TREATING TECHNOLOGY
Comparative study of DEA and MDEA
treatments of acid gas
N. S. ABAS, Gulf of Suez Petroleum Co., Cairo, Egypt; and
H. M. ASFOUR, M. Z. A. WAHAB AND E. A. ASHOUR, Minia University, Minia, Egypt
Egypt’s consumption of natural gas
for all end uses (residential, industrial,
commercial and power generation) has
increased rapidly due to the growth of
new markets, the use of natural gas in the
production of petrochemicals and fer-
tilizers, and rising demand for LPG. To
satisfy growing domestic natural gas de-
mand, Egypt has diverted its natural gas
supply away from exports and is leaning
on LNG imports to address the shortfall
in consumption.
Natural gas must be treated, or “sweet-
ened,” before it is fit for consumption by
end users. Hydrogen sulfide (H2S), car-
bon dioxide (CO2 ) and water must be
removed. Improvements in the efficiency
and cost of gas sweetening processes are
ongoing. Recent developments have fo-
cused on different kinds of adsorption
and absorption methods, including dry
adsorption and wet absorption.1
Methods for contaminants removal.
Many treatment methods are available
for the removal of H2S and CO2 from
natural gas. One method uses a single
chemical solvent, such as diethanol-
amine (DEA), methyl diethanolamine
(MDEA), diglycolamine (DGA), diiso-
propylamine (DIPA), piperazine (PZ),
monoethanolamine (MEA), sulfolane,
or triethylamine (TEA). Another meth-
od uses a mixture of chemicals, such
MDEA + PZ or MDEA + sulfolane.1 A
strong focus has been directed on single
amines—namely, DEA and MDEA.
This study examines the costs and ef-
ficiencies of DEA and MDEA for acid gas
treating, using a proprietary simulation
software program.a The study was car-
ried out at an industrial gas sweetening
plant operated by Gulf of Suez Petroleum
Co. (GUPCO) in Ras Shukeir, Egypt.
The feed gas used in the CO2 and
H2S capture study has the following
composition:
• Flowrate = 12 MMsft3d
• Temperature for rich acid gas = 41°C
• Pressure = 49 kg/cm2.
A detailed, rate-based model was
developed for the two amine solutions
in a water blend, using the simulation
program to assess both process and eco-
nomic performance. The study results
showed that DEA removed 100% of H2S
and 99.07% of H2S and CO2 from acid
gas. MDEA removed 99.95% of H2S and
68.85% of both H2S and CO2.
Phases of gas treatment. Gas con-
taining H2S can be divided into two cat-
egories:2 acid gas and sour gas. Natural
gas containing H2S or other sulfur com-
pounds is considered sour, while gas with
only CO2 is considered sweet. Acid gas
has high contents of CO2 and H2S, while
sour gas contains moderate amounts.3
High concentrations of H2S in pipe-
lines, tanks and separators can corrode
equipment and can, in some cases, cause
hazards to workers. H2S content in natu-
ral gas is limited to 4 ppm.2 CO2 is also
corrosive to equipment and reduces the
Btu value of gas. The normal accepted
content of CO2 in untreated natural gas is
4 mol%–5 mol%.4 Both acid gas and sour
gas also contain small amounts of other
sulfur compounds—e.g., thiols (CSH)
H H
H N̈ C N̈
H H
Ammonia Primary amine
FIG. 1. Amine types.
and carbonyl sulfide (COS). After re-
moval of these contaminants, natural gas
becomes suitable for use.
When a gas stream is added to an ab-
sorption column with a relatively high
flowrate, the corresponding amount
of amine will be relatively low. Water
is added, up to 75 mol%, to amine gas
sweetening solutions to ensure good
contact between the natural gas and liq-
uid and to increase the efficiency of the
sweetening process.5,6
Amines are organic compounds with
ammonia (NH3) as the fundamental base
compound. By replacing one or more of
the hydrogen (H2) atoms with an or-
ganic hydrocarbon group, different types
of amines are formed—i.e., a primary
amine, a secondary amine and a tertiary
amine (FIG. 1).
DEA is generally less reactive than
MEA. Applications with appreciable
amounts of COS and carbon disulfide
(CS2), such as refinery gas streams, can
generally be treated successfully. Advan-
tages include resistance to degradation
from COS and CS2 and low solvent vapor
pressure, which result in potentially low-
er solvent losses and a reduced corrosive
nature when compared to MEA, as well
as a lower solvent cost.
Disadvantages of DEA include low-
er reactivity compared to MEA and
DGA—essentially nonselective removal
C C
C N̈ C N̈
H C
Secondary amine Tertiary amine
Gas Processing & LNG | MAY/JUNE 202027
TREATING TECHNOLOGY

in mixed acid gas systems due to inad- reclaimed by conventional techniques. decade. Their commercial success is due
equate CO2 slip.7,8 DEA also has higher MDEA solvents have gained a sig- to the ability of MDEA to selectively
circulation requirements and cannot be nificant share of the market over the past remove H2S when treating a gas stream
containing both H2S and CO2 ,9 while
slipping a significant portion of the CO2.
This CO2 slippage can be useful in appli-
Lean amine
cations requiring upgrade of H2S content
PIC-4002 Treated gas to 14
4-V43 and 4-V143 for sulfur plant feed gas or for adjusting
pressure 80 psi
temperature 135°F the CO2 content of the treated gas while
To acid flare 4-T4 removing H2S to 4 ppm.
Originally, the most significant appli-
Sour gas
Skimmer 4-V38 LIC-4004 from 4-V15 cation of MDEA and formulated MDEA
LIC-4006 LIC-4005 4-V3T solvents was for tail gas treating units, but
the formulated solvents have increasingly
displaced primary and secondary amines
To flare
FIC-4009 300 gpm in refinery treating systems and in high-
LIC-4007 temperature 140°F pressure natural gas applications. MDEA
4
4E-23 3 4-P46 has low vapor pressure, which results in
potentially lower solvent losses, less cor-
Temperature 180°F PIC-4001 rosivity, high resistance to degradation,
Temperature
pressure 5 psi 190°F and efficient energy utilization for capital
To acid flare 4E-24 and operating cost savings.
Temperature Disadvantages of MDEA include
Data of 4-F19 130°F 11
20
higher solvent cost than MEA, DEA
pressure 85 psi
temperature 190°F LIC-4008 or DGA; lower comparative reactivity;
flowrate 300 gpm 4-V3T and inability to be reclaimed by conven-
Data of 4-F18 tional techniques.
pressure 43 psi Temperature
temperature 180°F 247°F
flowrate 80 gpm Batch setup and chemical analysis.
partial filtration 4-P47 4-T5
4-F19 The properties of rich acid gas feed to the
2 1
absorber at the GUPCO plant include:
4-F18
• Flowrate = 12 MMsft3d
FIC-4008 Amine heater • Temperature = 41°C
4-E25 temperature 245°F 4-H9
4-P48 flowrate 220 gpm
• Pressure 49 kg/cm2
• Concentration of H2S feed to
Strainer contactor = 600 ppm.
TABLE 1 shows the composition of rich feed
FIG. 2. Process flow diagram of amine unit at GUPCO plant. gas to the amine unit. FIG. 2 shows the batch

TABLE 1. Composition of GUPCO plant feed gas

Molar flow, Mass flow, Liquid volume flow, Liquid volume

Components MMsft3d Mole fraction kg/hr Mass fraction m3/hr fraction
DEA 0 0 0 0 0 0
H2O 0 0 0 0 0 0
CO2 0.0588 0.0049 128.8187 0.0105 0.1568 0.0044
H2S 0.0072 0.0006 12.2149 0.001 0.0192 0.0005
Methane 9.6503 0.8042 7,710.9674 0.6271 25.7426 0.7168
Ethane 1.2559 0.1047 1,881.0114 0.153 5.2991 0.1476
Propane 0.5646 0.0471 1,240.1503 0.1008 2.4508 0.0682
i-Butane 0.0855 0.0071 247.5564 0.0201 0.4409 0.0123
n-Butane 0.178 0.0148 515.2506 0.0419 0.8839 0.0246
i-Pentane 0.0485 0.004 174.1217 0.0142 0.2795 0.0078
n-Pentane 0.0411 0.0034 147.8311 0.012 0.235 0.0065
Nitrogen 0.0806 0.0067 112.4527 0.0091 0.215 0.006
n-Hexane 0.0295 0.0025 126.6371 0.0103 0.1912 0.0053

28MAY/JUNE 2020 | GasProcessingNews.com
 TREATING TECHNOLOGY

setup for the GUPCO amine unit. To eval-
uate the efficiency of the tray and packed
columns and to check the thermodynamic
models, DEA and MDEA treatments were
modeled in the simulation program.a
In the simulation, the acid gas enters the
absorber from the bottom, while the amine
solution enters from the top. The amine
is readied for reuse by passing the stream
through a mixer, where it is mixed with
makeup water. More of the amine solution
may be added to the mixer to ensure the
optimal composition for gas sweetening.
A booster pump then raises the pres-
sure to 47 bar, which is the operational
pressure of the absorber. A heat exchanger
cools the amine solution to the desired
removed. Removal of H2S and CO2 from creased from Tray No. 3 to Tray No. 22,
sweet gas was 68.85% at Tray No. 1. but CO2 was not removed completely.
FIG. 6 shows the simulated concentra-
tions of H2S and CO2 mole fractions with Results and discussion. The simula-
the tray number in the top of the desorb- tion results are considered to be reliable,
er. The concentration of H2S at Tray No. 3 since the thermodynamic model takes
in the full rich acid case immediately de- temperature, pressure and composition
creased and reached zero at Tray No. 5. into consideration when evaluating the
The concentration of CO2 gradually de- equilibrium of the reaction.
3.00e-002
CO2, light
H2S, light
2.50e-002
1.20e-002
CO2
Mole fraction

operational temperature of 47.3°C. The 1.50e-002

sweetened gas from the absorber is sent
to the pipe system for transport to an on- 1.00e-002
shore system for distribution.
The bottom liquid is then sent to a
5.00e-003
flash tank, where the stream is heated to H2S
flash out most of the hydrocarbons in the 0.000
stream. The amine solution is then sent 0 5 10 15 20 25
to a distillation tower, where the stream Tray number
is cleaned from H2S to the same level as FIG. 3. Composition of feed acid gas with tray position in absorber for DEA treatment.
the sweetened gas. Water is added to the
recovered amine and sent to the mixer to
be reused for the new sweetening cycle.
The simulation showed H2S removal
at 100%, and removal of both H2S and
CO2 of 99.07% for the 32 wt% DEA solu-
tion. FIG. 3 shows the simulated concen-
trations of H2S and CO2 mole fractions
with the tray number in the top of the
absorber. The concentration of H2S in
the full rich acid case gradually decreased
from Tray No. 24 to zero at Tray No. 15,
and the concentration of CO2 gradually
decreased from Tray No. 24 to zero at
Tray No. 3. Therefore, the removal of H2S
and CO2 is 99.07% at Tray No. 1.

THE CLEAR
FIG. 4 shows the simulated concentra-
tions of H2S and CO2 mole fractions with
the tray number in the top of the desorb-
er. The concentrations of H2S and CO2 at

CHOICE FOR 2020

Tray No. 3 in the full rich acid case gradu-
ally decreased to zero at Tray No. 15.
For the 32 wt% MDEA solution, H2S
removal was 99.95%, and removal of
both H2S and CO2 was 68.85%. FIG. 5
shows the simulated concentrations of PA R AT H E R M H E AT
H2S and CO2 mole fractions with the tray
number in the top of the absorber. The
TRANSFER FLUIDS
concentrations of H2S and CO2 at Tray
No. 24 in the full rich acid case gradually
decreased to zero at Tray No. 10. CO2 de- www.paratherm.com
creased gradually, but was not completely
Gas Processing & LNG | MAY/JUNE 202029
TREATING TECHNOLOGY

When comparing the results of the o Total mass flow required The simulation results show that both
simulated removal processes for the DEA for DEA = 794 kg/hr. DEA and MDEA are effective sweeten-
and MDEA solutions, it can be seen that • MDEA results: ing agents for acid gas. DEA provides the
DEA is the less costly and more effective o Removal of H2S from sweet gas = cheapest and most efficient treatment op-
removal solution: 99.95%, and removal of H2S tion overall, with H2S removal of 100%
• DEA results: and CO2 = 68.95% and H2S and CO2 removal of 99.07%.
o Removal of H2S from sweet o Average price of MDEA By contrast, H2S removal with MDEA
gas = 100%, and removal of chemical = 1,207,296 LE is 99.95%, and removal of both H2S and
H2S and CO2 = 99.07% (Egyptian pounds)/d CO2 is 68.85%. MDEA is both more ex-
o Average price of DEA chemical = o Total mass flow required pensive and more environmentally friend-
609,792 LE (Egyptian pounds)/d for DEA = 786 kg/hr. ly than DEA, and it removes H2S faster.
However, initial CO2 removal with MDEA
1.80e.003 did not reach acceptable levels, and it was
1.60e.003 CO2, light
necessary to add more MDEA and water
H2S, light to adequately sweeten the gas. GP
1.40e.003
1.20e.003 NOTE
CO2 a
Aspen HSYS
Mole fraction

1.00e.003
LITERATURE CITED
8.00e.004 1
Miller, L. N., R. A. Macriss and T. S. Zawacki,
6.00e.004 “Process for acid gas removal from gaseous mixtures,”
US Patent US4080424A, March 21, 1978.
4.00e.004 2
Kohl, A. L. and R. Nielsen, Gas Purification,
Gulf Professional Publishing, Houston, Texas, August
2.00e.004
H2S 28, 1997.
0.000 3
“Hydrogen sulfide,” PubChem Public Chemical
0 5 10 15 20 25 Database, U.S. National Center for Biotechnology
Tray number Information, February 8, 2020, online: https://pub-
chem.ncbi.nlm.nih.gov/compound/Hydrogen-sulfide
FIG. 4. Composition of feed acid gas with tray position in desorber for DEA treatment. 4
Mahajani, V. V. and P. V. Danckwerts, “The stripping of
CO2 from amine-promoted potash solutions at 100°C,”
Chemical Engineering Science, Vol. 38, No. 2, 1983.
2.00e.002 5
Cornelissen, A. E., “Simulation of absorption of H2S
1.80e.002 CO2, light and CO2 into aqueous alkanolamines in tray and
1.60e.002 H2S, light packed columns,” Chemical Engineering Research and
Design, Vol. 58, No. 4, 1980.
1.40e.000 6
Weaire, D. and S. Hutzler, “The physics of foams,”
Mole fraction

1.20e.002 CO2 Physics Today, Vol. 54, No. 3, March 2001.

7
1.00e.002 Astarita, G., D. W. Savage, and A. Bisio, Gas Treating
with Chemical Solvents, J. Wiley and Sons, Hoboken,
8.00e.003 New Jersey, 1983.
8
6.00e.003 Young, E. E., “ A method of preparation of sulfone and
its homologues,” Belgium Patent 616856A, October
4.00e.003 25, 1962.
2.00e.003 H2S 9
Huntsman Chemical Corp., “Choices of gas treating,”
0.000 Brochure, 1995.
0 5 10 15 20 25
Tray number NADY S. ABBAS is Process Section Head at Gulf of
Suez Petroleum Co. (GUPCO) in Cairo, Egypt. He has
FIG. 5. Composition of feed acid gas with tray position in absorber for MDEA treatment. 10 yr of working experience in gas production and
processing, with expertise in conceptual design of
chemical processes, plant commissioning, startup
1.40e.003 and troubleshooting. He is also highly experienced
in dynamic process simulation and process control.
1.20e.003 CO2, light
H2S, light He holds an MSc degree in chemical and petroleum
refining engineering and a PG diploma in chemical
1.00e.003 engineering, both from Minia University in Minia, Egypt.
CO2 He also holds a BSc degree in petroleum refining
Mole fraction

6.00e.004 engineering from Suez Canal University in Suez, Egypt.

6.00e.004 HASSANEIN M. ASFOUR is a Professor in the

Department of Engineering at Minia University
4.00e.004 in Minia, Egypt.

2.00e.004 MOHAMMED Z. A. WAHAB is a Professor in the

H2S Department of Engineering at Minia University
0.000 in Minia, Egypt.
0 5 10 15 20 25
Tray number EMAN A. ASHOUR holds a PhD and is a Professor
in the Department of Engineering at Minia University
FIG. 6. Composition of feed acid gas with tray position in desorber for MDEA treatment. in Minia, Egypt.

30MAY/JUNE 2020 | GasProcessingNews.com