Solutions for the treatment of highly

sour gases
Process technologies for the cost-effective treatment of natural gas with
high and ultra-high acid gas content

FRANÇOIS LALLEMAND and GAUTHIER PERDU Prosernat CRISTINA MARETTO and CLAIRE WEISS Total E&P
JULIA MAGNE-DRISCH and ANNE-CLAIRE LUCQUIN IFP Energies Nouvelles

F
or decades to come, gas
will be the energy source Relative technical cost of sour gas production vs acid gas content
of choice to meet increas-
ing energy demands. Those oil Sweet gas Highly sour 20% acid gas Ultra sour 40% acid gas
Sales gas, % of raw 98 75 52
and gas operators who have Capex, MM$ 100% 140% 185%
always preferred to produce Opex, MM$/year 100% 160% 200%
Technical cost, $/MMBtu 100% 200% 400%
gas from the technically easiest
to develop reservoirs will in Notes: Acid Gas = H2S+CO2Orders of magnitude for illustration purpose only

the future have to develop

fields with a higher acid gas Table 1
content. Effectively, 40% of the
world’s natural or associated exported volume of sales gas product from the production of
gas reserves currently identi- decreases because of the gases containing high amounts
fied as remaining to be reduced hydrocarbon content of H2S, formerly represented a
produced, representing over of the inlet raw gas and the substantial part of the revenues
2600 trillion cubic feet (tcf), are increased auto-consumption for drawn from the production of
sour, with both H2S and CO2 gas treatment. As a conse- such natural gases. It is no
present most of the time. quence, the technical cost per longer of economic interest to
Among these sour reserves, volume of exported sales gas is sell sulphur from several areas
more than 350 tcf contain H2S roughly doubled every 20-25% today, especially those loca-
in excess of 10%, and almost of additional acid gases present tions far from the sea and the
700 tcf contain over 10% CO2.1 in the raw gas (see Table 1). sulphur users. The world
Removing the undesired acid Very efficient technologies sulphur market is globally
gases from highly sour gases is are therefore necessary to sepa- saturated, as the supply of
a costly operation. The size and rate the large amounts of acid sulphur, mainly obtained from
cost of the acid gas separation gases from these fields. H2S separated from sour natu-
units and the acid gas-handling Solutions implemented by ral gases or sour crude, has
facilities (transformation of the Prosernat using the AdvAmine exceeded demand, essentially
H2S into sulphur and forming/ series of processes, some of from the fertilizer industry.
shipping of the produced which have been developed in Even though some companies
sulphur, or acid gas compres- collaboration with Total and have developed new sulphur
sion/pumping and re- IFPEn, to optimise amine proc- uses such as sulphur asphalt in
injection facilities) increase with esses are presented in this the 1970s or, more recently,
the amount of acid gases to article. sulphur concrete, most experts
separate. In the meantime, the Sulphur, the traditional sub- consider that this situation is

www.digitalrefining.com/article/1000356 Gas 2012 1

 Treated
gas
Acid
gas

Lean
solvent

Fuel
gas
LP
steam

Sour
gas
Rich solvent

Figure 1 Acid gas removal unit design

set to continue for several utilisation to enhance oil Optimisation of amine

decades, at least in several recovery (EOR) or just simple processes for highly sour gas
parts of the world. The produc- disposal to a depleted reservoir treatment
tion of major oil or gas fields in or an aquifer, as a feasible Amine processes (see Figure 1)
the Middle East or in the alternative to costly sulphur have been used for many years
Caspian Sea area could lead to recovery to a diminishing to remove acid gases from
the production of considerable sulphur market, or to limit natural and associated gas
quantities of additional sulphur atmospheric emissions of streams. They are very versatile
in an already saturated market, greenhouse gases — a number processes, which can be used
while the storage of extra of highly sour gas fields can be to treat all types of sour gas,
sulphur in the long term is an reconsidered as exploitable to regardless of the H2S and/or
issue that will require signifi- produce much-needed natural CO2 content, down to the most
cant capital costs to be resolved. gas. severe specifications, such as
This is why new production These new constraints lead to those imposed by gas liquefac-
methods must be developed for the development of more energy- tion plants.
sour fields, to limit the over- efficient technologies for acid But the cost of gas sweeten-
production of sulphur. gas separation, adapted to ing increases with the amount
Companies willing to these new production schemes. of acid gases to be separated,
produce large gas fields with With this objective, in addition requiring larger amine solution
very high amounts of CO2 have to the AdvAmine series of gas flow rates and higher energy
to face a different constraint sweetening processes using consumption for amine solu-
related to the essential need to amine-based solvents, Total, tion regeneration. On the other
reduce atmospheric emissions IFPEn and Prosernat have hand, amine processes, because
of greenhouse gases. developed Sprex and SprexCO2 of the variety of amines availa-
With the growing acceptance for the production of highly ble and the possibility to adapt
of the re-injection of separated sour gas reserves with acid gas and improve the process flow
H2S and CO2 — either for re- re-injection. schemes, can be efficiently used

2 Gas 2012 www.digitalrefining.com/article/1000356

 Treated
gas
Acid
gas

Lean
solvent

Semi-lean
solvent

Fuel
gas

LP
steam
Sour
gas

Figure 2 Conventional double-split flow design

for almost any type of gas Double-split flow process 2. Part of the amine solution is
sweetening application. Amine- configuration withdrawn from the regenera-
based technology can therefore Among the oldest process tor as a side stream, then
be considered as the workhorse configurations, the double-split cooled and pumped into the
of the sour gas processing flow design, sometimes called lower section of the absorber.
industry and, as such, still justi- the split-flow design, has been The amine in the side draw is
fies continuous technological used as an alternative flowsheet not fully regenerated and has a
improvements to extend the to minimise capital and operat- higher residual acid gas load-
economical limits of its applica- ing costs in several sour gas ing. However, as this semi-lean
tions. Issues like treatment processing plants. Generally solution contacts the incoming
costs and energy consumption used with primary or second- sour gas, it can still pick up the
are being addressed by such ary amines, this design allows bulk of the acid gas. Due to the
developments. for very severe treated gas semi-lean amine side draw, the
This article presents solutions specifications for the same amine flow to the regenerator
proposed by Prosernat for the reboiler duty as a conventional reboiler is reduced, and the
efficient and economic treat- process flow scheme, and was duty of the reboiler can be
ment of gases with a high acid documented probably for the decreased to achieve the same
gas content, either H2S or CO2. first time by Estep, McBride lean amine quality required on
These solutions benefit from and West in 1962.2 This design top of the absorber column to
the operating experience of also allows for the same treated meet the treated gas
Total in its highly sour gas gas specification as a conven- specification.
treatment plants and, while tional amine plant scheme,
some are proposed by other with a much-reduced reboiler Advantages of energizedMDEA
licensors, others have been duty when treating very sour for the treatment of very sour
developed through the joint gases. gases
R&D effort of Total, IFPEn and A conventional double-split The main factors affecting a
Prosernat. flow design is shown in Figure solvent’s performance for acid

www.digitalrefining.com/article/1000356 Gas 2012 3

 the blend of an energiser with
10000 MDEA, generally a secondary
DEA amine.3,5
MDEA The ability of energizedM-
Pressure, mm Hg

DEA to release a substantial

part of the absorbed acid gases
in a low-pressure flash can be
1000
combined with the introduction
of a semi-lean solvent in the
bottom part of the absorber, as
DEA in the double-split flow design
MDEA shown in Figure 4.
The rich amine solution after
100
0.0 0.2 0.3 0.4 0.5 0.6 0.7 0.8 letdown through a hydraulic
CO2/Amine, moles turbine is divested of co-
absorbed light hydrocarbons in
Figure 3 Equilibrium solubility of CO2 in aqueous amine solutions a first flash drum, as in the
conventional process, then
gas absorption are its ease of CO2 partial pressure than its further expanded to a low pres-
regeneration, and the solubility solubility in DEA. This is sure in a second flash drum to
and reactivity of the acid gases. shown by the slopes of the partially liberate CO2 and H2S.
Tertiary amines require less equilibrium solubility curves in The greater part of the rich
regeneration energy than Figure 3. amine, thus partially regener-
primary and secondary amines. The basic concept of an effi- ated, is returned to an
Being a tertiary amine, MDEA cient process for the removal of intermediate level of the
therefore requires less reboiling large quantities of acid gases absorber as a semi-lean solvent.
duty than DEA. It is, however, involves taking advantage of This semi-lean solvent loop is
well known that MDEA reacts the slopes of the equilibrium particularly economic, as it
slowly with CO2. This is an solubility curves of CO2 in reduces the thermal regenera-
advantage in selective H2S and aqueous MDEA solutions. This tor load and consumes only
controlled CO2 removal, but allows for the liberation of a pumping energy.
becomes a handicap in complete maximum amount of the acid When H2S is present and/or
acid gas removal, especially gas from the solution by simple the treated gas specification
when a substantial quantity of physical pressure letdown flash calls for the removal of CO2
CO2 has to be removed. To and thus substantially reduces below the 2 vol% range, thor-
overcome this kinetic obstacle, the thermal regeneration duty. oughly regenerated, virtually
it was necessary to find energis- For example, the MDEA solu- H2S- and CO2-free amine is
ers among the secondary amines tion releases almost twice as required. This is accomplished
that had high speeds of reaction much CO2 as the DEA solution in a conventional thermal
with CO2 to blend into the by a pressure letdown of 10 to regenerator, returning a small
otherwise desirable MDEA 1 bar (see Figure 3). In addi- flow of the leanest amine to the
solvent. Several energisers were tion, the equilibrium solubility top section of the absorber.
selected by Total from those of H2S in aqueous MDEA In 1990, the new solvent and
best suited to industrial condi- exhibits similar behaviour to regeneration system were
tions, taking into account CO2, allowing an equivalent tested on an existing DEA unit
commercial availability, cost amount of H2S at the Lacq sour gas plant,
and impact on the liberation by pressure letdown. southwest France, which was
environment.3 EnergizedMDEA approaches then converted to the ener-
While the reactivity of CO2 the equilibrium curve of MDEA gizedMDEA process.4,5
with MDEA is lower than with at high pressure, but behaves The performance of the ener-
DEA, its solubility in MDEA is like DEA at low acid gas partial gizedMDEA process is closely
more strongly influenced by pressures. This is achieved by related to site-specific treatment

4 Gas 2012 www.digitalrefining.com/article/1000356

 Treated
gas
Acid
gas

Lean
solvent

Semi-lean
solvent

Fuel
gas

LP
steam
Sour
gas

Figure 4 Split flow design with energizedMDEA

conditions; notably, feed gas consumption of the energized- the reboiler duty quickly
composition and treated gas MDEA unit increases as the brought some process develop-
specifications. Below are some treated gas specification ers, and later on plant
practical rules-of-thumb to becomes more stringent, since operators, to consider increas-
highlight the general interest of the amount of lean totally ing the acid gas loading of the
regeneration by flash:6 regenerated amine from the rich amine leaving the
• The greater the H2S and/or thermal regeneration increases. absorber.7 The maximum
CO2 partial pressure in the feed In some bulk CO2 removal cases achievable loading is controlled
gas, the greater the efficiency with no H2S, as mentioned, it by the thermodynamic equilib-
of the flash. In the case of the may even be possible to rium between the sour gas
Lacq sour gas plant, the acid completely eliminate the ther- entering the absorber and the
gas partial pressure of the feed mal regenerator. rich amine, and by the effi-
is approximately 15 bar in As a consequence of the ciency of the mass transfer in
comparison to a total pressure above attributes, the energized- the absorber. The higher the
of 2 bar in the second flash MDEA process is well adapted acid gases partial pressure in
drum. This gives a ratio of to the treatment of high pres- the sour gas, the higher the
7.5/1 (acid gas partial pres- sure and very sour gases, amine loading at thermody-
sure/flash pressure). In general, where the advantages of flash- namic equilibrium. High H2S
the advantage of the flash procured regeneration will be and CO2 partial pressures will
procured regeneration starts maximised to reduce the energy therefore invariably allow a
above a ratio of 3 footprint of the sweetening. high amine loading at the
• Targeting low H2S content in benefit of an improved effi-
the treated gas requests a ther- High loading in amine ciency of process. Loadings
mal regenerator to clean up the sweetening higher than 0.8 (mole of acid
solvent down to low H2S resid- An effort to moderate the gases per mole of amine) can
ual loading. The overall energy solvent flow rate along with theoretically be achieved when

www.digitalrefining.com/article/1000356 Gas 2012 5

 with thermal regenerator
Some AdvAmine units operated with high acid gas loading
(conventional double-split flow
design, as shown in Figure 1)
Amine type Feed gas Feed gas Feed gas Loading Startup year
• Split-flow process with flash-
pressure, bar H2S, vol% CO2, vol%
HiLoadDEA 65 4.2 6.0 0.64 1984 supported regeneration to
MDEAmax 70 4.0 5.6 0.71 2001 produce a semi-lean amine
energizedMDEA 105 Traces 9.2 0.72 1996 solution, as shown in Figure 3.
HiLoadDEA 66 8.5 9.5 0.77 1980
HiLoadDEA 66 21.5 14.7 0.85 1987 Both split-flow process
HiLoadDEA 70 15.8 9.8 0.85 1957 configurations require a lot
HiLoadDEA 70 34.6 6.1 0.90 1972 more equipment than the
single-flow process, due to the
Table 2 addition of a semi-lean amine
circuit, which includes a rich/
the partial pressure of the acid units have also been licensed semi-lean amine exchanger or a
gases is above 15-20 bar; that is to other operators. Table 2 rich amine preheater, a semi-
to say, when treating a very gives examples of such amine lean amine cooler and pumps.
sour gas at a high pressure. units. In addition, the flash-procured
The pH of the rich amine split-flow scheme needs an
solution decreases with its acid Case study: energizedMDEA for amine heater and an additional
gas loading, in turn increasing very sour gas sweetening flash drum at regenerator pres-
the tendency of the amine An example of the use of the sure. Both split-flow process
solution to corrode carbon energizedMDEA process for the configurations also need an
steel. This is why some opera- sweetening of a sour natural gas absorber with a slightly
tors prefer to limit the loading with a very high H2S content increased height compared to
to below 0.5 to 0.6. In fact, the follows. The sour gas composi- the conventional process
erosion/corrosion of carbon tion is shown in Table 3. configuration, to take into
steel can be controlled and This case study compares account the additional liquid
maintained under acceptable three different process configu- feed. As only a fraction of the
levels at a high solvent loading rations for the removal of H2S amine solution is fully regener-
under the operating conditions and CO2 down to a standard ated, the total amine solution
of an amine sweetening plant, commercial gas specification; flow rate (lean plus semi-lean)
provided the design of the unit namely, 4 ppm vol H2S and is also higher than that of the
and the operating procedures 2 vol% CO2: conventional process.
are following basic rules,8 such • Single-flow (conventional) On the other hand, the
as limiting the flow velocity in process reboiler duty is substantially
the rich amine line in the range • Double-split flow process decreased in both split-flow
of 1.4 to 1.5 m/s. In some configurations, and the whole
cases, for instance when treat- regeneration section is consid-
Case study: high H2S content
ing gases with a very high CO2 sour gas composition erably reduced in size in the
content and little or no H2S, flash-procured split-flow
the use of 316L stainless steel configuration. In large plants
Composition, vol%
will be necessary in limited, H2S 21.5 necessitating multiple treat-
susceptible areas of the amine CO2 14.8 ment trains, there may even be
unit. It should also be noted Nitrogen 2.8 fewer regenerator trains
that using stainless steel piping Methane 57.0 because of this reduced regen-
Ethane 1.8
lowers the bulk piping weight Propane 1.1 erator capacity.
of the unit. Butanes 0.4 Table 4 gives the comparative
Total has operated plants for Pentanes plus 0.5 energy consumptions for the
several decades, the Lacq plant Organic sulphur 0.1 treatment of the gas with the
Temperature, °C 40
being the first, with rich amine Pressure, bar 70 three schemes, as well as the
loadings above 0.6 and up to relative capital costs of the
0.85/0.90 without corrosion corresponding units.
issues. Several AdvAmine Table 3

6 Gas 2012 www.digitalrefining.com/article/1000356

Further increasing the loading Case study: energy consumption and capital cost comparison
of amine solutions
The loading of the rich amine
energizedMDEA process scheme Conventional Double-split Split-flow process
solution is limited by the ther- single-flow flow process with flash
modynamic equilibrium at the process supported
regeneration
absorber bottom and by the Acid gas loading (rich amine solution), mol/mol 0.85 0.86 0.92
approach to this equilibrium. Rich amine solution concentration, g/l 458 461 458
Thermal energy: reboiler 39
The thermodynamic equilibrium Rich amine preheater, MW
77 67.5
10
is a function of the partial pres- Power consumption, MW 2.7 2.7 3.6
Total energy demand*, MW 100. 5 (base) 89.1 (88.7% 69.6 (69.3%
sures of the acid gases in the of base) of base)
feed sour gas, and high loadings Capital cost, arbitrary unit 100 (base) 113.7 123.1
are favoured by a low tempera- * Steam boiler efficiency 83%, power generation efficiency 33%
ture (see Figure 5). Lowering
the rich amine solution temper- Table 4
ature on the lower part of the
absorber is therefore a means of ration, the semi-lean amine strates the incidence of an
increasing the loading of the solution is withdrawn from a absorber intercooler in the case
rich amine solution leaving the chimney tray, pumped through of the sweetening of a very
absorber. a cooler and re-injected to the sour gas, with the composition
It is generally not practical to tray just below the withdrawal shown in Table 5. The amine
reduce the temperature of the tray. solution temperature is
feed sour gas. This would The example below demon- decreased to 55°C in the inter-
require an expensive high-pres- cooler. As a result, the absorber
sure gas cooler and the use of a Case study: sour gas composition bottom temperature is reduced
refrigeration loop in many from 85.2°C to 71.2°C, and the
fields and, in any case, the cool- rich amine loading can be
ing would be limited by the Composition, vol% increased from 0.60 to 0.71 (see
H2S 11
hydrate formation temperature Figure 6).
CO2 11
of the gas. In addition, the Hydrocarbons Balance Table 6 shows the compara-
resulting lower temperature at Gas flow rate, 106 Sm3/d 5.1 tive energy consumptions for
the absorber top would slow Temperature, °C 50 the treatment of the gas with
Pressure, bar 66
the mass transfer of CO2 from the two schemes, as well as the
the gas to the amine solution, relative capital costs of the
which could, in some cases, Table 5 corresponding units.
impair the specification of the
treated gas.
20
The solution to lowering the
85ºC
absorber bottom temperature 18
Partial pressure H2S, bar

55ºC
without cooling the feed gas 16
and without decreasing the 14
temperature of the top trays is 12
the installation of a liquid
10
intercooler. This will remove
some heat from the amine 8
solution from an intermediate 6
tray, or section of packing, in 4
the absorber column, where 2
the temperature of the gas and ∆ = 0.15
0
the liquid is the highest 0.0 0.5 1.0
because of the exothermicity of Loading, mol H2S / mol MDEA
the absorption of the acid
gases. In this process configu- Figure 5 Rich amine loading as a function of temperature

www.digitalrefining.com/article/1000356 Gas 2012 7

 between 5% and 10%. With the
Lean solvent current status of this technol-
690m3/h
ogy, permeation membranes
can only be used to treat gases
with a very limited H2S content,
Lean solvent as they are very sensitive to
820m3/h
this chemical. Membrane units
are relatively simple and use
180 MMSCFD
very little energy. However,
H2S: 11% mol permeation membranes are not
CO2: 11% mol selective and one must accept
P = 66 bar abs Inter-cooling
to 55ºC
large methane losses with the
separated acid gases, even with
dual-stage membrane units
Rich solvent: Rich solvent: with inter-stage recompression.
85.2ºC 71.2ºC Provided an adequate precon-
ditioning of the gas is
Figure 6 Incidence of the intercooler on absorber operating conditions performed, membrane life is
considered as acceptable to
limit the cost of replacement.
Energy consumption and capital cost comparison However, the preconditioning
unit is generally fairly large,
energizedMDEA process scheme Conventional absorber Absorber with which substantially increases
No intercooler intercooler
Absorber bottom temperature, °C 85.2 71.2 the cost of the sweetening. The
Acid gas loading (rich amine solution), mol/mol 0.60 0.71 process further needs post-
Amine solution flow rate, m3/hr 820 690
Thermal energy: reboiler, MW 67.0 59.5
treatment with an amine
Power consumption, MW 2.40 2.05 solvent to reach tight CO2
Total energy demand*, MW 87.6 (base) 77.6 (88.5% of base) specifications.
Capital cost, arbitrary unit 100 (base) 96.4
Cryogenic distillation proc-
* Steam boiler efficiency 83%, power generation efficiency 33% esses offer many advantages
when the separated acid gases
Table 6 need to be reinjected, to limit
undesired sulphur production
Cryogenic distillation for the energy for the regeneration of or to minimise greenhouse
sweetening of super-sour the solvent than amines. gases emissions to the atmos-
gases Hybrid solvent processes are phere. They are very selective
Some gas fields contain very favoured by a high acid gas to light hydrocarbons, and the
high amounts of H2S (more partial pressure, which is the separated acid gases (H2S and/
than 30 vol%) or CO2 (up to 70 driving force of the absorption or CO2) are recovered in the
vol%) in natural or associated of acid gases. The drawback of liquid state under pressure.
gases. Even though amine proc- these processes is their limited Producing the acid gases under
esses can be optimised to treat selectivity to hydrocarbons, pressure reduces expensive and
very sour gases, as documented and their use should be limited energy-consuming compression
above, the high cost associated to the sweetening of natural requirements.
with sweetening may make the gases with a low heavy hydro- It is possible to produce pipe-
production of these super-sour carbons content. line-quality gas with cryogenic
gases uneconomic under certain Permeation membranes have distillation. Such technologies
gas price conditions. been commercially used since require dehydration of the sour
Hybrid solvent processes, the 1980s for the bulk removal gas prior to entering the cryo-
such as the recently developed of CO2 from gases with a very genic separation. Separating
HySweet from Total,9,10 may be high CO2 content down to a CO2 or H2S down to a commer-
considered, as they require less levered CO2 content generally cial specification requires a

8 Gas 2012 www.digitalrefining.com/article/1000356

very low temperature in the
reflux drum, corresponding to Sales gas
a significant refrigeration
requirement. Furthermore, CO2 AGRU
separation down to commercial Very sour Pre-ex
natural gas (acid gas
levels is limited by the CO2 removal unit)
freezing conditions in the top
section of the cryogenic distilla-
tion column. Some processes
Acid gas liquid Remaining
address this limitation by high pressure acid gas
adding, for example, a suitable
hydrocarbon solvent to the top Figure 7 Staged acid gas separation with the Sprex process
section of the demethaniser to
stay outside the CO2 freezing of these processes are limited When a pipeline or LNG
conditions, or by using a compared to those of other specification is required, the
column with a specific frozen cryogenic processes. Since the Sprex or SprexCO2 unit is easily
CO2 remelting zone. temperature in the SprexCO2 and economically combined
Sprex and SprexCO2, jointly unit is not as low, the operat- with a solvent-based acid gas
developed by Total, IFPEn and ing conditions are a long way removal unit.
Prosernat, are bulk fractiona- from the CO2 and aromatic
tion processes. Sprex, for bulk compounds freezing region, Bulk H2S removal with Sprex
H2S removal, does not require therefore avoiding the need for Sprex is based on an initial
prior dehydration of the gas. an additive fractionation and patent filed in 1994 by IFP, to
The refrigeration requirements recycle or for a remelting zone. improve the economics of the

Pipeline gas

Sprex®
TEG
Fuel
gas

–30ºC
energised Acid gas
MDEA
50-65
bar Ref.

Sour
30-35ºC

60-70ºC
H2S soup

Reinjection well

Figure 8 Sprex simplified process flow diagram

www.digitalrefining.com/article/1000356 Gas 2012 9

 Sprex economic comparison
dry H2S, dehydrates to some
extent the incoming gas in the
upper zone of the Sprex
Raw gas flow rate, MM Sm3/d 4.6 (165 MMSCFD) column. The minimum temper-
Treatment pressure, Bar g 70 (1000 psig)
AG injection pressure, Bar g 150 (2000 psig) ature reached in the unit’s
Raw gas composition, vol% H2S 35, CO2 7.5, C1 56.5, C2+ 1 low-temperature reflux drum is
Treated gas specs H2S 4 ppm, CO2 2% limited to about -30°C, so as to
Amine + acid Sprex + amine + acid remain outside the hydrate
gas compression gas pumping an compression
Capital cost, arbitrary unit Base 100 84 zone at all points of the unit.
Power consumption, MW 52 30 This rules out the need to
Steam consumption, MW 46 34 install a dehydration unit
upstream of the column.
Table 7 The H2S separated out in the
Sprex process is produced in a high-
production of ultra-sour gas processed by a smaller conven- pressure liquid phase, requiring
with a high H2S content when tional amine sweetening unit considerably less energy for
the separated H2S is reinjected. capable of meeting the most reinjection into an underground
The process was improved and severe H2S and CO2 gas specifi- reservoir, as the large multistage
several other patents were filed cations (pipeline gas or feed for acid gas compressors can be
in the 2000s.11 Figures 7 and 8 a LNG plant) replaced with injection pumps.
show the principles and process • It produces a high-pressure Now that the amine sweeten-
flow diagram of the staged acid liquid H2S soup (50 to 65 bar) ing unit located downstream
gas separation, from a very sour that can be easily reinjected has less H2S to separate, the
natural or associated gas using into a geological reservoir. amine solvent circulation rate
Sprex followed by a conven- In this basic version of the can be substantially decreased,
tional solvent sweetening plant. process, which has been as can the size of the equip-
The process has the following demonstrated in an industrial ment. This drastically reduces
advantages:6 context at the Lacq plant,12 the both the investment cost and
• It reduces the H2S content in H2S content in the gas leaving energy consumption.
the gas by producing a partially the Sprex unit is about 10-12%. Table 7 shows an estimation
sweetened gas that can then be The reflux, consisting of cold, of the savings on investment
and energy consumption for
treating 4.5 million Sm3/day of
20 raw gas containing 35% H2S
30 bar and 7% CO2 and reinjecting the
10
40 bar acid components at a wellhead
0 50 bar
pressure of 150 bar.
–10
The values shown in Table 7
–20 are for gas sweetening and
Gas
Temperature, ºC

–30 separated acid gases recompres-

–40 sion units (excluding field
–50 CO2 crystallisation limit facilities such as production
wells, flowlines and acid gas
–60
injector wells, but including the
–70
facilities for the generation of
–80 the energy required by the treat-
Liquid
–90 ment plant) using part of the
–100 export gas.
0 10 20 30 40 50 60 70 80 90 100
CO2, % mol Cryogenic bulk removal of CO2
with SprexCO2
Figure 9 CO2/C1 distillation chart Yet, with a dehydration unit

10 Gas 2012 www.digitalrefining.com/article/1000356

 Refrigeration
loop

To compression
and gas finishing
treatment

Sprex CO2
distillation

Reboiler
HX Boosting / transfer and
injection pumps

Pre-cooling / dehydration

Figure 10 SprexCO2 typical process scheme

upstream of the cryogenic frac- which is performed at condi- (membranes + amines) when
tionation column, the gases can tions outside the CO2 CO2 concentrations are higher
be cooled to well below the - crystallisation domain. The than 40% and CO2 reinjection is
30°C of the basic version of the parameters and limits to avoid required for enhanced oil
Sprex process, which improves crystallisation are illustrated in recovery (EOR) and/or carbon
the efficiency of the H2S separa- the distillation chart based on sequestration. When CO2 is
tion process and allows the main binary mixture (CO2/ being recovered in a liquid
separation of CO2 from the gas. C1). Figure 9 shows a typical “soup” phase, injection is real-
However, the limit then gas specification achievable in ised by pumps instead of
becomes the temperature at the distillation outlet; ie, multistage compressors, with
which CO2 crystallises. The around 20% CO2 mol, at 40 bar. considerable energy savings.
enhanced version of the Sprex SprexCO2 operation at a higher In order to match final gas
process, SprexCO2, allows for pressure, say 50 bar or above, export specifications (pipeline
bulk removal of CO2 from could improve gas specifica- or LNG plant feedstock), the
gases containing a very high tions by 8-10%. However, the unit can be associated with a
CO2 content (≥40% or so) possi- margin to critical point would finishing AdvAmine unit.
bly together with high be reduced, resulting in higher A typical SprexCO2 scheme,
concentrations of H2S. The vapour/liquid traffic in the including upstream pre-condi-
principle of the process is simi- column. In practice, the selected tioning units and downstream
lar to that of demethanisation range for bulk separation is CO2 boosting and transfer/
units —vapour/liquid separa- 18% to 25% CO2 mol. injection pumps, is shown in
tion at high pressure and low SprexCO2 is competitive in Figure 10. The main principles
temperatures. comparison with conventional are as follows:
The process is based on an CO2 separation processes • Feed gas pre-conditioning:
optimised CO2 distillation, (amines) or hybrid solutions ■ Feed gas pre-cooling

www.digitalrefining.com/article/1000356 Gas 2012 11

 The base case for natural gas
100 sweetening includes SprexCO2
Auto-consumption
90 for bulk removal of CO2 and a
HC losses
Material balance, vol%
80
Valorised gas
finishing gas treatment based
70 on AdvAmine technology (ener-
60 gizedMDEA). The membranes +
50 amine combination has been
40 evaluated as an alternative,
30 using commercial membranes
20 vendors’ design data.
10 The basic process steps
0
include:
0 Sprex C02 Membranes • Raw gas pretreatment,
including inlet gas/liquid sepa-
Figure 11 Overall performances comparison: SprexCO2 + amine vs membranes ration, gas pre-cooling and
+ amine dehydration
• Acid gas removal achieved in
■ Liquid removal (water, • The treated gas is transferred two steps: first, a bulk removal
condensate if any) to the finishing treatment (SprexCO2 or membranes) to
■ Gas dehydration • Bottom product: the liquid reach 20 vol% CO2 in the gas
■ Mercury removal unit, ensur- CO2 is pressurised towards stream. The gas stream exiting
ing compatibility with reinjection site the bulk separation is then
aluminium compact heat • Multistage refrigeration loop: treated in the finishing amine
exchangers ■ Using a C /C mixture (closed
2 3
unit to reach a CO2 concentra-
■ Gas filtration loop) tion fitting the gas export
• Gas cooling: ■ Refrigerant sub-cooling using specifications (pipeline or LNG
■ Using reboiler heat boosted CO2 liquid. plant feedstock)
exchanger The scheme in Figure 10 is • Compression of the CO2
■ Using multipass heat typical: some process scheme removed by the amine unit, for
exchangers system exchanging alternatives are achievable reinjection in the reservoir. CO2
with refrigeration loop and depending on the raw gas recovered from amine repre-
treated gas conditions and final specifica- sents less than 10% of the
• Cryogenic distillation tions required for export gas overall CO2 present in the raw
column: (pipeline, LNG feed or others). gas
■ Dual- or multi-entry points, An example of the use of • Pumping of the CO2 removed
improving overall efficiency SprexCO2 follows. The case by the SprexCO2 unit, or alter-
■ At the top of the column, the study compares the process + natively compression of the
refrigeration loop is used to amine combination and the membranes permeate stream
adjust the CO2 content of the membranes + amine combina- for reinjection in the reservoir
gas tion. The range of methane and • CO2 reinjection pipelines.
■ A reboiler at the bottom of CO2 in the raw gas composition Removing CO2 from 70% to
the column is used to adjust is given in Table 8. 20% (our reference case) repre-
the methane losses in the CO2 The gas contains a few sents more than 90% removal
■ The operating parameters are percentage of C2+ and inerts. of the CO2 from the feed gas.
optimised to keep a reasonable Subsequent amine units, using
safety margin towards CO2 the AdvAmine technology,
Fluid composition
crystallisation and to meet the remove all the remaining CO2,
product specifications: down to the gas specification
Mol%
▲ Reflux drum: 40 bar; -54°C as required.
Methane 24-27%
for a 20% CO2 gas specification CO2 68-71% The better performances of
▲ Bottom of the column : 40 the SprexCO2 option, compared
bar; 5°C controlling C1 losses Table 8 to those of the membrane alter-

12 Gas 2012 www.digitalrefining.com/article/1000356

native, are illustrated in Figures
11 and 12. The process maxim- 10
ises gas valorisation by halving 9
the overall auto-consumption 8

Consumption ratio
needs and significantly reduc-
7
ing overall hydrocarbon losses
6
with the separated CO2.
There is roughly an order of 5
magnitude difference in the 4
power required for CO2 recom- 3
pression (see Figure 12). From 2
an energetic point of view, one
1
point of interest is that the CO2
is recovered in liquid phase, 0
SprexCO2 Membranes
thus not necessitating a
compression step. The case
study also demonstrates that Figure 12 Power consumption dedicated to CO2 recompression: SprexCO2 +
the two processes are energeti- amine vs membranes + amine
cally paired, with utmost
benefits in terms of waste heat ral or associated gas are cooler scheme on the acid gas
recovery optimisation. numerous, but none have absorber was developed to
One of the advantages of the shown to be as versatile and further increase this loading
proposed CO2 separation economic as those using amine- and reduce the cost of highly
scheme is the possibility of based solvents. Amine sour gas sweetening.
increasing process flexibility to processes can be optimised to Even though amine sweeten-
a certain extent by means of efficiently and economically ing has proven to be a very
bulk and finishing separation treat any type of highly sour efficient technology, cryogenic
units in series, in order to cope gas. bulk removal of H2S or CO2
with fluctuations in feed gas To be truly competitive, the offers an economic advantage
composition or temporary removal of acid gas compo- when the separated acid gases
offset conditions. nents H2S and CO2 from highly from super-sour gas are rein-
The level of complexity of the or super-sour gases requires jected. Sprex and Sprex CO2
proposed CO2 separation the optimum choice of process. can be combined with an amine
scheme remains moderate: no Within the AdvAmine series of unit to reduce the cost of the
prototype equipment is processes, the energizedMDEA production of gases containing
required, minimum acid gas process can be optimised to more than 25-30% H2S or over
compression system is required reduce energy requirements, 40-45% CO2. They provide an
(only for the acid gas separated taking advantage of the ability economic and easy-to- use
in the amine unit) and spare of MDEA to release a substan- alternative to amines and to
capacity considered is sufficient tial part of the absorbed acid other more complex cryogenic
to achieve availability levels gases in a low- fractionation processes for
typical of acid gas removal pressure flash to produce the complete CO2 removal. These
units. semi-lean stream in a split-flow processes were demonstrated
In terms of capital invest- process configuration. The acid in a unit installed at the Lacq
ment, the estimation made in gas loading of amine solutions sour gas plant and are now
the case study shows an overall needs to be maximised to ready to be implemented on an
reduction of 17% to 20% by reduce the required amine industrial scale.
using the SprexCO2 bulk sepa- solution flow rate. Operating
ration instead of membranes. amine plants at high loadings
has been proven by Total AdvAmine, Sprex, SprexCO2, HySWEET
Conclusions through extensive operating and energizedMDEA are trademarks of
Technologies to treat sour natu- experience, and a liquid-side Prosernat and Total.

www.digitalrefining.com/article/1000356 Gas 2012 13

 References D, Lallemand F, Industrial operation acid gas operations for Total, and also of
1 Lallemand F, Aimard N, Rocher A, Sour of HySWEET, a new hybrid solvent R&D programmes and developments for
gas production: moving from conventional for improved mercaptan removal, 2nd gas sweetening processes.
to advanced environmentally friendly Annual Gas Processing Symposium, Cristina Maretto is a Senior Petroleum
schemes, Sogat Conference, Abu-Dhabi, Doha, Qatar, 10-14 Jan 2010. Architect with Total E&P. She has been
29 Apr-3 May 2007. 10 Shah V, Cadours R, Weiss C, HySWEET in charge of gas valorisation topics in
2 Estep J W, McBride G T Jr, West J process: an improvement in energy the Advanced Technology Department
R, The recovery of sulphur from sour efficiency, Abu Dhabi International and led the development programme for
natural and refinery gases, Advances in Petroleum Exhibition and Conference, SprexCO2 technology.
Petroleum Chemistry and Refining, Vol 6, Abu-Dhabi, 1-4 Nov 2010. Julia Magne-Drisch is Gas Treatment
1962. 11 Lallemand F, Lecomte F, Streicher C, Project Manager with IFP Energies
3 Elgue J, Peytavy J L, Tournier-Lasserve Highly sour gas processing: H2S removal Nouvelles, Rueil Malmaison, France,
J, Recent industrial developments in with the Sprex process, International where she is in charge of research
natural gas sweetening by MDEA, 18th Petroleum Technology Conference, and development dedicated to gas
World Gas Conference, Berlin, 1991. Doha, Qatar, 21-23 Nov 2005. sweetening processes, including
4 Elgue J, Lallemand F, MDEA based 12 Huygue R, Lemaire E, Lecomte F, optimisations of IFPEN group processes
solvents used at the Lacq processing Deixonne M, Lajeunesse H, Operational and new developments to address
plant, Gas Processors Association validation of the Sprex process for natural gas treatment challenges. She
European Chapter, London, 18 Jan 1996. bulk H2S removal, Sulphur Conference, holds a PhD in hydrotreatment and has
5 Elf Activated MDEA: an important Vienna, Oct 2006. been involved in several developments
improvement in natural gas sweetening in refining and petrochemistry.
processes, 19th World Gas Conference, Gauthier Perdu is a Deputy Process Anne-Claire Lucquin is a Senior Process
Milan, 1994. Director & Process Expert with Prosernat Engineer with IFP Energies Nouvelles.
6 Lallemand F, Minkkinen A, Processes in Paris, France, where he is also in charge She is involved in the development of
combine to assist acid gas handling, of development programmes for gas new processes for gas sweetening and
reinjection, Oil and Gas Journal, 21 Jan sweetening processes. He has worked at liquefied natural gas, and previously
2002. many gas plants as a process engineer, as worked for Axens as a process engineer
7 Streicher C, Lallemand F, Minkkinen a process lead, or as a startup engineer. and a project manager on selective
A, Lecomte F, A new look at amines: Francois Lallemand is a Senior Advisor hydrogenation and FCC gasoline
extending the gas industry “workhorse” at Prosernat and has spent most of desulphurisation.
to new limits, 83rd GPA Convention, his career in sour gas production and
New Orleans, Mar 2004. treatment for a major oil and gas
8 Kittel J, Bonis M, Perdu G, Corrosion operator.
control on amine plants: new compact Claire Weiss is Head of Acid Gas Links
unit design for high acid gas loadings, Group in the Process Department
Sogat Conference, Abu-Dhabi, 28 Apr-1 of Total E&P, Paris, where she is in More articles from the following
May 2008 and GPA Europe Conference, charge of all development studies and category:
Barcelona, 13-15 May 2009. designs regarding acid gas matters, of Gas Processing/Treatment
9 Cadours R, Shah V, Weiss C, Roquet troubleshooting and debottlenecking in

14 Gas 2012 www.digitalrefining.com/article/1000356