AGAT: GET AHEAD IN ACID GAS TREATING

FROM LABORATORY AND PILOT TESTS TO INDUSTRIAL DEMONSTRATION

Laurance Reid Gas Conditioning Conference

February 25-28, 2019 – Norman, Oklahoma USA

Julien Grandjean
IFP Energies nouvelles
Rond-Point de l’Echangeur de Solaize
BP3 69360 Solaize, France
+33-777-93-7485
julien.grandjean@ifpen.fr

Aurélie Wender
IFP Energies nouvelles
1 et 4 avenue de Bois Préau
92852 Rueil-Malmaison Cedex France
+33-147-52-7370
aurelie.wender@ifpen.fr

Abdelkader Lettat
IFP Energies nouvelles
Rond-Point de l’Echangeur de Solaize
BP3 69360 Solaize, France
+33-437-70-2293
kader.lettat@ifpen.fr

Marie Dehlinger
IFP Energies nouvelles
Rond-Point de l’Echangeur de Solaize
BP3 69360 Solaize, France
+33-437-70-3005
marie.dehlinger@ifpen.fr

John Roesler
IFP Energies nouvelles
Rond-Point de l’Echangeur de Solaize
BP3 69360 Solaize, France
+33-437-70-2897
john.roesler@ifpen.fr

Sébastien Gonnard
IFP Energies nouvelles
Rond-Point de l’Echangeur de Solaize
BP3 69360 Solaize, France
+33-437-70-2376
sebastien.gonnard@ifpen.fr
 Vincent Carlier
IFP Energies nouvelles
Rond-Point de l’Echangeur de Solaize
BP3 69360 Solaize, France
+33-437-70-3251
vincent.carlier@ifpen.fr

ABSTRACT
Gas operators are facing the challenge to remove the undesired acid gases and contaminants from
ever more sour gases with ever more stringent specifications. IFP Energies nouvelles developed
a new amine-based solvent named AGAT that offers a competitive advantage over commercially
available solvents to be considered either on swapping an existing plant or for new grassroots
projects.

The solvent has higher H2S and CO2 absorption capacity than piperazine-activated
methyldiethanolamine (MDEA). It also shows a higher mass transfer rate of CO2 and COS.
These properties result in decreased solvent circulation rates and reboiler duty leading to reduced
operating costs when swapping the solvent. For new units, a reduction of equipment sizes and
capital costs between 10 and 20% is expected.

The absorption and regeneration operation of the AGAT solvent was first carried out during a 6
weeks pilot test confirming a 30% reduction in the circulation rate compared to activated MDEA
with no significant degradation or corrosion. Complementary tests have shown the robustness of
AGAT with stability at high temperature comparable to activated MDEA. Corrosion rates were
measured to be much below 0,1mm/year which confirms the compatibility of materials
commonly used for DEA and activated MDEA units. The foaming tendency is reduced with
AGAT as compared with activated MDEA.

The first industrial demonstration was successfully completed in a plant processing up to

250 Nm3/h of gas mainly composed of methane and CO2. After a 6-month initial operation, the
piperazine - activated MDEA was removed and fully replaced with AGAT in July 2017. The unit
has been continuously operated since the swap. At nominal gas flow rate, a reduction of the
reboiler duty of 15% has been achieved with AGAT. Drastic reduction of absorption height has
also been evidenced with AGAT. These results are consistent with the calculations performed
with a mass transfer rate-based simulator developed for the design of future industrial units.
 AGAT : GET AHEAD IN ACID GAS TREATING
FROM LABORATORY AND PILOT TESTS TO INDUSTRIAL DEMONSTRATION

Julien Grandjean, IFP Energies nouvelles, Solaize, FRANCE

Aurélie Wender, IFP Energies nouvelles, Rueil-Malmaison, FRANCE
Abdelkader Lettat, IFP Energies nouvelles, Solaize, FRANCE
Marie Dehlinger, IFP Energies nouvelles, Solaize, FRANCE
John Roesler, IFP Energies nouvelles, Solaize, FRANCE
Sébastien Gonnard, IFP Energies nouvelles, Solaize, FRANCE
Vincent Carlier, IFP Energies nouvelles, Solaize, FRANCE

Introduction
For decades to come, gas will be an energy source of choice to meet increasing energy demand.
According to the International Energy Agency, natural gas demand is expected to grow
constantly until 2035, reaching levels nearly 50% higher than in 2011. 40% of total world proven
gas reserves of 6832 trillions of cubic feet (Tcf) estimated at the end of 2017 (British Petroleum
Statistical Review of World Energy 2018 [1]) contains acid gases (CO2 content higher than 2%,
H2S content higher than 100ppm).

While oil and gas operators have so far preferentially produced gas from the technically easiest
reservoirs, they are now facing fields with higher acid gas content and containing other
contaminants such as, for example, COS.

Removing the undesired acid gases and contaminants from sour gases is a costly operation. The
size and cost of the acid gas removal unit increase with the amount of pollutants to separate and
the severe specifications to be satisfied. Due to their flexibility and their ability to reach various
specifications, amine solvents are commonly used to achieve this operation.

In order to address the larger range of acid gas compositions and specifications, IFPEN has
started the development of a new solvent combining a higher absorption capacity of H2S and
CO2 than state-of-the-art MDEA-based solvents combined with faster kinetics of CO2 and COS
chemical reactions. This up-graded absorption performance will reduce the investment and
operating costs of the Acid Gas Removal Unit (AGRU).

After an initial task of solvent screening, complementary lab measurements were performed on
the selected system. The resulting data on CO2 and H2S absorption illustrate the performance of
the solvent related to piperazine activated MDEA and are also used to fit predictive VLE and
mass transfer rate models which are the basis of a rigorous simulation of the absorption-
regeneration process. Operation campaigns of 6 weeks on a pilot plant were performed to
confirm the performances and the choice of the formulation named AGAT 200. Key operating
properties such as solvent stability, corrosiveness and foaming tendency were also investigated
through laboratory and pilot tests.
The operability and high absorption performance of AGAT 200 was confirmed in 2017-2018 by
a first industrial demonstration in a plant processing a gas composed mainly of methane and 40%
CO2. The absorption section consists of two columns in series with the treated gas at the outlet of
the second column. After an initial 6 months ofoperation, the piperazine-activated MDEA was
removed and fully replaced with AGAT 200.The unit has been in operation continuously since
the swap. At the nominal gas flow rate, a 15% reduction of the reboiler duty has been achieved
with AGAT 200. Under the same operating conditions in terms of flow rate and duty, the CO2
specification for pipeline export has been reached at the outlet of just the first column whereas
25% of CO2 were still in the gas with the piperazine activated MDEA. CO2 concentration and
temperature profiles in the absorption column are consistent with the calculations from the mass
transfer rate based simulator.

Laboratory and Pilot Tests

Absorption Performance

The experimental apparatus used for measuring H2S solubility consists of a stirred cell reactor
designed to operate at pressures ranging from vacuum up to 10 bar. Injections of H2S in the
reactor are performed to obtain the VLE data. The device is described by Blanchon et al. (2008)
[2].

For CO2, VLE data are mainly obtained on an HTS apparatus consisting of six stirred cell
reactors. The device is detailed in Porcheron et al. (2011) [3].
Figure 1 shows the variation of the H2S partial pressure above the amine solution with the H2S
loading capacity of H2S in mole per kg of unloaded solution at 40°C. The dashed line represents
the usual limits of rich loading wherein the state-of-the-art piperazine activated MDEA (MDEA-
PZ) is operated. Inside this range the H2S loading capacity in the new solvent (AGAT 200
solution) is up to 40% higher than in the MDEA-PZ for a given partial pressure of H2S. This
means that it is possible to operate at a lower circulation rate with AGAT 200 in the range of
usual operating pressures. The gain compared to MDEA-PZ will be more important at higher
partial pressures of H2S in the gas to be treated.

Figure 1. Absorption isotherm of H2S at 40°C for MDEA-PZ and AGAT 200

Likewise, the gain of CO2 loading capacity over a large range of partial pressures and
temperatures is presented in Figure 2. The AGAT 200 solution has a higher loading than the
MDEA-PZ, so it is possible to operate the new solvent with a lower circulation rate. This will
reduce the investment and operating costs of the AGRU.

Figure 2 Absorption isotherms of CO2 at 40 and 80°C for MDEA-PZ and AGAT 200
The absorption kinetics of CO2 in the reference MDEA-PZ and AGAT 200 were measured with
a wetted wall reactor in CO2 unloaded and loaded solutions. Figure 3 presents relative CO2
absorption rate in unloaded solution at 45 and 60°C compared to MDEA-PZ at 45°C. As can be
seen on this diagram, the results show an enhanced mass transfer of CO2 by 20 to 30% into the
AGAT solvent, compared to MDEA-PZ.

Figure 3. Relative CO2 mass transfer rate in MDEA-PZ and AGAT 200 at 45°C and 60°C. V [MDEA-PZ] =
1.00 at 45°C.

Mass transfer rate at different CO2 loading was also measured in a 6-inch diameter absorption
column with a 60-inch-tall packed bed consisting of 7 elements of Sulzer Mellapak 250.X. The
column was operated at a pressure of 3 bara and a solvent inlet temperature of about 35 °C. The
solvent was recirculated from the bottom to the top of the column through a pump and liquid
reservoir filled to about 0.5 m3. The loading of the solvent at the column inlet therefore increased
progressively with time. The gas inlet CO2 mole fraction was set to 7% diluted in air.

Figure 4. Schematic of facility and set-up for absorption tests

The overall mass transfer rate was obtained by the difference between the inlet and outlet CO2
flow rates and is represented in Figure 5 as a function of the CO2 loading of the solvent (αCO2).
As can be seen in this figure, the mass transfer in the loaded new solvent is much faster than in
the MDEA-PZ system with a rate enhanced by over a factor 2 at a loading of 1 mol/kg. It can
also be observed that the same absorption rate can be achieved with a 60% increase of CO2
loading in the AGAT solvent compared to the MDEA-PZ system.

Therefore, it seems possible to reduce the height of the absorber and/or the circulation rate of the
new solvent compared to MDEA-PZ because of the enhanced mass transfer rate with a reduction
in investment costs as a consequence.

Figure 5. Comparison of CO2 mass transfer rate in CO2 loaded solutions

Preliminary experiments with COS in a stirred cell reactor also show an increase of COS
absorption rate by 30% at 40°C for an unloaded AGAT solution compared to MDEA-PZ.

Two six-week operation campaigns were performed on an in-house small pilot plant to check the
operability and select the best formulation to be tested for an industrial demonstration. A
simplified process flow diagram and a photograph of this facility are shown in Figure 6. The
plant was operated under conditions comparable to those of an actual plant in terms of operating
temperature and CO2 loading. The results indicated a potential reduction of the solvent flow rate
by 30% relative to the design flow rate with MDEA-PZ. Corrosion was negligible (less than
10µm/year) on both the carbon steel and the stainless steel coupons (316L and Duplex) installed
at the 3 locations specified as “CC × 2” in Figure 6. No solvent degradation could be detected in
the operating duration.
 Figure 6. Process flow sheet and photograph of the pilot plant

Solvent stability

Complementary tests were conducted in the lab to assess the stability of the AGAT solvent under
more severe conditions. Solvents were saturated under a partial pressure of 1.7 bar of CO2 at
60°C in a multi-reactor device as shown in the photograph of Figure 7. After equilibrium was
reached the reactor was isolated and heated to 140°C for 11 days. The degradation ratio was
determined by GC analysis of the solvent by difference of the initial and final masses of amines
in the formulation and compared to the degradation ratio of both the reference MDEA-PZ
formulation and DEA which is commonly used in gas treatment. According to the results shown
on the left of Figure 7, the new solvent is as stable as MDEA-PZ and has a degradation ratio that
is seven times less than DEA. Tests carried out in the presence of H2S and CO2 lead to the same
conclusion.

Figure 7. Stability tests on amine formulations (Left : degradation ratio after 11 days under rich CO2 loading
conditions at 140°C, Right : 6-reactor degradation device).
Corrosion

In order to complete pilot tests, the corrosiveness of different amine solvents was measured in a
Hastelloy batch reactor, where stainless steel and carbon steel coupons are put in contact with a
CO2 loaded solution. Regular injection of CO2 was performed to maintain a pressure of 35 bar at
110°C in the gas phase of the reactor during one month, after an initial one-week degradation
phase at 140°C. The solution used for this first step is regenerated by nitrogen stripping and the
corrosiveness of the resulting lean amine solution is then studied with new coupons for an
additional month at 120°C or 135°C for AGAT 200. The results presented in
Table 1 confirm that corrosion rates of carbon steel as well as stainless steel are negligible with
AGAT solvent and comparable to those of state-of-the-art MDEA-PZ. Therefore, construction
materials can be selected using the same practices as for conventional processes, with a carbon
steel resistance significantly improved compared to DEA.

Table 1. Corrosion rate measured on lean and rich amine solutions,

on carbon steel (CS) and stainless steel (SS).
Lean amine – 4weeks at 120°C Rich amine (35 bar CO2) – 4 weeks at
110°C after one-week degradation at
140°C
CS (1018) SS (316L) CS (1018) SS (316L)
AGAT 200 <1* <1* 10 <2
MDEA 47% 11 <5 21 <5
MDEA 40% + Piperazine 3% <5 <5 12 <5
DEA 40% 2040 8 145 15
* Corrosion tests on lean amine solutions were performed at 135°C for AGAT 200.

Foaming

The foaming tendency of the new solvent was evaluated and compared to that of MDEA-PZ
taking into account different parameters which can influence the formation of foam such as CO2
loading or soluble impurities such as hydrocarbons or degradation products. The height of foam
obtained in a beaker right after stirring was measured along with the breaking time of the foam,
which was less than 30 seconds in all cases.

The results presented in Table 2 show overall a lower foaming tendency relative to MDEA-PZ.

Table 2. Height of foam after stirring. in percents of initial volume.

MDEA-PZ AGAT 200
Lean solution 5-10% 5-10%
Rich solution (with CO2 ) 0-2,5% 0-2,5%
Satured with nC6 5-10% 0-2,5%
Satured withToluene 10-15% 5-10%
With degradation products +
>20% 5-10%
5% organic salts
 Industrial demonstration

AGAT has been tested on a first industrial unit treating up to 250 Nm3/h of a raw gas containing
40%vol of CO2 at ambient temperature and pressure (Figure 8). After a first step consisting of
water condensation and pre-treatment of H2S, the methane/CO2 mixture with less than 1%
oxygen and nitrogen flows through a packed column filled with 2 beds of M250X structured
packing. A second identical 300mm diameter column is necessary with MDEA-PZ to reach the
required specification (< 2.5 vol%) for pipe transportation at the design gas flow rate (250
Nm3/h). The solvent is regenerated in a third column also equipped with structured packing and
operated at 1 barg. The solvent is withdrawn from the bottom packed section and heated in a
reboiler with hot pressurized water. CO2 is extracted from the top of the column and released to
the atmosphere (Figure 9).

Figure 8 First industrial unit operated with AGAT solvent

Figure 9. General sketch of the absorption section (two columns) and regeneration column.
After a 6-month period of operation with MDEA-PZ, the amine unit was purged, washed and
filled with the AGAT solvent in July 2017. The unit has since then been operating without any
interruption due to the solvent. Figure 10 show the variation of flow rate for the treated gas
which is injected in the natural gas network after compression and drying. These variations are
directly related to the fluctuations of the production of raw gas.

The average concentration of CO2 in the treated gas is represented for 59 points corresponding to
stable operating conditions. While always below the specification for pipe transportation, the
most severe variations of outlet CO2 concentrations are observed to occur during the 5-week
performance test. During this period, different sets of operating conditions (solvent flow rate and
reboiler duty) were tested to validate the mass transfer rate-based simulator and to optimize the
energy performance of the new solvent at nominal gas flow rate (ca 120 Nm3/h of treated gas).

3,00% 140

Performance test 5 weeks

Pipe Specification for injection in the natural gas grid 120

Treated gas flow rate (day average in Nm3/h)

2,50%
yCO2, treated gas (%vol)
Day average flow rate of treated gas (Nm3/h) 100
y CO2 in treated gas (%vol)

2,00%

80

1,50%

60

1,00%
40

0,50%
20

0,00% 0
04/07/2017 23/08/2017 12/10/2017 01/12/2017 20/01/2018 11/03/2018

Figure 10. Flow rate and volume fraction of CO2 in the treated gas during operation with AGAT

The performances of AGAT 200 are compared to those of MDEA-PZ in Figure 11 at an inlet
nominal gas flow rate of 200 Nm3/h. Solvent flow rate and reboiler duty can be tuned to reach
the required specification at the outlet of the first or second column.
Figure 11. Y- axis Relative energy consumption for solvent regeneration (full symbols) and solvent flow rate
(empty symbols) at nominal gas flow rate (200 Nm3/h of raw gas). Reference A : optimal conditions with
MDEA-PZ to achieve pipe specification with one absorber. X-Axis : CO2 concentration at the oulet.

The specification for pipe transportation can be reached at the outlet of the first absorber for
reference point A ( MDEA-PZ) as well as operating points C, D and E (AGAT 200).

The outlet CO2 concentration in the treated gas from the first absorber and corresponding relative
values of solvent flow rate and duty are indicated in table 3 for points A, C and E.

Table 3. Operating conditions for A, C and E.

A C E
MDEA-PZ AGAT 200 AGAT 200
yCO2 (%) 0.7 % 0.8% 1.4%
outlet of absorber 1
Solvent Flow rate 1.00 0.93 0.88
(relative)
Duty (relative) 1.00 0.85 0.86

Point C shows a 15% reduction in the duty required for regeneration with a 7% reduction in
solvent flow rate and virtually the same outlet CO2 concentration close to 0.7%. The same
reduction in duty can be achieved with a 12% reduction of solvent flow rate for point E with an
outlet concentration of 1.4%.

Reduction of solvent flow rate and duty with MDEA-Pz from point A led to out of spec gas from
the first absorber (point B) which is also compared with point D in Table 4.
 Table 4. Operating conditions for A, B and D.
A B D
MDEA-PZ MDEA-PZ AGAT 200
yCO2 (%) 0.7 % 25% 1.0%
outlet of absorber 1
Solvent Flow rate 1.00 0.85 0.85
(relative)
Duty (relative) 1.00 0.92 0.92

Point D can be compared to operation with MDEA-PZ at exactly the same conditions (point B)
showing an outlet concentration of 25% from the first absorber instead of 1% for AGAT. This
result confirms the enhancement of mass transfer rates already observed on the lab and pilot
facilities as well as the opportunity for a drastic reduction in the required absorption height and
investments for grassroot projects with AGAT.

The design gas flow rate (250 Nm3/h) which could not be achieved with MDEA-PZ was tested
with AGAT.

In order to reach this 25% increase of CO2 absorption capacity, the solvent flow rate was
increased by only 10% compared to reference point A. With this increase in loading capacity of
14%, the same specific duty (in kWh/kg of CO2) is sufficient to get the same CO2 concentration
at the outlet of the first absorber.
Long term stability was evaluated by regular analysis of the solvent. After more than one year of
operationthe degradation observed by gas chromatography was still insignificant.

Figure 12 compares the build-up of heat stable salts analyzed by liquid chromatography for the
two solvents. In both cases, the operating pressure of the regenerator was set at 1 barg with a
regenerator bottom temperature of 120°C. We can extrapolate from these results that the build-up
rate of heat stable salts for AGAT is half of that for MDEA-PZ . The AGAT solvent can
therefore be operated for many years without any need for solvent reclaiming or replacement.

Figure 12. Solvent stability : comparison of salt accumulation during operation

with MDEA-PZ and AGAT 200.

Mass transfer rate-based simulator

A simulator is necessary to accurately describe e an acid gas treating process and to optimize its
design in order reduce the associated investment and operating costs. A mathematical model was
developed to describe the absorption column for gas treatment with conventional amine solutions
as well as with AGAT. This model was developed in-house in order to incorporate IFPEN’s
latest developments on acid gas absorption in terms of thermodynamics, kinetics and mass
transfer models. The model was integrated into Pro II software as simulation environment using
Cape-Open standard methodology.

The model developed here is rate-based and consists of an algebraic-differential numerical

resolution of gas and liquid mass and energy balances along the column as differential equations.
The mass transfer model is based on the double film theory and considers mass transfer
limitations in both gas and liquid phases, with a rigorous discretisation of the liquid film. The
various parameters of the different models for VLE, reaction enthalpies, physical-chemical
 properties and reaction mechanisms are fitted to in-house experimental data from our laboratory
tests. The hydrodynamic parameters are also obtained using in-house correlations.

Simulations are compared to the industrial demonstration plant operating with MDEA-PZ and
AGAT solvents, in terms of temperature and CO2 concentration profiles in the gas phase (Figure
13).

CO2 content (vol/vol) Temperature (°C) Temperature (°C)

0.0 0.1 0.2 0.3 0.4 0.5 20 40 60 80 20 40 60 80
0 0 0
C-301 B C-301 B C-301 B
2 2 2

4 4 4
Packing height (m)

6 6 6

8 8 8
C-301 A C-301 A C-301 A
10 10 10

12 12 12

14 14 14

MDEA+PZ solvent (exp) Gas phase (exp) Gas phase (exp)

MDEA+PZ solvent (model) Gas phase (model) Gas phase (model)

AGAT solvent (exp) Liquid phase (exp) Liquid phase (exp)

AGAT solvent (model) Liquid phase (model) Liquid phase (model)

(a) CO2 concentration profiles (b) Temperature profiles

AGAT and MDEA+PZ AGAT MDEA+PZ

Figure 13 : Comparison of CO2 concentration (a) and absorber temperature profiles (b) between simulations
and expirmental data on AGAT and MDEA-PZ at same operating conditions in the demonstration plant.

Very good agreement is observed between simulations and experimental data obtained during the
performance test for both temperature and concentration profiles. Figure 13 shows, for the two
solvents, a higher absorption rate in the bottom part of the absorption section, with the AGAT
solvent exhibiting a better efficiency than MDEA-PZ. This is highlighted by the CO2 mole
fraction in the gas phase between the two absorbers, reaching 6.3% vol for AGAT solvent, while
close to 20% vol for MDEA-PZ. This higher absorption rate is consistent with the higher
temperature increase observed for AGAT solvent in the bottom section.

These behaviors are consistent with thermodynamic and kinetic characteristics of the two
solvents, as described previously, and confirm that it is possible with the AGAT solvent to obtain
benefits in terms of absorber height, or solvent flowrate reduction. These simulations also
validate the simulator which can be used to simulate and optimize future designs of absorption
columns.
 References
1. BP Statistical Review of World Energy, 67th Edition, June 2018.
2. Blanchon Le Bouhelec-Tribouillois, E., Mougin, P., Barreau, A., Brunella, I., Le Roux, D.,
Solimando, R. (2008), "Simulatneous CO2 and H2S Solubility in Diethanolamine Aqueous
Solutions", Oil & Gas Science and Technology – Rev. IFP, Vol. 63, No. 3, pp. 363-372,
2008.
3. Porcheron, F., Gibert, A., Jacquin, J., Mougin, M., Faraj, A., Goulon, A., Bouillon, P.A.,
Delfort, B., Le Pennec, D., Raynal, L. (2011), "High Throughput Screening of amine
thermodynamic properties applied to post-combustion CO2 capture process evaluation",
Energy Procedia, 4, pp15–22.