Application Note

Refining

Process Gas Monitoring in Petroleum Refineries

Application

Emerson offers several Rosemount Analytical gasanalyzer

technologies to meet the process control and stream purity
monitoring needs of petroleum refineries.

Background

Gasoline, jet fuel, oils, asphalt and other petrochemicals are all
derived from crude oil. Initial distillation separates crude oil into
eight component types based on boiling points. These basic
components in order of low to high boiling point include:
Gas - light ends
Gasoline
Light and heavy naphtha
Kerosene
Light and heavy gas oils
Lubes
Asphalt
Residuals - heavy ends
With gasoline typically being the major processing priority, each
component above is subjected to additional value-added processing
steps necessary to reach the desired petroleum end-product. The
value-added processing may also involve several sequential unit
operations.
A summary of these unit operations is summarized below by major
crude cuts. See Figure 1.

Gas Light Ends

The light end gases are the top cut of crude distillation. Iso and
normal butanes (C4H10) and lighter gases such as methane (CH4),
ethane (C2H6), propane (C3H8) andhydrogen (H2) are then recovered
and separated in the refinery gas plant. Typically:
Hydrogen, methane, and sometimes ethane are diverted to the
refinery fuel gas header for use in site heaters and furnaces
Ethan is used as the chemical feedstock for ethylene upon
transfer to a petrochemical complex
Propane is used for liquefied petroleum gas (LPG) sales or as the
chemical feedstock for propylene
N-butane is used for motor gasoline blending
Iso-butane is used as feedstock to the alkylation process
Iso-butane is fed with propylene and other cracked gases form
heavy gas oil to the alkylation reactor to formgasoline components.
The alkylation process occurs with a catalyst of either sulfuric or
hydrofluoric acid.

Light and Heavy Naphtha

After the gasoline distillation cut, the next major crude cut is light
and heavy naphtha. The objective of this process step is to increase
the octane value of the light naphtha stream. Gasoline components
can be converted from light naphtha streams through isomerization
units. The isomerization reaction of C4, C5 and C6 factions occurs
over a platinum catalyst.
Aromatics can be retrieved from solvent extraction of the heavy
naphtha stream after that cut is first processed in the hydrotreater
/reformer units. Heavy naphthacontains undesirable sulfur
compounds. In thehydrotreating process, steam and hydrogen are
mixed with the heavy naphtha to remove the sulfur. The majority of
the sulfur compounds, primarily hydrogen sulfide (H2S), leave with
the gas stream. The catalytic reformer process then converts the
heavy naphtha to the more desirable parrafins and aromatics.

Light and Heavy Gas Oil

After the kerosene distillation cut, the light and heavy gas oil cuts are
converted to jet or diesel fuel and heating oils. Light gas oil may also
contain sulfur. Therefore anadditional hydrotreating step is required.
The large molecules of the heavy gas oil mix (C8+) are cracked into
smaller molecules in the cracking units.

Lubes, Asphalt and Residuals

The three bottom cuts are the lubes, asphalt and residuals. The
lubes are separated first and then directed to the lube plant for final
purification and blending. Asphalt and tars are removed at the final
major cut point. Column bottoms are collected as residuals and
then directed to the coker unit. The majority of the residuals are
converted to a coke product.

Refining

Gas Analyzer Applications

In addition to the traditional multi-component process gas analyses

typically performed by a process gas chromatograph, there are a
number of single component gas measurements found throughout
the refinery site. A summary of these applications follow per major
unit operation below.

Light Naphtha Isomerization Units

A number of gas measurements assists in the process control of

isomerization units. Two popular processes are the Penex and TIP
(total isomerization process). Theobjective of these processes is to
increase the octane value of the C5/C6 factions. The reactor effluent
passes through a stabilizer unit which separates net gas hydrogen
and light ends. The isomerate or C5/C6 product continues to the
gasoline blending areas.
To meet specific environmental gasoline requirements for low
benzene levels, the Penex-Plus process was developed to remove
benzene from light reformate or naphtha streams by saturating
it with hydrogen over a metal catalyst. The Penex-Plus process
integrates the benzene saturation step with the isomerization
reaction of the Penex process.
Butane (C4) isomerization occurs in a similar process as the C5/C6
isomerization steps. A popular butaneisomerization technology
process is referred to as the butamer process.
The UOP Company of Des Plaines, IL, is a major licensor of the
isomerization and benzene saturation processes.
The reformulated fuel requirements of the Clean Air Act
Amendments of 1990 resulted in an increased project activity in
the isomerization and benzene saturation areas of the refinery.
In California, a number of refineries funded projects of this type
commonly referred to as Clean Fuel or Reformulated Gasoline
projects.
1) Hydrogen in Make-up Hydrogen Gas to Combined Feed:
Hydrogen is combined with the C5/C6 charge feed to the
isomerization reactor. Proper C5/C6: H2 ratio iscontrolled by the flow
of make-up hydrogen. The content of the make-up hydrogen may
vary depending on the operation of various hydrogen recovery units
located throughout the refinery.
A typical stream composition may consist of 70 % H2 with the
balance being hydrocarbons. The butamer process has similar
process control objectives.
Solution: Monitoring the hydrogen concentration of the make-up
hydrogen with the Rosemount Analytical X-STREAM flameproof
analyzer can assist incontrolling the proper feed ratios to the
isomerizationreactor. A typical operating range is 50 to 100 % H2 for
the penex process and 70 to 100% for the butamer process.
2) Carbon Monoxide and Carbon Dioxide in Make-up
Hydrogen Gas to Combined Feed: Hydrogen produced in
reforming operations from methane gas contains impurities
such as carbon monoxide and carbon dioxide. These impurities
can have detrimental effects to many catalyst-based reactions of
hydrocarbons such as the type found in the isomerization reactor.
Monitoring of CO and CO2 impurities can help curb these effects.

Page 2

Solution: The Rosemount Analytical X-STREAM flameproof analyzer

can meet the needs of this gas monitoring application. A typical
operating range is 0 to 100 ppm CO or CO2.
3) Hydrogen in Scrubber Off Gas to Refinery Fuel Gas Header:
Monitoring hydrogen in scrubber off gas assists in overall process
control of the unit and determines concentration levels for feed to
the fuel gas header foruse in process heaters and furnaces.
Solution: The Rosemount Analytical X-STREAM flameproof analyzer
can be used to monitor hydrogen in this application. A typical
operating range is 0 to 50 % H2. A butamer process net gas scrubber
may have an operating range of 20 to 80 % H2.

Catalytic Reforming

The upgrade of heavy naphtha into an aromatics-rich product

occurs in the catalytic reforming process. One popular technology
is the UOP Companys CCR platforming process. This process
has the flexibility to produce either aromatics for downstream
petrochemical processes or material for unleaded or reformulated
gasoline. In both cases, the process provides a conti-nuous, reliable
source of hydrogen.
The reformulated fuel requirements of the Clean Air Act
Amendments of 1990 resulted in increased project activity in the
catalytic reforming area of the refinery. In California, a number of
refineries funded projects of this type commonly referred to as Clean
Fuel or Reformulated Gasoline projects.
4) Hydrogen in Product Separator Recycle Gas: Hydrogen, in a
mixture which is 80 % hydrocarbons, is recycled to the catalytic
reformer from a product separator. Monitoring hydrogen in the
recycle gas stream assists in overall process control of the unit.
Solution: The Rosemount Analytical X-STREAMflameproof analyzer
can be used to monitor hydrogenin this application. A typical
operating range is 50 to100% H2.
Changing hydrocarbon background composition in this application
can result in a change in the total thermal conductivity of the sample
without a real change in hydrogen concentration. This effect can
result in erroneous hydrogen readings. To improve analyzer accuracy
under changing backgrounds, special calibration procedures can be
implemented.
For the application above, special zero calibration gas consisting of
the following should be utilized:

50 % Hydrogen
5 % Methane
15 % Ethane
20 % Propane
2.5 % Butanes
4 % Pentanes
1 % Hexanes
The above component proportions can be varied to match true
process conditions.

Refining
5) Hydrogen in Net Gas from Net Gas Knockout Drum: The net
gas knockout drum removes entrained liquids from the reformer gas
stream. Monitoring hydrogen in the net gas stream assists in overall
process control of the unit and determines concentration levels for
feed to the net gas fuel header and the hydrogen-user process units.
Solution: The Rosemount Analytical X-STREAM flameproof analyzer
can be used to monitor hydrogen in this application. A typical
operating range is 10 to 50 % H2.
6) Hydrogen/Hydrocarbons in CCR Nitrogen Header Gas:
Monitoring hydrogen/hydrocarbons in the OCR nitrogen header
is important for maintaining nitrogen purity and overall process
control. The control and reporting of the make-up and consumption
of hydrogen as part of the total plant balance is an important
economic consideration in a petroleum refinery.
The monitoring of hydrogen for nitrogen purity in other related
applications such as lift gas for fluidized catalytic reactions and surge
hopper vents also has similar importance to the refinery.
Solution: The Rosemount Analytical X-STREAM flameproof analyzer
can be used to monitor hydrogen/hydrocarbons in nitrogen for
these applications. The analyzer is calibrated such that 0 % response
corresponds to 15 % hydrocarbons in 85 % nitrogen, 50 % response
to 100 % nitrogen, and 100 % response to 1% hydrogen in 99 %
nitrogen.
Manual introduction of calibration gases prior to analyzer is provided
via toggle operated shut-off valves. Regulating valves maintain
calibration gas flow rate. Three calibration gas ports are provided:
1% H2 in N2 high span, 100 % N2 mid-span, and 10.5 % propane,
4.5 % butane, 85 % N2 zero gas.

Fluidized Catalytic Cracking

Heavy gas oils and other high boiling materials are selectively
converted to higher value products through the fluidized catalytic
cracking process. The units operation primarily involves reaction
with a highly active, two-stage catalyst regeneration in a fluidized
bed.
7) Carbon Monoxide and Oxygen Monitoring of the Fluidized
Catalytic Cracking Unit Regenerator Gas: The waste slipstream of
the fluidized catalytic cracking unit regenerator gas is directed to
the CO boiler for energy recovery. Monitoring of oxygen and carbon
monoxide content aids in proper boiler control and stable operation
upon a changing gas stream.

Miscellaneous Applications

8) Oxygen in Hydrocarbon Compressors: Throughout the refinery,

many hydrocarbon streams flow through compressors as feed to the
various reactors associated with a specific units operation. Air leaks
at compressor inlets and diaphragms have the potential to cause an
explosive mixture.
Solution: Emersons Rosemount Analytical X-STREAM flameproof
analyzer, suited for Class I, Division 1 areas, can monitor the oxygen
content of hydrocarbon streams to alert operations of explosivemixture potential. A typical range for this application is 0 to 25 %.
9) Total Hydrocarbons in Low Pressure Steam: Continuous
monitoring of total hydrocarbons in low-pressure steam (20 psig)
can assist in detecting leaks at counter-current process exchange
points such as heat exchangers. Critical leaks resulting from tube
failures have detrimental effects on both the process side and steam
side systems. Early warning of contamination permits corrective
action to prevent costly equipment damage.
Solution: Emersons Rosemount Analytical NGA HFID Heated
Hydrocarbon Analyzer, utilizing the flame ionization detection
(FID) methodology, is ideally suited for this application. A typical
operating range is 0 to 1000 ppm THC calibrated on methane.
10) Total Hydrocarbon and Oxygen Monitoring of Ma
rine Unloading and Vapor Recovery Operations: Unloading
hydrocarbon product at marine stations along with their associated
vapor recovery requires special safety considerations. As vessels are
emptied, filled or purged, hydrocarbon vapors have the potential
to exceed their explosion limits. On-line gas monitoring enhances
safety during these operations.
The monitoring of oxygen content in vapor during marine unloading
is required by Coast Guard Regulation 33 CFR 1544.800.
Solution: Emersons Rosemount Analytical X-STREAM flameproof
analyzer meets the THC monitoring needs for these applications.
A range of 0 to 100 % methane is a typical operating range.
The X-STREAM flameproof analyzer also meets the O2 monitoring
needs of this application. A range of 0 to 25 % O2 is the typical
operating range.

Solution: The Rosemount Analytical X-STREAM analyzer meets the

CO monitoring needs for this application. A range of 0 to 500 ppm
CO is the typical operating range.
The X-STREAM analyzer also meets the O2 monitoring needs of this
application. A range of 0 to 25 % O2 is the typical operating range.

Page 3

Refining

Continuous Emissions Monitoring

Systems (CEMS)
A number of refinery process equipment and stacks are subject to
various local and national environmental emissions regulations.
Applications typically involve fuel sources such as natural gas,
refinery fuel gas, and other process gas streams. Process equipment
may involve emissions monitoring of boilers, process heaters,
thermal oxidizers, furnaces, selective catalytic reduction units and
incinerators.
11A. Process Heater/Furnace: Nitrogen Oxides

Nitorgen Oxides (NOx)................0 to 100 ppm

Oxygen (O2)................................0 to 25 %
11B. General Boiler/FCC Stack

Nitrogen Oxides (NOx)................0 to 100 ppm

Sulfur Dioxide (SO2)....................0 to 100 ppm

Carbon Monoxide (CO)...............0 to 100 ppm

Oxygen (O2)................................0 to 25 %
11C. SRU (Sulfur Recovery Unit) Incinerator/Tail Gas Stack:

Sulfur Dioxide (SO2)....................0 to 500 ppm

Oxygen (O2)................................0 to 25%

11D. SCR (Selective Catalytic Reduction) Unit for NOx Abatement

SCR Inlet: Nitrogen Oxides (NOx)..................0 to 250 ppm

SCR Outlet: Nitrogen Oxides (NOx)..............0 to 25 ppm

Oxygen (O2).................................................0 to 25 %
Refinery CEMS Applications: Depending on the site location and
applicable environmental CEMS regulations, the following CEMS
applications may be found in a typical petroleum refinery:
Solution: Emerson can supply either an X-STREAM, MLT Series
or NGA CLD analyzer for these applications depending on type of
measurements required.

Page 4

Refining
Table 1 - Petroleum Refinery Gas Analyzer Applications
No.

Application

Analyzer Model Selection

Range

Light Naphtha Isomerization Units

1

H2 in make-up hydrogen gas to

combined feed

X-STREAM

50 to 100 % H2 (Penex)
70 to 100% H2 (Butamer)

CO and CO2 in make-up hydrogen

gas to combined feed

X-STREAM

0 to 100 ppm CO
0 to 100 ppm CO2

H2 in scrubber off gas to refinery

fuel gas header

X-STREAM

0 to 50 % H2 (Penax)
20 to 80 % H2 (Butamer)

Catalytic Reforming
4

H2 in recycle gas from product separator

X-STREAM

50 to 100 % H2

H2 in net gas from net gas knock

out drum

X-STREAM

10 to 50 % H2

H2 /THC in CCR nitrogen header; H2

in lift gas, H2 in surge hopper vent

X-STREAM

0 to 1 % H2
10 to 50 % H2

Fluidized Catalytic Cracking

7

CO and O2 monitoring of the

fluidized catalytic cracking unit
regenerator gas

X-STREAM

0 to 500 ppm CO
0 to 25 % O2

X-STREAM

0 to 25 % O2

Miscellaneous
8

O2 in hydrocarbon compressors

THC in Low-Pressure Steam

10

THC and O2 monitoring of marine

unloading and vapor recovery operations

X-STREAM

Continuous Emission Monitoring

Systems (CEMS)

X-STREAM
MLT Series
NGA CLD

NGA FID

0 to 1000 ppm THC

0 to 100 % CH4
0 to 25 % O2

11A

Process heater/furnace

0 to 100 ppm NOx

0 to 25 % O2

11B

General boiler/FCC unit stack

0 to 100 ppm NOx

0 to 100 ppm SO2
0 to 100 ppm CO
0 to 25 % O2

11C

SRU incinerator/tail gas stack

0 to 500 ppm SO2

0 to 25 % O2

11D

SCR NOx abatement unit

SCR inlet
SCR outlet

0 to 500 ppm NOx

0 to 25 ppm NOx
0 to 25 % O2

Process Data Information

To ensure qualification of the correct methodoIogy in specifying
process gas analyzers in a refinery, it is important to know specific
application data information. Process pressures, temperatures,
particulate loading and background stream composition are all
necessary for the design of a reliable analyzer and associated sample
conditioning system.

Changing background gases can interfere with the measurement of

the desired gas. For example, the total thermal conductivity of a gas
stream may change while the concentration of hydrogen remains
the same. Special calibration considerations may be required to
compensate for measurements in a changing background stream.

Page 5

Refining

Sample Handling Requirements

As with any process analyzer application, a proper sample
conditioning system is required to obtain an accurate and reliable
analysis.
Usually, a gaseous phase sample is conditioned in approximately the
following sequence before analysis:

Initial filtration
Pressure reduction and control
Transport to analyzer location
Multiple stream switching (if required)
Sample and bypass flow control
Calibration gas switching (if needed)
Final guard filtration (if needed)

Maintaining high bypass flow rates relative to the tubing suze is an

effective means to assure fast equilibration of system and sample.
Sample return connections should also be considered. As with
any well-designed system, dead-end volume should be kept at a
minimum to reduce sample transport lag.
Sources:
Refining Handbook, Hydrocarbon Processing, November 1992
Lefler, William L., Petroleum Refining,Penn Well Publishing
Company, 1979
HPI Market Data, Hydrocarbon Processing, Gulf Publishing
Company, 1993.

Figure 1 - Process Gas Analysis in a Petroleum Refinery

Gas

Polymer
Unit

Gas Plant

Gasoline
Light Naphtha

CRUDE DISTILLATION

Heavy Naphtha

Kerosene

Light Gas Oil

Heavy Gas Oil
Lubes

Alkylation

Gasoline

Aromatics
Extraction

Aromatics

Isom Unit

Hydrotreaters

Reformer

Hydrotreaters
Crackers
Lube Plant

Lubes/
Asphalt
Coke

Asphalt
Residual

Jet Fuel/
Diesel
Heating
Oils

Coker

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