Ind. Eng. Chem. Res.

2007, 46, 3729-3733 3729

Aqueous Amines as Reactive Solvents for Mercaptan Removal

Stephen A. Bedell* and Michelle Miller
The Dow Chemical Company, 2301 N. Brazosport BouleVard, Freeport, Texas 77566

The solubilities of methyl mercaptan in a variety of aqueous amine solutions have been measured. Mercaptan
chemical solubility can be predicted by consideration of acid-base properties of the mercaptan and amine.
Chemical equilibrium constants have been used to separate the chemical and physical solubilities from
experimental results for 50 wt % methyldiethanolamine. At moderate acid loadings, the chemical solubility
is diminished and the physical solubility dominates. This methodology has been extended to aqueous solutions
of monoethanolamine, diethanolamine, and diglycolamine.

Introduction Static headspace gas chromatography measurements were

performed with a Perkin-Elmer Turbomatrix-40 headspace
Solvents have been used for decades for removal of acid gases
analyzer attached to an Agilent 6890N gas chromatograph. A
from a variety of gas streams.1,2 The simplest type of solvent is
capillary GS-Q column (i.d. 0.53 mm, 30 m) from J&W
referred to as a physical solvent, usually a pure organic
Scientific provided separation of methyl mercaptan from
compound that dissolves the acid gases through nonreactive
nitrogen and detection was performed by a standard thermal
interactions. The more commonly used solvent systems are
conductivity detector.
aqueous amine solutions which are called chemical solvents.
The transfer line of the headspace analyzer was connected
In addition to a certain degree of physical solubility, chemical
directly to the capillary column using a universal fused silica
solvents (aqueous amines in particular) can also react to form
Press-Tight (Restek) connector. Since the transfer line and GC
thermally regenerable salts with the acid gases.
column were directly connected, carrier gas flow through the
Though amine-based solvent systems have been designed for
column was supplied through the headspace analyzer. Sample
H2S and CO2, few data exist on the solubilities of mercaptans
equilibration time prior to injection onto the column was also
which are often found in H2S-containing gas streams. Many
controlled by the headspace analyzer. Each sample was equili-
confusing descriptions of amine-mercaptan interactions have
brated for 30 min (thermostating time) in the oven of the
been presented in the literature. For instance, Maddox and co-
headspace analyzer, which was set at 40 °C. At the end of the
workers3 state that “the exposure of methyl mercaptan to MEA,
thermostating time the vial was pressurized and the headspace
DEA, DGA, DIPA, DMEA, and MDEA4 did not lead to a
sample injected onto the column.
reaction”. Jou et al.5 write “the thiols are much weaker acids
than H2S, and they do not react with alkanolamines”. The
Results and Discussion
purpose of this work is to show that mercaptans are scrubbed
by aqueous amines due to a combination of physical and Henry’s Law. Henry’s law states that
chemical solubilities (reactions). Furthermore, the chemical
solubility can be predicted by understanding the mercaptan and pΦ ) xLKH (2)
amine acid-base properties.
where xL is the mole fraction of solute in solution, p is the partial
Experimental Section pressure of solute in the gas phase, and KH is Henry’s constant.
The experiments reported in this paper were performed at total
Fifty grams of each amine solution was loaded with sulfuric pressures less than 0.3 MPa and it was assumed that the fugacity
acid such that acid-loading ratios of 0, 0.005, 0.01, 0.02, 0.05, coefficient, Φ, was unity.
0.1, 0.2, 0.4, and 0.6 were obtained. The acid-loading ratio was The Henry constant represents the equilibrium constant for
defined as degassing. Therefore, lower values of KH translate to higher
solubilities of a gas in a solvent. The tendency for a gas to
acid-loading ratio ) mol of H+/mol of amine in solution dissolve in a liquid can better be represented by solubility,
(1)
Sol ) p × Ksol (3)
Calculations of the loadings for each solution assumed H2SO4
donates both protons. with Sol in units of mol/L with a solubility constant of
Once the acid-loaded solutions were prepared, 10.0 g of
solution was added to a headspace vial, which was sealed with Ksol ) mol of solvent/L ÷ KH (4)
an aluminum crimp cap containing a PTFE septum and star
spring. The headspace vial was then purged with nitrogen for and Ksol in units of mol L-1 MPa-1. This report presents Ksol
10 min and injected with 0.5 mL of methyl mercaptan using a values as measures of relative solubility at equal partial pressures
gastight syringe. After injection with methyl mercaptan, the vials of mercaptan.
were loaded onto the magazine of the headspace analyzer and In the reaction of acid gases with amines, Henry constants
sampled by gas chromatography. are often used to describe the overall solubility due to both
physical (hydrogen bonding, van der Waals forces, etc.) and
* To whom correspondence should be addressed. Tel.: 979-238- chemical solubilities. It should be realized that while values of
3240. Fax: 979-238-5183. E-mail: sabedell@dow.com. KH based only on physical solubility are likely to be linear with
10.1021/ie0611554 CCC: $37.00 © 2007 American Chemical Society
Published on Web 04/27/2007
3730 Ind. Eng. Chem. Res., Vol. 46, No. 11, 2007
Table 1. Ksol (mol L-1 MPa-1) for Sulfur Compounds in Water at
25 °C
Yaws Przyjazny Richon and Mather and
compound et al.6 et al.7 Sekyiamah8 co-worker9 co-workers10
MeSH 2.9 4.0 3.3
EtSH 3.5 2.8 2.1
iPrSH 2.2
nPrSH 2.4 2.5 1.2 2.3 (20 °C)
nBuSH 1.1 2.1 1.1 1.9 (20 °C)
tBuSH 1.9
Table 2. Ksol (mol L-1 MPa-1) for Methyl Mercaptan in Various
Solvents at 50 °C
solvent MeSH EtSH nPrSH nBuSH
H2O 1.9,a 2.110 1.1 0.67
n-hexane 5.5 7.7 13 14
toluene 17 40 55 55
a All values from ref 11 unless otherwise indicated.
pressure, those based on reactivity may change with increased
partial pressure as reactants in solution are consumed.
The purpose of presenting the solubilities in this report is to
understand some general principles guiding mercaptan solubility.
If these data are going to be used for predictive calculations,
the reader is encouraged to consult the original references and
select constants most appropriate to a specific application.
Mercaptan Solubility in Water. Several values have been
reported in the literature for solubilities of methyl mercaptan
in water. Original units have been converted to mol L-1 MPa-1.
Solubilities of higher mercaptans have not been as well studied.
In general, they show a slight decrease in solubility as the
mercaptan alkyl groups increase in size. Though Yaws and
Sekyiamah (these are not primary sources) both reported a very
high KH (low Ksol) value for nBuSH, they may have used the
same original source for the value. (See Table 1.)
Mercaptan Physical Solubility in Organic (Nonamine)
Solvents. Physical solvents (such as Selexol and sulfolane) are
used for bulk removal of acid gases. Limited data are available
for commercial physical solvents. To better understand the effect
of organic solvents on solubility, Table 2 shows solubility
constants for several mercaptans in water, n-hexane, and toluene.
It is clear that considerably more RSH dissolves in the organic
solvents compared to water. It is also apparent that the solubility
increases as the size of the mercaptan increases.
A major disadvantage of using physical solvents is the
cosolubility of hydrocarbons. This is demonstrated by the
substantially higher solubility of methane in the organic solvents
than in water. Table 2 also shows that the mercaptans are more
soluble in the organic solvents than is methane.
Solubility of Mercaptans in Aqueous Solutions of Amines.
To better understand the reaction between amines and mercap-
tans, the interactions of amines with the well-studied acid gases
H2S and CO2 should be considered. Shown in Figure 1 are the
solubility constants of H2S and CO2 as a function of acid gas
loading. The sharp inflection in solubilities with loading
resembles a titration curve for MDEA. As MDEA is neutralized
by the acid gas, the solubility decreases in a way that is
predictable from the acid-base properties of the amine and the
acid gas.
Mercaptans (RSH) are much weaker acids than H2S or CO2,
but can similarly react via salt formation with amines to form
mercaptide salts. This reaction adds a level of complexity to
solubility beyond that encountered in the discussion thus far.
This combination of physical solubility and chemical reaction
is illustrated in Figure 2.
2.9
CH4
0.006912
0.3113
0.2014
Figure 1. Ksol (mol L-1 MPa-1) for H2S and CO2 in MDEA at 40 °C.
(From ref 15, literature values for KH have been converted using estimates
of solution density.)
Figure 2. Schematic of RSH solubility.
Henry constants (or solubilities) in amines are often reported
as the overall constants which combine the physical and
chemical reaction solubilities. Thus, reports in the literature
showing Henry constants or mercaptan solubilities in aqueous
amine systems usually report values which are dependent on
the acid gas loadings.
Mercaptan solubility in an amine solution can be partitioned
into physical and chemical solubilities.
SolTotal ) Solchem. + Solphys ) p(Ksol-phys + Ksol-chem)
(5)
The chemical solubility in amines equals the amount of
mercaptide ([RS-]) in solution due to salt formation and can
be represented by the following relationship:
Solchem. ) pRSH × Ka(RSH) × Ksol-phys/[H+] (6)
where Ka(RSH) is the acid dissociation constant (Ka(RSH) )
[RS-] [H+]/[RSH]) for the mercaptan and Ksol-phys values are
in mol L-1 MPa-1. This relationship has the following conse-
quences:
1. Increased mercaptan removal is achieved by use of more
basic amines because they increase the solution pH. Increasing
the basicity of the amine will also decrease the reversibility of
the amine/RSH reaction and increase the energy needed for
regeneration. More basic amines will also remove more CO2,
which can be an advantage or disadvantage depending on the
situation. Stronger bases such as caustic will result in higher
RSH solubilities, but will not be reversible (thermally regen-
erable in a gas-treating plant).
2. Lower (C1, C2) mercaptans with higher acidities (larger
values of Ka(RSH)) will exhibit larger chemical solubilities than
higher mercaptans in amine solutions.
3. Because the RSH reaction is pH-dependent, any substantial
acid gas (CO2 or H2S) loadings will greatly limit the RSH
 Ind. Eng. Chem. Res., Vol. 46, No. 11, 2007 3731

Table 3. Comparative Gas Solubilities in Water

solubility at 40 °C
gas (mol L-1 MPa-1) ref
N2O 0.18 17
CO2 0.24 17
CH3SH 2.2 this work

Table 4. Ksol-phys for Various Solvents at 40 °C; Also Shown Are

Values of the Acid Dissociation Constant, Ka, from Ref 18
wt %| Ksol-phys log Ka
solvent water (mol MPa-1 L-1) at 40 °C
water 100 2.2
4.2 M MDEA 50 3.5 -8.20
4.2 M DEA 56 3.3 -8.53
4.2 M MEA 74 4.6 -9.08
4.2 M DGA 56 4.0 -9.00
35% DEA 65 3.1 -8.53
25% MDEA 75 2.6 -8.20
tetraglyme 0 32
sulfolane 0 22
reaction. Small loadings of the amine cause a steep decrease in
solution pH, which results in a lower degree of RSH ionization.
In addition to the acid-base reaction, the effect of amines
on physical solubility alone should be considered. The N2O
analogy16 is probably not appropriate for estimating methyl
mercaptan physical solubility. The arguments for comparing
water solubilities of reactive gases with the nonreactive N2O
assume similar interactions between the solvent and the two
gases. As seen in Table 3, this analogy is valid for prediction
of CO2 solubilities since the water solubilities of N2O and CO2
are close. CH3SH however exhibits an order of magnitude higher
solubility in water than does N2O.
To separate the effects of physical and chemical solubilities,
an equilibrium model was constructed. Amine dissociation
constants and heats of reaction were obtained from the NIST
database.18 The equilibrium constants used for the amines are
presented in Table 4. Protonation equilibrium constants and heats
of reaction for mercaptans were obtained from NIST and from
Crampton.19 The value of log Ka at 40 °C used in this study
was -10.08. The model takes these values, along with ap-
propriate amine and total mercaptan concentrations as well as
total acid loadings and calculates solution speciation. For
instance, in the MDEA example shown in Figure 3,
[MDEA]total × acid loading ) [MDEAH+] +
[RSH] + [H+] (7)
A total mercaptan loading of 0.0005 mol of RSH/mol of MDEA
was chosen (close to our experimental values and small relative
to total acid gas loadings) and the mass balance was solved by
iteration of solution pH. Speciation of the amine and mercaptan
was performed at the calculated pH.
Figure 3 shows comparative values for total solubility
constants from literature and values determined in this study.
The model line was constructed by adding the calculated
Ksol-chem value to the value of Ksol-phys chosen to best fit the
experimental results. The uncorrected model did not show the
diminished solubilities at high loadings. This is most likely due
to salting out effects on the physical solubility of CH3SH. A
salt correction (for sulfate salts) was added to the model
calculation, using the modified method of Onda et al.20 The
calculated physical solubilities are divided by 10(kI) where k is
the sum of constants for the ionic components and dissolved
RSH and I is the ionic strength calculated from the solution
speciation. The value of k for the 4.2 M MDEA example shown
in Figure 3 is 0.070.
Figure 3. Comparison of model and experimental data for CH3SH solubility
in 50% MDEA at 40 °C. Data from this work (9) and Jou et al.10 (2),
model shown in solid line, corrected for salting out effect.
The new data presented here (using strong acid neutralization)
are in fair agreement with the values reported by Jou et al.10
Figure 3 shows those values using total loadings of CO2 + H2S
+ CH3SH. The comparison of strong acid loading (mol of H+/
mol of amine) with H2S or CO2 loadings is valid for intermediate
loadings. At low amine loadings CO2 can contribute two protons,
and at high H2S loadings, significant amounts of H2S will remain
diprotonated. A correction for degree of protonation may be
added to strong acid neutralization headspace data for low and
high loadings of H2S or CO2. For the literature values shown
in Figure 3, all CO2 and H2S values shown were at intermediate
loading in which >90% of the acid gas molecules were in the
monoprotonated acid form. The value of Ksol-phys used for the
best line fit in Figure 3 was 3.5 mol L-1 MPa-1.
The shape of the curve in Figure 3 is similar to that shown
in Figure 1 for H2S and CO2. This sharp inflection is indicative
of typical acid-base reaction behavior for neutralization of
amines. The total solubilities are substantially lower for
CH3SH because the mercaptan is a much weaker acid than H2S
or CO2 and its Ksol-chem component is much smaller.
Both the model and our data show a sharp inflection at the
lower loadings that is also seen for the Jou et al.10 data, though
not to the same degree. At the low pressures of CH3SH used in
the present study, the loadings of mercaptan are much closer to
zero than those used in the higher pressure study of Jou et al.10
For that reason, the acid loadings shown in Figure 3 are
comprised of the sum of CO2 + H2S + CH3SH. Thus, for the
data points in which the H2S and CO2 loadings are zero, there
is enough mercaptan loading in the Jou et al.10 study to neutralize
some amine and reduce the solubility of CH3SH. The inflection
demonstrates how low lean loadings and high circulation rates
can be used to more effectively remove mercaptans from gas
streams with aqueous amines. At higher loadings, chemical
solubility is reduced and physical solubility dominates the
removal. This is illustrated in Figure 4 which used the model
calculations for 50% MDEA.
Further refinements to the model can be made by consider-
ation of amine activities. More rigorous VLE measurements
(utilizing loadings with CO2 and H2S as well as liquid-phase
analysis) may also be used. The purpose of this exercise is to
estimate the effect of various amine structures on physical
solubilities.
The same technique of experimental fitting was done to arrive
at values of Ksol-phys for several other aqueous amine mixtures
which are shown in Table 4. Initially, solvent concentrations
3732 Ind. Eng. Chem. Res., Vol. 46, No. 11, 2007
Figure 4. Degree of physical and chemical solubility of methyl mercaptan
in 50% MDEA at 40 °C with various acid loadings. Acid loading defined
in eq 1.
Figure 5. Chemical solubility at “zero” loading vs amine properties. Ka )
[amine][H+]/[amineH+], values from ref 18, Ksol-phys values from Table 4.
Ksol-chem ) Ksol-experimental - Ksol-phys. Zero loading refers to no sulfuric
acid added, mercaptan loadings in all experiments <0.001 mol/mol amine.
were chosen so that the amine molar concentrations were the
same as 50 wt % MDEA. Water also plays a key role as shown
by the reduced solubilities of diluted DEA and MDEA. More
complete data sets can be used to correlate solution composition
with mercaptan solubility.
An important observation is that the difference between water
and these amine solvents is not as great as those shown in Table
2 or Table 4 for pure organic solvents. Though the amines are
organic, they were designed to be quite hydrophilic, both to
facilitate water solubility and to minimize hydrocarbon cosolu-
bility.
Figure 5 shows the relationship between chemical solubility
and amine properties. For a given loading, [H+] is proportional
to the acid dissociation constant of the amine:
Ka(amine) ) [amine][H+]/[amineH+] (8)
Clearly, the chemical solubility for each amine can be related
to the physical solubility and the basicity of the amine as
represented in eq 6. This is in contrast to Jou et al.,5 who stated
that the solubility of both methyl and ethyl mercaptan is
independent of the type of amine. Their conclusion was based
on a study of MDEA and DEA, two amines whose log Ka(amine)
values differ by only 0.3 units under the conditions studied.
The data in Figure 5 show a strong correlation with amine
basicity over 0.9 units of log Ka(amine).
Improved Amine-Based Solvents.
As seen in Figure 3, aqueous amine solvents will lose much
of their mercaptan solvency as soon as they react with other
acid gases. Hybrid solvents (mixtures of amines with physical
solvents) allow for the same lean amine reactions plus sustained
greater physical solubility at the higher loadings. Other additives
have also been reported to substantially increase mercaptan
removal.21,22
Conclusions
The solubility of mercaptans in amines can be treated as the
sum of both a physical solubility and a chemical solubility. The
chemical solubility can be predicted from the acid-base
properties of both the amine and the mercaptan. At low loadings,
the chemical solubility dominates the total solubility. As the
acid loadings in the solution increase, chemical solubility is
substantially reduced and physical solubility dominates.
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ReceiVed for reView September 1, 2006
ReVised manuscript receiVed March 6, 2007
Accepted March 7, 2007
IE0611554