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

the future have to develop

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

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


Sour
gas
Rich solvent
Figure 1 Acid gas removal unit design
set to continue for several
decades, at least in several
parts of the world. The produc-
tion of major oil or gas fields in
the Middle East or in the
Caspian Sea area could lead to
the production of considerable
quantities of additional sulphur
in an already saturated market,
while the storage of extra
sulphur in the long term is an
issue that will require signifi-
cant capital costs to be resolved.
This is why new production
methods must be developed for
sour fields, to limit the over-
production of sulphur.
Companies willing to
produce large gas fields with
very high amounts of CO2 have
to face a different constraint
related to the essential need to
reduce atmospheric emissions
of greenhouse gases.
With the growing acceptance
of the re-injection of separated
H2S and CO2 — either for re-
2 Gas 2012
Lean
solvent
Fuel
gas
utilisation to enhance oil
recovery (EOR) or just simple
disposal to a depleted reservoir
or an aquifer, as a feasible
alternative to costly sulphur
recovery to a diminishing
sulphur market, or to limit
atmospheric emissions of
greenhouse gases — a number
of highly sour gas fields can be
reconsidered as exploitable to
produce much-needed natural
gas.
These new constraints lead to
the development of more energy-
efficient technologies for acid
gas separation, adapted to
these new production schemes.
With this objective, in addition
to the AdvAmine series of gas
sweetening processes using
amine-based solvents, Total,
IFPEn and Prosernat have
developed Sprex and SprexCO2
for the production of highly
sour gas reserves with acid gas
re-injection.
Treated
gas
Acid
gas
LP
steam
Optimisation of amine
processes for highly sour gas
treatment
Amine processes (see Figure 1)
have been used for many years
to remove acid gases from
natural and associated gas
streams. They are very versatile
processes, which can be used
to treat all types of sour gas,
regardless of the H2S and/or
CO2 content, down to the most
severe specifications, such as
those imposed by gas liquefac-
tion plants.
But the cost of gas sweeten-
ing increases with the amount
of acid gases to be separated,
requiring larger amine solution
flow rates and higher energy
consumption for amine solu-
tion regeneration. On the other
hand, amine processes, because
of the variety of amines availa-
ble and the possibility to adapt
and improve the process flow
schemes, can be efficiently used
www.digitalrefining.com/article/1000356

Sour
gas
Figure 2 Conventional double-split flow design
for almost any type of gas
sweetening application. Amine-
based technology can therefore
be considered as the workhorse
of the sour gas processing
industry and, as such, still justi-
fies continuous technological
improvements to extend the
economical limits of its applica-
tions. Issues like treatment
costs and energy consumption
are being addressed by such
developments.
This article presents solutions
proposed by Prosernat for the
efficient and economic treat-
ment of gases with a high acid
gas content, either H2S or CO2.
These solutions benefit from
the operating experience of
Total in its highly sour gas
treatment plants and, while
some are proposed by other
licensors, others have been
developed through the joint
R&D effort of Total, IFPEn and
Prosernat.
www.digitalrefining.com/article/1000356
Lean
solvent
Semi-lean
solvent
Fuel
gas
Double-split flow process
configuration
Among the oldest process
configurations, the double-split
flow design, sometimes called
the split-flow design, has been
used as an alternative flowsheet
to minimise capital and operat-
ing costs in several sour gas
processing plants. Generally
used with primary or second-
ary amines, this design allows
for very severe treated gas
specifications for the same
reboiler duty as a conventional
process flow scheme, and was
documented probably for the
first time by Estep, McBride
and West in 1962.2 This design
also allows for the same treated
gas specification as a conven-
tional amine plant scheme,
with a much-reduced reboiler
duty when treating very sour
gases.
A conventional double-split
flow design is shown in Figure
Treated
gas
Acid
gas
LP
steam
2. Part of the amine solution is
withdrawn from the regenera-
tor as a side stream, then
cooled and pumped into the
lower section of the absorber.
The amine in the side draw is
not fully regenerated and has a
higher residual acid gas load-
ing. However, as this semi-lean
solution contacts the incoming
sour gas, it can still pick up the
bulk of the acid gas. Due to the
semi-lean amine side draw, the
amine flow to the regenerator
reboiler is reduced, and the
duty of the reboiler can be
decreased to achieve the same
lean amine quality required on
top of the absorber column to
meet the treated gas
specification.
Advantages of energizedMDEA
for the treatment of very sour
gases
The main factors affecting a
solvent’s performance for acid
Gas 2012 3

10000
DEA
MDEA
Pressure, mm Hg
1000
100
0.0 0.2
Figure 3 Equilibrium solubility of CO2 in aqueous amine solutions
gas absorption are its ease of
regeneration, and the solubility
and reactivity of the acid gases.
Tertiary amines require less
regeneration energy than
primary and secondary amines.
Being a tertiary amine, MDEA
therefore requires less reboiling
duty than DEA. It is, however,
well known that MDEA reacts
slowly with CO2. This is an
advantage in selective H2S and
controlled CO2 removal, but
becomes a handicap in complete
acid gas removal, especially
when a substantial quantity of
CO2 has to be removed. To
overcome this kinetic obstacle,
it was necessary to find energis-
ers among the secondary amines
that had high speeds of reaction
with CO2 to blend into the
otherwise desirable MDEA
solvent. Several energisers were
selected by Total from those
best suited to industrial condi-
tions, taking into account
commercial availability, cost
and impact on the
environment.3
While the reactivity of CO2
with MDEA is lower than with
DEA, its solubility in MDEA is
more strongly influenced by
4 Gas 2012
DEA
MDEA
0.3 0.4 0.5 0.6 0.7 0.8
CO2/Amine, moles
CO2 partial pressure than its
solubility in DEA. This is
shown by the slopes of the
equilibrium solubility curves in
Figure 3.
The basic concept of an effi-
cient process for the removal of
large quantities of acid gases
involves taking advantage of
the slopes of the equilibrium
solubility curves of CO2 in
aqueous MDEA solutions. This
allows for the liberation of a
maximum amount of the acid
gas from the solution by simple
physical pressure letdown flash
and thus substantially reduces
the thermal regeneration duty.
For example, the MDEA solu-
tion releases almost twice as
much CO2 as the DEA solution
by a pressure letdown of 10 to
1 bar (see Figure 3). In addi-
tion, the equilibrium solubility
of H2S in aqueous MDEA
exhibits similar behaviour to
CO2, allowing an equivalent
amount of H2S
liberation by pressure letdown.
EnergizedMDEA approaches
the equilibrium curve of MDEA
at high pressure, but behaves
like DEA at low acid gas partial
pressures. This is achieved by
the blend of an energiser with
MDEA, generally a secondary
amine.3,5
The ability of energizedM-
DEA to release a substantial
part of the absorbed acid gases
in a low-pressure flash can be
combined with the introduction
of a semi-lean solvent in the
bottom part of the absorber, as
in the double-split flow design
shown in Figure 4.
The rich amine solution after
letdown through a hydraulic
turbine is divested of co-
absorbed light hydrocarbons in
a first flash drum, as in the
conventional process, then
further expanded to a low pres-
sure in a second flash drum to
partially liberate CO2 and H2S.
The greater part of the rich
amine, thus partially regener-
ated, is returned to an
intermediate level of the
absorber as a semi-lean solvent.
This semi-lean solvent loop is
particularly economic, as it
reduces the thermal regenera-
tor load and consumes only
pumping energy.
When H2S is present and/or
the treated gas specification
calls for the removal of CO2
below the 2 vol% range, thor-
oughly regenerated, virtually
H2S- and CO2-free amine is
required. This is accomplished
in a conventional thermal
regenerator, returning a small
flow of the leanest amine to the
top section of the absorber.
In 1990, the new solvent and
regeneration system were
tested on an existing DEA unit
at the Lacq sour gas plant,
southwest France, which was
then converted to the ener-
gizedMDEA process.4,5
The performance of the ener-
gizedMDEA process is closely
related to site-specific treatment
www.digitalrefining.com/article/1000356

Sour
gas
Figure 4 Split flow design with energizedMDEA
conditions; notably, feed gas
composition and treated gas
specifications. Below are some
practical rules-of-thumb to
highlight the general interest of
regeneration by flash:6
• The greater the H2S and/or
CO2 partial pressure in the feed
gas, the greater the efficiency
of the flash. In the case of the
Lacq sour gas plant, the acid
gas partial pressure of the feed
is approximately 15 bar in
comparison to a total pressure
of 2 bar in the second flash
drum. This gives a ratio of
7.5/1 (acid gas partial pres-
sure/flash pressure). In general,
the advantage of the flash
procured regeneration starts
above a ratio of 3
• Targeting low H2S content in
the treated gas requests a ther-
mal regenerator to clean up the
solvent down to low H2S resid-
ual loading. The overall energy
www.digitalrefining.com/article/1000356
Lean
solvent
Semi-lean
solvent
Fuel
gas
consumption of the energized-
MDEA unit increases as the
treated gas specification
becomes more stringent, since
the amount of lean totally
regenerated amine from the
thermal regeneration increases.
In some bulk CO2 removal cases
with no H2S, as mentioned, it
may even be possible to
completely eliminate the ther-
mal regenerator.
As a consequence of the
above attributes, the energized-
MDEA process is well adapted
to the treatment of high pres-
sure and very sour gases,
where the advantages of flash-
procured regeneration will be
maximised to reduce the energy
footprint of the sweetening.
High loading in amine
sweetening
An effort to moderate the
solvent flow rate along with
Treated
gas
Acid
gas
LP
steam
the reboiler duty quickly
brought some process develop-
ers, and later on plant
operators, to consider increas-
ing the acid gas loading of the
rich amine leaving the
absorber.7 The maximum
achievable loading is controlled
by the thermodynamic equilib-
rium between the sour gas
entering the absorber and the
rich amine, and by the effi-
ciency of the mass transfer in
the absorber. The higher the
acid gases partial pressure in
the sour gas, the higher the
amine loading at thermody-
namic equilibrium. High H2S
and CO2 partial pressures will
therefore invariably allow a
high amine loading at the
benefit of an improved effi-
ciency of process. Loadings
higher than 0.8 (mole of acid
gases per mole of amine) can
theoretically be achieved when
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
of amine solutions
The loading of the rich amine
solution is limited by the ther-
modynamic equilibrium at the
absorber bottom and by the
approach to this equilibrium.
The thermodynamic equilibrium
is a function of the partial pres-
sures of the acid gases in the
feed sour gas, and high loadings
are favoured by a low tempera-
ture (see Figure 5). Lowering
the rich amine solution temper-
ature on the lower part of the
absorber is therefore a means of
increasing the loading of the
rich amine solution leaving the
absorber.
It is generally not practical to
reduce the temperature of the
feed sour gas. This would
require an expensive high-pres-
sure gas cooler and the use of a
refrigeration loop in many
fields and, in any case, the cool-
ing would be limited by the
hydrate formation temperature
of the gas. In addition, the
resulting lower temperature at
the absorber top would slow
the mass transfer of CO2 from
the gas to the amine solution,
which could, in some cases,
impair the specification of the
treated gas.
The solution to lowering the
absorber bottom temperature
without cooling the feed gas
and without decreasing the
temperature of the top trays is
the installation of a liquid
intercooler. This will remove
some heat from the amine
solution from an intermediate
tray, or section of packing, in
the absorber column, where
the temperature of the gas and
the liquid is the highest
because of the exothermicity of
the absorption of the acid
gases. In this process configu-
www.digitalrefining.com/article/1000356
Case study: energy consumption and capital cost comparison
energizedMDEA process scheme Conventional Double-split Split-flow process
single-flow flow process with flash
process supported
regeneration
Acid gas loading (rich amine solution), mol/mol 0.85 0.86 0.92
Rich amine solution concentration, g/l 458 461 458
Thermal energy: reboiler 39
Rich amine preheater, MW
77 67.5
10
Power consumption, MW 2.7 2.7 3.6
Total energy demand*, MW 100. 5 (base) 89.1 (88.7% 69.6 (69.3%
of base) of base)
Capital cost, arbitrary unit 100 (base) 113.7 123.1
* Steam boiler efficiency 83%, power generation efficiency 33%
Table 4
ration, the semi-lean amine strates the incidence of an
solution is withdrawn from a absorber intercooler in the case
chimney tray, pumped through of the sweetening of a very
a cooler and re-injected to the sour gas, with the composition
tray just below the withdrawal shown in Table 5. The amine
tray. solution temperature is
The example below demon- decreased to 55°C in the inter-
cooler. As a result, the absorber
Case study: sour gas composition bottom temperature is reduced
from 85.2°C to 71.2°C, and the
rich amine loading can be
Composition, vol% increased from 0.60 to 0.71 (see
H2S 11
Figure 6).
CO2 11
Hydrocarbons Balance Table 6 shows the compara-
Gas flow rate, 106 Sm3/d 5.1 tive energy consumptions for
Temperature, °C 50 the treatment of the gas with
Pressure, bar 66
the two schemes, as well as the
relative capital costs of the
Table 5 corresponding units.
20
85ºC
18
Partial pressure H2S, bar
55ºC
16
14
12
10
8
6
4
2
∆ = 0.15
0
0.0 0.5 1.0
Loading, mol H2S / mol MDEA
Figure 5 Rich amine loading as a function of temperature
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
a significant refrigeration
requirement. Furthermore, CO2
separation down to commercial
levels is limited by the CO2
freezing conditions in the top
section of the cryogenic distilla-
tion column. Some processes
address this limitation by
adding, for example, a suitable
hydrocarbon solvent to the top
section of the demethaniser to
stay outside the CO2 freezing
conditions, or by using a
column with a specific frozen
CO2 remelting zone.
Sprex and SprexCO2, jointly
developed by Total, IFPEn and
Prosernat, are bulk fractiona-
tion processes. Sprex, for bulk
H2S removal, does not require
prior dehydration of the gas.
The refrigeration requirements
Very sour Pre-ex
natural gas
Acid gas liquid
high pressure
Figure 7 Staged acid gas separation with the Sprex process
of these processes are limited
compared to those of other
cryogenic processes. Since the
temperature in the SprexCO2
unit is not as low, the operat-
ing conditions are a long way
from the CO2 and aromatic
compounds freezing region,
therefore avoiding the need for
an additive fractionation and
recycle or for a remelting zone.
Sales gas
AGRU
(acid gas
removal unit)
Remaining
acid gas
When a pipeline or LNG
specification is required, the
Sprex or SprexCO2 unit is easily
and economically combined
with a solvent-based acid gas
removal unit.
Bulk H2S removal with Sprex
Sprex is based on an initial
patent filed in 1994 by IFP, to
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


To compression
and gas finishing
treatment
Pre-cooling / dehydration
Figure 10 SprexCO2 typical process scheme
upstream of the cryogenic frac-
tionation column, the gases can
be cooled to well below the -
30°C of the basic version of the
Sprex process, which improves
the efficiency of the H2S separa-
tion process and allows
separation of CO2 from the gas.
However, the limit then
becomes the temperature at
which CO2 crystallises. The
enhanced version of the Sprex
process, SprexCO2, allows for
bulk removal of CO2 from
gases containing a very high
CO2 content (≥40% or so) possi-
bly together with high
concentrations of H2S. The
principle of the process is simi-
lar to that of demethanisation
units —vapour/liquid separa-
tion at high pressure and low
temperatures.
The process is based on an
optimised CO2 distillation,
www.digitalrefining.com/article/1000356
Refrigeration
Sprex CO2
distillation
Reboiler
HX
which is performed at condi-
tions outside the CO2
crystallisation domain. The
parameters and limits to avoid
crystallisation are illustrated in
the distillation chart based on
the main binary mixture (CO2/
C1). Figure 9 shows a typical
gas specification achievable in
the distillation outlet; ie,
around 20% CO2 mol, at 40 bar.
SprexCO2 operation at a higher
pressure, say 50 bar or above,
could improve gas specifica-
tions by 8-10%. However, the
margin to critical point would
be reduced, resulting in higher
vapour/liquid traffic in the
column. In practice, the selected
range for bulk separation is
18% to 25% CO2 mol.
SprexCO2 is competitive in
comparison with conventional
CO2 separation processes
(amines) or hybrid solutions
loop
Boosting / transfer and
injection pumps
(membranes + amines) when
CO2 concentrations are higher
than 40% and CO2 reinjection is
required for enhanced oil
recovery (EOR) and/or carbon
sequestration. When CO2 is
being recovered in a liquid
“soup” phase, injection is real-
ised by pumps instead of
multistage compressors, with
considerable energy savings.
In order to match final gas
export specifications (pipeline
or LNG plant feedstock), the
unit can be associated with a
finishing AdvAmine unit.
A typical SprexCO2 scheme,
including upstream pre-condi-
tioning units and downstream
CO2 boosting and transfer/
injection pumps, is shown in
Figure 10. The main principles
are as follows:
• Feed gas pre-conditioning:
■ Feed gas pre-cooling
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-
ises gas valorisation by halving
the overall auto-consumption
needs and significantly reduc-
ing overall hydrocarbon losses
with the separated CO2.
There is roughly an order of
magnitude difference in the
power required for CO2 recom-
pression (see Figure 12). From
an energetic point of view, one
point of interest is that the CO2
is recovered in liquid phase,
thus not necessitating a
compression step. The case
study also demonstrates that
the two processes are energeti-
cally paired, with utmost
benefits in terms of waste heat
recovery optimisation.
One of the advantages of the
proposed CO2 separation
scheme is the possibility of
increasing process flexibility to
a certain extent by means of
bulk and finishing separation
units in series, in order to cope
with fluctuations in feed gas
composition or temporary
offset conditions.
The level of complexity of the
proposed CO2 separation
scheme remains moderate: no
prototype equipment is
required, minimum acid gas
compression system is required
(only for the acid gas separated
in the amine unit) and spare
capacity considered is sufficient
to achieve availability levels
typical of acid gas removal
units.
In terms of capital invest-
ment, the estimation made in
the case study shows an overall
reduction of 17% to 20% by
using the SprexCO2 bulk sepa-
ration instead of membranes.
Conclusions
Technologies to treat sour natu-
www.digitalrefining.com/article/1000356
10
9
8
Consumption ratio
7
6
5
4
3
2
1
0
SprexCO2
Figure 12 Power consumption dedicated to CO2 recompression: SprexCO2 +
amine vs membranes + amine
ral or associated gas are
numerous, but none have
shown to be as versatile and
economic as those using amine-
based solvents. Amine
processes can be optimised to
efficiently and economically
treat any type of highly sour
gas.
To be truly competitive, the
removal of acid gas compo-
nents H2S and CO2 from highly
or super-sour gases requires
the optimum choice of process.
Within the AdvAmine series of
processes, the energizedMDEA
process can be optimised to
reduce energy requirements,
taking advantage of the ability
of MDEA to release a substan-
tial part of the absorbed acid
gases in a low-
pressure flash to produce the
semi-lean stream in a split-flow
process configuration. The acid
gas loading of amine solutions
needs to be maximised to
reduce the required amine
solution flow rate. Operating
amine plants at high loadings
has been proven by Total
through extensive operating
experience, and a liquid-side
Membranes
cooler scheme on the acid gas
absorber was developed to
further increase this loading
and reduce the cost of highly
sour gas sweetening.
Even though amine sweeten-
ing has proven to be a very
efficient technology, cryogenic
bulk removal of H2S or CO2
offers an economic advantage
when the separated acid gases
from super-sour gas are rein-
jected. Sprex and Sprex CO2
can be combined with an amine
unit to reduce the cost of the
production of gases containing
more than 25-30% H2S or over
40-45% CO2. They provide an
economic and easy-to- use
alternative to amines and to
other more complex cryogenic
fractionation processes for
complete CO2 removal. These
processes were demonstrated
in a unit installed at the Lacq
sour gas plant and are now
ready to be implemented on an
industrial scale.
AdvAmine, Sprex, SprexCO2, HySWEET
and energizedMDEA are trademarks of
Prosernat and Total.
Gas 2012 13
 References
1 Lallemand F, Aimard N, Rocher A, Sour
gas production: moving from conventional
to advanced environmentally friendly
schemes, Sogat Conference, Abu-Dhabi,
29 Apr-3 May 2007.
2 Estep J W, McBride G T Jr, West J
R, The recovery of sulphur from sour
natural and refinery gases, Advances in
Petroleum Chemistry and Refining, Vol 6,
1962.
3 Elgue J, Peytavy J L, Tournier-Lasserve
J, Recent industrial developments in
natural gas sweetening by MDEA, 18th
World Gas Conference, Berlin, 1991.
4 Elgue J, Lallemand F, MDEA based
solvents used at the Lacq processing
plant, Gas Processors Association
European Chapter, London, 18 Jan 1996.
5 Elf Activated MDEA: an important
improvement in natural gas sweetening
processes, 19th World Gas Conference,
Milan, 1994.
6 Lallemand F, Minkkinen A, Processes
combine to assist acid gas handling,
reinjection, Oil and Gas Journal, 21 Jan
2002.
7 Streicher C, Lallemand F, Minkkinen
A, Lecomte F, A new look at amines:
extending the gas industry “workhorse”
to new limits, 83rd GPA Convention,
New Orleans, Mar 2004.
8 Kittel J, Bonis M, Perdu G, Corrosion
control on amine plants: new compact
unit design for high acid gas loadings,
Sogat Conference, Abu-Dhabi, 28 Apr-1
May 2008 and GPA Europe Conference,
Barcelona, 13-15 May 2009.
9 Cadours R, Shah V, Weiss C, Roquet
14 Gas 2012
D, Lallemand F, Industrial operation
of HySWEET, a new hybrid solvent
for improved mercaptan removal, 2nd
Annual Gas Processing Symposium,
Doha, Qatar, 10-14 Jan 2010.
10 Shah V, Cadours R, Weiss C, HySWEET
process: an improvement in energy
efficiency, Abu Dhabi International
Petroleum Exhibition and Conference,
Abu-Dhabi, 1-4 Nov 2010.
11 Lallemand F, Lecomte F, Streicher C,
Highly sour gas processing: H2S removal
with the Sprex process, International
Petroleum Technology Conference,
Doha, Qatar, 21-23 Nov 2005.
12 Huygue R, Lemaire E, Lecomte F,
Deixonne M, Lajeunesse H, Operational
validation of the Sprex process for
bulk H2S removal, Sulphur Conference,
Vienna, Oct 2006.
Gauthier Perdu is a Deputy Process
Director & Process Expert with Prosernat
in Paris, France, where he is also in charge
of development programmes for gas
sweetening processes. He has worked at
many gas plants as a process engineer, as
a process lead, or as a startup engineer.
Francois Lallemand is a Senior Advisor
at Prosernat and has spent most of
his career in sour gas production and
treatment for a major oil and gas
operator.
Claire Weiss is Head of Acid Gas
Group in the Process Department
of Total E&P, Paris, where she is in
charge of all development studies and
designs regarding acid gas matters, of
troubleshooting and debottlenecking in
acid gas operations for Total, and also of
R&D programmes and developments for
gas sweetening processes.
Cristina Maretto is a Senior Petroleum
Architect with Total E&P. She has been
in charge of gas valorisation topics in
the Advanced Technology Department
and led the development programme for
SprexCO2 technology.
Julia Magne-Drisch is Gas Treatment
Project Manager with IFP Energies
Nouvelles, Rueil Malmaison, France,
where she is in charge of research
and development dedicated to gas
sweetening processes, including
optimisations of IFPEN group processes
and new developments to address
natural gas treatment challenges. She
holds a PhD in hydrotreatment and has
been involved in several developments
in refining and petrochemistry.
Anne-Claire Lucquin is a Senior Process
Engineer with IFP Energies Nouvelles.
She is involved in the development of
new processes for gas sweetening and
liquefied natural gas, and previously
worked for Axens as a process engineer
and a project manager on selective
hydrogenation and FCC gasoline
desulphurisation.
Links
More articles from the following
category:
Gas Processing/Treatment
www.digitalrefining.com/article/1000356