Operational Improvements in Gas Processing

Current and Future Gas Treating Solvent Technologies

For Improved Mercaptan Removal

Gas Treating Team Dow Chemical

Abstract
Amine solvents have been used for several decades for removal of hydrogen sulfide and carbon dioxide
from a variety of gas streams, but have proven to be less effective for mercaptan removal. More stringent
regulations and legislation are pressuring gas processors to achieve deeper removal of sulfur compounds in
addition to hydrogen sulfide.
Today, hybrid solvents containing an amine and a physical solvent are often used for increased
mercaptan removal efficiencies. This paper describes the benefits as well as the disadvantages of hybrid solvents
in this particular application.
The Dow Chemical Company presents a new concept for increasing mercaptan solubility in aqueous
amine solutions. New mercaptan removal agents (MRAs) provide a different means for increasing mercaptan
removal.

Introduction
Since mercaptans are much weaker acids than H2S or CO2, they react to only a small degree with amines.
Improving mercaptan removal can offer significant advantages :

Elimination or reduced size of downstream treatment units.

Increased efficiency and extended cycle times of molecular sieve units.
Reducing or eliminating mercaptide and disulfide waste streams from caustic scrubbers.
Total sulfur content reduction in treated gas and natural gas liquids.

Historically, mercaptan elimination has been a side reaction in an amine unit. The amount of hydrogen
sulfide removal, as well as its predictability, has improved greatly with enhanced amine and amine hybrid
solvents. Downstream units often use polishing steps to remove mercaptans.
Eliminating mercaptans by gas treating solutions has always been a challenge due to the limited
solubility these compounds have in aqueous solutions and because of their low acidity. This is best thought of in
terms of both physical (solubility in the aqueous amine solution without reaction) and chemical solubility (the pHdependent reaction with the amine base).
In this paper, mercaptan removal efficiencies are presented for aqueous amine systems, amine hybrid
solvent systems and finally for aqueous amine solutions, dosed with Dows Mercaptan Removal Agents (MRAs).

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Henrys Law
At a constant temperature, the amount of a given gas dissolved in a given type and volume of liquid is
directly proportional to the partial pressure of that gas in equilibrium with that liquid :

p = xL KH
where : xL = mol fraction of solute in solution
p = partial pressure of solute in gas phase
KH = Henry constant (sometimes shown as Kh or H)
Sometimes, for low solubility gases in water, Henry constants are instead expressed in units of solution
molarity instead of mol fraction :
KH = p / M = p x liter/moles
Using molarity units is often advantageous in gas treatment, since it allows for comparison of different
solvents with respect to their volumetric gas capacity.

Figure 1 : Mercaptan Removal by Amine Solutions

From an equilibrium viewpoint, a Henry constant represents the equilibrium constant for a degassing
reaction. Therefore, lower KH values translate to higher gas solubility in the solvent. Solubility (dissolution) of gas
in the liquid at 1 unit of pressure can be expressed by 1/ KH. Mercaptan solubility in an amine solution is a sum of
the physical solubility which can be enhanced by co solvents and chemical solubility due to the reversible
reaction with amines. (See Figure 1).
1
KH(total)

1
KH(physical)

1
KH(chemical, amine)

The chemical solubility in this case can be estimated by the following relationship :
1
KH(chemical, amine)

p RSH x Ka(RSH)
KH(physical) [H+]

where Ka(RSH) is the acid dissociation constant for mercaptans.

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This relationship has the following consequences :

1. Improved mercaptan removal is achieved by using more basic amines, because this increases the
solution pH. Increasing the amine basicity will also decrease the reversibility of the amine/RSH reaction
and increase the energy required for regeneration. More basic amines will also remove more carbon
dioxide, which can be an advantage or disadvantage, depending on the situation.
2. Lower mercaptans (C1, C2) with high acidities (lower values of Ka(RSH)) will exhibit larger chemical
solubilities than higher mercaptans in amine solutions.
3. Since the RSH reaction is pH dependent, any substantial acid gas (H2S or CO2) loadings will greatly limit
the mercaptan reaction. Acid gas loadings cause a steep decrease in solution pH which results in a lower
degree of RSH ionization.
The behavior of a commonly used amine solution (50% MDEA) toward mercaptan solubility, as the
solution loading increases is given in Figure 2. The use of very lean loadings and high circulation rates can often
help mercaptan removal in an amine absorber, but most mercaptan removal rates are limited by the low degree of
reaction with the amine.

Figure 2 : Methyl Mercaptan Solubility at Various Acid Loadings

Mercaptan Removal Efficiency Using Formulated Aqueous Amines

The sulfur balance for a gas absorber of a US account in Wyoming is given below. The solvent is an amineonly formulated solvent (UCARSOL LE Solvent 777) operated at a 43% by weight concentration. The absorber
operating pressure is at 12 bar. Data are presented for two different liquid-to-gas ratios. Note the increase in
lower molecular weight mercaptan removal efficiency as the liquid-to-gas ratio is increased, and hence the rich
solvent loading is reduced.
Feed Gas Rate (Nm3/hr)
Feed Gas Temperature (C)
Lean Solvent Flow Rate (m3/hr)
Lean Solvent Temperature (C)

13,400 13,700
16.1 22.7
51.4 71.4
41.7 44.4

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Liquid-To-Gas Ratio (liter/Nm3)

Lean Solvent Loading (mol/mol)
Rich Solvent Loading (mol/mol)
L/G Ratio

3.75 5.30
0.0095 0.0125
0.205 0.268

3.75

5.30

ppmv IN

ppmv OUT

%Removal

ppmv IN

ppmv OUT

%Removal

C1SH

371.95

12.46

96.7

210.63

< 0.01

> 99.9

C2SH

109.28

9.63

91.2

78.28

< 0.01

> 99.9

iC3SH

22.31

8.88

60.2

18.49

0.03

99.8

nC3SH

5.09

1.45

71.5

4.21

0.75

82.2

iC4SH

2.65

0.37

86.0

3.16

0.08

97.5

nC4SH

4.47

0.66

85.3

5.88

1.37

76.7

Sec C4SH

1.30

0.23

82.3

1.64

0.71

56.7

Tert C4SH

6.83

1.07

84.3

5.28

2.89

45.3

C5+SH

10.26

3.38

67.1

8.13

3.55

56.3

Table 1 : Mercaptan Removal Efficiency at Different Liquid-To-Gas Ratios

Even considering the fact this gas contains around 9% hydrogen sulfide in the feed, which is reduced to
less than 1 ppm(v), RSH removal efficiency is quite high at elevated liquid-to-gas ratios. Total removal rates for
mercaptans and thiophenes were respectively 90.95% and 96.18%.
A similar performance was measured in the liquid/liquid contactor, equipped with 6 meters of 1.5 inch
Raschig Rings. The low rich loading of the solvent (0.04 mol/mol) allows higher than normal mercaptan removal
rates. At a solvent-to-LPG ratio of 1.6, the total mercaptans and thiophenes removal rate was 82.6%.

Mercaptan Removal Efficiency Using Formulated Hybrid Amines

Physical solvents can be used for increased removal of organic sulfur compounds, but that advantage is
often a tradeoff with higher hydrocarbon solubility. To bridge the gap, hybrid solvents were developed.
Hybrid solvents are combinations of amines and physical solvents. As water is replaced in a solvent
formulation with a hybrid solvent better suited for mercaptan removal, the value of 1/ KH(physical) is increased. They
provide the advantages of deeper H2S and/or CO2 removal found in amine solvents with sustained mercaptan
solubility at higher loadings. Hydrocarbon solubility is greater than aqueous amines, but less than the pure
physical solvents.

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A commonly used hybrid solvent system is the blend of Sulfolane, MDEA and water a mixture
commonly attributed to Sulfinol-M 1 . As seen in Figure 2 above, this blend demonstrates higher solubility at the
higher acid loadings.

Dows hybrid solvent UCARSOL LE Solvent 701 consists of MDEA and a proprietary physical solvent
additive. It is typically used at concentrations varying between 70% and 80% by weight. The operating data set
below is from an account in The Republic of Kazakhstan.
Feed Gas Rate (Nm3/hr)
Feed Gas Temperature (C)
Lean Solvent Flow Rate (m3/hr)
Lean Solvent Temperature (C)
Liquid-To-Gas Ratio (liter/Nm3)
H2S Concentration in Inlet (%v)
CO2 Concentration in Inlet (%v)
RSH Concentration in Inlet (ppmv)

118,000
33
325
54
2.75
3.7
5.7
300 450 *

* Mercaptan Composition (%v)

Methyl mercaptan
Ethyl mercaptan
Isopropyl mercaptan
n-Propyl mercaptan
t-Butyl mercaptan
n-Butyl mercaptan
1-Pentanethiol

51.1
32.3
11.3
1.87

H2S Concentration in Treated Gas (ppmv)

CO2 Concentration in Treated Gas (%v)
RSH Concentration in Treated Gas (ppmv)
Percent RSH Removal (%)

0.5 3
2.6 3.5
20 42
85 92

0.45
2.64
0.34

The ratio between the chemical (amine) and physical component in hybrid solvents can be modified as a function
of the clients requirements. Another account in British Columbia uses UCARSOL LE Solvent 703. The key
difference with the above mentioned LE-701 is the higher physical solvent additive
contents in this formulation.
Feed Gas Rate (Nm3/hr)
Feed Gas Temperature (C)

91,700
20 30

Trademark of Shell Oil. Formulation cited in Kohl, A and Nielson, R., Gas Purification, 5th edition, 1997, Gulf Publishing Co., Houston

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Lean Solvent Flow Rate (m3/hr)

Lean Solvent Temperature (C)
Liquid-To-Gas Ratio (liter/Nm3)
H2S Concentration in Inlet (%v)
CO2 Concentration in Inlet (%v)
RSH Concentration in Inlet (ppmv)

167
37
1.82
2.1
3.1
300 400 *

* Mercaptan Composition (%v)

Methyl mercaptan
Ethyl mercaptan
Isopropyl mercaptan
n-Propyl mercaptan
t-Butyl mercaptan
n-Butyl mercaptan
sec-Butyl mercaptan
Methyl Ethyl mercaptan
Dimethyl sulfide
Other S species

50.0
20.0
13.3
2.00

H2S Concentration in Treated Gas (ppmv)

CO2 Concentration in Treated Gas (%v)
Total S Concentration in Treated Gas (ppmv)
Percent RSH Removal (%)

0.6 1.6
1.5 1.9
< 16
95

1.00
0.34
3.68
1.65
3.66
4.37

Mercaptan Removal Agents (MRA)

New mercaptan removal agents (MRA) provide another reactive means for increasing mercaptan removal
(See Figure 3). MRA reacts with the RSH to form an MRA complex. The equilibrium constant between MRA and
RSH is large enough to allow a substantial reaction to occur at lower pH regions than the reaction of the amine and
RSH.

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Figure 3 : Mercaptan Removal Scheme with MRA

The alkanolamine works without the MRA to remove H2S, CO2, and to a lesser degree, RSHs. The MRA
then acts to remove the remaining RSHs. The complex formed is also heat regenerable so that the RSH can be
stripped off and it exits with the stripper off gas as free RSH. The total mercaptan solubility can now be
represented as :
1
KH(total)

1
KH(physical)

1
KH(chemical, amine)

1
KH(chemical, MRA)

MRA can be added in different quantities to achieve various degrees of RSH removal. MRA is also
compatible with many amine blends, which allows for custom blends tailoring achieving desired RSH, CO2 and H2S
removal levels.

Comparative Solubility Study of Gas Treating Solvents

During thorough laboratory and pilot plant studies, MRA was added to MDEA in three different
concentrations. At 0.2 X concentration, MRA substantially elevates MDEA performance for mercaptan removal. At
1 X concentration, the MRA/MDEA formulation exhibits solubilities comparable to the pure physical solvents and
at 2 X greatly exceeds those solubilities. The X refers to the relative MRA concentration used.
Since the MRA/MDEA formulation has about 50% water, hydrocarbon solubility is low, about equal to
50% aqueous MDEA. The results of the comparative solubility study of methyl mercaptan in different gas treating
solvents are shown in Figure 4.

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Figure 4 : Comparative Solubility of Gas Treating Solvents

MRA Commercial Testing

In order to test the performance of MRA on a larger scale, the MRA was added to an existing plant while it
was operating. The amine unit ran using an MDEA-based blend of amines with an inlet composition as given below
:

H 2S
CH3SH
C2H5SH
C3H7SH

300 1,000 ppmv

500 900 ppmv
500 900 ppmv
100 200 ppmv

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Typical plant operating conditions during the 5 week test run were :
Feed Gas Rate (Nm3/hr)
Feed Gas Pressure (bar)
Lean Solvent Flow Rate (m3/hr)
Lean Solvent Temperature (C)
Liquid-To-Gas Ratio (liter/Nm3)

1,450
21.7
3
49 - 60
2.04

Changes in plant operating conditions and inlet feed composition resulted in some variability in
mercaptan removal. The average removal efficiencies for different levels of MRA are given in Figure 5. The X
refers to the relative MRA concentration used.

Figure 5 : Performance of MRA formulation in a commercial plant

Tests completed at the end of the five week period showed that all additive remaining in the plant was
active. Slow additive loss was difficult to quantify due to solution concentration variations and because only a
small amount was lost during the testing period.
Plant management reported substantial sulfur reductions in the treated product. After the performance
test, the solution was removed from the plant. During shutdown, inspection of the plant showed no abnormalities.
The amine formulation in the plant was a blend that represented one of the better combinations for RSH
removal. Though this amine formulation did a reasonably job of mercaptan removal on its own, the addition of
MRA substantially improved RSH removal performance. Although mercaptan removal by amines is very dependent
on solution pH and lean loading, the performance of MRA is mostly independent of pH changes encountered in
normal gas treating operations. MRA reacts to a minimal degree with H2S, so mercaptan removal by MRA is
slightly dependent on H2S concentration. Pilot plant testing with several percent H2S levels demonstrated a high
selectivity of MRA towards mercaptans.

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Conclusions
The solubility of mercaptans in amines can be treated as the sum of both physical solubility and a
chemical solubility. The chemical solubility can be predicted from the acid-base properties of both amine and the
mercaptans. At low loadings, the chemical solubility dominates the total solubility. As the acid loadings in the
solution increase, chemical solubility is substantially reduced and the physical solubility dominates. By using
appropriate co solvents, the physical solubility can be greatly increased. These hybrid solvents however
demonstrate a higher hydrocarbon solubility, compared to aqueous amine formulations.
The addition of MRA to aqueous amine formulations demonstrates substantial reduction of mercaptans
in laboratory tests, pilot plant and commercial plant studies. Some additional work remains on additive
production and solvent formulation. Larger scale commercial trials are currently being discussed with a few Dow
Gas Treating accounts.

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