DESIGN AND OPERATION OF SOUR GAS TREATING PLANTS FOR

H2S, CO2, COS, AND MERCAPTANS

A.F. Carlsson
T. Last
C.J. Smit

Shell Global Solutions International B.V.

Amsterdam, The Netherlands

ABSTRACT

Natural gas must be purified before it can be sold, liquefied, or fed to a gas-to-liquids
process. Growing demand for natural gas is leading to an increase in the production of
stranded and contaminated natural gas. In general, the contaminants that must be removed by
gas treating are H2S, CO2, COS, and mercaptans (RSH), which are often removed using a
combination of chemical solvents, physical solvents, and solid adsorbents – optimal
combinations of these were discussed at the 2005 Gastech conference in Bilbao. Amines are
commonly used for the removal of H2S and CO2 via chemical absorption and reaction in a
trayed or packed column, while the solvent is continuously regenerated at low pressure and
high temperature in a separate regenerator column. Molecular sieves can be used in a
temperature-swing adsorption process downstream an amine or physical solvent to remove
traces of mercaptans. The design and operation of the mol sieve unit involves a number of
challenges due to possible BTX co-adsorption and potentially fast deactivation of the sieves.
In addition, the transient nature of the temperature-swing adsorption process introduces
challenges in the design of the sulphur recovery unit (SRU) and the regeneration-gas treating
for the mol sieve unit. Deactivation can be mitigated using a novel regeneration process,
while transients in the regeneration gas can be smoothed using a peak-shaving scheme. These
and other process and engineering solutions to design and operational challenges encountered
by Shell Global Solutions are discussed herein.

1
DESIGN AND OPERATION OF SOUR GAS TREATING PLANTS FOR
H2S, CO2, COS, AND MERCAPTANS

INTRODUCTION

Natural gas must be purified before it can be sold, liquefied, or fed to a gas-to-liquids
process. Growing demand for natural gas [1-3] is leading to an increase in the production of
stranded and contaminated natural gas [4, 5]. Significant reserves [6] of natural gas in the
Middle East and Central Asia containing H2S, CO2, COS, and mercaptans (RSH) are being
developed [4, 7] to meet the growing demand.
First, it is relevant to have a basic idea of what gas compositions might be expected in
practice from contaminated fields. Although a wide range of gas compositions are possible, a
typical composition containing all the aforementioned contaminants is: 1-4mol% H2S, 1-
4mol% CO2, 10-50ppmv COS, and 50-400ppmv RSH.
While the removal of acid-gas components such as H2S and CO2 from natural gas have
been well established [8] for decades, the removal of mercaptans and COS from natural gas
in combination with H2S and CO2 are not as well established [9]. A number of different gas
processing options are possible, and different approaches have been used in various locations
[7-11] depending on the source, destination, and composition of the gas.
Amines remove H2S and CO2 from natural gas via chemical reaction in an acid-gas
removal unit (AGRU). In the AGRU, impurities of H2S or CO2 are extracted from natural gas
with an amine solution in a gas-liquid contactor such as a trayed column, and the
corresponding amine salt or carbamate is formed with H2S or CO2. The loaded amine is then
routed to a regenerator where H2S or CO2 is liberated from the solution at low pressure and
high temperature. Unfortunately, the solubility of mercaptans in aqueous amine solutions is
limited, and alternative approaches must be used for mercaptan removal.
One approach is to use a physical solvent for mercaptan removal (figure 1). Rather than
using a separate gas-liquid contactor with a physical solvent, a physical-solvent component
can be added to the amine unit to form a mixed solvent, such as Sulfinol. An advantage to
this approach for mercaptan removal is that large amounts of mercaptans can easily be
removed in a continuous and steady process. A disadvantage to this approach is that the
physical solvent used for mercaptan removal also co-absorbs hydrocarbons from the natural
gas, particularly those of higher molecular weight. Heavy hydrocarbons co-absorbed in the
physical solvent leave the process at low pressure from the flash gas or the overhead of the
regenerator. While the flash-gas could be re-compressed, the regenerator overheads are sent
to the sulphur-recovery unit (SRU), and thus some hydrocarbons cannot be recovered.

2
 Feed Gas
from slug
catcher

H2S + RSH
Amine & Amine &
Physical Solvent Physical Solvent
Absorber Regenerator

Mol sieve unit Sulphur-

H2O
H2O Recovery Unit

NGL-Extraction S
CH4

NGL
Figure 1. Block scheme for a gas processing plant with full RSH removal via a physical
solvent in the AGRU. The simplicity of scheme comes at the cost of hydrocarbon losses.

An effective solution for minimizing hydrocarbon losses when using a combined

chemical/physical solvent in the AGRU is to remove only part of the mercaptans in the
AGRU, thus mitigating hydrocarbon co-aborption (figure 2). For example, Sulfinol can be
used to remove ~80% of the mercaptans, while 20% of the mercaptans are allowed to slip
past the Sulfinol absorber. The balance of mercaptan and hydrocarbon absorption is affected
by the fraction of physical solvent in the mixture, the solvent circulation rate and
temperature, and the specific column design. The small amount of mercaptans not removed
by the AGRU can be removed from the gas stream using a molecular sieve unit.
Molecular sieves effectively concentrate mercaptans from the main process stream into a
stream of regeneration-gas. When natural gas is brought into contact with molecular sieves,
components from the gas phase such as water and mercaptans adsorb on the internal surfaces
of the sieve at low temperature, and can be desorbed from the sieve at high temperature. In
practice, a set of 2 or more vessels is used, where each bed cycles through adsorption,
heating, and cooling steps such that feed gas is continuously processed. A heated gas stream
is used to regenerate a bed at the end of the adsorption step, and the desorbed mercaptans
thus concentrate into the regeneration-gas stream, which is typically ~10% of the main gas
stream. The bulk of the mercaptans are removed from the regeneration-gas stream using a

3
physical solvent, and the remaining gas, still containing a small concentration of mercaptans,
is recycled to the front end of the mol sieve unit (figure 2).

Feed Gas
from slug
catcher

Common H2S + RSH

Amine absorber
regenerator

RSH Sulphur-
Mol sieve unit Regen-gas
H2O & RSH Recovery Unit
absorber (RSH)

S
NGL-Extraction CH4

NGL
Figure 2. Block scheme for a gas processing plant with partial removal of RSH in the AGRU,
followed by polishing with mol sieves. A common regenerator is used for the amine
originating from the main amine unit and the regeneration-gas treating unit.

Molecular sieves are particularly well suited for the removal of trace components. Mol
sieves typically used for water or mercaptan removal (4A, 5A, 13X) have polar internal
surfaces that interact favourably with polar molecules such as water or mercaptans, making it
possible to adsorb very low concentrations of mercaptans from the gas phase [12]. In
contrast, the uptake of mercaptans in a physical solvent is typically not as favourable [9] at
low partial pressures. On the other hand, mol sieves are not well suited for removing high
concentrations of contaminants due to the amount of regeneration gas required for large
volumes of sieve.
When mercaptan concentrations are low, the combination of an aqueous amine and a mol
sieve unit may be considered. When an aqueous amine solution (e.g. MDEA, optional
accelerator, and water) is used in the AGRU, a limited fraction of mercaptans are removed
from the gas phase, due to the limited solubility of mercaptans in aqueous solutions. The
majority of mercaptans are subsequently removed using a mol sieve unit. In contrast to the
Sulfinol option, where a single solvent can be used in both the main AGRU and the mol sieve
regen-gas treating with a common regenerator [11], a separate regeneration-gas treating unit
4
is required for the regen-gas of the mol sieve unit when an aqueous amine is used in the
AGRU.

Feed Gas
from slug
catcher

Amine H2S
Amine Absorber
Regenerator

Regen-gas Sulphur-
Mol sieve unit
absorber Recovery Unit
H2O & RSH

Regen-gas RSH
absorber S

NGL-Extraction CH4

NGL
Figure 3. Block scheme for a gas processing plant with Removal of nearly all RSH in a mol
sieve unit downstream an AGRU with an aqueous amine.

In summary, there are three basic options for the combined removal of mercaptans (RSH)
in combination with the use of amines for H2S and/or CO2 removal:
1. Full RSH removal via a physical solvent in the AGRU (figure 1)
2. Partial removal of RSH in the AGRU, followed by polishing with mol sieves (figure
2)
3. Removal of nearly all RSH in a mol sieve unit downstream an AGRU with an
aqueous amine (figure 3).

The economics of these three options, which depend heavily on the gas composition, have
been considered at recent conferences [13, 14].
In this paper, the design and operational issues associated with mercaptan removal in a
molecular sieve unit are discussed. The complexities of mercaptan removal using mol sieves
5
can affect the net present value (NPV) of an investment due to operational difficulties
resulting in unplanned downtime, or a failure to meet design capacity for a certain period. For
example, a single unplanned shutdown of 10 days to replace deactivated mol sieves could
easily cost on the order of 10MM$ in lost production and reputation for meeting contractual
cargos in the case of LNG production; this sum could have been used to make a more robust
design for a unit that may have had a total installed cost of less than 40MM$.

The Use of Molecular Sieves for Mercaptan Removal

Molecular sieves (mol sieves) with polar surfaces can be used for mercaptan removal
down to very low concentrations because of the affinity of the mercaptan molecule for
adsorption on the surface. Zeolites having the general formula Mx/n[(AlO2)x(SiO2)y]zH2O
where n is the valence of the cation, and M is the metal ion inside each aluminosilicate cage
[15-17], afford polar surfaces for mercaptan adsorption. The type of mercaptan that can fit
into the micropores of the zeolite depends on the size of the cation in the zeolite structure.
The 3A mol sieve is constructed using K cations, and has a nominal micropore aperture of
3Å, which is too small for mercaptan adsorption. Similarly, the 4A mol sieve is constructed
with Na cations, and has a nominal micropore aperture of 4Å, which is also too small for
mercaptan adsorption. The 5A mol sieve, with Ca cations, has a micropore aperture of 5Å,
which is large enough to admit H2S, CH3SH, C2H5SH, and n-C3H7SH. Mol sieve 13X, with
Na cations, has a pore diameter of about 7.4Å, allowing it to adsorb i-C3H7SH as well as the
aforementioned mercaptans.
When mol sieves are used for mercaptan removal, water must be removed upstream of the
mercaptan-removal bed. Water has a small effective molecular diameter compared with
mercaptans, and water can adsorb on 3A, 4A, 5A, and 13X mol sieves. Furthermore, the
affinity of the 5A and 13X mol sieves for water is greater than the affinity for mercaptans,
because the polar interactions of the zeolite surface with water are stronger than the
interactions with mercaptans. Thus, the removal of water and mercaptans on mol sieves is
often combined in a single vessel, where the first layers of mol sieve remove water, and
subsequent layers of mol sieve remove mercaptans. Often, 4A mol sieves are used for water
removal because they have a high capacity for water adsorption; furthermore, 4A mol sieves
are more resistant to hydrothermal deactivation as compared with 5A or 13X mol sieves. A
Shell operated gas plant (NAM-GZI/Emmen) has worked successfully for the past 15 years
using successive layers of 4A, 5A, and 13X mol sieves for the removal of water, light
mercaptans, and heavy mercaptans, respectively [11].

Kinetics of Adsorption
The first difficulty with the removal of mercaptans using mol sieves is that the kinetics of
mercaptan adsorption on mol sieves is generally slow. During operation, the static capacity is
not the same as the dynamic capacity that results when gas flows past the adsorbent [15]. The
adsorption process consists of a number of mass transport steps [18, 19] before mercaptans
are finally bound within the mol sieve. As the concentration front of mercaptans moves
through the bed, a gradient in concentration forms due to the kinetics of adsorption on the

6
mol sieve. In the saturation zone (SZ), the mol sieve is saturated with mercaptans, and in the
mass transfer zone (MTZ), where there is a concentration gradient, the mol sieve is only
partially saturated. This is shown in the diagram of figure 4. The non-utilized zone (NZ) is
the part of the bed that has not come into contact with mercaptans yet because all mercaptans
were adsorbed in the SZ and MTZ. If a stream containing mercaptans were allowed to flow
through the bed for a long enough time, mercaptans would break through at the end of the
bed. It is generally accepted [15, 16] that the capacity in the MTZ is roughly half of the
capacity in the SZ, where the adsorption kinetics have reached equilibrium. Because the
kinetics of mercaptan adsorption are slower than the kinetics of water adsorption, a relatively
large amount of mol sieve is required for mercaptan removal as compared with water
removal.

Contaminant conc. in process stream

Product Feed
Spec. Concentration
Direction
of the flow

a) The saturated zone (SZ) wherein the

adsorbent has achieved its maximum
loading and the concentration of the
Saturated Zone (SZ) contaminant in the process stream does not
change.

b) The mass transfer or chemical reaction

zone (MTZ/CZ) wherein the adsorbent is
only partially loaded and the contaminant
level drops from its feed concentration
down to the product level.
Mass transfer or
chemical reaction
zone (MTZ/CZ)
c) The non-utilised zone (NZ) wherein both
concentration and adsorbent loading
Non-utilised zone (NZ)
changes are negligible.

Figure 4. Schematic representation of the adsorption zones in an adsorber vessel.

7
Co-Adsorption of Hydrocarbons, CO2, and COS (BTX separately)
Mol sieves such as 5A and 13X typically used for mercaptan adsorption also have a
significant capacity for hydrocarbon, CO2, and COS adsorption. While the saturation-zone
and part of the mass transfer zone are loaded with water and mercaptans, the non-utilized
zone and part of the mass transfer zone (figure 4) become loaded with hydrocarbons, CO2,
and COS if these are present in the feed gas. In particular, 5A mol sieves have a capacity of
roughly 10 to 15wt% for linear hydrocarbon adsorption [20-23] and roughly 10 to 20wt% for
CO2 adsorption at typical feed-gas concentrations.

Depending on the conditions of the mol sieve and the cycle time, a significant portion of
the mol sieve can be available for hydrocarbon, CO2, and COS adsorption. Typically, the
water capacity at end-of-run conditions is roughly ½ of the capacity available from fresh mol
sieves. Using the same number of cycles for water and mercaptan adsorption, the mercaptan
capacity is typically much less than ½ of the capacity available from fresh mol sieves. If a
mol sieve unit is started with an adsorption time designed for end-of-run conditions, then
roughly half the mol sieve volume is available for co-adsorption of hydrocarbons and CO2.
During the heating step, the hydrocarbons, CO2, and COS desorb from the mol sieve,
resulting in significant concentrations of these components in the regeneration gas.

Transients Created by the Mol Sieve Unit

The mol sieve unit creates composition transients in both the regeneration gas and the
effluent product due to the cyclical nature of the process. While one or more mol sieve bed(s)
are in adsorption mode, other bed(s) are in regeneration mode. All the mercaptans that adsorb
on the bed from the feed-gas stream are released into the regeneration-gas stream when the
bed is heated during a short period of time. In most cases, the mercaptans must be removed
from the regeneration-gas stream – this is often done using a physical solvent or an amine
with a component of physical solvent such as Sulfinol. The peaks of mercaptans in the regen-
gas translate into peaks in mercaptan concentration in the acid gas being fed to the sulphur-
recovery unit (SRU). In addition, co-adsorbed hydrocarbons, CO2, and COS peaks in the
regeneration gas are absorbed by the regen-gas absorber, resulting in peaks of these
components in the sulphur recovery unit (SRU).
The rapid changes in the oxygen demand introduced in the SRU by varying concentrations
of mercaptans can be difficult for the control scheme of the SRU to handle. In the SRU, H2S
generated by the AGRU is burned with a sub-stoichiometric
amount of oxygen to produce elemental sulphur via the Claus reaction [9], first in a
homogeneous burner and then in subsequent catalytic stages. A tail-gas analyser detecting the
amount of SO2 in the tail gas typically regulates the amount of oxygen fed to the SRU burner.
Because of the residence time of gases in the SRU, the delay in control by the tail-gas
analyser makes it difficult to compensate the amount of oxygen fed to the burner for changes
in the feed-gas composition. This is particularly difficult when the feed-gas to the SRU
contains mercaptans and hydrocarbons, which require several mols of oxygen for the
complete combustion of one mol of mercaptan or hydrocarbon. In addition to the transients

8
compositions of mercaptans and hydrocarbons originating from the mol sieve unit, the SRU
must also contend with the transient concentration of CO2 resulting from co-adsorption in the
mol sieve unit if CO2 is absorbed in the regen-gas treating unit.
The consequence of transient compositions and poor control in the SRU can be off-
specification liquid sulphur. Depending on the type of hydrocarbons present, a certain
temperature is required in the SRU burner to ensure complete combustion of hydrocarbons
and avoid soot formation. The temperature in the burner depends strongly on how much fuel
(H2S, hydrocarbons, mercaptans) and oxygen there is in the feed gas compared with the
amount of diluents such as CO2 from the AGRU and mol sieve unit, or N2 from the air
supplying oxygen. When the flame temperature becomes too low due to insufficient
combustion, soot formation subsequently leads to “black” or off-spec liquid sulphur, which
must be disposed of sometimes at a cost, because it cannot be easily sold. For a plant
producing hundreds of tons of sulphur per day with only a few hours or days of sulphur
storage capacity, the production of off-spec sulphur can become a critical issue in operation.
Only a very small amount of soot can contaminate a large volume of bright yellow liquid
sulphur. Again, it should be stressed that it is the changes in composition originating from
the mol sieve unit that make control and operation of a stable flame in the SRU difficult.
Clearly, there would be a benefit to smoothing the transients caused by the mol sieve unit
before they are propagated to the SRU. While it would be impractical to smooth the
concentrations of the regen-gas or acid-gas streams due to the volumes involved, it is
possible to smooth the concentrations of mercaptans in the solvent circulation of the regen-
gas treating unit. For example, if Sulfinol is used to remove mercaptans from the mol sieve
regen gas, then the loaded solvent can be passed through a large stirred buffer tank before
being fed to the regenerator, thus smoothing the concentration of mercaptans over time (see
figure 5 for an example). Alternatively, a system of Sulfinol tanks can be used, where the
solvent is fed to a one tank during the peak, and to another during the off-peak time, while a
steady flow of solvent is drawn from both tanks to create an even concentration of
mercaptans flowing to the regenerator. In a third alternative, a control scheme could be used
for partial peak-shaving in order to minimize the size of the vessels.

9
 Single stirred tank over several periods
3 3
flow = 5m /min, volume in m
1.2

1
Fraction of inlet

100
concentration
0.8
300
0.6 600
0.4 900

0.2 1200

0
0 500 1000 1500 2000
t [min]

Figure 5. The fractional outlet concentration, Cout/Cin, for a single stirred tank at a flow rate of
5m3/min (300m3/h) for volumes between 100m3 and 1200m3. Several cycles are shown.
Larger tank sizes result in a smoother outlet concentration.

Simply optimising the cycle timing of the mol sieve unit can dampen transient
compositions of hydrocarbons, CO2, and COS in the mol sieve regeneration gas. At long
adsorption times, more water and mercaptans are adsorbed on the mol sieves compared with
short adsorption times; because water and mercaptans displace hydrocarbons, CO2, and COS,
the co-adsorption of hydrocarbons, CO2, and COS is minimised at long adsorption times.
Naturally, the adsorption time is limited by the breakthrough of mercaptans at the outlet of
the bed. As the capacity of the mol sieve to adsorb water and mercaptans diminishes over a
number of adsorption and regeneration cycles, the adsorption time must be shortened
periodically.
An added advantage of variable cycle time is that mol sieve deactivation is minimized
over calendar time. Deactivation of mol sieves used either for water or mercaptan adsorption
occurs primarily during the regeneration step at high temperature. Minimizing the number of
regeneration steps in a given calendar year thus minimizes the deactivation over that same
period.

Deactivation
An often-underestimated difficulty with the removal of mercaptans using mol sieves is the
deactivation of the mol sieve. The deactivation of mol sieves used for water-removal is well
known, and there is abundant operational experience to allow prediction of deactivation rates.
In contrast, the removal of mercaptans using mol sieves is a relatively new field in the
industry, and deactivation rates have not been well documented. When the mol sieve is
heated, mercaptans desorb from the micropores of the zeolite crystals and begin to diffuse out

10
through the micropores and macropores of the mol sieve pellet. During the diffusion process,
there is an equilibrium between re-adsorption and desorption. When the temperature of the
surface becomes high enough, the rate of dissociation of mercaptans on the surface becomes
appreciable [24, 25]. Thus, over a number of cycles of adsorption and regeneration, the mol
sieve becomes coked with decomposition products. Indeed, spent mol sieves that have been
used for mercaptan-removal turn from a white to a black colour.
Operational data from the Shell operated gas plant in Emmen, covering mol sieves of
several vendors, has shown that mol sieves used for mercaptan removal deactivate at a much
faster rate that that observed with mol sieve that is used for water-removal only [26].
Decomposition of mercaptans on the mol sieve at NAM-GZI in Emmen has resulted in a
decrease in the capacity for CH3SH from 12 wt%S to 1wt%S at 25oC over the lifetime of 3
years. This twelve-fold decrease in mercaptan-removal capacity starkly contrasts the usual
two-fold decrease in water-removal capacity often observed over a similar lifetime.
Designs of mol sieve units for mercaptan-removal need to account for the conditions at the
end of the mol sieve lifetime. A mol sieve unit is usually designed such that a single batch of
mol sieve can last for the period of time between planned shutdowns, which is often 3-4
years. Thus, the unit must be designed with enough mol sieve volume to allow for a
minimum regeneration time after going through 3-4 years worth of deactivation. Because the
deactivation rate changes over time, operational data is essential to predicting the form of the
deactivation curve. Furthermore, the kinetics of adsorption change as the mol sieve
deactivates, thus changing the characteristics of the mass transfer zone, further affecting the
effective capacity of the mol sieve to adsorb mercaptans.
Clearly, a process that retards the deactivation of mol sieves used for mercaptan removal
would be beneficial. For a given schedule of planned shutdowns, a slower deactivation rate
would translate directly to a smaller capital expenditure, because a smaller volume of mol
sieve would be required for mercaptan adsorption at the end-of-run conditions.

After the adsorption step, where mercaptans from the feed gas adsorb on the mol sieve,
heated gas is used to regenerate the mol sieve bed. In the traditional process, a slipstream of
dry treated gas is heated in a furnace and passed through the bed in regeneration mode [11],
causing mercaptans and water to desorb. During the heating step, a fraction of the adsorbed
mercaptans decompose on the mol sieve [24, 25], causing deactivation.
It has been found [26] that adding a small amount of water to the regeneration-gas stream
during the heating step mitigates the decomposition of mercaptans on the mol sieve during
the heating step. There are at least three possible mechanisms that achieve this result:
1. Water hinders the transient adsorption of mercaptans on the mol sieve at high
temperature, thereby preventing the decomposition of mercaptans leading to coke
formation.
2. Water co-adsorbs with mercaptans at low temperature during the beginning of the
heating step, and hinders the decomposition of mercaptans by preventing the
formation of reaction intermediates.

11
 3. Water displaces adsorbed mercaptans at the beginning of the temperature ramp,
preventing them from decomposing simply because they are not adsorbed on the sieve
anymore by the time high temperatures are reached.

The implementation of the wet-regeneration scheme in an operating plant is simple. A

small amount of water needs to be added to the regeneration-gas stream at the start of the
heating step, and subsequently the addition of water must be terminated at some point prior to
the cooling step to avoid pre-loading the bed with water. The first possibility is to inject a
small amount of steam into the regeneration gas before it enters the bed in heating mode. A
second possibility is to use a slipstream of untreated gas, which is often saturated with water
from the acid-gas removal unit. In either case, the valve for the addition of water can be
controlled on the timing sequence of the mol sieve unit. Excessive addition of water to the
regeneration gas can lead to hydrothermal deactivation of the mol sieve [26] via the
mechanism of de-alumination [17, 27, 28].
The wet-regeneration process has been described in detail elsewhere [26], but is
summarized here because of its relevance. A comparison of dry and wet regeneration has
been made using cycles of adsorption and regeneration in an adsorption test unit (ATU). The
ATU is a bench scale unit specially developed to screen mol sieves for its deactivation when
operated with rapid adsorption/desorption cycles (Figure 6). Aging using wet regeneration
was compared with dry regeneration for 100 cycles for i-C3H7SH adsorption on a 13X sieve.
During the “wet” regeneration, 2000Pa of water was added to the regeneration stream.
Clearly the sample exposed to the wet regeneration conditions (blue, upper curve) was not
deactivated as quickly as the sample exposed to dry regeneration conditions (red, lower
curve). The solid lines are best-fits of the function (%wt S) = Ae-Bn where A and B are fitting
constants and n is the number of cycles; for wet regeneration A=7.6025 and B=-0.0011,
whereas for dry regeneration, A=8.2 and B=-0.0085. Such an exponential decay in capacity
with the number of cycles results from first order kinetics, where the rate of destruction of
adsorption sites only depends on the number of active sites remaining [26].

12
 Comparison of wet and dry regeneration
10
Difference in initial load is
9 caused by the w ater capacity of
i-C3H7SH load [%wt (S)]

the sieve at regeneration

8
temperature
7 Wet Regeneration
6
5
Dry
4
Regeneration
3
Pre-aged sieve
2
1
0
0 200 400 600 800 1000
Number of adsorption/regeneration cycles

Figure 6. Isopropyl mercaptan loading capacity on 13X mol sieve as a function of the number
of adsorption / regeneration cycles. Points are actual measurements in the laboratory, and the
lines are fitted exponential-decay equations.

Pre-aged mol sieve samples were used to check the extrapolation of the exponential-decay
model to high numbers of regeneration cycles. Pre-aged samples, prepared by exposure to a
constant stream of mercaptans at high temperature, were measured for an initial capacity. The
effective number of regeneration cycles was then calculated for that initial capacity using the
fitted curves in figure 6, and the initial capacities were plotted on the deactivation curves
(figure 6, labelled “Pre-aged sieve”). The pre-aged samples were then exposed to cycles of
adsorption and regeneration (wet or dry), and the capacity was periodically measured. The
number of additional cycles completed was added to the initial effective number of
regeneration cycles, and the capacity was plotted. Thus, the pre-aged sieve was used to check
the extrapolation of the aging curves.
The wet-regeneration scheme has been applied in practice at the NAM-GZI gas processing
plant in Emmen, The Netherlands, since September 2004. The plant in Emmen, operating
since 1988, has the capacity to process 2*150 MMscfd [11] of natural gas (currently
processing ~95 MMscfd), containing H2S, CO2, CH3SH, C2H5SH, n-C3H7SH, and i-C3H7SH.
Sulfinol is used to remove H2S and the bulk of mercaptans while slipping CO2. Downstream
of the Sulfinol unit, a mol sieve unit removes water and the remaining mercaptans from the
gas before the treated gas is sent to the pipeline.
As shown in figure 7, there has been very little deactivation of the mol sieves with the use
of the wet-regeneration scheme over time, as compared with normal dry regeneration. The
13
exponential-decay aging curves for wet and dry regeneration were calculated as follows. The
test of the wet-regeneration scheme began when the mol sieve had already deactivated from
800 cycles of adsorption and regeneration. At this point, the capacity of the mol sieve was
0.163wt% mercaptans, and the pre-exponential factor (A) in the model (%wt) = Ae-Bn was set
to 0.163wt%. The exponential factor, B, was set to the value found in the laboratory for wet
or dry regeneration, respectively. The data from Emmen were determined during capacity
test-runs, where it was found that the dynamic capacity was roughly a linear function of
mercaptan concentration in the feed gas. Thus, a linear fit to the data was used to calculate a
best-fit for a single feed-gas concentration, at 15mg/Nm3. These points are plotted in figure 7.
As shown in figure 7, the test runs conducted using the wet-regeneration scheme show
slower deactivation than that predicted by either the dry regeneration or the wet regeneration
models. In fact, the capacity of the mol sieve appeared to be increasing slightly, although the
increase was not considered statistically significant. In any case, it is clear that the wet-
regeneration scheme mitigates the deactivation of mol sieves used for mercaptan removal in
actual operation. The capacity of the mol sieves for mercaptan-removal is low due to the
history of the beds, which have experienced many cycles of adsorption and regeneration, and
the low concentration of mercaptans in the feed gas. The success of the wet-regeneration
scheme in Emmen has allowed the operating company to postpone a shutdown for the
change-out of the mol sieve material.
Since the first publication of this data in March 2005 [26], the wet regeneration scheme
has continued to perform successfully, though changes in operating conditions preclude a
straight forward comparison over a longer period than that shown in figure 7.

Mitigated deactivation at NAM-GZI Emmen

0.2
Emmen Data; fit for 15mg/Nm 3 RSH
0.18
Loading [wt%]

0.16

0.14
Prediction - wet regen
Prediction - dry regen
0.12

0.1
790 810 830 850 870 890 910

Number of cycles

Figure 7. Demonstration of the wet-regeneration scheme in operation at NAM-GZI Emmen.

The wet-regeneration scheme was started when the mol sieve had already experienced 800
cycles of adsorption/regeneration.

14
 Another solution for mitigating the deactivation of mol sieves is to use a gradual
temperature ramp during regeneration. When the mol sieves are heated to a temperature
below the temperature where mercaptans begin to react [24], mercaptan molecules desorbed
from the internal surfaces of the sieve have a good chance of diffusing out of the mol sieve
pellet before re-adsorption followed by reaction can occur. At sufficiently low temperature,
mercaptan molecules in re-adsorption and de-sorption equilibrium with the internal surfaces
of the sieve have a low probability of surmounting the activation energy barrier to form
reaction products which can cause deactivation.

H2S Formation during Regeneration

The mechanism of deactivation of mol sieves leads to another design and operational
complexity: the formation of H2S in the regeneration gas from the mol sieve unit. The
specification on H2S at the outlet of the AGRU is typically <5ppmv, while the concentration
of mercaptans may be in the range of hundreds of ppmv. Despite this large difference,
significant amounts of H2S may be observed in the regeneration gas relative to the total
mercaptan concentration. The evolution of H2S along with mercaptans during regeneration
can be illustrated with the following example from the laboratory.
After loading the mol sieve with n-C3H7SH until breakthrough was detected, a mol sieve
sample was regenerated and the effluent gases were measured during regeneration, as shown
in figure 8. Under these conditions, no H2S was adsorbed. During the early stages of
regeneration, a sharp peak of H2S desorption was observed, followed by a roughly an
exponential decay in H2S concentration. The sharp spike in H2S evolution suggests that H2S
is formed from a reaction within a small temperature range, and the exponential decay may
result from the diffusion of produced H2S out of the macropore structure of the mol sieve
pellet.
The point at which H2S suddenly begins to form corresponds to a temperature of 200C.
This is exactly the temperature at which differential scanning calorimetry (DSC)
measurements have shown the onset of a steep exotherm in the usually endothermic
desorption of mercaptans [24]. In other words, the observed evolution of H2S probably
corresponds to a reaction on the surface. Possible reactions are [25, 29]:

3 R-SH => R-S-S-R + H2S + RH (with zeolite and heat)

½ O2 + 2 R-SH => R-S-S-R + H2O (with zeolite and O2)
R’-CH2-CH2-SH => R’-CH=CH2 + H2S (with zeolite)

The reaction mechanism converting mercaptans to the corresponding alkene and H2S is
relevant for C2H5SH, n-C3H7SH, i-C3H7SH, and butyl mercaptans, but not CH3SH.

15
 Desorption of n-C3H7SH from 5A mol sieves
(in N2 at 40bara, 40- 290 °C)

10000 350
9000
300
Concentration [ppmv]

8000 Temperature

Temperature [°C]
7000 250
6000 200
n-propyl RSH
5000
4000 150
3000 100
H2S
2000
50
1000
0 0
15 20 25 30 35 40
Run time [hours]

Figure 8. The desorption of n-C3H7SH from 5A mol sieves after the adsorption of n-
C3H7SH from the feed gas of N2. The feed concentrations were 9075ppmv n-C3H7SH in a
balance of N2 at 40bara and 40C during adsorption. The regeneration gas was dry nitrogen.

The evolution of H2S during regeneration of mol sieves used for mercaptan removal
suggests that the regeneration-gas treating unit should be capable of quantitatively removing
H2S from the regeneration gas. A mixed solvent containing an amine and a physical solvent
component, such as Sulfinol, is perfect for this task, combining both chemical H2S absorption
and physical mercaptan absorption. The consequence of not removing H2S from the regen-
gas is that regen-gas would need to be recycled to upstream the AGRU, thus resulting in a
larger AGRU, in addition to the regen-gas treating unit.

H2S Conversion to COS

Aside from deactivation, a further complexity in the design and operation of a mol sieve
unit is the formation of COS from H2S and CO2. In general, an amine unit for H2S and/or
CO2 removal precedes a mol sieve unit used for mercaptan removal, with a typical H2S
specification of a few ppmv. The amount of CO2 in the feed gas to the mol sieve unit depends
on the destination of the treated gas. However, the concentration of CO2 often exceeds the
concentration of H2S in feed to the mol sieve unit.

COS is formed on the mol sieve by the following reaction:

H2S + CO2 ⇔ COS + H2O

16
 [COS ][ H 2 O]
Kp =
[ H 2 S ][CO2 ]

Table I. The equilibrium constant for COS formation at various temperatures.

Temp (degrees C) Kp
20 1.38 x 10-6
100 3.16 x 10-5
200 3.64 x 10-4
300 1.8 x 10-3
400 5.4 x 10-2

As shown in the table above, the equilibrium lies far to the left at normal adsorption
temperatures (25C), and even at regeneration temperatures (300C) [30]. However, when the
mol sieve removes water, the equilibrium is shifted to the right. The rate of COS formation
is dependent on the type of mol sieve – i.e. the conditions of reactive site where COS is
formed. It has been noted [30] that more basic sites contribute to a faster rate of COS
formation. COS formation is relatively fast on the 4A sieve, which has mono-valent Na ions
in the cavities. In contrast, COS formation is slower on the 5A sieve, because the di-valent
Ca ions in the cavities reduce the effect of the basic sites. The disadvantage of using a 5A
sieve for water removal is that it is somewhat more prone to deactivation compared with the
4A mol sieve [26].
Test runs by Zeochem [30] have shown that up to 100% of a 15ppmv H2S stream in
natural gas with 1% CO2 can be converted to COS on a 4A sieve at 27oC and 49bara. Thus,
as a conservative estimate, it can be considered that all H2S is converted to COS under
adsorption conditions in the presence of CO2.
In addition to the COS formed on the mol sieve, some COS in the feed-gas may slip
through the amine unit. The total COS level in the product gas from the mol sieve unit must
be taken into consideration in the design of the NGL-extraction unit, because COS
concentrates into the LPG phase, where it can be removed using amines and/or molecular
sieves.
The following solutions can be considered when dealing with COS formation on mol
sieves:
1. Some mol sieve vendors offer “COS-minimizing” molecular sieves, which
presumably have a proprietary additive in the binder.
2. A 3A molecular sieve could be considered for water removal, because H2S adsorption
is excluded from the 3-Ångstrom pore opening of the sieve. However, the 3A sieve is
best regenerated at ~240C, whereas 5A and 13X molecular sieves used for mercaptan
removal require temperatures above this for full regeneration.
3. A 5A mol sieve can be used for combined water and mercaptan removal, with the
compromise that faster deactivation of the 5A mol sieve can be expected when used
for water removal.
17
 4. COS formation from a small H2S concentration can be accepted, and the formed COS
can be removed in the extracted LPG downstream of the mol sieve unit.

In any case, some degree of uncertainty must be accounted for in the COS concentration
expected downstream the molecular sieve unit – only a few ppmv of uncertainty in COS
concentrations can make a significant difference in the basis of design for the COS-removal
unit in the LPG treating section.

BTX Co-Adsorption
A final complexity in the design and operation of a mol sieve unit for mercaptan removal
is the co-adsorption of BTX. The affinity of 13X mol sieves for BTX (benzene, toluene, and
xylenes) is slightly greater than their affinity for mercaptans [29]. An amount of BTX in the
feed gas roughly equal to the amount of mercaptans in the feed gas severely hinders
mercaptan adsorption. Furthermore, a high concentration of BTX in the feed gas relative to
the concentration of mercaptans results in almost negligible adsorption of mercaptans on the
13X mol sieve (shown by example below). In contrast to 13X sieves, the adsorption of BTX
is not an issue for 5A mol sieves, because BTX molecules are too large to fit into the 5A
zeolite structure.
An example of the co-adsorption of toluene and i-C3H7SH measured in the laboratory is
shown in figure 9. In this experiment, a micro-flow reactor was filled with 13X mol sieve and
heated to 300C to regenerate the mol sieve. A flow of nitrogen at 5bara and 40C containing
99ppmv i-C3H7SH and 1842ppmv toluene was then fed to the reactor, and the concentrations
of i-C3H7SH and toluene were measured using a gas chromatograph (GC) at the outlet of the
reactor. From the period of 0 hours to 10 hours, both toluene and i-C3H7SH adsorbed on the
mol sieve, and thus no toluene or i-C3H7SH was detected at the outlet of the reactor. At 10
hours, both toluene and i-C3H7SH began to break through at the outlet of the reactor. As the
concentration of toluene rose to a value equal to the feed concentration, the concentration of
i-C3H7SH rose far above the concentration of 99ppmv in the feed gas. Finally, the
concentration of i-C3H7SH returned to a value equal to the concentration of i-C3H7SH in the
feed gas.
The breakthrough experiment shown in figure 9 suggests that toluene displaces i-C3H7SH
adsorbed on the 13X mol sieve. During the initial adsorption period (0-10h), both toluene and
i-C3H7SH adsorbed on the mol sieve. However, when both components began to break
through, toluene began to displace i-C3H7SH from the mol sieve, causing the concentration of
i-C3H7SH in the effluent to rise above the inlet concentration. Only when nearly all the i-
C3H7SH had been displaced by toluene did the toluene concentration reach a value equal to
the concentration of toluene in the feed gas.

18
 Adsorption of iso-propyl mercaptan and toluene on
13X mol sieve (pressure = 5 Bara, Temperature 40 °C)
2000 Feed concentration toluene = 1842ppmv
concentration [ppmv]

1500 isopropyl RSH

toluene
1000

500
Feed concentration i-C3H7SH = 99ppmv
0
0.0 5.0 10.0 15.0
Adsorption time [hour]

Figure 9. The concentration profiles of i-C3H7SH and toluene measured at the outlet of the
reactor during a dynamic adsorption experiment. The feed concentrations were 99ppmv i-
C3H7SH and 1842ppmv toluene in a balance of nitrogen at 5bara and 40C.

One solution for dealing with the combined removal of BTX and mercaptans is to use
Sulfinol in the main amine unit, with only 5A sieves in the mol sieve unit. The solubility of
BTX is generally greater in Sulfinol than in aqueous amines, resulting in some BTX removal
in the amine unit upstream the mol sieve unit. Furthermore, Sulfinol removes the heavy
branched mercaptans that generally require a 13X sieve for removal in the mol sieve unit
more easily that it removes light mercaptans such as methyl or ethyl mercaptan. Thus, when
using Sulfinol, it may be possible to use a 5A mol sieve for mercaptan removal without a
13X mol sieve, thus avoiding the problem of BTX co-adsorption altogether.
A second solution for dealing with the combined removal of BTX and mercaptans is to
use Sulfinol or an aqueous amine in the main amine unit, with both 5A and 13X sieves in the
mol sieve unit, accounting for some BTX co-adsorption. In this case, BTX co-adsorption in
the mol sieve unit would be greater when using an aqueous amine as compared with Sulfinol
due to relative solubilities. BTX desorbed during the regeneration step may be absorbed by
the physical solvent in the regeneration-gas treating unit and subsequently routed to the SRU.
BTX destruction in the SRU requires high flame temperatures and accurate control in order
to avoid black sulphur formation – if possible, it is desirable to avoid BTX in the SRU. If
BTX is not removed in the regen-gas treating unit, there is a danger of building up BTX in
the mol sieve regeneration gas loop, thereby displacing mercaptans from the 13X mol sieve.
A third solution for dealing with the combined removal of BTX and mercaptans is to use
an aqueous amine or Sulfinol with mercaptan slip, and use only a 5A mol sieve for mercaptan
removal. In this case, branched mercaptans slip past the mol sieve unit and report to the LPG
and/or condensate streams from the NGL extraction unit, where they must be removed.
19
Advantages of Integrating Regen-Gas and Acid-Gas Treating Units
Using the same solvent for both the main acid-gas removal unit (AGRU) and the mol
sieve regeneration-gas treating has the advantage that only two separate absorbers are
necessary rather than two separate solvent systems. The regenerator, tanks, pumps, and
perhaps even flash vessels can be shared between the two units. It may be more effective to
use a separate absorber for the mol sieve regen-gas and main AGRU rather than to recycle
the mercaptan-laden regen-gas to the front end of the AGRU, because solvent rates and tray
layouts for optimal mercaptan-removal may be different from the optimal tray layout and
solvent rates in the AGRU.

CONCLUSIONS
Molecular sieves are particularly well suited for the trace removal of contaminants from
natural gas, such as water and mercaptans. Depending on the mercaptan concentration, it can
also be effective to use a physical solvent for mercaptan removal, although this comes with
the trade-off of hydrocarbon co-absorption.
Complexities in the design and operation of a mol sieve unit for mercaptan removal
include the following.
1. Co-adsorption of hydrocarbons, COS, and CO2 can cause unexpected transients in
concentrations of these components in the regeneration gas. Optimising the cycle
time of the mol sieve unit can help to mitigate co-adsorption.
2. The transient nature of the mol sieve unit creates transients in the regen-gas treating
unit and sulphur-recovery unit, which cause difficulties in the control and operation of
these units. Transients in composition may also be caused downstream the mol sieve
unit. Transients can be mitigated by controlling the mol sieve cycle time and using a
peak-shaving scheme in the regen-gas treating unit.
3. Mol sieves deactivate rapidly when used for mercaptan removal, as compared with
dehydration. Various approaches have been proposed to mitigate deactivation,
including temperature ramps and the wet-regeneration scheme.
4. During the regeneration step, mercaptans decompose to form H2S, which
subsequently must be removed. The production of H2S during regeneration can make
a combined amine and physical solvent an ideal choice for regeneration-gas treating.
5. H2S slip from the AGRU is converted to COS in the presence of CO2 on the mol
sieve, when the mol sieve removes water. COS can subsequently be removed from
extracted natural gas liquids, or COS-minimizing mol sieves can be used.
6. BTX (benzene, toluene, xylene) is adsorbed more strongly than mercaptans on 13X
mol sieves. Physical solvents can be used to remove BTX upstream the mol sieve
unit. Alternatively, a 5A sieve can be used for linear mercaptan removal, because
BTX does not fit in the 5Å pore opening.

20
 Optimal gas treating solutions depend on the gas composition and economics [13, 14], but
also on the operability of the unit. The complexities involved in the design and operation of a
mol sieve unit used for mercaptan removal presented herein suggest that potential lost
production or difficulty in meeting design capacity needs to be carefully considered when
choosing the optimal process line-up.

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22