Gas Sweetening Processes: Aqueous Solution Wt. % Mole % Mdea 50 13.13 H2O 50 86.87 Total 100 100.00

"OIL AND GAS PROCESSING PLANT DESIGN 2002
AND OPERATION TRAINING COURSE"

Page 21
DGEP/SCR/ED/ECP "GAS SWEETENING PROCESSES"
Conversely MDEA is also interesting for the bulk removal of CO2 due to its low heat of reaction
with this compound (energy saving at the level of the regeneration section). Generic MDEA is
available on the market of chemical products (HUNTSMAN for instance) but almost all processes
based on the use of MDEA are from licensers. Licensers add activated agents to the MDEA to suit
the type of acid gas removal requirements.
Main licensers of MDEA-based processes are :
 BASF : Activated MDEA (aMDEA). The first industrial plant was built in 1971. Now,
there are 80 worldwide references (22 % in Natural gas). The activated agent,
Piperazin, is added to the MDEA.
 DOW CHEMICAL : Gas-Spec Process using an activated MDEA derived product (Gas
Spec SS Selective Solvent) originally preferably used for the selective removal of H2S
with high CO2 slippage percentages: % slippage = 100 x (Outlet gas CO2 content/Inlet
Gas CO2 content).
The formulation of the solvent is such that it can be also used for controlled CO2
removal (CS-3 MDEA solvent) to adjust the GCV of an export gas.
 EE(P) : Activated MDEA process (see figure XI-B.9). The activated agent added to the
MDEA is adapted to the type of contaminant to be preferably removed. The specific
feature of this design is that a small portion of the rich amine solution is regenerated in
the conventional regeneration section (with a fractionation column with reboiler and
condenser). The rest of the rich solution is regenerated by multi-stage (generally 2
stages) flash separation (semi-lean solution).
 UOP : Amine Guard process (see figure XI-B.10) using generic MDEA and a collection
of so-called Ucarsol solvents (fabricated by UOP and designed for selective removal
of H2S, deep removal of both H2S and CO2, removal of CO2 from H2S free feed gas).
 Concentration
Pure MDEA is generally used in aqueous solutions with concentrations between 35 and 50 Wt. %.
The molar composition of a 50 Wt. % MDEA solution is as follows:
Aqueous Solution Wt. % Mole %

MDEA 50 13.13
H2O 50 86.87
total 100 100.00
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 Utilization
Generic MDEA is used to remove selectively H2S (down to 4 ppm V and even lower) from a feed
gas containing both CO2 and H2S (CO2 slippage: 60 to 80 %). Activated MDEA (through
licensers) can be used for deep removal of both H2S and CO2 (to satisfy a LNG specification for
instance).
When CO2 is the sole gas contaminant, bulk removal can be realized with generic MDEA but this
would require higher circulation rates than with primary and secondary amines (thermal energy,
however would be lower). For deep removal of CO2, activated MDEA from licensers will be
required.
 Chemical reaction
- H2S
H2S reacts immediately with MDEA.
R2NCH3 + H2S  R2NHCH3HS
- CO2
MDEA being a tertiary amine, the molecule does not have an hydrogen atom attached directly to
the nitrogen atom. This has an important impact on the chemistry of CO2/MDEA reaction. The
carbamate formation which is important for primary and secondary amines is inhibited and the
bicarbonate formation (easy to remove from the rich solution to reconstitute a poorly CO2 loaded
lean solution) becomes the only important reaction.
R2NCH3 + CO2 + H2O  R2NHCH3HCO3

where R= C2H4OH
The above reactions are reversible.
 MDEA Solution Loading
For generic MDEA solutions free from licenser’s processes, the gross acid gas pick-up must
remain below 0.45 mole/mole of pure MDEA to avoid corrosion.
The lean solution CO2 loading is around 0.01 mole CO2/mole pure solvent.
Other sound amine process : Hindered Amine

EXXON is a licenser for processes (Flexorb processes) using formulated amines (hindered
amines). The solvent (based on alkanolamine) is formulated according to the acid gas pick-up
requirements. The different type of processes are as follows :
 Flexorb SE (commercially available since 1983) for the selective removal of H2S
 Flexorb PS (available since 1984) for both removal of H2S and CO2 (and COS). In this
case, the formation of stable carbamate with CO2 and classical primary and secondary
amines (which limit the acid gas pick-up to 0.45/0.5 mole of CO2/mole of pure amine) is
reduced. According to EXXON tests, Flexorb agent also offers a capacity advantage over
MDEA.
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 Flexorb HP for removal of CO2 when the feed gas is free from H2S.
Remark: When dealing with a licenser, for any kind of gas sweetening study (feasibility study, pre-
project, basic engineering), a secrecy agreement has to be signed between the Company and the
licenser and then the licenser will start the requested work and disclose the features of its design
(process flow diagram, material balance, utility balance, preliminary sizing of the major equipment,
cost of solvent, inventory, chemical consumption’s).
A licensing fee is then requested by the licenser when a firm contract is signed between the
Company and the licenser.
2.1.7. Potassium Carbonate
Potassium carbonate (K2CO3) is an alkaline salt which is used for the removal of acid gas. At
ambient condition, Potassium carbonate is under solid form. It is used in aqueous solution. In order
to keep the carbonate dissolved in the water, the solution must be kept under temperature (more
than 60 deg.C for a 30 Wt. % carbonate solution).
Unlike amine solutions, Potassium carbonate solution is not susceptible to oxygen contamination.
The product is available on the market but processes based on its use are developed by licensers.
The major licenser is UOP with the Benfield processes which have the largest number of industrial
references in natural gas sweetening.
CATACARB process is also based on Potassium carbonate but with less industrial reference.
 Concentration
Potassium carbonate is used in aqueous solutions with concentrations around 30 Wt. % (molecular
weight of Potassium carbonate is 138.2).
The molar composition of a 30 Wt. % HPC solution is as follows:
Aqueous Solution Wt. % Mole %

Potassium Carbonate 30 5.29
H2O 70 94.71
total 100 100.00
 Chemical reaction
- H2S
The chemical reaction with H2S is as follows :
K2CO3 + H2S  KHS + KHCO3
The absorption reaction is exothermic : Heat of reaction of K2CO3 with H2S is 22 BTU/SCF (819
kJ/Sm3 of H2S).
The Potassium bisulfide (KHS) is very difficult to regenerate so the Hot Pot process is not suitable
for sweetening gas mixtures containing little or no CO2.
Excerpt from PRODEM

Gas Sweetening Processes: Aqueous Solution Wt. % Mole % Mdea 50 13.13 H2O 50 86.87 Total 100 100.00

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"OIL AND GAS PROCESSING PLANT DESIGN 2002

AND OPERATION TRAINING COURSE"

Aqueous Solution Wt. % Mole %

Excerpt from PRODEM

R2NCH3 + CO2 + H2O  R2NHCH3HCO3

 MDEA Solution Loading

Other sound amine process : Hindered Amine

Excerpt from PRODEM

2.1.7. Potassium Carbonate

Aqueous Solution Wt. % Mole %

Excerpt from PRODEM

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