DOI 10.

1515/revce-2013-0017 Rev Chem Eng 2013; 29(6): 449–470

Ahmed Daham Wiheeb, Ili Khairunnisa Shamsudin, Mohd Azmier Ahmad, Muhamad Nazri
Murat, Jinsoo Kim* and Mohd Roslee Othman*

Present technologies for hydrogen sulfide

removal from gaseous mixtures
Abstract: Natural gas, refinery gas, and coal gas contain acid 1 Introduction
gases such as hydrogen sulfide (H2S) and carbon dioxide that
must be removed from the gas stream due to the toxicity of
Hydrogen sulfide (H2S) has unpleasant smell and is toxic;
H2S and to prevent corrosion to piping and production facil-
even in small amounts, it can be lethal to both animals
ity caused by the acid gases. In this article, current technolo-
and human beings (Ni et al. 2000, Hendrickson et al.
gies for the acid gas removal are selected and reviewed. The
2004). Human nose can sense H2S at very low concentra-
review includes absorption, adsorption, conversion of H2S
tions (0.4 ppb). The toxicity threshold of H2S to human is
into elemental sulfur, and membrane reactor for H2S decom-
about 10 ppmv (Chou 2003), and the health risk increases
position and desulfurization. Recently, hollow fiber mem-
with the increase of the gas concentration. Table 1 sum-
brane contactor has been in the limelight of research in H2S
marizes the H2S concentration range that can adversely
absorption from gaseous mixture due to its potential to over-
affect human health.
come problems such as foaming and loading. Recent trends
Beside its toxicity, H2S is also extremely corrosive to
on Claus tail gas cleanup technologies are highlighted due to
piping and production facility in both gaseous form and
the recent progress in membrane technology. The article also
in solution (Garcia-Arriaga et al. 2010). When oxidized to
suggests current research on the acid gas removal technol-
sulfur oxide (SO2) on combustion and released to atmos-
ogy using catalytic membrane reactor. The interest on find-
phere, SO2 can cause acid rain (Turpin et al. 2008, Pillai
ing suitable active component and support and studying the
et al. 2009). In many industrial processes such as hydro-
membrane structure for enhanced removal of acid gases is
genation, ammonia synthesis, and fuel cells, H2S has a
likely to be rekindled in the near future.
serious poisoning effect on noble metal catalyst even in
trace amount (Jose and Amitesh 2000, Zhang and Tong
Keywords: cleaner production; corrosion; energy; mem-
2006). Therefore, it is imperative to remove the gas from
brane; natural gas; separation.
the production facility.
H2S is emitted largely from chemical industries such
*Corresponding authors: Jinsoo Kim, Department of Chemical as natural gas processing and utilization, hydrodesulfuri-
Engineering, Kyung Hee University, Global campus, 1 Seocheon-dong, zation of crude oil, and coal chemistry (Zhang et al. 2010).
Giheung-gu, Yongin-si, Gyeonggi-do 446-701, Republic of Korea, H2S is also extremely corrosive to carbon steel, which
e-mail: [email protected]; and Mohd Roslee Othman, School of
is usually used as a pipeline material in the oil and gas
Chemical Engineering, Universiti Sains Malaysia, 14300 Nibong
Tebal, Penang, Malaysia, e-mail: [email protected] industry. Table 2 summarizes the effect of increasing H2S
Ahmed Daham Wiheeb: School of Chemical Engineering, Universiti gas concentration on the corrosion rate of ASTM A-106
Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia; and carbon steel (Shahid and Faisal 2009).
Department of Chemical Engineering, College of Engineering, The international environmental regulations for gas
University of Tikrit, Salah ad Din, Iraq
emission by the industries have become stringent with
Ili Khairunnisa Shamsudin, Mohd Azmier Ahmad and Muhamad
Nazri Murat: School of Chemical Engineering, Universiti Sains
respect to the release of gas containing sulfur. To meet the
Malaysia, 14300 Nibong Tebal, Penang, Malaysia regulation requirement, various purification technologies
Mohd Roslee Othman: Department of Chemical Engineering, Kyung have been used. These include absorption, adsorption,
Hee University, Global campus, 1 Seocheon-dong, Giheung-gu, chemical conversion, and, recently, catalytic membrane.
Yongin-si, Gyeonggi-do 446-701, Republic of Korea Microbiological treatment may also be considered as an
alternative treatment for H2S-containing gases. However, it
is not discussed in the present review because it has been
exclusively reviewed elsewhere (Jensen and Webb 1995).
In conventional absorption columns, the most
common technique for removing H2S from sour natural

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450 A.D. Wiheeb et al.: Acid gas removal technologies

Table 1 Toxic effects on human health at various H2S concentra- Claus process can remove H2S from sour or acid gases,
tions (Chou 2003). which contain high H2S concentrations. It was patented in
1883 (Claus 1883) and later improved in 1930 (Baehr 1938).
Exposure Observations and health effects
The Claus process consists of two steps: thermal oxida-
ppm mg/m3 tion and catalytic reaction. These two steps help remove
0.008 0.011 Odor threshold H2S but, because of the thermodynamic limitations, 3–5%
2 2.8 Bronchial constriction in asthmatic individuals of H2S is left untreated (Nasato et al. 1994, Monnery et al.
4 5 Increased eye complaints 2000). The H2S from untreated (also called as a tail) gas
5 or 10 7 or 14 Increased blood lactate concentration, from the Claus process is removed using a selective cat-
decreased skeletal muscle citrate synthase
alytic oxidation on a fixed-bed reactor (FBR). Here, it is
activity, decreased oxygen uptake
4–21 5–29 Eye irritation operated in two modes: above sulfur dew point (180°C)
20 28 Fatigue, loss of appetite, headache, and below sulfur dew point, both of which are working
irritability, poor memory, dizziness with or without water vapor (Lagas et al. 1988, Berben and
> 140 > 100 Olfactory paralysis Geus 1989, Chun et al. 1998, Keller et al. 1999, Bandel and
> 560 > 402 Respiratory distress
Willing 2000, Lee et al. 2005a).
≥ 700 ≥ 502 Death
In a catalytic membrane reactor, H2S is decomposed at
700°C into sulfur and hydrogen. Commonly, ceramic and
gas is by using aqueous solutions of alkanolamines. These composite metal membranes are used to increase the rate
columns can be either packed or plate columns working of H2S decomposition and to selectively remove hydrogen
at temperature ranging from 35°C to 50°C and at absolute gas from the reaction products to shift the equilibrium
pressure between 5 and 205 atm (Lu et al. 2006, Godini and forward (Kameyama et al. 1983, Edlund and Pledger 1994,
Mowla 2008). In addition to packed columns, hollow fiber Zaman and Chakma 1995, Edlund 1996, Ohashi et al. 1998,
membrane contactor can also be used in the absorption 2000, Chan et al. 2000, Akamatsu et al. 2008, Trujillo
process operating at low temperatures (25–50°C). In fact, et al. 2008). The membrane reactor has also been applied
membrane contactor has been increasingly researched to in desulfurization using a separated reactant feed config-
overcome the disadvantages present in the conventional uration (Sloot et al. 1990, Jalan and Ryu 1994, Neomagus
absorption processes such as high operation, regenera- et al. 1998).
tion costs, and equipment failure due to corrosion (Li et al. To achieve cleaner and more sustainable production,
1998, 1999, Wang et al. 2004a, Faiz and Al-Marzouqi 2010, H2S impurity must be removed effectively and efficiently.
2011). This article reviews the different technologies for H2S
In adsorption, H2S is removed via two types of adsor- removal from gaseous mixture and addresses the prospect
bents. The first type is made of carbonaceous material, of future research efforts on the desulfurization process
which physically adsorbs H2S at room temperature. The using a catalytic membrane reactor.
removal efficiency can be improved by impregnating it
with caustic materials, such as NaOH and KOH (Bandosz
1999, Bagreev and Bandosz 2000, 2002, 2004, Feng et al.
2005, Seredych and Bandosz 2009). The second type is
2 Technologies for H2S removal
metal-oxide adsorbents, which can work throughout a
wide range of temperatures (25–1600°C) and can lower 2.1 Absorption
H2S concentration down to 10 ppm (Ko et al. 2005, Dolan
et al. 2012). 2.1.1 Conventional absorption process

Table 2 H2S concentration and corrosion rate in 14% DEA solutions Absorption has been used in petroleum and gas industries
(Shahid and Faisal 2009). to remove H2S and carbon dioxide (CO2) from sour natural
gas and refinery gas. This removal is called gas sweeten-
H2S concentration Corrosion rate ing, which involves transferring of H2S from a gaseous
(ppm) (millinch/year) phase (feed) into a liquid phase (solvent). Figure 1 illus-
0 0.046 trates the flow diagram of the conventional absorption-
900 0.724 stripping of an industrially acclaimed Benfield process. In
1550 2.29 this process, the sour gas enters the absorber at high pres-
2900 9.12
sure (5–205 atm) and low temperature (35–50°C), whereas

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 A.D. Wiheeb et al.: Acid gas removal technologies 451

Condenser
Sweet gas
Acid gas
H2S+CO2

Lean Reflux
Makeup Rich
solvent drum
water solvent

Pump

Regenerator
Absorber

Sour gas Vapor

Steam

Reboiler
Liquid
Condensate

Rich
solvent
Lean
solvent
Pump

Figure 1 Flow diagram of conventional absorption-regeneration process for acid gas removal.

the rich solvent enters the regenerator at high temperature butylamino-2-ethoxyethanol (TBEE), to get the required
(115–130°C) and low pressure (1.4–1.7 atm). The absorption effect and performance. For instance, the primary or sec-
process occurs either physically or chemically. Sodium ondary amine has higher reaction rates, whereas MDEA
hydroxide (NaOH) is used as the solvent to dissolve H2S has a higher equilibrium capacity. Blending the solvents
and CO2 (Brettschneider et al. 2004). Other type of sol- together offers the combined effect of high reaction rate
vents such as sodium hypochlorite (NaClO) (Turpin et al. and high equilibrium capacity (Mandal and Bandyopad-
2008), sodium or potassium carbonate (Na2CO3 or K2CO3) hyay 2005, Lu et al. 2006, Dubois and Thomas 2010). It
(Faiz and Al-Marzouqi 2010), monoethanolamine (MEA) is also not uncommon to mix three different types of
(Godini and Mowla 2008), diethanolamine (DEA), di- solvents to achieve the desired effect. The application of
isopropanol amine (DIPA) (Mandal and Bandyopadhyay multisolvent system, however, can involve highly complex
2005), and methyldiethanolamine (MDEA) (Su et al. 2010) chemical reactions, making the rich solvent difficult to
can also be used, but their absorption performance may regenerate.
vary. The reaction of CO2 with the aqueous solvents gives
Among these solvents, MEA and DEA or a combina- bicarbonate as the final products:
tion thereof are mostly used in the sweetening of sour
CO2 +R1 R2 NH+H 2O ↔ R1 R2 NH 2+ +HCO3- (1)
natural gases and refinery off-gases. However, aqueous 
MDEA is preferred in the industry due to its substan-
tially high absorption capacity, low energy requirement With a three-solvent mixture,
for regeneration of the rich MDEA, low vapor pressure,
CO2 +R1 R2 R3 N+H 2O ↔ R1 R2 R3 NH + +HCO3- (2)
and low level of corrosion (Lu et al. 2006, Su et al. 2010). 
MDEA has also been used together with a primary or sec-
ondary amine, such as MEA, DEA, DIPA, diglycolamine The reaction of H2S with MDEA and another solvent
(DGA), 2-amino-2-methyl-l-propanol (AMP), and 2-tertiary involves a proton transfer (Lu et al. 2006):

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452 A.D. Wiheeb et al.: Acid gas removal technologies

H 2 S+R1 R2 NH ↔ R1 R2 NH 2+ +HS- (3) short small-diameter tube in the co-current mode. A short

time contactor device is used to enhance the absorption.
With a three-component mixture, The conventional absorption apparatus for the acid
gas removal can be in the form of packed column, spray
H2S+R1R2R3N↔R1R2R3NH++HS-(4)
column, bubble column, wetted wall columns, and tray
Generally, aqueous NaOH is selected due to its avail- towers. The packed column is the most effective, economi-
ability and inexpensiveness, but it is known to be nonre- cal, and widely used in the petroleum and gas industries,
generable for the acid gases (H2S and CO2). As such, the use although there are problems involving foaming, flooding,
of NaOH solution is usually applied when the gas contains high-pressure drop, and large investment cost (Jefferson
small volume of H2S (Brettschneider et al. 2004, Mamrosh et al. 2005, Mandal and Bandyopadhyay 2005, Turpin
et al. 2008). Whereas the absorption efficiency of H2S using et al. 2008).
NaOH is reportedly high (of ∼86%), the CO2 absorption is When using packed column, the absorption effi-
less than 6% (Bontozoglou and Karabelas 1993). H2S is ciency for a mixed gas containing 1.2% H2S, 7.92% CO2,
absorbed in sodium hydroxide in the following ways: and 90.88% N2 is reportedly 99.0% to 99.8% at room con-
ditions (Lu et al. 2006). The H2S removal efficiency and
H2Saq+NaOHaq↔NaHSaq+H2O(5)
selectivity decreased from 98.6% and 99.8% to 92.8%
NaHSaq+NaOHaq↔Na2Saq+H2O(6) and 94.8%, respectively, when the absorption temper-
ature is increased from 20°C to 60°C. Other operating
Figure 2 presents the flow diagram of the selective parameters such as the gas flow rate, mole ratio of CO2/
removal process of H2S from geothermal steam with a gas H2S in the gas feed mixture, and the aqueous blend-
mixture containing 900 ppm H2S and 1% CO2 (Bontozoglou ing characteristics can also influence the absorption
and Karabelas 1993). The acid gas absorption occurs in a performance.

Sampling port

Contact
device

Steam from generator

Rotameters

Gas-mixing
tank

NaOH supply Pump Cooling

tank water
CO2

H 2S

NaOH solution Condenser

Figure 2 Flow diagram of H2S absorption process by short contact device (Bontozoglou and Karabelas 1993).

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 A.D. Wiheeb et al.: Acid gas removal technologies 453

2.1.2 Membrane contactor transfer resistance caused by the latter (Mansourizadeh

and Ismail 2009, Lu et al. 2010).
Membrane contactor has been introduced lately to Figure 4A shows the favorable mode (dry or nonwet-
enhance absorption performance and overcome prob- ted) in which the gas completely fills the pores and no
lems such as foaming, unloading, flooding, and corrosion absorbent wets the membrane pore wall. To avoid the for-
typically observed in the conventional absorption process mation of bubbles, the pressure in the gas side is prop-
(Wang et al. 2004c, Zhang and Tong 2006, Rajabzadeh erly controlled so that it is slightly lower than the pressure
et al. 2009, Mansourizadeh et al. 2010). Membrane is used in the liquid side. The gas-liquid interface is preferably
to serve as a barrier between the liquid phase and the gas located in the liquid side of the hydrophobic membrane
phase that allows the transport of special species of gas pore mouth (Li et al. 1998, Li and Chen 2005, Boucif et al.
into the liquid phase without dispersing one phase into 2008, Mansourizadeh and Ismail 2009, Lu et al. 2010).
the other (Gabelman and Hwang 1999, Lu et al. 2010). Figure 4B shows the wetting mode in which the absor-
Usually, hollow fiber membrane is used in acid gas bent fills the pores. This happens because the pressure
removal and the separation driving force is concentration in the gas side is lower than the pressure in the liquid
gradient. This is different from microfiltration, ultrafiltra- side. Increasing the pressure in the gas side is therefore
tion, and reverse osmosis, where the driving force is typi- important to sustain dry mode condition, prevent forma-
cally pressure difference. In the acid gas removal, the gas tion of liquid drops in the gas phase, and achieve the pre-
flows inside the tube, while the liquid solvent flows in ferred gas-liquid interface at the membrane pore mouth.
the shell side of module or vice versa and in co-current or Although completely dry mode is desirable, it may not
counter-current configuration. be achieved in practice because some types of absorbent
Figure 3 shows a schematic diagram of a hollow fiber solutions such as alkanolamines have the affinity for the
gas-liquid membrane contactor module in a parallel flow membrane surface (Faiz and Al-Marzouqi 2009) and the
mode. Hollow fiber membrane is frequently selected as operational requirements are not conducive to dry mode
the contactor due to its high contact surface area of about establishment (Gabelman and Hwang 1999, Lu et al. 2008,
8000 m2/m3 (Boucif et al. 2008). The flow resistance in the 2010). By making the membrane more hydrophobic,
membrane can be reduced further by reducing its thick- wetting can be minimized. The wetting of microporous
ness so that the gas permeability through the membrane membrane contactor is influenced by such factors as the
can be increased. The absorption performance of H2S transmembrane critical pressure and chemical reaction
and CO2 using hollow fiber membrane contactor varies, between the membrane and absorbent solution.
depending on the operating factors and other parameters, The transmembrane critical pressure difference,
which has been reported rather extensively elsewhere (Li ΔP, can be determined from the Laplace-Young equation
et al. 1998, 1999, Wang et al. 2002, 2004c, 2005, Dindore (Franken et al. 1987, Kim and Harriott 1987),
et al. 2005, Zhang et al. 2006, 2008, Atchariyawut et al.
ΔP = 2γcosθ/r,(7)
2007, Al-Marzouqi et al. 2008, Delgado et al. 2009, Faiz
and Al-Marzouqi 2009, 2010, 2011, Rajabzadeh et al. 2009). where γ is the liquid absorbent surface tension, θ is the
Another flexible feature is observed when membrane contact angle, and r is the pore radius.
contactor is used in the acid gas removal. The membrane The wetting or partial wetting of microporous mem-
can be made hydrophilic or hydrophobic, highly porous brane contactor occurs when the pressure at the liquid
or dense, depending on the type of its precursor materi- absorbent stays high for a long operation time (Malek
als and preparation technique. However, it is important et al. 1997) and/or due to the potential chemical reaction
that the membrane pores be totally filled with gas instead between the membrane and absorbent solution (Mavroudi
of liquid absorbent (wetting mode) to reduce the mass et al. 2006).

Gas in Gas out

Liquid in Liquid out

Figure 3 A parallel-flow hollow fiber gas-liquid membrane contactor.

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454 A.D. Wiheeb et al.: Acid gas removal technologies

A NaOH solution (Li et al. 1998). For gas stream containing

Liquid
Gas-liquid higher concentration of H2S (1200 ppm), membrane con-
Pore interface
tactor made from polyvinylidene fluoride (PVDF) is found
Gas Gas to be more suitable than polypropylene (PP) (Li et al. 1999,
2000). Figure 5 shows the flow diagram of H2S gas removal
using PVDF membrane contactor.
Although PVDF membrane contactor has demon-
Non-wetting mode
strated promising result, it does not live up to the industrial
application due to the fact that the polymeric membrane
B Liquid
Gas-liquid does not tolerate high-temperature off-gases containing
Pore interface H2S. The gas must be cooled down first before absorption
Gas Gas process can proceed. However, this means more energy
will be consumed. This problem can be solved by using
ceramic membrane contactor. Despite having a great
potential, the ceramic membrane suffers from wetting
Totally wetting mode
phenomenon that decreases the absorption efficiency.

C Liquid Gas-liquid
Pore
interface 2.2 Adsorption
Gas Gas
2.2.1 Carbonaceous adsorbents

An activated carbon is commonly used as an adsorbent

Partial–wetting mode material in the adsorption of gases and vapors. Acti-
vated carbon has high specific surface area of more than
Figure 4 Operation mode in hollow fiber membrane contactor: (A) 1000 m2/g. The surface area, the pore volume, and the
nonwetting mode, (B) totally wetting mode, and (C) partial-wetting
surface chemistry promote many catalytic reactions. Car-
mode (Kim and Harriott 1987).
bonaceous materials are usually obtained from different
organic precursors, such as peat, wood, coconut shells,
The level of absorption is related to the surface tension and petroleum pitch. The carbon materials are activated
of the absorbent. Knowledge of the surface tension is very physically and chemically. In physical activation, the pre-
important because low surface tension can cause wetting cursor is carbonized at 700°C–1000°C and later activated
to progress over time and result in decreased absorption by steam or CO2 at 800°C–1000°C. In chemical activation,
rate (Wang et al. 2004c, 2005, Atchariyawut et al. 2007).
The surface tension of absorbent solution is increased by
adding organic components or more alkanolamine solu-
tions (Mansourizadeh and Ismail 2009). Mass flow meter
The use of MEA, AMP, DEA, and MDEA reportedly
increases the wetting and decreases the absorption rate
(Wang et al. 2004c, 2005, Atchariyawut et al. 2007). Car-
bonate absorbent solutions such as aqueous carbonate,
H2S or SO2 in N2

HFM module

bicarbonate, and hydroxide can be a good alternative

when the other absorbents fail to function due to the unfa-
Continuous toxic
vorable wetting behavior (Li et al. 1998, 2000, Wang et al.
Rotameter

Gas monitor
2002, Dindore et al. 2005, Boucif et al. 2008, Faiz and Al-
Marzouqi 2010). Feed gas
Beside absorbent wetting behavior, the membrane NaOH
solution
material can also affect the absorption performance. For Mass flow Pressure
controller gauge
example, a hollow fiber membrane made from polysul-
fone absorbs H2S better than polyethersulfune from gas Figure 5 Flow diagram of H2S gas removal process by hollow fiber
stream containing 16–24 ppm H2S balanced with N2 using membrane module (Li et al. 2000).

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 A.D. Wiheeb et al.: Acid gas removal technologies 455

chemicals such as phosphoric acid, zinc chloride, or Sodium hydroxide reacts with H2S to form HS- ion,
potassium hydroxide are mixed with the precursor after which is influenced by increasing the carbon pH value.
carbonization (Bansal et al. 1988, Manahan 1994, Bagreev An elemental sulfur or sulfuric acid is produced from HS-
et al. 2001). The performance of carbon materials in the ion oxidation (Bagreev and Bandosz 2002). The following
adsorption depends largely on the properties of the reactions have been proposed on the surface of the caustic
adsorbed molecules. Typically, microporous carbons are impregnated carbon (Bagreev and Bandosz 2004):
used for the sorption of light gases, whereas carbons with
NaOH+H2S→NaHS+H2O(8)
wide pore size distributions are useful for larger organic
molecules (Leon et al. 1992, Adib et al. 2000). 2NaOH+H2S→Na2S+2H2O(9)
Unactivated or neutral carbon does not adsorb H2S, as
expected, because its microporosity or active site does not NaHS+0.5O2→S+NaOH(10)
develop (Bandosz 1999). The adsorption is usually high
if the activated carbon has small pore size (Bagreev and Na2S+0.5O2+H2O→S+2NaOH(11)
Bandosz 2004, Feng et al. 2005), so that stronger interac-
tion between H2S and carbon can take place (Adib et al. 2NaOH+H2SO4→Na2SO4+2H2O(12)
2000). The activated carbon also utilizes van der Waals
The reactions are exothermic and the heat may
forces to draw the H2S out of the gas mixture and attach
damage the adsorptive site of the carbon. When H2S
it to the carbon.
adsorption performance using activated carbon impreg-
The surface chemistry of the activated carbon can
nated with different alkaline solutions, such as NaOH,
change progressively during adsorption or catalytic reac-
KOH, K2CO3, and Na2CO3, is compared such as shown in
tions (Adib et al. 2000). To improve the catalytic proper-
Figure 6, NaOH outperformed the other alkaline solutions,
ties of an activated carbon, impregnation with alkaline
despite the weakness described earlier (Tsai et al. 1999).
chemicals such as sodium or potassium hydroxide, salts
An activated carbon modified by impregnation with
(sodium or potassium carbonate or iodide), potassium
urea is also used for H2S adsorption. It is reported that the
permanganate, ammonia, urea, and nitric acid, oxida-
basic nitrogen groups in the urea promote high adsorption
tion, and introducing heteroatoms other than oxygen are
capacity and yield. H2S is oxidized primarily to water-solu-
often performed (Tsai et al. 1999, Adib et al. 2000, Cal et al.
ble sulfur components due to the direct contact of HS- ions
2000, Bagreev and Bandosz 2004, Seredych and Bandosz
with largely dispersed basic nitrogen groups (Adib et al.
2009).
2000). The H2S oxidation is reportedly influenced by the
The modifications of the activated carbon surface
local pH and surface chemistry. When the carbon surface
promote reactive adsorption and chemical bonds forma-
is very acidic (characterized by lower pH), the yield of
tion with the species to be adsorbed. Activated carbons
water-soluble products is higher, but the total sorption
remove H2S through dissociation of H2S into HS- ion. The
latter is oxidized either by oxygen from air or by electrons
and received by a catalyst-like iron oxide (Bandosz 2006,
Seredych and Bandosz 2009). The basicity of carbon 20
surface comes from oxygen and/or nitrogen function-
alities (Bandosz 2006), caustic materials (Bagreev and
Bandosz 2000), alkali metal salts (Przepiorski and Oya 15
Adsorption capacity

1998), or oxides (Graham and Cheng 2005).

Activated carbon impregnated with caustic materials
(mg/g)

10
such as NaOH and KOH to reduce the adsorbent porosity
and increase H2S adsorption has been widely used. The
adsorbent porosity can also be reduced if the sorbent is 5
impregnated with metal hydroxide solutions (Nguyen and
Bandosz 2005). Another method to increase H2S adsorp-
tion and to oxidize it directly to sulfur is through the 0
AC KOH-AC K2CO3-AC NaOH-AC Na2CO3-AC
impregnation of carbons with oxidants such as potassium
iodide or permanganate. However, the physical sorption Figure 6 Adsorption capacity of H2S on activated carbon and
capacity of carbon may be decreased due to additive com- alkaline activated carbon in a single-component adsorption system
pounds that block the micropore opening (Bandosz 1999). (Tsai et al. 1999).

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456 A.D. Wiheeb et al.: Acid gas removal technologies

capacity is low. For a small increase in an average pH (half Table 4 Sorbents metal oxides used in the desulfurization process
a unit), a 15-fold higher capacity is obtained (Adib et al. (Dolan et al. 2012).
1999). Table 3 summarizes the H2S breakthrough capacity
Sorbent Temp. range Sorbents Temp. range
on carbon at different pH values.
required for more speciation of speciation
than 98% H2S at 2.0 MPa (°C)
sorption (°C)
2.2.2 Metal oxide adsorbents
Cu2O 0–800 Cu2S(s) 200–1130
Cu2S(l) 1130–1600
The removal of H2S at high temperature has received much NiO 40–630 Ni3S2(s) 200–790
attention due to its potential in reducing H2S concentra- Ni3S2(l) 790–1210
tion down to 10 ppm while avoiding a heat loss (Ko et al. CoO 110–620 Co9S8(s) 200–870
FeO 180–200 FeS2(s) 200–260
2005). There are many metal oxides that can be used to
FeS(s) 260–1100
adsorb H2S from gas mixtures at high temperature. Exam-
MnO 340–580 MnS(s) 200–1520
ples of such oxides include FeO, Cu2O, MnO, ZnO, CoO, 1170–1350 MnS(l) 1520–1600
NiO, and MoO, alkaline earths (CaO, SrO, and BaO), and ZnO 90–990 ZnS(s) 200–1220
alkalis (Li2O, K2O, and Na2O). Table 4 enlists some of these MoO 90–660 MoS2(s) 200–790
metal oxide sorbents used in desulfurization. H2S sorption Li2O 1130–
Na2O 1140–1330
is high (98%) on a metal oxide even at high temperature.
K2O 1140–1240
Numerous refractory oxides, such as SiO2, Al2O3, Y2O3, CaO 1010–1520
SrO 980–
BaO 1030–
Table 3 pH values of carbon surfaces and adsorption capacity of
H2S (Leon et al. 1992).

Sample Initial pH H2S breakthrough

ZrO2, and TiO2, do not adsorb H2S, but they can be used
capacity (mg/g carbon) as inert support species in mixed-oxide sorbents (Dolan
et al. 2012). The desulfurization on the metal oxide can
N 7.7 96
N1 4.5 48
occur with the formation of a solid or liquid phase that
N2 3.6 28 contains the sorbent metal and sulfur. Generally, the
N-A1 1.9 2 ­desulfurization reactions can be represented as follows:
N-A2 2.1 28
S 6.9 112 MO+H2S→MS+H2O(13)
S1 4.6 15
where MO and MS are the metal oxide and metal sulfide,
S2 3.7 12
S-A1 2.1 22 respectively.
S-A2 2.2 18 Iron oxide is reportedly used to adsorb H2S (100 ppmv)
W1 4.4 295 in syngas and at temperature below 500°C. Above the
W2 4.0 17 reduction temperature, carbide formation reduces the
W3 5.6 230
adsorption performance (Gasper-Galvin et al. 1998).
W3-Al 1.9 5
W1-H90 9.1 140
Iron oxide is cost effective but nonregenerable. As such,
W2-H90 6.0 92 huge volumes of sulfide can go to waste (Xie et al. 2010).
W1-H45 6.3 65 Other studies have shown that iron is only appropriate
W2-H45 3.1 3 for d
­ esulfurization in a moderate temperature range. As
RB-4 11.2 112 a result, it is mostly used in combination with zinc and
V 6.8 121
manganese oxides to enhance the sorbent stability at
R 8.6 69
higher temperature (Zhao et al. 2008).
N, S, W1, W2, W3, RB, V, and R refer to carbon. Beside iron, zinc oxide is also used as H2S adsorbent
S and N carbons were oxidized with nitric acid and ammonium at high temperature of about 400°C with almost complete
persulfate. Digit “1” stands for nitric acid and “2” for ammonium
removal of 10,000 ppmv H2S. The activity of ZnO-based
persulfate.
N-A1, N-A2, S-A1, S-A2, and W3-A1 carbons treated with hydrochloric
sorbents is reduced during the regeneration due to the
acid. sintering, reduction of the active metal into metallic ele-
W1-H45 and W2-H45 carbons treated with N2 at 450°C for 1 h. ments, and sulfate formation, which is similar to the other
W1-H90 and W2-H90 carbons treated with N2 at 900°C for 1 h. metal-based sorbents (Ko et al. 2004, Park et al. 2005b,

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 A.D. Wiheeb et al.: Acid gas removal technologies 457

Zhao et al. 2008). ZnO has high volatility and strength that the core reaction (Fenouil and Lynn 1995). Thus, a large
is necessary for making granular sorbents. Zinc ferrite and surface area is necessary to enhance the conversion. This
titanate are reportedly used to decrease zinc volatilization can be achieved by grinding the particles or dispersing
losses, so that better regenerability of zinc can be obtained them on a porous support.
(Slimane and Abbasian 2000). Nevertheless, zinc titanate The regeneration process of the sorbent materials
sorbents demonstrate a steady decline in the sulfur capac- is economically important. In general, the regeneration
ity with further cycling (Mojtahedi and Abbasian 1995). reaction is of the form:
H2S is reportedly removed from a gas mixture contain-
MS+1.5O2→MO+SO2(14)
ing 1.5% H2S, 11.7 H2, 9.6% CO, and 5.2% CO2 balanced with
N2 using mixed oxide of zinc, cobalt, nickel, and titanium During regeneration, air-N2 for Cu-Cr (Su et al. 2010),
dioxide with an inorganic binder bentonite to make Zn-Ti- air-steam for Cu-Mo-Mn (Gasper-Galvin et al. 1998), and
based sorbents. These sorbents give good sulfur removal 2–6% O2 in N2 for ZnTi (Slimane and Abbasian 2000) are
capacities at 480°C, without deactivation even after 15 applied. The most important factor in the regeneration is
cycles of the desulfurization and regeneration processes. the avoidance of sulfate formation, because it is not regen-
The nickel and cobalt serve as active sites in the sorbents erable. The disadvantage of H2S removal by means of the
throughout the desulfurization process. In addition, the adsorption is that the stoichiometric reaction between
sorbent structure is stabilized to avoid any change in the metal oxide and H2S may require a large quantity of
sorbents physical properties. The regeneration ability of sorbent. The exothermic reaction during sorbents regen-
the Zn-based sorbents is increased by nickel addition that eration produces pollutant such as SO2, which limits the
prevents SO2 slippage (Jun et al. 2001). use of this technique in a large scale.
Copper-based sorbents have been increasingly used Maintaining high attrition resistance and high H2S
to adsorb H2S despite its propensity to reduce to the metal- sorption capacity with fast reaction kinetics is another
lic form in the syngas environment and agglomerate technical challenge in the development of sorbents for
(Dolan et al. 2012). The copper-based sorbents are devel- commercial application. Developing highly durable
oped to adsorb H2S down to 5 ppmv in a temperature range sorbent (usually gauged by the number of cycle it can pass;
of about 550°C–650°C. From thermodynamic standpoint, the higher, the better) with high sorption capacity (the
chromia (Cr2O3) is preferred for the stabilization of copper amount of sulfur removed) is often faced with a dilemma
oxide (Cu2O) against a total reduction to the elemental of choosing between sorbent mechanical strength and
copper when it is in contact with the fuel gas in the des- sulfur removing (sorption) capacity. Although mechani-
ignated temperature range (Abbasian and Slimane 1998). cally durable sorbent (high attrition resistance) ensures
The reactivity and stability of Cu2O increase when it is good regeneration/recycling ability, it usually exhibits low
doped with manganese-based sorbents, but an excessive adsorption capacity due to its less active surface. This is the
thermal sintering is also observed (Alonso et al. 2000). reason most of metal oxides are embedded with different
Limestone has been used in hot desulfurization elements to increase its sorption capacity at reduced dura-
because of its inexpensiveness. Limestone decomposes to bility. Microanalysis of the sorbent after repeated cycles
lime at temperature above 800°C. For this reason, lime- and report on the effort to improve its sulfur recovery at
stone is added directly to a gasifier to be decomposed into increasing cycle if readily available can be very interesting.
CaO, whereas limestone is added in the postgasification Attrition resistance is generally represented by a
to remain as carbonate. The sulfidation of granular lime- value (an index) that indicates the tendency of the sorb-
stone can occur when it is added with coal in the gasifier ents to chip to smaller particles or dust at 10 slpm over 5 h
feed. The intrinsic trouble of this approach is that the addi- of operation. For a commercial grade sorbent, the attrition
tion of CaO can interfere with slag in the gasifier. Lime- index (AI) of ≤ 20% is required (Gupta et al. 1998). High
stone is frequently added as a flux in slagging gasifiers to attrition resistance (low AI) is usually obtained by increas-
decrease the slag viscosity to permit tapping. The outer ing calcination temperature during sorbent preparation.
wall of limestone is protected by the slag layer in some For example, spherically shaped zinc-based sorbents
gasifiers, but there are some restrictions with the amount prepared from spray drying reportedly exhibit AI of mere
of limestone to the feed before this protective function is 4.8% when calcination temperature of 850°C is used. The
lost (Borgwardt et al. 1987, Abbasian et al. 1990). The con- sorbents show reasonably consistent sorption capacity
version of limestone particles having diameters equal or and regenerability without SO2 slippage after repeated
larger than 15 μm is achieved at about 10% due to the for- cycles in a fluidized reactor, although reduction of BET
mation of sulfide, which coats the particles and prevents surface area is observed (Ryu et al. 2002).

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458 A.D. Wiheeb et al.: Acid gas removal technologies

2.3 Conversion technology converts H2S into two process steps: thermal oxi-
dation and catalytic reaction (Sassi and Gupta 2008).
2.3.1 Claus process In the thermal oxidation, one-third of H2S is partially
oxidized with air into SO2 in furnace operating at high
Claus process is a patented technology for converting temperatures (1300–1700 K),
gaseous H2S into elemental sulfur. The process is carried
H2S+3/2O2→SO2+H2O ΔHr = -518 kJ mol-1(15)
out in a sulfur recovery unit (SRU). Claus process produces
sulfur from H2S present in the natural gas, specifically from The H2S cracking rate is insignificant at tempera-
the side-product sour gases, refining petroleum crude oil tures less than 1000°C and at residence times less than
and other industrial processes. Sulfur production from H2S 0.5 s (Hawboldt et al. 2000). At longer residence time and
is an important industrial process. It is needed to meet the temperature of less than 950°C, the overall conversion of
strict environmental laws for H2S emissions (Eow 2002). H2S is still low. As a result, the reaction furnace must give
Claus process was developed in 1883 (Claus 1883) and con- optimum temperature and residence time to obtain the
siderably modified in the 1930s (Baehr 1938), but the most exit ratio of H2S to SO2 of 2:1 (Monnery et al. 2000). The
important enhancements are not seen until the 1950s. furnace products are sulfur dioxide, water, and unreacted
This technology has been further advanced to increase H2S. The sulfur dioxide formed in the furnace reacts with
the overall sulfur recovery from 90% to 92% to the level of H2S in the furnace to produce sulfur according to the reac-
98–99% of inlet sulfur (Laperdrix et al. 2000, Ledoux et al. tion below (Sassi and Gupta 2008):
2000, Mora 2000). Most of the Claus process feed gases
2H2S+SO2→3/2S2+2H2O ΔHr = +47 kJ mol-1(16)
come from the absorption units containing H2S, CO2 and
H2O as the main components and N2, NH3, and hydrocar- The desired reactions occurring in the furnace produce
bons as secondary components (Laperdrix et al. 2000). sulfur and decompose pollutants (Kaloidas and Papayan-
Figure 7 shows the schematic of Claus process. H2S is nakos 1989, Hawboldt et al. 2000, Monnery et al. 2000).
absorbed from the host gas stream using an amine extrac- On the contrary, the undesired side reactions produce
tion and later is fed into the Claus unit. The waste heat boiler more pollutants and reduce the recovery of sulfur (Basu
and the furnace are usually treated as a one unit. Claus et al. 1996).

Recycle from Tail-Gas unit

To tail-gas unit
Acid gas
feed Air Air
Preheater(1) Preheater(2)

SWS
feed
Steam

Reaction First Second

Air Waste heat
fumace reactor reactor
boiler

Boiler feed
water
Condenser (1) Condenser (2)

Sulfur pit

Figure 7 Flow diagram of two-stage Claus process (Eow 2002).

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 A.D. Wiheeb et al.: Acid gas removal technologies 459

The exit furnace products are cooled from 1188°C 1968). The use of SiC and nickel as a support increases the
to 154°C into the waste heat boiler (typically a shell and activity, selectivity, and stability of the catalyst in the pres-
tube heat exchanger) to condense the sulfur and produce ence of water even at high sulfur loading of > 60%. The
low-pressure steam for the Claus catalytic stages (Nasato sulfur produced on the hydrophilic part of the active phase
et al. 1994, Monnery et al. 2000). Two reactions might take particles is removed mechanically by water and trans-
place in the waste heat boiler tubes (Eow 2002): ported to the hydrophobic part of the support, leaving the
active particles free for reactions (Monnery et al. 1993).
2H2+S2↔2 H2S(17)
Most of the sulfur (S8) produced in the catalytic reac-
2CO+S2↔2COS(18) tion stage occurs exothermically, whereas, in the thermal
oxidation stage, S2 is the main product and the reaction is
In the catalytic reaction, the product from the Claus endothermic. Other sulfur components are possibly pro-
furnace contains unreacted H2S (∼70% from the inlet H2S), duced in smaller quantities. The overall reaction for the
which is reacted with the formed SO2 in the furnace at Claus process is (Sassi and Gupta 2008)
lower temperatures (470–620 K) over a catalyst to form
3H2S+1.5O2→3/nSn+3H2O ΔHr = -626 kJ mol-1(22)
more sulfur (Sassi and Gupta 2008):
The condensed sulfur is separated from the gas
2H2S+SO2↔3/8S8+2H2O ΔHr = -108 kJ mol-1(19)
stream by draining it into a container. Liquid sulfur can
This reaction is in equilibrium in the presence of a have high viscosity at high temperature in similar manner
catalyst (Puchyr et al. 1996, Eow 2002). The overall H2S polymerization take place at about 430 K. The tempera-
conversion can reach 99.5% when using fluidized-bed ture of the condensed sulfur must be carefully monitored
reactors. When the equilibrium conversion is reached, it is to avoid polymerization and blockage of pipes used in the
possible to use a FBR that maintains the sulfur dew point process (Sassi and Gupta 2008). Usually, 3–5% of H2S is
temperature. Nonpromoted spherical activated alumina not converted to sulfur in Claus process due to the thermo-
is reportedly used as the catalyst in the Claus process to dynamic limitations.
increase the rate of the equilibrium reaction. Recently, the environmental protection law requires
Elemental sulfur can be produced directly from the that the remaining gas from the Claus unit (called tail gas)
reaction of SO2 with H2S using Co-Mo/Al2O3 at a temper- be further treated. Different commercial tail gas treatment
ature lower than that is usually used (Paik and Chung (TGT) processes have been developed and deployed. The
1995). Carbon disulfide (CS2) and carbon oxysulfide (COS) processes involve an absorption step, in which the tail gas
are produced in the Claus process and are typically con- is fed to the alkaline bath to absorb the unreacted H2S. Dif-
verted to H2S and CO2 in the catalytic reactors according to ferent commercial processes based on adsorption, absorp-
the following reactions: tion, wet oxidation, and dry catalytic processes have also
been used to treat H2S in the tail gas from the Claus plant
COS+H2O→H2S+CO2(20)
or any other emission sources (Eow 2002).
CS2+2H2O→2H2S+CO2(21)

The activity of alumina and titania catalysts is reduced 2.3.2 Selective catalytic oxidation
in the presence of O2 in the mixture of CS2-H2O due to sulfa-
tion [Al2O3 converted to Al2(SO4)3]. Titania has better resist- The selective catalytic oxidation of H2S into elemental
ance to the sulfation than alumina at operating temperature sulfur is one of the treatment methods employed for the
of about 320°C (Laperdrix et al. 1998). However, alumina removal of H2S from the Claus process tail gas (Pi et al.
catalyst is effective at a temperature that is above the sulfur 2004, Lee et al. 2006). The catalytic oxidation of H2S can
dew point (George 1974, Chun et al. 1998). ­Nevertheless, be performed above or below the sulfur dew point (180°C).
thermodynamics favors an operation at low temperature to The super-Claus process developed in 1985 and continu-
increase the reaction efficiency (Ledoux et al. 2000). ously improved afterwards can attain an overall desulfuri-
At low temperature, the produced sulfur deposited in zation efficiency of about 99.5% at 240°C. The elemental
the pore reduces the pore volume and surface area and sulfur produced is condensed outside the reactor, and the
eventually deactivates the catalyst by fouling (Ledoux catalysts used in this process are Fe and Cr supported on
et al. 2000, Mora 2000). The presence of water particularly alumina or silica (Berben and Geus 1989, Keller et al. 1999,
at low temperature adds to the adversity by reducing the Lee et al. 2005a). The doxosulfreen process (Elf-Lurgi)
catalyst activity via the hydrolysis of COS (Landau et al. operates at temperatures below the sulfur dew point

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460 A.D. Wiheeb et al.: Acid gas removal technologies

(between 90°C and 140°C) in an adiabatic system. The H2S oxidation (in an adiabatic mode, 60°C increase per per-
elemental sulfur produced in this process remains on the centage of H2S converted) leads to formation of hotspots on
catalyst bed. The catalysts are regenerated by heating the the catalyst and assist in forming of SO2. This undesirably
reactor in such a way that the sulfur liquefies and flows leads to decreased selectivity (Nguyen et al. 2009).
outside the catalytic bed. Copper catalyst supported on Catalytic oxidation of H2S into elemental sulfur by
modified alumina is reportedly used in the process in a oxygen using activated carbons as catalysts or catalyst
discontinuous mode of reaction/regeneration with an support in a wide range of temperatures (20–250°C) has
overall sulfur removal efficiency of about 99.9%. been investigated recently (Lampert 2004, Bagreev et al.
The most attractive processes that have been used 2005, Wu et al. 2005, Wang et al. 2006, Bashkova et al.
lately in the catalytic oxidation are Mobil direct oxida- 2007, 2009, Xiao et al. 2008). The drawback of carbon
tion process (MODOP) and super-Claus process. The direct catalyst is that the oxidation of sulfur to SO2 leads to COS
oxidation of H2S to elemental sulfur and water has high formations (Wu et al. 2005, Bashkova et al. 2007, 2009).
conversion because it is not a thermodynamically revers- These compounds hold sulfur and regeneration of the
ible reaction. In MODOP, the direct oxidation of H2S into spent carbon consumes much energy.
elemental sulfur occurs on a TiO2 catalyst with a stoichio- Alternatively, zeolites can be employed as a catalyst
metric amount of oxygen. The disadvantage of the MODOP for the catalytic oxidation of H2S by molecular oxygen (Lee
process is that the presence of water in the feed deacti- et al. 2005b, 2006). They have high sorption capacity for
vates the catalyst. In super-Claus process, H2S is oxidized low concentration of H2S. Their catalytic activity is largely
without removing water from the tail gas because Fe2O3/ dependent on the pore diameter (d) (Konshenko et al.
SiO2 catalyst resists up to 30 vol.% water vapor. Neverthe- 2001), such that
less, the super-Claus process can treat H2S concentrations
NaX (d = 0.85 nm) > CaA (d = 0.43 nm) > NaA (d = 0.36 nm)
that are below 2 vol.%. This is because it is essential to
provide a large amount of oxygen (typically 10 times the Zeolites exhibit high activity for the selective oxida-
stoichiometric amount) (Chun et al. 1998, Lee et al. 2006). tion of H2S when operating under water-free conditions
The MODOP and super-Claus processes can be described (Lee et al. 2005b), but they become deactivated by strong
by the following four reactions. The main reaction is the adsorption of water vapor. When zeolite is mixed with a
irreversible oxidation of H2S to sulfur [reaction (23)], and the metal oxide such as V2O5, the activity and selectivity of the
rest are side reactions (24) and (25) and the reversible Claus catalytic oxidation are increased under water conditions
reaction (26) (Keller et al. 2001, Pi et al. 2004), due to the improved structure (Lee et al. 2006).
Although alumina and silica can be used as catalysts
H2S+1/2O2→1/nSn+H2O(23)
for direct oxidation of H2S into sulfur, the results report
1/nSn+O2→SO2(24) low activity and selectivity (Wu et al. 2005, Lee et al.
2006). This is due to alumina surface that suffers fast
H2S+3/2O2→SO2+H2O(25) deactivation under the reaction medium effect. The activ-
ity and selectivity of alumina and silica can be increased,
2H2S+SO2↔3/nSn+2 H2O(26) however, if they are impregnated with iron, copper, zinc,
silver, cadmium, chromium, molybdenum, cobalt, tung-
The catalyst used in the direct oxidation is inert to sten, platinum, or palladium compounds (Lee et al. 2006).
hydrocarbon and can selectively convert H2S into elemen- In addition to the catalysts discussed earlier, iron oxide
tal sulfur while preventing the formation of SO2 and other is another promising catalyst for the direct oxidation of H2S
byproducts under low oxygen concentration (Konshenko to elemental sulfur. Figure 8 illustrates the flow diagram of
et al. 2001). The major problem of the catalyst used in the the direct oxidation process in a FBR containing iron oxide.
catalytic oxidation of H2S is its high activity that leads to The direct oxidation reaction occurred in a FBR, at high
the formation of SO2 reduces the selectivity of the reaction space velocity (1000–4000 h-1), temperature (200–275°C),
(23) and the catalyst stability. O2/H2S ratio of about 2.5, and in the presence of water vapor
Most of the oxide support used in the H2S oxidation (20 vol.%) (Keller et al. 2001, Nguyen et al. 2009). At tem-
processes is sulfated with time in the existence of sulfur and perature below 200°C, the sulfur produced remains in the
steam. This reduces the activity and subsequently leads to reaction zone and is not completely removed, whereas, at
the catalyst destruction. The selective oxidation of H2S with temperature higher than 275°C, sulfur dioxide is formed in
oxygen is necessary to circumvent the SO2 formation (Uhm the products, resulting in decreased oxidation selectivity
et al. 1999). In addition, the high exothermic nature of the (Konshenko et al. 2001). The high H2S conversion (100%)

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 A.D. Wiheeb et al.: Acid gas removal technologies 461

MFC
H2S

Vent
MFC
O2

MFC
Thermocouple
He

CPG

Steam generator

Figure 8 Schematic diagram of the apparatus used for the direct oxidation of H2S (Nguyen et al. 2009).

and selectivity into elemental sulfur (90–95%) is obtained to apply aqueous, homogeneous, and nontoxic iron che-
using Fe2O3/SiC (Keller et al. 2001, Nguyen et al. 2009). The lates of ethylenediaminetetraacetic acid (EDTA) or related
high selectivity is due to the capability of the SiC support to ligands followed by redox couple that is more inclined
resist heat transfer from the active site to the catalyst body. toward the use of Fe(III)/Fe(II) system. This system has
It also prevented the formation of hotspots, which have been used since its inception and continuously upgraded.
adverse effect on the selectivity. Other redox couples such as As(V)/As(III), V(V)/V(IV),
Table 5 summarizes the reaction conditions using dif- and Co(III)/Co(II) can be also used as intermediates in the
ferent catalysts in direct oxidation of H2S into elemental LRSR process, but the iron redox couple Fe(III)/Fe(II) is
sulfur. The reactions occur with or without water vapor preferred due to its favorable oxidative potential toward
and the reaction temperature ranges from 60°C to 300°C. sulfide (Hua et al. 2001, Heguy and Nagl 2003).
An interesting effort in LRSR has been made recently.
A fuel cell-assisted iron redox (FCIR) process for simul-
2.3.3 Liquid redox sulfur recovery
taneous sulfur recovery and electricity generation from
aqueous sulfide has been introduced (Zhai et al. 2002).
A liquid redox sulfur recovery (LRSR) process utilizes oxi-
It is based on LRSR with a fuel cell extension from the
dation of H2S into elemental sulfur by means of an oxidiz-
oxidizing unit to make the system more sustainable and
ing solution and a metal oxide couple (DeBerry 1997). In
commercially attractive. The oxidizing reactor recovers
the early LRSR process, iron oxide particles (catalysts) sus-
the sulfur from sulfide, whereas the fuel cell regenerates
pended in Na2CO3 solution were used to oxidize H2S into
Fe(III) from Fe(II). During the process, electricity is gener-
elemental sulfur in the following ways (Hua et al. 2001):
ated and harnessed (Figure 9).
H2S+H2O→H3O++HS-(27) The main reactions take place in the oxidizing reactor
where sulfide ion (S2-) reacts with hydrogen ion (H+) to
Fe2O3+3HS-→Fe2S3+3OH-(28) form H2S in acidic solution. The H2S is oxidized to elemen-
tal sulfur by Fe3+, which is then reduced to Fe2+. In the fuel
2Fe2S3+3O2→2Fe2O3+6S(29) cell, Fe2+ is oxidized back to Fe3+ in the presence of excess
acid. The complete reactions can be expressed as follows:
Although this process has been applied commercially
In the oxidizing unit:
such as in American Ferrox process, the German Gluud
process, and the British Manchester process, the formation S2-+2H+→H2S(30)
of thiosulfate and sulfate from its intermediate and side
reactions have been undesirable. The next development is H2S+2Fe3+→S+2Fe2++2H+(31)

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 462

Table 5 Different catalysts used in direct oxidation of H2S to elemental sulfur.

Feed Catalyst Reaction parameters Conversion % Selectivity % References

Catalyst Temp. O2/H2S Water vapor GHSV h-1

loading (%) range (°C) (vol.%)

5 vol.% H2S balanced with He TiO2/SiO2 10 275 0.5 – 3000 93–94 98–99 (Chun et al. 1998)
0.91 vol.% H2S balanced with He Fe2O3/SiC 5 240 2.51 20 1050 100 90 (Landau et al. 1968)
0.2 vol.% H2S balanced with He NiS2/SiC 3.9 100 1.6 20 1050 100 100 (Keller et al. 1999)
5 vol.% H2S, 5 vol.% NH3 balance with He V2O5-TiO2 10% 260 0.5 – 30,000 98.9 21.5 (Cho et al. 2009)
gels V2O5
5 vol.% H2S balanced with N2 Zeolite-NaX – 200 0.5 – 20,000 90 100 (Lee et al. 2005b)
zeolite-KX 250 86 100
A.D. Wiheeb et al.: Acid gas removal technologies

1 vol.% H2S balanced with N2 V2O5/zeolite-NaX 1:1 ratio 175 0.6 10 – 90 100 (Lee et al. 2006)
5 vol.% H2S, 5 vol.% NH3 balance with He LaSrCoO4 – 260 0.5 60 30,000 99.1 6.4 (Yang et al. 2007)
5 vol.% H2S, 5 vol.% NH3 balance with He LaSrCoO3.6F0.4 – 260 0.5 60 30,000 55.6 67.6 (Yang et al. 2007)
5 vol.% H2S, 5 vol.% NH3 balance with He Bi4V2-xSbxO11-y – 260 0.5 60 12,000 81.4 96 (Park et al. 2005b)
At x = 0.2
1 vol.% H2S balance with He Fe2O3/β-SiC 3 250 2.5 30 3000 100 95 (Nguyen et al. 2009)

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5 vol.% H2S, 10 vol.% NH3 balance with He V2O5/SiO2 10 240 0.5 60 30,000 80 – (Park et al. 2002)

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V2O5/TiO2 86
5 vol.% H2S, 10 vol.% NH3 balance with He V2O5+Sb2O4 mixtures 1:1 ratio 280 0.5 60 12,000 88.8 – (Park et al. 2002)
0.2 vol.% H2S balance with He NiS2/SiC 5 60 1.6 >5 1000 100 100 (Ledoux et al. 2000)

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5 vol.% H2S balance with He CrOx/SiO2 10 300 0.5 – 1500 84 89 (Uhm et al. 1999)
0.1 vol.% H2S, 50 vol.% H2, 15 vol.% CO2, Activated carbon (WSC) – 150 2 < 24% 3100 100 100 (Bashkova et al. 2007)
9 vol.% CO, 2 vol.% N2, balance with H2O
0.1 vol.% H2S, 50 vol.% H2, 15 vol.% CO2, Activated carbon (WSC) Impregnated 150 2 < 24% 3100 100 100 (Bashkova et al. 2009)
9 vol.% CO, 2 vol.% N2, balance with H2O with 10%
NaOH
 A.D. Wiheeb et al.: Acid gas removal technologies 463

This is technically achievable in a membrane reactor

-
e because the reaction and separation of products take place
Oxidizer ← Fe3+ Fuel ← O2 simultaneously. In the previous studies, the generated
H2Saq →
cell sulfur is removed from the reaction zone by condensa-
tion, whereas the generated hydrogen is directly extracted
using membrane (Zaman and Chakma 1995, Edlund 1996).
Fe2+ → However, the conversion is low because the total splitting of
H2S is not thermodynamically favorable and the separation
↓ H2O
↓S of hydrogen is poor. In another effort, Vycor glass mem-
brane having a surface area of 191 m2/g, porosity of 0.79,
Figure 9 FCIR consisting of oxidizing unit and fuel cell for sulfur
recovery and electricity generation (Zhai et al. 2002).
and mean pore diameter of 4.5 nm is loaded with MoS2 cat-
alyst to decompose H2S (Kameyama et al. 1983). The Vycor
glass particles do not show catalytic activity and the test
In the fuel cell anode: shows that the conversion remains unchanged when using
an empty tube. The membrane is stable when it works in
2Fe2++6H2O→2Fe(OH)3+6H++2e-(32)
H2 and H2S atmosphere between 500°C and 700°C for 216 h
2Fe(OH)3+6H+→2Fe3++6H2O(33) of operation. Above 700°C, a notable shrinking occurs,
indicating that the Vycor glass is limited to temperature
In the fuel cell cathode: below 700°C. The hydrogen separation factor is improved
when increasing the temperature and the surface diffusion
1/2O2+2H++2e-→H2O(34)
mechanism is neglected beyond 300°C. Sulfur is concen-
The coupling operation reportedly yields sulfide trated in the undiffused gases side because of its low per-
removal efficiency of 99.90%, sulfur recovery efficiency of meation through the Vycor glass membrane.
78.6 ± 8.3%, columbic efficiency of 58.6 ± 1.6%, Fe3+ recov- Alumina membrane with pore diameter of 102 nm is
ery efficiency of nearly 100%, and electricity generation reportedly used to separate hydrogen gas from the H2S
maintained for 104 h at an average current density of decomposition products. Alumina membrane can toler-
79.2 ± 2.1 mA m-2. The problem encountered in the process ate temperature above 1073 K with permeability 30 times
stems from iron precipitation and premature oxidation higher than that of the Vycor glass membrane. However,
due to oxygen crossover. Further improvement of this alumina membrane demonstrates poor hydrogen separa-
process is expected, especially if higher efficiency fuel cell tion ability (separability) due to the big pore size, which is
technology that is specifically catered for this process can not suitable for separating hydrogen from H2S.
be made available in the future. The zirconia-silica microporous membranes have
been applied as a perm-selective membrane to extract
hydrogen from the reaction zone, although the hydrogen
2.4 Catalytic membrane reactor separation factor is low and limited by the Knudsen selec-
tivity (Ohashi et al. 1998). Alternatively, amorphous silica
2.4.1 H2S decomposition membrane prepared by the CVD method with tetramethoxy­
silane and oxygen is used as a perm-selective membrane
The thermal decomposition of H2S into hydrogen and in the H2S decomposition. High hydrogen permeance
sulfur can take place in the presence or absence of cata- (10-7 mol m-2 s-1 Pa-1) and high hydrogen/nitrogen perm
lysts. Thermal decomposition of H2S into hydrogen and selectivity are obtained at 873 K. However, the conver-
sulfur is highly endothermic and the equilibrium conver- sion is poor (∼69%) due to the low hydrogen separability
sion occurs at high temperatures of about 1000°C (Park (Akamatsu et al. 2008).
et al. 2002, 2005a, Yang et al. 2007, Ma et al. 2008, Cho There are increasing efforts to increase the separability
et al. 2009, Bineesh et al. 2010, 2011). The clear disadvan- of membrane in many reactions. For example, in methane
tage of H2S decomposition at high temperature is attrib- steam reforming (Tsuru et al. 2004, Nomura et al. 2006) and
uted to the required high energy and endothermicity of in the dehydrogenation of organic chemical hydrides (Itoh
the reaction. To overcome this, the reaction products are et al. 2003, Battersby et al. 2006), the membrane shows
removed from the reaction zone to shift the equilibrium promising results at temperatures ranging from 773 K to 973 K
reaction forward, beyond the thermodynamic equilib- (Govind and Atnoor 1991, Edlund and Pledger 1994, Chan
rium, and the reaction temperature is reduced. et al. 2000, Ohashi et al. 2000, ­Akamatsu et al. 2008, Trujillo

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464 A.D. Wiheeb et al.: Acid gas removal technologies

et al. 2008). Metallic membranes, such as Pd, combine high these disadvantages occur in the conventional packed
separability of H2 with excellent mechanical strength and bed reactor. The use of catalytic membrane technology is
high thermal durability. This leads to the deployment of pal- expected to increase the reaction rate and improve both
ladium membrane reactor in the cyclohexane dehydrogena- conversion and selectivity. At the same time, it reduces
tion. However, Pd is incompatible with H2S because it causes the operating cost. The catalytic membrane reactor com-
the metal pores to swell, resulting in reduced hydrogen bines the conversion effect (catalyst) and separation effect
selectivity (Itoh 1987, Govind and Atnoor 1991). A composite (membrane) in a single unit. The effect of separation and
metal membrane can be used to circumvent this constraint reaction is realized simultaneously within the membrane.
and it is cheaper than membranes made from pure Pd or Pt. This is particularly evident for reactions limited by
A composite metal membrane containing Pt is report- thermodynamic equilibrium considerations, such as in the
edly used in the decomposition of H2S from natural gas catalytic dehydrogenation or in the esterification reactions
(Edlund and Pledger 1994). The membrane consists of of hydrocarbon (Marcano et al. 2002). The selective oxi-
vanadium that serves as the base metal and SiO2 as inter- dation process of propane to acrolein using flow-through
metallic-diffusion wall, and Pt is used for the separation catalytic membrane reactor (FTCMR) is reportedly better
of hydrogen. This composite membrane is stable at an than that in FBR. A short and controlled contact time over
operating temperature up to 700°C with 35% conversion 5–10 μm thin catalytic layer is used to avoid the total oxi-
of H2S. Figure 10 illustrates the typical flow diagram of dation of propane. The modified sol-gel method is used
H2S decomposition using composite membrane reactor to generate tubular mesoporous mixed oxide catalytic
in natural gas processing. It shows that the permeate H2 membrane. The selective catalytic oxidation is conducted
reacts with oxygen from air to produce H2O. at atmospheric pressure and temperature of 400°C. The
catalyst loading for the FTCMR is 50–100 mg, whereas the
FBR is loaded with 2 g of catalyst. The selectivity toward
2.4.2 H2S desulfurization acrolein is more than 50% in the FTCMR, whereas, in the
FBR, it is < 10%. The main products in the liquid phase are
The catalytic oxidation of H2S into elemental sulfur and methanol and acetic acid (Zhu et al. 2003).
water are normally carried out in a FBR. The reaction There are very limited studies on the catalytic oxida-
equilibrium limitations include reactants premixing and tion of H2S using catalytic membrane reactor. The known
the contact between reactants, intermediate, and prod- studies mainly concern with the application of separated
ucts that may lead to an uncontrollable reaction. All of reactants feed (Sloot et al. 1990). Figure 11 depicts the

Metal Process
membrane heater

Sweetened Air
natural gas

Blower/
Sulfur compressor
condenser
Reactor

H2S
recovery

Heat S2 + H 2 H2+O2
Heat

recovery
H2O

Sour natural S2
gas

H2O
Air
Process
heater

Figure 10 Flow diagram of the decomposition process of H2S in natural gas (Edlund and Pledger 1994).

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 A.D. Wiheeb et al.: Acid gas removal technologies 465

H2S H2S + S + H2O H2S+MOX→MSX+H2O(35)

S + H2O
H2S
where M is any suitable metal oxide, such as copper, zinc,
SO2 + S + H2O
SO2
S + H2O iron, magnesium, vanadium, calcium, barium, strontium,
S + H2O
and any mixture thereof and X is 1–3. At the opposite metal
SO2 oxide membrane side, an oxidant, such as air or O2, SO2, or
a mixture of two or more of such gases, contact the mem-
brane surface and react with MSX to form MSX and SO2
according to the following reaction:
SO2 + S + H2O
MSX+O2→MOX+SO2(36)
Figure 11 Desulfurization inside catalytic membrane reactor (Sloot The SO2 reacts with MSX to form MOX and S according
et al. 1990, Eow 2002).
to the following reaction:
MSX+SO2→MOX+S(37)
desulfurization process using catalytic membrane reactor.
The overall reaction of this process is
The reactants are fed to a reactor containing a porous non-
perm-selective membrane (α-Al2O3) impregnated with cata- H2S+1/2O2→H2O+S(38)
lysts (γ-Al2O3). The membrane serves as a physical barrier
This method is expected to be economical because
between the reactants being fed in different membrane
the reaction and separation of H2S occur simultaneously
sides. The advantage of this arrangement is that a strict sto-
in the catalytic membrane reactor. The thickness of the
ichiometric feed of reactants can be supplied. Any variation
reactive metal oxide membrane used in this technique can
in the reactant molar flux can shift the reaction zone. Thus,
range from 0.1 to 10 μm, whereas the support thickness is
it is important to maintain the reaction in a stoichiometric
2 mm. The selective oxidation of H2S into elemental sulfur
condition. An overpressure (0.5 bar) is applied to the H2S
and water using catalytic membrane reactor described
side to facilitate the combined effect of convective and dif-
above can be an attractive research area in the near future.
fusive flows that cause the sulfur to exit from the SO2 side.
Further pieces of research on the reaction mechanisms of
In the previously reported work, a sintered stainless steel
H2S oxidation on the catalytic membrane are expected
membrane is used to oxidize H2S into SO2 using the same
to be available. Research and development of a suitable
concept of separated reactant feed (Neomagus et al. 1998).
active component and support and the membrane struc-
A continuous desulfurization process using the pat-
ture in this area of research are still scarcely addressed
ented catalytic membrane reactor, consisting of a reactive
and are expected to be the subject of future effort.
metal oxide deposited on an inert porous support, is also
reported (Jalan and Ryu 1994). Figure 12 illustrates the
arrangement of the catalytic membrane reactor for pro-
cessing the Claus tail gas. The gas mixture, containing
3 Conclusion
H2S, enters the reactor at high temperature (440–1000°C)
A review on the technologies to remove acid gases from
and pressure (0–3000 psig) at one side of the membrane.
gaseous mixture from several commercial and labora-
It further diffuses through the porous ceramic support
tories settings is presented in this article. Novel trends
to react with a reactive metal oxide on the opposite side
in the conversion of H2S into elemental sulfur have been
according to the following reaction:
highlighted, including FCIR process that simultaneously
recovers sulfur from aqueous sulfide and generates.
H2S free gas mixture Three techniques have been introduced to improve
the treatment of Claus tail gas namely, absorption of H2S
from gas mixtures using hollow fiber membrane contac-
Gas mixture containing SO2 recycle tor, decomposition of H2S into hydrogen and sulfur using
H 2S
catalytic membrane reactor, and continuous and direct
Sulfur condenser
Oxidant oxidation of H2S into elemental sulfur using porous cata-
Vent lytic membrane reactor.
Elemental sulfur
The application of membrane has the potential to over-
Figure 12 Schematic representation of catalytic membrane reactor come the problems of foaming, flooding, corrosion, and the
(Jalan and Ryu 1994). high operating cost. The wetting phenomena associated

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466 A.D. Wiheeb et al.: Acid gas removal technologies

with the membrane contactor and that reduces the absorp- is a new concept that can be used to improve the Claus TGT.
tion rate can be resolved by selecting a suitable solvent and It is expected to pave the way into the future for cleaner,
by modifying the membrane structure so that it becomes greener, and more sustainable production.
highly hydrophobic. The decomposition of H2S into hydro-
gen and sulfur using a catalytic membrane reactor enhances Acknowledgments: The support from the Universiti Sains
the reaction and shifts the endothermic equilibrium reac- Malaysia under Membrane Science and Technology
tion forward. Although this technique is promising, it still Research Cluster, RU-PRGS grant scheme and Short Term
needs further research on finding suitable membrane mate- grants are gratefully acknowledged.
rials that can tolerate high temperature and resist the H2S
corrosion. The continuous and direct oxidation of H2S into Received May 19, 2013; accepted July 31, 2013; previously published
elemental sulfur using porous catalytic membrane reactor online September 17, 2013

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Ahmed Daham Wiheeb is a PhD student at the School of Chemical

Muhamad Nazri Murat (PhD) is a Senior Lecturer at the School
Engineering, Engineering Campus, Universiti Sains Malaysia. He is
of Chemical Engineering, Engineering Campus, Universiti Sains
also an Assistant Professor at the Department of Chemical Engineer-
Malaysia.
ing, University of Tikrit, Iraq.

Ili Khairunnisa Shamsudin is a PhD student at the School of Chemi-

cal Engineering, Engineering Campus, Universiti Sains Malaysia.
Jinsoo Kim (PhD) is a Professor at the Department of Chemical
Engineering, College of Engineering, Kyung Hee University, Republic
of Korea.

Mohd Azmier Ahmad (PhD) is an Associate Professor at the School

of Chemical Engineering, Engineering Campus, Universiti Sains
Malaysia.

Mohd Roslee Othman (PhD) is an Associate Professor at the School

of Chemical Engineering, Engineering Campus, Universiti Sains
Malaysia.

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