Module-1

Petroleum
Petroleum Refining-The
Refining-The Basics
Basics
**CRUDE
CRUDE OIL
OILCHARACTERSTICS
CHARACTERSTICS

Petroleum Ref./Upes/GCT/July-05/ Mod-1/01

 Crude Oils

Crude oils are complex mixtures of hundreds of different

species of chemical compounds. Most of these
compounds are hydrocarbons, principally, paraffin's,
napthenes (cycloparaffins); aromatics or a combination
of these. During processing of crude oils and its cuts in
the Refinery, Olefins may also be present in some
refinery streams. It is however, generally believed that
olefins are not present in the produced crude oils but
may get produced due to decomposition during the
distillation of the crude .

Petroleum Ref./Upes/GCT/July-05/ Mod-1/02

Non-hydrocarbon content:

Principal among these is Sulfur in the form of free sulfur,

Hydrogen Sulfide, Mercaptan (RSH), Thiophene etc. Sulphur
in petroleum product causes corrosion producing sulfur Di-
oxide when burnt which is the main component of acid rain.
Sulfur is also poisonous to some catalysts. Petroleum
industry is a large producer of sulfur as a product from
treating H2S separated from petroleum products.
Nitrogen is another undesirable element occurring in crude
oil since this also is poison to some catalysts. Other catalyst
poisons include Arsenic, Vanadium and Nickel compounds
containing oxygen, notably naphthenic acid are corrosive
particularly when the process temp is 2200c-4000c and the
stream velocity is high as in nozzles, 2 phase flow line such
as transfer line and return bends.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/03

 Salts primarily chlorides, sulfates and carbonates of
sodium, calcium and magnesium are another problem
causing materials present in the crude oil. This occurs in
the crude in the form of fine droplets containing salt or
minute particles of salt. Salt in itself, causes corrosion and
fouling in the heat exchanges etc. but in combination with
Hydrogen Sulfide and Water; it can severely corrode most
carbon steels and stainless steels.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/04

Properties of Hydrocarbons and crude oil
properties
Combustibility:

1) One familiar characteristic of Petroleum products (and thus of

Hydrocarbons) is their combustibility. Flash point is the
temperature at which the liquid (hydrocarbon) generates
enough vapors to support combustion when ignited.
2) The Autoignition temperature (AIT) is the temperature at which
a vapour will ignite spontaneously (in the absence of a flame).
For example gasoline or Naphtha could ignite spontaneously
on coming into contact with a 3750C surface.
3) The upper and lower explosive limits of hydrocarbons defines
the range in which the mixture is within the flammability limits-
below the lower limit the mixture is too lean to flash-above too
rich.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/05

• Specific Gravity of crude oils:-

1) Specific gravity of crude oils and Petroleum products is

generally expressed as degrees API which is defined as:
0API= 141.5 - 131.5

Sp.gr
Lower the 0API number; heavier is the crude and vice-
versa. 0API of above 33 will qualify crude as being a light
one; between 23-330API as medium and below 230A as
heavy crudes.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/06

 K-Factor for crude characterization:
The characterization factor, KUOP, is developed by Union oil products
co. USA and defines the basic characteristics of the crude oil. This
factor correlates boiling point with specific gravity.
Kuop= (Tb)1/3
Sp.gr.
Tb=The avg. boiling point is OR (4600+0F) at 1atm and sp. Gr. Of the
oil at 15.5OC. The Avg. boiling point is obtained from ASTM distillation
curve by averaging the temperatures at 10%, 30%, 50% and 90%
volume distilled. For mixtures or blends this K- factor is additive on a
weight basis.
Values of Kuop for different classes of hydrocarbons are as follows:

Type of KUop
Hydrocarbons
Paraffin 12.5-13.0
Napthenes 11.0-12.0
Aromatics 9.0-11.0
Petroleum Ref./Upes/GCT/July-05/ Mod-1/07
 ● Sulfur in Crude oil:

Sulfur is a measure of ‘sourness’ and ‘sweetness’ of crude.

Sweet grades< 0.5 % sulfur
Sour grades> 0.5% sulfur

Petroleum Ref./Upes/GCT/July-05/ Mod-1/08

• Salt Content:

1) Salt as is contaminants in crude oil cause overhead

corrosion or fouling of heat exchangers by settling and
scaling. It is removed in desalting operation by washing
and settling.
2) Salts may vary widely in ratio of metal ions, though most
common averages are: Na-70-75%; Mg: 15-20%; Ca-10%
3) Mg is most prolific producer of HCl with Ca and Na in the
descending order.
4) Small quantities of HCl will substantially enhance corrosion
of sulfur compounds.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/09

• Sediments & Water:

1) Sediment has no relationship with salt content but both may

increase with increased formation water content.
2) Sediments-Fine particles of clay-sand, ash, mud, rust, iron-
sulfides etc.
damaging effects-plugging abrasion and residual product
contamination.
Water also causes difficulties in distillation.
3) Lower the sediments and water, higher the reliability of the
unit. It is also a major pointer for corrosive materials in crude.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/10

• Pour Point & Wax content in Crude oil:

1) Pour Point: is the temperature below which the crude may

pose problems in pumping and transportation. It is an
indication of wax present in crude oil. This property of crude
oil along with its viscosity is required to establish the
pumping characteristics of crude oil.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/11

2) Wax Content: Normal paraffins above C16 are solid at
near to ambient temperatures and are likely to affect the
flow behavior of crude. They affect the product quality of
gas oil, VGO and asphalt and will also influence the lube
manufacturing characteristics of the crude.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/12

● Asphaltenes, Carbon Residues & Ash
content:

1) Asphaltenes are generally considered as highly aromatic

materials of fairly high molecular weight. The asphaltenes
content affects the physical characteristics of Bitumen. In
fact. Bitumen can be regarded as a colloidal system
consisting of asphaltenes dispersed in lower molecular
wt, oily medium. Increasing the asphaltenes content in
this suspension-by air blowing produces harder, more
viscous bitumen with lower penetration values, higher
softening points and viscosities.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/13

● Carbon Residue:

1) Carbon residue can be defined as the amount of carbon

residue left after evaporation and pyrolysis of an oil and is
intended to provide indication of relative coke forming
tendency.
2) Carbon residue indicates the extent to which heavy
hydrocarbons are present in crude oil.
3) Either conradson method or Ramsbottom method may be
used to determine the carbon residue of petroleum
products.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/14

3) Viscosity:

It is a measure of resistance to flow and is an important

parameter for effective desalting. It is highly dependent on
temperature.
High viscosity crude require high temperatures for
effectives desalting.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/15

 ● TAN-(Total Acid Number):

TAN is a measure of total Naphthenic Acid content in the

crudes. This leads to corrosion in various sections of
the unit. Detailed metallurgical reviews and monitoring
mechanisms are needed to provide for TAN combat.

Petroleum Ref./Upes/GCT/July-05/ Mod-1/16

● CRUDE ASSAYS
Crude Assay is the details of properties of various fractions of
crude oil.
Crude Assay data are utilized for following :
• Crude oil selection
• Crude oil grading
• Crude valuation
• Crude swapping
• Crude purchasing
• Crude processing
• Refinery configuration
• Production planning
• Inventory management
• Demand / Supply gaps
Petroleum Ref./Upes/GCT/July-05/ Mod-1/17
Crude Distillation: Typical Products

• Overhead gases (mainly Methane, Ethane, Propane & Butane)

• C5-900C: Light Naphtha
• 900C-1400C: Heavy Naphtha
• 1400C-2040C: Mineral Turpentine oil
• 1400C-2400C ATF
• 1400C-2700C Kerosine
• 2700C-3400C Gas Oil
• 3400C-3660C Jute Batching Oil (JBO)

Petroleum Ref./Upes/GCT/July-05/ Mod-1/18