The Watson characterization factor :KW ~15 for highly
paraffinic compounds , KW <10 for highly aromatic
materials and KW vary from 10.5 to 12.9. For a highly
naphthenic crude it is 10.5 to 12.9 for a paraffinic base
crude.
The correlation index is useful in evaluating individual
fractions from crude oils. The CI scale is based upon
straight-chain paraffins having a CI value of 0 and
benzene having a CI value of 100 and is defined as
follows:
C.I = 87552/TB + 473.7 G – 456.8
The CI values are not quantitative, but the lower the CI
value, the greater the concentration of paraffin

33
hydrocarbons in the fraction; and higher the CI value,
greater the concentration of naphthenes and aromatics.

Nitrogen Content, wt%

High nitrogen content is undesirable in crude oils

because organic nitrogen compounds cause severe
poisoning of catalysts used in processing and cause
corrosion problems. Crudes containing nitrogen more
than 0.25% by weight require special processing to
remove the nitrogen.[19,20]

Distillation Range

The boiling range of the crude gives an indication of the

quantities of the various products present. The most
useful type of distillation is known as a true boiling. point
(TBP) distillation and generally refers to a distillation
performed in equipment that accomplishes a reasonable
degree of fractionation. There is no specific test
procedure called a TBP distillation, but the U.S. Bureau
of Mines Hempel and ASTM D-285 distillations are the
tests most commonly used. Neither of these specify
either the number of theoretical plates or the reflux ratio
used and, as a result, there is a trend toward using the
results of a 15:5 distillation (D- 2892) rather than the
TBP. The 15:5 distillation is carried out using 15
theoretical plates at a reflux ratio of 5: 1. The crude
distillation range has to be correlated with ASTM
distillations because product specifications are generally
based on the simple ASTM distillation tests like D-86 and
D-1160 etc.[20]

Metals Content, ppm

The metals content metals (nickel, vanadium, and

copper) of crude oils vary from a few parts per million
to more than 1000 ppm. Minute quantities of some of
these metals can severely affect the activities of
catalysts and result in a lower value product distribution.
Vanadium concentrations above 2 ppm in fuel oils can
lead to severe corrosion to turbine blades and
deterioration of refractory furnace linings and stacks.
Distillation concentrates the metallic constituents of

34
crude in the residues, but some of the organometallic
compounds are actually volatilized at refinery distillation
temperatures and appear in the higher-boiling
distillates. The metallic content may be reduced by
solvent extraction with propane or similar solvents as
the organometallic compounds are precipitated with the
asphaltenes and resins.

API GRAVITY(Indicates the crude sp.gr) (American

petroleum Institute)
API=141.5/Sp.Gr. – 131.5
• Heavy oils: Petroleum- materials less than
200o API
• Heavy oils: API gravity range of 10o to 15oAPI
• Bitumen : API gravity 5o to 10oAPI
• Atmospheric residua: 10o to 15o API
• vacuum residua : 2o to 8o API

UOP Characterization Factor/ Waston

Characterization Fator[23]

Characterization factors: K=(TB)1/3/d

(Correlates boiling point with sp.Gr.)
where TB is the average boiling point in degrees Rankine
(= F + 460) and d is the specific gravity 60 oF/60 oF.
(Also Kuop= (Tk)3/0.827 G, if T in K)
K:additive on a weight basis.
Highly paraffin oils:K : 12.5 to 13.0
Cyclic (naphthenes) oils have K : 10.5 to 12.5.
Aromatics: 9.0- 10.5

Correlation Index (C.I.)[23]

• According to the chemical composition of the

250 oC to 300 oC fraction has been used.
• But the difficulty is that in the fractions boiling
above 200 oC (390 oF) the molecules can no longer
be placed in one group, because most of them are
of a typically mixed nature.
• More direct chemical information is desirable and
can be supplied by means of the correlation index
(CI).

35
 • The CI, developed by the U.S. Bureau of Mines, is
based on the plot of specific gravity vs the
reciprocal of the boiling point in Kelvin .

For pure hydrocarbons,the normal paraffin series is

given value of CI=0 and for benzene CI = 100.
CI= 473.7d - 456.8 + 48,640/TK
Where, TK for a petroleum fraction is the average boiling
point (K) and ‘d’ is the specific gravity
• CI Values between 0 and 15 : indicates a
predominance of paraffin hydrocarbons in the
fraction.
• CI Values 15 to 50 : indicates predominance of
either naphthenes or of mixtures of paraffins,
naphthenes, and aromatics.
• CI values more than 50 : indicates a
predominance of aromatic species.

Characterization of crude:

Crude Oil Properties

Crude of petroleum is very complex except for the low-

boiling components, no attempt is made by the refiner
to analyze for the pure components that contained in
the crude oil. Relatively simple analytical tests are run
on the crude and the results of these are used with
empirical correlations to evaluate the crude oils as
feedstocks for the particular refinery. Each crude is
compared with the other feedstocks available and,
based upon the operating cost and product realization,
is assigned a value. The useful properties are discussed.

API Gravity:The density of petroleum oils is expressed

in the United States in terms of API gravity rather than
specific gravity; it is related to specific gravity in such a
fashion that an increase in API gravity corresponds to a
decrease in specific gravity. The units of API gravity are
API and can be calculated from specific gravity (sp. Gr.)
by the following:

36
API=141.5/Sp.Gr-131.5
Sp. Gr. of rude oil may vary from less than 10oAPI to
over 50oAPI but most crudes fall in the 20 to 45o API
range. API gravity always refers to the liquid sample at
60 oF (15.6 oC). API gravities are not linear and,
therefore, cannot be averaged. For example, a gallon of
20o API gravity hydrocarbons when mixed with a gallon
of 30oAPI hydrocarbons will not yield two gallons of
25o API hydrocarbons, but will give two gallons of
hydrocarbons with an API gravity different from 250 API.
On the other hand Specific gravities of different oils can
be averaged.

Sulfur Content, wt%[20]

Sulfur content and API gravity are two properties which

have the greatest influence on the value of crude oil,
although nitrogen and metals contents are increasing in
importance. The sulfur content is expressed as percent
of sulfur by weight and varies from less than 0.1% to
greater than 5%. Crudes with greater than 0.5% sulfur
generally require more extensive processing than those
with lower sulfur content.

Pour Point[20]

The pour point of the crude oil, in oF or oC, is a rough

indicator of the relative paraffinicity and aromaticity of
the crude. The lower the pour point, the lower the
paraffin content and the greater the content of
aromatics.

Carbon Residue[20]

Carbon residue is determined by distillation to a coke

residue in the absence of air. The carbon residue is
roughly related to the asphalt content of the crude and
to the quantity of the lubricating oil fraction that can be
recovered. In most cases the lower the carbon residue,
the more valuable the crude. This is expressed in terms
of the weight percent carbon residue by either the
Ramsbottom (RCR) or Conradson (CCR) .

Salt Content[20]

37
If the salt content of the crude, when expressed as NaCl,
is greater than 10 lb/ 1000 bbl, it is generally necessary
to desalt the crude before processing. If the salt is not
removed, severe corrosion problems may be
encountered. If residua are processed catalytically,
desalting is desirable at even lower salt contents of the
crude. Although it is not possible to have an accurate
conversion unit between lb/1000 bbl and ppm by weight
because of the different densities of crude oils, 1
lb/1000 bbl is approximately 3 ppm.

Characterization Factors[20]

There are several correlations between yield and the

aromaticity and paraffinicity of crude oils, but the two
most widely used are the UOP or Watson
‘‘characterization factor’’ (KW) and the U.S. Bureau of
Mines ‘‘correlation index’’ (CI).
KW= TB1/3/ G , Where,TB is the mean average boiling
point, R and G is the specific gravity at 60 oF.
The Watson characterization factor :KW ~15 for highly
paraffinic compounds , KW <10 for highly aromatic
materials and KW vary from 10.5 to 12.9. For a highly
naphthenic crude it is 10.5 to 12.9 for a paraffinic base
crude.
The correlation index is useful in evaluating individual
fractions from crude oils. The CI scale is based upon
straight-chain paraffins having a CI value of 0 and
benzene having a CI value of 100 and is defined as
follows:
C.I = 87552/TB + 473.7 G – 456.8
The CI values are not quantitative, but the lower the CI
value, the greater the concentration of paraffin
hydrocarbons in the fraction; and higher the CI value,
greater the concentration of naphthenes and aromatics.

Nitrogen Content, wt%

High nitrogen content is undesirable in crude oils

because organic nitrogen compounds cause severe
poisoning of catalysts used in processing and cause
corrosion problems. Crudes containing nitrogen more

38
than 0.25% by weight require special processing to
remove the nitrogen.[19,20]

Distillation Range

The boiling range of the crude gives an indication of the

quantities of the various products present. The most
useful type of distillation is known as a true boiling. point
(TBP) distillation and generally refers to a distillation
performed in equipment that accomplishes a reasonable
degree of fractionation. There is no specific test
procedure called a TBP distillation, but the U.S. Bureau
of Mines Hempel and ASTM D-285 distillations are the
tests most commonly used. Neither of these specify
either the number of theoretical plates or the reflux ratio
used and, as a result, there is a trend toward using the
results of a 15:5 distillation (D- 2892) rather than the
TBP. The 15:5 distillation is carried out using 15
theoretical plates at a reflux ratio of 5: 1. The crude
distillation range has to be correlated with ASTM
distillations because product specifications are generally
based on the simple ASTM distillation tests like D-86 and
D-1160 etc.[20]

Metals Content, ppm

The metals content metals (nickel, vanadium, and

copper) of crude oils vary from a few parts per million
to more than 1000 ppm. Minute quantities of some of
these metals can severely affect the activities of
catalysts and result in a lower value product distribution.
Vanadium concentrations above 2 ppm in fuel oils can
lead to severe corrosion to turbine blades and
deterioration of refractory furnace linings and stacks.
Distillation concentrates the metallic constituents of
crude in the residues, but some of the organometallic
compounds are actually volatilized at refinery distillation
temperatures and appear in the higher-boiling
distillates. The metallic content may be reduced by
solvent extraction with propane or similar solvents as
the organometallic compounds are precipitated with the
asphaltenes and resins.

39
API GRAVITY(Indicates the crude sp.gr) (American
petroleum Institute)
API=141.5/Sp.Gr. – 131.5
• Heavy oils: Petroleum- materials less than
200o API
• Heavy oils: API gravity range of 10o to 15oAPI
• Bitumen : API gravity 5o to 10oAPI
• Atmospheric residua: 10o to 15o API
• vacuum residua : 2o to 8o API

UOP Characterization Factor/ Waston

Characterization Fator[23]

Characterization factors: K=(TB)1/3/d

(Correlates boiling point with sp.Gr.)
where TB is the average boiling point in degrees Rankine
(= F + 460) and d is the specific gravity 60 oF/60 oF.
(Also Kuop= (Tk)3/0.827 G, if T in K)
K:additive on a weight basis.
Highly paraffin oils:K : 12.5 to 13.0
Cyclic (naphthenes) oils have K : 10.5 to 12.5.
Aromatics: 9.0- 10.5

Correlation Index (C.I.)[23]

• According to the chemical composition of the

250 oC to 300 oC fraction has been used.
• But the difficulty is that in the fractions boiling
above 200 oC (390 oF) the molecules can no longer
be placed in one group, because most of them are
of a typically mixed nature.
• More direct chemical information is desirable and
can be supplied by means of the correlation index
(CI).
• The CI, developed by the U.S. Bureau of Mines, is
based on the plot of specific gravity vs the
reciprocal of the boiling point in Kelvin .

For pure hydrocarbons,the normal paraffin series is

given value of CI=0 and for benzene CI = 100.
CI= 473.7d - 456.8 + 48,640/TK

40
 Where, TK for a petroleum fraction is the average boiling
point (K) and ‘d’ is the specific gravity
• CI Values between 0 and 15 : indicates a
predominance of paraffin hydrocarbons in the
fraction.
• CI Values 15 to 50 : indicates predominance of
either naphthenes or of mixtures of paraffins,
naphthenes, and aromatics.
• CI values more than 50 : indicates a
predominance of aromatic species.

VISCOSITY[19,20]

• Materials having viscosity less than 10,000 centipoises (cp) are

conventional petroleum and heavy oil.
• Tar sand bitumen has a viscosity greater than 10,000 cp.
• In order to classify petroleum, heavy oil, and bitumen the use of a single
parameter such as viscoity is not enough.

Other properties such as API gravity, elemental analysis,

composition, and the properties of the
fluid in the reservoir as well as the method of recovery need to be
acknowledged

Fig.1.8 Classification of petroleum, heavy oil, and bitumen by API

gravity and viscosity

POUR POINT[20]

41
• Tar sand bitumen is a naturally occurring material that is immobile in
the deposit and cannot be recovered by the application of enhanced oil
recovery technologies, including steam –based technologies.
• Heavy oil is mobile in the reservoir and can be recovered by the
application of enhanced oil recovery technologies,including steam–
based technologies.
• Pour point is the lowest temperature at which oil will move, pour , or
flow when it is chilled without disturbance under definite conditions
(ASTM D97).
• The pour point and reservoir temperature present a more accurate
assessment of the condition of the oil in the reservoir an indicator of the
mobility of the oil in the reservoir.
• when used in conjunction with reservoir temperature, the pour point
gives an indication of the liquidity of the heavy oil or bitumen and,
therefore the ability of the heavy oil or bitumen to flow under reservoir
conditions.
• In summary, the pour point is an important consideration because, for
efficient production, additional energy must be supplied to the reservoir
by a Thermal process to increase the reservoir temperature beyond the
pour point.
• Pour point offers more general applicable to the conditions of the oil in
the reservoir or the bitumen in the deposit and comparison of the two
temperatures(pour point and reservoir temperatures) that shows
promise and warrants for further consideration.

Fig:1.9
CRUDE DISTILLATION

42
 Overview

Purpose
• To recover light materials.
• Fractionate into sharp light fractions.

Configuration —May be as many as three columns in series

• Crude Stabilizer/Preflash Column

Reduce traffic in the Atmospheric Column

• Atmospheric Column
• Vacuum Column

Reduced pressure to keep temperatures below 650o F

Crude Oil Fractionation / Distillation

• Crude oil is heated to 750 oF (400 oC)

• Heated crude is separated into rough "cuts“

• Different boiling point are drawn from the distillation tower.

• Light compounds (fuel gas and LPG) rise to the top of the tower,
Heavy material (asphalt) falls to the bottom of the tower.

Petroleum Refining Operations.

• Petroleum refining begins with the distillation, or fractionation,

of crude oils into separate hydrocarbon groups like Light ends,
naphtha/gasoline kerosine diesel and residue etc.
• The resultant products are directly related to the characteristics
of the crude processed.(T 650-750 deg oF) or (310 oC-350 oC)
• Most distillation products are further converted into more usable
products by changing the size and structure of the hydrocarbon
molecules through cracking, reforming, and other conversion
processes.

43
 Fig 1.10 Atmospheric Distillation[19]

Fig:1.11 Typical Configuration Atmospheric Column w/o

Preflash[19,20]

44
 Fig:1.12 ADU & VDU OVERVIEW [24,25]

Wash Zone
• Couple trays between flash zone & gas oil draw.
• Reflux to wash resins & other heavy materials that may
contaminate the products.

Condenser
• Typically 0.5 to 0.2 psig.
• Balancing act
▪ Low pressure reduce compression on overhead system.
▪ High pressure decrease vaporization but increases flash
zone temperature & furnance duty: affects yields.

Pumparounds
• Reduces overhead condenser load & achieves more uniform
tower loading.

45
• provides liquid reflux below liquid draws.

• Side draws & strippers cut point related to final boiling point of
draw steam.
• Side strippers remove light component tail & return to main
column.
• Steam strippers traditional.
• Reboiled strippers reduce steam usage & associated sour water.

Trays & pressure profile [19,20,24,25]

• Typically 32 in tower 0.1 to 0.2 psi per tray.
• Condenser & accumulator 3 to 10 psi across condenser liquid
static head in accumulator.
• Typically 6 to 16 psi across entire column.

46
Fig:1.13 A typical configuration of Atmospheric column with
stripping section and reflux drum arrangement.

47
Fig:1.14[19]A typical configuration of two stage hydrocracking unit.

Table:1.4

Typical Crude Tower Cut Points [19,20]

CUT TBP IBP(oF) TBP EP(oF)

Light Naphtha(LSR
80 to 90 180 to 220
Gasoline)

Heavy Naphtha 180 to 220 330 to 380

Distillate (Kerosene) 330 to 380 420 to 520

AGO(Atm Gas Oil) 420 to 520 650

LVGO(Light Vac Gas Oil) 650 800

48
 950 to
HVGO(Heavy Vac Gas Oil) 800
1100

950 to
Vaccum Resid -
1100

REFINERY PRODUCTS

Generally,the products which dictate refinery design are relatively few in number, and the basic
refinery processes are based on the large-quantity products such as gasoline, diesel, jet fuel, and
home heating oils. Storage and waste disposal are expensive, and it is necessary to sell or use all
of the items produced from crude oil even if some of the materials, such as high-sulfur heavy
fuel oil and fuel-grade coke, must be sold at prices less than the cost of fuel oil. Economic
balances are required to determine whether certain crude oil fractions should be sold as is (i.e.,
straight-run) or further processed to produce products having greater value. Usually the lowest
value of a hydrocarbon product is its heating value or fuel oil equivalent (FOE). This value is
always established by location, demand, availability, combustion characteristics, sulfur content,
and prices of competing fuels. Low-Boiling Products

• The compounds which are in the gas phase at ambient temperatures and pressures
methane, ethane, propane, butane, and the corresponding olefins.

Methane (C1)

• It is usually used as a refinery fuel, but can be used as a feedstock for hydrogen
production by pyrolytic cracking and reaction with steam.
• It is generally expressed in terms of pounds or kilograms, standard cubic feet (scf) at 60
°F and 14.7 psia, normal cubic meters (Nm3) at
• 15.6 °C and 1 bar(100 kPa), or in barrels fuel oil equivalent (FOE) based on a lower
heating value (LHV) of 6.05 x106 Btu (6.38 x106kJ).

Refinery Gases

• Ethane (C2) can be used as refinery fuel or as a feedstock to produce hydrogen or

ethylene, which are used in petrochemical processes.
• Ethylene and hydrogen are recovered in the refinery and sold to petrochemical plants.

Refinery Products

• n-butane has a blending octane in the 90s and is a low-cost octane improver of gasoline.
• Isobutane used as a feedstock to alkylation units, where it is reacted with unsaturated
materials (propenes, butenes, and pentenes) to form high-octane isoparaffin compounds
in the gasoline boiling range.

49
 Liquified Petroleum Gas (LPG) Mixture of light HCs propane and butane,gases at ambient
temperature but condensed to liquid state by applying moderate pressure.
• Mainly consists of propane, propylene, butane, butene, and iso - butane.
• A significant amount of isobutane is converted to isobutylene which is reacted with methanol
to produce methyl tertiary butyl ether (MTBE).
• Used as an additive for gasoline.
• n-butane as LPG has the disadvantage of a fairly high boiling point [32 °F (0 °C) at 760
mmHg] and during the winter is not satisfactory for heating when stored outdoors in areas
which frequently have temperatures below freezing.
• Isobutane has a boiling point of 11 °F (12 °C) and is also unsatisfactory for use in LPG for
heating in cold climates.
• Butane–propane mixtures are also sold as LPG, and their properties and standard test
procedures are also specified by the GPA.
• Use Domestic fuel, feed stock for various chemicals and fuel for IC engine.
Table:1.5[19,20]

Properties Of Comercial Propane And

Butane
Commercial Commercial
Property
Propane Butane

Vapour Pressure,Psig

70oF(21.1oC) 124 31

100oF(38oC) 192 59

130oF(54oC) 286 97

Specific Gravity Of
0.509 0.582
Liquid,60/60o

Intial Boiling Point

-51(-47.4) 15
At 1 Bar oF(oC)

Dew Point At 1
-46(-44.6) 24
Bar oF(oC)

Sp.ht.Liquid At 60oF,15.6oC

Btu/lb(oF) 0.588 0.549

Kj/(kg)(0C) 2.462 2.299

Limits Of Flammability,Vol% Gas In Air

50
 Upper Limits 2.4 1.9

Lower Limits 9.6 8.6

Latent Heat Of Vaporization At VP

Btu/lb 185 165

Kj/(kg) 430.3 383.8

Gross Heating Values

Btu/lb Of Liquid 21,550 21,170

Btu/ft3 Of Gas 2,560 3,350

Kj/(kg) Of Liquid 50,125 49,241

Kj/m3 Of Gas 9,538 12,482

LPG Production Methods of Extraction of LPG from NG

• Compression and cooling.

• Adsorption.
• Absorption.

Cryogenic process:

• Refrigeration by direct expansion based on Joul Thomson effect.

• Cascade refrigeration using (C3) as refrigerant.
• Turbo expander

Gasoline /Motor Spirit[19,20]

• Gasolines are complex mixtures of hydrocarbons having typical boiling ranges from 100
to 400 °F (38 to 200 °C)as determined by the ASTM method.
• Hydrocarbon range:C5-C10(mainly n-paraffins, iso paraffins,naphthenes and aromatic
hydrocarbons)
• Components are blended to promote:
• high antiknock quality (High octane number)
• ease of starting
• quick warm-up
• low tendency to vapor lock
• And low engine deposits

51
Production of

Gasoline
Fig:1.15
Gasoline Specifications Most important properties wide greatest effects on engine performance
are: Reid vapor pressure,Boiling range,and Antiknock characteristics.The Reid vapor pressure is
approximately the vapor pressure of the gasoline at 100 °F (38 °C) in absolute units (ASTM
designation D-323).The Reid vapor pressure (RVP) and boiling range of gasoline governs ease
of starting,engine warm-up,rate of acceleration,loss by crankcase dilution,mileage economy,and
tendency toward vapor lock.

• Engine warm-up time is affected by the percent distilled at 158 °F (70 °C) and the 90%
ASTM distillation temperature.
• Warm-up is expressed in terms of the distance operated to deveop full power without
excessive use of the choke.A two-to four-mile (3 to 7 km) warm-up is considered
satisfactory.
• Altitude affects several properties of gasoline, the most important of which are losses by
evaporation and octane requirement.
• Octane number:requirement is greatly affected by altitude and, for a constant spark
advance, is about three units lower for each 1000 ft(305 m) of elevation.In practice,
however the spark is advanced at higher elevations to improve engine performance and
the net effect is to reduce the PON of the gasoline marketed by about two numbers for a
5000- ft (1524-m) increase in elevation.

Octane Number[19,20]

• Octane numbers are obtained by two test procedures; those obtained by the first method
are called motor octane numbers(indicative of high-speed performance)and those
obtained by the second method are called research octane numbers (indicative of normal
road performance).
• Octane numbers quoted are usually, unless stated otherwise, research octane numbers. In
the test methods used to determine the antiknock properties of gasoline,comparisons are

52
 made with blends of two pure hydrocarbons, n-heptane and iso-octane (2,2,4-
trimethylpentane).
• Octane numbers quoted are usually, unless stated otherwise, research octane numbers. In
the test methods used to determine the antiknock Properties
• Iso-octane has an octane number of 100 and is high in its resistance to knocking; n-
heptane is quite low (with an octane number of 0) in its resistance to knocking.

Gasoline/ Motor spirit[19,20]

• Posted octane numbers (PON) are arithmetic averages of the motor octane number
(MON) and Research octane number (RON) and average four to six numbers below the
RON.
• PON is the arithmetic average of the research and motor octane numbers [(RON
+MON)/2].
• The posted method octane number (PON) of unleaded regular gasolines :~ 87 and
• premium gasolines :ranged from 89 to 93.
• For all gasolines, octane numbers average about two numbers lower for the higher
elevations of the Rocky Mountain states.
• The difference between the research and motor octane is an indicator of the sensitivity of
the performance of the fuel to the two types of driving conditions and is known as the
‘‘sensitivity’’ of the fuel.
• Aviation gasoline: higher volatility and higher octane number
• Other Activity: antioxidants, metal deactivators, and anti stall agents, are included with
the cost of the antiknock chemicals added.
• Light straight-run (LSR) : gasoline consists of the (C5)-190 °F (C5)-88 °C) fraction of
the naphtha from the atmospheric crude still.
• ( C5)-190 °F fraction means that pentanes are included in the cut but that (C4) and lower-
boiling compounds are excluded and the TBP end point is approximately 190 °F.

Technological Option For MS Quality ImprovementHydroprocessing:

• For Sulphur Reduction

• For Benezene saturation
• For Olefin Reduction

Isomerisation:

• For Ocatane Improvement

Reforming:

• For Ocatane Improvement

• Use Of Oxygenates For Octane Improvement

Table:1.6

53
 WORLDWIDE - GASOLINE QUALITY
New
Attribu Indi Euro Jap Kor South
Unit Zeala China Taiwan
tes a ll an ea Africa
nd
91/ 89/ 91/ 90/93 92/95/9
RON Min 91 91/95 95/97
95 96 94 /95 8
Sulphu PPM 350/1 80/120/ 1000/1
150 150 100 130 800
r Min 50 180 500
30
Aroma Vol%
42 42 . or 48/42 40 . .
tics Max
35
23
Vol% 21/ 21/ 20 or
Olefins . or 35 . .
Max 18 18 25
18
70- 45
35- 60& 44- 59/59/6
RVP KPA S,96 KPA 88(W) 45-75
60 70 78 1
-W min
Gasoline

• Catalytic reformate is the C5 gasoline product of the catalytic reformer(table 1.5).[19,20]

• Heavy straight-run (HSR) and coker gasolines are used as feed to the catalytic reformer,
and when the octane needs require, FCC and hydrocracked gasolines of the same boiling
range may also be processed by this unit to increase octane levels.
• The FCC and Hydrocracked gasolines: Generally used directly as gasoline blending
stocks, but in some cases are separated into light and heavy fractions with the heavy
fractions upgraded by catalytic reforming before being blended into motor gasoline.
• Motor gasoline is unleaded and the clear gasoline pool octane is now several octane
numbers higher than when lead was permitted.

Gasoline/Motor spirit/Petrol

• The reformer increases the octane by converting low octane paraffins to high-octane
aromatics.
• Some aromatics (e.g. Benzene) have high rates of reaction with ozone to form visual
pollutants in the air and some are claimed to be potentially carcinogenic by the EPA
• This restricts the severity of catalytic reforming and will require refiners to use other
ways to increase octane numbers of the gasoline pool by incorporating more oxygenates
in the blend(Table 1.6).[19,20]

Table:1.7

54
 GASOLINE QUALITY REQUIREMENTS(Euro
Norms)
EURO- EURO- EURO- EURO-
Property
I(92) II(96) III(00) IV(05)

RON 95 95 95 95

MON 85 85 85 85

S% Wt,Max 0.05 0.05 0.015$ 0.005

Bz.,%Vol.,
5.0 5.0 1.0+ 1.0
Max

Arom.,%Vol.,
- - 42 35
Max

Olef.,%Vol.,
- - 18 ?
Max

Lead.,
0.013 0.013 0.005 0.005
gm/litre
Polymer gasoline :Manufactured by polymerizing olefinic hydrocarbons to produce higher
molecular weight olefins in the gasoline boiling range. Refinery technology favors alkylation
processes rather than polymerization for two reasons:[19,20]1- Larger quantities of higher
octane product can be made from the light olefins available2- The alkylation product is paraffinic
rather than olefinic, and olefins are highly photo reactive and contribute to visual air pollution
and ozone production. Alkylate gasoline :It is the product of the reaction of isobutane with
propylene, butylene, or pentylene to produce branched-chain hydrocarbons in the gasolineboiling
range.Alkylation of a given quantity of olefins produces twice the volume of high octane motor
fuel as can be produced by polymerization.In addition, the blending octane (PON) of alkylate is
higher and the sensitivity (RON -MON) is significantly lower than that of polymer gasoline.

• Normal butane is blended into gasoline to give the desired vapor pressure.The vapor
pressure [expressed as the Reid vapor pressure (RVP) of gasoline is a compromise
between a high RVP to improve economics and engine starting characteristics and a low
RVP to prevent vapor lock and reduce evaporation losses.
• Normal butane is blended into gasoline to give the desired vapor pressure.The vapor
pressure [expressed as the Reid vapor pressure (RVP)of Butane has a high blending
octane number and is a very desirable component of gasoline; refiners put as much in
their gasolines as vapor pressure limitations permit.
• Isobutane can be used for this purpose but it is not as desirable because its higher vapor
pressure permits a lesser amount to be incorporated into gasoline than n-butane.
• Normal butane is blended into gasoline to give the desired vapor pressure.

55
 • Concern over the effects of hydrocarbon fuels usage on the environment has caused
changes in environmental regulations which impact gasoline and diesel fuel
compositions.
• The main restrictions on diesel fuels limit sulfur and total aromatics contents and gasoline
restrictions include not only sulfur and total aromatics contents but also specific
compound limits (e.g., benzene), limits on certain types of compounds (e.g., olefins),
maximum Reid vapor pressures,and also minimum oxygen contents for areas with carbon
monoxide problems.

Distillate Fuels[20,26,27] Middle Distillate fuels can be divided into three types:

• Jet or turbine fuels,diesel fuels,and heating oils.These products are blended from a variety
of refinery streams to meet the desired specifications.
• Kerosine type jet fuels: mainly used in commercial jet airlines.
• Military jet aircraft use a 30:70 blend of a kerosine fraction and a low octane straight run
heavy naptha fraction. Butane is added for adjusting volatility.

Jet and Turbine Fuels

• Jet fuel is blended for use by both commercial aviation and military aircraft.
• Also known as turbine fuel and there are several commercial and military jet fuel
specifications.
• For most refineries the primary source of jet fuel blending stocks is the straight-run
kerosine fraction from the atmospheric crude unit because
• Kerosene (kerosine):also called paraffin or paraffin oil, is a flammable pale-yellow or
colorless oily liquid with a characteristic odor.
• It is obtained from petroleum and used for burning in lamps and domestic heaters or
furnaces, as a fuel or fuel component for jet engines,and as a solvent for greases and
insecticides.
• Kerosene is intermediate in volatility between gasoline and gas diesel oil. It is a medium
oil distilling between 150 oC and 300 oC(300 oF to 570 oF).(HC: C10-C14).
• Kerosene has a flash point of about 25 oC (77 oF) and is suitable for use as an illuminant
when burned in a wide lamp.
• Fuel oil :any liquid or liquid petroleum product that produces heat when burned in a
suitable container or that produces power when burned in an engine.

Kerosine Composition

• Chemically, kerosene is a mixture of hydrocarbons; the chemical composition depends on

its source, but it usually consists of about 10 different hydrocarbons, each containing
from 10 to 16 carbon atoms per molecule; the constituents include n-dodecane (n-C12H26),
alkyl benzenes,and naphthalene and its derivatives.
• Kerosene is less volatile than gasoline; it boils between about 140 oC (285 oF) and 320oC
(610 oF).
• Kerosene, because of its use as a burning oil, must be free of aromatic and unsaturated
hydrocarbons, as well as free of the more obnoxious sulfur compounds.The desirable

56
 constituents of kerosene are saturated hydrocarbons, and it is for this reason that kerosene
is manufactured as a straight-run fraction, not by a cracking process.
• Typical hydrocarbon chain lengths characterizing JP-4 range from C4 to C16.
• Aviation fuels consist primarily of straight and branched alkanes and cycloalkanes.
• Aromatic hydrocarbons are limited to 20% to 25% of the total mixture because they
produce smoke when burned.
• A maximum of 5% alkenes is specified for JP-4. The approximate distribution by
chemical class is:
• straight chain alkanes (32%),
• branched alkanes (31%),
• cycloalkanes (16%), and
• aromatic hydrocarbons (21%).
• Jet fuel comprises both gasoline and kerosene type jet fuels meeting specifications for use
in aviation turbine power units and is often referred to as gasoline-type jet fuel and
kerosene type jet fuel.
• Jet fuel is a light petroleum distillate that is available in several forms suitable for use in
various types of jet engines.
• The major jet fuels used by the military are
• JP-4, JP-5, JP-6, JP-7, and JP-8.
• JP-4 is a wide-cut fuel developed for broad availability.
• JP-6 has a higher cut than JP-4 and is characterized by fewer impurities.
• JP-5 is specially blended kerosene, and
• JP-7 is high flash point special kerosene used in advanced supersonic aircraft.
• JP-8 is kerosene modeled on Jet A-l fuel (used in civilian aircraft).
• Usually jet fuels sell at higher prices than diesel fuels and No. 1 and No. 2 heating oils,
and it is more profitable for the refiner to blend the kerosine fractions from the
atmospheric crude unit and the hydrocracker into jet fuel rather than other products.
• Commercial jet fuel is a material in the kerosine boiling range and must be clean burning.

Characteristics of ATF fuels

Table:1.8

Characterstics Of Aircraft Turbine Fuels(ASTM D-1655 and

DERD 2494)
DERD
Property Jet A JP-5 JP-8
2494

Aromatics,Vol%,Max 20 25 22.0 22.0

Combustion Prop

Smoke
25 19 - 25
Point,mm,min,or

57
 Smoke
18v - 19 20
Point,mm,min,and

Napthalenes,vol%,ma
3.0 - 3.0 3.0
x

Distillation,D-86,oF(oC)

10% 400(205 400(205 401(205 401(205

Recovered oF(oC),max ) ) ) )

50%
report report report report
Recovered oF(oC),max

572(300 554(290 572(300 572(300

FBP oF(oC),max
) ) ) )

Flash point,oF(oC),min 100(38) 140(60) 100(38) 100(38)

Freeze -52.6(- -52.6(-

-40(-40) -51(-46)
point,oF(oC),max 47) 47)

Sulfur,wt%,max 0.30 0.4 0.3 0.3

Two of the critical specifications relate to its clean burning requirements and limit the total
aromatics as well as the content of double ringaromatic compounds are :

• Smoke point,expressed in mm of MAXIMUM flame height at which smoking is

detected,and the volume percent total aromatics and naphthalenes.
• Specifications limit total aromatic concentration to 20% and the naphthalene content to
3% or 3.0% depending upon the specific specifications.
• Hydrocracking saturates many of the double ring aromatics in cracked products and
raises the smoke point. (Improves the quality)
• The desired freeze point specification is very low [-40 to -58 °F max(-40 to -50 °C max.)]
and hydrocracking is also used to isomerize paraffins and lower the freeze point.
• Jet fuel is blended from low sulfur or desulfurized kerosine, hydrotreated light coker gas
oil, and hydrocracked blending stocks.
• The smoke point and percent aromatics specifications limit the amount of cracked stocks
which can be blended into jet fuels.
• The two basic types of jet fuels are naphtha and kerosine.
• Naphtha jet fuel is produced primarily for the military and is a wide-boiling-range stock
which extends through the gasoline and kerosine boiling ranges.
• The naphtha-type jet fuel is more volatile and has more safety problems in handling,.
• JP-8 jet fuel is being phased in for military application.
• The JP-8 jet fuels are blended from the various components to arrive at the lowest-cost
blend that meets specifications.

58
 AUTOMOTIVE DIESEL FUELS Volatility, ignition quality (expressed as cetane number or
cetane index), viscosity, sulfur content, percent aromatics, and cloud point are the important
properties of automotive diesel fuels.

• No.1 diesel fuel ( super-diesel) is generally made from virgin or hydrocracked stocks
having cetane numbers above 45.
• It is has a boiling range from 360 to 600 °F (182 to 320 °C) and is used in high-speed
engines in automobiles, trucks, and buses.
• High speed engines above 1500 rpm, need high C.N 45-50.
• No.2 diesel fuel is very similar to No. 2 fuel oil, and has a wider boiling range than No.1.
• It usually contains cracked stocks and may be blended from naphtha, kerosine, and light
cracked oils from the coker and the fluid catalytic cracking unit.
• Limiting specifications are flash point [125 °F (52 °C)], sulfur content (0.05% max.),
distillation range, cetane number or cetane index (40 min.),percent aromatics, and cloud
point.

PRODUCTION OF DIESEL

Fig:1.16

59
DISTILLATE
BLENDING

Fig:1.17
Fuel Quality control

• The main restrictions on diesel fuels limit sulfur and total aromatics contents and gasoline
restrictions.
• Include not only sulfur and total aromatics contents but also specific compound limits
(e.g., benzene).
• Limits on certain types of compounds (e.g., olefins), maximum Reid vapor pressures.

Diesel Cetane Number

• One key to diesel quality Measures the ability for auto-ignition

• Essentially the opposite of octane number May be measured but frequently approximated
• ASTM D 976 —Standard Test Methods for Calculated Cetane Index of Distillate Fuels

Trends

• High demand.
• Heavier crudes with narrow diesel cuts.
• More stringent emissions requirements necessitate higher cetane.

WORLDWIDE-DIESEL QUALITY
Table:1.9

60
 New
Austral
Europe Zeala India (BIS)
S.N ia Japa
Attributes nd
O n
Dir.98/70/E Jan- Bhar Bhar Bhar
Jan-02
EC 04 at II at III at IV
Cetane
1 51 49 - 48 51 51 45
Number
Cetane
2 - 47 46 46 46 46
Index
Density @ 820- 820- 820- 820- 820-
3 845 860
15 oC 860 860 860 845 845
2.0- 2.0- 2.0-
4 KV @ 40 oC - 1.5-4.5 2.0-4.5 2.7
5.0 4.5 4.5
5 T 90 deg C - - - - 360
6 T 95 deg C 360 370 370 370 360 360

50/1
7 Total Sulfur 50 & 10 3000* 500# 350 50
0
500
8 Flash Point 61 61.5 35/66 35 35
Polyaromat
9 11 - - - 11 11 -
ics
Water
10 0.02 - 0.05 200 200
Content
11 Lubricity 460 460 460# 460 460 -

Table:1.10

Diesel Specification
NO.1 NO.2 NO.4

Minimum Cetane 40 40 30

Sulphur
0.5 0.5 2.0
Current,wt%

Low Sulphur 500

Diesel ppm

61
Ultra Low 15
Sulphur Diesel ppm

Temp For 90%

Recovery

MinimumoF 540

MaximumoF 550 640

Mostly From Virgin

Stock."SuperDiesel"
NO.1
Used For Auto & High
Speed Engines

Wider Boiling & Contain

Cracked Stock.Very
NO.2
Similar To Home Heating
Fuel(w/o additives)

Traditionally Largest
Volume Produced.Used
NO.4 For Marine,Railroads,&
Other Low To Medium
Speed Power Plant

Ignition Delay

• The time interval between injection and the onset of the pressure rise.
Ditillate fuels having high cetane number will show a short ignition delay period while
those fuels with poor cetane number will give long ignition delay period.
• Self ignition temperature: low for paraffins (higher MW paraffins have lower ignition
temperature (desired).Aromatics have high self ignition temperatures (undesired).
• Rapid pressure rise results from the accumulation of fuel in the combustion chamber
during ignition delay period. And large number of ignition points occurring throughout
the fuel/air mixture
• With long ignition delay time, rapid rapid pressure rise causes uncontrollable inefficient
engine smoking.
• Rapid pressure rise results undesirable knocks, high stresses and severe engine vibration
(Diesel knocking).

Cetane number

• The ignition properties of diesel fuels are expressed in terms of cetane number or cetane
index.

62
 • These are very similar to the octane number (except the opposite) and the cetane number
expresses the volume percent of cetane(C16H34,high-ignition quality =>100 CN) in a
mixture with alpha-methyl-naphthalene (C11H10, (Aromatic)low ignition quality CN= 0).
• The fuel is used to operate a standard diesel test engine according to ASTM test method
D-613. Since many refineries do not have cetane test engines,a mathematical expression
developed to estimate the cetane number is used.
• High Cetane No: shorter ignition delay period, low pressure rise rates and hence tend to
cause less combustion noise.
• tremely high cetane number cause incomplete combustion because of insufficient fuel or
air mixing due to very short ignition delay period
• The higher the H/C ratio, the better the burning characteristics (i.e., the higher the smoke
point and the higher the cetane index) To improve air quality, more severe restrictions are
placed on the sulfur and aromatic contents of diesel fuels. As the cetane index is an
indicator of the H/C ratio, it is also an indirect indicator of the aromatic content of the
diesel fuel.
• Therefore, frequently a minimum cetane index specification is used an alternative to
maximum aromatics content.Lowering sulfur and aromatics contents specifications also
lowers the particulate emissions from diesel engines.
• Aniline point: Defined as temperature at which a liquid just becomes completely miscible
with equal volume of aniline.
• Aromatics are easily miscible=>. Low A.P
• Paraffins have high A.P.
• Diesel Index= A.P.(F)x Degree API/ 100

Table:1.11

DIESEL QUALITY REQUIREMENTS(Euro

Norms)
EURO- EURO- EURO- EURO-
Property
I(92) II(96) III(00) IV(05)

Cetane Number 49 49 51 54

S% Wt.,Max 0.20 0.05 0.035 0.005

T95,Deg.c.Max 370 370 360 360

PAHs.,%Wt.,Max - - 11 11
Future Strategy For Deisel Quality Improvement For Sulphur Reduction & Cetane
Improvement

• Setting Up High Pressure DHDT That Can Handle Cracked Stocks Also.
• Capacity Expansion/New Unit For Hydrocracker.
• VGO Hydrotreatment.

63
 • Replacement Of Catalyst By New Highly Catalyst.
• Use Of High Performance Internals In Existing DHDS.

Fuel Quality Improvement To Meet Emission Norms PETROL

• Reduction Of Benezene 5 To 1 (%V) Lower VOC

• Reduction Of Olefins To 21(R),(18)P Emission
• Reduction Of Sulphur 500-150-50ppm-Lower SO2
• Increase In Octane To 91-Energy Efficiency,Lower CO2

DIESEL

• Sulphur Reduction 2500-350-50ppm-Lower SO2

• Cetane Increase 48-51-Better Efficiency-Lower CO2
• PAH Control 11% max/mass-Lower Hydrocarbon Emission
• End Point And Density Reduction

Lower CO,NOx,VOCs,So Have Indirect Influence On The Formation Of

2

GHGs HEATING OILS

• The principal distillate fuel oils: No. 1 and No. 2 fuel oils.
• No. 1 fuel oil :very similar to kerosine, but generally has a higher pour point and end
point. Limiting specifications are distillation, pour point, flash point, and sulfur content.
• No. 2 fuel oil:very similar to No. 2 diesel fuel, contains cracked stock, and is blended
from naphtha, kerosine, diesel, and cracked gas oils.Limiting specifications are sulfur
content, pour point, distillation, and flash point.

Table:1.12

Heating oil specifications

NO.1 NO.2 NO.4 NO.6

FlashPoint.oF(oC),min 100(38) 100(38) 130(55) 140(60)

PourPoint.oF(oC),max 9(-18) 28(-6) 28(-6) -

Distillation TempoF(oC)

10% Recovered,
419(215) - - -
Max.

90% Recovered,
- 540(282) - -
Min.

64
 Max 550(288) 640(388) - -

Viscosity,mm2/s at 104oF(40oC)

Min 1.3 1.9 >5.5 -

Max 2.1 3.4 24.0 -

at 212oF(100oC)

Min - - - 15.0

Max - - - 50.0

Density,kg/m3 60oF(15oC)

Max (oAPI min) 850(35) 876(30) - -

RamsbottomCarbon
Residue On 10% 0.15 0.35 - -
btms,wt%,max

Ash,wt%,max - - 0.10 -

Sulphur,wt%,max 0.50 0.50

Water & Sediment

0.05 0.05 0.50 2.00
Vol%,Max
Lube oils

• Principle source: fraction left after gasoline kerosine and diesel oil.
• ASTM Boiling point>35 oC
• Mainly composed of paraffins,Naphthenes and aromatics.
• Use: machine engine oils, turbine oils, Transformer oils
• Viscosity Index: Change in viscosity with temperature
• V.I = (L-U)/ (L-H)

Atmospheric Gas Oil:

• ASTM end point 42oC

• Not a market product
• VGO: Producr obtained from vacuum distillation unit. ASTM boiling range 420-600 C.

Bitumen:

• Residue obtained from CDU.

• Solid at room temperature. Highly viscosity.

65
 • Asphalt: mixture of bitumen in oil containing mineral matter.

Use: high way construction, water proofing coating RESIDUAL FUEL OILS:

• Residual fuel oil :composed of the heaviest parts of the crude and is generally the
fractionating tower bottoms from vacuum distillation.
• Critical specifications:viscosity and sulfur content. Sulfur content specifications are
generally set by the locality in which it is burned.Only low sulfur fuel oils can be burned
in some areas and this trend will continue to expand.
• Heavy fuel oils: with very low sulfur contents are much in demand and sell at prices near
those of the crude oils from which they are derived.

Asphalt

• Mixture of Bitumen in oil containing much mineral matter

• Bitumen obtained from distillation column is poor in quality.
• Air blowing is done to obtain suitable grade.
• Use: High way construction, water proofing coating etc.

Alternate Energy Sources

• World petroleum demand is growing at an unsustainable rate.

• Conventional oil supplies are defined.
• All available carbon resources need to be considered,engaged and utilized.
• New technologies need to be deployed.
• Depending on physical location – GTL/CTL are viable near-term solutions.

66
Road Map Of Energy Resources And Demanded
Product

Fig:1.18
Alternative Energy and Technology Option for Transportation Gaseous
Fuel(CNG,LPG) Bio-Fuels Ethanol Biodeisel Hydrogen Fueled Cars Major Thrust is
Currently on Bio-Fuel and Hydrogen Compressed Natural GAS(CNG)

• Mixture of hydrocarbons ~ 80 to 90 % methane.

• Compressed to a pressure 200 to 250 kg/cm2( to enhance the vehicle onboard in cylinder)
• Energy value:

43.6 Mj/kg (H2 = 140.4 Mj/kg)6860 Mj/M3at 200 atm and 15oC(H2 = 1825 Mj/ M3)

• Better cold start conditions than gasoline.

WOBB INDEX: Indicates the heat input to the engine. Calculated by dividing the heating value
of the gas by the square root of its gravity.W.I = Heat of combustion/ (sp. Gr)0.5Desired value
(NG) 48.5- 53 MJ/M3LPG 72- 83 MJ/M3 Advantages of Natural Gas

• Clean fuel requiring little processing.

• Easily transported via pipelines.
• CO2 emission per unit of energy lower than other fossil fuels.
• Unburned molecules released into the atmosphere contribute less to smog formation than
gasoline molecules.
• methane’s single C is reactive than carbons of longer hydrocarbon chains.

67
Disadvantages of Natural Gas

• Requires high pressures (200 Atm.)or low temperatures (-161deg C) to compress into a
volume suitable for applications such as automotive transport.
• An unburned CH4 molecule is 20x more potent than a CO2 molecule as a greenhouse gas
.
• Methane’s unreactivity results in a long atmospheric lifetime.

Table:1.13

Biomass Feedstocks , Especially Cellulosic, are Cost competitive with oil

& gas
Cost/Difficulty of
Energy Carrier Price
Subsequent Conversion
Common $/GJ

Petroleum $50/bbl $8.80 Low

Gasoline $ 1.67/gala $13.80 -

Natural gas $7.5/ scf $7.90 Low

Coal $20/ton $0.94 Moderate to high

Higher w/CO2 capture

Electricity $0.04/kWh $11.10 Very low for many applications;

High for storage as H2 batteries

Biomass

Soya oil $0.23/lb $13.80 Very low

Corn kernels $2.25/ bu $6.50 Low

Cellulosic crops $50/Ton $2.50 High now;

Cellulosic residues < crops b Moderate/ Low in the future

aWholesale

68
 b e.g. switch grass, short rotation polar

Ethanol Feedstocks and Processes

Feedstocks Process
Sugar cane/Beet molasses & Juice Fermentation
Grain and Tubers(other starchy Enzyamatic Saccharification and
sources) Acidic Hydrolysis
Acidic Hydrolysis and Enzyamatic
Lingocellulosic Biomass
Saccharification

Fig:1.19

Table:1.14

Biomass Classification
Oxegenates Generation Process

Methanol 2nd Thermal

Biological or
Ethanol 1stand2nd
Thermal

Biological or
Buthanol 1stand2nd
Thermal

Mixed
2nd Thermal
Alcohols

DME 2nd Thermal

Hydrocarbons

Biodeisel 1st Phys/Chemical

69
Synthetic Thermal(Long
2nd
Diesel Term Bio

Synthetic
2nd Thermal
Gasoline

Thermal or
Hydrogen 1stand2nd
Biological

CRUDE OIL PRETREATMENT (DESALTING)

• Crude oil contains water, inorganic salts, suspended solids, and water-
soluble trace metals.
• First step in the refining process is to remove salt and solids to reduce
corrosion, plugging, and fouling of equipment and to prevent poisoning
of the catalysts in processing units.
• contaminants must be removed by desalting (dehydration).
• If the salt content of the crude is greater than 10 lb/1000 bbl (expressed
as NaCl), the crude requires desalting to minimize fouling and corrosion
caused by salt deposition on heat transfer surfaces and acids formed by
decomposition of chloride salts.(<1000 lb/bbl).

Typical Configuration Atmospheric Column w/o Preflash[1,2]

70
Fig:2.1 Typical Configuration Atmospheric Column w/o Preflash[3]

71
 Fig:2.2 Atmospheric Distillation Unit Overview [3]

Most typical methods of crude-oil desalting:

• Chemical and Electrostatic separation:Washing of the salt from

crude oil with water oil and water phases are separated in a settling tank
by adding chemicals to assist in breaking up emulsion or by the
application of electrostatic field to colapse the droplets of saltwater more
rapidly.
• Chemical desalting:Water and chemical surfactant (demulsifiers) are
added to the crude, heated so that salts and other impurities dissolve
into the water or attach to the water, and then held in a tank where they
settle out.

72
 • Electric desalting:Under charge condition polar molecules get oriented
and get separated. More than 90% of salt can be removed in just less
than half an hour.

Desalting of Crude

Fig:2.3 Desalting of Crude

Electric Dehydration and desalting[1-3]

• Electrical desalting is the application of high-voltage electrostatic

charges to concentrate suspended water globules in the bottom of the
settling tank.Either AC or DC fields may be used and potentials from
12,000 to 35,000 volts are used to promote coalescence.
• Surfactants are added if the crude has a large amount of suspended
solids.
• The feedstock crude oil is heated to between 150 and 350 oF to reduce
viscosity and surface tension for easier mixing and separation of the
water.
• The temperature is limited by the vapor pressure of the crude-oil
feedstock.

73
Electric desalting[1]

• The dual field electrostatic process provides efficient water separation

at temperatures lower than the other processes and as a result,higher
energy efficiencies are obtained.
• The salts are dissolved in the wash water and the oil and water phases
separated in a settling vessel either by adding chemicals to assist in
breaking the emulsion or by developing a high-potential electrical field
across the settling vessel to coalesce the droplets of salty water more
rapidly.
• Desired pH <6,at higher pH emulsion forms.
• Ammonia is used to reduce corrosion. Caustic or acid may be added to
adjust the pH of the water wash.
• Wastewater and contaminants are discharged from the bottom of the
settling tank to the wastewater treatment facility.
• The desalted crude is continuously drawn from the top of the settling
tanks and sent to the crude distillation (fractionating) tower.

Wash water and T requirement in Desalter:[1,2]

• (3-4vol%, T 240-260oF (API >30), to 7-10 vol%,T 280-300o F for

API<30)
• For single-stage desalting units 90 to 95% efficiencies are obtained and
two-stage processes achieve 99% or better efficiency.
• Efficiencies of up to 99% water removal in a single stage are claimed
for the dual field process. About 90% of desalters use AC field separation
only.
• Heavy naphthenic crudes form more stable emulsions than other crudes.
Higher temperature is required.

Crude Electrostatic desalting

74
 Fig:2.4 Crude Electrostatic desalting[1,2]

Crude Assay, ASTM, TBP distillations, Evaluation of

crude oil properties.

Crude Oil Distillation

• Crude oil distillation is an open art technology.

• The crude oil is distilled at atmospheric pressure and
separated into various fractions as desired in Crude oil
distillation unit .
• The reduced crude oil is further fractionated under
vacuum to produce vacuum gas oil (VGO) as a feed to
Hydrocracker or FCCU in a Fuel type Vacuum Unit,or
distilled to produce Lube oil feed stock in a Lube type
Vacuum Unit.

Crude Oil Distillation Scheme[1,2]

75
 Fig:2.5 Crude Oil Distillation Scheme

Crude Oil Properties

• Sulfur, nitrogen, and metals content.

• Sulfur.
• Sour vs sweet — ~0.5 wt% cutoff restrictions on sulfur
in final products.
• Nitrogen
• Usually tolerate up to 0.25 wt%.

Nickel, vanadium, copper

• Can poison catalysts.
• Tend to be in the largest molecules/highest boiling
fractions.

Properties appropriate for certain boiling point

ranges[1,2]
• Octane number
• Cetane number
• Viscosities
• Carbon residue

Crude Assay

76
The complete and definite analysis of a crude oil is called crude
assay.A complete crude assay will contain some or all of the
following:
1. Whole crude gravity, Viscosity, ‘S’ content, pour point
etc.
2. TBP curve, Mid Volume plot of gravity, Viscosity etc.
3. Light end analysis up to C8 and C9.
4. Properties of fractions. (naphtha, middle distillates, gas
oil residue).Yield vs Vol.%, gravity, S, viscosity, octane
no., diesel index, Flash point , Fire point, Smoke point,
Pore point, Vapor Pressure etc.
5. Properties of lube distillates ( only if the crude is suitable
for the manufacture of lube base stocks).
6. Properties of asphalt (only if residue have suitable
characteristics for preparation of asphalt.
7. EFV curve run at atm. Pressure. Not useful for design
work but is of great importance to the refinery or to a
crude oil purchaser.

Crude Oil Characterization[1,2]

• Trading: Density,API Gravity

• Transportation: RVP,Pour Point,KV,Wax content
• Contamination: Salt content,BS&W
• Processability: Sulfur,Nitrogen,TAN,Asphaltene,MCR
• Cracking Point: ASTM Distillation
• LPG Potential: Light hydrocarbons(GC)
• Classification: Characterization factor

API & S, N & Asphaltene

77
 Fig:2.6 API & S, N & Asphaltene

Crude Oil Assay

• Indicates distribution quantity and quality of crude oil

feedstock based upon boiling point temperature range.
• Represents expected products from crude and vacuum
distillation.

Quality measures[1,2]

• Specific gravity and API gravity.

• Sulfur content.
• Octane number and Cetane number.
• Viscosity.
• Carbon residue.

TBP Curves

78
 Fig:2.7 TBP Curves

Watson characterization factor.

• 12 – 13 (Paraffinic) to 10 (Aromatic)

Laboratory Distillation[1-6]

• Helps to characterize a product and also helpful in data

designing.
• Forms a basis of design of distillation.

Three different types:

A:True boiling point distillation (TBP) for crude used to obtain
true boiling point distillation curve good fractionation.
• Number of plates and amount of reflux must specified.
▪ True Boiling Point(TBP)(ASTM D2892)
• 10 to 20 theroretical stages near infinite
reflux.
• 1 atm; no hotter than 650oF minimize
cracking.

TBP DATA

79
 • Large no. of stages and a high reflux to distillate ratio so
as the temperature at any point on temperature Vs
volumetric yields curve represents the actual boiling
(true boiling) points of the hydrocarbon material present
at the Vol. % point.
• Hempel Distillation:Semi fractionating type
distillation, but can be used TBP data, where TBP data
are insufficient.

ASTM Distillation or Engler Distillation

• Simple distillation carried out with standard ASTM flask

of 100, 200, 500 ml capacity.
• No reflux is provided.
• Rapid batch distillation employing no trays or reflux
between the still pot and condensation.

Separation is poorer: more volatile and high volatile

components are present in initial condition. So IBP is higher
than TBP.[1,7]

Distillation Analyses

• ASTM D86
• Low resolution - no packing reflux from heat loses.
• 1 atm; no hotter than 650 oF minimize cracking.
• Correlation to correct to TBP basis.

ASTM Distillation Analyses

• ASTM D1160
• Used on Resids (650 oF).
• Relatively low resolution.
• Vaccum conditions- 10 to 40mmHg,no hotter than
1000oF AEBP.
• Correlations to correct to atmospheric pressure &
TBP basis.

ASTM Distillation

80
 ▪ At the end in TBP only pure component less volatile
component is present. Whereas in ASTM more volatile
components and less volatile both are present so FBP is
lower in ASTM.
▪ Separation is poorer compared to TBP.
▪ IBP for ASTM is higher than that for the TBP.
▪ FBP for ASTM is lower than that for the TBP.

e.g. Kerosene TBP Range 135-300oC.

ASTM range 160-275oC.

Equilibrium Flash Vaporization[1,2,7]

• By conducting operation at a series of

temperature,curve,% vaporized Vs temperature may be
plotted.
• Mixture is heated without allowing the vapor to separate
from the remaining liquids, the vapor assist in causing
the high boiling point of the mixture to vaporize.
• Similar to ASTM but vapor and liquid are kept in contact
till the desired degree of vaporization is reached. Poorer
separation. (Higher IBP LOWER FBP than ASTM).

API gravity Various average boiling points and mid

percent corves

Different types of boiling points/ functional values

Table:2.1 For narrow boiling cuts (TBP slope less than 2) all above
mentioned boiling points tend to equal.[1,2,6,7]

Average
Physical property for which it is distinct.
Boiling Point

Volume
Used for liquid viscosity, Specific gravity.
Average

81
 Weight
Critical properties
Average

Characterization factor, Thermal Expansion of

Molal Average
liquid.

Molecular weight, Sp. gravity, Heat of combustion,

Mean Average
Sp. heat etc.

For additive properties, viscosities are additive

Cubic Average
when expressed on cubic average.

Average Boiling Points: To specify certain properties of the fraction

1:Vol. Avg. - Based on the boiling temperature of different cuts.VABP

Used for distinguishing physical property like Liquid Viscosity, Specific Gravity.

2. Weight Average Boiling point- For Critical Temperature.

% calculation based on weight.

Mol. Average-based on boiling temperature of different mole fraction.

(Characterization factor, Thermal expansion of liquid, based upon boiling
temperature at different mole fraction.)Molal average

t1, t2, t3 are at respective mole fraction.

X1, X2, X3 are mole fraction

Mean Average Boiling Point

82
(For Estimating Mol.wt, Sp. Gravity, Sp.heat of fraction.)
Mean Avg B.P=(Molal avg. B.P + Cubic avg. B.P)/2
Cubic Avg. B.P:

Va= Vol. Fraction

Average Boiling Point for a Fraction (summary)

five types are defined in the API Technical Data Book :

Volume average boling point

Mass average boling point

Molar average boling point

Cubic average boling point

Mean average boling point

Will generally use boiling point at mid-cumulative yield

Interconversion of Boiling points

• Calculate slope of Distillation curve of a fraction.
• ASTM/TBP/EFV Slopes
• TBP Slope = (t70%– t10%/60)

70% and 10% are volumetric boiling points.

83
 Fig:2.8 Conversion of TBP slope to ASTM on EFV slope[1,2]

CRUDE OIL PROPERTIES

These are required for estimating property of cut ranges in the manual
method.
• Mid percent API Gravity (density ) is drawn along with TBP
• Mid percent Mol. Wt. is drawn along with TBP

Evaluation of crude properties

• Calculate Mean average boiling point from TBP slope and correction
factor (From graph)

MABP = VABP+ Correction factor

• Calculate Characterisation factor (Kw) and API gravity for fractions.

• Kw is assumed constant for whole crude and its fraction.
• 50% BOILING POINTS OF ASTM : Calculated from the slope of TBP
Curve of a crude and its 50% B.P.

For Fractions: Separate IBP and volume percent for crude fractions
• Calculate MABP (VABP, SLOPE and Watson Characterization factor)
• Calculate API of fractions
• Calculate Molecular weight of the fractions using graph
• Plot MID Volume percent vs API gravity and M.W

84
 Mean AVG /Molal Avg BP

Fig:2.9 Mean AVG /Molal Avg BP[1,2]

85
 Fig:2.10 Molal Average Bolling Point [1,2]

50% Boiling Point on ASTM curve :can be calculated from the slope
of TBP curve of a crude and its 50% B.P can be estimated

86
 Fig:2.11 50% Boiling Point on ASTM curve :can be calculated from
the slope of TBP curve of a crude and its 50% B.P can be estimated

Fig:2.12 Relationship between ASTM and TBP 50 volume points [1,2]

87
Fig:2.13 Characterization factor vs B.P and API gavity [1,2]

Calculation of Molecular weight

88
Fig:2.14 Calculation of Molecular weight

89
Fig:2.15 ASTM true boiling point and equillirium flash vaporisation
Distillation curves for a Naphtha kerosine Blend [1,2]

90
Fig:2.16 D1160 Temperature Difference[F][1,2]

91
 Fig:2.17 TBP Temperature oF

Crude Oil Properties

Distillation analysis/Boiling point range
• Amount collected from batch distillation at the indicated temperature
• Most useful is TBP (True Boiling Point)
• Standardized tests —ASTM D86, D1160,

API gravity

Standard Conditions (Temperature & Pressure)

92
“Standard conditions” may vary between countries and even states within the
US Standard temperature 60°F.Other typical values are 14.73 psi & 14.503
psi.

Normal conditions
• 0°C and 100 kPa (32°F and 14.50 psi)
• Almost exclusively used with metric units

..

Evaluation of properties of crude oil and its fractions.

General Procedure for evaluation of crude oil/ fractions

1. From the crude distillation data,plot TBP and gravity- midpercent
curves.
2. Select TBP cut-points of products to be made from atmospheric and
vacuum pipe stills.
3. From TBP and gravity curves, determine percentages and gravities of
fractions.
4. Convert volumes percent to weight percents.
5. Determine weight of bottoms stream by difference.If the volume of
bottom stream is taken from the TBP curve, then gravity is calculated
from weight and volume.
6. For crude oils containing significant amounts of sulfur or nitrogen, it is
also necessary to make sulfur and/or nitrogen balances around each
unit.

Example: Whole crude TBP Data (API Gravity 36.3)

Table:2.2 Plot TBP, M.W , API AND Wt% CURVES FOR THE CRUDE oil

Volume
5 10 20 30 40 50 60
percent

TBP
Temperature 62 144 255 344 437 531 623
(oF)

Volume percent 70 80 85

93
 TBP Temperature (oF) 717 819 897

CALCULATIONS

SP.Gr.For whole crude = 141.5/ (131.5+ API)

Sp. Gr. = 0.84 (for the crude oil)
VABP for whole crude = (t20+t50 + t 80)/3
==>VABP =[ ( 255+ 531+819)/3 ]= 535 oF
TBP Slope =[ (t70- t10)/ 60 ]

= (717-144)/60

= [9.6 oF/%]

• Correction Factor (from graph ) = - 70 oF

• Mean Average Boiling Point ( MABP) = 535 - 70 = 465 oF
• Characterisation Factor Kw = 11.5 (Assumed constant) (From graph)
• Divide whole crude into various cuts

Basis :100 Barrel of crude oil ( 1bbl= 42 US gallon, 1 US Gallon= 3.78

L)

Basis 100 Barrel of crude oil( Weight of the crude = 100x0.843x

349.7=29500 Lb)

(density of water = 349.7 lb/bbl)

Table:2.3[1,2]

Boiling
Cumulative VABP( Mid
range MABP(F) API M.W
vol.% F) vol%
(F)

IBP-
15 110 110 65 78 7.5
200

200-
25 251 251 15 112 20
300

300-
46.5 482 482 35 186 41.0
400

94
 Calculation for weight percent

Table:2.4[1,2]

Wt.%
Density Cumulative
Vol.%cuts API Sp.Gr weight of
(lb/bbl) wt.%
cuts

15 65 0.72 251.7 3770 12.8 12.8

15-25 51 0.78 272.7 2727 9.2 22.0

25-35.5 44 0.81 283.2 2973 10.1 32.8

wt.%,calculated based on total mass of crude (29500 lb)[1,2]

95
Fig:2.18 wt.%,calculated based on total mass of crude (29500 lb)[1,2]

Exercise
• Complete the Table for other fractions (cuts).
• Plot API vs mid volume, Molecular weight vs MID Volume and weight
percent vs mid volume for these cuts.
• Calculate 50% ASTM and 50%EFV Boiling temperatures for each fraction
and plot. Draw astm and EFV curves for the crude.

96
 Fig:2.19

Crude Oil Assay Example-1

Table:2.5

97
Table:2.6

98
Table:2.7

99
50% Boiling Point on ASTM curve :can be calculated from the slope
of TBP curve of a crude and its 50% B.P can be estimated

Fig:2.20

Fig:2.21 Different Slope and Interconversion

Table:2.8

100
101
Fig:2.22

102
 Fig:2.23

Linearized Distillation Yield Curves

103
 Fig:2.24 Linearized Distillation Yield Curves

Design concept of crude oil distillation column design.

Distillation Column Design

The design of a distillation can be divided in the following steps.

▪ Specify the degree of separation:- Set product specification.
▪ Select the operating conditions:- Operating pressure.
▪ Determine the stage and reflux requirement:- The number of
equilibrium stages.
▪ Select type of contacting device:- Plates or packing.

104
 ▪ Size the column:- Diameter, number of real stages.
▪ Design the column internals:- Plates,Distributors,Packing Supports etc.
▪ Mechanical design:- Vessel and Internal fittings.

Arrangement of Towers

Three types of arrangements ( How heat is removed)

1. Top Tray Reflux : Reflux is only at top tray only
• Reflux is cooled and sent into the Tower.
• Heat input: Through Tower bottom.
• Removal: at the top.
• Thus requires large tower diameter.
• Improper reflux and poor quality of fraction. Economic utilization
of heat is not possible.
2. Pump back reflux.
3. Pump around Reflux.

Fig:2.25 Vacuum Distillation Unit Overview [7]

105
Pump back Reflux:

• Reflux is provided at regular intervals.

• This helps every plate to act as a true fractionator.( because there is
always good amount of liquid).
• Tower is uniformly loaded, hence uniform and lesser diameter tower will
do.
• Heat from external refluc can be utilised as it is at progressively higher
temperatures.
• However design of such tower is costly, but provides excellet service.
• Most common in refineries.

Top Tray reflux

Fig:2.26 Top Tray reflux[1,2]

Pump Around Reflux:

• In this arrangement reflux from a lower plae is taken, cooled and fed
into the column at a higher section by 2 to 3 plates.

106
• This creates local problem of mixing uneven composition of reflux and
liquids present on the tray.
• Designers treat all the plate in this zone as one single platre, the result
gives large number of plates and high tower height.

Fig:2.27 Atmospheric Distillation Unit Middle [8]

107
Fig:2.28 Typical Configuration of Single Feed and Multiple Feed into
Distillation Unit [1,2,11]

Some Basis

• Section above feed point-Rectifying/Enrichment Section

• Section below Feed-Stripping Section
• Reflux ratio R= Flow returned as reflux/Flow of top product design
• Minimum reflux Rmin:-Reflux below which stage required is infinity.
• Optimum reflux ratio typically lines between 1.2 to 1.5 times the
minimum reflux ratio.
• Relative Volatility αij=Pi/Pj=Ki/Kj
• y=αX/(1+(α-1)x) for contruction of y-x diagram.

108
 Fig:2.29 Stage Equations For Distillation Unit

Mesh Equations

Material Balance

Vn+1Yn+1 + Ln-1Xn-1 +FnZn =VnYn +LnXn +snXn............Equ 1

Energy Balance

Vn+1Hn+1 +Vn-1Hn-1 +Fhf +qn =VnHn +Lnhn +Snhn.........Equ 2

Equilibrium Relation:

Yi =KiXi........Equ 3

Summation Equitation:For Liquid & Vapor composition

109
These Four equations are the called MESH EQUATION i:e Material Equilibrium,
Summation and Heat (Energy)Balance Equation.MESH Equation can be written
for each stage and for reboiler and condenser.The Solution of the set of
equations forms the basis of rigorous methods.

Basic Processes

• Separation by Boiling point difference.

• Crude Assay provides estimates of various products obtainable from a
particular crude.

Table:2.9[1,2]

Typical Products TBP CUT RANGE

Unstabilized Naphtha IBP-120oC

Heavy Naphtha 120oC-140oC

Kerosene 140oC-270oC

Light Gas Oil 270oC-330oC

Heavy Gas Oil 330oC-370oC

Reduced Crude Oil 370oC +

110
Fig:2.30[1,2]

111
Fig:2.31 Atmospheric Distillation Unit Bottom [9]

112
 Fig:2.32 Vacuum Distillation Unit Overhead [10]

Process Design Basics

Heat and material balance calculations

• Compute hydrocarbon material balancefor feed and products.
• Steam rates to stripping sections and steam distributions between
overhead distillates vapors and liquids.
• Hydrocarbon material balances around product strippers.
• Atmospheric EFV Temperatures for products corresponding to the
estimated strip out for each product.
• Draw Tray locations, Number of trays in each sections and total number
of trays in the Tower.
• Heat input to the base section of the tower from feed and bottoms
stripping steam, heat outflow in the bottoms liquid and external heat
quantities at the flash zone.

113
Product Yield Determination

• Desired ASTM distillation of product(s) of interest is decided and ASTM

is converted to TBP.Product TBP is applied to the whole crude TBP cruve
to eastimate volumetric yields TBP cut volume is eastimate.
• ASTM(5-95) GAP/OVERLAP between adjacent cuts determined.

Separation Criteria

• DEGREE OF SEPARATION:Difference between ASTM- 5% of heavier

distillate and ASTM -95% point of lighter distillate.
• DEGREE OF DIFFICULTY OF SEPARATION:Difference between ASTM
50% point of the distillate fraction in questions.

Separation Criteria

Degree of Separation
• Defined in terms of product purities or component recoveries.
• Greater the degree of separation, greater will be recovery of the light
component in the distillate and the heavy component in bottoms.
• Degree of difficulty of separation : Defined as the relative difficulty
encountered in separating the two compounds, regardless the purity
requirements set by process specifications~ inversely proportional to
the relative volatility between the two components.

ASTM Gap and Overlap

• Fractionation is the difference between 5% ASTM curve of Heavy cut

and the 95 % point on the ASTM curve of a lighter cut of two adjacent
side product.
• Positive difference is called Gap.
• Negative difference is called overlap.
• ASTM Boiling range gives general composition of fractions.
• 5- 95 GAP: Defines the relative degree of separation between adjacent
fractions.
• Determined by subtracting 95 vol.% ASTM Temperature of a fraction
from the 5 Vol. % ASTM temperature of the adjacent heavy fraction.

• (5-95) Gap = (t5H-T95L)ASTM

114
 • 5H=5% OF THE HEAVIER FRACTION
• 95L= 95% OF THE LIGHTER FRACTION
• TBP CUT POINT = (TOH+ T100L)/2
• TBP Over lap= [T100L – TOH]

TBP CUT , GAP & OVERLAP

Fig:2.33 TBP Cut , Gap & Overlap[1,2]

General observation for separation

For a given system

• No. of trays required increases markedly as purity requirement
increases, but reflux requirements increases only a small amount.
• Tray and reflux requirements increases as relative volatility decreases
i.e separation becomes more difficult.

Separation Criteria

115
 • For a fixed number of trays,reflux reqirement is directly proportional to
the degree of difficulty of separation.

Qualitatively

• At reflux condition exceeding minimum requirements =>Tray

requirements are directly proportional to the required degree of
separation.
• The degree of difficulty of separation inherent in the physical chemical
system under consideration.

Crude Column Design

INPUT REQUIRED
• Crude TBP (essential)
• Density/API gravity (essential)
• Molecular Weight(optional)
• Viscosity(optional)

SPECIFICATION REQUIRED
• Column Pressure
• Product specification can be given in terms of fix draw or distillation
point.
• Pump around duties need to be specified.
• Column top temperature can be specified.

Process design

• Prepare TBP Distillation and equilibrium Flash Vaporisation curves of

crude to be processed.
• Using crude assay data construct TBP curves for all products except gas
and reduced crude. Convert these to ASTM & EFV.
• Convert TBP data to EFV curves.
• Prepare material balance of crude distillation column, on both volume
and weight basis.

Fractionation requirements: ASTM gap and overlap

116
Knowing gaps as the design parameters correlate deviation or gap with F
factor( product of number of plates between two adjacent side draws off
stream and internal reflux ratio.

Packie’s Method

• Degree of difficulty of separation : The difference between 50 vol.%

temperatures of the fractions under study.
• Convert 50% TBP temp to ASTM.
• Separation Capability (F):defined as the product of the reflux to feed
ratio at the upper draw tray as calculated on the volumetric basis and
the number of actual trays in that section.(F, Factor related to gap and
overlap).
• Packie method: Based on Gap and overlap.
• Number of plates in particular section depends on gap and reflux ratio.
• F= Reflux ratio x Number of plates in that section.

F=(LN/DN)NT,(NT: No of trays of distillation column)

L/D= Reflux ratio

TBP VS ASTM 50% B.P

Fig:2.34 TBP VS ASTM 50% B.P[1,2]

117
Relation Between TBP and ASTM 50% Boiling Point

IBP AND FBP OF ASTM & TBP

Fig:2.35 IBP AND FBP OF ASTM & TBP[1,2]

Relation Between IBP and FBP of ASTM and TBP

118
 Fig:2.36 Relation Between IBP and FBP of ASTM and TBP[1,2]

EXAMPLE
In a refinery side stream operation the fraction to be collected is diesel. The
diesel entering the side stripper is 4000 bbl/h, the 50 percent point of the cut
is 275 oC and contained with Kerosine whose mid boiling point is 145 oC. If
the stripper is having 4 plates find the actual amount of diesel coming out of
the stripper if the ASTM GAP is 20 o C.
SOLUTION
Calculate F Factor from Packie method for side stream stripper.
ASTM ΔT50%= 275- 145= 130oC (254 oF)

ASTM GAP= 20 oC = 36 oF

F= (L/D)NT=>L/D= 5/4= 1.25

V= L+D = 4000

119
Hence D( Actual amount of diesel )= 1778 bbl.

Calculation of minimum number of stage

Fenske equation is used for Nm

Calculation of minimum reflux ratio

Using Underwood Equation:

q = heat to vaporize 1 mole of feed / molar latent heat of vaporization.

θ = Root of underwood equation.
Calculate Rm using Erbar- Maddox(or Gilliland)correlation calculate R actual.

CALCULATION OF REFLUX RATIO

120
 Fig:2.37 CALCULATION OF REFLUX RATIO[1,2]

Kirkbride equation is used for feed tray location.

log[Nr/Ns]= 0.206log[(B/D)(Xf.LK/Xd.HK)2].........Krikbride Equation

Where
Nr= Number of stages above the feed,including any partial condenser.
Ns= Number of stages below the feed,including the reboiler.
B= Molar flow bottom product.
D= Molar flow top product.
Xf.HK = concentration of the heavy key in the feed.
Xf.LK = concentration of the light key in the feed.
Xd.LK = concentration of the heavy key in the top product.
Xb.LK = concentration of the light key in the bottom product.
In simulation method,it is known as short cut mettod

121
 Fig:2.38[1,2]

Optimization Criteria in Design

• Maximization of distillates.
• Maximization of desired product(s).
• Quality of reduced crude.
• Overflash control to optimize energy.
• Optimization of pumparound in yield.

Optimization of particular product(s).

Flash Zone operating conditions-FZ temperature is limited by advent of

cracking.
• FZ pressure is set by fixing the reflux drum pressure and adding to it to
the line and tower pressure drop.
• Over flash:Over flash is the vaporisation of crude over and above the
crude overhead and side stream products.
• Over flash is generally kept in the range of 3-6 liquid volume %. Kept
at minimum value as a Larger over flash consumes larger utilities.

Over flash prevents coking of wash section plates and carryover of coke to the
bottom side streams by and the tower bottom by providing reflux to the plates
between the lowest sidestream and the flash zone.

122
Flash Zone Temperature

• Crude TBP provides estimate of total distillate.

• EFV cruve of the crude is derived from the TBP and converted to the
flash zone pressure.
• Overflash quantity is selected included this material balance and heat
balance arount the bottom section including feed section is done to fix
the flash zone temperature.
• Flash zone temperature thus fixed ensures desired total distillate yield.

Product Yield Detrmination[1,2,6]

• From ASTM curve:1 ATM EFV curve are develoved and extrapolated to(-
) 50% VOL% vaporized as an initial estimate.
• Stripping steam to the stripper is set at about 10LB/BBL of stripped
product bubble point of unstripped side stream is estimated.

123
 Fig:2.39

EFV TEMP VS DRAW TRAY TEMP

Fig:2.40 EFV TEMP VS DRAW TRAY TEMP[1,2]

FLASH ZONE

124
 Fig:2.41 FLASH ZONE[1,2]

• D= Sum of all streams.

• V= % OF VAPORISATION in Flash zone.
• Lo = Overflash.
• SF= Total amount of hydrocarbons stripped out by steam.
• Thus V= D + Lo - SF
• From the flash curve(EFV) of the crude, the temperature at which this
vaporisation is achieved at the FZ Pressure is determined.
• This T should not exceed the maximum permissible temperature. If does
quantities of Overflash and stripping steam are changed until a
permissible temp is obtained.
• Stripped out HC Fraction (Sf) depends on amount of stripping steam.
• W= Lofz- Vso,( W=Vol. % Feed leaving the bottom).
• Lofz= Lo (Overflash)+ W
• V= Lo+100- W/(1-Sf) vol.% of of feed flashed at FZ inlet.
• Sf= fraction of strip out vapor (Lofz(1-Sf)= W).

EXAMPLE: It is planned to yield as a side stripper from an atmospheric crude

tower, 100 bbl per hour of a light distillate product having a TBP cut point
range of 400-525 oF (volume range 27-39%, API 39.8). The estimated draw
tray temperature is 425oF. The liquid is to be stripped in a 4 tray column using
500oF Steam. The stripping rate is 10 lb/bbl of stripped product. Calculate the
temperature of stripped product stripping the bottom of the stripper.

125
Solution:100 bbl of LD to be producd, TBP Cut 27-39 % =12 vol.%, Mid vol
%33
• Strip out vapor= Sf= 23.8 vol.%.
• Feed (F)= w/1-sf.
• = 100/(1-238).
• = 131.2 bbl/h/ 100 BBL OF LD.
• Therefore Feed F= 12X1.312=15.74 % OF CRUDE.

Heat into FZ, QFZ1= V’H+W’H.

Selection of Column Pressure

Pressure to be adequate that dew point (for the composition of top product)
is more than cooling hot water temperature around 45oc + ΔT(15oc)=60oc
with cooling water inlet temperature of 33oc with condensate temperature of
40o - 45o can be obtained eith consideration of 10o- 15o ΔT .The column
pressure to be adequate that bubbles point of the top product is 40o - 45o.

i.e

at column pressure and drum temp of 45o

Or

ΣPi calculated at 45oC for all the components.

ΣPi=ΣXiPi or ΣYiPt=ΣXiPi

For crude Distillation Column

The top product is a mixture of light end and top naptha(C5-140o).The naptha
TBP is subdivided 10oC or 20oC cuts eg.70o-80o,80o-90o,90o-100oetc and
midpoint are tabulated.

K values estimated from de-priester chart.

Table:2.10

126
 Comp./cut Ki 45oC,1.6
B.P.T Xi Ki Xi
range(TBP) Kg/cm2g

C1 B1 K1 X1 K1 X1

C2 B2 K2 X2 K2 X2

C3 B3 - - - -

C4 B4 - - - -

C5 B5 - - - -

70o-90o 80o - - - -

90o-110o 100o - - - -

110o-130o 115o - - - -

130o-150o 140o Kn Xn Kn Xn

Σni=1KiXi

It ΣKiXi=1 then the pressure is OK.

If not 1 then repeat trial with another value of pressure till ΣKiXi is 1.
Same method is applied for discrete component and mixture of pure
component and fixes the reflux drum pressure.

Top Temperature Estimation

Top temperature is dew point of top vapor at column top pressure.Once reflux
drum pressure is fixed PD(say)the column top pressure is estimated after
adding the pressure drop across condenser/OH line.Typically 0.3kg/cm2-0.5
kg/cm2 is taken as pressure drop.

Column top pressure = PD+0.5

Again calculation is performed at top pressure for determining the dew
point.Assume a top temperature and calculate.
Σyi/Ki till it becomes 1.

Calculation of Vapor/Liquid Profile

127
 Fig:2.42 Calculation of Vapor/Liquid Profile[1,2,11]

This is done by performing material balance & heat balance in

envelopes.

Atmospheric distillation unit

• Tower Dia :5- 8 m.

• No.of Plates : 25-40(depends on No. of draws).
• Maxm.Allowable pressure drop per plate :0.015 kg/cm2).
• Pressure drop from furnace outlet to Flash zone : 0.3 – 0.4 kg/cm2.
• Pressure at top of the tower : 1.2 -1.4 kg/cm2
• No.of plates required for separation.

• LN – HN (80-130 C): 6-8

• HN- LD (180C): 5-6
• LD- MD (250C): 4-6
• MD- GAS OIL(330 C): 3-4

128
 • Flash zone to First draw tray: 3
• FZ TO BOTTOM : 3
• Reflux drum pressure: 1.1-1.15 kg/cm2 abs.
• Steam rate /bbl of crude: 4-5 kgs
• Reflux ratios : 2-3 (for light fractions)for Heavy fractions 1.5- 2.5.

Contacting Device

• Cross Flow
• Counter flow

Cross Flow

Fig:2.43 Cross Flow

Counter Flow :Packing,Heat transfer trays.

H dry -->dry tray pressure drop,inches.

H dry = C1+C2V 2/2gC

ΔP dry=K2(VH)2DV/DL-unit full open.

Tray Pressure Drop

HT= H dry+ How+ Hw
ΔPT = ΔP dry +0.4(gpm/lwi)2/3+0.4 HW

Pumparound Duties

• Pumaround duties need to be maximized for energy efficiency point of

view.

129
 • This is limited by Gap/Overlap specification between adjacent products
and minimum internal reflux specification.
• Pumparound duties are maximized and reflux ratio is brought close to
1.5 to 1.8.

Vacuum Column

(ΔT)Hy.Diesel PA :70oC-90oC
(ΔT)LVGO PA :50oC
(ΔT)HVGO PA :55oC

Stages in vacuum column:-

Top PA =1 stage.
Top Hy.Diesel-LVGO =2-3 stage.
LVGO PA =1 stage.
LVGO-HVGO =1 stage.
HVGO PA =2-3 stage.
Wash =2-3 stage.
Wash liquid at bottom of wash bed˜0.3M3/hr/M2column C.S area.
Thermodynamics - BK10/GSI.
Transport Property - PETRO.
Density - API.

Vacuum Distillation Unit[1,11]

• The primary objective of a vacuum distillation is to produce either

feedstock for FCCU or HCU. This type of vacuum distillation units are
termed as Fuel Type Vacuum Unit.
• The other kind of vacuum distillation unit is a Lube Type Vacuum Unit
and deployed for production of fractions for Lube Oil Base stocks.
• In a Fuel Type Vacuum distillation Unit the VGO TBP cut point is
controlled for Maximizing profitability while containing the level of
contaminants acceptable by downstream secondary Units.

VACCUM DISTILLATION

130
Fig:2.44 VACCUM DISTILLATION[1,2]

Vacuum Distillation unit:cont

Fig:2.45 Vacuum Distillation unit[1,2]

131
Different Configuration of Vacuum Column
1. Dry (no stripping, no coil steam).
2. Wet (Precondenser limiting column overhead pressure to cooling water
temperature limitations).
3. Dump column without stripping (no precondenser, coil steam used to
adjust flash zone oil partial pressure).
4. Dump column with stripping steam (no precondenser, coil and stripping
steam used).

Different Configuration of Vacuum Column

• The first one operates typically at 8-12 mm Hg (a) at top. The vapour
directly goes to ejectors.
• The second type operates at 60-70 mm Hg (a) at top and have a
precondenser, the non-condensable are pulled by ejector.
• The third type of operation is done at 18-25 mm Hg (a) at top.
• Without stripping steam has a booster ejector followed by condenser.
• This fourth type again operates with a top pressure of 18-25 mm Hg (a)
and uses stripping steam and Coil steam both. This type is considered
best to increase cut point of VGO limiting the contaminants like V, Ni
etc. in VGO with same number of stages in wash section as compared
to other configurations.

Furnaces

1.Introduction:

Furnaces are used throughout the industry to provide the heat, using the
combustion of fuels. These fuels are solid, liquid or gaseous. Furnaces consist
essentially of an insulated, refractory lined chamber containing tubes. Tubes
carry the process fluid to be heated, and sizes are device for burning the fuel
in air to generate hot gases. A great variety of geometries and sizes are used,
and much of the skill employed in their design is based on experience.
However, all furnaces have in common the general feature of heat transfer
from hot gas source to a cold sink, and in the past few decades theoretical

132
models of increasing complexity and power have been developed to aid the
designer.[1,2,3]

2.Types of furnaces used in process plant[1-6]

An industrial furnace or direct fired heater is equipment used to provide heat

for a process or can serve as reactor which provides heats of reaction. Furnace
designs vary as to its function, heating duty, type of fuel and method of
introducing combustion air. However, most process furnaces have some
common features. Fuel flows into the burner and is burnt with air provided
from an air blower. There can be more than one burner in a particular furnace
which can be arranged in cells which heat a particular set of tubes. Burners
can also be floor mounted, wall mounted or roof mounted depending on
design. The flames heat up the tubes, which in turn heat the fluid inside in the
first part of the furnace known as the radiant section or firebox. In this
chamber where combustion takes place, the heat is transferred mainly by
radiation to tubes around the fire in the chamber. The heating fluid passes
through the tubes and is thus heated to the desired temperature. The gases
from the combustion are known as flue gas. After the flue gas leaves the
firebox, most furnace designs include a convection section where more heat
is recovered before venting to the atmosphere through the flue gas stack.
(HTF=Heat Transfer Fluid. Industries commonly use their furnaces to heat a
secondary fluid with special additives like anti-rust and high heat transfer
efficiency. This heated fluid is then circulated round the whole plant to heat
exchangers to be used wherever heat is needed instead of directly heating the
product line as the product or material may be volatile or prone to cracking at
the furnace temperature.)

The radiant section is where the tubes receive almost all its heat by radiation
from the flame. In a vertical, cylindrical furnace, the tubes are vertical. Tubes
can be vertical or horizontal, placed along the refractory wall, in the middle,
etc., or arranged in cells. Studs are used to hold the insulation together and
on the wall of the furnace. The tubes are a distance away from the insulation
so radiation can be reflected to the back of the tubes to maintain a uniform
tube wall temperature. Tube guides at the top, middle and bottom hold the
tubes in place. The convection section is located above the radiant section
where it is cooler to recover additional heat. Heat transfer takes place by
convection, and the tubes are finned to increase heat transfer. The first two
tube rows in the bottom of the convection section and at the top of the radiant
section is an area of bare tubes (without fins) and are known as the shield
section, so named because they are still exposed to plenty of radiation from
the firebox and they also act to shield the convection section tubes, which are
normally of less resistant material from the high temperatures in the firebox.
The area of the radiant section just before flue gas enters the shield section

133
and into the convection section called the bridge zone. Crossover is the term
used to describe the tube that connects from the convection section outlet to
the radiant section inlet. The crossover piping is normally located outside so
that the temperature can be monitored and the efficiency of the convection
section can be calculated.

In petrochemical industries, furnaces are used to heat petroleum feedstock

for fractionation, thermal cracking, and high-temperature processing. Usually,
these furnaces are fired by oil or gas. They have to be designed to ensure that
the fluid receives the correct amount of heat and has sufficient residence time
within hot zone. While at the same time excess temperatures have been
avoided. These excess temperatures lead to degeneration of the product or
damage to the furnace. The balance is achieved by appropriate disposition of
the tubes carrying the fluid within the furnace, and careful control of firing
rate and fluid flow Calculations are required to determine the fuel consumption
and the maximum temperatures of the tube and walls. Tube temperatures in
some plant may be as high as 900 °C, and combinations of high pressure
(e.g., 200 atm) and relatively high temperatures (e.g., 450 °C) are not
uncommon. Process heaters come in many shapes and sizes; Figures 3.1, 3.2
and 3.3 show typical arrangements.Fig.3.1 is a vertical cylindrical process
heater with a band of vertical tubes in the radiation zone and a bank of
horizontal tubes at the outlet that receive heat mainly by convection. The
latter may have fins attached to enhance heat transfer, except for the base of
the furnace and the flames are vertically oriented. Typical heat transfer rates
for the vertical tubes in the radiation zone are about 50 kW/m2, and the total
heat rating is usually in the range 3 to 60 MW.

134
Fig.3.2[1]shows an alternative arrangement, where the tubes are horizontal
and cover not only the vertical walls but also the sloping roof of the “cabin”.
Units of this type are used for a similar range of duty as is the aforementioned
vertical cylinder. Fig.3.3[1] shows the more unusual design for smaller heat
loads, where a single central wall of horizontal tubes is heated on both sides
by two sets of burners set in the base.

3.Furnace heat transfer[1-8]

A fuel-fired furnace consists of a gaseous heat source, a heat sink, and a

refractory enclosure, as illustrated diagrammatically in Fig.3.4.[1] Heat is
transferred to the heat sink by radiation and convection from the hot gases
and by reradiation from the refractory walls. In developing any model of the
process, it is necessary to consider two heat transfer phenomena:

▪ The heat emission from hot gases containing combustion products, i.e.
the heat source.
▪ The heat absorbed by the tubes, taking into account their geometrical
configuration and material properties (the heat sink), composed of

135
 primary heat transfer from hot gases and secondary heat exchange with
the refractory walls.

3.1.Furnace heat balance

Heat is released in a fuel-fired furnace as a result of combustion, and the rate

of heat generation, Qf, is equal to the rate of combustion of fuel, Mf, multiplied
by its lower calorific value, Δhf:

Qf = Mf Δhf...............................(1)

The heat generated by the combustion process appears initially as sensible

heat in the steam of hot gases, consisting of combustion products and excess
air, passing through the furnace at a rate Mg. Part of this heat is transferred
to the heat sink at a rate Qg, part is lost through the furnace walls at a rate
Ql, and the remainder is carried out of the furnace through the exhaust stack
as the sensible heat of the partially cooled combustion products at a rate Q p.
As illustrated in Fig. 3.5[1] the heat balance for this process may be expressed
as:
136
 Qf = Qg + Ql +Qp...............................(2)

If there were no heat sink and no losses, all the heat released by combustion
would go into heating the gases produced, which would then attain a
temperature, Tf, known as the adiabatic flame temperature. The adiabatic
flame temperature is, therefore given by:

Qf = Mgcpg (Tf-To)...............................(3)

Where To is the air inlet temperature and cpgis an appropriate average value
of the gas specific heat for the range To to Tf.

In a real furnace the gases do not attain the adiabatic flame temperature, due
to the heat sink and wall losses. For example, neglecting losses but allowing
for heat removal by the sink at a rate of Qg), the theoretical gas temperature,
Tg) is given by

Qf -Qg=Mgcpg Tg-To...............................(4)

Hence, combining equations (3) and (4)

This equation shows how the gas temperature, Tg is related to the rate of heat
transfer of the sink, Qg, by heat balance. However, Qg is also related to Tg by
the heat transfer characteristics of the hot gas and of the sink. A solution of
the problem requires a combination of these two sets of equations.

137
 Furnaces

3.2 Hot gases as heat source

The chemical composition of the gases produced by the combustion of

hydrocarbons depends upon the choice of fuel and the amount of excess air
employed above the stoichiometric requirements. In practice, excess air is
required to ensure complete combustion; typical values are 10% for gaseous
fuels, 15 to 20% for liquid fuels, and 20% for pulverized fuel, although lower
percentages can be achieved with efficient burners.

As we know, gaseous combustion products radiate heat when raised to

temperatures above their surroundings. When solid particles are present in
the furnace gas stream they become incandescent, radiating both heat and
light, so producing a glowing or luminous flame. Gaseous fuels burn with a
nonluminous flame, but liquid and solid fuels produce luminous flames due to
the presence of particles of carbonaceous material. For example, soot or coke
resulting from the incomplete combustion of the hydrocarbons and mineral

138
matter originally in the fuel. In general, solid fuel produces a more luminous
flame than does liquid fuel.

Carbon dioxide and water vapor are the main sources of radiation for
nonluminous flames, and the total emissivity εg of a volume of combustion
gases is dependent upon the temperature Tg and product of partial pressure
and effective path length PL . The total absorptivity of a gas also depends upon
its temperature and partial pressure path length product, but in addition upon
the temperature Ts of the source of the radiation that is being absorbed.[1,9,10]

3.3 Heat Sink

The rate at which heat is transferred by radiation from the hot gases to sink
depends not only upon the emissivity of the gas and emissivity of the sink
surface, but also upon the relative size of the sink. This is because the
unconverted refractory lining radiates back into the furnace heat that it has
received from the flame, and some of this is absorbed by the heat sink.

This compound effect is illustrated in Fig. 3.6, where two extreme cases are
shown. The diagram on the left represents the case in which the sink area is
very small, and that on the right represents the case in which the sink is very
large and completely covers the furnace walls.

In the case of refractory surface, assuming no heat loses, is in equilibrium

with the gases and reradiates all the heat falling upon it. The total radiation
flux within the enclosure is equal to that emitted by a blackbody at
temperature Tg . Under these circumstances the heat flux to the sink is
independent of the gas emissivity, depending only on the emissivity of the
sink itself. The rate of heat transfer to a very small sink at temperature T 1 is
therefore

QgA1-->0 = A1ε1σ(Tg4-T14)....................(6)

In the second case,where the sink covers the whole of the interior of the
furnace, the situation is analogous to the exchange between two parallel party
reflecting surfaces. It was already known that the rate of heat transfer is given
by

139
Intermediate situations can be estimated by using the equation for the simple
case when the sink and the refractory are intimately mixed (Hottel and
Sarofim, 1967). This is called the speckled surface equation and is quite
adequate for preliminary estimates of furnace performance. It gives

Where C is the ratio of the sink area to the total area, i.e. A1/At.

Fig. 3.6 shows an example of the way of the effective emissivity (the term in
the curly braces in Equation 8) varies with C. The example assumes a gas
emissivity is close to that of the gas, εg of 0.3 and a sink emissivity, ε1 , 0f
0.85, the latter being typical of tube surfaces. For large values of C the
effective emissivity is close to that of gas, εg , and is intensive to the value of
the sink emissivity, ε1 . For this reason the emissivity of tube surfaces in the
fire tube boilers, where the sink entirely encloses the hot gas stream, may
often be taken as unity for calculation purposes.

Fig:3.6[1]

140
Fig. 3.6 Effect of heat sink area on effective emissivity. (a) small heat sink
area; (b) large heat sink area; (c) blackbody analogous to (d) exchange
between reflecting surfaces;

Fig:3.7

Fig (3.7) an example(εg, ε1) speckled surface equation.[1]

εc=(1/(1/ε1+C(1/ εg)-1)),C=A1/At

3.4 Effect of tube geometry on the heat sink characteristics

So far the heat sink has been treated as a plain surface. In practice, however,
it consists of one or more banks of tubes usually mounted close to the
refractory wall, as shown diagrammatically in Fig. 3.7. Normally there is a
space between the tubes and consequently some of the radiation from the hot
gases is not intercepted and impinges on the refractory wall behind the tubes.
Most of this heat is reradiated and part contributes to the heat flow to the
sink. This is a complex situation and complete formal analysis is very difficult.
Because of mutual shielding effects of adjacent tubes, the radiation heat flux
varies circumferentially around the tubes, as shown diagrammatically in Fig.
3.8.[1] The surface of the tube facing inward (position 1 in the figure) receives
maximum heat flux because it is subject to radiation from a total angle of
141
180°. Point 2 receives radiation from a smaller angle and point 3 only from a
very narrow beam; beyond this point there is an area of the tube that receives
no direct radiation from the hot gases. There is, of course, an additional
component of heat flux, mainly on the back of the tubes, due to reradiation,
but this is much smaller in magnitude.

The ratio of peak to mean heat flux is a function of tube pitch to diameter
ratio, B, as shown in Fig.3.9[1] for three typically configurations. This factor is
important in assessing the permissible heat rating of a furnace, because it is
the peak heat flux, which is usually the limiting factor. A simplification of this
complex situation was proposed by Hottel in which the heat sink is defined as
an equivalent plain surface having an area equal to that covered by the tubes,
as shown in Fig. 3.10, and an effective emissivity, eeff, which would give the
same radiative heat transfer as the tube bank.

The first step in calculating the equivalent emissivity of the plain surface is to
determine the fraction, F, of radiation intercepted by the tubes. The equation
for F is based on optical path geometry, namely,

F = 1-(1/B){(B2-1)1/2-cos-1(1/B)}..............(9)

This function is plotted in Fig.3.11[1] for a single and a double row of tubes.

The interception factor, F,can then be used in calculating the effective

emissivity of the tube bank, including radiation from an adiabatic refractory
backing,as:

εeff= 1/{(1/F(2-F)) + ((B/π)(1/ε1-1))}..................(10)

142
Effective emissivity based on this equation is plotted in Fig. 3.12[1] as a
function of tube pitch to diameter ratio for a tube material emissivity of 0.85.
It is clear from the form of the equation and the shape of the curve that tube
spacing has a very powerful effect. This is partly due to the fact that the actual
tube surface area per unit of total projected area, A, is proportional to 1/B, a
fact reflected in the reduction in the fraction, F, of radiation intercepted, which
plays a predominant role in determining eeff. The foregoing equations apply
to true banks adjacent to the refractory wall. A similar approach can be made
to the case of a centrally mounted tube bank, but here a different form of
equivalent plain area has to be used. Procedures for this type of furnace
geometry are outlined in the Heat Exchanger Design Handbook (Truelove,
1983).

143
4. Furnace models

The full mathematical description of practical furnaces is exceedingly complex,

combining aerodynamics, chemical reactions, and heat transfer, and computer
programs are necessary for detailed solutions. Advanced methods of
calculation may be divided into zone methods and flux methods.

Zone methods are employed when the heat release pattern from the flame is
known. They start by dividing the furnace and its walls into discrete zones.
The effective exchange areas between zones are determined, and the
radiative heat transfer corresponding to the prescribed heat release pattern is
calculated. In flux methods, instead of dividing the space into zones the
radiation arriving at a point in the system is itself divided into a number of
characteristic directions, representing averages over a specified solid angle.
Flux methods are well suited for use in combination with modern methods of
prediction of fluid flow and mixing pattern. Simultaneous solutions of the
radiative heat transfer equations using flux methods and turbulent flow
models are feasible.

4.1 “Well Stirred” furnace model[1-16]

This is the simplest approach to the assessment of furnace performance. One

of the first versions is the method of Lobo and Evans (Lobo and Evans, 1939),

144
which was used in Process Heat Transfer (Kern, 1986). Subsequently an
improved version, expressed in nondimensional terms, which made the
calculations easier, was presented in the book Radiative Heat Transfer (Hottel
and Sarofim, 1967). These authors also introduced additional terms to allow
for incomplete mixing and wall losses. Their model, later reviewed by Hottel
(1974), still forms the basis of most simple calculation procedures (e.g.,
Truelove, 1983).

The furnace is modeled in three zones as shown, Fig.3.13[1] namely, the

central hot gas zone, the heat sink, and the refractory walls. The combustion
region and the space occupied by hot products of combustion are lumped
together in the central hot gas zone (hence the alternative title “lumped
model”), which transfers heat by radiation to the heat sink, here shown
diagrammatically as a tube bank, and to the refractory walls containing the
furnace.

The following simplifying assumptions are made:

▪ The hot gases are perfectly mixed and at a uniform temperature, Tg.
▪ The heat sink is gray and has a uniform temperature, T1.
▪ The refractory surface is radiatively adiabatic, that is to say it radiates
all the heat that is receives.

The “well stirred” furnace model is based on a combination of the balance

equation for the furnace (Equation 5), namely.

(Qf-Qg)/Qf=(Tg-To)/(Tf-To)..................................(11)

And the expression for heat transfer to the sink based on the“specked surface”
model (Equation 8),namely.

Qf= A1{1/((1/εeff) + C(1/εg-1))} σ (Tg4-T14)=gr σ

(Tg4-T14).....................(12)

Where, gr, the total heat transfer factor for radiation from gas to sink, is

gr= A1/{1/eeff+C(1/εg-
1)}....................................(13)

Note that εeff(Equation 10) has replaced ε1, because

the model is using the projected area, A1, of the tube
bank as illustrated in Fig. 3.10.

145
If the furnace contains a convectively heated section, the total heat transfer
factor can be modified to introduce both radiation and convection,as

Qg =gr σ(Tg4-T14) +αAc(Tg-T1)................................(14)

Where,gr = total heat transfer factor for radiation from the gas to the sink,
including reradiation from the refractory walls and multiple reflection.
α= convective heat transfer coefficient from the gas to the sink.

Ac = area of the sink subject to convective heat transfer.

Because the convective component is usually small compared with that of

radiation it may be submitted in the gr,term as follows.Let

αAc (Tg-T1)= (αAc/4σT3g1)σ(T4g-

T41)..........................(15)

where

Tg1≈(Tg+T1)/2........................................................
(16)

Then

Qg=grc σ(Tg4-
T14).....................................................(17)

where

grc=gr+(α Ac/4σT3g1)...............................................
..(18)

Fig. 13 Simple well stirred Furnace model

Equations (11) and (17) can be combined to give

(Qg/σ grc)+T41=T4f{1-(Qg(Tf-
To)/QfTf}4...........................(19)

It is convenient to apply this expression in a

nondimensional form involving the terms:

146
Q,g =Qg(Tf-To)/QfTf =reduced furnace density
..................(20)

D, =Qf/σ grc3f(Tf-To) =reduced firing

density......................(21)

T,1 =T1Tf =reduced sink

temperature................................(22)

Equation (19) then reduced to

Q,gD,+(T,1)4) =(1-
Q,g)4...................................................(23)

Coking and Thermal Process, Delayed Coking

Fig:4.1 Simplified Refinery Flow Diagram [1,2]

• Treatment processes : To prepare hydrocarbon streams for

additional processing and to prepare finished products.

147
 • Treatment: It include the removal or separation of aromatics
and naphthenes as well as impurities and undesirable
contaminants.
• Treatment involve:chemical or physical separation such as
dissolving, absorption,or precipitation using a variety and
combination of processes including
desalting,drying,hydrodesulfurizing,solvent
refining,sweetening,solvent extraction, and solvent dewaxing.

Fig:4.2 Thermal Processes [2,6]

Delayed Coking

Using time and high temperature one can break large asphalt
molecules into gasoline and diesel.Petroleum coke is a solid
by product and is blended with coal to use as a solid fuel in
power plants.[5,8]

148
 Fig:4.3

Cracking

Dissociation of high molecular weight hydrocarbon into a smaller

fragments through agency of heat alone is termed as thermal
cracking or pyrolysis.

Can also be done in presence of catalyst.

CnH2n+2 Cn/2Hn+2 + Cn/2Hn (T= 400o C)

C12 C6 + C6
C6 C4 + C2 /C3 + C3

Cracking proceeds via free radical mechanism.

RCH2.CH3 RCH2 + CH3

Unsaturated (olefins) obtained in the process crack again.[3,6]

• C4H8 C2H6 + H2/C2H4 + CH4 + C

• C4H8 CH4 + C3H4 (diolefins / alkynes)
• C2H4C3H4 C + H2

Olefins cracks on dehydrogenation to diolefin or an

alkyne.[1,2,6]

• Hydrogenation also occur but to less extent.

• C3H4 + H2 C3H6

Saturates are converted to unsaturates:

149
 Ring opens in the extreme conditions of cracking

Chemistry of Catalytic Cracking[1-2,6-8]

Paraffins Paraffins + Olefins

150
 Thermal cracking operation [1,2]

Tab:4.1

Cracking
Nature of
temperature Products
operation
(C)

425-460 Visbreaking Fuel oil

Gas, gasoline, Tar oils,

460-520 Thermal cracking
circulating oils

Low temperature
520-600 Gas, asoline , soft coke
coking

800-1000 High temperature Gas , heavy aromatics

Above 1000 decomposition H2, gas, carbon black

Thermal cracking[1,2,6-8]

Properties of cracked materials

151
Product properties are extensively dependent on the conditions of
cracking.The properties that undergo changes during cracking are:

a) Characterisation factor (decreases due to high aromatic content)

b) Boiling point , viscosity, pour point decreases.
c) Unsaturation and Aromatisation increases.
d) Octane number of gasoline increases.
e) Sulphur content in the cracked product increases as the rule
although the maximum amount in heavier portion only.

Cracking[1,2,6-8]

It is a endothermic process , so external heat is required.

Main parameters affecting cracking:
• Pressure
• Temperature
• and time of cracking.

Pressure has no direct effect on velocity of the reaction. If more

gases to be produced then low pressures are desirable.
• With higher pressures gas to gasoline ratio becomes less.
• Reaction velocity is directly dependent upon temperature .

152
 Fig:4.4

Visbreaking[1,2,8]

• Reduction in viscosity is Visbreaking.

• Materials like residuums are not of direct utility or stocks
decided with difficulties due to high pour point , from palapable
feed stock for this operation.
• Liquid products may be used as cycle stocks for crackers
commercially valuable main products know as fuel oil.
• Light fraction gas and gasoline.

Basic parameters:

Cracking temperature and residence time Soaker type (more gas) or

coil type visbreaker(more gasoline due to for short residence time)

High temperature soaker visbreaking[1,2,9-12]

Soaker drum : Large vessel designed to allow for a long residence

time for the feedstock.
Cracking in the furnace is minimised by using high liquid velocity and
steam injection.

153
With increase in T and cracking time : light fraction increase => fuel
oil yield decrease.

High conversion soaker visbreaking

• Gives higher conversion and more stable residue compare to

conventional soaker visbreaking.
• Feed stocks : Heavy crude oil, oil shale, long and short residue,
visbroken residue.

Fig:4.5

Operating conditions and products:[1,2,9-16]

• Increase in cracking time and temperature increases the

lighter fraction and decreases the fuel oil yield.
• Pressure has negligible effect on velocity of reaction. At high
pr. gas / gasoline ratio is less.
• Pressure retards cracking reactions

154
 Fig:4.6

Visbreaking Operation[1,2]

Feed stock: Asphalt, Short residuum to residuums,and medium oil

Steps:

1) Preheating of feed upto 250oC

2) Heating in furnace up to 470o C.
3) Pressure 10-15 kg/cm2 necessary to avoid coke formation.
Steam admission in to feed stocks also checks coke formation.
4) Fraction (Light and heavy) from quencher goes to distillation
column.

Theory of cracking:

Thermal cracking proceeds via free radical machanism.[1,2,8-17]

Free radicals : atom or group of atom with bare unpaired electron.

RCH2CH3 RCH2O + CH3O

155
Unpaired electrons are very active and try to form stable compound
by acquiring unpaired electrons from sources available.
HC (charged) ions are usually referred as carbonium ions.

• Paraffins rate of reaction increases with increase in carbon

number.
• olefins cracks much faster compared to paraffins.

Chemistry of catalytic cracking[1,2,3-14]

Large molecules smaller Fragments with double bond

Hydrogen demand net through creation of double bond by means of
:
• Hydrogen Transfer
• Cyclization
• Aromatization

Effect of pressure on cracking:

Pressure retards cracking reactions. But in practice a positive

pressure of 10 to 15 Kgs/cm2 is used to minimize coke
formation.Recycling increases refractory nature of stocks and hence
recycling should not exceed 2 to 3 times of fresh stock for economic
operation.

Catalytic Cracking [3-16]

• Catalytic Cracking is the most widely used refinery process for

converting heavy oil into gasoline of high octane value.
• Catalyst Cracking is distinguished from Thermal Cracking in the
reaction mechanism Which is called carbonium- ion
mechanism.
• Carbonium ion mechanism gives more stable saturated
compounds.

156
 Protonation of an olefins: [1,2,5-13]

RCH:CH2 + H+ RCH+.CH3 / RCH2CH2+

Bronsted Acid

Catalytic cracking, Cracking reactions, Zeolite catalysts

Catalytic Cracking Reactions:

H vary depending upon the compound:

• Cracking:(+ve) endothermic
• H-Transfer:(-ve) Exothermic
• Isomerization mildly:Exothermic
• Cyclization :(-ve) Exothermic
• Cyclization :Dealkalization :(+ve)

Catalytic cracking, Main Catalysts: Acidic catalysts.[1,2,6-18]

157
 Fig:4.7 The typical sketch and relationship between the Acid
strength of different catalyst versus different reaction carried out for
different hydrocarbon products.

Addition of Lewis Acid:

• RCH:CH2 + BF3 / AlCl3 / FeCl3 RCHF.CH2+ + BF2-

• Life time of a Carbonium ion may vary from a fraction of second to
minutes.
• Tertiary Carbonium ion is stablest one followed by secondery and
primary Carbonium ion.
• When protonation takes place, a Carbonium Ion may result.

Paraffin Reactivity:

Rate of reaction increases with carbon number but rate of coke formation also
increases with (carbon number) molecular weight characterized by high
production of C3 and C4 in the cracked gas.

Olefin Reactivity:

158
These cracks at a much faster rate compared to paraffins and subject to rapid
isomerization.

Naphthene Reactivity:

They cracks at a faster rate compared to corrsponding paraffins.

Aromatics:

Alkyl Aromatics

Stability of the ring:

So ring does not crack because of alkyl group. But removal of alkyl group is
easy and it is again by ß-scission.

Cracking reactions:[1,2,9-20]

Alkyl Naphthene Naphthene + Olefin

Alkyl Aromatic Aromatic + Olefin

N-Octane cracking, C8H18 (where R= CH3CH2CH2CH2CH2----)

Step1: mild thermal cracking initiation reaction.

nC8H18 CH4 + RCH=CH2

Step2: Proton shift

Step3:

159
Step4: Rearrangement towards more stable structure
stability tertiary > secondary > primary

Step5: Hydrogen ion transfer

Cracking Catalyst

Acidic catalyst : which can supply proton.

• Acid treated natural alumino silicates.

• Amorphous synthetic silica-alumina catalyst.
• Crystalline (aluminosilicates) synthetic. Silica alumina ctalyst zeolite or
moleculor sieve.
• Zeolites have more active sites and adsorption capacity which helps in
faster cracking rate.

Advantages of zeolite catalyst:[1,2,8-20]

1. Zeolite has tremendous advantages over amorphous silica-alumina.

2. Higher activity: factor of 100 higher than amorphous silica-alumina
catalyst.
3. Higher gasoline yield at a given conversion however octane number of
gasoline obtained from zeolite cracking is lower by 2-3 numbers
compared to amorphous catalyst.
4. Production of gasoline containing a large number of paraffin and
aromatic hydrocarbons.

Tab:4.2

Paraffin Aromatics Naphthenes Olefins

Amorphous 38 10 0.45 10

Zeolite 45 20 0.15 20

160
 Olefins are lower & paraffins and aromatics are higher. This is because
of superior Transfer facility of zeolites.

• O+N P+A
• O P+A
• Cyclo-olefins N+A

Gasoline yield is higher with zeolite. This is because of:

• C16 C16+
• C16+ C16+ + C3

5. Lower coke yield.

6. Increased iso- butane production.( this is again because of H- Transfer)
7. Increased iso- butane production.( this is again because of H- Transfer)
8. Lower dry gas yield.( C1-C4 HC’s) [more gasoline, less coke and less
gas yield are its main advantages.]

Characteristics

• Residence time ~ 1 -4 sec.

• Zeolite – Y : generally used as a cracking catalyst.
• Faujasite: naturally occuring crystalline alumino-silicates.
• Zeolite –Y : synthetic form of Faujasite.
• Composition: 0.9 ± 0.2 Na2O . Al2O3.wSiO2.xH2O (sodium form of
zeolite.)
3<w<6 ,x<9
but Na is poison to cracking reaction. So it must be in ion form. So
converted to acidic form.
• Cation exchange with a medium containing rare earth cation ( cesium,
lanthanum etc.)

Catalytic Cracking processes

• Fixed bed , Houdry

• Moving bed- Air lift- Thermofer catalytic cracking
• Fludised bed:

161
 • FCC , UOP, Texaco
• Kellog (Orthoflow)
• Fexi cracking

Cracking Feedstocks and reactors,Effect of process

variables

REFINING[1,2,12]
• Process to produce useful fuels from crude oil.
• Separation, Conversion, Treatment and Blending.
• Primary processes- fractionation
• Secondary Processes-conversion processes
• improve the product quality.
• upgrade heavier ends to lighter products.
• Predominantly catalytic processes.

Fig:4.8 A typical sketch of refinery operations integrated with

its profit margin, product pattern shift, with deteriorating crude
quality and stringent emission control parameters.

• Crack carbon-carbon bonds in gas oils.

• Fine catalyst in fluidized bed reactor allows for immediate
regeneration.

162
 • Lowers average molecular weight and produces high yields
of fuel products.
• Produces olefins.

• Attractive feed characteristics.

• Small concentrations of contaminants Poison the catalyst.
• Small concentrations of heavy aromatics Crack and deposit
coke on catalyst.

• Products may be further processed.

• Further hydrocracked.
• Alkylated to improve gasoline antiknock.
• Early Fixed and Moving Bed Catalytic Cracking.

• Cyclic fixed bed catalytic cracking commercialized in late 1930s.

• Houdry Process Corporation formed in 1930.
• First Houdry catalyst cracker started up at Sun Oil’s
Paulsboro, New Jersey, refinery in June 1936.
• Three fixed bed reactors and processed 2,000 barrels/day
12,000 barrels/day commercial unit went on stream at Sun’s
Marcus Hook Refinery in 1937.
• Other adoptees: Gulf, Sinclair, Standard Oil of Ohio, and The
Texas Company.

• Sun & Houdry Process Corporation started development on a

moving bed process in 1936.
• Pilot Thermofor catalytic cracker was started in 1941.
• First commercial 20,000-barrel/day unit commissioned at
Magnolia’s Beaumont Refinery in 1943.

Catalytic cracking[1,2,12]

• The process flows of both types of processes are similar. The hot
oil feed is contacted with the catalyst in either the feed riser line
or the reactor.
• As the cracking reaction progresses, the catalyst is progressively
deactivated by the formation of coke on the surface of the catalyst.
• The catalyst and hydrocarbon vapors are separated mechanically,
and oil remaining on the catalyst is removed by steam stripping
before the catalyst enters the regenerator.
• The oil vapors are taken overhead to a fractionation tower for
separation into streams having the desired boiling ranges.

163
 • The spent catalyst flows into the regenerator and is reactivated by
burning off the coke deposits with air. Regenerator temperatures
are carefully controlled to prevent catalyst deactivation by
overheating and to provide the desired amount of carbon burn-off.
• This is done by controlling the air flow to give a desired CO2/CO
ratio in the exit flue gases or the desired temperature in the
regenerator.
• The flue gas and catalyst are separated by cyclone separators and
electrostatic precipitators.
• The catalyst in some units is steam-stripped as it leaves the
regenerator to remove adsorbed oxygen before the catalyst is
contacted with the oil feed.

FLUIDIZED-BED CATALYTIC CRACKING[1,2,12]

The FCC process employs a catalyst in the form of very fine particles
[average particle size about 70 micrometers (microns)] which behave as
a fluid when aerated with a vapor.The fluidized catalyst is circulated
continuously between the reaction zone and the regeneration zone and
acts as a vehicle to transfer heat from the regenerator to the oil feed
and reactor.
• Two basic types of FCC units in use today are:
• side-by-side type,where the reactor and regenerator are separate
vessels adjacent to each other,and the Orthoflow, or stacked type,
where the reactor is mounted on top of the regenerator.

One of the most important process differences in FCC units relates to the
location and control of the cracking reaction. Until about 1965, most
units were designed with a discrete dense-phase fluidized-catalyst in the
reactor vessel.The units were operated so most of the cracking occurred
in the reactor bed

The extent of cracking was controlled by varying reactor bed depth

(time) and temperature. Although it was recognized that cracking
occurred in the riser feeding the reactor because the catalyst activity and
temperature were at their highest there, no significant attempt was
made to regulate the reaction by controlling riser conditions.After the
more reactive zeolite catalysts were adopted by refineries, the amount
of cracking occurring in the riser (or transfer line) increased to levels
requiring operational changes in existing units.

The fresh feed and recycle streams are preheated by heat exchangers
or a furnace and enter the unit at the base of the feed riser where they

164
are mixed with the hot regenerated catalyst.The heat from the catalyst
vaporizes the feed and brings it up to the desired reaction temperature.
The mixture of catalyst and hydrocarbon vapor travels up the riser into
the reactors. The cracking reactions start when the feed contacts the hot
catalyst in the riser and continues until the oil vapors are separated from
the catalyst in the reactor. The hydrocarbon vapors are sent to the
synthetic crude fractionator for separation into liquid and gaseous
products.

The catalyst leaving the reactor is called spent catalyst and contains
hydrocarbons adsorbed on its internal and external surfaces as well as
the coke deposited by the cracking. Some of the adsorbed hydrocarbons
are removed by steam stripping before the catalyst enters the
regenerator. In the regenerator, coke is burned from the catalyst with
air.

The regenerator temperature and coke burnoff are controlled by varying

the air flow rate. The heat of combustion raises the catalyst temperature
to 1150 to 1550oF (620oC–845oC) and most of this heat is transferred by
the catalyst to the oil feed in the feed riser. The regenerated catalyst
contains from 0.01 to 0.4 wt% residual coke depending upon the type
of combustion (burning to CO or CO2) in the regenerator.

The regenerator can be designed and operated to burn the coke on the
catalyst to either a mixture of carbon monoxide and carbon dioxide or
completely to carbon dioxide.Older units were designed to burn to
carbon monoxide to minimize blower capital and operating costs because
only about half as much air had to be compressed to burn to carbon
monoxide rather than to carbon dioxide.Newer units are designed and
operated to burn the coke to carbon dioxide in the regenerator because
they can burn to a much lower residual carbon level on the regenerated
catalyst. This gives a more reactive and selective catalyst in the riser
and a better product distribution results at the same equilibrium catalyst
activity and conversion level.

For units burning to carbon monoxide, the flue gas leaving the
regenerator contains a large quantity of carbon monoxide which is
burned to carbon dioxide in a CO furnace (waste heat boiler) to recover
the available fuel energy.The hot gases can be used to generate steam
or to power expansion turbines to compress the regeneration air and to
generate electric power.

165
Fig:4.9 Older fluid catalytic-cracking (FCC) unit configurations[1,2]

166
 Fig:4.10 UOP reduced crude cracking(RCC)[1,2]

NEW DESIGNS FOR FLUIDIZED-BED CATALYTIC CRACKING

UNITS[1,2,12]

Zeolite catalysts have a much higher cracking activity than amorphous

catalysts, and shorter reaction times are required to prevent
overcracking of gasoline to gas and coke. This has resulted in units which
have a catalyst-oil separator in place of the fluidized-bed reactor to
achieve maximum gasoline yields at a given conversion level. Many of
the newer units are designed to incorporate up to 25% reduced crude in
the FCC unit feed. Schematic drawings of Exxon Research and
Engineering’s FLEXI CRACKING IIIR design.

167
These units incorporate a high height-to-diameter ratio lower
regenerator section for more efficient single-stage regeneration and an
offset side-by-side or stacked vessel design. UOP-designed units utilize
high velocity, low inventory regenerators, and Kellogg-designed units
use plug valves to minimize erosion by catalyst containing streams . All
units are now designed for both complete combustion to CO 2 and CO
combustion control.

The large differential value between residual fuel and other catalytic
cracking feed stocks has caused refiners to blend atmospheric and
vacuum tower bottoms into the FCC feed. Residual feed stocks have
orders of magnitude higher metals contents (especially nickel and
vanadium) and greater coke forming potential(Ramsbottom and
Conradson carbon values) than distillate feeds. These contaminants
reduce catalyst activity, promote coke and hydrogen formation, and
decrease gasoline yield. It has been shown that catalyst activity loss due
to metals is caused primarily by vanadium deposition, and increased
coke and hydrogen formation is due to nickel deposited on the catalyst.

The high coke laydown creates problems because of the increase in coke
burning requirement with the resulting increased air or oxygen demand,
higher regenerator temperatures, and greater heat removal. For feeds
containing up to 15 ppm Ni V, passivation of nickel catalyst activity can
be achieved by the addition of organic antimony compounds to the feed
with reductions in coke and hydrogen yields up to 15% and 45%,
respectively. For feeds containing 15 ppm metals and having Conradson
carbon contents above 3%, hydroprocessing of the FCC feed may be
required to remove metals, reduce the carbon forming potential, and to
increase the yield of gasoline and middle distillates by increasing the
hydrogen content of the feed.

Feeds for Catalytic Cracking[1,2,12]

• Aromatic rings typically condense to coke

• No hydrogen added to reduce coke formation.
• Amount of coke formed correlates to carbon residue of feed
normally 3-7 wt% CCR.
• Catalysts sensitive to heteroatom poisoning
• Sulfur and metals (nickel, vanadium, and iron).
• Feeds normally hydrotreated.
• Atmospheric and vacuum gas oils are primary feeds
• Could be routed to the hydrocracker for diesel production
Not as expensive a process as hydrocracking.

168
• Dictated by capacities of gasoline/diesel economics.

Fig:4.11 FCC Products[1,2]

169
Fig:4.12 FCC unit with coke productions during cracking
reactions[1,2]

170
 Fig:4.13 FCC regeneration unit[1,2]

PRODUCT YIELDS

• Produces high yields of liquids small amounts of gas coke Mass

liquid yields are usually 90%-93%; liquid volume yields that are
often more than 100%(Rule of thumb) Remaining mass yield split
between gas and coke.
• The yield pattern is determined by complex interaction of feed
characteristics and reactor conditions that determine severity of
operation.
• Conversion defined as relative to what remains in the original
feedstock boiling range of Conversion =100%-(Gas Oil Yield).

Catalytic Cracking Catalysis & Chemistry[1,2,8-19]

171
• Zeolite catalysts
• High activity.
• Good fluidization properties.
• High gasoline and low coke yields.
• Acid site catalyzed cracking and hydrogen transfer via carbonium
mechanism.
• Basic reaction —carbon-carbon scission of paraffins,
cycloparaffins aromatics to form olefins lower molecular
weight paraffins.
• Olefins exhibit carbon-carbon scission and isomerization with
alkyl paraffins to form branched paraffins.
• Cycloparaffins will dehydrogenate (condense) to form
aromatics.
• Small amount of aromatics and olefins will condense to
ultimately form coke.
• Research continues by catalyst suppliers and licensors
• Recognition that both crackability of feed and severity of
operations are factors.
• Theoretical basis for cracking reactions lead to more precise
catalyst formulation.
• Catalyst can be tailored to maximize gasoline yield or
increase olefin production.

CATALYTIC CRACKING[1,2,12]

172
Fig:4.14 Catalytic Cracking[1,2]

173
Fig:4.15 Exxon FLEXCRACKING IIIR FCC unit(courtesy of Exxon
Research and Engineering)

FCC Cracking, Catalyst coking and regeneration,

Design concepts, New Designs for Fluidized-Bed
Catalytic Cracking Units
▪ Refining Process and Catalysts.[1,2,21,22]
▪ Fluid Cracking Catalyst (FCC).
▪ FCC additives.
▪ Reforming Catalyst.
▪ Catalyst Characterization.
▪ R & D & Commercialization Status in India.
▪ Conclusion.

174
FCC SCENARIO IN INDIA

• FCC Units in Operation :15

• Total FCC Capacity ~ 26 MMTPA
• Future FCC Capacity ~ 42 MMTPA

FCC PROCESS

Fig:4.16 FCC PROCESS

FCC RISER/REGENARATOR COMBINATION

175
Fig:4.17 FCC/RISER/REGENARATOR COMBINATION

KELLOG DESIGN RISER UNIT

176
 Fig:4.18 KELLOG DESIGN RISER UNIT[1,2]

KELLOG RESID FLUID CATALYTIC CRACKING(RFCC)

177
Fig:4.19 KELLOG RESID FLUID CATALYTIC CRACKING(RFCC)[1,2]

ZEOLITE STRUCTURE[23]

178
 Fig:4.20 Zeolite Structure

FCC: Some Interesting Facts

• Nearly 20% of crude is being processed at FCC.

• Larger FCC units holds about 400 Tonnes of catalyst.
• Four major manufactures (Grace Davision, Engelhard, Akzo Nobel,
CCIC)supply 1400 tons of catalyst daily to process 12 million barrels per
day (600 MMT/day).
• 400 FCC units in world.

PROCESS VARIABLES

In addition to the nature of the charge stock, the major operating variables
effecting the conversion and product distribution are the cracking
temperature, catalyst/oil ratio, space velocity, catalyst type and activity, and
recycle ratio. For a better understanding of the process, several terms should

179
bedefined.
Activity :Ability to crack a gas oil to lower boiling fractions.
Catalyst/oil ratio (C/O) =lb catalyst/lb feed.
Conversion =100 (volume of feed volume of cycle stock)/volume of feed.
Cycle stock :Portion of catalytic-cracker effluent not converted to naphtha
and lighter products [generally the material boiling above 430°F(220°C)]
Efficiency =(% gasoline)conversion.
Recycle ratio=Volume recycle/volume fresh feed.
Selectivity:The ratio of the yield of desirable products to the yield of
undesirable products (coke and gas).
Space velocity:Space velocity may be defined on either a volme (LHSV)or a
weight (WHSV) basis. In a fluidized-bed reactor, the LHSV has little meaning
because it is difficult to establish the volume of the bed.The weight of the
catalyst in the reactor can be easily determined or calculated from the
residence time and C/O ratio.
LHSV = Liquid hour space velocity in volume feed/(volume catalyst)(hr).
WHSV =(Weight hour space velocity in lb feed)/(lb catalyst) (hr).

Within the limits of normal operations, increasing[1,2,23]

1. Reaction temperature
2. Catalyst/oil ratio
3. Catalyst activity
4. Contact time

Results in an increase in conversion, while a decrease in space velocity

increases conversion. It should be noted that an increase in conversion does
not necessarily mean an increase in gasoline yield, as an increase in
temperature above a certain level can increase conversion, coke and gas
yields, and octane number of the gasoline but decrease gasoline yield . In
many FCC units, conversion and capacity are limited by the regenerator coke
burning ability. This limitation can be due to either air compression limitations
or to the after burning temperatures in the last stage regenerator cyclones.
In either case FCC units are generally operated at the maximum practical
regenerator temperature with the reactor temperature and throughput ratio
selected to minimize the secondary cracking of gasoline to gas and coke. With
the trend to heavier feedstocks, the carbon forming potential of catalytic
cracker feeds is increasing, and some units limited in carbon burning ability
because of limited blower capacity are adding oxygen to the air to the
regenerator to overcome this limitation. Oxygen contents of the gases to the
regenerator are being increased to 24–30% by volume and are limited by
regenerator temperature capability and heat removal capacity

GROWTH OF CATALYSTS IN FCC

180
 Fig:4.21 Growth of catalysts in FCC

Fluid Catalytic Cracking

Reactions in FCC[1,2,21,22]

▪ Paraffins are cracked to give olefins and smaller paraffins.

▪ Olefins are cracked to give smaller olefins.
▪ Napthenes (cycloparaffins) are cracked to olefins.
▪ Alkyl aromatics lose their side chains.
▪ Isomerisation of olefins to iso-olefins.
▪ H-transfer reactions.

181
Acidity of solid catalysts

FCC Catalyst
▪ Catalyst Components
▪ Zeolite
▪ Matrix
▪ Binder
▪ Filler

Structure of Zeolite [23]

182
Fig:4.22 Structure of Zeolite

Zeolite

Fig:4.23 Zeolite

183
 Further treatments of NaY zeolite
• Ion Exchange.
• RE Exchange.

Preparation methods of High-Silica Y zeolites[23]

• Thermal and hydrothermal modification.
• Chemical modification.
• Combination of hydrothermal and chemical modification.

Ion Exchange

Thermal and hydrothermal modification

184
 Fig:4.24

Framework Stabilization:

185
 Fig:4.25 Framework Stabilization

Zeolite properties[23]

1. Introduction

The word ‘Zeolite’ is derived from the Greek word, which means ‘boiling
stone’[24] (2002). Zeolites are water-containing crystalline aluminosilicates
with highly ordered structures. They can be of naturally originated or
synthesized and consist of SiO4 and AlO4- tetrahedra. These tetrahedras are
interlinked through common oxygen atoms to give a three-dimensional
network through which long channels run[25] (2006).
A representative empirical formula for a zeolite can be written as
Mx/n [(AlO2)x (SiO2)y]mH2O. Where, M is the cation of valency n; x and y
represents Si/Al ratio and having value from 1 to 8. When M cations are
replaced by H+ions, the active catalysts can be generated and used in the
petroleum industries for cracking, hydrocracking and isomerization
reactions[26] (1982). Zeolites provide excellent shape selectivity and acidic
sites. Due to these characteristics, zeolites have dominant applications in
petroleum industries.
186
Hydrocracking and hydroisomerization are the two of the most important
processes of the petroleum refineries, which are not possible without
application of suitable catalysts (Fig.4.26). The continuous increase in global
demand of the petroleum products increases the valuation of these processes
in modern refineries. Hydroisomerization is termed as the isomerization of n-
paraffins into branched isomers. Hydroisomerization of C4–C7 hydrocarbons
has been applied for the production of gasoline with a high octane number.
Hydroisomerization of C7 –C15 paraffins applies to improve diesel fuel cold flow
properties, such as viscosity, pour point and freezing point. The
hydroisomerization reaction is always accompanied by a hydrocracking
reaction that lowers more or less the yield of that the isomerized feed
molecules[27] (2005).
Catalysts used for hydroisomerization reactions are bifunctional in nature.
They generally contain metal such as Pt, Pd, Ni etc. dispersed on acidic
supports. While hydroisomerization and hydrocracking reactions, metals are
responsible for hydrogenation-dehydrogenation agent and acidic supports are
responsible for isomerization and cracking of the substances[28] (2003). Zeolite
acidity (number and strength distribution) and pore structure play important
role in overall reactions.
Typical acidic supports of bifunctional catalysts used are amorphous oxides or
mixture of oxides (i.e. HF-treated Al2O3, SiO2–Al2O3, ZrO2/SO42-); zeolites (Y,
Beta, Mordenite, ZSM-5, ZSM-22, ZSM-12 etc.); silicoaluminophosphates
(SAPO-11, SAPO-31, SAPO-41) and mesoporous materials (MCM-41, AlMCM-
41) (Deldari, 2005).
Gasoline and diesel are the most important and valuable fractions generated
by petroleum refineries. The demand of these two fractions have globally
increased since last few years. The average demand for diesel will be almost
twice than that of the demand of gasoline in next few years (Fig.4.27). So,
major part of the investments of the petroleum refineries have covered
processes for production or upgrading of middle distillate fractions to make
them suitable for diesel blendstock[29] (2010).
So, objective of this work is to develop suitable molecular sieve based
catalysts for the hydroisomerization of middle distillate fractions. The catalyst
should provide transition shape selectivity for branched isomers. Also, the
catalyst should provide good mechanical strength during reaction conditions
and structure (especially in the case of molecular sieves) should not collapse
at reaction conditions. The zeolite molecular sieves successfully fulfilled all
these criterions and have been commercially used since their invention.
Therefore, development of the noble metal (i.e. Pt, Pd etc.) loaded zeolite (i.e.
ZSM-12, ZSM-22, ZSM-48) supported catalysts, is the major objective. Also,
development of kinetic model for hydroisomerization followed by
hydrocracking reactions will also be performed.

187
Fig:4.26 Schematic flow diagram of a modern refinery [29] (2010)

188
 Fig:4.27 Incremental transportation fuel demand from 2008 to
2015[29](2010)

2.1 Introduction to molecular sieves and zeolites (Szostak, 1989)

In 1932, McBain proposed the term “Molecular Sieve” for the materials which
have selective adsorption properties and these materials separate
components of a mixture on the basis of difference in molecular size and
shape. The different classes of molecular sieves are listed in Fig.4.28 Structure
of many of these materials are analogous, but all are different in terms of
elemental composition and aluminosilicates have been given the classical
name ‘Zeolites’.
Structurally zeolites are the crystalline aluminosilicates with a framework
based on an extensive three-dimensional network of oxygen ions. The
AlO2- tetrahedra in the structure determine the framework charge and is
balanced by cations, which occupy non-framework positions. The crystalline
framework structure contains voids and channels of discrete size. The pore
opening ranges from 3 to 8Ao. The negative charge has been created by
AlO2- tetrahedra and balanced by cations like alkaline (Na+, K+, Rb+, Cs+),
alkaline earth (Mg+2, Ca+2), NH4+, H3O+ (H+), TMA+ (Tetramethylammonium),
other nitrogen containing organic cations, and rare-earth and noble metal
ions. All aluminosilicates are molecular sieves but not zeolites. An
aluminosilicate is called zeolite if it contains at least one aluminium ion per
unit cell based on the bulk composition of the sample, with no allowance made
for inhomogeneities within the individual crystal on the microscopic level.

189
 Fig:4.28 Classification of molecular sieve materials indicating the
extensive variation in composition[30] (1989)

Fig:4.29 Examples of pore opening in the zeolite molecular

sieves[25] (2006)

Zeolites have been classified on the basis of different structural elements. The
kind of building unit most suitable for the classification of the zeolites depends
on the property under consideration. If we are able to identify ability of a
perticular zeolite to selectively adsorb one component of a mixture over
another, understanding of the detailed complex structure of that perticular
zeolite would not be necessary. Size of the pore opening of the perticular
zeolite is responsible for selective adsorption of perticular components. So, we
can classify zeolite from on the basis of pore size to sequence of building
blocks which form the regular network pattern characteristic of the zeolite.

190
Each level acts as a model to understand, describe or visualize a specific
aspect of a material.
The first level of classification is based on pore size. All the zeolites used for
catalytic or adsorption operations can be classified by the number of T atoms,
where T is Si or Al that define pore opening. Till date only three types of pore
openings are known and of practical interest. They are 8-member ring (small
pore), 10-member ring (medium pore) and 12-member ring (large pore)
zeolites (Fig.4.29). The distribution of products for different zeolites depends
upon difference in their pore sizes. Example of 8-member ring zeolites are
Erionite, Chabazite and Type A. ZSM-5, ZSM-11, ZSM-22, EU-1 and Theta-1
comes under the category of 10-member ring zeolites. Whether Type Y,
Mordenite (synthetic), ZSM-12 and ß are the examples of 12-member ring
zeolites.
Second level of classification is based on the number of dimensions
encompassed by the pores and shape of the pore mouth. There are one-, two-
and three-dimensional tubes or channels can be viewed in the zeolite
structures. Analcite is the example of one-dimensional channels, while
Mordenite has two-dimensional intersectig channel system. ZSM-5 and ZSM-
11 contain intersecting three-dimensional 10 ring channel system. The
difference in shape and size of channel interaction are responsible for subtle
difference in selectivity between different zeolites. The size and shape of the
pore opening can be determined by configuration of T and O atoms relative to
each other, Si/Al ratio, size and location of the cation and temperature.
Pore openings and channel systems determine catalytic and adsorptive
properties of the zeolites. But, as also mentioned earlier they don’t provide
any information on structural properties of the zeolites. Lack of information
on structural properties of the zeolites led to develoment of Structural Building
Units. The Structural Building Units can be classified into Primary Building
Units, Secondary Building Units, Extended Chain Building Units and Sheet
Building Units. A primary building unit is the individual tetrahedral TO4 unit,
where T is either Si or Al. A secondary building unit (SBU) is the geometric
grouping of those tetrahedra. These SBU’s contain 4, 6, and 8-member single
rings; 4-4, 6-6, and 8-8 member double rings; and 4-1, 5-1, and 4-4-1
branched rings. Most of the zeolites frameworks can be generated by the
arrangement of different SBU’s. ZSM-5 and Ferrierite can be described by their
5-1 building uits. Offretite, zeolite L, Cancrinite, and Erionite are generated
using only single 6-member rings. Some zeolite structures can be generated
by various SBU’s. For example, the sodalite structure can be built from either
the single 6-member or the single 4-member ring (Fig.4.30).

191
Fig:4.30 Generation of sodalite structure from either 6-member rings
or 4-member rings[30] (1989).

Arrangement of the secondary building units in space generates chain building

units, which add further dimensions to secondary building units. Various types
of chains found in the zeolite structures is shown in Fig.4.31.

Fig:4.31 Chains found in zeolite structures: (a) zig-zag (b) sawtooth

(c) double crankshaft (d) narsarsukite (e) natrolite 4=1 and (f)
pentasil chains [29](2010).

Chain building units rearrange and form the sheet building units. Generally,
chain building units are one-dimensional and sheet building units are two-
dimensional. In Fig.4.32 successive built up of the ZSM-5 (MFI) is shown.

192
Fig:4.32 The ZSM-5 (MFI) structure can be built up successively: (a)
the pentasil unit; (b) chains of pentasil units; (c) layers of these
chains; and (d) layers linked across inversion centres[29] (2010).

2.2 Hydrothermal synthesis of zeolites (Cundy[31] Cox, 2005)

In late 1940s, Richard Barrer and Robert Milton have started synthesis of
zeolites by conversion of known mineral phases under the action of strong salt
solutions in the temperature range of 170 to 270oC. By 1953, Milton and his
colleagues had synthesized 20 zeolites including 14 unknown as natural
minerals. Initially the aim of study was to understand complex synthesis
processes and later it has been shifted to discoveries of new materials,
advances in synthesis techniques, innovations in theoretical modelling
methods, development of new techniques for the investigations of reaction
mechanisms and development of the new techniques for the characterization
of the materials.

A typical hydrothermal zeolite synthesis can be described in brief as follows:

▪ Silica and alumina sources in the amorphous form have been mixed
together in the alkaline pH and in an aqueous medium with a cation
source.
▪ The reaction mixture has been heated in a sealed autoclave at
temperature above 100oC and autogeneous pressure.
▪ After reaching the appropriate temperature, reactants remain
amorphous for some time and this time is known as “induction period”.
Crystallization starts after this period of time.
▪ After appropriate time period, all the amorphous materials will be
converted into zeolite crystals. These crystals are recovered by filtration,
washing and drying.

193
The Si and Al sources have been used in an oxide form and these amorphous
precursors contain Si-O and Al-O bonds. At the end of the hydrothermal
synthesis crystalline zeolite products containing Si-O-Al linkages has been
created in the presence of “mineralizing” agent (generally alkali metal
hydroxide). The bond type of the product is very similar to the bond types of
precursor oxides. So, it can be concluded that, no great enthalpy changes has
been takes place. In fact, overall free energy change of the reaction is small
enough to become the overall reaction kinetically controlled. This gives the
benefit of generation of metastable products. To make the synthesis process
industrially important, the product must contain reproducibility and the same
specification each time. This needs to develop exact conditions for product
optimization. This influences the choice of starting reagents from wide
varieties of simple oxides or hydroxides to sodium silicate solution and solid
sodium aluminate. Usage of sodium silicate solution or solid sodium aluminate
gives not only benefits in terms of cost or ease of operation but also they offer
optimum routes to particular materials. Flexibility in the choice of reagents
enables equilibria to be approached from various directions. We may also get
the kinetic benefits like preferred nucleation of one phase over another in the
situations of possibility of co-crystallization of the materials.
Now let’s come to the synthesis mechanism for zeolites. The most probable
pathways can be given as induction period, nucleation and crystal growth in
sequence. Induction period is the time (t) between the notional start of the
reaction and the point at which the first crystal formation can be observed.
According to the classical nucleation theory, the induction period has been
divided into three subunits as relaxation time (tr), time for formation of stable
nucleus (tn) and time for the nucleus to grow to a detectable size (t g).
‘Nucleation’ is defined as the series of atomic or molecular processes by which
the atoms or molecules of a reactant phase rearrange into a cluster of the
product phase large enough as to have the ability to grow irreversibly to a
macroscopically larger size. The ‘cluster’ is defined as nucleus or critical nuclei.
The rate of nucleation (i.e., the number of nuclei formed per unit time per unit
volume) can be expressed by an Arrhenius-type equation[29] (2010):

J = A exp (-ΔG*/kT).................(1)

Where, ΔG* is the critical Gibb’s free energy, k is rate constant at temperature
T. Cations and organic-structure-directing agents also involved in the
nucleation process by surrounding themselves with metal-oxide species in
preferred geometries. Crystal growth is considered as one of the most
important step and studies tell that zeolite growth increases linearly during
most of the crystallization process for both gel and clear solution synthesis.
Temperature, gel composition, agitation and aging are the various parameters
which affect the zeolite growth[29] (2010).

194
2.3 Characterization of zeolites

Characterization of the synthesized zeolites is very important aspect. A

particular zeolite must contain good crystal structure, required Si/Al ratio,
desired BET surface area and pore size, desired acidic and metal sites, good
dispersion of metal sites, proper crystal morphology etc. for particular
application. Each of the above mentioned properties can be verified by various
characterization techniques like X-Ray Diffraction (XRD), BET surface area
analyzer, Solid state Nuclear Magnetic Resonance (Solid NMR), NH3 or Pyridine
Temperature Programmed Reduction (NH3 -TPD or Pyridine-TPD), H2 -
Chemisorption or CO-Chemisorption, Scanning Electron Microscopy (SEM) and
Transmission Electron Microscopy (TEM) (both normal and high resolution)
etc.

2.4 Classification of zeolites

Zeolites are comprehensively classified on the basis of their morphology,

crystal structure, Chemical composition, effective pore diameter, origin of
trivalent species donor.

2.4.1 Morphology

Fibrous: Tetrahedra linked more numerous in one crystallographic .Lamellar

(Open framework): Tetrahedral linkages within similar plane.Zeolites have
been structurally classified on the basis of Secondary Building Unit (SBU).
They can be explained as cage, ring or cage like structures which forms the
basic architecture of zeolites. Fig.4.33 shows some of the SBU.

4.33 SBU in zeolite skeleton.

2.4.2 Unit cell size:

195
It is an elementary building block of the zeolite crystal.
It is a measure of aluminium sites or the total potential acidity.
Nsi + NAi = 192
Al/Unit cell= 111.52 (UCS – 24.191) developed by Breck and Flannigan.

Tab:4.3

cell UCS(oA) Al/Unit

NaY (As synthesized) 24.64 – 24.67 54

USY 24.50 – 24.54 40

Equilibrated USY 24.25 – 24.30 2 - 13

2.4.3 Rare earth level:

Rare earth elements serve as a bridge to stabilize aluminium atoms in the

zeolite structure.

Tab:4.4

Rare earth
zeolite(oA) USY
exchanged

High UCS Low

High Zeolite activity Low

Gasoline
High Low
selectivity

Low RON High

High Hydrogen transfer Low

Hydrothermal
High Medium
stability

2.4.4 Chemical Constitution

Zeolites are classified on the basis of their framework silicon and aluminum
constitution. This classification is mainly done on the basis of the Silicon to
196
 Aluminum ratio and was introduced by Flanigen[32] (1982). Table 1 vividly
describes some of the zeolites.

Tab:4.5 Silica rich and poor zeolites.

ure Silica Zeolites Si/Al = 8 Si-MEL (silicalite-2), Si- MFI (silicalite-1), Si-FER
gh Silica Zeolites Si/Al = 5-500 MFI, BEA, FER etc.
mediateSilica Zeolites Si/Al = 2-5 Erionite, Chabazite, MOR, L, X, Y etc.
ow Silica Zeolites Si/Al = 1-1.5 A, X, Sodalite, etc.

2.4.5 Pore Size Diameter

Different zeolites have different opening ring combination. Such as Fig.4.34

a) displays the graphical view of MFI zeolite with 10 Member Ring (M.R.)
opening structure. While Fig.4.34 b) displays dimensions of LTA zeolite with 8
M.R. Structure. Fig.4.34 c) elaborates dimensions of VPI-5 with 18 M.R. Some
example s of different zeolites containing.

Fig:4.34 Ring opening structures along [001] of some zeolites.

(Units mentioned in fig are in Angstrom unit)

Tab 4.6 Classification based on ring opening

mall Pore 8 M.R. Medium Pore10 M.R. Medium Pore 12, 14 M.R. Large Pore18, 20 M.R
Chabazite MOR CIT-5 (14) VPI-5 (18)
Erionite VPI-8 UTD-1F (14) Cloverite (20)

197
LTA ZSM-22 AlPO-5 (12)
ITQ-3 ZSM-18 ZSM-12 (12)

2.5 Characteristics and Physicochemical properties of zeolites

(Deldari, 2005)

Global rise in demand of zeolites can be justified with the help of some
following properties of zeolites followed by discussing the chief properties of
zeolites. High surface area, uniform micropore size, high hydro thermal
stability, intrinsic acidity, ability to accommodate active metal species,
introducing constraints to undesired species by molecular sieving effect (shape
selectivity), environmentally harmless, non-corrosive, show ease of
separation from reaction mixture compared with homogeneous catalysts.

2.5.1 Framework Cation Exchange

4.35 Fixed pore opening[25] (2006)

The zeolite framework is comprised of Silicon and Aluminum linked together

with oxygen atoms to form tetrahedra. To stabilize the structure or to
compensate negative charge imparted by aluminum due to its valency, a
cation is required. Cation exchange properties of zeolite is function of its
intrinsic properties like (i) Framework topology (ii) Ion size and shape (iii)
Charge density of anionic framework (iv) Ion valence (v) Electrolyte
concentration in aq. Phases.

2.5.2 Size Constraints or Molecular sieving or Shape selectivity

198
Due to rigid skeletal system, zeolite window has intact window size due to
which molecules having size larger than this window dimensions often
experience constraints in accessing the intrinsic sites. Thus, prevents
undesired large molecules to enter network. Depending upon this shape
selectivity is being classified into three main subdivisions as described in brief
below.

2.5.2.1 Reactant Shape selectivity

This refines the accessibility molecules inside pore geometry of zeolite by

imparting the fixed window opening, thus limits the diffusion of molecules with
kinetic diameter larger than this window. This allows shape selective entrance
of molecules, activity of such molecules is often hindered. Fig.4.36 shows the
shape selectivity of n- butane and iso-butane over zeolites.

4.36 Shape selectivity of hydrocarbon reactants on to zeolite

framework.

2.5.2.2 Transition Shape selectivity

Transition shape selectivity refers to curbing of intermediate compounds

formed therin the framework whose size is larger than skeleton size. Fig.4.37
shows formation of small sized isomer compared to bulky ones.

199
 4.37 Shape selective transition compound formation restriction.

2.5.2.3 Product Selectivity

Due to restricted pore size products diffusing through these materials

experience constraints and so product formed is also selective in nature. But
however sometimes this bulky products accumulate over a position of zeolite
blocking the accessibility of virgin molecules resulting into coking or
deactivation of catalyst.

4.38 Shape selective product formation

2.5.2.4 Molecular Traffic Control

200
In case of some selected zeolites, having multi dimensional channels, in such
cases reactants access pores other than what product diffuse out. This
becomes easier as counter diffusion is prevented. Several probing techniques
are investigated for having clear idea on shape selectivity of zeolites amongst
which some includes: (i) Constraint Index (ii) Refined constraint index (iii)
Spacious Index, o-p index.

2.6 Applications of zeolites

2.6.1 Ion-exchange

Natural zeolites have a very gifted tendency to ion exchange some water
pollutants. Clinoptilolite is successfully employed for removing Ammonium
from municipal sewages. Regeneration is performed by NaCl and CaCl2.
Ammonia is air stripped in regeneration and absorbed by sulphuric acid to give
ammonium sulphate, a kind of fertilizer. An advantage of zeolites for elevated
resistance compared to organic resins for wastewaters of nuclear industry has
been investigated.

2.6.2 Agricultural Uses

Soils of volcanic origin are prone to have some fraction of natural zeolites, so
they give some indications for their application in improving soil fertility.
Natural zeolites helped many plants including spinach, radish, sugar beet,
tomato, maize, rice, potato and cucumber[33] (2011).

2.6.3 Adsorption

Most of the applications are based on water vapour adsorption. Based upon
such properties zeolites are used as drying media for air, sour natural gas and
other artificial gas streams. Water adsorption-desorption cycles chabazite,
clinoptilolite gave some good inferences in air conditioning and refrigeration.
Their applications based on adsorption of pollutants gas such as SO2 from gas
effluents attributed to the fact that selectivity was found to be good for polar
molecules rather than non-polar molecules. Gas separation technologies are
also under investigation, of these O2 from air by pressure swing adsorption
method are employed using mordenite rich tuffs. Some lab scale
investigations of water-ethanol vapour separations by Phillipsite were
performed knowing that it provides selectivity to ethanol.

2.6.4 Catalysis: Petroleum Refining and Petrochemistry, Application

to Hydroisomerization and Hydrocracking[29] (2010)

201
Due to stupendous shape selectivity and acidic sites provided by zeolites they
have found their dominant applications in petroleum industry, especially for
hydrocracking and hydroisomerization. As mentioned earlier, long-chain n-
paraffins present in the petroleum products, have bad effect on some
properties like octane number of gasoline and cold-flow properties of diesel
fuel. It is desired to remove or convert them into isomers. Conventionally
hydroisomerization process has been used for this. The isomerization process
usually takes place in the presence of hydrogen, and in this case it is referred
to as hydroisomerization [27](2005).
The term cold-flow properties refer to the flow characteristics of a diesel fuel
after at low temperature range. If cold-flow properties don’t change with
respect to temperature, it is termed as good. It is the ability to operate under
cold weather conditions. Petroleum products contain different hydrocarbons
like n-paraffins, i-paraffins, olefins, naphthenes, and aromatics. Among these,
normal and slightly branched paraffins have relatively high melting points in
the typical range of 250–360 oC. The melting point of normal paraffins ranges
between 10 and 40oC, while the melting point of the heaviest methyl paraffin
present (C21) is, depending on the position of the branching, between –4 and
13 oC. The extent of decrease in the melting point significantly depends on the
degree, the position, and the length of the branching. Branching positions in
the middle of the chain have a higher effect than those near the end of the
chain, while longer side chains lead to a higher decrease of melting point.
Engines running on diesel should be able to operate even in cold weather
conditions where temperature can reach values well below 0oC. On the basis
of the data presented above it is evident that such temperatures may cause
the crystallization of those compounds presenting the highest melting points,
thereby affecting the flow characteristics, and ultimately may lead to
solidification of the product. Standard test methods for determining these
properties are cloud point (CP; ASTM D2500), pour point (PP; ASTM D97), and
cold filter plugging point (CFPP); IP 309). The CP is the temperature at which
a haze of wax crystals is formed; PP is the highest temperature at which the
product still flows, while CFPP is the highest temperature at which the wax
crystals severely reduce the flow through a filter. Different options are
available to improve the cold-flow properties of gas oil:

• The simplest is to reduce the backend cutpoint and add kerosene

blendstock. This action removes the heavier paraffinic molecules that
tend to precipitate at higher temperatures. However, reduction of the
end point results in significant reduction of diesel yield from the crude.
• Removal of wax-forming components by crystallization after dilution of
the feedstock with a suitable solvent and chilling (i.e., solvent
dewaxing). This option is generally economical only for feedstocks with
a high content of paraffins, and it is mainly used for the production of
lubricating oil base stocks.

202
 • Usage of cold-weather additives to meet seasonal low-temperature.
• Catalytic dewaxing process wherein the waxy paraffin are selectively
cracked or isomerized.

All of above mentioned techniques; catalytic dewaxing process is of our

interest. Catalytic dewaxing is a process where the products are removed
which are responsible for the degradation of the cold-flow properties. They are
removed by selective cracking to lighter compounds, by boiling in the gasoline
and LPG range (i.e., cracking dewaxing), or by isomerization into more
branched lower melting point structures minimizing as much as possible the
cracking (i.e., isomerising dewaxing).

The detailed mechanism of the hydroisomerization and hydrocracking of n-

alkanes on bifunctional catalysts is shown in Fig.4.39

4.39 Proposed mechanisms for hydroisomerization and

hydrocracking of n-alkanes on bifunctional catalysts[29] (2010)

A catalyst can be used for hydroisomerization, if it contains following

properties [27](2005):

• It should provide good selectivity of isomerized products.

• It should have proper balance of acidic and metal sites.
• It should be able to withstand high pressure and temperature.

203
 • The pore opening of the catalyst is small enough to restrict the larger
isoparaffins from reacting at the acidic sites inside the pore.

2.6.5 Matrix

▪ Physical functions

• Binder
• Diffusivity
• Diluting medium
• Sodium sink
• Heat transfer

▪ Manufacturing

204
4.40 Main Reactions in FCC Catalysis

FCC Catalyst

205
 4.41 FCC Catalyst

ROLE OF ADDITIVES

4.42 Role of Additives

FCC Additives

206
 4.43 FCC Additives

ZSM-5 additive
• Octane boosting.
• Increase in C3 and C4 olefins and LPG maximization.
• Preference for higher butylene yield.
• Initially ZSM-5 cracks paraffins and olefins. As cycle time increases,
olefin isomerisation dominates while gasoline loss and octane
improvement is minimum.

207
Fig 4.44 A typical flow sheet for higher molecular hydrocarbons
(feed) cracking with ZSM-5 towards propylene and butylenes.

How to Maximize Propylene Yield?

208
 Fig 4.45 A typical flow sheet for higher molecular hydrocarbons
(feed) cracking with ZSM-5 towards lighter olefins, napthenes,
paraffins and aromatics.
Cracking by ZSM-5 favored by:[23]
• Low pressure
• High Tempreature
• Fast diffussion of primary cracking product from the catalyst.

Secondary catalyst reactions

• Hi-transfer.isomerization,cyclization favored by:
• High host catalyst ZM
• High zeolite acid strengh,high UCS.
• Slow diffusion of primary cracking product from the catalyst.

Suppressing competitions from secondary reaction is the major key for

maximizing propylene.

Hydrogen Transfer Index

• The relative activity of the host FCC catalyst for secondary reactions can
be quantified using the Hydrogen Transfer Index (HTI):

Designing a Max C3= Catalyst for Resid[23]

REQUIREMENTS:
▪ Minimize Hydrogen Transfer to increase C3= plateau.
▪ Vanadium tolerance for good hydrothermal stability.
▪ Good bottoms cracking ability.
▪ Low coke selectivity.
▪ High accessibility reduces HTI. Primary cracking products can diffuse
from the catalyst faster and are less likely to undergo secondary
reactions.

Balance between HTI and Activity

▪ Low Hydrogen Transfer maximizes propylene.
▪ If achieved by reducing Rare Earth, activity is lower.
▪ There is a limit to how much zeolite can be used in catalyst to
compensate for activity loss.
▪ Dilution effects from large amounts of ZSM-5 must also be overcome.

209
 ▪ The challenge, particularly for Resid, is achieving high propylene yield
AND good conversion with acceptable catalyst addition rate.

Vanadium
• At regenerator conditions, Vanadium on equilibrium catalyst exists as
V+5.
• In the regenerator ‘V’ presented on the catalyst converted Vanadium
pentoxide (V2O5).
• Under regenerator conditions V2O5 is mobile because it melts at
regenerator conditions.
• In the presence of steam V2O5 is converted to Vanadic acid H3VO4.

Ni passivators
• ‘Ni’ passivating agents are antimony, bismuth and rare earth compounds
(Ce, La, etc…).
• Antimony: This is a first commercially used additive.Ni-Sb alloys formed.
1. Antimony will block ‘Ni’ active sites.
2. Alternation of electronic and chemisorption properties.
3. The amount of antimony available to passivate nickel will be
determined by the equilibrium between antimony and nickel.

Draw back: Antimony effects on CO combustion promoters.

Vanadium Passivators[1,2,23]
• Vanadium passivating agents are Tin, Titanium, Zirconium and rare
earth compounds.
• Other than the above stated passivating agents there are other
passivating agents are also reported. They are germanium, gallium,
indium, tellurium, aluminium, barium, zinc, boron, phosphorous,
tungsten, tantalum, lithium and cadmium.

Metal traps
• Metal traps are added to the FCC Catalyst as separate particle or
incorporated directly into the catalyst particle.
• These metal traps react with incoming metals like nickel and vanadium
and form an inert compounds.

210
Fig 4.46 A typical FCC flow sheet in petroleum refining system which
incorporates an FCC to distill high-octane gasoline and LPG from the
heavy contents of the crude oil with sulphur

Catalyst/Additives for Sulphur Control

• Grace
• GSR Technology for sulphur reduction 15-25%
• Sulphur reduction is achieved mainly from front end .
• For Gasoline.

• AKZO
• Resolve FCC catalyst selective matrix activity
▪ 15-30% Sulphur reduction.
▪ Optimized access.
▪ For Gasoline.

• BCA Additive
• 20-30% achieved pesovskite /Spinel.
• Alumina Matrix.
• Sulphur capture by Matrix.

Objective and application of catalytic reforming

process, reforming catalyst.
211
 • Fundamental of Catalytic Reforming [1-4]
• Objective.
• Reaction-Desirable & Undesirable.

• Process
• Semi Regenerative Reforming.
• Dualforming.
• Continuous Catalytic Regenerative Reforming.
• Process Variable.

• Reforming Catalytic
• Types.
• Poisons.

• Some Recent Advance in Reforming

• Semi Regenerative Reforming.
• Update on CCR Technology/Catalyst.
• Update on SR Technology/Catalyst Debottlenecking Option.

Introduction of Catalytic Reforming[1-4]

Catalytic reforming is a chemical process used to convert petroleum

refinery naphthas, typically having low octane ratings, into high-octane liquid
products called reformates which are components of high-octane gasoline
(also known as petrol). Basically, the process rearranges or restructures the
hydrocarbon molecules in the naphtha feedstocks as well as breaking some of
the molecules into smaller molecules. The overall effect is that the product
reformate contains hydrocarbons with more complex molecular shapes having
higher octane values than the hydrocarbons in the naphtha feedstock. In so
doing, the process separates hydrogen atoms from the hydrocarbon
molecules and produces very significant amounts of byproduct hydrogen gas
for use in a number of the other processes involved in a modern petroleum
refinery. Other byproducts are small amounts of methane, ethane, propane
and butanes. This process is quite different from and not to be confused with
the catalytic steam reforming process used industrially to produce various
products such as hydrogen, ammonia and methanol from natural gas, naphtha
or other petroleum-derived feedstocks. Nor is this process to be confused with
various other catalytic reforming processes that use methanol or biomass-
derived feedstocks to produce hydrogen for fuel cells or other uses.

History[5-11]

212
Universal Oil Products (also known as UOP) is a multi-national company
developing and delivering technology to the petroleum refining, natural gas
processing, petrochemical production and other manufacturing industries. In
the 1940s, an eminent research chemist named Vladimir Haense working for
UOP developed a catalytic reforming process using a catalyst containing
platinum. Haensel's process was subsequently commercialized by UOP in 1949
for producing a high octane gasoline from low octane naphthas and the UOP
process become known as the Platforming process.The first Platforming unit
was built in 1949 at the refinery of the Old Dutch Refining Company in
Muskegon, Michigan. In the years since then, many other versions of the
process have been developed by some of the major oil companies and other
organizations. Today, the large majority of gasoline produced worldwide is
derived from the catalytic reforming process.

To name a few of the other catalytic reforming versions that were

developed, all of which utilized a platinum and/or a rhenium catalyst:
Rheniforming: Developed by Chevron Oil Company.
Powerforming: Developed by Esso Oil Company, now known as ExxonMobil.
Magnaforming: Developed by Englehard Catalyst Company and Atlantic
Richfield Oil Company.
Ultraforming: Developed by Standard Oil of Indiana, now a part of the British
Petroleum Company.
Houdriforming: Developed by the Houdry Process Corporation.
CCR Platforming:A Platforming version, designed for continuous catalyst
regeneration, developed by UOP.
Octanizing:A catalytic reforming version developed by Axens, a subsidiary of
Institut francais du petrole (IFP), designed for continuous catalyst
regeneration.Chemistry
Before describing the reaction chemistry of the catalytic reforming process as
used in petroleum refineries, the typical naphthas used as catalytic reforming
feedstocks will be discussed.Typical naphtha feedstocks.A petroleum refinery
includes many unit operations and unit processes. The first unit operation in
a refinery is the continuous distillation of the petroleum crude oil being
refined. The overhead liquid distillate is called naphtha and will become a
major component of the refinery's gasoline (petrol) product after it is further
processed through a catalytic hydrodesulfurizer to remove sulfur-containing
hydrocarbons and a catalytic reformer to reform its hydrocarbon molecules
into more complex molecules with a higher octane rating value. The naphtha
is a mixture of very many different hydrocarbon compounds. It has an initial
boiling point of about 35 °C and a final boiling point of about 200 °C, and it
contains paraffin, naphthene (cyclic paraffins) and aromatic hydrocarbons
ranging from those containing 4 carbon atoms to those containing about 10
or 11 carbon atoms.

213
The naphtha from the crude oil distillation is often further distilled to produce
a "light" naphtha containing most (but not all) of the hydrocarbons with 6 or
less carbon atoms and a "heavy" naphtha containing most (but not all) of the
hydrocarbons with more than 6 carbon atoms. The heavy naphtha has an
initial boiling point of about 140 to 150 °C and a final boiling point of about
190 to 205 °C. The naphthas derived from the distillation of crude oils are
referred to as "straight-run" naphthas.

It is the straight-run heavy naphtha that is usually processed in a catalytic

reformer because the light naphtha has molecules with 6 or less carbon atoms
which, when reformed, tend to crack into butane and lower molecular weight
hydrocarbons which are not useful as high-octane gasoline blending
components. Also, the molecules with 6 carbon atoms tend to form aromatics
which is undesirable because governmental environmental regulations in a
number of countries limit the amount of aromatics (most particularly benzene)
that gasoline may contain.It should be noted that there are a great many
petroleum crude oil sources worldwide and each crude oil has its own unique
composition or "assay". Also, not all refineries process the same crude oils
and each refinery produces its own straight-run naphthas with their own
unique initial and final boiling points. In other words, naphtha is a generic
term rather than a specific term.The table just below lists some fairly typical
straight-run heavy naphtha feedstocks, available for catalytic reforming,
derived from various crude oils. It can be seen that they differ significantly in
their content of paraffins, naphthenes and aromatics:

Tab:5.1

Typical Heavy Naphtha Feedstocks [5-11]

Barrow Mutineer- Draugen

Crude oil name => CPC Blend
Island Exeter North
Location => Kazakhstan
Australia Australia Sea

Initial boiling
149 140 149 150
point, oC

Final boiling
204 190 204 180
point, oC

Paraffins, liquid
42 62 57 38
volume %

Naphthenes, liquid
42 32 27 45
volume %

214
 Aromatics, liquid
12 6 16 17
volume %

Purpose of Reformer

• The purpose of Reforming process is to produce high octane number

reformate reformate, which is a main component for motor,
fuel,aviation gasoline blending or aromatic rich feedstock.Hydrogen rich
gashydrogen gas Due to the nature of the reactions, reforming process
produces :LPG
• Reformer Feed of Either:
-Low Quality straight Run Naphtha.
-or cracked naphtha generally mixed with straight Run Naphtha.
• Reformer Feed Pretreatment:
Due to the Presence Contaminants in all cases and to specific
characterstics of cracked naphtha .Naphtha Pretreating Unit(s) ios are
always necessary.
• Refining Process & Catalysts
• Fluid Cracking Catalyst (FCC)
• FCC additives

Reforming Catalyst[1-13]

• Catalyst Characterization
• R & D & Commercialization Status in India
• Conclusion

Catalytic reforming

Chemical process to convert petroleum refinery naphthas, typically having low

octane ratings, into high-octane liquid products called reformates which are
components of high-octane gasoline (also known as petrol).Process re-
arranges or re-structures the hydrocarbon molecules in the naphtha
feedstocks Breakes some of the molecules into smaller molecules.

Overall effect

Product reformate contains hydrocarbons with more complex molecular

shapes having higher octane values than the hydrocarbons in the naphtha
feedstock.

By-products
215
The process separates hydrogen atomsfrom the hydrocarbon molecules and
produces very significant amounts of byproduct hydrogen gas for use in a
number of the other processes involved in a modern petroleum refinery.Other
byproducts are small amounts of methane,ethane.

CATALYTIC REFORMING[5-7,9-11]

• A major conversion process in petroleum refining and petrochemical

industries.
• Process converts straight run naphtha (C6-C10, Straight chain paraffins
and naphthenes) to gasoline components of high antiknock quality.
• Manufacture of Hydrogen and LPG as bye-products.
• The octane of reformate is provided mainly by aromatics having 6 to 10
carbon atoms and light iso paraffins.
• Alkanes and cycloalkanes are selectively converted to aromatic
hydrocarbons.
• Transforms low octane naphtha to high octane reformate.
• Reaction temperature 700-800 oK,pressure 70-450 psi
• Reaction is carried out in hydrogen atmosphere even though the
hydrogen is one of the product.
• Reforming is primarily endothermic.

Reforming Reactions[6-13]

Some refinery naphthas include olefinic hydrocarbons, such as naphthas

derived from the fluid catalytic cracking and coking processes used in many
refineries. Some refineries may also desulfurize and catalytically reform those
naphthas. However, for the most part, catalytic reforming is mainly used on
the straight-run heavy naphthas, such as those in the above table, derived
from the distillation of crude oils.There are a good many chemical reactions
that occur in the catalytic reforming process, all of which occur in the presence
of a catalyst and a high partial pressure of hydrogen. Depending upon the
type or version of catalytic reforming used as well as the desired reaction
severity, the reaction conditions range from temperatures of about 495 to
525oC and from pressures of about 5 to 45 atm.The commonly used catalytic
reforming catalysts contain noble metals such as platinum and/or rhenium,
which are very susceptible to poisoning by sulfur and nitrogen compounds
Therefore, the naphtha feedstock to a catalytic reformer is always pre-
processed in a hydrodesulfurization unit which removes both the sulfur and
the nitrogen compounds.

The four major catalytic reforming reactions are:[1-7,11-13]

216
1:The dehydrogenation of Naphthenes to convert them into aromatics as
exemplified in the conversion methylcyclohexane (a Naphthenes) to toluene
(an aromatic), as shown below:

2:The dehydrogenation of naphthenes to convert them into aromatics as

exemplified in the conversion methylcyclohexane (a naphthene) to toluene
(an aromatic), as shown below:

3:The dehydrogenation and aromatization of paraffins to aromatics

(commonly called dehydrocyclization) as exemplified in the conversion of
normal heptane to toluene, as shown below:

217
4:The hydrocracking of paraffins into smaller molecules as exemplified by the
cracking of normal heptane into isopentane and ethane, as shown below:[1-7,11-
13]

The hydrocracking of paraffins is the only one of the above four major
reforming reactions that consumes hydrogen. The isomerization of normal
paraffins does not consume or produce hydrogen. However, both the
dehydrogenation of naphthenes and the dehydrocyclization of paraffins
produce hydrogen. The overall net production of hydrogen in the catalytic
reforming of petroleum naphthas ranges from about 50 to 200 cubic meters
of hydrogen gas (at 0 oC and 1 atm) per cubic meter of liquid naphtha
feedstock. In the United States customary units, that is equivalent to 300 to
1200 cubic feet of hydrogen gas (at 60 oF and 1 atm) per barrel of liquid
naphtha feedstock. In many petroleum refineries, the net hydrogen produced
in catalytic reforming supplies a significant part of the hydrogen used
elsewhere in the refinery (for example, in hydrodesulfurization processes).
The hydrogen is also necessary in order to hydrogenolyze any polymers that
form on the catalyst.

Process description[9-13]

The most commonly used type of catalytic reforming unit has three reactors,
each with a fixed bed of catalyst, and all of the catalyst is regenerated in situ
during routine catalyst regeneration shutdowns which occur approximately

218
once each 6 to 24 months. Such a unit is referred to as a semi-regenerative
catalytic reformer (SRR).Some catalytic reforming units have an extra spare
or swing reactor and each reactor can be individually isolated so that any one
reactor can be undergoing in situ regeneration while the other reactors are in
operation. When that reactor is regenerated, it replaces another reactor
which, in turn, is isolated so that it can then be regenerated. Such units,
referred to as cyclic catalytic reformers, are not very common. Cyclic catalytic
reformers serve to extend the period between required shutdowns.

The latest and most modern type of catalytic reformers are called continuous
catalyst regeneration reformers (CCR). Such units are characterized by
continuous in-situ regeneration of part of the catalyst in a special regenerator,
and by continuous addition of the regenerated catalyst to the operating
reactors. As of 2006, two CCR versions available: UOP's CCR Platformer
process[13] and Axen's Octanizing process.[14] The installation and use of
CCR units is rapidly increasing. Many of the earliest catalytic reforming units
(in the 1950's and 1960's) were non-regenerative in that they did not perform
in situ catalyst regeneration. Instead, when needed, the aged catalyst was
replaced by fresh catalyst and the aged catalyst was shipped to catalyst
manufacturer's to be either regenerated or to recover the platinum content of
the aged catalyst. Very few, if any, catalytic reformers currently in operation
are non-regenerative.

219
 Fig:5.1 The process flow diagram below depicts a typical semi-
regenerative catalytic reforming unit

Schematic diagram of a typical semi-regenerative catalytic reformer unit in a

petroleum refinery The liquid feed (at the bottom left in the diagram) is
pumped up to the reaction pressure (5 to 45 atm) and is joined by a stream
of hydrogen-rich recycle gas. The resulting liquid-gas mixture is preheated by
flowing through a heat exchanger. The preheated feed mixture is then totally
vaporized and heated to the reaction temperature (495 to 520 °C) before the
vaporized reactants enter the first reactor. As the vaporized reactants flow
through the fixed bed of catalyst in the reactor, the major reaction is the
dehydrogenation of naphthenes to aromatics (as described earlier herein)
which is highly endothermic and results in a large temperature decrease
between the inlet and outlet of the reactor. To maintain the required reaction
temperature and the rate of reaction, the vaporized stream is reheated in the
second fired heater before it flows through the second reactor. The
temperature again decreases across the second reactor and the vaporized

220
stream must again be reheated in the third fired heater before it flows through
the third reactor. As the vaporized stream proceeds through the three
reactors, the reaction rates decrease and the reactors therefore become
larger. At the same time, the amount of reheat required between the reactors
becomes smaller. Usually, three reactors are all that is required to provide the
desired performance of the catalytic reforming unit.

Some installations use three separate fired heaters as shown in the schematic
diagram and some installations use a single fired heater with three separate
heating coils. The hot reaction products from the third reactor are partially
cooled by flowing through the heat exchanger where the feed to the first
reactor is preheated and then flow through a water-cooled heat exchanger
before flowing through the pressure controller (PC) into the gas separator.
Most of the hydrogen-rich gas from the gas separator vessel returns to the
suction of the recycle hydrogen gas compressor and the net production of
hydrogen-rich gas from the reforming reactions is exported for use in other
the other refinery processes that consume hydrogen (such as
hydrodesulfurization units and/or a hydrocracker unit). The liquid from the
gas separator vessel is routed into a fractionating column commonly called a
stabilizer. The overhead offgas product from the stabilizer contains the
byproduct methane, ethane, propane and butane gases produced by the
hydrocracking reactions as explained in the above discussion of the reaction
chemistry of a catalytic reformer, and it may also contain some small amount
of hydrogen. That offgas is routed to the refinery's central gas processing
plant for removal and recovery of propane and butane. The residual gas after
such processing becomes part of the refinery's fuel gas system. The bottoms
product from the stabilizer is the high-octane liquid reformate that will become
a component of the refinery's product gasoline.

REACTOR DESIGN[1-2,11-13]

Fixed-bed reactors used for semiregenerative and cyclic catalytic reforming

vary in size and mechanical details, but all have basic features as shown in
Figure. Very similar reactors are used for hydrotreating, isomerization, and
hydrocracking.The reactors have an internal refractory lining which is
provided to insulate the shell from the high reaction temperatures and thus
reduce the required metal thickness. Metal parts exposed to the high
temperature hydrogen atmosphere are constructed from steel containing at
least 5% chromium and 0.5% molybdenum to resist hydrogen embrittlement.
Proper distribution of the inlet vapor is necessary to make maximum use of
the available catalyst volume. Some reactor designs provide for radial vapor
flow rather than the simpler straight-through type.

221
 Fig:5.2 Typical fixed-bed downflow catalytic reformer

The important feature of vapor distribution is to provide maximum contact

time with minimum pressure drop. Temperature measurement at a minimum
of three elevations in the catalyst bed is considered essential to determine
catalyst activity and as an aid in coke burn-off operations.

CATALYTIC REFORMERS IN INDIA[1-2,11-15]

• 14 plants having capacity of 4.5 MMTPA are operating.

• Four SR and three CCR plants have been licensed jointly by IIP-IFP in
India
• IIP-IPCL state of art bimetallic Pt-Re catalyst in two reformers.

OCTANE NO. OF GASOLINE

What is Octane Number?

• An empirical number measuring anti-knocking capacity .
• RON (research): Represents low speed driving.
• MON (motor): Repressents high speed driving.
• Average = (MON+RON)/2

222
 OCTANE NO Vs CARBON NO

Fig:5.3 Octane NO Versus Carbon No for important Hydro carbon

group in Reforming

Reforming Catalyst

• First recognized dual function catalyst.

• Cracking/hydrogenation/dehydrogenetaion.
• Isomerization.
• Sulfur tolerant.
• Low coke generation.

CATALYST COMPOSITIONS[1-2,11-18]

• Pt/Alumina (Chlorinated Gamma alumina).

• Pt-Re/Alumina (Decreased coke formation than Pt/Alumina).
• Pt-Ir/Alumina
• Hydrogenation and dehydrogenation activities are associated with
metal component.
• Activity for acid catalysis resides on the carrier surface.
• Performance depends on Pt crystallite size and promoter metals.

223
Catalyst Mechanism[19-21]

Most catalytic reforming catalysts contain platinum or rhenium on a silica or

silica-alumina support base, and some contain both platinum and rhenium.
Fresh catalyst is chlorided (chlorinated) prior to use. The noble metals
(platinum and rhenium) are considered to be catalytic sites for the
dehydrogenation reactions and the chlorinated alumina provides the acid sites
needed for isomerization, cyclization and hydrocracking reactions. The activity
(i.e., effectiveness) of the catalyst in a semi-regenerative catalytic reformer
is reduced over time during operation by carbonaceous coke deposition and
chloride loss. The activity of the catalyst can be periodically regenerated or
restored by in situ high temperature oxidation of the coke followed by
chlorination. As stated earlier herein, semi-regenerative catalytic reformers
are regenerated about once per 6 to 24 months.Normally, the catalyst can be
regenerated perhaps 3 or 4 times before it must be returned to the
manufacturer for reclamation of the valuable platinum and/or rhenium
content.
• Platinum or rhenium on a silicaor silica-alumina support base.
• Some contain both platinum and rhenium.
• Fresh catalyst is chlorided(chlorinated) prior to use.
• The noble metals are considered to be catalytic sites for the
dehydrogenation reactions and the chlorinated alumina provides the
acid sites needed for isomerization, cyclization and hydrocracking
reactions.
• The LIFE of the catalyst is reduced over time during operation by
carbonaceous coke deposition and chloride loss.
• Catalyst can be periodically regenerated or restored by in situ high
temperature oxidation of the coke followed by chlorination.
• Normally, the catalyst can be regenerated perhaps 3 or 4 times before
it must be returned to the manufacturer for reclamation of the valuable
platinum and/or rhenium content.

Catalyst Manufacture[1-2,19-21]

• Acidic Support(Alumina from Aluminium chloride).

• Spray drying of aluminum hydroxide solution to produce alumina .
• Removal of excess chloride by slurrying.
• Spray dried or extrudates formed.
• Impregnation of metals, e.g PtCl3.
• drying.

224
 • Refining Process & Catalysts.
• Fluid Cracking Catalyst (FCC).
• FCC additives.
• Reforming Catalyst.

Catalyst Characterization:

• R & D & Commercialization Status in India

• Conclusion.

Octane Rating

• The octane rating is a measure of the autoignition resistance of gasoline

and other fuels used in spark-ignition internal combustion engines. It is
a measure of anti-detonation of a gasoline or fuel.
• Octane number is the number which gives the percentage, by volume,
of iso-octane in a mixture of iso-octane and normal heptane, that would
have the same anti-knocking capacity as the fuel which is under
consideration. For example, gasoline with the same knocking
characteristics as a mixture of 90% iso-octane and 10% heptane would
have an octane rating of 90.

Research Octane Number (RON)

RON is determined by running the fuel in a test engine with a variable

compression ratio under controlled conditions, and comparing these results
with those for mixtures of iso-octane and naphthenes.

Motor Octane Number (MON)

MON testing uses a similar test engine to that used in RON testing, but with
a preheated fuel mixture, a higher engine speed, and variable ignition timing
to further stress the fuel's knock resistance. Depending on the composition of
the fuel, the MON of a modern gasoline will be about 8 to 10 points lower than
the RON.

Tab:5.2

CATALYTIC REFORMERS IN INDIA

225
 CAPACITY TYPE OF CATALYST
S.NO REFINERY DUTY
MMTPA PROCESS BY

1 BPCL 0.33 SR Benzene Procatalyse

2 BRPL 0.11 SR Xylenes Procatalyse

3 CPCL 0.09 SR Octane IPCL-IIP

IOCL,
4 0.3 SR Octane Procatalyse
Barauni

IOCL,
5 0.09 SR Octane Procatalyse
Digboi

IOCL,
6 0.196 SR Octane Procatalyse
Haldia

IOCL
7 0.5 CCR Octane Procatalyse
Mathura

IOCL,
8 0.5 CCR Octane Procatalyse
Panipat

IOCL, Aroma-
9 0.33 SR Procatalyse
Vadodara tics

IPCL,
10 0.11 SR Xylenes IPCL-II
Vadodara

11 KRL 0.248 SR Benzen Criterion

12 MRPL 0.3 CCR Octane UOP

RIL,
13 0.233 CCR Xylenes UOP
Patalganga

RPL,
14 - CCR Octane UOP
Jamnagar

Reformer feed, Reforming reactor design, Continuous

and semi regenerative process.

FEED[1-2]

226
 • Reformer feed, Reforming reactor design, Continuous and semi
regenerative process.
• Naphtha from thermal & catalytic crackers can also be used.

Tab:5.3

Characteristic of Typical Reformer

Feeds
PARAMETERS PARAFFINIC NAPHTHENIC

RONC 50 66

66.8
P/N/A(%vol) 29.3/61.85/8.85
/21.8/11.4

ASTM
- -
Distillation

IBP 92 88

30 115 115

50 123 123

70 133 132

90 147 145

95 152 150

- 155 161

Chemical Reactions

• Two types of reaction involved in the octanizing process:

• Desirable Reaction which lead to higer octane number and to higher
purity hydrogen production.They are the reaction to promote.
• Adverse Reaction which lead to decrease of octane no and a decrease
in hydrogen purity.They are the reaction to minimize.

RON:Research Octane Number

MON:Motor Octane Number

227
 Tab:5.4 [1-2,19-21]

RON MON

Cyclohexane 83 77.2

MethlyCyclohexane 74.8 71.1

1.3 Dimethlycyclohexane 71.7 71

Benzene 114.8 100

Toluene 120 103.5

m-Xylene 117.5 115

Desirable reactions with H2 production[1-5,12,17-21]

• Naphthenes dehydrogenetion
• Naphthenic compound dehydrogeneted into aromatic with
production of 3 moles of H2 per mole of napthene.
• Promoted by the metallic function.
• Highly Endothermic.
• Thermodynamically favored by high temperature,low pressure
and high number of carbons.
• Kinetically favored by high temperature ,high no. of carbons;not
affected by hydrogens partial pressure.
• At the selecting operating conditions,reaction is very fast and
almost total.

Desirable reactions

228
• Paraffin's Dehydrocyclization
• Multiple step reaction.
• Promoted by both acidic and metallic function.
• Kinetically favored by high temperature and low temperature.
• Dehydrogenation step become easier as paraffin molecular weight
increases but is competed by Hydro cracking.
• At the selected operating condition much lower rate than that of
Dehydrogenetionm.

• Linear Paraffin Isomerization

• Promoted by acidic function.
• Slightly Exothermic.
• Fast.
• Thermodynamically dependant on temperature:pressure has no
effect.
• Kinetically favored by high temperature:not effected by the
hydrogen partial pressure.

• Naphthenes Isomerization
• Desirable reaction because the subsequent dehydrogenation of
the alkylcyclohexane into an aromatic.

229
 • Difficulty of ring rearrangement and high risk of ring opening
(paraffin formation).
• At the selected operating condition.theoretically low rate but
subsequent dehydrogenation shift the reaction towards the
desired direction.
• Slightly endothermic.
• Easier reaction for higher carbon number.

Naphthenes isomerisation

Tab:5.5

RON MON

Ethylcyclopetane 67.2 61.2

MethlyCyclohexane 74.8 71.1

Toluene 120 103.5

Adverse reactions[1-2,15-22]

• Hydrocraking
• Hydrocracking effect either paraffin and olefins.
• Promoted by both acidic and metallic functions.
• Favored by high temperature and high pressure.
• Exothermic risk of runaway reaction.
• At the selected operating condition,hydro cracking reaction could
be complete but is limited by kinetics.

230
Adverse reaction

• Consequences of Cracking
• Decreases of paraffins and increases of aromatics proportion(i.e
increases in octane)in the reformate and a loss of reformate yield.
• Decreases in hydrogen production(cracking reaction consuming
hydrogen).
• Increase of light end production and low molecular weight
paraffins.
• Hydrogenolysis
• Promoted by metallic function.
• Favored by high temperature and high pressure.
• Exothermic(risk of runaway reaction).

• Hydrodealkylation

231
 • Breakage of the branched radicial of an aromatic ring.
• Promoted by metallic function.
• Favored by high temperature and low temperature.
• Consumes hydrogen and produces methane.
• But at selected operating condition and with the selected
catalyst,this reaction is not significant.

• Alkylation
• Additioh of an olifen molecule on an aromatic ring.
• Promoted by metallic function.
• Lead to heavier molecules which may increase the end point of
the product.
• High tendency to form coke must be avoided.

• TransAlkylation(alkyl disproportionation)
• Dismutation of 2 toulence ring to produce benzene and xylene.
• Promoted by metallic function.
• Favored by very serve condition of pressure and temperature.
• At the selected operated conditions,and with the selected catalyst
this reaction is negligible.

232
 • Coking
• Result from complex group of reaction.Deatailed machanism not
fully known yet.
• Linked to heavy unsaturated products(polynuclear aromatics) and
heavy olifins traces or diolefins present in the feed or in CCR
reaction.
• Coke deposit reduces active contact area and reduces catalyst
activity.
• Favoured by low pressure:In octanizing operating conditions
necessity of a continous regeneration to maintain a low level of
coke.

Chemical Reaction[1-2,24-26]

All these reaction occur in series and parallel to each other producing a
complicated reaction scheme.In an effort to simplify the scheme according to
the reaction rates the main reaction take place in the following order:

Tab:5.6

1 1st Reactor Dehydrogenetion/Isomerization

2nd and 3rd Dehydrogenetion/Isomerization/Cracking

2
Reactor and Dehydrocyclization.

3 4th Reactor Cracking/Dehydrocyclization.

• The catalyst distribution is:

• R1= 10%
• R2= 15%

233
 • R3= 25%
• R4= 50%

Tab:5.7

Heat of Relative
Reactions
Reaction(1)KCAL/MOLE Rate(2)Approx

Naphthenes
-50 30
dehydrogenetion

Paraffin
-60 1 base
dehydrocyclization

Isomerization:paraffins +2
3
Naphthenes +4

Cracking +10 0.5

Heat of reaction <0 = endothermic reaction
For pressure below 15kg/cm2

Conventional unit [1-2,15-25]

234
Fig 5.4 Conventional unit

Fig 5.5

235
Continuous catalytic regenerative reforming

Fig 5.6 Continuous catalytic regenerative reforming

Continuous catalytic regenerative reforming

Fig 5.7 Continuous catalytic regenerative reforming

236
 Objective of regenerative unit

Recover initial catalyst activity

• Coke Removal -2 Burning Zones

• Metal Redistribution & chloride adjustment -Oxychlorination
• Catalyst drying -calcination

Fig 5.8 A typical FCC flow sheet to regenerate catalyst from spent
catalyst (Regeneration process)

Catalyst regenerator

237
 Fig 5.9 Catalyst regenerator

Process variables[1-2,22-29]

• Pressure
• Temperature
• Space velocity
• Hydrozen partial pressure(H2/HC)
• Quality of the feed
• Operating parameters summary.

Process variables

• Each of them can be fixed by operator within the operating range of the
equipment independently from the others.
• For one set of independent variable for same feed characterstics there
is only one performance of the unit i.e one set of value for:
• Product yields
• Product quality(octane)
• Catalyst stability(coke make)
• Pressure is the basic variable because of its inherent effect on reaction
rates.
• Effect of pressure on reactions
238
 • Low pressure enhance hydrogen production by these
reactions:dehydrogenations dehydrocyclisation coking.
• Cracking rate reduces.
• The lower the pressure the higher the yields of reformate and
hydrogen for a given octane number.But it developer high coking
rate(compensated by continous regeneration).
• Average catalyst pressure used is close to last reactor inlet pressure.
• During transient condition(startup,shutdown,upset)it is recommended
to increase the pressure to lower coke formation.
• Limit of operation action.
• Pressure rise limited by equipments design pressure.
• Pressure lowering limited by recycle compressor design for power
and intake volume.

Effect of temperature

• Most important and used operating parameter is space velocity.

• Catalyst activity is directly related to reactor temperature.By simply
raising or lowering reactor inlet temperature operator can raise or lower
product quality and yield.
• It is commonly accepted to consider the weight average inlet
temperature(WAIT).

where Ti 1,Ti 2 .......are inlet tempreature of reactor

(wt catalyst of R1)....... are weight of catalyst in reactor

• An increase of temperature (i.e WAIT) has the following effect.

• Increase octane.
• Decrease of yield (of C5+Fraction).
• Decrease of H2 purity.
• Increase of coke deposit.
• A slight increase of temperature(WAIT) through the life of the catalyst
make up for this activity loss.
• Larger and temporary changes in temperature required.

239
 • To change octane-at contant feed quality and quantity.
• To change feed quantity and still maintain octane
• To change feed quality and still maintain octane

Space velocity

• Linked to resident time of feed in the reactor and effect the kinetics of
the reforming reaction.

• Operator must careful in mind that each time liquid feed rate is changed
a temperature correction must be applied if octane is to be maintained.
• Important Recommendation
• Always decrease reactor inlet temperature first and decrease feed
flow rate afterward.
• Always increase feed flow rate first and increase reactor inlet
temperature afterward.

Effect of Hydrogen to Hydrocarbon Ratio

where R is the recycle flow in Kg l h (or lb l h)

M is the recycle gas molecular weight
F is the feed rate in kg l h(or lb l h)
m is the feed molecular weight

240
Y vol fraction of H2in the recycle gas

• The recycle gas MW is obtained by chromatographic analysis as well as

the H2 vol fraction(Y)
• The feed MW is obtained by chromatographic analysis or by correlation
from its distillation range and specific gravity.
• Operator can change H2/Hc ratio by lowering or increassing the recycle
compressor flow.
• For a given unit the amount of recycle is limited by the recycle
compressor characterstics(power suction flow).
• The H2/Hc ratio has no obvious impact on the product quality or yield.
• But a high H2/Hc ratio reduces the coke build up.
• It is stirctly recommended to operate with a H2/Hc ratio equal to (or
higher than) design figure.

Effect of feed quality chemical composition

• Characterization of the Feedstocks:0.85 N + A

• With a higher 0.85 N + A .
• The same octane content will be obtained at a lower
severity(temperature)and the product yield will be higher.
• Or the same severity temperature the octane content will be
higher.
• The endothermic reaction heat increases and the feed flow rate
will be limited by the heater design duty.
• With a higher 0.85 N + A .
• Higher paraffin and napthanic content obtained.The hydrogen
purity of the recycle gas decrease and operation will be limited by
the recycle compressor capacity.
• Impurities
• Temporary or permanent reduction of catalyst activity by poisons
contained in the feed.

Feed quality

• The feed distillation range is generally as follows:

• IBP (Initial Boling Point) 70-100oc
• EP(End Boiling Point)150-180oc
• Light fraction:
Cyclization of c6 more difficult than that of C7-C8.The lighter the feed,the
higher the required severity for a given octane.

241
 • Heavy Fraction:
High naphthenic and aromatic content.Lower severity to obtain good
yield.But polycyclic compounds which favor coke deposit.
EP higher than 180oc are generally not recommended.

Operating parameters summary

• Here after the theoretical effect on the unit performance of each

independent processes variable taken separately:

catalyst[21-30]

• Reforming of catalyst are bimetallic catalyst consisting of platinum plus

promoters on alumina support, rhenium being essentially used.
• The main features of these catalyst are:
• High purity alumina support-High mechanical resistance.
• Platinum associated with Rhenium high stability and selectivity.
• High regenerability.
• The combination of these qualities give the following advantage:
• High Reformate Yield.
• High Hydrogen yield.
• High on stream Factor.
• Low Catalyst Inventory.

242
The main characterstics of catalyst other than it physical and
mechanical properties are:[1-2,25-32]

• The Activity
• Catalyst increase the rate of desired reaction.
• Is measured in term of temperature
• The Selectivity
• Catalyst ability to favor desirable reaction.
• Practicle measured by the C5 + Reformate and hydrogen yield.
• The Stability
• Change of catalyst performance(activity,selectivity) with time.
• Caused chiefly by coke deposit and traces of metal in feed.
• Measured by the amount of feed treated per unit weight of
catalyst.C5 + Wt reformate yield is also an indirect measure of the
stability.

• Platinum (pt) plus other promoter(s) impreganted on to gamma alumina

containing around 1% wt chloride provide to acidity.
• Since 1967 bimetallic catalysts have been widely used.
• The second metal come from the group of metal like:
• Rehinium(Re)
• Tin(sn)
• Iridium(Ir)
• Germanium(Ge)

Selection of metal

• Depend on what you want from the catalyst:The Objectives

• Stability and Cycle life
• Selectivity towards
• Hydrogen H2
• Liquid Reformate(C5 + Reformate)
• Benzene yield in C5 + Reformate
• Normal causes foa catalyst ageing/deactivation
• Mental sintering
▪ Temperature
▪ Metallic Phase
▪ Presence of Chloride
• Deposition of coke on metal and acid sites.Coking effect can be
split.
▪ Degree of poisoning of deposited coke.
▪ Relative coking rate

243
 • The relative rate of coking is proportional to the hydrogenation function
of the catalyst this is dependant on the metallic phase.

Fig 5.10

selectivity[1-4,12-22]

• Desired yields are:

• Hydrogen
• C5 + Reformate
• Low benzene
• Benzene
• Yield can be minimised by pre-factionnating the precursors
(MCP,CH,nC6P)which are present in the fraction boiling between
70 to 85oC.
• Benzene is also produced by the hydro alkylation of alkyl
benzenes.
• Loss of desired yield is caused by cracking
• Hydrocracking involving the metal plus acid sites.
• Hydrogenolysis involving the metal in the presence of hydrogen.

Catalytic Reforming

244
Types of Catalytic Reformers[1-4,25-34]

• Steam reforming Catalyst regenerated in-situ during shut-downs(6-24

months)
• CCR
• Continuous Catalyst Regeneration.
• In-situ regeneration of part catalyst in a special regenerator.
• Continous addition of regenerated catalyst.

245
Fig 5.11 A typical FCC flow sheet integrated with CDU, HDSD, VRDS,
FCC to generate different hydrocarbons from crude oil

Tab 5.8

RON & MON OF VARIOUS

MOTOR FUEL STOCKS
Stock RON MON

Butane 95 92

Iso-pentane 92 89

Medium pressure
94 85
reformate

Low pressure reformate 99 88

Heavy reformate 113 102

FCC gasoline 91 80

246
 Alkylate 95 92

Isomerate 85 82

MTBE 115 99

Important Properties of FCC catalysts

• Surface Area /Pore Size Distribution

• Zeolite Area
• Matrix Area
• Pore Volume
• Crystallinity
• Unit Cell Size
• Silicon-Alumina ratio
• Particle Size Distribution and Average particle Size
• Attrition Resistance
• Thermal properties/ Hydrothermal properties
• Metal Content
• Density
• Carbon and Sulphur Content
• Acidity

Surface Area / Zeolite to Matrix ratio, Pore size distribution

• Scope
• Measurement of SA, Z/M ratio and Pore size distribution of
fresh/equilibrium FCC catalysts/additives, zeolite, clay, alumina,
etc.
• Principle
• Nitrogen at various pressures are adsorbed at liquid nitrogen
temperature on the samples and isotherms are generated.With
the help of BET, BJH, T-Plot etc., the above mentioned properties
are measured.
• Instruments
• Flowsorb-2300, ASAP2010 of M/s Micromeritics,USA.
• Typical range of SA for FCC catalysts 80-300 m2/g.

Implications of SA

• Surface Area (Fresh=175-300, E-cat: 80-150).

247
 • Indirect measurement of activity and stability of the catalysts.
• Z/M ratio gives information about SA of zeolites (small pores of
<20 Ao)and SA of matrix,(large pores>20 Ao).
• Matrix area does not tell whether the matrix is active or non-active.
• Loss of SA due to
• Hydrothermal deactivation (zeolite destruction).
• Thermal deactivation (high regn. Temp.).
• Increased metal deposition on catalyst.
• Reduced Fresh catalyst addition rate.
• SA of 10 units can decrease the MAT activity by about 2-5 units.

Pore Volume by Water Titration

▪ Scope: Measurement of Pore volume of Fresh and equilibrium catalysts.

▪ Principle: Catalyst is titrated by water until the fluidity of the sample
is destroyed. Pore volume is calculated as volume of water titrated over
weight of catalyst.
▪ Procedure: Sample calcined to remove carbon and moisture.Titrated
with distilled water or DM water.
▪ Typical range: 0.15-0.45 cc/g Simple method, PV measurement can
be done at Refinery

Pore Volume[19-21]

• Indications/Directions: Generally, higher pore volume in fresh

catalyst means higher levels of active matrix components.
• Decrease in pore volume in e-cat means
• Thermal deactivation.
• Hydrothermal deactivation of catalyst has little effect on pore
volume.
• Changes in Unit operation .
• May indicate damage in the regenerator air grid/ catalyst
distributor.

X-RAY Diffraction (XRD) Analysiss[19-21,33-36]

• Scope
• To identify and quantify crystalline phase, to detect impurities, to
measure crystallite size, UCS and Silica-alumina ratio.
• Principle

248
 • X-ray patterns of test and standard samples are compared.
Integrated intensities of the peaks provide quantitative data.
• Instruments
• Rigaku, Japan XRD equipment.
• Typical Range
• Zeolite in FCC catalyst from 5-40%; Fresh catalyst: 15-40% E
cat: 5 - 15 %.

UCS of Y Zeolite[19-21,33-36]

• It is a measure of aluminium sites or the total potential acidity per

cell.UCS is a indicator of zeolite acidity. As the UCS decreases, acid sites
become further apart since Al4+ion is bigger than Si4+ion.
• SiO2/Al2O3 mol ratio =2, UCS=25 Ao;
SiO2/Al2O3 mol ratio =15, UCS=24.4 Ao
• Lower UCS means fewer active sites per unit cell.The fewer acid sites
are further apart and therefore inhibit hydrogen transfer
reactions,which in turn increases gasoline octane as well as production
of C3 and lighter components.

PSD by Micromesh[19-21,33-36]

• Scope
• Determination of Particle size and average particle size of FCC
catalysts in the range of 20-150 microns.
• Principle
• Dry sieving procedure for determination of particle size in FCC
catalysts by means of calibrated sieves of uniform and precise
square opening.
• Procedure
• Sample placed on top sieve, set shaken for specified time. Each
sieve is weighed.
• Instrument
• Robot shifter RPS 75,Japan.

• Typical Range

• APS= 80 microns

Significance of PSD

249
 ▪ PSD is an indicator of fluidisation properties of catalyst. 0-40 micron
particles (5-20 wt%) improves the fluidisation.
▪ PSD is a function of cyclone performance, catalyst properties, catalyst
make-up rate and unit operating conditions.
▪ Case-1: A decrease in the percentage of smaller particles (fines)
possibly due to (a) deteriorating cyclone performance. (b)Reduced
Catalyst attrition (c) Lower fines in the fresh catalyst.
▪ Case-2: An increase in fines may indicate increased catalyst attrition
possibly due to (a) changes in the fresh catalyst
composition, (b) increased fines in the fresh catalyst (c) internal
damage such as air distributor or slide valve.

Attrition Resistance[19-21,33-36]

• Scope
• To measure ability of the catalyst to maintain integrity in the FCC
system.
• Principle
• Calcined catalyst microspheres are subjected to high velocity air
jet.Catalyst fines are removed from the attrition zones and
weighed.Attrited catalyst is expressed as weight percentage and
termed as Attrition Index (AI).Higher the index lower is the
attrition resistance.
• Instrument
• In house fabricated.
• Typical Range
• AI of FCC catalyst 5-15%.
• Increased attrition possibly due to
• Problem in the regenerator air grid.
• Large amounts steam to the regenerator/regenerated catalyst
line.
• Excessive velocities (>300 FPS) in the feed nozzle can also cause
attrition.
• Problem in the catalyst.

Apparent Bulk Density

• Scope
• Apparent Bulk density (ABD) of fresh, equilibrium FCC catalyst
having size less than 150 microns.
• Principle

250
 • Calcined catalyst sieved and taken into cylinder kept under given
vibration to increase the packing efficiency, mass/unit volume is
calculated to get ABD.
• Instruments
• Bulk density meter, Model 1H 2000, Seishin, Japan.
• Typical Range
• 0.7 -0.9 g /CC.

Significance of ABD[19-21,33-36]

• ABD is a also function of catalyst composition, manufacturing process

and other physical properties such PV and PSD. Generally does not
change unless the catalyst type changes.
• Normally ABD of E-cat is higher than the fresh catalyst due to thermal
& hydrothermal changes in the pore structure that occur in the unit and
also due to catalyst loss.
• If we compare one catalyst with other, slightly higher ABD catalyst can
increase the pressure drop across the slide value and improve the
catalyst circulation.
• High ABD (>1.0) can restrict fluidisation.
• Low ABD (<0.6) indicates A) Change in Catalyst B) Fines loss.

Hydrothermal treatment of FCC Catalyst and additives[1-3,19-21,33-36]

• Scope
• Fresh catalysts can be hydrothermally deactivated to simulate
equilibrium catalysts.
• Principle
• Hydrothermal deactivation of fresh FCC catalysts is done at 788 oC
for 3 hours at 100% steam whereas 750 oC for ZSM-5 additive.
• Instruments
• Xytel and In house fabricated.

Significance of Metal Analysis

▪ Alumina (Al2O3) content and Rare earth content is determined by

catalyst formulations.Changes in Alumina/ Rare earth content can be
used to track catalyst change out.Unexpected change indicate a change
in catalyst formulations.

251
 ▪ The alumina content (25-55%)indicate the in-active alumina and active
alumina i.e. Alumina from clay, binder and zeolite.CO Promoter additive
and SOx additives.
▪ The Sodium (Na) in the E-Cat is the sum of sodium added from the feed
and sodium in the fresh catalyst. Severe problem if the Na >>0.5%;
Lower in unit conversion &loss in Octane Number. A Increase in Na level
of 0.1 unit can decrease MAT conversion by 3 units.
▪ Ni, V, Fe & Cu has the gas making tendencies of the catalyst, when
deposited on FCC catalysts.These metals originate from the FCC feed.

Carbon on FCC Catalyst[14-21,33-36]

• Scope
• To measure percent Carbon content of regenerated or spend
catalyst.
• Principle
• Carbon is determined by combustion in a stream of dry oxygen
and measuring carbon dioxide by IR analyser.
• Instruments
• Lebold Heraus,Germany;Analysis time: >1 minute Carbon range
from 0.001-6 wt%.
▪ Carbon level on the E-cat is the indicator of the regenerator
effectiveness.
▪ Carbon on the catalyst:
For complete combustion mode: 0.05% wt.
For partial combustion mode: 0.1 or higher.

Contents

• Refining Process and Catalysts.

• Fluid Cracking Catalyst (FCC).
• FCC additives.
• Reforming Catalyst.
• Catalyst Characterization.
• R & D & Commercialization Status in India.
• Conclusion.

Catalyst Changeover

▪ FCC Daily charge for replenishment, reactor- regenerator cycle.

▪ Hydrocracking- total charge, regeneration every 2-3 yrs.

252
 ▪ Reforming- total charge, regeneration every 3 or more yrs.

Wide Range of Catalysts[14-21,33-36]

▪ All units do not use same catalyst.

▪ Requirement of each unit are different in terms of catalyst requirement
for different setup reaction scheme.
▪ Custom catalyst- need of the day.

Catalyst & Additive Sourcing – Needs Consideration[11-21,33-36]

▪ India is totally dependant of overseas supply.

▪ R & D have acquired many patents for catalys and additive formulations
as well as manufacturing process.
▪ Since Large amount of catalyst is required for a plant trial, decent size
manufacturing facility is to be created at first.
▪ Most of the refining catalysts are imported.
▪ Catalyst consumption is increasing.
▪ No major manufacturing facilities in the country.
▪ Research and development confined to isolated pockets.
▪ Urgent need to bridge gaps in scale-up and commercial activities.

Catalyst & Additive Sourcing – Needs Consideration

• Excellent Knowledge base.

• Laboratory stage developments.
• Large gap between laboratory to plant.

Tab 5.9

Olefin yield comparison off Indmax

with FCC & DCC
Process FCC DCC INDMAX

Yield,Wt%

Ethylene - 5.1 3.1

253
 Propylene 3.6 17.4 23.2

Isobutylene 1.2 4.8 10.0

Total butylene -- 11.0 18.9

Gaps to be bridged for catalyst breakthrough

• Rigorous evaluation under simulated conditions in association with user.

• Manufacturing Facility-to solve problems of
• catalyst manufacture.
• scale-up.
• Willingness to take risk by refineries.

Hydroprocessing : Hydrocracking & Hydrotreating

Purpose

• Hydrotreating[1,2]
• Remove hetero atoms and saturate carbon-carbon bonds
• Sulfur, nitrogen, oxygen, and metals removed
• Olefinic and aromatic bonds saturated
• Reduce average molecular weight & produce higher yields of fuel
products
• Minimal cracking
• Minimal conversion – 10% to 20% typical
• Products suitable for further processing or final blending
• Reforming, catalytic cracking, hydrocracking
• Hydrocracking
• Severe form of hydroprocessing
• Break carbon-carbon bonds
• Drastic reduction of molecular weight
• 50%+ conversion
• Products more appropriate for diesel than gasoline

Hydroprocessing Trends[1-6]

• Hydrogen is ubiquitous in refinery and expected to increase

• Produces higher yields and upgrade the quality of fuels
• The typical refinery runs at a hydrogen deficit

254
 • As hydroprocessing becomes more prevalent, this deficit will
increase
• As hydroprocessing progresses in severity, the hydrogen demands
increase dramatically
• Driven by several factors
• Heavier and higher sulfur crudes
• Reduction in demand for heavy fuel oil
• Increased use of hydrodesulfurization for low sulfur fuels
• More complete protection of FCCU catalysts
• Demand for high quality coke
• Increased production of diesel

Sources of Hydrogen[2-4,6-15]

Catalytic Reforming from steam reforming of NG and Naptha reforming

methods and also from the catalytic reformer one at Al2O3.
Cryogenic Pressure swing adsorption Membrane separation.
• Steam-Methane Reforming
• Most common method of manufacturing hydrogen
• 90 to 95 vol% typical purity
• Synthesis Gas
• Gasification of heavy feed
• Hydrogen recovery – pressure swing adsorption or membrane
separation
• More expensive than steam reforming but can use low quality by
product
• Steam-Methane
• Reforming. Endotherm catalytic reaction 1400-1500 °C.

• Steam-Methane
• Shift conversion. Exothermic fixed-bed catalytic reaction 650°C.

255
 • Gas Purification:Absorption of CO2 in amine or hot K2CO3 solution.
• Methanation. Trace amounts of carbon monoxide & carbondioxide
removed. Exothermic fixed-bed catalytic reactions,700-800 °C.

Hydrogen (H2) is identified to be an ideal energy carrier with high efficiency,

since it possesses LHV of 121 MJ/kg compared to any other known fuels and
burns cleanly, without generating any environmental pollutants. H2 production
is an attractive subject of current interest for fuel cell applications which are
considered to have the potential to provide a clean energy source for
automobile as an alternative to gasoline or diesel engines. H2 is also one of
most important chemicals and is widely used for ammonia production, oil
refineries, and methanol production etc. In view of growing environmental
concerns, such as global warming and the depletion of fossil fuel, major efforts
are being dedicated to develop the utilization of renewable energy sources.
Bio oil produced from biomass has been proposed as an alternative to produce
hydrogen; because this renewable rich energy resource does not contribute
to a net increase in atmospheric CO2. Bio-oil is a dark brown organic liquid.
Bio-oil exhibits a complex composition with more than 200 different
compounds including acids, alcohols, aldehydes, ketones as well as lignin
derived oligomers, which are emulsified with water hence difficult to reform.
In general, the steam reforming of bio-oil is simplified in terms of the
oxygenated organic compounds (CnHmOk) by the following reactions:

The above reaction is followed by the water–gas shift reaction:

The overall process can be represented as followes:

Steam reforming of the main component in bio-oil such as acetic acid (12-14
by wt %) can offer the information for active catalyst preparation and the

256
knowledge about the potential catalytic behaviour of bio-oil in steam
reforming.

Reaction involved in steam reforming of acetic acid

Reforming of acetic acid for H2 production can be summarized as followes:

First, Steam reforming of acetic acid reaction has discussed as stated below:-

Followed by water gas shift reaction

The overall steam reforming reaction of acetic acid is

The maximum stoichiometric yield of H2 for acetic acid reforming is 2 mole to

mole of carbon. However some undesired reactions take place inside the
reactor. Hence there is large possibilities of decomposition of acetic acid to
lower molecular weight oxygenates, lighter hydrocarbons (CH4, C2H4) and
coke.

Some amount of coke can also be formed via Boudouard reaction.

The desired gaseous product i.e. hydrogen is lost through methanation

reaction and reverse water gas shift reaction.

257
Small amount of acetone may be formed by ketonization reaction of acetic
acid.

The terms % H2 yield, % acetic acid (acetic acid) conversion and % selectivity
of gaseous product distribution were used to describe the catalytic results in
reforming of the oxygenate. The definitions are given below.

Where RR is H2/CO2 reforming ratio and RR=4/2.

258
 Fig:6.1 Transportation Fuel Evolution [1-2,12-16]

TRANSPORTATION FUELS

• Exhaust from automobiles major pollutant

• Strict emission norms all over the world
• Corresponding changes in fuel quality specifications
• Indian fuel quality standards following Euro norms

Table:6.1 [1-6]

WORLD CRUDE OIL QUALITY °C

Proprties of
1985 1990 1995 1999 2010
Crude Oil

S in crude
1.14 1.12 1.31 1.41 1.51
oil(wt%)

API Gravity Of
32.7 32.6 32.4 32.2 31.8
Crude Oil

259
 Residue in
Crude 19 19.4 19.8 20.2 21.3
Oil(vol%)

Metals in crude
275 286 297 309 320
oil Residue

S in crude
3.07 3.26 3.61 3.91 4.0
oil(wt%)

Table:6.2 Key Specifications of MS [1-6]

Euro-III Equ Euro-IV Equ

ification BIS 2000 BS-II
Regular Premium Regular Prem
ppmw(max) 1000 500 150 150 50 5
ON,Min 88 88 91 95 91 9
ON,Min No spec No spec 81 85 81 8
KI,Min 84 84 No spec No spec No spec No
e,Vol%(max) 5 3 1 1 1
s,Vol%(max) No spec No spec 42 42 35 3
Vol%(max) No spec No spec 21 18 21 1

Table:6.3 DIESEL SPECIFICATION IN INDIA[16-19]

Parameter BIS-2000 Bharat-II Bharat-III EURO-IV

Sulfur,ppm 2500 500 350 50
Cetane Number(*) 48 48 51 51
Density,kg/m3 820-860 820-860 820-845 820-845
95% Recovery,oC 370 370 360 360
PAH,wt% 11 11
Metros 2000-2001 April 1,2005 April 1,2010
Year of
Mega Cities April 1,2003 April 1,2005 April 1,2010
implementation
Rest of india April 1,2000 April 1,2005 April 1,2010

260
Fig.6.2 Future Production of Clean MS [1-6,12-19]

261
Fig.6.3 Steam-Methane Reforming[1-2,11-18]

262
Catalyst

• Catalyst is a material that can influence a chemical reaction without

changing itself chemicallly
• It makes reaction faster by reducing activation energywithout affecting
equillibrium
• Can selectively favor a certain over other
• Key Factors
• Activity(reaction temperature)
• Selectivity(desired product)
• Stability(deactivation rate)
• Hardness/crushing strength

263
 Fig.6.4 Hydrocracking Catalyst[1-6,15-25]
Catalyst Charateristics

Important characteristics of catalysts which influence its performance are :-

▪ Partical size
▪ Pore volume
▪ Size distributor
▪ Pore diameter
▪ Surface area
▪ Shape of catalyst particles

Catalyst

Catalyst used in hydroprocessing

• Typical composition
▪ CoO 2-6wt%
▪ MoO3 10-25wt%
▪ Al2O3
• Factor helping catalyst activity
▪ Higher H2 partial pressure
▪ Lower liquid hourly space velocity(LHSV)
▪ Lower H2 recycle gas

264
 Fig.6.5 Catalyst[1-5,15-25]

Catalyst Loading

• Special technique is used to load catalyst into reactor to maximise bulk

density.This is callled dense loading
• Dense loading helps in
▪ Liquid distribution in the bed
▪ Minimising bed slumping
▪ Achieving longer cycle length
▪ Maintaining lower operating temperture for same hetero atom
removal and saturation
▪ Reducing deactivation rate

Catalyst Deactivation[1-6,12-16,26-30]

• Catalyst activity gradually reduce with time

• If reacting molecules cannot reach all catalyst active sites,rate of
reaction decreases.It is called catalyst deactivation.
265
 • Catalyst Deactivation study necessary at higher reactor temperature for
same S,N,O removal/saturation
• Two types of deactivation temporary and permanent
• Major cause of temporary deactivation is coke deposition in catalyst due
to undesireable side reaction
• Coke can cover active catalyst sites and block the entrance of pores
leading to active sites
• During plant upsets,coke deposition acclerates
• When temperory deactivation reaches the limits,catalyst regeneration is
necessary.
• Permanent deactivation is caused due to metal accumulation in catalyst
• Metals like Pb,Fe,As,P,Na,,Ca,Mg and orgonomettalic compounds are
poisonous to catalyst
• Process parameter which significantly influence catalyst deactivation
▪ Reactor temperature
▪ Feed boiling range/°API
▪ Feed Rate
▪ H2 partial pressure
▪ Recycle gas rate
▪ Feed contamination

Catalyst Regenration[1-6,20-28]

• Hydroprocessing catalyst cost is a significant fraction of unit cost

processing
• To reduce operating cost it is better to regenerate
• Strict environmental norms for disposing spent catalyst also encourage
regeneration of catalyst and reuse
• Normally two regeneration are allowed and its impart total life of 3-5
years to catalyst
• Catalyst regeneration involves removal of deposited coke in oxidised
atmoshere using stem/airs.

Diesel Hydrotreating[1-2,24-30]

• Feed
▪ Straight run:SRGO(HGO and LGO),VLGO,SRVD,SO
▪ Cracked stock VBGO,LCO

Typical Operating condition :-

▪ Temperature 320-400°C
▪ H2 pressure 40-100 bar

266
 ▪ LHSV 0.5-3.5h-1
▪ H2:Oil Ratio 160-550Nm3/m3
▪ Catalyst Ni/Mo/Al2O3 CoMoAl2O3

Hydrocracking[1-6,20-28]

• Feed :VGO,RESID,DISTILLATES
• Typical operating condition
o Conversion 50-100%(Normally low for once thru and high for
recycle configuration)
o Temperature 350-425° C
o H2 pressure 100-200 bar
o LHSV 0.5-2.0 h-1
o H2 oil ratio 700-2000 Nm3
• Catalyst Ni/Mo or Ni/W on Amorphous Si/O2/Al2O3 or zeolyte

Table:6.4 Hydroprocessing Reaction-Effects Of Operating Condition

267
 Fig.6.6 Diesel Quality Issues[17-19]

Effect of Process Variables on Cetane Index[17-19]

268
 Fig.6.7 Effect of Process Variables on Cetane Index

Hydrocracking - Feeds[17-19]

1. Hydrocracking does a better job of processing aromatic rings without

coking than catalytic cracking.
2. Hydrogen used to hydrogenate polynuclear aromatics (PNAs)
3. Reduces frequency of aromatic condensation.
4. Hydrocracking more severe for resids high in resins, asphaltenes and
heteroatom compounds.
5. Heteroatoms and metals prevalent in resins & asphaltenes poison
hydroprocessing catalysts.
6. Feedstock selection in much more sophisticated than mare
determination of CCR
7. Distribution of aromatic, naphthenic, and paraffinic structures important

Hydrocracking - Products[1-6,17-18]

1. Hydrocracking primary to make distillates

2. Intent is to minimize the production of heavy fuel oil
1. Lights ends are approximately 5% of the feed
2. Middle distillates<(kerosene,jet fuel,diesel,heating oil) still
contain uncracked polynuclear aromatics
3. All liquid fraction are low in sulphur and olefins

Hydrocracking - Chemistry[1-8]

Cracking Reaction
1. Saturated Paraffins cracked to form lower molecular weight olefins and
paraffins
2. Side chain cracked off small ring aromatics(SRA) and
cycloparaffins(napthenes)
3. Side chained cracked off the resins and asphaltenes heaving thermally
stable polynuclear aromatics(PNAs)
4. But condensation(dehydrogenation) also occurs if not limited by
hydrogenation

Isomerization Reactions[1-4]
• Isomerisation provides branching of alkyl groups of paraffins and
opening of naphtic rings
• Condensation Reaction

269
 • Suppresed by hydrogen

Hydrogen - H2 Consumption[7-19]

Carbons bonds with hetero atoms and saturated

• Create lights ends

• Heavier distillates make more lights from breakings more complex
molecules
• Sulphur converted to hydrogen sulfide
• Nitrogen converted to ammonia
• Oxygen converted to water
• Organic chlorides converted to hydrogen chloride

Typical chemical hydrogen consumption 2-3 wt% on feed

Hydrcracking catalyst[1-19]

Hydrocracking catalyst generally a crystalline silica alumina base with rare

earth metal deposited in lattice
• Acid function is provided by silica alumina base
• Chloride not required in catalyst formation

Feed stock may be hydrotreated

• Acid function is provided by silica alumina base
• Chloride not required in catalyst formation

• Catalyst suspectible to sulphur poisioning if hydrogen sulphide is present

in large quantities
• Catalyst activity affected by ammonia if present in large quantities
• Something necessary to remove moisture to protect the crysatlline
structure of catalyst
• Hydrocracking with a mettalic hydrogenation function is sensitive to
matal contamination

Hydrocracking catalyst Deactivaton & Regeneration[1-19]

Catalyst deactive and coke does from even from hydrogen present

270
 • Hydrocracker reqires peroidic regenration of fixed bed catalyst
system.Typical catalyst cycle length is 2 years

Channeling caused by coke accumulation a moajor concern

• Can create hot spot that can leads to temperature runaway

Continuous withdrawal of catalystfrom an expanded circulating bed for

regeneration

• For use in hydrocracking whole crude or short resid

Hydrocracking Effect of Process Variables[7-19,22-30]

Crackability of feed desired yields of products determine operating

severity.Operating Severtiy

• Catalyst
• Space Velocity
• Total Pressure
• Hydrogen partial pressure

Severe operation needed to significantly reduce molecular weight of feed &

increase the hydrogen:carbon ratio in product

Severity

• Mild operation for diesel or fuel oil from heavy gas oil
• Severe operation for kerosene or naphtha from light gas oil

Temperature

• Temperature not used to increase severity

• Temperature adjusted to offset decline in catalyst activity
• Consider 343°C to 400°C as a description of mild operation and 400°C
to 450°C to severe operation

Hydrocracking process

Single stage or two stage process

271
 • Unit size
• Severity of operation
• Product desired
• Nature of feedstock
• Feed pretreating for conntaminant removal

Single stage Hydrocracking[11-27]

Simple hydrocracker single reactor combining modest desulphurization with

hydrocracking of gas oil to distillates
• Hydrogen sulfide must be relatively low and not be a problem for these
catalysts
• Desulphurisation catalyst in the top bed and sulphur intensitive
hydrocracking catalyst in lower bed

Oleffins saturation can be a problem in term of heat release

• Hydrogen quence
• Additional quence netween hydrocracking catalyst beds

Single stage Hydrocracking

Fresh feed recycle feed,and hydrogen heated in furnace to reactor

temperature approx 700&d F.Operating pressure1,200 psig or more.1000
scl/bblor more hydrogen for combined desulphurization and hydrocracking
Product Separation
• Reactor product is flashed to recycle hydrogen as high a pressure as
poosible
• Minimize recompression horsepower
• Gas from low pressure(50 to 75 psig) flash to gas plant

liquid from flash fractionated overhead condition

• Straight run gasoline
• Naphtha siuitable for reforming
• Distillates either jet fuel/kerosene or diesel treating oil
• Bottom for recycle
• Some bottom may be pursed to fuel oil,which would reduce severity

272
 Fig.6.8 Single Stage Hydrocracking with Recycle [1-2]

Two Stage Hydrocracking[1-2]

Use separate reactor with desulphurisation and olefins saturation in 1st

reactor and hydrocracking in 2nd reactor

• 1st reactor removes contaiminats and saturate aromatics

• It Can also do part of th hydrogenation conversion

Effluent from 1st reactorsent to fractionator - fractionator bottoms sent to 2nd

stage hydrocracking reactor.May need a separate internal hydrogen sulphide
removal

273
Fig.6.9 Two Stage Hydrocracking with Recycle & Separator System [1-

2]

Hydro treating process and catalysts Resid hydro processing,Effects

of process variables,Reactor design concepts.

Table:6.5

Technology to Improve HSD Quality [1-2,17-19]

DHDS(35+bar
When one sulfur reduction is required
pressure)

DHDT(85+bar Large sulfur reduction & high cetane gain

pressure) coupled with T-95 point improvement

For middle distillate maximisation along with

Hydrocracker cetane improvement & very high sulfur
reduction

274
Purpose

• Hydrotreating[1-2]
• Remove hetero atoms and saturate carbon-carbon bonds Sulfur,
nitrogen, oxygen, and metals removedOlefinic & aromatic bonds
saturated
• Reduce average molecular weight & produce higher yields of fuel
products
• Minimal cracking
• Minimal conversion – 10% to 20% typical
• Products suitable for further processing or final blending
• Reforming, catalytic cracking, hydrocracking
• Hydrocracking
• Severe form of hydroprocessing
• Break carbon-carbon bonds
• Drastic reduction of molecular weight
• 50%+ conversion
• Products more appropriate for diesel than gasoline

Hydroprocessing Trends[1-2,17-18]

• Hydrogen is ubiquitous in refinery and expected to increase

• Produces higher yields and upgrade the quality of fuels
• The typical refinery runs at a hydrogen deficit
• As hydroprocessing becomes more prevalent, this deficit will
increase
• As hydroprocessing progresses in severity, the hydrogen demands
• increase dramatically
• Driven by several factors
• Heavier and higher sulfur crudes
• Reduction in demand for heavy fuel oil
• Increased use of hydrodesulfurization for low sulfur fuels
• More complete protection of FCCU catalysts
• Demand for high quality coke
• Increased production of diesel

Increased production of diesel[17-20]

• Catalystic Reformer
• The most important source of hydrogen for the refiner
• Continuously regenerated reformer: 90 vol%
• FCCU Offgas
• 5 vol% of hydrogen with methane, ethane and propane
• Several recovery methods (can be combined)

275
 • Cryogenic
• Pressure swing adsorption
• Membrane separation
• Steam-Methane Reforming
• Synthesis Gas
• Gasification of heavy feed
• Hydrogen recovery – pressure swing adsorption or membrane
separation
• More expensive than steam reforming but can use low quality by
product streams

Sources of Hydrogen[1-2,15-16]

• Catalytic Reformer
• The most important source of hydrogen for the refiner
• Continuously regenerated reformer: 90 vol%
• Semi-continuously regenerated reformer: 80 vol%
• FCCU Offgas
• 5 vol% hydrogen with methane, ethane and propane
• Several recovery methods (can be combined)
• Cryogenic
• Pressure swing adsorption
• Membrane separation
• Steam-Methane Reforming
• Synthesis Gas
• Gasification of heavy feed
• Hydrogen recovery – pressure swing adsorption or membrane
separation
• More expensive than steam reforming but can use low quality by
product streams

• Reforming Endotherm catalystic reaction 750-815°C

• Shift Conversion.Exothermic fixed bed catalystic reaction 650°C

• Gas purification.Absortion of CO2 in amine or hot K2CO3 solution
• Methanation.Trace amount of carbon monoxide and carbon dioxide
removed.Exothermic fixed-bed catalystic reaction,700-800°C

Table:6.6
276
 Technologies to Improve MS Quality [1-2,17-20]

Separation of Benzene rich light cut

Reformate Splitter
from rest of reformate

Isomerisation Benzene Saturation & Octane increase

Continuos catalystic
Octane increase
Reforming

Separation of light cut,mid cut & heavy

FCC Gasoline Spiltter
cut

Selective
Sulphur reduction
desulpurisation

Hydroprocessing Catalysts

• Hydrotreating
• Desired function Cobalt molybdenum : sulfur removal and olefin
saturation Nickel molybdenum: nitrogen removal & aromatic
saturation
• Reactor configurationFixed bed – temperature to control final
sulfur content
• Selective catalysts for sulfur removal without olefin saturation
Maintaining high octane rating
• Hydrocracking
• Crystalline silica alumina base with a rare earth metal deposited
in the lattice Platinum, palladium, tungsten, and/or nickel
• Feed stock must first be hydrotreated
• Catalysts deactivate and coke does form even with hydrogen
present Hydrocrackers require periodic regeneration of the fixed
bed catalyst systems Channeling caused by coke accumulation a
major concern Can create hot spots that can lead to temperature
runaways
• Reactor configuration Ebullient beds – pelletized catalyst bed
expanded by upflow of fluids Expanded circulating bed – allows
continuous withdrawal of catalyst for regeneration

Hydrodesulfurization[1-2,31-33]

• Sulfur

277
 • Sulfur converted to hydrogen sulfide (H2S) Added hydrogen
breaks carbon-sulfur bonds and saturates remaining hydrocarbon
chains
• Form of sulfur bonds Sulfur in naphtha generally mercaptans
(thiols) and sulfides In heavier feeds, more sulfur as disulphides
and thiophenes
• Light ends Heavier distillates make more light ends from breaking
more complex sulfur molecules
• Unsaturated carbon-carbon bonds
• Olefins saturated – one hydrogen molecule added for each double
bond Olefins prevalent in cracked streams – coker or visbreaker
naphtha, catalytic cracker cycle oil, catalytic cracker gasoline
• Aromatic rings hydrogenated to cycloparaffins (naphthenes)
Severe operation Hydrogen consumption strong function of
complexity of the aromatics prevalent in heavy distillate
hydrotreating, gas oil hydrotreating, hydrocracking
• Selective catalysts available for hydrotreating cat gasoline for sulfur
removal but not saturate olefins
• Maintain high octane ratings

Hydrogen Consumption[1-2,12-16]

• Chemical consumption due to hydrogenation reactions

• Cracking reactions of carbon-carbon bonds minimal in
hydrotreating, even during aromatic saturation
• Hydrogen is lost in equilibrium with light gases
• Amount is significant and may double amount required for sulfur
removal
• Hydrogen absorbed in liquid products
• Usually small compared to sulfur removal needs – 1 lb/bbl
• Hydrogen removed with purge gas
• Used to maintain a high purity of hydrogen — light ends dilute the
hydrogen concentration
• Usually small compared to sulfur removal needs

General Effects of Process Variables[1-2,12-16]

• Reactor inlet temperature and pressure

• Increasing temperature increases hydrogenation but decreases
the number of active catalyst sites
• Temperature control is used to offset the decline in catalyst
activity

278
 • Increasing pressure increases hydrogen partial pressure and
increases the severity of hydrogenation
• Recycle hydrogen
• Require high concentration of hydrogen at reactor outlet
Hydrogen amount is much more than stoichiometric High
concentrations required to prevent coke laydown & poisoning of
catalyst Particularly true for the heavier distillates containing
resins and asphaltenes
• Purge hydrogen
• Removes light ends and helps maintain high hydrogen
concentration

• Naphtha hydrotreated primarily for sulfur removal

• Mostly mercaptans (RSH) and sulfides (R2S)
• Some disulfides (RSSR), and thiophenes (ring structures)
• Cobalt molybdenum on alumina most common catalyst
• Chemical hydrogen consumption typically 50 to 250 scf/bbl
• For desulfurization containing up to 1 wt% sulfur — 70 to 100
scf/bbl
• Significant nitrogen and sulfur removal — 250 scf/bbl

Naphtha Hydrotreating Process[1-2,12-16]

Fig:6.10 Naphtha Hydrotreating Process

279
 • Liquid hourly space velocity ~ 2
• Hydrogen Recycle about 2000 scf/bbl
• Stripper overhead vapour to saturate gas plant
• Recovery of light hydrocarbons and remove H2S
• Fractionator Pentane/hexane overhead to isomerization
• Bottom to reformer

Hyrdoprocessing Basics[1-2,12-16,31-33]

Fig:6.11 HydroProcessing Family

INTRODUCTION
• Why Hydro processing ?
• Need to increase automotive fuel yield and quality
• Petroleum fractions contain organic Sulfur, Nitrogen etc. which cause
Increased air pollution Equipment corrosion
• Difficulties in further processing (catalyst poisoning etc.)
• Stringent Government regulation for Sulfur in fuel.

What is Hydroprocessing[1-2,31-35]

Hydrotreating

280
 • Remove hertro atoms and saturation of carbon-carbon bonds
• Nitrogen,oxygen and metals removed
• Olefinic and Aromatic bonds saturated
• Reduced average molecular weight and produce higher yields of fuel
products

Hydrotreating[1-2,30-35]

• Catalystic Hydrogenation process to remove contaminats(S,N,O) to

upgrade fuel quality with negligible effect on their boiling range
• Also saturate olefins/aromatics to improve Cetane
• Degree of hydroprocessing depends uppon the nature of feedstock &
extends of pollutants removal required
• Used to upgrade Gasoline,Diesel and Lube base stocks.

Hydrotreating[1-2,30-35]

• Sulphur is converted to hydrogen sulphide H2S

• Added hydrogen breaks carbon-sulphur bonds & saturates
remainining hydrogen carbons
• Creates some light ends
• Heavy distillates makes more light ends from breaking more complex
sulphur molecules
• Form of sulphur bonds
• Sulphur is naphtha Mercaptans(Thiols) and sulfides
• In heavier feeds,more sulphur as Disulphides and Thiopenes
• Nitrogen is converted to ammonia(NH3)
• Pyridines and Pyyroles are nitrogen containing componds
• Nitrogen removal minor in naphtha hydrotreating
• As the feeds become heavier de-nitrogenation becomes more
significant,such as heavy distillate and gas oil hydrotreating
• Nitrogen removal requires about 4 times as much hydrogen as
equivalents of sulphur removal

Major Hydrotreating Reactions[1-2,30-35]

Removal of Hetro Atoms

281
Major hydrotreating reaction[1-2,30-35]

Hydrotreating-Effect of Process Variables[1-2,30-35]

Reactor inlet temperature and pressure

• Increasing temperature increases hydrogenation but decreases the
number of active catalyst sites
• Temperature control is used to offset the decline in catalyst activity

282
 • Increasing pressure increases hydrogen partial pressure and the
increases the severity of hydrogenation

Recycle Hydrogen

Requires high concentration of hydrogen reactor outlet

• Hydrogen amount is much more than stoichiometric
• High concentration require to prevent coke laydown and poisoning of
catalyst
• Particularly true for the heavier distillate containing resins and
asphaltenes

Pure Hydrogen
• Help to maintain high hydrogen concentration

Increases severity
• Naphtha Hydrotreating
• Distillate(Light and Heavy) hydrotreating
• Gas oil hydrotreating

Fig:6.12 Hydrogen Consumption

283
 Fig:6.13 HydroProcessing Catalyst share in Refinery

Hydrotreating Trends[1-2,24,30-35]

Trend is more hydroprocessing is driven by several factors :-

• Heavier and higher sulphur crudes
• Reduction in demand for heavy fuel oil
• Increased used of hydrodesulfurization for low sulphur fuels
• More complete protection Of FCCU cactalyst
• Demand of high quality coke

284
 Fig:6.14 Catalyst in DHDS/DHDT Reactor

Fig:6.15 Catalyst in Hydrocracking Reactor

Challenges in HydroProcessing[1-2,30-35]

• Design of new catalyst formulation for :-

o Diesel end point reduction
o Selective ring opening for cetane improvement with less hydrogen
consumption
• Design of improved reactor internals
• Process and catalyst for slurry reaction based hydroprocessing

285
 Table:6.7
Reaction Chemistry-Indicative Quality
Changes
Boiling
Reaction Hydrogen Density Cetane
Point

moles kg/m3 °C Number

1-2 2 -40 -16.5 +10

1-2-3 3 -110 -28 +45

1-2-4 5 -90 -16.5 +30

Good Distributors

• Decrease radial thermal distributions

• Increase volume for catalyst loading

Leading to
• Increased cycle length
• Higher throughput
• Increase conversion
• Improved product quality
• Improved product consistency

Naphtha Hydrotreating-Hydrogen Consumption[1-2,30-35]

• For desulphurisation containing upto 1 wt% sulphur 70 to 100 scf/bbl

• Higher nitrogen levels increase hydrogen consumption proportionately
• Signifant nitrogen and sulphur removal-250 scf/bbl

This is chemical hydrogen consumption

• Add for mechanical loss and loss with the light hydrocarbon vapours

286
 Fig:6.16 Naphtha Hydrotreating-Process

Naphtha Hydrotreating - Process[1-2,30-35]

• Feed & hydrogen fed to furnace

• Vapors passed down - flow over the catalyst bed
• Outlet vapors about 370°C
• Outlet cooled and flashed at 370°C to separate light ends
• Exchange with feed(for heat integration)
• Final exchange with cooling water
• Single stage flash adequate
• Bulk of flash gas recycled
• Flashed liquid fed to stripper for removal of light ends of hydrogen
sulphide and sour water

Distillate Hydrotreating

• In general , all liquid distillate Streams contain sulfur compounds that

must be removed needs the treatment.

287
 • Saturation of aromatics in diesel is essential to improve the cetane
number.

Distillate Hydrotreating-Hydrogen Consumption[1-2,30-35]

• Light distillate hydrotreating (kerosene and jet fuel) requires more

hydrogen than Naphtha hydrotreating.

Heavy distillate (diesel) hydrotreating consumption quite variable

• Can consume considerable quantities of hydrogen at higher severity
• Hydrogen consumption and operating pressure are a function of the
stream being treated, the degree of sulfur and nitrogen removal, olefin
saturation, aromatic ring saturation,…..

Typical conditions – 300oC – 425oC ; 300 psig and greater Modest temperature
rise since reactions are exothermic
• Hydrogen recycle rate starts at 2,000 scf/bbl;
• Consumption of 100 to 400 scf/bbl
• Conditions highly dependent upon feedstock
• Distillate (jet fuel & diesel) with 85% - 95% sulfur removal
• 300 psig & hydrogen consumption of 200-300 scf/bbl
• Saturation of diesel for cetane number improvement
• over 800 scf/bbl hydrogen & up to 1,000 psig

288
 Fig:6.17 Typical Distillate Hydrotreater for Base Metal Catalyst

Gas Oil Hydrotreating[1-2,30-35]

• Catalystic cracker feed stocks (atmospheric gas oil, light vacuum gas
oil, solvent deasphalting gas oil) hydrotreated severely Sulfur removal
Opening of aromatic rings removal of heavy metals
• Desulphurization of gas oil can be achieved with a relatively modest
decomposition of structures Gas oils can be contaminated with resins
and asphaltenes deposited in hydrotreater.
• Require catalyst replacement with a shorter run length than determined
by deactivation
• Guard chamber may be installed to prolong bed life Nickel Molybdenum
catalyst system from severe hydrotreating

Gas Oil Hydrotreating - Process[1-2,30-35]

• Normally requires two reactors with two beds

• Effluent from the second reactor is flashed in to two stages
• High-pressure flash provides recycle of hydrogen gas
• Low-pressure flash separates light ends for hydrogen sulfide recovery

289
 • Low-pressure flash liquid is treated as gas oil and sent to catalyst
cracker
• The initial temperature is expected to be of the order of 350°C
• Hydrogenation highly exothermic-care must be taken to avoid runaways

Hydrocracking Trends[1-2,30-35]

Hydrocracking does a better job of processing aromatic rings without cooking

than catalystic cracking
• Hydrogen reduced to hydrogenate polynuclear aromatics(PNAs)
• Reduce the frequency of aromatic considensation

• Hetroatom and metals prevalents in resins and asphaltenes poison

hydroprrocessing catalyst

Feedstock selection is much more sophisticated than determination of CCR

• Distribution of aromatic,naphthenic and paraffinic structure is important

Hydrocracking Feeds
• Typical Feeds
• Cat cracker "cycle oil"
• Cat cracker "cycle oil"
• Highly aromatic with sulphur,small ring and polynuclear
aromatics,catalyst fines usually has high vescosity
• Hydrocracked to form high yield of jet fuel,kerosene,diesel &
heating oil
• Gas oil from visbreaker
• Aromatic
• Gas oil from delayed cocker
• Aromatic olefinic with sulphur

Residue Hydrotreating[1-2,30-35]

Residuum technology is widely used for pretreating residuum to produce RFCC

feed,hydrotreating coker feed,hydrotreating visbreaker/FCC feed or to
produce Low sulphur Fuel Oil(LSFO)
Most new residuum hydrotreating units pretreat for an RFCC,allowing a very
high conversion to high value product with this combined processing

290
The RDS process reduces metals,sulphur,nitrogen and carbon residue in the
residuum
By pretreating the residuum with an RDS,the yields and quality of RFCC
products are greatly improved

Residue Hydrocracking

This technology provides the means to convert residuum to lighter petroleum

fraction such as naphthna and distillates are greater than 70% conversion of
heavy residual 975° F (524° C) material
The unconverted residue is usually blended as fuel oil as if the conversion is
less than 80%
Conversion greater than 80% & as high as 97% has been achieved
commercially but the unconverted residue may be unstable as a fuel oil blend
stock
Along with high conversion,feed desulphurization of 80-85% is typical for most
designs

Hydrotreating of Diesel[1-2,30-35]

Unionfining

Fixed bed catalysic process developed by UOP

Adopted for diesel Hydro-desulphurization
Key Features
• Operates at about 36 Kg/cm2
• Operates at about 360-400°C temperature
• Hydrogen is consumed
• Heat is released
• Products are saturated
• Products are nearly free of hetero atoms(S,N,O)

HYDROTREATING FLOW SHEET[1-2,30-35]

291
 Fig:6.18 Hydrotreating Flow Sheet

DHDS Process Variable[1-2,30-35]

• Some important process variable affects the catalyst stability and

product quality
• These variable needs to be monitored regularly for consistent operation
& longer cycle length
• The Process Variables :-
• Reactor temperature
• Feed rate quality
• Liquid Hourly Space Velocity
• Recycle gas rate
• H2S partial pressure

DHDS Process Variable

Reactor Temperature
• Temperature of the reactor effluent is more than that of the reactor inlet
stream
• The hydesulphurisation reaction are exothermic
• The reactor temperature is most vital control parameter
• Best way to control reactor temperature is to control WABT by adjusting
quench flow

292
 • Increasing reactor temperature increases severity of reaction of
constants like H2 partial pressure
• Higher reactor temperature causes more hetero atom(S,N,O) removal
and saturation
• Higher reaction leads to higher catalyst deactivation (more coke
deposit) and lower cycle time of plant
• Higher reactor temperature may have adverse impact on treated diesel
color stability

Feed Quality & Rate

• DHDS feed streams are SR Gas oil,LCO from FCCU,gas oil from
CIDW,kerosene cuts etc.
• Straight run components are easier to treat
• Cracked product /unsaturated are difficult to process as they require
more heat during reaction
• Regular monitoring of SG,sulphur contents of feed is vital
• Higher S content in feed requires more severity,H2 consumption and H2S
reaction
• Liquid hourly space velocity is defined as M3/Hr of feed (at 15°C)per
M3 of catalyst
• Design value of LSHV depends upon feed stock quality,product quality
stipulation and channeling that may occur inside reactor,leading to
unusual deactivation of catalyst bed
• Operate near design value,do not go below trundown ratio

H2 Partial Pressure[1-2,30-35]

• This is the design criteria and critical process variable for good hetero
atom(S,N,O) removal
• It is defined as System Pressure * H2 Purity
• Lower H2 partial pressure reduces reaction rate
• Lower H2 partial pressure increases rate of coke deposition on catalyst
• Lower H2 partial pressure leads to higher reactor temperature the
(S,N,O)removal and reduce cycle length

Recycle Gas Rate

Higher Recycle Gas Flow Rate Helps in

• Supplying excess H2 is to ensure reaction completion
• Absorbing heat of reaction to control bed temperature

293
 • Ensuring good linear velocity in heater and exchange to control
temperature
• Another related process variable is gas-to oil ratio and has same effect.It
is defined as Total gas flow(NM3/Hr)/Feed rate(NM3/Hr)at 15°C

Hazards of Hydrogen[1-2,13-16,30-35]
Hydrogen gas is colorless and odorless and not detectable by human senses

Properties of Hydrogen

What Is Hydrogen?
Hydrogen is a colorless, odorless, tasteless, flammable nontoxic gas. It is the
lightest of all gases, with a specific gravity of 0.0695. The hydrogen content
of atmospheric air at sea level is 0.5 ppm. Hydrogen has two isomers (forms):
ortho-hydrogen, in which the two atomic nuclei spin in the same direction;
and para-hydrogen, in which they spin in opposite directions. There is no
difference in the chemical properties of the two forms of hydrogen, but there
are slight differences in physical properties. Gaseous hydrogen is a mixture of
75% ortho-hydrogen and 25% para-hydrogen at room temperature; this
mixture is called normal hydrogen (CGA G5 1991).

Hydrogen Has Unique Properties[1-2,13-16]

Several unique properties contribute to the hazards associated with gaseous
and liquid hydrogen systems:
• Hydrogen is flammable over a wide range of concentrations.
• The ignition energy for hydrogen is very low.
• A single volume of liquid hydrogen expands to about 850 volumes of
gas at standard temperature and pressure when vaporized. At 7,000 ft
elevation, this expansion rate is increased to approximately 1,000
volumes of gas at standard temperature.
• Hydrogen is able to reduce the performance of some containment and
piping materials, such as carbon steel.

Properties of Hydrogen continued[13-16]

Flammability
Hydrogen burns with a nearly invisible bluish flame, unless it is contaminated
with impurities, in which case a pale-yellow flame is easily visible in the dark.
The temperature of burning hydrogen in air is high 2050 oC (3,713 oF), as
compared with 1250 oC (2,276 oF) for gasoline), and warm hydrogen gas rises
rapidly because of its buoyancy. Hydrogen forms a flammable mixture over a
wide range of concentrations in air and requires a minimum ignition source,
294
 only one-tenth of the energy required for gasoline vapors. It is the
combination of these factors that contributes to the flammability hazard
associated with hydrogen gas. (See the table below for a summary of the
physical properties of hydrogen.)

Embrittlement
Because of its small molecular size, hydrogen can easily pass through porous
materials and is capable of being absorbed by some containment materials,
which can result in loss of ductility or embrittlement. At elevated
temperatures, this process is accelerated. Because of the possibility of
hydrogen embrittlement of some materials, piping and component materials
that are not subject to this form of degradation should be
selected.Recommended materials include 300-series stainless steels, copper,
and brass.

Properties of Hydrogen continued

The following table lists the physical properties and characteristics of hydrogen
and their values.

Table:6.8
Physical Properties and Characteristics of Hydrogen
Property/Characteristic Values(approximate)
Color None
Odor None
Toxicity Nontoxic
Density/Liquid(boiling point) 4.4lb/ft3 (0.07 g/cm3)
Boiling Point(1atm) -423.2 F (-252.9°C)
Critical Temperature(188.2 paisa) -400.4 F(-240.2°C)
stoichiometric mixture in air 29 vol %
Flammability limits in air 4-75 vol %
Detonation limits in air 18-60 vol %
Minimum ignition energy in air 20 uj
Autoignition temperature 1,085 °F(585 °C)
1:53
Volume Expansion
1:16
Liquid(-252.9°C) to gas (-252.9°C)
1:848

295
gas(from -252.9°C to 20 °C)

liquid(-252.9°C)to gas (20°C)

Hazards of Hydrogen[13-16,36]

Flammability and Explosivity are Primary Hazards

The primary physical hazards associated with hydrogen gas are its
flammability and explosivity. This is because hydrogen can form a flammable
mixture with air over a wide range of concentrations (4%Ð75%), and very
low energy is needed to ignite hydrogen-air mixtures. Once hydrogen is
ignited, the reaction can proceed either by deflagration (subsonic
propagation) or detonation (supersonic propagation). Deflagration in a closed
volume can cause a pressure increase of almost eight times the initial
pressure. Detonation from a low-energy ignition source is possible in
hydrogen-air mixtures of 18 to 60% vol% that are well mixed and confined.
Although hydrogen - air mixtures have the same calorific value per pound as
TNT, the rate of energy release is much slower for hydrogen-air mixtures.
Hydrogen detonations, although rare, are characterized by pressure increases
so rapid that pressure-relief devices are usually ineffective. When using
hydrogen in enclosed areas, consult National Fire Protection Association
documents 68 and 69.

Effects on Health
Hydrogen is nontoxic and has even been used as a filler for oxygen sources
for underwater diving. The primary health effect associated with hydrogen is
the possibility that it could displace air in a poorly ventilated or confined space,
resulting in asphyxiation. However, because it is flammable at only 4% in air,
the most significant concern should be the physical hazard of flammability and
the possibility of burns resulting from fires and explosions. When working with
liquid hydrogen, there is an additional health hazard of cryogenic burns.

Table:6.9
Flammability Limits
Hydrogen Propane

LFL 4.1% 2.1%

UFL 75% 9.5%

Explosive Limits

296
 LEF 18.3 UEL 59

Average velocity in air at 20°C

Hydrogen Oxygen

39MPH 10MPH

Auto ignition temperature °C

Hydrogen Propane

400 450

An invisible spark or static spark from a person can cause ignition

• Hydrogen therefore easily ignited and burns rapidly
• Hydrogen-pure air flames are colorless
• Colorless Hydrogen flames can cause severe burns
• For occuptional exposure H2 is classed as as aphyxiant

Isomerization process, Reactions, Effects of process

variables.

Isomerization[1-3]

The octane numbers of the LSR naphtha [C5-180oF (C5-82oC)]

can be improved by the use of an isomerization process to
convert normal paraffins to their isomers.This results in
significant octane increases as n-pentane has an unleaded
(clear) RON of 61.7 and isopentane has a rating of 92.3. In
once-through isomerization where the normal and iso
compounds come essentially to thermodynamic equilibrium,
the unleaded RON of LSR naphtha can be increased from 70
to about 82–84. If the normal components are recycled, the
resulting research octane numbers will be about 87–93 RONC.

Reaction temperatures of about 200–400oF (95–205oC) are

preferred to higher temperatures because the equilibrium
conversion to isomers is enhanced at the lower temperatures.

297
At these relatively low temperatures a very active catalyst is
necessary to provide a reasonable reaction rate. The available
catalysts used for isomerization contain platinum on various
bases. Some types of catalysts require the continuous addition
of very small amounts of organic chlorides to maintain high
catalyst activities. This is converted to hydrogen chloride in
the reactor, and consequently the feed to these units must be
free of water and other oxygen sources in order to avoid
catalyst deactivation and potential corrosion problems. A
second type of catalyst uses a molecular sieve base and is
reported to tolerate feeds saturated with water at ambient
temperature.

A third type of catalyst contains platinum supported on a novel

metal oxide base. This catalyst has 150oF (83oC) higher activity
than conventional zeolitic isomerization catalysts and can be
regenerated. Catalyst life is usually three years or more with
all of these catalysts. An atmosphere of hydrogen is used to
minimize carbon deposits on the catalyst but hydrogen
consumption is negligible .The composition of the reactor
products can closely approach chemical equilibrium. The actual
product distribution is dependent upon the type and age of the
catalyst, the space velocity, and the reactor temperature. The
pentane fraction of the reactor product is about 75 to 80 wt%
iso-pentane, and the hexane fraction is about 86 to 90 wt%
hexane isomers .

Isomerization Processes[1-5]

• Vapor phase process

▪ Hydrogen used to suppress the dehydrogenation
and coking.
▪ High yields and high selectivity to high-octane
isomeric forms.
▪ Provides moderate (but important) contribution to
the gasoline pool.
• Catalyst types
▪ Chloride alumina catalyst.
▪ Organic chloride deposited on active metal sites.
▪ High temperature treatment with carbon
tetrachloride.
▪ Chlorides are sensitive to moisture – drying of feed
& hydrogen.
• Make-up essential

298
 ▪ Acidic zeolite with noble metal catalyst.
▪ Platinum catalyst.
▪ Does not require activation by hydrogen chloride.

Isomerization Processes[1-7]

• Pros
▪ Reforming conditions not appropriate for the
paraffinic components in SRG.
▪ Essentially zero benzene, aromatics, & olefins.
▪ Very low sulfur levels.
• Cons
▪ High vapor pressure.
▪ Moderate octane levels — (R+M)/2 only 85.

Feedstocks
• Lightest naphtha feed stock (SRG) with pentanes,
hexanes, and small amounts of heptanes.
▪ Feed often debutanized —"Debutanized Straight
Run".
• Sulfur and nitrogen must be removed since catalysts
employ an ‘acid site’ for activity.
▪ Merox
▪ Clay treating
▪ Hydrotreating
• Common for Straight Run Gasoline and Naphtha to be
hydrotreated as one stream and then separated.

Products
• Products
▪ Isoparaffins and cycloparaffins.
▪ Small amounts of light gasses from hydrocracking
.
▪ Unconverted feedstock.
• Increased severity increases octane but also increases
yield of light ends.
• Yields depend on feedstock characteristics and product
octane.
▪ Poor quality feeds might yield 85% or less liquid
product.

299
 ▪ Good feeds might yield 97% liquid product.

Catalytic Reforming and Isomerization[3-9]

If the normal pentane in the reactor product is separated and

recycled the product RON can be increased by about 3
numbers (83 to 86 RONC).If both normal pentane and normal
hexane are recycled the product clear RON can be improved
to about 87 to 90. Separation of the normals from the isomers
can be accomplished by fractionation or by vapor phase
adsorption of the normals on a molecular sieve bed. The
adsorption process is well developed in several large units.

Some hydrocracking occurs during the reactions resulting in a

loss of gasoline and the production of light gas. The amount of
gas formed varies with the catalyst type and age and is
sometimes a significant economic factor. The light gas
produced is typically in the range of 1.0 to 4.0 wt% of the
hydrocarbon feed to the reactor. For preliminary estimates the
composition of the gas produced can be assumed to be 95 wt%
methane and 5 wt% ethane. For refineries that do not have
hydrocracking facilities to supply isobutane for alkylation unit
feed, the necessary isobutane can be made from n-butane by
isomerization. The process is very similar to that of LSR
gasoline isomerization but a feed deisobutanizer is used to
concentrate the n-butane in the reactor charge. The reactor
product is about 58 to 62 wt% isobutane. A representative
flow scheme for an isomerization unit is shown in Figure below.

300
 Fig:7.1 A representative flow scheme for an
isomerization unit

Isomerization Chemistry

• Primary reaction is to convert normal paraffins to

isomeric paraffins.
• Olefins may isomerize and shift the position of the
double bond.
▪ 1-butene coluld shift to a mixture of cis-2-butene
and trans-2-butene
• Cycloparaffins (naphthenes) may isomerize and break
the ring forming an olefin.
▪ Cyclobutane to butene.

301
Example
Cost Included
1. Feed Drying
2. Drying of hydrogen makeup
3. Complete preheat reaction and hydrogen circulation
facilities
4. Product stabilization
5. Sufficient heat exchange to cool product to ambient
temperature
6. Central control
7. Paid up royality

Cost not Included

1. Hydrogen source
2. Cooling water,steam and water supply
3. Feed desulfurization
4. Intial catalyst charge about $100/BPD of reactor feed

Royalities
▪ Paid up rayalty is about $90 to$160/BPD

Utility data(per bbl,"fresh"feed)

Power Kwh -1.0
Cooling water gal(0C F) 600-1000
o

Fuel(LHV),MMBtu 0.20
Catalyst replacement,$ 0.05
Hydrogen makeup,sef 40

Example Problem

Calculate the length of time between regeneration of catalyst

in a reformer operating at the following conditions:
Liquid hourly space velocity (LHSV) = 3.0 v/hr/v
Feed rate = 5000 BPSD
Feed gravity = 55.0oAPI
Catalyst bulk density =50 lb/ft3
Hydrogen-to-feed ratio = 8000 scf/bbl
Number of reactors =3
Catalyst deactivates after processing 90 barrels of feed per
pound of catalyst.If the catalyst bed is 6 ft deep in each
reactor, what are the reactor inside diameters? Assume an
equal volume of catalyst in each reactor.

Solution

302
 Time between regenerations:
5000 BPD =1170 ft3/hr
Total catalyst = 1170/3 = 390 ft3
(390 ft )
3 (50 lb/ft )
3 = 19,500 lb
(19,500 lb) (90 bbl/lb)/5,000 bbl/day = 351 days
Inside diameter:
Volume of catalyst per reactor = 390/3 = 130 ft3
Inside area = (130 ft3)/(6 ft) = 21.67 ft2
Inside diameter = 5.25 ft

Alkylation process, Feedstocks, reactions, products, catalysts and

effect of process variables.

Catalytic Alkylation[1-7]

Catalytic alkylation process is used in refineries to upgrade light olefins

(produced from catalytic crackers as well as from cokers viz breakers) and
isobutene into a highly branched paraffins. In petrochemical industry it is used
to produce alkylate benzenes and other petrochemical products.
The alkylation reaction involves the addition of photon H+( supplied by an acid
catalyst),to the double bond of an olefin to form carbonium ion. This ion then
adds to another olefin molecule to form a new carbonium ion which abstracts
a hydride ion, H-, and from isobutene to become a paraffin. At the same time
new carbonium ion is produced to continue the reaction.

STEP 1: Addition of proton H+(supplied by Acid catalyst to propagate double

bond of olefin)

Carbonium ion Formation[5-12]

STEP 2: Addition of this ion to another olefin.

303
STEP 3: Abstraction of Hydride ion H- from olefin.

Alkylation process are conducted by Lewis acids like sulphuric acid,

hydrofluoric acid, aluminium chloride (obsolete). Highly exothermic reaction
HP = - ( 630 to 700 Btu/lb for isobutane alkylation).

Side Reactions

304
Feed Stocks

i-butane, Propenes, butenes.(olefins and isobutenes are alkylation feed

stocks)
T = 10-20o C for H2SO4 alkylation.
Low temperature required for H2SO4 because at higher temperature tar
formation occurs due to oxidation-reduction reactions.
Acid strength 88-90% .High Acid concentration – for alkylation
reaction.Weaker acid gives polymerization reaction.
For HF, temperature is higher T ~ 38oC .Liquid phase reaction in both cases.

Process for H2SO4 alkylation:[5-12]

Fig:7.2 Sulphur Acid Alkylation Processes

Process has been applied to isobutanes and butenes.

Important features:

305
Absorption of olefinic HC occurs hundred times faster as fast as the absorption
of paraffins and sent to the stabilizer hence in order to maintain proper
concentration of the two HC in the acid. It is necessary to recycle large access
of saturated HCs through the system. Higher the ratio of paraffin to olefin in
the feedstock, greater the yield, higher O/W and smaller the acid
consumption.

Operating Variables:

Acid concentration is kept high because of strong acid catalyst alkylation

reaction where as acid catalyst polymerization reaction occurs.

Cascade Refrigeration Process

Fig:7.3 Cascade Refrigeration Process

Uses of multistage reactors with mixers at each stage is to emulsify the

hydrocarbon and mixture of olefin in split in parallel in various reactions occurs
whereas i-butane in series feed to the system. This increases i-butane to olefin

306
ratio. Refrigeration by vaporization of a portion of hydrocarbon in each
reaction is necessary.

H F alkylation:

▪ Highly successful process for combining isobutane and isobutene.

▪ No refrigeration.
▪ Feed is dried.

Special material of construction is required (monel) because HF is very much

corrosive.
HF process is favorable for small plant but for large plant H2SO4 catalytic
process is used.

Process Variables (Alkylation):

(for both process) Major Variables are:- Reaction T, Acid strength, I-butane
concentration, olefin space velocity.

Reaction Temperature:

Low T increases octane number & reduces H2SO4acid

requirements.Unfortunately low T also requires higher refrigeration
investment & operating cost. Miixing is difficult.
High T ---> acid attacks the olefins significant sensitive to temp.
HF alkylation ---> less sensitive to temperature. Increase in T from 30Co to
100oC.
307
Isobutane Recycle Rate:

High isobutane recycle rate increases the octane number and lowers acid
requirements. However high isobutane rate also increases the investment
required for deisobutanizer and increase the operating cost of the tower
because of the higher steam requirements.

Space Velocity:

velocity of olefin/h / velocity of acid in reactor.Low space velocity increases

octane number and lowers acid requirements.High space velocity increases
formation of acid sulphates which are corrosive to downstream fractionation
facilities.

Spent acid strength:

High spent acid strength tends to increases octane No, but also increases
make up acid requirements. Low spent acid strength tends to decrease make
up acid requirements, it increases risk of acid runaway.93-95% acid by
weight, 1-2% water remainder, Hc diluents. Some water is initially added to
the acid which promotes the proton transfer for alkylation reaction. Lowering
olefin space velocity reduces the amount of High boiling hydrocarbon
produced, increases the product octane and lowers acid consumption.

Contact Time:

Residence time of (fresh feed + external recycled i-butane in the reactor.)

5-25 minute-->HF alkylation
5-40 minute-->H2SO4 alkylation

Isobutane concentration:

Excess of i-butane/olefin ratio desirable. It increases the octane number.

Catalytic consumption is less.

Miixing:

i-butane solubility in H2SO4--> 0.1% by weight

i-butane solubility in HF-->3% by weight
solubility of i-butane in acid is very small (sparingly soluble) Olefins relatively
soluble in acids. So proper mixing is required otherwise polymerization will
take place instead of alkylation.

308
IE ---> isobutane in reactor effluent.
(I/O)F ---> (value of isobutane/olefin) in feed.
(SVo) ---> olefin space velocity

F = 10-40
Higher the 'F' better is the Quality product.

Alkylation of benzene:

With ethylene -----> gives ethylbenzene Starting material for styrene

production cat AlCl3
CH2= CH2 + HCl -----> CH3CH2Cl
HCl is used as promoter for Aluminium Chloride and lowers its consumption.

Exothermic reaction ΔH = 110 KJ/mol

Dehydration of ethylbenzene gives styrene.
Cat Fe2CO3 with metallic oxide or ZnO
T = 600C –
o 630oC
Addition of K2CO3 reduces coke on catalyst.

Cumene:By alkylation of propylene with benzene yields Isopropylbenzene.

Cumene is used for production of phenol and methyl styrene.

309
Alkylation and polymerization[1-2,7-12]

The addition of an alkyl group to any compound is an alkylation reaction but

in petroleum refining terminology the term alkylation is used for the reaction
of low molecular weight olefins with an isoparaffin to form higher molecular
weight so araffins Although this reaction is simply the reverse of cracking,
where as that of paraffin hydrocarbons are chemically inert and belived to be
delayed in its discovery until 1935. Although alkylation can take place at high
temperatures and pressures without catalysts, the only processes of
commercial importance involve low temperature alkylation conducted in the
presence of either sulfuric or hydrofluoric acid. The reactions occurring in both
processes are complex and the product has a rather wide boiling range. By
proper choice of operating conditions, most of the product can be made to fall
within the gasoline boiling range with motor octane numbers from 88 to 94
and research octane numbers from 94 to 99.

Alkylation of olefins was developed to improve the octane of aviation

gasoline.Catalyst: aluminum chloride
• FCC significantly increased the production of light ends. High
concentration of the C2, C4, & C5 isomers, both olefinic & paraffinic which
led to development of both catalytic polymerization and
alkylation.Processes are used to make gasoline components from
materials that are too light to otherwise be in gasoline.
• Alkylation forms a longer chain highly branched isoparaffin by reacting
an alkyl group ( isobutane) with a light olefin ( butylene). This process
produces high-octane gasoline.
• Polymerization is the formation of very short chains product is nearly all
olefinic high research octane but moderate motor octane number.
Sulfuric acid, hydrogen fluoride, and aluminum chloride are the main
catalysts used commercially. Sulfuric acid is used with propylene and
higher- boiling feeds, but not with ethylene because it reacts to form
ethyl hydrogen sulphate and a suitable catalyst contains a minimum of
85% acidity. The acid is pumped through the reactor and forms an air
emulsion with reactants. The emulsion is maintained at 50% acid. The
rate of deactivation varies with the feed and iso-butane change rate.
Butene feedstocks cause less acid consumption than propylene feeds.
Aluminum chloride is not widely used as an alkylation catalyst , but when
employed hydrogen chloride is used as a promoter and water is injected
to activate the catalyst .
• The form of catalyst is an aluminum chloride–hydrocarbon complex, and
the aluminum chloride concentration is 63% to 84%. The advantage of
hydrogen fluoride is that it is more readily separated and recovered from

310
 the resulting product. The usual concentration is 85% to 92% titratable
acid, with about 1.5% water.

Sulfuric Acid Alkylation

• A consortium of major refiners and contractors developed process with

sulfuric acid as the catalyst.
• Sulfuric acid alkylation required access to acid regeneration on a large
scale.
▪ Most sulfuric acid alkylation plants were located on deep water for
barge transport of spent acid to regeneration at acid plants &
return of fresh acid.

HF Acid Alkylation
• Phillips Petroleum & UOP developed process using hydrofluoric acid as a
catalyst.
▪ HF could be readily regenerated in alkylation plant facilities.
▪ No need to transport catalyst in large quantities for regeneration.
• HF alkylate in general was not quite as high quality as sulfuric acid
alkylate.

Feedstocks

• Olefinic stream from the catalytic cracker.

▪ Butylene is the preferred olefin since it produces the highest
octane number & yields.
▪ Isobutane & isopentane can be reacted with the olefin- Isopentane
not usually used since it is a good gasoline blend stock.
• High octane number & low vapor pressure.
• Catalytic cracker feed contains significant sulfur.
▪ Treating unit often precedes alkylation unit.

Products

• Alkylate desirable component for high performance automotive fuels.

▪ Very high octane index (R+M)/2 of 95.
▪ Low vapor pressure.
▪ Vapor pressure is adjusted for final boiling point.
▪ IBP adjusted for addition of normal butane.
▪ Low sulfur levels.

311
 ▪ Essentially no olefins, benzene or aromatics.
• Contributes large volume to the gasoline pool (19% vol).
▪ Catalytic cracker (34% vol).
▪ Reformer (28% vol).
▪ Isomerization unit (15% vol).

Process Chemistry

• Propylene, butylene, & pentenes are olefins used —butylene preferred.

▪ High octane isooctane alkylate produced.
▪ Lower reactant consumption.
• Alkylation reactions have complex mechanisms & it may produce many
different varieties.

Alkyaltion and Polymerisation Reaction[5-15]

• Formation of tert-butyl carbonium ion:

312
Operating Variables & Their Effects
• Capacity is expressed in terms of alkylate product, not feed capacity.
• Most important variables are type of olefin (Propylene, butylene, or
pentene), Isobutane concentration, Olefin injection & mixing, Reaction
temperature, and Catalyst type and strength.The critical measures for
success is based on the Alkylate octane number, volume olefin and
isobutane consumed per volume of alkylate produce, degree of
undesirable side reactions, and acid consumption.

These effects are briefly discussed below:

• Type of Olefin
• Butylene is preferred.
▪ Produces the highest isooctane levels.
▪ Resulting Research Octane Numbers of 93-95 (with
isobutane).
▪ RON and MON are about equal for alkylation.
▪ Amounts of butylene consumed per alkylate produced is the
lowest.
▪ Side reactions are limited.
• Propylene is worse.

313
 ▪ Octane numbers are low (89-92 RON).
▪ Propylene and acid consumption are high.
• Pentene results are mixed.
▪ Side reactions are frequent

• Isobutane concentration.
• Excess isobutane required —normal volume ratio of isobutane to
olefin in the feed is 6-10.
▪ Limited isobutane solubility in acid phase.
▪ Olefins need to be surrounded by isobutane exposed to acid
— if not, olefins will polymerize instead of alkylate.
• Newer plants have multi injection and vigorous mixing systems.
▪ Effect of isobutane is expressed in terms of concentration in
the reaction zone
▪ Isobutane to olefin ratios maintained at 10,000 to 1.

• Isobutane/Olefin Injection and Mixing.

• More important in sulfuric acid systems.
▪ Acid viscosity at operating temperatures.
• Provide optimal reaction conditions for the very fast reaction.
▪ Inject olefin feedstock in incremental fashion to increase
isobutane/olefin ratios
▪ Newer plants designed for multi-injection locations into an
agitated emulsion to disperse olefin as rapidly as possible.
• Systems with single point injection can easily have an overload of
olefin in the emulsion.
▪ Leads to lower quality & higher acid consumption from
esterification reactions.

• Reaction Temperature
• Most noticeable variable in both reaction systems.
• Increasing temperature reduces octane number.
▪ HF systems run at 35oC.
▪ Sulfuric acid systems run at 7oC.
▪ Often employ auto refrigeration of the reactant mass to
provide coolant for the reactors.

• Acid Type and Strength

• HF acid strength is not an important variable in the range of 80%
to 95%.
• Sulfuric acid strength is somewhat a function of the diluent.
▪ Water lowers acid activity 3 to 5 times as fast as
hydrocarbon diluents.

314
 ▪ Acid is considered "spent" at around 88% sulfuric acid.

Sulfuric vs HF Acid Alkylation[1-2,5-19]

• Principal difference is operating temperature.
▪ Sulfuric acid alkylation — refrigeration required
▪ HF alkylation – can operate at cooling water temperatures.
• Sulfuric acid alkylation is dominant process.
• Sulfuric acid plants require extensive recuperation of the spent
acid—generally done off site.
• Larger coastal refiners tend to have sulfuric acid alkylation plants
with barge or short haul transportation to acid regeneration
facilities.
• HF plants generally smaller and catalyst regeneration is done inplant
with a small acid makeup.
▪ Urban community concerns to hazards of HF escape.

Table:7.1

Operating conditions in Alkylation

Variables H2SO4 HF

Iso butane concentration

40-80 30-80
(Vol.%)

1200- 500-
Total HC contact time (s)
1800 1200

Temperature(oC) 2-16 16-46

Acid(Concentration wt.%) 88-95 80-95

Acid in emulsion (vol.%) 40-60 25-80

Polymerization: Objectives, process, Reactions,catalysts and effect

of process variables.

Polymerisation[1-2,14-21]
Polymerization is a process in which a substance of low molecular weight is
transformed into one of the same composition but of higher molecular weight,

315
maintaining the atomic arrangement present in the basic molecule. It has also
been described as the successive addition of one molecule to another by
means of a functional group, such as that present in an aliphatic olefin. In the
petroleum industry, polymerization is the controlled process by which olefin
gases are converted to liquid condensation products that may be suitable for
gasoline (hence polymer gasoline, polymerate) or other liquid fuels. The
feedstock usually consists of propylene, propene (CH3-CH=CH2), and
butylenes (butenes, various isomers of C4H8) from cracking processes or
might even be selective olefins for dimer, trimer, or tetramer production:

nCH2=CH2-->H-(CH2CH2)n-H

In this process, n is usually 2 (dimer), 3 (trimer), or 4 (tetramer); the

molecular size of the product is limited to give products boiling in the gasoline
range constituents. Thus, in polymerization all attempts are made to
terminate the reaction at the dimer or trimer (three monomers joined
together) stage. The four-carbon to twelve-carbon compounds that is required
as the constituents of liquid fuels are the prime products. Polymerization may
be accomplished thermally or in the presence of a catalyst at lower
temperatures. Thermal polymerization is regarded not as effective as catalytic
polymerization but has the advantage that it can be used to polymerize
saturated materials that cannot be induced to react by catalysts.
The process consists essentially of vapor-phase cracking of, say, propane and
butane followed by prolonged periods at high temperature (51 oC to 59oC)for
the reactions to proceed to near completion. On the other hand, olefins can
be conveniently polymerized by means of an acid catalyst. Thus, the treated
olefin-rich feed stream is contacted with a catalyst (sulfuric acid, copper
pyrophosphate, or phosphoric acid) at 15oC to 22oC and 150 to 1200 psi,
depending on feedstock and product requirement. The reaction is exothermic,
and the temperature is usually controlled by heat exchange. Stabilization and
fractionation systems separate saturated and unreacted gases from the
product. In both thermal and catalytic polymerization processes, the feedstock
is usually pretreated to remove sulfur and nitrogen compounds.

Polymerization ties two or more olefins together to make polymer gasoline.

The double bond in only one olefin is changed to a single bond during each
link between two olefins. This means the product will still have a double bond.
For gasoline, these polymer stocks are good for blending because olefins tend
to have higher octane numbers than their paraffin homologs. However, the
olefinic nature of polymer gasoline can also be a drawback. During long
storage in warmer climates, the olefins can continue to link up to form bigger
molecules of gum and sludge. This effect, though, is seldom important when
the gasoline goes through ordinary distribution systems.

316
Thermal polymerization is regarded not as effective as catalytic polymerization
but has the advantage that it can be used to polymerize saturated materials
that cannot be induced to react by catalysts. The process consists essentially
of vapor-phase cracking of, say, propane and butane followed by prolonged
periods at high temperature (50oC to 59oC) for the reactions to proceed to
near completion.

Polymerization reaction and operating condition[1-2,20-27]

Typical Operating conditions for polymerisation reaction are as follows:

T: 175-240 0C,P:400-1500 psia, space velocity:l/kg-h

SOLID PHOSPHORIC ACID CONDENSATION[1-2]

The catalytic polymerization process operates upon olefin-containing gases at

70C and 200 pounds pressure, producing a liquid boiling in the gasoline range.
Catalytic dehydrogenation of paraffin gases such as propane and butanes
takes place at 350oC. and atmospheric pressure with a yield of over 90 per
cent olefins. Comparison of the various methods of producing gasoline from
propane and butanes shows that two steps are desirable-( 1) dehydrogenation
to produce olefins that readily polymerize and (2) catalytic polymerization of
these olefins. The mildest operating conditions and maximum yields of
polymer gasoline are obtained when each of these operations is carried out
under its respective optimum conditions in the presence of catalysts.
The catalytic gas polymerization process of the UOP operates on olefin-
containing gases. The source of these gases may be the cracking process or
the catalytic dehydrogenation or cracking of propane butanes into olefins. The
liquid product from the polymerization process - within the gasoline range
and. As produced, has an octane rating of 80 to 83 or, on a blending basis, an
octane number up to 135, depending upon the percentage used in the blend
and the octane rating of the gasoline to which it is added. The catalytic
polymerization process is carried out to polymerise selectively the isobutene
present to isooctane in which, it hydrogenation to yield 95 to 100 octane
gasoline. Olefins can be conveniently polymerized by means of an acid
catalyst. Thus, the treated olefin-rich feed stream is contacted with a catalyst

317
(sulfuric acid, copper pyrophosphate, or phosphoric acid) at 15oC to 22oC and
150 to 1200 psi, depending on the feedstock and the desired product(s). The
reaction is exothermic, and temperature is usually controlled by heat
exchange. Stabilization and fractionation systems separate saturated and
unreacted gases from the product. In both thermal and catalytic
polymerization processes, the feedstock is usually pretreated to remove sulfur
and nitrogen compounds. This process converts propylene and butylene to
high-octane gasoline or petrochemical polymers.

Fig:7.4 process converts propylene and butylene to high-octane

gasoline or petrochemical polymers

Lube oil processing:propane deasphalting Solvent extraction,

dewaxing,Additives production from refinery feedstocks.[1-4]

Solvent selection criterion:

Y = extract
X = Raffinate
B = aromatics
A = Non aromatics

318
Solvent power -> should have high power for aromatics would lead to
lower S/F for given aromatics extraction capability.
Solvent Power generally decreases with increasing selectivity.
T increases the solvent power (exception is propane deasphaltive).
Corrosion -> It should not be corrosive.
Liquid SO2 (for H2O extraction)
70.05 wt% H2O causes severe corrosion.

Toxicity = should not be toxic

• Liquid SO2 need replacement with H2O solvent.
• Phenol extraction of lubes is being displaced by NMP.

Melting point(MP):

MP should be lower than ambient temperature for easy handling.

Interfacial Tension (IFT)[2-6]

▪ High IFT permits rapid settings due to easier coalescence.
▪ Low IFT facilitates dispersion (drops are smaller and more interfacial
area for mass transfer) whereas too low IFT lead to emulsification
and coalescence.
▪ Density difference between disperse and continuous phase S must
be large for ease of setting of phases.
▪ Viscosity: High viscosity of either phase reduces master efficiency.
▪ Low viscosities are preferred for rapid setting of phases ( more
viscosity phase is usually dispersed).
▪ Low viscosity is preferred for ease of pumping.

Dewaxing:

Waxes are large MW Paraffinic compounds having melting point 32- 100
°C.
High viscosity Index lube oil cuts: contain large amount of wax.
• Lower wax content: lower the pour point
• Dewaxing is done to lower the pour point.
• All heavy fraction of crude oil contains at least some amount of waxy
material.
• Waxes: It can not be distilled as it boils in the range of lubricating
oils( can not be distilled)
• Classified based on penetration index and melting point

319
Dewaxing Process:[6-12]
1. Chilling and Pressing (Filteration).
2. Solvent Dewaxing.
3. Urea Dewaxing- Urea forms complex compound with large chain
paraffin i.e wax range higher molecular weight of HCs but not within
the lubrication oil ( some m.w paraffins).

Dewaxing method without soluent (chilling and pressing)

Dewaxing method is simple process but time consuming.Based on the
principle of decreases solubility of wax in cold setting process.
Dilutant such as naphtha added to speed setting.
1. Paraffins wax cannot be separated by setting on certifying.
2. Filteration can be used.

Cold pressing
T= -17 °C (O° F)
P=35°C to 300°C

For microcrystalline wax cold pressing cannot be used because these wax
either pass through filter on may clog it.
Lighter change-Pressing.
Heavier change-Setting.

Solvent dewaxing :[9-15]

Most widely used solvent are MEK or propane .
Expensive process for separating lube oil.

MEKDewaxing:Twocomponents
Aromatic components – benzene or Toluene Maintains good oil solubility
and Dewaxing temperature.Ketone (MEK) – used to maintain wax
solubility. It Causes the wax to solidify in a easy of filterable form.In
absence of MEK , it spread between filtration temperature and pourpoint
of dewaxed oil.
Solvent concentration: Maximum MEK concentration required in order to
obtain highest filtration rate.

Iso dewaxing:[6-12,16-18]
• Isomerizes a significant portion of the wax to lubes.
• Selective for mid distillates By products.
• Isodewaxing has a VI and yield advantage.

320
 Fig:8.1 Propane Dewaxing

Propane Dewaxing: Same as MEK.Propane is cheaper easily available.

321
Urea Dewaxing:[1-2,16-19]
Urea forms solid filterable complex ( adducts) at room temperature with
large paraffic ( > C18 ) HCs with no branching. To increase the rate of
adduct formation some activator ( methanol) is added.

Urea Dewaxing is more effective with lighter stocks.

Fig:8.2 Urea Dewaxing

Additives:
• VI improver ( poly isobutlene, poly methyl methacrlyates (PMMA)
• Pour point depressants ( Poly alkylated condensed aromatics).
• Anti oxidants – phenols, N compounds.
• Detergency dispersants – alkyl phosphates, petroleum sulfonates.

Iso Dewaxing:

Advantages of Iso dewaxing Technology:

• Has much lower capital and OP cost than solvent dewaxing.
• Give higher VI base oils than solvent and catalytic dewaxing.
• Has flexibility to handle or broad range of wax content in feed.

322
 • Increases lube yields and extends catalyst life in Lube
hydrocrackers.
• Can produce ultra low pour point base oils.

Iso Dewaxing Process Conditions (depend on feed and product

requirement)

LUBE OIL PROCESSING

The lube oil base stocks are prepared from selected crude oils by
distillation and special processing to meet the desired qualifications. The
additives are chemicals used to give the base stocks desirable
characteristics which they lack or to enhance and improve existing
properties. The properties considered are:

1. Viscosity
2. Viscosity change with temperature (vicosity index)
3. Pour point
4. Oxidation resistance
5. Flash point
6. Boiling temperature
7. Acidity (neutralization number)

Viscosity index is the most important characterisitics of a lube oil. It is

defined as the rate of change of viscosity with temperature is expressed
by the viscosity index (VI) of the oil. The higher the VI, the smaller its
change in viscosity for a given change in temperature. The VIs of natural
oils range from negative values for oils from naphthenic crudes to about
100 for paraffinic crudes. Specially processed oils and chemical additives
can have Vis of 130 and higher. Additives, such as polyisobutylenes and
polymethacrylic acid esters, are frequently mixed with lube blending
stocks to improve the viscosity– temperature properties of the finished
oils. Lube oil blending stocks from paraffinic crude oils have excellent
thermal and oxidation stability and exhibit lower acidities than do oils from
naphthenic crude oils. The neutralization number is used as the measure
of the organic acidity of an oil; the higher the number, the greater the
acidity.

Lube oil treatment[1-4,20]

The first step in the processing of lubricating oils is the separation of the
crude oil distillation units for the individual fractions according to viscosity
and boiling range specifications. The heavier lube oil raw stocks are
323
 included in the vacuum fractionating tower bottoms with the asphaltenes,
resins, and other undesirable materials. The raw lube oil fractions from
most crude oils contain components which have undesirable
characteristics for finished lubricating oils. These must be removed or
reconstituted by processes such as liquid–liquid extraction, crystallization,
selective hydrocracking, and/or hydrogenation. The undesirable
characteristics include high pour points, large viscosity changes with
temperature (low VI), poor oxygen stability, poor color, high cloud points,
high organic acidity, and high carbon- and sludge-forming tendencies.

The processes used to change these characteristics are:

1. Solvent deasphalting to reduce carbon- and sludge-forming
tendencies
2. Solvent extraction and hydrocracking to improve viscosity index
3. Solvent dewaxing and selective hydrocracking to lower cloud and
pour points
4. Hydrotreating and clay treating to improve color and oxygen
stability
5. Hydrotreating and clay treating to lower organic acidity

Sulphur Recovery Process:-[1-4]

Major cause of air pollution because of S compounds

HDS to H 2S can be converted to S.
S recovery process from acid gas (H2S).

Claus process :- H2S oxidation process)

Overall reaction H2S + 1/2 O2 -> S + H2O

In two step:
H2S+3/2 O2-> SO2 + H2 O
2H2S+SO2 3S+2H2O Clave reaction exothermic
As 22% solution of KOH in water.For maximum sulphur recovery H2S/SO2 mole
reaction. S recovery efficiency for 3 cascade reactor stage is 96-97% With rich
acid gas feed(~50%H2S) reaction became exothermic where T reactor ~
1200oC(thermal process)

Clause Process :-

Work well for gas strem containing greater than 20% H2S(by value) and less
than 5% HCS .When reaction is.

324
 1. Heat is recovered from the reaction gases in the waste heat boiler by
generating high pressure steam.
2. Reaction gases leaving the waste heat boiler are then passed to a
condenser where cooling to 150-190oC result in condensation to
elemental S formula.
3. The gases containing unconverted H2S passed to a reactor containing
bed of bauxite cat.
4. Finally waste gases are incinerated to oxidize the last traces of H2S and
elemental S and then vented to atmosphere via stack.

Total S recovery with the subsequent class stages ranges from 94 to 96

percent.Complete conversation of H2S to SO2 elemental sulphur is not possible
due to thermodynamic chemical equilibrium of class reaction. Selective
oxidation of H2S to sulphur can be thermodynamically complete by reaction:
H2S +1/2 O2 S+H2O
Series of proprietary catalyst for direct oxidation of H2S to elemental S are
used (Hi activity process).

Sweetening process

Alkyl & aromatic mecaptans :-

Important S compounds distributed in petroleum products.Cause foul odour
oxidative determination towards metals. Also mercaptans cause oxidation
determination as well as inhibit the performance of various
additives(TEL,antioxidants) in finished products.Removal of is essential
(sweetening process).

Mercaptas removal Process

1. Caustic scrubbing, merox extraction.
2. Convation of mercaptous to disulfide include doctor sweetenies ,merox
sweetening ,copper chloride sweetening.
3. Acid treating ,clay treating ,catalytic process.

Doctor 2 Sweetening-A

Feed:All naphthas.
mercaptan level :no limits.
Very versatile process.
Disadvantages:Polysulfide formation

Copper Sluxry :[1-2,5-8]

325
Feed :Most cracked & straight from napththas . mercaptons level = up to
0.04%

Doctor Treating Process:

(Also caleed sodium plumbite treating)Na2PbO2.

Doctor solution:Active reagent sodium plumbite in aqueous caustic
soda.Doctor solution reacts with mercaptans to form lead mercaptides
.Sulphur reacts and leads mercaptides and gives disulphide’s and lead
sulphide.Lead sulphide is regenerated by air , NaOH to sodium plumbite again.
Disadvantage :Difficulty of controlling poly sulphide formation , which
reduces octane number,gum content and color stability.

Reaction Involved:
▪ PGO + 2NaOH -> Na2PGO2 + H2O
▪ 2RSH + Na2PGO2 ->(RS)2p +2NaOH
▪ (RS)2PG + S -> R2S2 +PGS

Aesenuation def:
PGS + 2NaOH +1/2 O2->-> Na2PGO2 +S + H2O

Coppa Chloride Sweetening

Used to sweeter gasoline and kerosene by direct oxidation of mercaptons to

disulfides by direct oxidation of mercaptans to disulfides by using cupric
chloride oxidation as oxidizing agents.
Fundamental reaction invalid are:
▪ 2RSH + CuCl2 -> (RS)2 Cu + 2HCL.
▪ (RS)2 CU + CuCl -> RSSR + Cu2Cl2
▪ Cu2Cl2 + 2HCL -> C42CL2 2HCL
▪ Cu2 Cl22HCL + ½ O2 -> 2C4Cl2+H2O

Water produced must be removed continuously to maintain connect reaction

condition.

Advantage:
No loss of octane no.

Alternative source of Energy[3-4]

326
• Due to world population growth and the advance of technologies that
depend on fossil fuels, reserves of fossil fuel eventually will not be able
to meet energy demand.
• Energy experts point out that reserves are less than 40 years for
petroleum, 60 years for natural gas and 250 years for coal.
• Fossil fuel costs are likely to increase in the near future. This will allow
renewable energy sources such as solar, wind, hydrogen, etc., to be
utilized.

Ethanol Production From Sugar Crops

Fig:9.1 Ethanol Production From Sugar Crops[4-9]

Table:9.1
Properties Of Conventional and Alcohol Fuels
Characterstics Diesel Gasoline Methanol Ethanol

Energy
42.5 44.0 20.0 26.9
Content(MJ/Kg)

140-
Bioling Point,oC 37-205 65 78
360

Reaserch
- 87-98 106 107
Octane No

327
 Motor Octane
- 80-90 92 89
No

Cetane No 45-55 0-5 5 5

Emissions with Ethanol Gasoline Blends

Fig:9.2 Emissions with Ethanol Gasoline Blends[8,9]

Ethanol as Transport Fuel[3-7,9-14]

Ethanol Advantage as Transport Fuel

• Octane Enhancer
• No engine modification required for E10 and lower blend
• Higher compression operation of the engine feasible

Environmental Benefits
• Lower emission of CO,VOC and Hydrocarbons
• Lower CO2 emission with higher compression ratio
• Complete CO2 cycle
• Higher biodegradability and low toxicity

5% Ethanol blending in gasoline is mandatory in india.

Further,BIS is examining the issues related to E10 blending.

CO2 Cycle of Ethanol Production From Sugarcane

328
 Fig:9.3 Cycle of Ethanol Production From Sugarcane

Observation of Physico-Chemical Properties of Blend

• Octane number of gasoline increases with ethanol blending which offer

apportunities to refineries for reducing benzene and MTBE.
• Copper impurity in the anhydrous ethanol act as precursor for oxidation
of the blend.
• Additional dosage of anti-oxidants will be required to meet potential
gum specification and engine deposit formation.
• Addition of corrosion inhibitor required as blend have been reported to
cause problem on carburetor needles of two wheelers.

BIO-DIESEL[7-9]

329
 Biodiesel is a monoalkylester of long
chain fatty acids produced from the
trans-esterification reaction of
vegetables oils with alcohol in
presence of catalyst and can be used
as a fuel.

Fig:9.4

BIODIESEL-Fuel From Oil Crops

Feed Stocks
Rapeseed Oil
Palm Oil (Malaysia)
(Europe)
Sunflower Oil (Italy & Linseed,Olive Oil
France) (Spain)
Soybean Oil (USA & Jatropha & Karanjia
Brazil) (India)
Production Process:Transesterification Path

. High Cetane

. Better Lubricity

. No Sulphur

. Can be directly used in

Fig:9.5 diesel engine

330
 .
Environment Friendly

.
Complete CO2Cycle

Table:9.2 Transesterification Reaction for Biodiesel Production[8,9]

Wide Global Acceptance of Biodiesel

• Zero Emissions
• By leading automobile manufacturers Audi, BMW, Kubota, Massey-
fergusan, Mercedes-Benz, Nissan Peugeot, Renault, Skoda,
Volkswagen,Volvo etc.
• By the Fuel Trade:Chevron-Texaco,Shell,TOTAL,Exxaon Mobile,BP etc
• By end user enterprises:Bus companies,taxi-fleets,forestry
enterprises,railroad,boat owners etc

Raw Material for Biodiesel Production

• Rapeseed Oil (Europe)

• Sunflower Oil (Italy & France)
• Soybean Oil (USA & Brazil)
• Palm Oil (Malaysia)
• Linseed,Olive Oil (Spain)
• CottonSeeds oil(Greece)
• Jatropha & Pongamia (Karanja) in India
• Jatropha (Nicaragua & SouthAmerica)

331
 Impact of Bio-diesel on Emissions

Fig:9.6 Impact of Bio-diesel on Emissions

2nd Generation Biofuels[3-6]

• 2nd generation biofuels have high emissions reduction potential.

• Biomass to be used include woody crops and grasses(not competitive
with food crops).
• High yield/Hectare as compare to first generation biofuels (BTL>3100
L/HC oo HSD equivalent)
• BTL result in designer fuels compatible with new technologies
• Technology option for 2nd generation fuels:
• Direct fired combustion
• Gasification
• Pyrolysis
• Cofiring

Various Biomass Conversion Technologies

332
 Fig:9.7 Various Biomass Conversion Technologies

Hydrogen as Future Fuel

• Available from water using non petroleum fossil fuel or renewable

energy resourse.
• Recycle rapidly and cleanly from hydrogen to water.
• Clean burning-potiential enviornmental benefits.
• Provides High efficiency energy conversion process
• Compatiable with all energy uses.

Table:9.3
Compansion of key properties for hydrogen and other
fuels
Specific
Energy Per Energy Per
Motivity Carbon
Fuel type Unit Unit
Factor Emission(kg
Mass(j/kg) Volume(j/m3)
C/kg fuel)

Liquid
141.90 10.10 1.00 0.00
Hydrogen

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 Gaseous
141.90 0.013 1.00 0.00
Hydrogen

Fuel Oil 45.50 38.65 0.78 0.84

Gasoline 47.50 34.85 0.76 0.86

Jet Fuel 46.50 35.30 0.75 -

LPG 48.80 24.40 0.62 -

LNG 50.00 23.00 0.61 -

Methanol 22.30 18.10 0.23 0.50

Ethanol 29.90 23.60 0.37 0.50

Bio diesel 37.00 33.00 - 0.50

Natural
50.00 0.04 0.75 0.46
gas

Charcol 30.00 - - 0.50

Current & Future Hydrogen Production Options[8-9]

Thermal Processes
Reforming of Natural Gas/Naptha
Gasification of Extra Heavy Oil /Coal/Biomass
High-Temperature Water Splitting

Eletrolytic Processes
• Electricity from renewable sources like wind,solar,hydel etc.

Photolytic Processes
• Photobiological Water Splitting
• Photoelectrochemical Water Splitting

Other Options
• Chlor-Alkali Plants
• Co-generation electricity from Bagasse at sugar mills

H2PRODUCTION-GASIFICATION OPTION

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 Fig:9.8 H2 PRODUCTION-GASIFICATION OPTION
Fuel Cells[18-19]

• Fuel cell is essentially a battery that does not need recharging. As long
as hydrogen and oxygen fuel are supplied, it can continue to supply heat
and an electrical current indefinitely.
• Fuel cell consists of an electrolyte(a conductor of charged particles)
between an anode(negatively charged electrode)and a cathode (a
positively charged electrode).
• Once activated by a catalyst, the hydrogen gas separates into protons
and electrons, and the electrons are conducted through a wire, forming
an electrical current.
• The protons move through the electrolyte, where they combine with
oxygen and other electrons to produce heat and a water by product.

FUEL CELL [18-22]

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 Fig:9.9 Fuel Cell

Fuel Cell Benefits[18-22]

Zero Emissions
High Efficiency
Enviornmentally Benign
Quiet and Quick and Easy Refueling
Wide Range of Operating Temperatures
Minimal Maintainence
Reliability and Quick Startup
Load Following
Ultimate Solution for Hydrogen Commercialization

Pollution control in Refining[22-24]

A petroleum refinery is generally considered as a single energy object, the

energy efficiency of which is approximately17 -20%. This is primarily due to
the inadequate utilization of secondary energy resources in the process units
(30-35%) and the almost complete loss of low-potential heat. To do enhance
the energy recovery , energy-technological schemes must be introduced more
widely, process units must be fitted with boiler utilizers, the energy from liquid
and vapor streams must be used to produce electric power, and the
efficiencies of heat exchange equipment must be increased. A considerable
fuel saving can be achieved by the use of low-potential heat in heat pumps.

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Possibilities are available for the reduction of discharges of sulfur dioxide,
hydrogen sulfide, and other sulfur compounds that pollute the biosphere.
Coming into petroleum refineries every year along with the crude oil is up to
five million metric tons of sulfur, which is a raw material in short supply for
the production of sulfuric acid. However, thus far no more than 10% of this
sulfur has been recovered from petroleum. The remain'rag sulfur either passes
into the petroleum products, is partly burned in flares with the acid gases, is
discharged to the atmosphere, or is dissolved in the wastewater. On the
average, in the combustion of medium- sulfur fuel in tube furnaces, the
combustion of product vapors in flares, and the burnoff of coke in catalytic
cracking units, theprocessing of one metric ton of crude oil results in the
discharge of up to 14 kg of sulfur dioxide and 0.23 kg of hydrogen sulfide to
the atmosphere.

Sources of waste water generated from Refineries[22-25]

Refinery waste waters can be characterized as:-

▪ Cooling Towers
▪ Boiler Feed water treatment units
▪ Process Units
▪ Desalter brine
▪ Tank Farms
▪ Chemical waste
▪ Sanitary and miscellaneous use
▪ Fire protection

The capacity of the environment to absorb the effluents and other impacts of
process technologies is not unlimited, as some would have us believe. The
environment should be considered to be an extremely limited resource, and
discharge of chemicals into it should be subject to severe constraints. Indeed,
the declining quality of raw material s, especially petroleum and fossil fuels
that give rise to many of the gaseous emissions of interest in this text, dictates
that more material must be processed to provide the needed fuels .

Oil from subterranean and submarine reservoir extraction can be

environmentally damaging. Crude oil and refined fuel spills from tanker ship
accidents have damaged fragile ecosystems. Burning oil releases carbon
dioxide into the atmosphere, which contributes to global warming. Thus, both
the production and processing of crude oil involve the use of a variety of
substances, some toxic, including lubricants in oil wells and catalysts an d
other chemicals in refining. The amounts used, however, tend to be small an

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d relatively easy to control. M ore detriment al to the environment is the
spillage of oil, which has been a particularly common event.

Minor losses from truck and car accidents can affect rivers and streams.
Leakage from underground gasoline storage tanks, many abandoned decades
ago , has contaminated some local water sup plies and usually requires
expensive operation s either to clean or seal off. Both the production and
processing of crud e oil involve the use of a variety of substances, some toxic,
including lubricants in oil wells and catalysts and other chemic also in refining.
The amounts used, however, tend to be small and relatively easy to control.
More detrimental to the environment is the spillage of oil, which has been a
particularly common event.

Minor losses from truck and car accidents can affect rivers and streams.A
pollutant is a substance present in a particular location (ecosystem) when it
is not indigenous to the location or is present in a greater-than-natural
concentration. The substance is often the product of human activity.

Pollutants are subdivided into two classes: primary and secondary.

Source -> Primary pollutant -> Secondary pollutant

GASEOUS EMISSIONS[24-26]

Gaseous emissions from petroleum refining create a number of environmental

problems.During combustion, the combination of hydrocarbons, nitrogen
oxide, and sunlight results in localized low-levels of ozone, or smog. This is
particularly evident in large urban areas and especially when air does not
circulate well. Petroleum use in automobiles also contributes to the problem
in many areas. The primary effects are on the health of those exposed to the
ozone, but plant life has been observed to suffer as well.Refinery and natural
gas streams may contain large amounts of acid gases, such as hydrogen
sulfide (H2S) and carbon dioxide (CO2).

Hydrogen chloride (HCl), although not usually considered to be a major

pollutant in petroleum refineries can arise during processing from the
presence of brine in petroleum that is incompletely dried. It can also be
produced from mineral matter and other inorganic contaminants and is
gaining increasing recognition as a pollutant which needs serious attention.
Acid gases corrode refining equipment, harm catalysts, pollute the
atmosphere, and prevent the use of hydrocarbon components in
petrochemical manufacture. When the amount of hydrogen sulfide is large, it
may be removed from a gas stream and converted to sulfur or sulfuric acid.

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Some natural gases contain sufficient carbon dioxide to warrant recovery as
dry ice, that is, solid carbon dioxide. And there is now a conscientious effort
to mitigate the emission of pollutants from hydrotreating process by careful
selection of process parameters and catalysts.

The terms refinery gas and process gas are also often used to include all of
the gaseous products and by-products that emanate from a variety of refinery
processes. There are also components of the gaseous products that must be
removed prior to release of the gases to the atmosphere or prior to use of the
gas in another part of the refinery, that is, as a fuel gas or as a process
feedstock. In addition to the gases obtained by distillation of petroleum, more
highly volatile products result from the subsequent processing of naphtha and
middle distillate to produce gasoline.Hydrogen sulfide is produced in the
desulfurization processes involving hydrogen treatment of naphtha, distillate,
and residual fuel; and from the coking or similar thermal treatments of
vacuum gas oils and residual fuels. The most common processing step in the
production of gasoline is the catalytic reforming of hydrocarbon fractions in
the heptane (C7) to decane (C10) range.

Natural gas is also capable of producing emissions that are detrimental to the
environment. While the major constituent of natural gas is methane, there are
components such as carbon dioxide (CO), hydrogen sulfide (H2S), and
mercaptans (thiols; R–SH), as well as trace amounts of sundry other
emissions. The fact that methane has a foreseen and valuable end-use makes
it a desirable product, but in several other situations it is considered a
pollutant, having been identified a greenhouse gas.

In addition to the corrosion of equipment of acid gases, the escape into the
atmosphere of sulphur containing gases can eventually lead to the formation
of the constituents of acid rain, that is, the oxides of sulfur (SO 2 and SO3).
Similarly, the nitrogen-containing gases can also lead to nitrous and nitric
acids (through the formation of the oxides NOx,) which are the other major
contributors to acid rain. The release of carbon dioxide and hydrocarbons as
constituents of refinery effluents can also influence the behavior and integrity
of the ozone layer. Gases such as sulfur oxides (usually sulfur dioxide, SO 2)
as well as nitrogen oxides (NOx) react with the water in the atmosphere to
form acids. Acid rain has a pH less than 5.0 and predominantly consists of
sulfuric acid (H2SO4) and nitric acid (HNO3). As a point of reference, in the
absence of anthropogenic pollution sources the average pH of rain is 6.0
(slightly acidic; neutral pH 7.0).

In summary, the sulfur dioxide that is produced during a variety of processes

will react with oxygen and water in the atmosphere to yield environmentally
detrimental sulfuric acid. Similarly, nitrogen oxides will also react to produce

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nitric acid. Hydrogen chloride, if produced during refining, quickly picks up
moisture in the atmosphere to form droplets of hydrochloric acid and, like
sulfur dioxide, is a contributor to acid rain. However, hydrogen chloride may
exert severe local effects because, unlike sulphur dioxide, it does not need to
participate in any further chemical reaction to become an acid and under
atmospheric conditions that favor a buildup of stack emissions in the area of
a large industrial complex or power plant, the amount of hydrochloric acid in
rainwater could be quite high.

Liquid Effluents

Crude oil, as a mixture of hydrocarbons, is (theoretically) a biodegradable

material. However, in very general terms, petroleum is a mixture of: (a)
hydrocarbons, (b) nitrogen compounds, (c) oxygen compounds, (d) sulfur
compounds, and (e) metallic constituents. It is convenient to divide the
hydrocarbon components of petroleum into the following three classes: Crude
oil also contains appreciable amounts of organic no hydrocarbon constituents,
mainly sulfur, nitrogen, and oxygen-containing compounds and, in smaller
amounts, organometallic compounds in solution and inorganic salts in colloidal
suspension. These constituents appear throughout the entire boiling range of
the crude oil but tend to concentrate mainly in the heavier fractions and in the
non-volatile residues.

Air Quality Standards:

They are the standards that specify allowable emission.

It can either be related to:

1. Quality of the air in the surrounding atmosphere (ambient air quality) –
Useful for the protection of the health of living populations, animals and
of property.
2. Gaseous emissions from a particular unit ( emission standard) - used
for planning pollution control strategy.

Ambient Air Quality Standards:

In India, for AAQS, various areas have been classified into 3

categories:
1. Category A:covers Industrial and mixed – use areas.
2. Category B:Covers residential and Rural areas.
3. Category C:Covers sensitive areas such as sanctuaries, national parks,
hill stations etc.

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 Table: 9.4 Ambient Air Quality Standards: India

Category/ Area Concentration in micrograms/ m3

SPM SO2 NOx CO

A.Industrial & Mixed Use 500 120 120 2000

B.Residential & Rural 200 80 80 1000

C.Sensitive 100 30 30 500

Supporting Processes
• Not directly involved in the processing of petroleum based fuels
• Processes
▪ Hydrogen production and purification
▪ Gas processing units
▪ Acid gas treating
▪ Sulfur recovery
▪ Water treatment

Hydrogen Production & Purification

• Sources of hydrogen
▪ Catalytic Reformer

Majority of hydrogen used in refinery

▪ FCCU Off Gas
▪ Steam-Methane Reforming

Most common method of manufacturing hydrogen Methane, ethane, or heavy

components reformed to hydrogen, carbon dioxide, & water in a series of three
reactions .Hydrogen purity typically 90 to 95 vol%
▪ Synthesis Gas

Chemical solvent processes

• Amine sweetening (MEA, DEA, MDEA, DGA)
• Hot potassium carbonate
▪ Physical solvent processes
▪ Selexol
▪ Propylene carbonate
▪ Sulfinol

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 ▪ Rectisol
▪ Dry absorbents
▪ Molecular sieve
▪ Activated charcoal
▪ Iron sponge
▪ Zinc Oxide

..

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