FLEXSORB SOLVENTS
Better acid gas
D. Perry, R.B. Fedich and
L. E. Parks of ExxonMobil
Research and Engineering
Company discuss the
advantages of FLEXSORB
solvents for acid gas
enrichment. Substantial
savings in investment cost
and operating costs have
been demonstrated in both
new plants and retrofits in
numerous AGE units around
the world.
38
enrichment
any natural gas fields contain
M more CO2 than H2S. When these
acid gases are removed from the
methane sales gas, the resulting acid gas
stream is likely to contain low H2S concen-
trations (<20 mol-%) making it unsuitable
for sulphur recovery using the conventional
Claus process. Acid gas enrichment (AGE)
has become an enabling technology to eco-
nomically produce these natural gas
reserves. As the name implies, an AGE unit
enriches the H2S content of the acid gas
stream making it practical to recover sul-
phur in a Claus unit. Alternatively, AGE tech-
nology can also be used to minimise the
volume of acid gas for re-injection or to
debottleneck existing facilities if new,
sourer fields are developed. There are a
limited number of these AGE units in oper-
ation (some report as few as 25 world-
wide). FLEXSORB SE or SE PLUS solvents
have been specified for 20 AGE units
including the QatarGas II LNG Project
(Trains 4 and 5) gas treating facilities which
were successfully started in 2009.
Acid gas removal process
To bring natural gas to the market, either
via pipeline to nearby consumers or via liq-
uefaction to distant markets, various impu-
rities in the produced gas must be
removed among these are H2S and CO2.
These acid gas components are removed
from the sales gas using traditional absorp-
tion processes also known as acid gas
removal (AGR) units. Typically, AGR units
utilise an amine solvent but depending on
the gas composition AGRs can use hot
potassium carbonate, a physical solvent,
or a blend of amine and physical solvent.
The AGR absorbers are run at a high pres-
sure 35-83 barg (500-1200 psig) to min-
imise recompression costs.
Typical specifications for H2S in sales
gas are <4 vppm. For pipeline gas, the
residual CO2 is usually determined by over-
all heating value of the gas stream, but
generally ranges between 2 to 5 mol-%. For
Liquefied Natural Gas (LNG), the H2S and
CO2 specifications are significantly reduced
to <2 and <50 vppm respectively to avoid
corrosion and freezing problems in down-
stream processing.
As a result of the sales gas specifica-
tions, AGR units remove essentially all of
the H2S and CO2 from the produced natural
gas. AGR units can utilise a variety of sol-
vents, including generic or formulated
MDEA. In some cases, controlled CO2
removal can be achieved using a selective
solvent such as FLEXSORB or MDEA, to
leave some of the CO2 in the sales gas.
Gas fields with high CO2 to H2S ratios, the
acid gas stream from the AGR regenerator
will have an unfavorably low H2S concen-
tration resulting in a poor quality feed to a
Claus plant.
As the amount of sulphur removed from
the sales gas exceeds a threshold limit
between 1 and 10 t/d, depending on local
regulations, it is generally required to
recover the sulphur. The preferred recovery
technology is the modified Claus process.
One of the keys to good Claus plant per-
formance is to maintain a stable flame and
high temperatures in the main reaction fur-
nace (>926C, 1700F). Higher tempera-
tures increase the conversion of H2S to
elemental sulphur. CO2 in the acid gas feed
to the Claus unit acts as a diluent, reducing
reaction furnace temperatures. To achieve
high temperatures in the conventional
Claus furnace an acid gas feed stream typ-
ically requires at least 50 mole percent
H2S. If the H2S concentration in the acid
gas from the AGR is lower than 50%, sev-
eral alternative Claus plant design options
are available. The most common is the
split-flow design where a portion of the
dilute acid gas is bypassed around the front
of the main reaction furnace. All of the com-
bustion air and a fraction of the acid gas
are fed to the main burner. Bypassing some
of the acid gas to a second furnace cham-
ber raises the temperature in the combus-
tion zone but lowers the sulphur recovery
efficiency. If the acid gas H2S concentration
is below 20%, a split flow design cannot
achieve the required temperature in the
Sulphur 326 | January -February 2010

main reaction furnace. In these cases,
Claus plant designers can choose to fire a
supplemental fuel, or utilise oxygen enrich-
ment of the combustion air, or preheat the
air and/or acid gas feed to the Claus fur-
nace to maintain the proper temperatures.
None of these options are preferred.
Acid gas enrichment process
In the last two decades, a new option to
process dilute acid gas streams, acid gas
enrichment, has become an increasingly
economic option. As the name implies, acid
gas enrichment concentrates the H2S from
the AGR system by further gas treatment in a
second amine unit utilising a selective amine
solvent. Except for the use of the selective
amine solvent, an AGE unit is similar to other
traditional amine treating units. Figure 1
shows a simplified process flow diagram of a
FLEXSORB acid gas enrichment unit. The AGR
acid gas is fed to the base of an absorber
column equipped with either trays or packing
where the H2S is absorbed via counter-
current contacting with the descending amine
solvent. The AGE absorber typically operates
at low pressure (~0.5 barg, 7 psig),
compatible with the operating pressure of the
upstream AGR regenerator overhead system.
Fig 1: Standalone AGE flow diagram
treated gas
make-up water
AGE absorber
lean
solution
filter
10
water wash 8
pump 6
1 lean amine pump
AGR
acid gas
rich amine pump
Sulphur 326 | January -February 2010
The selective amine in the AGE preferentially
absorbs the H2S and allows the CO2 to
remain in the treated gas (also known as
CO2 slip). Since this is a low-pressure
application, a water wash zone is
recommended on top of this tower to
minimise the loss of FLEXSORB solution with
the treated gas. The water wash purge is
combined with the rich amine to maximise
recovery of the FLEXSORB solution.
The rich amine from the bottom of the
absorber is then pumped through a rich-
lean heat exchanger and on to a regenera-
tor tower. The rich/lean exchanger can
either be a plate and frame type (as shown)
or a conventional shell and tube exchanger.
In the regenerator, the acid gas is stripped
from the FLEXSORB solution by counter-cur-
rently contacting with steam generated in
the reboiler. The gas exiting the stripping
section of the regenerator tower is then
washed in the reflux (rectifying) section,
which is located at the top of the tower.
The overhead gas from the reflux section
is cooled by the overhead condenser and
separated from the condensed water. The
condensed reflux water is returned to the
regenerator. From the reboiler, the hot lean
FLEXSORB solution is sent back through
the rich/lean heat exchanger and further
carbon fines
treater filter lean surge vessel
lean cooler
rich/lean exchanger
sump filter
sump pump
sump drum
FLEXSORB SOLVENTS
cooled in the lean cooler. Downstream of
this cooler there is a lean surge vessel and
a lean amine pump to feed the FLEXSORB
solution back to the absorber. A portion
(typically a 25% slipstream) of the lean
solution is filtered to avoid build-up of con-
taminants in the amine solution.
To achieve the twin goals of low H2S in
the treated gas and low CO2 in the enriched
acid gas, the AGE amine solvent must max-
imise the selectivity for absorbing H2S. AGE
process simulations by Weiland1 have
demonstrated that the CO2 and H2S partial
pressure driving forces in the AGE absorber
work against achieving these goals simul-
taneously. As the gas moves up the
absorber tower, the H2S partial pressure is
decreasing reducing the mass transfer driv-
ing force. At the same time, the CO2 par-
tial pressure is increasing, making CO2
pick-up more difficult to avoid.
ExxonMobil Research and Engineering
Company (EMRE) has developed and com-
mercialised a suite of gas treating tech-
nologies and absorbents known broadly as
FLEXSORB. The FLEXSORB SE and FLEX-
SORB SE Plus solvents utilise proprietary,
severely hindered amines designed for the
selective removal of H2S in the presence
of CO2. The choice between SE and SE
enriched acid gas
overhead condenser
reflux drum
regenerator
purge
reflux pump
1
reboiler
steam
condensate
39
 FLEXSORB SOLVENTS
Table 1: FLEXSORB AGE Experience Bands
Acid Gas Feed Conditions
Rate, kNm3/h (MSCFD)
Pressure, barg (psig)
Temperature, C (F)
Inlet H2S, mol-%
Fig 2: Acid gas enrichment capabilities
FLEXSORB SE and SE PLUS acid gas enrichment
80
H2S in enriched acid gas, mol-% (wet)
70
60
50
40
30
20
10
0 and lean amine temperatures. Lower tem-
0 10
Plus is made for each case based on the
specific treating requirements to minimise
capital and operating costs. The technol-
ogy and absorbents have been widely
applied in petroleum refining and natural
gas production including offshore and
onshore production sites around the world.
FLEXSORB SE and SE PLUS solvents
have the desirable characteristic of absorb-
ing essentially all of the H2S (below 10
vppm), while rejecting as much as 95% of
the CO2 into the treated gas stream. It is
also extremely effective at low pressure
which makes it well suited for AGE appli-
cations.
Chludzinski and Iyengar2 describe the
application of these sterically hindered
amines to AGE units as well as outline the
operating conditions and some of the pos-
sible unit configurations.
What levels of enrichment are
possible?
The level of H2S enrichment depends pri-
marily on the H2S concentration in the feed
gas and of course, the solvent selection.
The H2S specification in the treated gas,
40
Minimum Maximum
2.0 (1.8) 76.2 (68.3)
0.3 (4.5) 0.8 (11)
27 (80) 49 (120)
1.4 39
20 30 40 50 60 70
H2S in feed gas, mol-% (wet)
process operating temperatures, and the
design of the AGE absorber tower internals
can also be important considerations.
Higher processing temperatures or lower
specification for H2S in the treated gas
stream may require increased lean amine
circulation rate and/or increased mass
transfer area to ensure that the H2S spec-
ification in the treated gas is met. Increas-
ing the amine rate or mass transfer area
will directionally reduce H2S selectivity.
The design of the tower internals influ-
ences the mass transfer rates and H2S
selectivity as highlighted by Weiland. Exxon-
Mobil has found that tray columns gener-
ally provide better selectivity than packed
columns in AGE service. One of the rea-
sons is that in a tray column, the mass
transfer parameters can be finely tuned by
adjusting the number of liquid passes, weir
heights and open area on the trays. It is
also easier to provide multiple lean amine
inlets in a tray column for optimising the
mass transfer zone, thereby providing oper-
ators with additional flexibility to meet
changing gas feed compositions.
To successfully achieve the AGE treat-
ing goals of a low H2S content in the
treated gas and maximum CO2 slip
requires a solid base of supporting data
and careful engineering. Figure 2 illustrates
the range of H2S enrichment that can be
achieved using FLEXSORB SE or SE PLUS
solvent in a single enrichment step.
At very low levels of H2S in the AGR acid
gas (<2%), two consecutive stages of
enrichment can be used to achieve suffi-
ciently high levels of H2S in the Claus plant
feed. Alternatively, a recycle of AGE
enriched acid gas back to the AGE
absorber inlet can be used.
Due to its higher selectivity for H2S, FLEX-
SORB SE Plus has replaced MDEA-based
solvents in several high temperature (>40C)
applications to reliably meet treated gas H2S
specifications. However, there is a practical
upper limit to the feed gas temperature.
EMRE has designed several commercial AGE
units to operate with feed gas temperatures
of 48-50C. Although we do not have written
confirmation, it is reasonable to assume
that some of these units have actually oper-
ated with temperatures of 50C or higher.
Yet, there are several process and eco-
nomic advantages for lowering the feed gas
perature reduces the equilibrium partial
pressure of the H2S over the lean amine
solution and slows the CO2 reaction rate.
This increases the H2S selectivity in the
absorber and reduces the required lean
amine flow rate. Lower amine circulation
rate reduces the size of the regeneration
system and lowers the utility requirements.
In one recent application, prediction model
results showed that lowering the feed tem-
perature from 52 to 49C reduced the
FLEXSORB SE Plus circulation rate by 10%.
ExxonMobil working with various engineer-
ing firms and end-user companies has
studied the impact of temperature for sev-
eral large Middle East gas projects. In each
case, an acid gas cooler to lower the AGE
feed gas temperature to 43-50C was
found to be the best solution.
Commercial experience
Several published case studies have docu-
mented the engineering details, project eco-
nomics and operating results of FLEXSORB
AGE units. Collectively, these case studies
illustrate the wide variety of process config-
urations that can be utilised with the FLEX-
SORB SE or SE PLUS solvent. The optimum
configuration for each new project must be
determined by the individual project con-
straints including local environmental regu-
lations, gas compositions, and economics.
Sulphur 326 | January -February 2010
 FLEXSORB SOLVENTS
Table 1 provides a concise summary of
the range of experience for FLEXSORB SE
and SE PLUS AGE units.
Royan et al.3 described the per form-
ance of a FLEXSORB AGE with a very high
CO2 to H2S ratio. A single stage FLEXSORB
AGE is used to produce an enriched acid
gas of about 20% H2S which was then
processed in a split flow Claus plant. The
FLEXSORB AGE unit also produced less
than 10 vppm H2S in the treated gas which
was vented to the atmosphere.
ExxonMobil started gas production at
the Mobile Bay plant in March 1994. Natu-
ral gas is produced offshore where associ-
ated liquids are separated. The gas is then
treated for hydrocarbons, dehydrated and
piped onshore for further treating and sul-
phur recovery4. The gas is produced from
separate formations where the H2S con-
centration can vary from 50 vppm to 1.5
mol-%. The CO2 concentration was rela-
tively constant at 3 to 4 mol-%.
Because of the possible wide variability
in the inlet H2S concentration, the onshore
gas treating facilities were designed to be
very flexible. The sales gas is first treated
to produce a pipeline gas containing less
than 4 vppm H2S and 2 mol-% CO2. The
acid gas from the AGR regenerator con-
tains from about 1% to 25 mol-% H2S. This
AGR acid gas is treated in an AGE absorber
using FLEXSORB SE PLUS solvent utilising
a lean / semi-lean configuration. The lean
FLEXSORB SE PLUS is fed to the top
absorber section and the partially-loaded
rich solvent from the two tail gas treating
(TGT) absorbers is fed along with additional
lean solvent to the lower section of the
absorber. The lean plus semi-lean solvent
configuration in the AGE reduces the total
solvent circulation rate and thereby
reduces the size of the regenerator and its
auxiliary systems. The lean plus semi-lean
combined AGE/TGT units have demon-
strated total solvent circulation savings of
20% or more compared to the solvent
required for two independent absorbers.
The total rich solvent from the AGE is sent
to the FLEXSORB SE regenerator to pro-
duce an enriched acid gas feed to the two
Claus plants. Typically, the enriched acid
gas contains about 70 to 80 mol-% H2S
and essentially no hydrocarbons.
Garrison et al.5 describes a retrofit
application where the AGE unit was added
to an existing gas plant to help meet new,
higher sulphur recovery requirements. A
detailed engineering study compared the
performance of FLEXSORB SE PLUS to a
42
proprietary MDEA solvent. FLEXSORB was
chosen because it offered higher H2S in
the enriched acid gas, lower H2S in the
treated gas, lower circulation rate and
lower capital cost. Due to the enrichment
capabilities of the FLEXSORB SE PLUS sol-
vent, part of the primary acid gas was
bypassed around the AGE while still being
able to meet the minimum H2S concentra-
tion required for the Claus plant feed. This
approach helped minimise the capital cost
of the new facilities. The FLEXSORB AGE
consistently enriched the acid gas from
about 30 mol-% to 65 mol-% H2S.
Jones et al.6 describes the integration
of an AGE unit followed by acid gas injec-
tion. The AGE unit utilises FLEXSORB SE
solvent to reduce the volume of acid gas
to be compressed and re-injected by an
order of magnitude from 15.6 kNm3/h to
1.45 kNm3/h (14 to 1.3 MSCFD). This
project also illustrated the operating flexi-
bility advantages of designing the AGE
absorber with alternate lean amine feed
locations. Operating experience demon-
strated that using the lowest lean amine
inlet with only four actual trays maximised
CO2 slip and still met H2S specification in
the treated gas.
Hanna and Ilyasak7 describe the newly
commissioned Qatargas LNG trains 4 and
5 (also known as the QatarGas II Project or
QGII) which use FLEXSORB SE PLUS solvent
in both the AGE and TGT units. The QGII
trains are the worlds largest LNG trains
rated for 7.8 million tons of LNG per year.
The AGE absorber feed gas H2S concentra-
tions ranged from 16 to 34 mol-% for the
design cases studied. The CO2-rich treated
gas from the AGE absorber can be sent to
the TGT absorber or directly to the incinera-
tor. The treated gas from the TGT absorber
is sent to the incinerator. Each treated gas
stream from the AGE or TGT contains less
than 150 vppm H2S with lean amine tem-
peratures as high as 45C (113F).
The AGE tower is fitted with 12 valve
trays with three alternative lean amine inlet
locations while the TGT absorber and
regenerator towers are designed using
50mm random packing. Each absorber
also includes a small water wash section
to minimise solvent losses. The recirculat-
ing water wash has an intermittent purge
that is sent with the rich amine stream to
recover the FLEXSORB SE PLUS.
Qatargas III and IV Projects will share
essentially the same design as QGII and will
utilise FLEXSORB SE PLUS in an additional
four trains each with an AGE and TGTU.
Conclusions
EMREs FLEXSORB SE or SE PLUS solvents
are in use in wide variety of acid gas enrich-
ment unit designs around the world. These
units include both ExxonMobil affiliates and
licensees. These plants range in size from
three to more than 1000 t/d of sulphur
capacity. CO2 slip ranges from 73-94%.
Multiple independent project analyses
have repeatedly demonstrated the advan-
tages of FLEXSORB SE and SE PLUS over
competing MDEA-based solvents. FLEX-
SORB SE has advantages in improved H2S
selectivity and lower circulation rates. This
property allows FLEXSORB SE to achieve
higher H2S cleanup in the AGE treated gas
and higher H2S concentration in the
enriched acid gas. These advantages
result in substantial investment savings for
new units, debottleneck capacity for retro-
fit applications, and operating cost savings
for either type.
References
1. Weiland R. H.: Acid Gas Enrichment - Maxi-
mizing Selectivity, Proceedings of the 2008
Laurance Reid Gas Conditioning Conference,
Norman, Oklahoma, USA (2008).
2. Chludzinski G. R., and Iyengar J.N.: Lean
Acid Gas Enrichment with Selective Hindered
Amines, World Intellectual Property Organi-
zation, Patent Number WO 93/10883, (June
10, 1993).
3. Royan T., Warchola R. and Clarkson M.: Acid
Gas Enrichment Using FLEXSORB, Pro-
ceedings of the 1992 Laurance Reid Gas
Conditioning Conference, Norman, Okla-
homa, USA (1992).
4. True W.R.: New Mobile Bay complex exploits
major sour gas reserve, Oil & Gas Journal,
v 92, n 21, pp 49-51 (May 23, 1994).
5. Garrison J., Loucks S., Moore B.K, Sheth
P.S., and Tanzi C.S: Keyspan Energy Canada
Rimbey Acid Gas Enrichment with FLEXSORB
SE PLUS Technology, Proceedings of the
2002 Laurance Reid Gas Conditioning Con-
ference, Norman, Oklahoma, USA (2002).
6. Jones S.G., Rosa D.R, and Johnson J.E.: De-
sign, Cost & Operation of an Acid Gas Enrich-
ment and Injection Facility, Proceedings of
the 2004 Laurance Reid Gas Conditioning
Conference, Norman, Oklahoma, USA (2004).
7. Hanna J. M. and M. Ilyasak M.: Qatargas Ex-
pansion Projects: Why Change the Gas Treat-
ing Concept from Sulphinol-D, SOGAT 2009,
Proceedings of the 5th International Confer-
ence, Abu Dhabi, UAE (March 31 April 1
2009).
8. Clark D.S. and Sibal P.W.: Gas Treating Al-
ternatives for LNG Plants, Proceedings of
the Seventy-Seventh GPA Annual Conven-
tion, pp 185-190, Gas Processors Associa-
tion, Tulsa, Oklahoma, USA (1998).
Sulphur 326 | January -February 2010