Proceedings of the 2nd Annual Gas Processing Symposium

Farid Benyahia and Fadwa T. Eljack (Editors)

© 2010 Elsevier B.V. All rights reserved. 229

FLEXSORB ® SE A Proven Reliable Acid Gas

Enrichment Solvent
L. E. Parks, D. Perry , R. Fedich
ExxonMobil Research and Engineering Company, 3225 Gallows Road, Fairfax, Va
22037, USA

Keywords: amine; sulfur; gas absorption; hydrogen sulfide; selective removal

1. AGE Background

To bring natural gas to market, either via pipeline to nearby consumers or via
liquefaction to distant markets, various impurities in the produced gas must be removed.
Chief among these are H2S and CO2. These acid gas components are removed from the
sales gas using traditional amine treating processes also known as Acid Gas Removal
(AGR) units. Typically, the AGR absorbers are run at high pressure 35-83 barg (500-
1200 psig) to minimize recompression costs.
Typical specifications for H2S in sales gas are <4 vppm. For pipeline gas, the residual
CO2 is usually determined by the overall heating value of the gas stream, but generally
ranges between 2-5 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 downstream processing.
As a result of the sales gas specifications, AGR’s remove essentially all of the H2S and
CO2 from the produced natural gas. AGRs can utilize a variety of solvents, including
generic and formulated MDEA. In some cases, controlled CO2 removal can be used
using a selective solvent such as FLEXSORB or MDEA, to leave some of the CO2 in
the sales gas. For gas fields with high CO2 to H2S ratios, the acid gas stream from the
AGR regenerator will have an unfavorably high CO2 to H2S ratio resulting in a poor
quality feed to a Claus plant.
As the amount of sulfur removed from the sales gas exceeds a threshold limit between 1
and 10 MT/D, depending on local regulations, it is generally required to recover the
sulfur. The preferred recovery technology is the modified Claus process. One of the
keys to good Claus plant performance is to maintain a stable flame and high
temperatures in the main reaction furnace (>926°C, 1700°F). Higher temperatures
increase the conversion of H2S to elemental sulfur. CO2 in the acid gas feed to the
Claus unit acts as a diluent, reducing reaction furnace temperatures. To achieve high
temperatures in the Claus furnace an acid gas feed stream typically requires at least 50
230 FLEXSORB A Proven Reliable Acid Gas Enrichment Solvent

mole percent H2S. If the H2S concentration in the acid gas from the AGR is lower than
50%, several 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 combustion air and a fraction of the acid gas are fed to
the main burner. Bypassing some of the acid gas to a second furnace chamber raises the
temperature in the combustion zone but lowers the sulfur recovery efficiency. If the
acid gas H2S concentration is below 20%, a split flow design cannot achieve the
required temperature in the main reaction furnace. In these cases, Claus plant designers
can choose to fire a supplemental fuel, or utilize oxygen enrichment of the combustion
air, or preheat the air and/or acid gas feed to the Claus furnace to maintain the proper
temperatures. None of these options are preferred.

In the last two decades, a new option to process dilute acid gas streams called Acid Gas
Enrichment (AGE) 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 utilizing 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 flow diagram of an 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. 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”). The rich amine from the
bottom of the absorber is then pumped through a rich-lean heat exchanger and on to a
regenerator tower. The regenerator produces an enriched acid gas product overhead and
the lean amine bottoms product to be recycled to the absorber.

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 maximize the selectivity for absorbing H2S.
AGE process simulations by Weiland (2008) have demonstrated that the CO2 and H2S
partial pressure driving forces in the AGE absorber work against achieving these goals
simultaneously. As the gas moves up the absorber tower, the H2S partial pressure is
decreasing reducing the mass transfer driving force. At the same time, the CO2 partial
pressure is increasing, making CO2 pick-up more difficult to avoid.

The severe steric hindrance of the FLEXSORB SE molecule is specifically tailored to

give high H2S absorption capacity in the presence of CO2. This allows FLEXSORB SE
and SE PLUS solvents to achieve high H2S cleanup, high solvent capacity and high H2S
L.E. Parks et. al 231

selectivity at low solvent circulation rates. The FLEXSORB SE PLUS solvent is

especially formulated to facilitate lean solvent regeneration, thus allowing treatment of

Figure 1: Standalone AGE Flow Diagram

gases to less than 10 vppm H2S. No solvent reclaiming is required in AGE or TGTU
services because the FLEXSORB SE amine molecule is chemically very stable.

Chludzinski and Iyengar (1995) describe the application of these sterically hindered
amines to AGE units as well as outline the operating conditions and some of the
possible unit configurations.

2. What levels of enrichment are possible?

The level of H2S enrichment depends on several factors including the H2S concentration
in the feed gas, the H2S specification in the treated gas, process operating temperatures,
the design of the AGE absorber tower internals, and of course, the selective solvent
selection. Higher processing temperatures may require increased lean amine circulation
rates to ensure that the H2S specification in the treated gas is met. Increased lean amine
circulation rate generally reduces selectivity. Similarly, a tight specification for residual
232 FLEXSORB A Proven Reliable Acid Gas Enrichment Solvent

H2S in the treated gas (CO2 rich) stream may also require higher lean amine circulation
rates or greater mass transfer contacting area, both of which will directionally reduce
selectivity.
The design of the tower internals influences the mass transfer rates and H2S selectivity
as highlighted by Weiland. ExxonMobil has found that tray columns generally provide
better selectivity than packed columns in AGE service. One of the reasons 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 optimizing the mass transfer zone,
thereby providing operators with additional flexibility to meet changing gas feed
compositions.
To successfully achieve the AGE treating goals of a low H2S content in the treated gas
and maximum CO2 slip requires a solid base of supporting data and careful engineering.
Table 1 below, illustrates the range of H2S enrichment that can be achieved using
FLEXSORB SE or SE PLUS solvent in a single enrichment step.

Table 1: Examples of H2S enrichment

Project A B C D

Inlet H2S,
4.0 14.7 21.9 32.1
mol% (wet)
Enriched H2S,
41.5 51.4 59.5 75.3
mol% (wet)

At very low levels of H2S in the AGR acid gas, two consecutive stages of enrichment
can be used. Alternatively, a recycle of AGE enriched acid gas back to the AGE
absorber inlet can be used to achieve sufficiently high levels of H2S in the Claus feed.

3. Commercial Experience

Several published case studies have documented the engineering details, project
economics and operating results of FLEXSORB AGE units. Collectively, these case
studies illustrate the wide variety of process configurations that can be utilized with the
FLEXSORB SE or SE PLUS solvent. The optimum configuration for each new project
must be determined by the individual project constraints including local environmental
regulations, gas compositions, and economics.

Table 2 provides a concise summary of the range of experience for FLEXSORB SE and
SE PLUS AGE units.
L.E. Parks et. al 233

Table 2: FLEXSORB AGE Experience Bands

Minimum Maximum
Acid Gas Feed Conditions:
Rate, kNm3/h (MSCFD) 2.0 (1.8) 76.2 (68.3)
Pressure, barg (psig) 0.3 (4.5) 0.8 (11)
Temperature, °C (°F) 27 (80) 49 (120)
Inlet H2S, mol% 1.4 39

Royan et al. (1992) described the performance 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 also produced less than 10 vppm H2S in the treated gas which was vented
to atmosphere.

ExxonMobil started gas production at the Mobile Bay plant in March 1994. Natural gas
is produced offshore where associated liquids are separated. The gas is then treated for
hydrocarbons, dehydrated and piped onshore for further treating and sulfur recovery.
(True, 1994) The gas is produced from separate formations where the H2S
concentration can vary from 50 vppm to 1.5 mol%. The CO2 concentration was
relatively constant at 3-4 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 raw acid
gas from the AGR regenerator contains from 1% to 25 mol% H2S. This raw acid gas is
treated in an AGE absorber using FLEXSORB SE PLUS solvent utilizing 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 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 demonstrated total solvent circulation savings of 20%
or more compared to the solvent required for two independent absorbers. The rich
solvent from the AGE is sent to the FLEXSORB SE regenerator to produce 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. (2002) describes a retrofit application where the AGE was added to an
existing gas plant to help meet new, higher sulfur recovery requirements. A detailed
234 FLEXSORB A Proven Reliable Acid Gas Enrichment Solvent

engineering study compared the performance of FLEXSORB SE PLUS to a 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 solvent, part of the primary
acid gas was bypassed around the AGE while still being able to meet the minimum H2S
concentration required for the Claus plant feed. This approach helped minimize 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. (2004) describes the integration of an AGE followed by acid gas injection.
The AGE unit utilizes 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 flexibility advantages of
designing the AGE absorber with alternate lean amine feed locations. Operating
experience demonstrated that using the lowest lean amine inlet maximized CO2 slip and
still met H2S specification in the treated gas using only four actual trays.

Hanna and Ilyasak (2009) describe the newly commissioned Qatargas LNG trains 4&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 world's largest LNG
trains rated for 7.8 million tons of LNG per year. The AGE absorber feed gas H2S
concentrations ranged from 16-34 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
incinerator. 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 temperatures as high as 45°C (113°F).

The AGE tower is fitted with 12 valve trays with 3 alternate 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 minimize solvent
losses. The recirculating water wash has an intermittent purge that is sent with the rich
amine stream to recover the FLEXSORB SE PLUS.

Qatargas III and IV (trains 6 and 7) will share essentially the same design as QGII.

4. Conclusion

ExxonMobil's FLEXSORB SE or SE PLUS solvents are in use in a wide variety of acid

gas enrichment unit designs around the world. These units include both ExxonMobil
L.E. Parks et. al 235

affiliates and licensees. These plants range in size from 3 to more than 1000 tons per
day sulfur capacity. CO2 slip ranges from 73-94%.

Multiple independent project analyses have repeatedly demonstrated the advantages of

FLEXSORB SE and SE PLUS over competing MDEA-based solvents. FLEXSORB SE
has advantages in better 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 retrofit
applications, and operating cost savings for either type.

References

Chludzinski, G. R., and J. N. Iyengar, 1993, "Lean Acid Gas Enrichment with Selective
Hindered Amines," World Intellectual Property Organization, Patent Number WO
93/10883, June 10, 1993.
Garrison, J., S. Loucks, B. K. Moore, P. S. Sheth, and C. S. Tanzi, 2002, "Keyspan
Energy Canada Rimbey Acid Gas Enrichment with FLEXSORB SE PLUS
Technology," Proceedings of the 2002 Laurance Reid Gas Conditioning Conference,
Norman, Oklahoma, USA.
Hanna, J. M. and M. Ilyasak, 2009, "Qatargas Expansion Projects: Why Change the Gas
Treating Concept from Sulfinol-D?," SOGAT 2009, Proceedings of the 5th
International Converence, March 31-April 1, 2009, Abu Dhabi, UAE.
Jones, S. G., D. R. Rosa, and J. E. Johnson, 2004, "Design, Cost & Operation of an Acid
Gas Enrichment and Injection Facility," Proceedings of the 2004 Laurance Reid Gas
Conditioning Conference, Norman, Oklahoma, USA.
Royan, T., R. Warchola, and M. Clarkson, 1992, "Acid Gas Enrichment Using
FLEXSORB®," Proceedings of the 1992 Laurance Reid Gas Conditioning
Conference, Norman, Oklahoma, USA.
True, W.R. (1994), "New Mobile Bay complex exploits major sour gas reserve," Oil &
Gas Journal, v 92, n 21, pp 49-51, May 23, 1994.
Weiland, R. H., 2008, "Acid Gas Enrichment - Maximizing Selectivity," Proceedings
of the 2008 Laurance Reid Gas Conditioning Conference, Norman, Oklahoma, USA.