March 2011

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Cost Effective Technology for Organic Sulfur Removal from
Refinery Fuel Gas
NPRA 2011 MEETING SAN ANTONIO TX
AM-11-74

Raymond F. Drnevich, Praxair & Vasilis Papavassiliou, Praxair, Tonawanda, NY; John
Scalise Burr Ridge IL; Ramchandra Watwe, Praxair, Houston TX

Abstract
Presently, sulfur removal from refinery fuel gas is focused primarily on hydrogen
sulfide (H
2
S). H
2
S can be effectively absorbed from gas stream with an amine system and
converted to elemental sulfur in a Claus plant. However refinery gas streams, especially those
derived from cokers, contain other sulfur compounds such as mercaptans, thiophenes and
sulfides which are not effectively treated by an amine system. Praxair has developed a new
technology based on a short contact time catalyst that can reliably convert organic sulfur to
H
2
S which can then removed in a conventional amine treater.
Introduction
Refinery gas fuel has been recognized as one of the two major sources of sulfur
emissions from refineries (the other being the Fluid Catalytic Cracking Unit or FCCU). Since
refinery gas usually represents the majority of fuel that is used in refinery heaters and boilers
any sulfur in refinery gas will convert to SO
x
during the combustion process and end up as
emissions from the refinery stacks. Refinery gas is amine treated to remove H
2
S but refinery
gas streams, especially those derived from cokers contain other sulfur compounds such as
mercaptans, thiophenes and sulfides which are not effectively treated by an amine system.

Additional processing steps are needed to take out these sulfur compounds. One
approach is to add caustic treatment such UOP MEROX process
1
after the amine unit. This
solution is effective but can be expensive and generates waste in the form of spent caustic that
must be regenerated or treated for disposal.

A second option to address non-H
2
S sulfur is the installation of scrubbers to remove
SO
x
at the combustion emission point. This approach is both logistically complex and cost
prohibitive since multiple stack-specific units are needed as opposed to a single centrally
located sulfur removal system.

A third option employs a conventional hydtrotreater to convert non-H
2
S sulfur species
to H
2
S which is subsequently removed by the amine system. The use of a hydrotreater better
integrates with existing refinery operations but has a few shortcomings. For one, a large,
expensive reactor is needed due to the low pressure operation, the presence of sulfur species
that are difficult to convert to H
2
S and low activity of traditional hydrotreater catalysts.

1
MEROX is a registered trademark of UOP



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Furthermore, multiple reactors may be needed to convert diolefins, oxygen and COS
(carbonyl sulfide). Conventional hydrotreater technology is using a CoMo or NiMo catalyst
and is very effective in natural gas pretreatment technologies for the production of hydrogen
in steam methane reformers. Natural gas however contains less than 10 ppm mercaptan and
H
2
S. In addition plenty of waste heat is available from the hydrogen plant to preheat the
natural gas for effective treatment in the hydrotreater. Refinery gas typically has variable
olefin content, high content of C
2+
hydrocarbons and, particularly if derived from coker gas, a
high content of non-H
2
S sulfur components. High olefins present significant problems for
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. In order to
control the exotherm the refinery stream must be diluted with some of the treated gas from the
hydrotreater which must be cooled and recycled to the feed. This necessitates the use of a
high temperature blower or booster compressor. Recycle compressors have been used but
they introduce reliability concerns and increase capital and maintenance costs. If the refinery
gas contains less than 3% olefins then heat must be supplied from an external source like a
fired heater which creates additional complexity, expense and emissions.
Praxair Concept Description
Praxair has developed an alternative solution that retains many of the positive
attributes of the conventional hydtrotreater but remedies its shortcomings. The Praxair
technology can be applied to any type of refinery gas. The key to this concept is the
development of a cost effective short contact time reactor (Refinery Gas Processor or RGP).
RGP has been developed for conditioning refinery gas to be used as a feed for a steam
methane reformer for hydrogen production or a gas turbine for electricity production
2
. As is
described below RGP operation can be adapted to convert non-H
2
S sulfur to H
2
S which can
be then efficiently removed in an amine system.

RGP contains a precious metal catalyst that can operate over a wide temperature range
to respond to olefin variation (no recycle gas compressor is required). Non-H
2
S sulfur
conversion occurs optimally around 700 F but the reactor can operate as a high as 1100 F
with no need for feed dilution. No external energy source is required. The energy demand is
satisfied with either olefin hydrogenation or addition of oxygen if olefin levels in the refinery
gas are low. RGP can operate with high olefin levels and in that case the heat required to
convert organic sulfur components to H
2
S is easily provided by the olefin hydrogenation
reactions. However, if the olefin concentration in the feed is low, some oxygen can be added
to the RGP reactor to provide make-up heat. The oxygen can be in the form of pure oxygen
or air if dilution of nitrogen is acceptable. The oxygen will react selectively with hydrogen to

2
Ramona Dragomir, Raymond F. Drnevich, J effrey Morrow, Vasilis Papavassiliou, Gregory Panuccio,
Ramchandra Watwe, TECHNOLOGIES FOR IMPROVED REFINERY GAS UTILIZATION, NPRA 2010
MEETING PHOENIX AZ, AM-10-178.





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produce water and heat, which will enable the conversion of organic sulfur to H
2
S. No other
oxygen side reactions occur.

RGP with or without oxygen can convert all other sulfur species to H
2
S which can be
then removed by a conventional amine system. A single reactor is used in both operational
modes. More importantly the same reactor can operate with variable oxygen addition to
respond to changing levels of olefins in the refinery gas and maintain reactor operating
temperature in optimum range for sulfur conversion to H
2
S. Composition variation is
common characteristic of refinery gas that is derived from complex refinery processes and a
major attribute of RGP is its ability to respond to composition variation without the need of
external heating of recycle compressor.

A simplified process flow diagram with RGP is presented in Figure 1. The refinery
gas flows to the RGP unit after removal of bulk sulfur (H
2
S). The cold refinery gas feed is
heat exchanged with hot reactor product to preheat it to the desired temperature. Oxygen is
added as needed. The amount of oxygen required is dependant on the olefin content of the
refinery gas. When required, oxygen addition is generally less than 3% of the refinery gas
flow on a molar basis; however if olefin content is sufficiently high, no oxygen is added. The
cost of the oxygen is an insignificant component of the total removal cost.

RGP
O
2
Lean
Solvent
H
2
S-Rich
Solvent
A
b
s
o
r
b
e
r

S
t
r
i
p
p
e
r
Reboiler
Amine Unit
Sour
Refinery Fuel Gas
Refinery Fuel Gas
Header
RGP
O
2
Lean
Solvent
H
2
S-Rich
Solvent
A
b
s
o
r
b
e
r

S
t
r
i
p
p
e
r
Reboiler
Amine Unit
Sour
Refinery Fuel Gas
Refinery Fuel Gas
Header
Figure 1. RGP process for organic sulfur removal from refinery fuel gas.



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Refinery gas typically contains enough hydrogen to completely hydrogenate olefins,
convert organic sulfur to H
2
S and react with oxygen. In cases where the feed stream is
hydrogen deficient, hydrogen can be added from any convenient source with high hydrogen
content such as hydrotreater purge gas or hydrogen plant product.

An alternative process option using RGP is presented in Figure 2, where only the
coker gas is treated to convert organic sulfur to H
2
S. Since the coker gas is the primary
source of organic sulfur, it may be less costly to treat it separately. The balance of the RGP
configuration and operation remains substantially the same as in Figure 1. The applicability
of this solution will likely depend on whether the coker gas is amine treated to remove H
2
S
separately from the rest of the refinery gas.
Cost competitiveness
Emission control technology for refinery gas can be classified as post-combustion and
pre-combustion. Post combustion technologies include dry and wet scrubbers and pre-
combustion includes wet scrubbers, conventional hydrotreaters/amine systems and
RGP/amine systems. Both pre and post combustion technologies can achieve similar removal
efficiencies. Post combustion is unlikely to be cost effective due to the large number and
diverse location of refinery process heaters and boilers. Pre-combustion has the additional
RGP
O
2
Lean
Solvent
H
2
S-Rich
Solvent
A
b
s
o
r
b
e
r

S
t
r
i
p
p
e
r
Reboiler
Amine Unit
Sour
Coker Gas
Refinery Fuel Gas
Header
Low organic sulfur
Refinery Fuel Gas
RGP
O
2
Lean
Solvent
H
2
S-Rich
Solvent
A
b
s
o
r
b
e
r

S
t
r
i
p
p
e
r
Reboiler
Amine Unit
Sour
Coker Gas
Refinery Fuel Gas
Header
Low organic sulfur
Refinery Fuel Gas
Figure 2. RGP process for organic sulfur removal from coker gas.



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benefit that can target the gas stream that contains the majority of organic sulfur which can
reduce cost and increase effectiveness. Pre-combustion technologies can be in the form of
retrofit of existing amine system by replacing the amine with one that is more selective to
organic sulfur or can be in the form of new system such as caustic treatment (MEROX). Cost
effectiveness for a caustic system (ISBL) was estimated
3
to be $46,500 per ton SOx for a
system treating 17.3 MMSCFD of coker off-gas containing 85 ppm sulfur (with non-H
2
S
sulfur compounds 90 percent of the total).

Praxair estimates that RPG/amine cost (ISBL) for a similar stream as the one
referenced above is in the range of $12,000 per ton SOx (both capital and operating cost).
The estimate for RGP assumes that only a new amine contactor will be needed and an existing
amine regenerator can be utilized. These numbers should be regarded as guidelines since it is
not possible to calculate exact cost without a specific location and refinery gas stream
definition. Since amine systems are common to refineries today it is expected that the RGP
system will be easier to integrate into refinery operations.
Technology Status
RGP technology is ready for commercial deployment. Praxair has completed a three
year test campaign using a sub-scale demonstration unit (RGP alpha) located at a US Gulf
Coast refinery treating actual refinery gas. The RGP alpha unit demonstrated greater than
95% conversion of organic sulfur to H
2
S for reactor exit temperatures of 650-700 F. It has
operated successfully with olefin levels as high as 17% in the feed. Safe oxygen addition with
a mixer designed by Praxair was also demonstrated. Currently, discussions are underway
with a refinery to site the first commercial RGP unit for organic sulfur removal.

Figure 3 depicts the composition of the sulfur species during a three-month span of
plant operation. The species analysis was done by collecting gas samples in Tedlar bags and
analyzing them with gas chromatography within twenty four hours. The analysis was
performed by a certified laboratory. From Figure 3 it can be observed that the majority of the
sulfur species in RFG were mercaptans. The low level of H
2
S is due to the fact that the RFG
was already amine treated.

Figure 4 depicts 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 ability of RGP to respond to a range of olefin concentrations (typical of
refinery gas) with no additional equipment and no effect on performance is a critical
advantage of the technology because it permits high on-stream factors and high reliability.

3
ETS, 2008-1. SOx RECLAIM Study - Final Report Module 2: Refinery Fuel Gas Treatment
and Sulfur Recovery/Tail Gas Units. AEC Engineering Inc./ETS, Inc. April 20, 2009



Page 6 of 7


The refinery gas treated in the pilot plant contained significant amount of sulfur in the
refinery gas stream that was not in the form of H
2
S. Samples were taken at points before and
after the RGP reactor and analyzed by outside laboratory to monitor conversion of mercaptans
and other sulfur compounds into H
2
S. The results are summarized in Figure 5 where the non-
H
2
S sulfur species conversion to H
2
S is plotted as a function of the average reactor
temperature (600-800 F). In general, organic sulfur conversion increased with increasing
reactor temperature and increasing molecular weight for given family of sulfur compounds.
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 :
Ethylene
Propylene
Butenes
Pentenes
Figure 4: RGP feed and product olefin composition from demonstration plant
results.
0.1
1
10
100
1000
6/1 6/15 6/29 7/13 7/27 8/10 8/24 9/7
Date
R
F
G

S
u
l
f
u
r

p
p
m
v
H2S Mercaptans Sulfides Disulfides Thiophenes Total
Figure 3; Refinery fuel gas feed sulfur species analysis from demonstration plant (sulfides
include COS)



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Overall a 90-95% conversion to H
2
S was achieved at temperatures above 650 F. The RGP
sulfur conversion performance is more than adequate for refinery gas which contains mostly
mercaptans in the non-H
2
S sulfur component.

Conclusions
A new technology (RGP) that can effectively convert organic sulfur to H
2
S in refinery
fuel gas has been developed by Praxair. Once the sulfur is converted to H
2
S it can be
removed by conventional amine systems. This technology is flexible in operating with high
or low olefin content, generating energy in-situ either by olefin hydrogenation or oxygen/air
addition, it can operated at high or low pressure and can be easily integrated with the rest of
refinery operations. The RGP system can be skid mounted for easy delivery and installation.
0
10
20
30
40
50
60
70
80
C
o
n
c
e
n
t
r
a
t
i
o
n
,

p
p
m
Mercaptans COS/Sulfides Disulfides Thiophenes
Inlet
Outlet
Figure 5: Non H
2
S sulfur species conversion to H
2
S from demonstration plant results