1

TECHNOLOGIES FOR ENHANCING REFINERY GAS VALUE

AIChE 2010 SPRING PROCEEDINGS

Ramona Dragomir, Praxair Houston, TX, Raymond F. Drnevich, Praxair, Tonawanda, NY,
Jeffrey Morrow, Praxair, Tonawanda, NY, Vasilis Papavassiliou, Praxair, Tonawanda, NY,
Gregory Panuccio, Praxair, Tonawanda, NY, Ramchandra Watwe, Praxair, Houston TX

Abstract

The trend of processing more heavy and sour crudes, the shift in demand away from
gasoline towards more distillate, and more stringent fuel qualities change the fuel and
hydrogen balances in most refineries. Finding the right solution to managing fuel gas and
hydrogen requirements has become essential for refineries to remain profitable. The refinery
gas value is higher for hydrogen generation than for generating power and slightly lower than
the value for using it as chemical feedstock. A combination of proven and new technologies is
required to address refinery fuel long situations. Select refinery gas streams can be
processed to recover hydrogen or as feed to SMRs. Cryogenic processing of refinery fuel gas
to recover valuable products (hydrogen, olefins and LPG) is a viable option, and can be
integrated with hydrogen post-purification technologies (e.g. PSA). Praxair has also developed
a new patented refinery gas processor based on a short contact time catalyst that can reliably
process refinery streams with high olefin and hydrocarbon with more than two carbon atoms
concentration and convert them into SMR suitable feed. Different technologies that are suited
to different refinery gas streams and how to optimize hydrogen recovery given differing energy
and capital cost constraints is presented below.

1 Introduction
Refinery fuel gas management has been recognized as a key element for optimum
refinery operation. Refineries face pressure to increase their processing intensity in order to
remain profitable and are seeking to increase their ability to process heavy and sour crude in
order to achieve needed operational flexibility. These two main trends cause the demand for
hydrogen to rise due to the increasing severity of hydroprocessing operations required to
process the heavy and sour crude and yet meet the stringent product quality requirements.
The increased processing severity has caused increased refinery gas (i.e. H
2
, C
1
-C
5
)
production, which exceeds in many cases the capability of the refinery to use it as fuel, forcing
the refiner to change refinery operations to meet fuel gas constraints, produce and vent
unneeded steam, flare fuel gas, or sell fuel at a discount. Furthermore, there is a shift in
demand away from gasoline and towards more distillate. Some refiners are choosing to curtail
their naphtha reforming capacity to address this market need. As a result, a significant source
of hydrogen in a refinery is lost, thus widening the gap between hydrogen supply and demand.
Refiners are likely to find themselves in a position with more fuel gas and less hydrogen, which
has generated an increased interest in fuel gas management projects.
Managing the fuel gas system provides multiple benefits such as Increased
operational flexibility and profitability, optimized hydrogen sourcing, reduced fuel demand,
improved fuel gas quality, burner control and emissions and decreased CO
2
emissions. These
are obvious direct benefits to upgrading the refinery fuel gas and implementing hydrogen
2
recovery systems, but there is also an indirect benefit to raising the overall hydrogen system
purity. Rather than routing low-to-mid purity hydrogen to hydrotreaters, greater value from
these process streams can be obtained by upgrading the hydrogen quality. Higher hydrogen
purity will increase the purity of the recycle stream and reduce fuel gas production in the
hydrotreating units. This can lead to both improved yields and performance or longer catalyst
run lengths in hydrotreating units.
Another indirect benefit of better fuel gas management is that it is an enabler for other
energy reduction projects. These projects generally lower the demand for fuel gas in various
refinery operations, but the lack of an outlet for the saved fuel gas may become an
impediment in the implementation of the energy conservation projects. Conversely, such
projects achieve higher benefits if the
saved fuel gas is utilized in a
productive manner.
Refineries that are fuel long
generally seek to export energy in the
form of refinery fuel gas or look for
other ways to extract value from the fuel
gas system. Pressure Swing Adsorption
(PSA) and cryogenic based separation
methods are commonly used to recover
hydrogen and hydrocarbons
respectively from the fuel gas. Another
approach is to use the gas as fuel for
electric power generation, but this is
usually the lowest value alternative.
Fuel gas can also be used as feed to
hydrogen plants (Steam Methane
Reformers-SMRs). Generally such
approaches are applicable to selected
high-hydrogen, low-olefin streams (PSA
systems or SMRs), or require chemical
facilities nearby to use the recovered
products (olefin recovery with cryogenic
systems). Praxair economic analysis
indicates that the value created by
using refinery gas for hydrogen generation is higher than the value for generating power and
slightly lower than the value for using it as chemical feedstock (Figure 1). Power generation
from steam at refinery conditions is disadvantaged compared to power from other sources
which tend to use higher efficiency combined-cycles. Refinery fuel gas is unsuitable as a feed
to gas turbines with Dry Low NO
x
(DLN) combustors. The typical DLN burner fuel
specifications for hydrogen and C
2
+are 10% and 15% maximum, respectively. Refinery fuel
gas likely has hydrogen and C
2
+ content that exceeds these limits. Furthermore, olefins
contained in the fuel gas tend to form soot and a minimal compositional variation is required to
maintain NO
x
performance of the DLN combustors. A common approach to get around these
limitations is to use fuel gas as a supplemental fuel to the heat recovery steam generators
(HRSG) in gas turbine cogeneration plant or as a fuel to the SMR furnace. However, this
approach limits the amount of fuel gas that can be used and/or the value obtained from use of
the fuel gas.
Figure 1: Refinery Gas Value for Different
Applications Expressed as a % of the Value of
Natural Gas
3
In addition to economic analysis technical analysis of refinery gas utilization
opportunities is required to develop an appropriate solution. In the next paragraphs we
discuss technical solutions utilizing existing technology as well as new technologies developed
to address refinery gas with high olefin content.
2 Solutions for Fuel Gas Management
2.1 Integration with Hydrogen Production
There are different degrees of integration between hydrogen production and fuel gas
management. Praxair has three distinct designs linking fuel gas management and hydrogen
production that have been put into practice. The first design is a simple recovery of hydrogen.
Figure shows a block diagram of a PSA based hydrogen recovery system. The refinery gas is
compressed and then fed to a
PSA. The tail gas is compressed
and returned to the refinery fuel
system, and the product hydrogen
is compressed and delivered to a
high pressure hydrogen consumer
in the refinery. All three
compression services are
designed on a common
reciprocating compressor frame.
Praxair installed three 50% compressors to ensure high reliability.
Simple recovery reduces the amount of on-purpose hydrogen that may be required to
satisfy incremental demand. Other designs can integrate refinery streams into on-purpose
hydrogen production. Praxair has implemented a second design where refinery gas can be
used as a feedstock to a SMR hydrogen plant, with supplemental feed in the form of natural
gas. In this specific example, the refinery gas feed is a light hydrocarbon stream with
approximately 25% hydrogen by volume and 4% olefins. The refinery gas makes up
approximately 45% of the total SMR feed, with the balance natural gas and contributes 42% of
the total feed plus fuel to the facility. This configuration is shown in Figure 3. In addition to
reducing the energy content required for on-purpose hydrogen production, this design also
allows the hydrogen in the refinery gases, which is too low in concentration for economic PSA
recovery, to be recovered the steam methane reforming process.
In the event that hydrogen recovery makes economic sense, but does not provide the
total amount of additional hydrogen required by a refiner, a third design of PSA recovery
integrated with on-purpose hydrogen production can be an attractive solution. Praxair is
currently installing a facility
that recovers hydrogen
from a collection of refinery
gases, and then uses the
PSA tail gas as a SMR
feedstock supplemented
with natural gas as shown
in Figure 4. This system
leads to a high recovery of
the hydrogen contained in the refinery gases because the PSA tail gas containing unrecovered
Figure 2: Refinery Gas PSA Configuration
Figure 3: Refinery Gas as SMR Feed
4
hydrogen is further processed as
SMR feed. In this case, the
refinery gases again contribute
45% of the total SMR feed and
42% of the feed+fuel to the
facility.
Recovering hydrogen
from refinery streams decreases
the need for on purpose
hydrogen and can also reduce
greenhouse gas emissions.
Recovering 1 MMSCFD of
hydrogen from the fuel header and displacing 1 MMSCFD of on purpose generation from a
typical modern SMR will avoid the generation of approximately 22 Metric Tons of CO
2
(without
fuel replacement of the recovered hydrogen). If the recovered hydrogen displaced on-purpose
hydrogen from an older and less efficient SMR, the avoided CO
2
generation is even higher.
2.2 Hydrogen and Hydrocarbon Recovery with Cryogenic Systems
Recovering hydrogen and heavier hydrocarbons from refinery fuel gas can help
refineries with both hydrogen and fuel costs. Cryogenic separation is typically viewed as being
the most thermodynamically efficient separation technology. The higher capital cost
associated with pre-purification and the low flexibility to impurity upsets has limited its use in
hydrogen recovery.
However, it would
be one of the first choices
when higher value can be
obtained from other
products (olefins, LPG),
especially when BTU
removal from the fuel-gas
system is of high priority.
Figure 5 presents
the basic configuration of a
two-stage partial conden-
sation process for hydrogen
recovery from refinery
gases, with post purification
via PSA and crude LPG
recovery. The keys steps in
this process involve first
compressing and pre-
treating the crude refinery
gas (RG) stream before
chilling (in BAHX1) to an
intermediate temperature (-
60 to -120 F). This partially
condensed stream is then
Natural
Gas
SMR
Feed
Pre-Treatment
Shift PSA H2
Product
Feed
Compression
PSA
System
Tail Gas
Compression
Low Pressure
Refinery Gas
Refinery
Gas
Figure 4: Integrated Hydrogen Recovery and Generation
from Refinery Gas


To FG Header
Crude LPG
Min 65%
H
2
H
2
Product

PSA Tailgas

PT
BAHX1
FD2
FD1
C1
BAHX2
To FG Header
PSA
High Purity H
2
(Optional)
Refinery Gas
Figure 5: Integrated Cold Box and PSA Process for H
2
and
Crude LPG Recovery
5
separated in a flash-drum (FD-1). The liquid stream from FD-1 is expanded through a J oule-
Thompson (J T) valve to generate refrigeration and then is fed to the wash column C1.
Optionally, column C1 can be replaced by a simple flash drum, with penalty on ethane/propane
recovery. A crude LPG stream is collected at the bottom of the column, and a methane rich
vapor is obtained at the top. The methane rich vapor is, after recovering refrigeration in
BAHX1, sent to compression and then to fuel. The vapor from FD1 is further cooled in a
second heat exchanger (BAHX2) before being fed to flash drum FD2, where it produces a
hydrogen rich vapor and a methane rich liquid. The liquid is expanded in a J T valve to
generate refrigeration, and then is sent back to BAHX2 to provide cooling. The resulting vapor
is sent to column C1, and then processed as described above. The hydrogen rich gas is then
sent to a PSA for further purification. The PSA tail gas is compressed and returned to fuel
together with the methane rich gas from BAHX1. This cryogenic process/PSA integration can
provide high purity hydrogen and LPG recovery from refinery gas.
2.3 Refinery Gas Processing for SMRs
Existing SMR integration technologies typically require refinery streams with high
hydrogen and low olefin content [1] but the majority of refinery gas available does not meet
these criteria. Refinery gas composition is typically highly variable with high olefin, C
2
+and
sulfur content which makes it difficult to process in SMRs. Refinery gas composition is very
different than natural gas, as shown in Table 1. Praxair has developed a new technology to
address the limitations of typical refinery gas streams for hydrogen production and to permit
their use in SMRs and Gas.
2.3.1 RFG constraints as SMR feed
Existing technology for treating refinery gas is based [1] on natural gas pretreatment
and is not capable of reliably treating high olefin streams at a reasonable cost. Refinery gas
used as feed to SMRs is preferably high in
hydrogen, which can be routed to the PSA
or low in olefins to facilitate treatment with
conventional natural gas pretreatment
technologies using a CoMo or NiMo
catalyst. Much more readily available is
refinery gas from a common refinery fuel
header which is the outlet for by product
streams from various refinery operations.
As such it typically has high olefin content,
high content of C
2+
hydrocarbons and high
compositional variability. High olefins
present significant problems for a
conventional hydrotreater, which operates within a narrow temperature window from about 550
to 750 F. Olefin hydrogenation reactions are exothermic and each percent of olefins in the
feed results in about 40-50 F temperature rise in the hydrotreater. A refinery stream must
contain less than 5% olefins to be fed to a conventional hydrotreater. Higher olefin
concentrations can lead to temperatures that can cause catalyst deactivation and compromise
the reliability of the SMR. In order to control the exotherm and avoid catalyst deactivation the
refinery stream must be diluted either by the addition of natural gas or some of the treated gas
from the hydrotreater must be cooled and recycled to the feed. The former reduces the
amount of refinery gas that can be fed to the SMR and the latter necessitates the use of a high
Table 1: Typical Natural Gas and Refinery Gas
Compositions
Name
Refinery Gas Natural Gas
Mol % Mol %
Hydrogen 28.00 -
Methane 28.00 95.00
C2+parafins 24.00 3.50
Olefins 10.00 0.00
Nitrogen 3.50 1.00
Carbon Dioxide 3.00 0.50
Carbon Monoxide 3.50 0.00
Total 100.00 100.00
Sulfur ppm 25-250 5
6
temperature blower or booster compressor. Recycle compressors have been used but they
introduce reliability concerns and increase capital and maintenance costs. Since
compositional variations are very common with refinery gas streams, it is difficult to design and
operate a hydrotreater with recycle to account for all possible variations. If off-spec refinery gas
stream is detected the hydrogen plant must discontinue the use of the refinery gas to protect
the SMR.
Refinery gas may also contain C
2
+hydrocarbons (e.g. ethane, propane) in amounts
that far exceed what is contained in natural gas. If the hydrocarbons in refinery gas are
represented by the formula C
x
H
y
then x is an effective carbon atom number that can provide
information about the content of C
2
+hydrocarbons. For methane x=1 so the higher x is for a
given refinery gas composition the higher the amount of C
2
+is in the refinery gas. The
effective carbon atom number can be calculated by the refinery gas composition. Figure 6
depicts the effective carbon atom variation of refinery gas at a U.S. refinery over a period of
about two months. A significant variation can be observed in both short term and longer term
composition which necessitates careful design of the SMR control system. To accept these
streams in a SMR a prereformer or an alkalized reforming catalyst can be used which may not
be an option for existing SMRs. Alternatively the steam to carbon ratio may have to be
increased to a higher value which depends on the C
2
+hydrocarbon content; however, this will
reduce the thermal efficiency of the plant. Refinery gas composition variability must be taken
into account in the plant design to prevent situations that compromise the reliability of the
SMR, such as operating with steam to carbon ratios that are either too low (catalyst coking) or
too high (energy loss). Variable composition can lead to swings in SMRs operating
performance. A highly responsive analysis technique such as a mass spectrometer or
calorimeter would be required for predictive control. Although with advances in controls and
analytical techniques these issues can be addressed with proper design it is still desirable to
have a technology that can eliminate or reduce the severity of these problems.
2.3.2 Refinery Gas Processing (RGP) Technology
Praxairs refinery gas processor is based on a novel short contact time catalyst
capable of operating at a space velocity of at least 50,000 hr
-1
. This catalyst has an extended
Figure 6: Refinery gas effective carbon atom variability
0.5
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
5/8 5/18 5/28 6/7 6/17 6/27 7/7 7/17 7/27
Time
E
f
f
e
c
t
i
v
e

c
a
r
b
o
n

a
t
o
m
7
temperature window of operation (300-1600 F) which permits operation with levels of olefins
previously unachievable without feed dilution. The catalyst is in monolith form and can be on a
metallic or ceramic support. A precious metal like rhodium or platinum is deposited on the
monolithic support. The catalyst is derived from catalytic partial oxidation type catalysts
pioneered by Schmidt et al [2] at the University of Minnesota. These catalysts have been
used in partial oxidation of methane to produce synthesis gas [3] and for oxidative
dehydrogenation of paraffins to olefins (e.g. ethane to ethylene). It has been discovered [4, 5]
that the same catalyst is very effective in the hydrogenation of olefins.
Based on this discovery a process that can operate under hydrogenation or oxidation
conditions with the same catalyst was developed. Firstly in hydrogenation mode (no oxygen)
the reactor converts olefins to paraffins with the contained or supplemental hydrogen but with a
much wider operating temperature window compared with conventional technology. The RGP
permits utilization of refinery gas streams with high olefin content and high olefin variability.
Secondly with the addition of small amounts of oxygen (up to 10% of RGP feed) and steam (up
to 1:1 steam to carbon ratio) the reactor can operate in a prereforming mode that reduces the
amount of hydrocarbons with two or more carbon atoms in addition to reducing olefin levels.
By tuning the oxygen consumption, the refinery gas composition variations can be reduced
thus improving the operation of the SMR. The same reactor can be used in both operational
modes and no shut-down is required to transition between modes. The dual operation can
expand the type of refinery gas composition that can be routed to the SMR and can replace
two unit operations, a hydrotreater and a prereformer. In addition, RGP offers higher reliability
due to the elimination of the recycle gas compressor and the ability to regulate refinery gas
variability. The simple and flexible flowsheet makes it easier to retrofit existing SMRs to
operate with refinery gas as a feed.
2.3.3 RGP Performance Results
Extensive laboratory testing
was undertaken at Praxairs Tech-
nology Center (2005-2007) with
simulated refinery gas to perform
parametric analysis, develop efficient
operating conditions, select appro-
priate catalyst and test the ability to
operate in hydrogenation mode or
prereforming mode. Since it is not
possible to simulate all of refinery gas
characteristics in the laboratory a
pilot test unit was designed and built
at a refinery location. The design and
construction was done by Praxairs
engineering. The pilot unit picture is
shown in Figure 7.
A process flow diagram of the pilot unit is depicted in Figure 8. The refinery gas was
received from the refinery gas fuel header and passed through a condensate separator to
remove any free liquids. Then the fuel gas was passed to a coalescing filter before a bulk
sulfur removal bed. The reduced sulfur feed was then compressed with a two stage
reciprocating compressor to about 220 psig. The compressed gas was heated and then
Figure 7: RGP Pilot Unit at a US Refinery
8
passed to a finer sulfur removal bed. The gas was then preheated to the desirable
temperature (up to 700 F) before send to the reactor. The reactor product was cooled with
boiler feed water injection and after liquid separation it was send to the flare. Optional oxygen,
steam and natural gas could be added to reactor feed for specific tests. Samples from various
parts of the process were send to the analytical system that comprised a calorimeter, a gas
chromatograph, a sulfur analyzer and oxygen analyzers which were housed in a separate
enclosure.
The pilot unit was designed to treat 5000 scfh of refinery gas from the refinery fuel
header. The pilot unit operated from 2007-2009 for more than 6000 hours and was able to
demonstrate that the technology is uniquely capable of treating refinery gas. The unit operated
with up to 17% olefins in the feed and up to 450 ppm organic sulfur. The unit was able to
respond to feed variability, demonstrated acceptable catalyst life, switched between oxidation
and hydrogenation mode seamlessly, demonstrated safe operation and increased hydrogen
production in prereforming mode.
Figure 9 presents the feed and product olefin composition for a period of two months
with significant olefin variations in the feed (4-17%) but with product composition that remained
below 1% for the majority of time. Only when the unit was operated with very high propylene
in the feed did the exit olefin composition approach 2% at the high reactor exit temperature
(1100 F), where propylene conversion was limited by thermodynamic equilibrium. The level of
olefins achieved at the exit of the RGP can be easily handled by the SMR hydrotreater, and
allows for reliable plant operation with refinery gas feed. Praxair is finalizing the parameters
that allow the RGP to be used to increase hydrogen production and displace a pre-reformer.
Condensate
Coll ect ion
Tank
Compressor Package
Inl et Feed
Coal escer
Sulf atreat
Bed
El ectri c
Heater
Guard
Bed
Electri c
Preheater
Test Uni t
React or
Mi xer
Cool ing Water
Heat Exchanger
Test Uni t
Separator
Drain Drai n Drain
Nitrogen
Steam
Natural Gas
Quench BFW
Oxygen
N
2
Purge
Purge to
Fl are
Processed
Refinery
Fuel Gas
Produced
by Test
Unit t o
Flare
RFG
Fuel Header
Condensat e
Separator
Drai n
Disposal
vi a Vacuum
Truck
RefineryFuel Gas
Header
Off Skid On Skid
Condensate
Coll ect ion
Tank
Compressor Package
Inl et Feed
Coal escer
Sulf atreat
Bed
El ectri c
Heater
Guard
Bed
Electri c
Preheater
Test Uni t
React or
Mi xer
Cool ing Water
Heat Exchanger
Test Uni t
Separator
Drain Drai n Drain
Nitrogen
Steam
Natural Gas
Quench BFW
Oxygen
N
2
Purge
Purge to
Fl are
Processed
Refinery
Fuel Gas
Produced
by Test
Unit t o
Flare
RFG
Fuel Header
Condensat e
Separator
Drai n
Disposal
vi a Vacuum
Truck
RefineryFuel Gas
Header
Off Skid On Skid
Fi gure 8: RGP pilot unit process flow diagram
Condensate
Coll ect ion
Tank
Compressor Package
Inl et Feed
Coal escer
Sulf atreat
Bed
El ectri c
Heater
Guard
Bed
Electri c
Preheater
Test Uni t
React or
Mi xer
Cool ing Water
Heat Exchanger
Test Uni t
Separator
Drain Drai n Drain
Nitrogen
Steam
Natural Gas
Quench BFW
Oxygen
N
2
Purge
Purge to
Fl are
Processed
Refinery
Fuel Gas
Produced
by Test
Unit t o
Flare
RFG
Fuel Header
Condensat e
Separator
Drai n
Disposal
vi a Vacuum
Truck
RefineryFuel Gas
Header
Off Skid On Skid
Condensate
Coll ect ion
Tank
Compressor Package
Inl et Feed
Coal escer
Sulf atreat
Bed
El ectri c
Heater
Guard
Bed
Electri c
Preheater
Test Uni t
React or
Mi xer
Cool ing Water
Heat Exchanger
Test Uni t
Separator
Drain Drai n Drain
Nitrogen
Steam
Natural Gas
Quench BFW
Oxygen
N
2
Purge
Purge to
Fl are
Processed
Refinery
Fuel Gas
Produced
by Test
Unit t o
Flare
RFG
Fuel Header
Condensat e
Separator
Drai n
Disposal
vi a Vacuum
Truck
RefineryFuel Gas
Header
Off Skid On Skid
Fi gure 8: RGP pilot unit process flow diagram
9
Testing has demonstrated pre-reforming activity in oxidation mode and economic analysis
indicates that an RGP system could have a substantial capital advantage when compared to a
pre-reformer in a debottleneck scenario.
2.3.4 Kinetic Model
Analysis of the RGP alpha plant data showed that several parameters affected the
reactor performance when operating in hydrogenation mode. The ROG feed gas temperature
and concentration of olefins, type of olefin, hydrogen partial pressure, and total sulfur had the
greatest effect on the olefin conversion.
Space velocity and reactor pressure also
impacted the product distribution. An
empirically derived global kinetic reaction
model was constructed that incorporated
all of these variables. As shown in Figure
10 there is a good match between the
experimental data and the model
predictions.
2.3.5 Other RGP Applications
The RGP can be used in oxidation
mode not only to eliminate olefins but to
increase the hydrogen content of the
refinery gas and reduce the amount of C
2
+
hydrocarbons. This can be exploited
advantageously by either reducing the
heat load of the SMR to produce the same
amount of hydrogen or by maintaining the
same heat load and increasing the amount of hydrogen that can be produced. Since the
system can operate in either hydrogenation or oxidation mode with the same reactor, the
oxidation mode with increased hydrogen production could be used at times of high hydrogen
0
2
4
7
9
11
13
16
18
20
5/28 6/1 6/5 6/9 6/13 6/17 6/21 6/25 6/29 7/3 7/7 7/11 7/15
Time
O
l
e
f
i
n
s

m
o
l
e

%
Total Olefins In Total Olefins Out
Olefins include:
Ethyl ene
Propylene
Butenes
Pentenes
Figure 9. RGP Feed and Product Olefin Composition from Pilot Plant Experiments
0
2
4
7
9
11
13
16
18
20
5/28 6/1 6/5 6/9 6/13 6/17 6/21 6/25 6/29 7/3 7/7 7/11 7/15
Time
O
l
e
f
i
n
s

m
o
l
e

%
Total Olefins In Total Olefins Out
Olefins include:
Ethyl ene
Propylene
Butenes
Pentenes
0
2
4
7
9
11
13
16
18
20
5/28 6/1 6/5 6/9 6/13 6/17 6/21 6/25 6/29 7/3 7/7 7/11 7/15
Time
O
l
e
f
i
n
s

m
o
l
e

%
Total Olefins In Total Olefins Out
Olefins include:
Ethyl ene
Propylene
Butenes
Pentenes
Figure 9. RGP Feed and Product Olefin Composition from Pilot Plant Experiments
-200
-160
-120
-80
-40
0
50 70 90 110 130 150 170 190 210
Ethylene In
E
t
h
y
l
e
n
e
Expt 1
Expt 2
Expt 3
Expt 4
Expt 5
Figure 10. Plot of change in ethylene scfhas a
function of the inlet ethylene comparing
experimental results (points) against model
predictions (lines) for five different experimental
conditions.
-200
-160
-120
-80
-40
0
50 70 90 110 130 150 170 190 210
Ethylene In
E
t
h
y
l
e
n
e
Expt 1
Expt 2
Expt 3
Expt 4
Expt 5
Figure 10. Plot of change in ethylene scfhas a
function of the inlet ethylene comparing
experimental results (points) against model
predictions (lines) for five different experimental
conditions.
10
demand, and hydrogenation mode operation with normal hydrogen production the rest of the
time. Praxair estimates that 10-20% production increase can be achieved in oxidation mode in
an existing plant depending on refinery gas composition and other hydrogen plant bottlenecks.
In addition to using RGP for SMR feed treatment, the technology could also be used to
treat refinery gas so it can be used in gas turbines as substitute natural gas. Gas turbines with
DLN combustors can be designed to operate on refinery gas provided the amount of heavier
hydrocarbon and hydrogen are controlled. High levels of higher molecular weight
hydrocarbons, especially olefins, can form carbon within gas turbine combustors and result in
erosion and fouling of gas turbine components and the emission of "smoke" in the gas turbine
exhaust. Hydrogen and olefins can also ignite prematurely and compromise the gas turbine
DLN combustor. The RGP operating in hydrogenation or oxidation mode can control the level
of olefins, C
2
+hydrocarbons and hydrogen within acceptable levels.
3 Conclusions
The following staged approach is used by Praxair to assist refineries in their efforts to
obtain cost reduction, profit improvement and regulatory compliance by better fuel gas and
hydrogen management:
Perform an evaluation of the overall hydrogen and fuel/energy systems which will assist
in identifying potential value-added opportunities;
Work closely with the refinery to fine-tune and validate the opportunities identified;
Develop the solution, based on refinerys feedback and final optimization
A combination of proven and new technologies is available to provide solutions to
refinery fuel long situations. If refinery gas with high hydrogen and low olefins is available
then a PSA or a conventional SMR can be used as outlets. If high olefins, variability and high
hydrocarbons are concerns then RGP technology is available to address these issues. If
hydrocarbon recovery is desired a cryogenic system can be designed to simultaneously
produce LPG or chemical feedstock and high purity hydrogen.
A new technology has been developed to allow use of refinery gas streams with high
olefin concentration in SMRs and gas turbines. Using a short contact time monolith reactor
olefins can be reduced to levels that are manageable by the SMR HT. This new technology
can also be used to control feed composition variations and to optimize hydrogen production.
4 References
1. K. Chlapik, B. Slemp, "Alternative Lower Cost Feedstock for Hydrogen Production",
102nd NPRA Annual Meeting, San Antonio, Texas, USA, 2123 March 2004.
2. Hickman D. A., Schmidt L.D., Synthesis gas formation by direct oxidation of methane
over Pt monoliths, Jr. of Catalysis, 1992, 138, 267.
3. V. Papavassiliou, P. Pacouloute, KT Wu, R. Drnevich, D. Vlachos, J . Hemmings and L.
Bonnel, Catalytic Partial Oxidation Pilot Plant Study, Ind. Eng. Chem. Res., 2010, 49
(1), pp 94103
4. Drnevich R. F. and Papavassiliou V., Steam Methane Reforming Method, US Patent
No. 7,037,485B1, 2006.
5. Drnevich R. F. and Papavassiliou V., Gas Turbine Fuel Preparation and Introduction
Method, US Patent No. 7,395,670B1, 2008.