PETROCHEMICALS & GAS PROCESSING

Predicting amine blend

performance
A process simulator is able to predict the performance of an Iranian gas-sweetening
plant. Various mixtures of diethanolamine (DEA) and Methyl diethanolamine
(MDEA) are used to investigate the potential for an increase in plant capacity
Hamid Reza Khakdaman and Ali Taghi Zoghi National Iranian Oil Company
Majid Abedinzadegan Abdi Memorial University of Newfoundland

echnology using alkanolamines,

or amines, for the removal of
hydrogen sulphide and carbon
dioxide from natural gases has been
around for decades. Since the 1960s
and 1970s, several amines have come
into general use, but there is little
information available on which
amine is best suited to a particular
service. Many inefficient amine gassweetening units can be optimised
by simply changing their amine
solutions.
The basic flow scheme for an aminesweetening unit is shown in Figure 1. In
the design of the process, the primary
concern is that the sweetened gas
should meet the required purity
specifications with respect to H2S and
CO2. The secondary objective is to select
the amine, which optimises equipment
size and minimises plant operating
costs. The following points should also
be addressed in the selection of the
proper amine for the design or
evaluation of an existing plant:
Can the amine circulation rate be
reduced by selecting an amine that may
be used at a higher concentration
and/or at a higher acid gas loading?
Could the equipment be designed
more efficiently using an amine that
requires a lower circulation rate and/or
has lower heats of reaction with H2S and
CO2?
Could H2S be selectively absorbed
from the sour gas while CO2 is rejected?
Can the selective absorption of H2S and
CO2 from the sour gas be optimised by
the use of a suitable amine blend?
Could corrosion and solvent loss
problems be improved with an amine or
mixture of amines more resistant to
degradation?
Between 5070% of the initial
investment for an amine-sweetening
unit is directly associated with the
magnitude of the solvent circulation
rate, and another 1020% of the initial
investment depends on the regeneration energy requirement (Astarita et al,
1983). Approximately 70% of gas-

Stripper
O/H
condenser

Sweet
gas
Lean amine
cooler

Storage
tank

Booster
pump
Sour
gas

Acid gas

Reflux
pump

Stripper

Absorber

Reboiler

Stm.
Cond.

Cross
exchanger

Figure 1 Process flow diagram for a common sweetening plant

Typical operating conditions and data for amines
Alkanolamine type
MEA
DEA
DGA
MDEA
Solution strength, wt%
1520
2535
5070
2050
Acid gas loading, mole/mole
0.300.35 0.300.35 0.300.35 Unlimited
Ability for selective absorption of H2S
No
Under limited
No
Under most
conditions
conditions

Table 1
sweetening plant operating costs,
excluding labour expenses, are due to
the energy required for solvent
regeneration.
Appropriate
amine
selection can significantly reduce the
regeneration energy requirement and
solution circulation rate. Therefore, the
selection of amines best suited to the
process conditions can have a dramatic
impact on the overall costs associated
with a sweetening unit.
Several alternative flow schemes for
amine-sweetening plants were discussed
in detail by Polasek, Donnelly and
Bullin (1983) and therefore will not be
discussed here.

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w w w. e p t q . c o m

General considerations for

amine selection
The general criteria for amine selection
in sweetening plants have changed
over the years. Until the 1970s,
monoethanolamine (MEA) was the only
amine considered for any sweetening
application. In the 1970s, as exemplified
in papers by Beck (1975) and Butwell
and Perry (1975), a major switch from
MEA to diethanolamine (DEA) occurred.
In the past ten years, MDEA, DGA and
mixed amines have steadily gained
popularity too.
In order to become accepted on an
industry-wide basis, different operating

PETROCHEMICALS & GAS PROCESSING

and Danckwerts (1979). MDEA can,
however, react with H2S by the same
proton transfer mechanism of primary
and secondary amines (Jou et al, 1982):

Heat of reaction for different types of amines

Amine
Solution strength
Acid gas loading, mole/mole
Hr for H2S, Btu/lb
Hr for CO2, Btu/lb

MEA
1520
0.30.4
550
825

DEA
2535
0.30.4
511
653

DGA
4060
0.30.4
674
850

MDEA
3050
Unlimited
522
600

(2)

Table 2
conditions should be tested and proven
with a particular amine. Each alkanolamine solution has an accepted
range of process conditions and
parameters associated with it. Typical
operating conditions for common
alkanolamines are summarised in
Table 1.

Diethanolamine (DEA)
DEA is the most commonly used amine,
within the 2535 wt% range. The total
acid gas loading for DEA is limited to
0.300.35 mole/mole for carbon steel as
the equipments construction material.
DEA can be safely loaded up to
equilibrium level (~1 mole/mole) when
stainless steel is used. The degradation
products of DEA are relatively less
corrosive than those of MEA. Exposure
to oxygen forms corrosive acids, and
COS and CS2 may, to some extent, react
irreversibly with DEA. DEA is not
reclaimable under regenerator conditions; it decomposes below its boiling
point at atmospheric pressure. Vacuum
reclaimers, however, have been successfully used to reclaim DEA solutions
(Meisen et al, 1996).
Since
DEA
is
a
secondary
alkanolamine, it has a reduced affinity
for reaction with H2S and CO2.
Therefore, it may not be able to produce
pipeline-quality gas for some lowpressure gas streams. In general, as the
gas pressure is lowered, the stripping
steam must be increased or a split flow
design used. In some cases, even these
measures will not suffice and another
solvent must be used.
Under some conditions, such as low
pressures and a liquid residence time on
the tray of about two seconds, DEA is
selective toward H2S and will permit a
significant fraction of the CO2 to remain
in the sales gas.

Methyldiethanolamine
(MDEA)
An accepted set of operating conditions
has not been firmly established for
MDEA, as compared to the previously
mentioned amines. This is due to the
flexibility and versatility of MDEA, and
the resulting wide range of applications.
MDEA is a tertiary amine and
commonly used in the 2050 wt%
range. Solutions with lower amine

concentration are typically employed in

low-pressure, high-selectivity applications such as the selective removal of
H2S in the Shell Claus off-gas treating
(SCOT) units.
Due to the considerably reduced
corrosion problems, acid gas loadings as
high as 0.70.8 mole/mole are
considered practical in carbon steelmade equipment. Higher loadings may
also be possible with a few problems.
MDEA exposure to oxygen forms
corrosive acids, which, if not removed
from the system, can result in the buildup of iron sulphide in the system.
MDEA has several distinct advantages
over primary and secondary amines,
which include lower vapour pressure,
lower heats of reaction, higher
resistance to degradation, fewer
corrosion problems and selectivity
toward H2S in the presence of CO2.
Most of these advantages have also
been reported by Blanc et al (1982).
Depending on the application, some of
them have special significance; for
example, due to its lower heat of
reaction, MDEA can be employed in
pressure swing plants for bulk CO2
removal. Here, the rich amine is merely
flashed at or near atmospheric pressure
and little or no heat is added for
stripping.
The overwhelming advantage that
MDEA currently possesses over the other
amines is that it is readily selective
toward H2S in the presence of CO2. At
high CO2/H2S ratios, a major portion of
the CO2 can be slipped through the
absorber and into the sales gas while
removing most of the H2S. The
enhanced selectivity of MDEA for H2S is
attributed to the inability of tertiary
amines to form carbamates with CO2.
MDEA does not have a hydrogen
attached to the nitrogen and cannot
react directly with CO2 to form
carbamate. The CO2 reaction can only
occur after the CO2 dissolves in water to
form a bicarbonate ion, which then
undergoes an acid-base reaction with
the amine:
(1)
At least six mechanisms for the CO2MDEA reaction have been proposed by
Cornelissen (1982), Barth et al (1981)

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Selective absorption of H2S can be

enhanced by optimising absorber design
to obtain a liquid tray residence time of
1.53.0 seconds and by increasing the
temperature in the absorber. Both of
these conditions favour H2S absorption
with CO2 rejection.

Mixed amines
Amine blends are generally mixtures of
MDEA and DEA or MEA and are used to
enhance CO2 removal by MDEA, as
described by Polasek, Bullin and IglesiasSilva (1992). Such mixtures are referred
to as MDEA-based amines, with DEA or
MEA as the secondary amines. The
secondary amines generally comprise
less than 20% of the total amine content
on a molar basis. At lower concentrations of MEA and DEA, the overall
amine concentration can be as high as
55 wt% without the implementation of
exotic metal equipment.
MDEA-based mixtures are normally
used to increase the CO2 pickup in cases
where the MDEA is allowing too much
CO2 to slip overhead in the absorber.
Spiking the MDEA with MEA or DEA to
achieve the desired CO2 pickup is often
preferable to a complete amine switchout to a DEA or MEA system, because
the MDEA regenerator reboiler may be
undersized for a purely formulated DEA
or MEA system. Operating problems
associated with mixed amines influence
amine mixture concentration and its
maintenance.
However, finding an optimum
concentration for mixed amines
(DEA+MDEA) strongly depends on the
H2S and CO2 content of the sour gas,
operating pressures and sale gas
specifications.
For
natural
gassweetening purposes, mixed amines are
typically mixtures of MDEA and DEA or
MEA, which enhance CO2 removal
while retaining desirable characteristics
of MDEA, such as reduced corrosion
problems and low heats of reaction

Case study
A typical Iranian gas plant is selected for
this study. The gas-sweetening facility
has five identical amine trains for H2S
and CO2 removal. The plant management decided to consider one of the
units for substituting DEA with a
mixture of DEA and MDEA. Each train
was composed of two absorbers and two
stripper columns, which operated in
parallel in the unit. The HYSYS plant
simulator was used to simulate the

PETROCHEMICALS & GAS PROCESSING

Gas-sweetening operating conditions

Absorbers feed gas composition

(design basis)
Flow rate,
kmole/hr
H2O
4.28
N2
75.94
CO2
936.3
H2S
562.36
COS
0.26
C1
12 909.22
C2
81.8
C3
13.16
i-C4
2.92
n-C4
4.38
i-C5
2.92
n-C5
2.92
C6+
14.62
DEA

Total
14 611.16
Pressure, bara
1063
Temperature, C
21

Mole %
0.03
0.52
6.41
3.85
17ppm
88.35
0.58
0.09
0.02
0.03
0.02
0.1

0
100

Table 3
process. The absorber feed gas
composition is shown in Table 3, and
operating conditions are summarised in
Table 4.
Current plant operating conditions
were initially simulated to obtain the
confidence that the simulation was
performed effectively. The simulation
produced a very good agreement
between the HYSYS-generated results
and the actual operating data. The
results are listed in Table 5.
The process was subsequently
simulated using various mixtures of DEA
and MDEA with the following
constraints:
Solution circulation rate was
3
considered constant at 935m /hr
H2S content in sweet gas should be
kept less than 2ppm
CO2 content in sweet gas should be
kept less than 1%
Duty of each reboiler was considered
constant at 1.32e+8kJ/hr (125MMBTU/hr)
Condenser temperature equals 52C.
DEA and MDEA concentrations in the
solution were changed from 1030 and
from 539 wt% respectively. The amine
mixtures, which met a targeted value for
the following parameters, were selected
as the alternative solvent for optimum
mixture concentration:
Amine system

Parameter
Amine circulation rate, m3/hr
Absorber col. top/bottom pressure, bara
Absorber col. top/bottom temperature, C
Stripper col. top/bottom pressure, bara
Stripper col. top/bottom temperature, C
No. of actual tray (absorber)
No. of actual tray (stripper)

Typical value
935
1058/1063
55.0/77.0
22.0/27.9
52.0/120.4
20
24

Table 4
Comparison between simulation and actual operating data
Parameter
Rich amine loading
Lean amine loading
H2S in sweet gas, ppm
CO2 in sweet gas, mol%
Absorber col. top/bottom temperature, C
Stripper col. top/bottom temperature, C

Operating data
0.450.50
0.0270.031
1.52.5
0.01
55.0/77.0
52.0/120.4

Simulation results
0.49
0.028
2.0
0.01
61.5/86.2
1

1 The condenser temperature was set to 52C and the reboiler duty of 125MMBTU/hr caused the
reboiler temperature of 120.4C.

Table 5

250 MMBtu/hr
Total amine 35%
Total amine 40%

20 500
Sour gas flowrate, kmole/hr

Component

Total amine 45%

Total amine 49%

20 000
19 500
19 000
18 500
18 000
17 500
17 000
5

10

15

20
DEA, %

25

30

35

Figure 2 Unit revamp at fixed reboiler duty

Acid gas composition in the

sweetened gas (absorber overhead)
Figure 2 shows how the plant
capacity can be increased for various
amine blends. The throughput can be
raised from the base value of
approximately 14 600kmole/hr to the
indicated gas flow rate shown in Figure
4 for various amine
blend compositions,
mol CO 2 + mol H 2S
o Rich amine loading: (
), H2S(v/v)=
and will be further
mol MDEA + mol DEA
discussed. It should
be noted that the
H2S
Vol .Flow
CO 2
Vol .Flow
, CO2 (v/v)=
reboiler duty and
A min e
Vol .Flow
A min e
Vol .Flow
other
parameters
previously indicated
o Lean amine loading: ( mol CO 2 + mol H 2S ) , H2S(v/v), CO2 (v/v) were fixed and that
mol MDEA + mol DEA
only
the
gas
throughputs were

00
P T Q Q4 2005

changed. Since the maximum MDEA

concentration
in
an
industrial
application is limited to below 50%, the
total composition was kept below this
percentage. It can be concluded that a
49% amine blend with 2030% DEA
content
will
be
an
optimised
composition. A lower-end (closer to
20%) concentration for DEA will be
recommended due to the need for
solution corrosion and viscosity control.
As can be seen, by blending DEA and
MDEA mixtures, for the indicated
composition, the plant capacity can be
increased to 17 00020 000 kmole an
rise of approximately 1637%.
In order to check if the plant can
handle higher gas flow rates, other
pieces of equipment and plant parts,

PETROCHEMICALS & GAS PROCESSING

MDEA capabilities
0.14
0.12

CO2, %

0.10
Total amine 35%
Total amine 40%
Total amine 45%
Total amine 49%

0.08
0.06
0.04
0.02
0.00
5

10

15

20
DEA, %

25

30

35

Figure 3 CO2 concentration in sweet gas for different amine mixtures (DEA+MDEA)

Total amine 35%

Total amine 40%
Total amine 45%
Total amine 49%

14.0
12.0

H2S, ppm

10.0
8.0
6.0
4.0
2.0
0.0
5

10

15

20
DEA, %

25

30

35

Due to its lower corrosion tendency and

heat of reactions with acid gases
compared to other amines, MDEA is a
favourable option. Using the HYSYS
plant simulation, different mixtures of
DEA and MDEA were investigated. Since
mixed amines have a higher capacity for
acid gas removal at constant amine
circulation rates compared to DEA
solvents, the gas-processing capacity of
gas-sweetening units can be increased.
These results show that the gas flow rate
capacity for a typical unit can easily be
increased by up to 20%.
References
1 Beck J E, Diethanolamine an energy
conserver, Laurence Reid Gas Conditioning
Conference, Norman, Oklahoma, 1975.
2 Donnelly S T, Henderson D R, A new
approach to amine selection, Proceedings
of the AIChE Spring National Meeting New
York, 1982.
3 Holmes J W, Spears M L, Bullin J A,
Sweetening LPGs with amines, Chemical
Engineering Progress, 80, 5, 47, 1984.
4 Jou F Y, Lal D, Mather A E, Otto F P,
Solubility of H2S and CO2 in aqueous
methyldiethanolamine solutions, Ind. Eng.
Chem. Proc. Des. Dev., 21, 539, 1982.
5 Kohl A and Riesenfeld F, Gas purification,
Gulf Publishing Company, Houston, Texas,
1979.
6 Meisen A, Abedinzadegan Abdi M, Abry R,
Millard M, Degraded amine solutions:
nature, problems, distillative reclamation,
Proceedings of the 45th Annual Laurence
Reid Gas Conditioning Conference,
Norman, Oklahoma, 168190, 1996.
7 Polasek J C, Bullin J A, Selective absorption
using amines, Proceedings of the 61st
Annual Gas Processors Convention, Tulsa,
USA, 1992.
8 Polasek J C, Bullin J A, Iglesias-Silva G A,
Using mixed amine solutions for gas
sweetening, presented at the 71st Annual
Gas Processors Association 2528 February,
Norman, Oklahoma, 2001.

Figure 4 H2S concentration in sweet gas for different amine mixtures (DEA+MDEA)
including heat exchangers, pumps, pipe
sizes and towers, should be examined. It
was observed that the diameter of the
existing absorption tower columns
could handle an increase in gas
throughput of around 22%. Using this
figure, the performance of the plant was
then evaluated using various amine
blends. The lean loading increases with
DEA content, as a higher heating rate is
required to release the acid gas from the
amine. The rich amine loadings remain
relatively constant for a particular
amine blend, but since a solvent blend
with a higher concentration of total
amine can naturally absorb more acid
gas a reduction of acid gas loading will
be expected when the total amine
content increases.
Figure 3 and the previously
mentioned Figure 4 show a variation in
the acid gas (CO2 and H2S) content of
the sweetened gas for the enhanced
capacity scenario a 22% gas flow rate
increase when the amine flow rate and

reboiler duties were kept constant. It is

evident that unless the total amine
concentration was increased beyond the
35 wt% mark, the acid gas specifications
could not be met. Beyond this total
amine composition, the acid gas
content of the sweetened gas remains
nearly constant for varying DEA
content.

Since mixed amines have a

higher capacity for acid gas
removal at constant amine
circulation rates compared
to DEA solvents, the
gas-processing capacity of
gas-sweetening units can be
increased

00
P T Q Q4 2005

Hamid Reza Khakdaman is head of the

modelling and simulation department at
the das division of the Research Institute of
Petroleum Industry (RIPI) of the National
Iranian Oil Company (NIOC), Tehran,
Iran. He is involved in natural gas
sweetening and gas-to-liquids processes as
a research engineer. He holds a BSc from
the Iranian University of Science and
Technology (IUST) and MSc from Tehran
University, both in chemical engineering.
Email: khakdamanhr@ripi.ir
Ali Taghi Zoghi is a senior project
engineer at NIOC-RIPI, Tehran, Iran where
he is involved in gas-processing projects.
He holds a BSc from Tehran University and
MSc from IUST, both in chemical
engineering. Email: zoghiat@ripi.ir
Majid Abedinzadegan Abdi is the former
director of the gas division at NIOC-RIPI,
Tehran, Iran and is currently a faculty
member at the Memorial University of
Newfoundland and process engineering
lead at the centre for marine CNG in St
Johns, NL, Canada.
Email: abdi@engr.mun.ca