Mercaptans removal from gases by
absorption into amines and caustic
Clayton E Jones, Nathan A Hatcher and Ralph H Weiland Optimized Gas Treating, Inc.
A
mass transfer rate-based model of the
absorption process is used to discuss quan-
titatively the ease and extent of removal of
methyl through n-butyl mercaptans from gases
using MDEA and caustic soda of various
strengths. A direct positive relationship is found
between the absorption rate into amines and the
molecular weight of the mercaptan. The relation-
ship is inverted when the solvent is caustic soda.
Sulphur emissions from refinery combustion
sources are traditionally reported by measuring
H2S in the fuel gas before combustion and
converting the H2S to an equivalent amount of
post-combustion SO2. In reality, all sulphur
species present in the fuel gas (not just H2S)
contribute to SO2 emissions, and some operating
facilities have to report the total sulphur emis-
sions. Mercaptans are commonly present in
refinery gases in small amounts. As the regula-
tory limits on emissions are progressively
lowered, knowledge of the behaviour of mercap-
tans in amine and caustic treating systems
becomes increasingly important for designers
and operators both to track accurately and to
comply with total sulphur emissions restrictions.
The ProTreat® gas treating process simulator
makes exclusive use of the mass transfer rate
approach to predicting the separation that will
actually be achieved in a given tower containing
specific internals under actual operating condi-
tions. Absorption (and stripping) rates are
calculated directly from knowledge of the mass
transfer characteristics of the internals, the
hydraulic conditions within the tower, and the
driving force for the absorption process.
The driving force for absorption relates
directly to the difference between actual and
equilibrium concentrations of the mercaptan
dissolved in the solvent. Indeed, even if we
choose to use an equilibrium stage model of the
column and to step off ideal stages, equilibrium
www.digitalrefining.com/article/1000903
mercaptan solubility is still an important param-
eter. Thus, an essential factor to consider is the
solubility of the mercaptans in treating solvents.
Because mercaptans hydrolyse as weak acids in
water, proper accounting of the chemistry is vital
to predicting accurately their solubility
behaviour.
To provide perspective to the substance of this
article, we begin with a general description of
what constitutes a mass transfer rate model, and
what enables it to be truly predictive, as opposed
to just descriptive. This leads to an account of
the equilibrium solubility of the C1 through nC4
mercaptans in amine and inorganic caustic treat-
ing solutions, together with an explanation for
the differences amongst the mercaptans and
between the solvents. The mass transfer rate
model is then used to show how mercaptan
concentrations can be expected to vary within a
real absorber when MDEA and a caustic soda
solution are used for their removal. The focus is
on how process variables affect mercaptan
removal. Stripping of the absorbed mercaptans
from a spent treating solution is left for a future
article.
Mass Transfer Rates for Column Calculations
An ideal stage is a theoretical concept that, in
principle at least, allows one to replace a certain
number of real trays or a certain depth of real
packing in a column with a hypothetical equiva-
lent in which all the streams leaving each ideal
stage are in perfect equilibrium. The origin of
the concept is obscure, but a simple physical
example is a flash tank in which feed is flashed
into vapour and liquid, assumed to be in mutual
equilibrium. The first method for calculating a
multistage column separation can probably be
attributed to Ponchon1 and Savarit2, although
the method of McCabe and Thiele3 has seen the
most widespread use. The methodology is
March 2014 1
 schematically two phases being
contacted in some portion of the
biphase on a tray or in a segment of
packing within a column.
Transferring components (H2S,
RSH and H2O as shown in the
diagram) first diffuse through the
vapour to the interface where they
then dissolve into the liquid and
diffuse away, perhaps accompanied
by chemical reaction and the libera-
tion of associated heat. The diffusion
process is by both molecular and
convective means. It depends on the
size of molecules (molecular means)
and on the state of agitation of the
individual phases (convective means).
The central understanding, however,
is that diffusion by whatever means is
a rate process. It takes place at a rate
that can be calculated, and the sepa-
ration actually achieved is governed
by that rate. The separation really
reached (on a given tray, for exam-
ple) does not depend on the efficiency
of the tray — it depends on the rate
Figure 1 Schematic of Vapour and Liquid Elements Being Contacted in at which the mass transfer process
the Biphase of an Absorber takes place.
The mass transport process is char-
elegant in its simplicity, requiring only phase acterised by mass transfer coefficients. In heat
equilibrium data and the flow, composition and transfer these coefficients are known as heat
thermal condition of the tower feeds. It has one transfer coefficients corresponding to either side
great weakness, however: it has no direct of the heat transfer surface. The overall heat
connection to real equipment. The way this kind transfer coefficient for a given exchanger is
of theory is connected to equipment is usually obtained by combining the film coefficients via
through stage efficiency or height equivalent to a the law of additivity of resistances. The film
theoretical plate. Unfortunately, the weakness coefficients themselves are found from charts (or
continues: efficiencies and height equivalents are internally by software) where very well-estab-
not easily related to the construction and func- lished generalised coefficients have been plotted
tioning of equipment, and in multicomponent or tabulated against flow parameters and physi-
mixtures, their behaviour can be extremely cal properties (c.f. Kern5). This is the way heat
confusing (see Kooijman and Taylor4). A true exchangers have been designed for nearly a
mass transfer rate model suffers from no such century, so the concept of a transfer rate-based
drawbacks. process is anything but new. Indeed, heat
At its core, a mass transfer rate model focuses exchangers are probably the best analog of the
on the rate of interchange of chemical compo- rate model for mass transfer. Mass transfer
nents between two phases as driven by the equipment has been designed this way only since
extent to which temperatures and species the mid-1980s, not because the mass transfer
concentrations between phases depart from rate-based concept was new, but because the
equilibrium. This is the very antithesis of the computing power needed to perform the calcula-
ideal stage model with its assumption of perfect tions on large numbers of components over
equilibrium, not disequilibrium. Figure 1 shows multiple trays only became available then.

2 March 2014 www.digitalrefining.com/article/1000903

 Mass transfer coefficients and interfacial areas
are in no sense adjustable parameters any more
than heat transfer coefficients are. The flow of
high and low viscosity fluids across trays and
over packing agitates the fluid and results in
unique values for mass transfer coefficients.
Engineers are not free to pick and choose coeffi-
cient values to obtain the preferred result or
some preconceived notion of what the separation
should be. On the contrary, values of the coeffi-
cients are a result of fluid flows, fluid properties,
and the mechanical design of the specific tower
internals using well-established correlations. The
parallel with heat transfer is extremely close.
Tower performance is predetermined and
predictable in exactly the same way and to
exactly the same extent as heat exchanger
performance.
Ideal stages do not exist in the real world;
there are only real trays and real packing. Each
tray is a real tray, and a column containing a
certain number of real trays should be modelled
exactly that way — as real trays. Each of these
trays has its own unique mass transfer charac-
teristics that depend on the temperature,
pressure, flows, and composition on that tray
and on the mechanical design of the tray. If one
is dealing with packing, the continuous nature of
contact in a packed column is modelled by divid-
ing the height into a large number of smaller
segments and integrating across the column.
Each small segment has its own unique charac-
teristic mass transfer coefficients and interfacial
area and the transfer rates of components
between phases depends on the particular pack-
ing (vendor, material, size) in each
segment. It should be no surprise
that the separation a given column is
predicted to achieve using mass
transfer rate-based simulation
depends very strongly on exactly
what is in the column. This is
completely in line with the reality of
processing using actual real equip-
ment, a reality theoretical stage
approaches of whatever ilk simply
cannot achieve.
Solubility of Mercaptans in MDEA
and Caustic Soda
The four mercaptans of interest in
this article are: methyl mercaptan Figure 2 Simultaneous Reactions and VLE with H2S and MeSH
www.digitalrefining.com/article/1000903
(methanethiol, MeSH), ethyl mercaptan (ethan-
ethiol, EtSH), propyl mercaptan (propanethiol,
PrSH) and butyl mercaptan (butanethiol, BuSH).
Mercaptans are both hydrocarbons and acid
gases, and they have the properties of both
classes of compounds. As will be seen, the rela-
tive importance of these two aspects of their
dual nature governs much of the mercaptans’
behaviour with regard to solubility in treating
solutions.
Acidity
Mercaptans are only weak acids relative to the
traditional acid gases H2S and CO2. The C1
through nC4 mercaptans have essentially the
same acidity, with a pKa of 10.6 at 25°C6. This is
considerably less acidic than H2S which has a
pKa of 7.0 at 25°C6 for its first dissociation
reaction.
Acidity is important because the relative acid-
ity of dissolved gases has a strong effect on the
equilibrium between the liquid and vapour
phases. This effect is described in Figure 2 which
illustrates vapour-liquid equilibrium for H2S and
methyl mercaptan in water. The molecular form
of H2S reaches equilibrium across the vapour-liq-
uid interface, but some of the dissolved H2S
dissociates into ionic species to an extent
controlled by reaction equilibrium. Methyl
mercaptan participates in analogous equilibria.
Note that both the H2S and MeSH dissociation
reactions produce an H+aq ion. This is a common
ion. H2S is the stronger acid, so it dissociates to
a greater extent than MeSH, producing a relative
abundance of H+aq ions. This larger concentra-
March 2014 3
 Sour Gas Composition
Compound Mol%
Water 0.77
Hydrogen Sulfide 0.03
Methyl Mercaptan 0.03
Ethyl Mercaptan 0.03
Propyl Mercaptan 0.03
Butyl Mercaptan 0.03
Methane 48.63
Ethylene 4.24
Ethane 18.59
Propene 2.45
Propane 3.94
n-Butane 3.05
Hydrogen 13.66
Nitrogen 4.52
Table 1
tion of H+aq ions pushes the MeSH dissociation
equilibrium towards the molecular form,
MeSH. Having a larger fraction of the aqueous
MeSH in molecular form then pushes MeSH
into the vapour. In summary, the stronger acid
(H2S) generates a significant concentration
of the common ion H+aq and this keeps most
of the weaker acid (MeSH) out of the solution.
In other words, gases that are stronger
acids push gases that are weaker acids out of
solution.
Solubility
The solubility of mercaptans in water is a domi-
nant factor in determining their solubility in
aqueous treating solutions. Mercaptans with
longer hydrocarbon chains, however, have a
more hydrocarbon-like character, making the
heavier mercaptans less soluble in water but
more soluble in relatively hydrocarbon-like
alkanolamines such as methyldiethanolamine
(MDEA). As will be seen, solubility in water
alone governs which mercaptan species can be
most effectively removed by caustic.
Interactions between species
The interactions of mercaptans with water,
amines, and acid gases significantly affect
vapour-liquid equilibrium (VLE) behaviour. In
the ProTreat® software, these interactions are
quantified through the use of the Deshmukh-
Mather activity coefficient model for the aqueous
phase and through binary interaction parame-
ters used in the Peng-Robinson equation of state
4 March 2014
for the vapour phase. Several sources of VLE
data7-15 were used to regress interaction parame-
ters in the ProTreat model. Two examples of
important interactions are interactions between:
(1) caustic and water that influence water’s
vapour pressure over caustic solutions, (2)
mercaptans and amines that govern which
mercaptan species can be most effectively
removed by an amine solution.
Equilibrium Solubility of Mercaptans
The phase equilibrium of mercaptans in MDEA
and caustic soda partially determines the driving
forces that affect absorption rates in real
processes. Factors that determine the equilib-
rium solubility of a mercaptan in a treating
solvent include its solubility in water, non-ideal
interactions with solvent molecules, and the
reaction equilibrium between all of the species
in the solution.
The following cases are based on equilibrium
flash calculations performed in the ProTreat
simulation software. Various solutions were
brought to simulated equilibrium with the typi-
cal refinery fuel gas (Table 1) containing 300
ppmv each of the four mercaptans of interest.
For clarity, only methyl mercaptan and butyl
mercaptan are shown in the figures. Flash calcu-
lations were done at 185 psia and 115°F (1.28
MPa and 46°C), conditions typical of refinery
fuel gas systems.
MDEA solutions
Mercaptans have a dual chemical nature: part
acid and part hydrocarbon. The solubility of
mercaptans in MDEA solutions reflects this dual
chemical nature. Hydrocarbon-like behaviour is
exhibited since increasing MDEA strength
increases mercaptan solubility, especially for the
heavier mercaptans. Acid-like behaviour is
exhibited by the reduction of mercaptan solubil-
ity in the presence of H2S.
Effect of amine strength
Fractional removal of H2S and mercaptans from
the fuel gas stream is plotted against the concen-
tration of MDEA in the treating solution in
Figure 3. As expected, H2S removal is much
deeper than mercaptans at all MDEA concentra-
tions. At solution concentrations less than about
15 wt% MDEA, water solubility (Henry’s law)
dominates the equilibrium behaviour.
www.digitalrefining.com/article/1000903
Consequently, the lower molecular
weight mercaptans are removed more
effectively than those of higher
molecular weight. As solution
strength increases above 20 wt%
MDEA, the solvent’s ability to absorb
hydrocarbons increases due to molec-
ular interactions. These interactions,
referred to as “salting in”, are quanti-
fied using activity coefficients or
salting-in parameters. In this region
of higher amine strength, the higher
molecular weight mercaptans are
removed more effectively than their
low molecular weight counterparts.

NaOH solutions Figure 3 Mercaptan Removal vs. MDEA Strength. Solvent to gas ratio
Solutions of NaOH are much more is 5.9 gal/mscf
effective than MDEA at absorbing
mercaptans. This observation has
been leveraged successfully for many
years by UOP and Merichem in the
application of the MeroxTM process
and FIBER FILM® contactors. Until
now, however, most of the finer
process insights have been confiden-
tial to the licensors.
As a fresh solution of NaOH
absorbs acidic species, its basicity is
spent, and in turn, this reduces the
solution’s ability to absorb further
acidic species. A common industry
rule of thumb is that NaOH effec-
tively absorbs mercaptans until the
caustic becomes 70% spent. Figure 4
shows how the validity of this rule of Figure 4 Effect of Percent Caustic Spent on Mercaptan Removal.
thumb depends on which particular Solvent to gas ratio is 5.9 gal/mscf. Caustic is 10 wt%
mercaptan is being considered. In a
single equilibrium flash, a solution of 10 wt% Rate Model of Mercaptan Absorbers
NaOH which is 70% spent will absorb 75% of the MDEA Absorber
methyl mercaptan from fuel gas, but it will Figure 5 shows removal effectiveness of a 2.5’
absorb only 30% of the butyl mercaptan. diameter absorber with 20 valve trays at 2’ spac-
Therefore the rule of thumb is applicable for ing which is treating 8.8 MMSCFD of a virtually
gross approximations, but a more rigorous treat- H2S-free fuel gas with 93 gpm of 45 wt% MDEA.
ment is needed to accurately quantify the The sour gas contains 300 ppmv of each of the
amount of mercaptan slip as a caustic solution C1 through nC4 mercaptans; for comparison
becomes more spent. In contrast, the ability to purposes this puts all four mercaptans on an
absorb H2S remains close to 100% until the equal footing. The lean amine contains no
NaOH solution is almost completely spent. In mercaptan but varying amounts of H2S. It can be
the context of this article, spent caustic is calcu- seen that for this particular tower at these condi-
lated as (moles H2S + RSH in solution) / (moles tions, the removal effectiveness of methyl
NaOH in solution mercaptan is worse than that of butyl mercap-

www.digitalrefining.com/article/1000903 March 2014 5

 condition. Knowing which param-
eter limits the removal of each
mercaptan for a particular system
is a key insight that contributes to
more confident designs for new
towers, and to improved opera-
tional flexibility for existing
towers. The interaction of the
process variables is complex and
defies prediction using simplified
methods, especially in multi-stage
counter-current contact. A mass
transfer rate based model is
needed to quantify the perfor-
mance of an amine absorber with
respect to mercaptans.
Figure 5 Effect of Lean Loading on Mercaptan Removal in a Trayed MDEA The dual physical/chemical
Absorber solubility of mercaptans in aque-
ous solutions requires a VLE
model that accounts both for
vapour and liquid phase non-ide-
alities as well as chemical
reactions. Simple oil-boiling
hydrocarbon VLE representation
fails miserably to predict the true
behaviour of these types of
systems. Mercaptans only
partially dissociate in alkanola-
mine solutions (weak bases), and
this can make their behaviour
non-intuitive. For example, butyl
mercaptan, having greater solu-
bility than MeSH, imparts some
aqueous H+ common ion, which
works to some degree to titrate
Figure 6 Effect of Percent Spent on Mercaptan Removal in a Trayed NaOH out propyl and lighter mercap-
Absorber Using 10 wt% Caustic tans. Because H2S is a several-fold
stronger acid than mercaptans, it
tan, but both are reduced as the presence of H2S takes very little H2S to affect their removal
increases. significantly (see Figure 5).
Although not shown here, vapour phase molar
flow rate of each mercaptan was plotted against NaOH Absorbers
tray number in the absorber. These profiles indi- Absorbers using caustic soda solutions remove
cated that typically MeSH was rich-end pinched mercaptans differently than do absorbers using
(removal was controlled by solvent capacity for MDEA. Figure 6 shows the performance of a
MeSH), while BuSH was continually removed 4.1-ft diameter absorber with 5 valve trays at 2-ft
throughout the column and was therefore mass spacing which is treating 31 MMscfd of fuel gas
transfer rate limited. Calculations showed that with 128 gpm of 10 wt% NaOH. The sour gas
with higher lean loadings more typical of a refin- contains 300 ppmv of each mercaptan but no
ery primary amine system treating H2S, MeSH H2S. To study the effect of spending the caustic,
still had a rich-end pinched profile, and that the caustic solution contains varying amounts of
BuSH also began to approach a rich-end pinched H2S. Again, in the context of this article, spent

6 March 2014 www.digitalrefining.com/article/1000903

caustic is calculated as (moles
RSH + H2S in solution)/(moles
NaOH in solution). It can be
seen that the simulated mercap-
tan removal effectiveness is
close to 100% when the caustic
is less than 60% spent. For this
particular tower, the rule of
thumb that mercaptan removal
drops off at 70% spent is aggres-
sive for butyl mercaptan but too
conservative for methyl mercap-
tan. As the caustic becomes
increasingly spent, the mercap-
tan removal effectiveness falls
off at a different rate for each
mercaptan. Figure 7 shows how Figure 7 Vapour Phase Profiles of Mercaptans in Trayed Absorber Using
the vapour phase mercaptan 10 wt% NaOH, 72% Spent With H2S
profiles within the absorber
change when the caustic is more spent. predict total sulphur distribution through
Relative removal rates of the different mercap- sulphur processing systems. Finally, mercaptan
tans are consistent with the equilibrium study behaviour in aqueous solutions has been shown
above. Caustic removes lighter mercaptans more to be governed by multiple interacting factors.
effectively than heavier mercaptans because of Accurately predicting the behaviour of mercap-
their greater solubility in water; MDEA removes tans requires rigourous treatment of solution
heavier mercaptans more effectively than lighter non-idealities and reaction chemistry, as well as
mercaptans through salting-in. mass transfer rate-based simulation. With the
A caustic absorber requires fewer trays than an power of a first-principles, mass transfer rate-
MDEA absorber. This benefit is somewhat coun- based simulator in hand, accurate distribution of
ter-balanced by the fact that maintaining fresh mercaptans in sulphur removal and processing
NaOH strength and controlling percentage spent units has been predicted for the first time at the
is more difficult than regenerating MDEA refinery level, permitting better unit processing
solutions. decisions to be made. Without mass transfer
rate-based simulation, none of this would be
Conclusions possible.
By using case studies, the ability of MDEA and
caustic soda solutions to remove mercaptans has Literature Cited
been shown to be influenced by several factors. 1 Ponchon, M., Tech. Moderne, 13, 20 (1921).
Caustic soda solutions are more effective at 2 Savarit, R., Arts et metiers, (1922), cited by Kister, H.,
removing lighter than heavier mercaptans Distillation Design, McGraw-Hill, Book Co., p. 86, 1992.
because of their relative solubilities in water. 3 McCabe, W. L. and Thiele, E. W., Ind. Eng. Chem., 17, 605
MDEA solutions, on the other hand, are more (1925).
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accessed 12 Oct 2013.
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5 Kern, D. Q., Process Heat Transfer, McGraw-Hill Book Co., New
the mercaptan and MDEA molecules. Even
York, 1950.
though MDEA may not remove enough mercap- 6 Tsonopoulos, C., Coulson, D., Inman, L., J. Chem. Eng. Data,
tan to achieve processing objectives, it does 21, 190 – 193 (1976).
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problems in downstream units. With this knowl- 8 Jou, F-Y., Mather, A., Schmidt, K., Ng, H.-J., J. Chem. Eng. Data,
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www.digitalrefining.com/article/1000903 March 2014 7

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8 March 2014 www.digitalrefining.com/article/1000903