Journal of Natural Gas Science and Engineering 69 (2019) 102941

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Journal of Natural Gas Science and Engineering

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Modification of zeolite by metal and adsorption desulfurization of organic T

sulfide in natural gas
Lijun Zhua,*, Xinfeng Lva, Shuyue Tongb, Tingting Zhanga, Yurou Songa, Yongjie Wanga,
Zhao Haoa, Chao Huanga, Daohong Xiaa
a
State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (East China), Qingdao, 266580, China
b
Sinopec Petroleum Engineering Zhongyuan Corporation, China

ARTICLE INFO ABSTRACT

Keywords: The metal modified zeolite was prepared by impregnation combined with roasting and the adsorption perfor-
Natural gas mance of organic sulfur in natural sulfur was evaluated. The zeolite type, ion concentration, calcination tem-
Metal modification perature, anion and cationic species all have effect on the desulfurization performance. Anions have a great
Zeolite influence on the performance of the zeolite modified by copper ions. Ag/13X had the highest adsorption capacity
Adsorption desulfurization
to methyl sulfide and the adsorption capacity increased by 1.6 times than that of the unmodified 13X zeolite. The
order of adsorption capacity to sulfide by Cu/13X is ethyl mercaptan > methyl sulfide > dimethyl disulfide.
And the adsorption capacity to the mixed sulfide is greater than that of the single sulfide, but less than the sum of
the single sulfides. After regeneration by calcination, the adsorption capacity is basically recovered. Metal-
modified zeolites are well suited for the deep removal of organic sulfur from natural gas.

1. Introduction
The direct release of SOx from the combustion of sulfur compounds
in fuel into the atmosphere can cause serious environmental pollution,
so the deep removal of sulfides from fuels has become an urgent issue
worldwide (Glindemann et al., 2006; Ma et al., 2005). With the motor
vehicle emission standards are constantly upgrading, the corresponding
oil quality is also upgrading, particularly, the gasoline standard has a
strict limit on the sulfur content. For example, the sulfur content limit of
gasoline in China is 10 ppm (ppm is the solution concentration unit,
10 ppm is 10 parts per million) in Chinese GB Standard (GB 17930-
2016). The natural gas is an important supplementary fuel for gasoline.
For example, natural gas is often used as fuel or chemical raw materials
in refinery and chemical plant. In addition the compressed natural gas
is an important fuel for automobiles other than gasoline (Aguiar and
Coelho, 2017). However, according to the GB18047-2017 “Compressed
Natural Gas for Vehicles” of China, the total sulfur content is less than
or equal to 100 mg/m3, which is equivalent to a sulfur content limit of
139 ppm in weight. This shows that natural gas desulfurization has
become an important task for fuel desulfurization. At the same time,
when using natural gas as a raw material, the presence of organic sulfur
can reduce or even completely deactivate the catalyst activity of the
fuel cell (Strohm et al., 2006). It is of great significance to research the
deep desulfurization of natural gas. The natural gas purification process
generally includes desulfurization, which can remove hydrogen sulfide
to below 10 ppm (Rufford et al., 2012), but the process has almost no
removal effect on organic sulfur such as methyl sulfide, carbonyl sul-
fide, etc. (Satokawa et al., 2005).
Methyl sulfide is one of the most difficult organic sulfur compounds
to be removed in natural gas. It is stable in nature and has a special
odor. It has been used as an odorant in many countries and is artificially
added to natural gas (Glindemann et al., 2006; Gaylord Chemical
Corporation, 2007), but some natural gas contains a higher con-
centration of methyl sulfide produced in some areas for geological
reasons (Farrauto et al., 2003). Through a large number of studies, it is
found that methyl sulfide is one of the most difficult organic sulfur
components in natural gas (Alptekin, 2004). Therefore, in order to re-
duce the total sulfur content in natural gas, the development of an
adsorbent with high performance of adsorption of methyl sulfide has
important theoretical and industrial application value for the devel-
opment of organic sulfur removal technology in natural gas (Cui and
Turn, 2009).
The organic sulfide is removed by the dry adsorption desulfurization
technology by passing the natural gas through a bed of solid particulate
adsorbent. Dry adsorption desulfurization has many advantages such as
simple process operation, low energy consumption and high removal

*
Corresponding author.
E-mail address: zhulj2002@163.com (L. Zhu).

https://doi.org/10.1016/j.jngse.2019.102941
Received 1 February 2019; Received in revised form 11 July 2019; Accepted 11 July 2019
Available online 15 July 2019
1875-5100/ © 2019 Elsevier B.V. All rights reserved.
L. Zhu, et al.
efficiency (Chen et al., 2016). At present, in the natural gas industry,
activated carbon, zeolites, zinc or iron oxides are often used as ad-
sorbents to remove methyl sulfide (Wakita et al., 2001).
However, Israelson (2004) found that activated carbon materials
loaded with different metal ions have lower adsorption capacity for
methyl sulfide. Velu et al. (2003) and Hernandez-Maldonado and Yang,
2003 found that zeolite modified with copper ions, silver ions and
nickel ion can adsorb sulfides well. Satokawa et al. (2005) found that
Ag-NaY zeolite have a very good adsorption effect on methyl sulfide.
Crespo et al. (2008) loaded CuCl into mesoporous zeolite MCM-41 and
SBA-15, and investigated adsorption performance for hydrogen sulfide
and methyl sulfide in natural gas at room temperature. The results show
that the modified mesoporous zeolite has larger pore size, less diffusion
resistance and easy regeneration, and has a good application prospect
in natural gas desulfurization.
Song et al. (2014) studied organic-inorganic modification of MCM-
41 mesoporous zeolites, CuO active components was introduced by
loading method, or the Cu(NO3)2 active components was introduced by
coordination after grafted organosilanes. The desulfurization perfor-
mance of adsorbents for typical sulfides (tert-butyl mercaptan, methyl
sulfide, dimethyl disulfide) in mixed C4 Hydrocarbon was investigated.
It has been found that tert-butyl mercaptan is easily removed in three
sulfides, which not only easily forms sulfur-metal bonds with metal
active components, but also form thiolates. However, dimethyl sulfide
and dimethyl disulfide are relatively difficult to remove, mainly be-
cause the polarity and reactivity are weak, which is not conducive to
the formation of sulfur-metal bonds. Ozaydin et al. (2008) modified the
MCM-41 zeolite by one-step hydrothermal synthesis method to in-
troduce copper into the MCM-41 framework and directly loading the
copper ions in the pores. After comparing the adsorption performance
of the adsorbent from the two modified methods to H2S, it was found
that, the direct loading modified zeolite is better than the embedded
modified zeolite.
Barelli et al. (2015) tested the adsorption properties of activated
carbon, impregnated activated carbon and natural zeolite on dimethyl
sulfide. The effects of gas space velocity, adsorption bed geometry and
filtration devices were investigated. The stratified adsorption of di-
methyl sulfide is achieved by the selectivity of various adsorbents to
dimethyl sulfide. Xi et al. (2018) prepared Zn, Co and Ag modified Na/
X zeolite by ion exchange method, and evaluated the selective ad-
sorption performance of H2S and COS in Claus exhaust in fixed bed
adsorption tower. The Ag/X has the best adsorption performance,
among which H2S and COS have the highest adsorption capacity. The
Ag/X zeolite used can also be regenerated by heat treatment in an air
atmosphere of 350 °C. The DFT studies have shown that H2S or S-M
bonds between COS and metal ions can form during the adsorption
process. In addition, the sulfide complex exhibits the strongest S-M
interaction, thus facilitating the adsorption of H2S and COS on the Ag
exchange zeolite X.
The key to the development of desulfurization adsorbent is to in-
crease the sulfur capacity of the adsorbent, and the surface properties of
the adsorbent are the key factors affecting the adsorption capacity of
the adsorbent. The sulfide adsorption capacity can be significantly in-
creased by ion modification. Ion exchange refers to the exchange of
compensation ions outside the framework of the zeolite. The compen-
sating ions are generally protons, alkali metals or alkaline earth metals,
which are easily ion-exchanged by various valence states metal salts in
an aqueous solution, thereby realizing modification of the zeolites.
After the introduction of the metal ions, the surface of the zeolite is
modified, and the adsorption performance is improved (Wang et al.,
2009).
At present, most studies on zeolite modification are directed to the
removal of thiophene sulfides from gasoline by using metal modified
zeolite as an adsorbent (Miao et al., 2012; Hernández-Maldonado et al.,
2004; Zhang et al., 2008; Sun et al., 2015). However, there are few
studies on the removal of light sulfides (such as methyl sulfide,
2
Journal of Natural Gas Science and Engineering 69 (2019) 102941
ethanethiol, etc.) in natural gas, especially the effects by anions and
cations and the preparation methods are basically not reported.
Therefore, the metal is used to modify the zeolite by the impreg-
nation method, and the removal performance of the modified zeolite on
the organic sulfide in the gas is systematically studied from the aspects
of ion selection and preparation methods. This study is of great sig-
nificance for industrial application of the adsorption of organic sulfur
compounds in natural gas.
2. Experimental
2.1. Reagent and raw material
Various metal salts (analytical grade) were purchased from Aladdin
Reagent Co., Ltd., and 5A and 13X zeolites were purchased from
Zhengzhou Zeolite Co., Ltd., which is spherical with a diameter of about
3–5 mm. Hβ, Y, and ZSM-5 zeolites were powdered and purchased from
Xiya Reagent Company. The raw materials are ground and sieved to
obtain 40–60 mesh particles. And then the particles were placed in a
muffle furnace, calcined at 450 °C for 5 h for activation, the activated
zeolite is placed in a desiccator to cool to room temperature.
2.2. Modification of zeolite
An ion-modified zeolite adsorbent is prepared by an equal volume
impregnation method. Typical process is as follows:A certain amount of
the corresponding metal salt solid was weighed, placed in a beaker, and
dissolved in deionized water to prepare an aqueous solution of the
corresponding concentration. The 2.0 g of activated zeolites were mixed
with an equal volume of metal ion salt solution (about 3.2 mL), stirred
uniformly, and impregnation was performed at room temperature for
24 h. Then the zeolite was thoroughly washed with deionized water to
remove the surface salt solution of the zeolite, filtered, placed in a
drying oven at 80 °C for 2 h, and then placed in a muffle furnace to be
calcined at a certain temperature to obtain an adsorbent.
2.3. Simulated natural gas preparation and analysis
The simulated gas used in this experiment was the organic sulfide-
nitrogen simulated gas sample with a sulfur content of 200 μg-S/g. The
flow rate is adjusted by a gas flow regulating valve to obtain a gas of a
certain flow rate. The organic sulfur content in this experiment was
determined by Bruker GC-450 gas chromatograph (PFPD detector).
2.4. Organic sulfide adsorption experiment
Fixed bed adsorption evaluation: The measurement of the adsorp-
tion breakthrough curve was carried out in a fixed adsorption bed. The
adsorption bed is a quartz glass tube 20 cm long and 2 mm inner dia-
meter. The adsorbent bed containing the 40 mg adsorbent was im-
mersed in a super constant temperature bath at 25 °C to ensure that the
temperature was kept constant during the experiment, and the flow rate
of the mixed gas was controlled by the rotameter to maintain a flow
rate of 80 mL/min. The adsorption bed outlet is connected to a gas
chromatograph, and various sulfide contents are measured by a gas
chromatograph with a gas injector.
The effective adsorption time is defined as the adsorption time at
which the outlet concentration reaches 10% of the inlet concentration.
The saturation adsorption time is defined as the adsorption time at
which the outlet sulfur concentration reaches the inlet concentration
for the first time.
The saturation adsorption capacity is defined as the mass of the
sulfide (calculated as sulfur) adsorbed by the adsorbent, when the
outlet sulfur concentration reaches the inlet sulfur concentration (i.e.,
the outlet sulfur concentration is 200 μg-s/g).
The evaluation device of adsorbent flow chart is shown as Fig. 1.
L. Zhu, et al.
Fig. 1. Flow chart of adsorption performance evaluation.
1-cylinder of sulfur-containing gas, 2- cylinder of nitrogen, 3- Ball
valve, 5- Blender, 4, 10-Flow meter, 6, 9- Shut-off valve, 7- Adsorbent
bed, 8- Gas chromatography, 11-Tail gas treatment.
2.5. Characterization of adsorbents
X-ray diffraction pattern (XRD) Characterization: After the sample
was vacuum dried at 100 °C for 5 h, the sample was ground to a powder.
An X′ Pert Pro MPD polycrystalline powder X-ray diffractometer man-
ufactured by Panalytical in the Netherlands was used. Test conditions:
Cu target, Kα radiation source (λ = 0.15406 nm), tube voltage 40 kV,
tube flow 40 mA. X-ray phase analysis scanning speed 3.0°/min, scan-
ning range: 5.0°–60.0°.
Fourier transform infrared (FTIR): The infrared absorption spectrum
of the modified zeolite was carried out by a Nicolet 6700 FT-IR spec-
trophotometer using KBr (absorption peak range, 4000-400 cm−1;
number of scans, 64; DTGS detector).
Temperature programmed desorption (TPD): Desorption of ad-
sorbent was investigated on a dynamic adsorption instrument (TP-
5076). About 0.1 g catalyst (40–60 mesh) sandwiched by quartz wool,
was loaded in a quartz tube. Samples were heated from room tem-
perature to 600 °C with a rate of 10 °C/min under Helium flow (30 mL/
min). The change in the composition of the outlet gas was measured
using a thermal conductivity detector.
3. Results and discussion
3.1. Adsorption performance evaluation of adsorbent before modification
The adsorbent (5A, 13X, Hβ, HY, ZSM-5, activated carbon (AC),
chromatography silica gel) with the same weight and particle size was
loaded into the adsorption tube, and the sulfur concentration of outlet
gas was determined by gas chromatography.
The adsorption capacity was evaluated by measuring the break-
through curve. The adsorption of dimethyl sulfide in the gas by various
adsorbents is shown in Fig. 2, and the results are shown in Table 1.
The dynamic adsorption evaluation method was used to compare the
adsorption performance of activated carbon with four kinds of zeolites and
silica gel. It can be seen that the adsorption performance of different ad-
sorbents is very different. The silica gel has no adsorption performance.
The sulfide passed through the adsorption bed within 3 min, and the ad-
sorption capacity of HY zeolite is very small for 7 min. Therefore, silica gel
and HY zeolite have not been studied. The order of adsorption perfor-
mance of adsorbents is: 13X > Hβ > 5A > AC ≫ HY > Silica gel. The
adsorption capacity has a certain correlation with the pore size, and the
13X pore size is the largest and the adsorption performance is the best (Ge
et al., 2018). It can be explained by the zeolite pore size selection
3
Journal of Natural Gas Science and Engineering 69 (2019) 102941
Fig. 2. The breakthrough curves for various porous adsorbents to methyl sul-
fide.
Table 1
Comparison of adsorption performance of various porous adsorbents on methyl
sulfide.
Adsorbent 5A HY Hβ Silica gel AC 13X
Effective adsorption time/min 15 –a 21 –a 21.2 30.7
Saturation adsorption time/min 30.2 12.0 27.1 8.0 29.7 40.0
Saturation adsorption capacity/mg- 18.6 7.4 16.7 4.9 18.4 24.7
S/g
a
It is not detected the data less than 10%.
mechanism. The pore size of other adsorbents is 2–8 Å, which is obviously
less than 10 Å of 13X zeolite, and the molecular size of thioether is 4.6 Å,
which leading to easy adsorption of sulfide molecules on the 13X zeolite
(Dyke et al., 2005). The influence of diffusion resistance is quite different.
The metal ion modification process will result in a further reduction in the
pore size of the zeolite, which will limit the interaction of the sulfide
molecules with the metal ions, thereby reducing the adsorption perfor-
mance (Wang and Zhu, 2006). Therefore, the 13X zeolite with the largest
pore diameter was finally selected for further improvement.
During the adsorption experiment, we found that as the adsorption
progressed, the outlet sulfur concentration continued to increase, and
sometimes the value of C/C0 would exceed 1.0. This may be due to the
temporary adsorption of some organic sulfur molecules on the ad-
sorbent, small amount of the sulfide desorb from the adsorbent, re-
sulting in the concentration of the outlet is greater than that of the inlet.
3.2. Effect of ion concentration on adsorption performance
During the impregnation process, the concentration of metal ions
has an effect on the ion exchange rate and the exchange capacity, which
determines the adsorption performance. In order to further study the
effect of ion concentration in the impregnation solution on the ad-
sorption performance, the copper nitrate solution with corresponding
ion concentration was prepared and used to impregnate 13X zeolite for
24 h, then calcined at 450 °C for 5 h, and then the adsorption perfor-
mance was measured.
It can be seen in Fig. 3 and Table 2 that in the concentration range of
the experiment, the adsorption performance of the zeolite increases
with the increase of the metal ion concentration, but when the con-
centration of the metal ion is too large, the adsorption performance of
the modified zeolite decreases. Finally, the ion concentration of
0.1 mol/L was selected for further research.
Different ionic solubility has a significant effect on the adsorption
performance. This may be because the modification by the metal salt
increases the number of active sites of the zeolite and improves the
L. Zhu, et al. Journal of Natural Gas Science and Engineering 69 (2019) 102941

Fig. 3. The effect of ion concentration on the adsorption performance of Cu/ Fig. 4. The effect of calcination temperature on adsorption performance of Cu/
13X 13X

Table 2 attached to the surface of the zeolite or the pores of the zeolite, which
Comparison of adsorption performance of Cu/13X modified with different ion increases the number of active sites adsorbed by the zeolite, and also
concentrations on methyl sulfide. improves the activity of the surface adsorption center, thereby im-
proving the adsorption performance of the zeolite.
Concentration of ion/(mol/L) 0.01 0.05 0.1 1.0
Effective adsorption/min 38.3 47.6 55.2 23.0 However, as the temperature continues to rise, when the tempera-
Saturation adsorption time/min 67.9 69.7 72.6 49.1 ture is too high, the desulfurization performance is seriously reduced.
Saturation adsorption capacity/mg-S/g 41.9 43.0 44.8 30.3 This is because the crystal structure of the modified zeolite is subjected
to high temperature destruction, and the modified zeolite pore col-
lapses. Moreover, if the temperature is too high, the metal ion salt will
activity of the adsorption center on the surface of the zeolite. The ad- be sintered and inactivated, causing the surface of zeolite to be covered
sorption mechanism is converted into coordination adsorption by by metal, thereby seriously affecting the adsorption and adsorption
physical adsorption of the pores. As the concentration increases, the performance (Jian et al., 2018).
activity level increases, so the adsorption performance increases as the
concentration increases. However, when the concentration of metal
ions is too large, excessive metal ions may remain in the surface of the 3.4. Effect of different anions on adsorption performance
zeolite or in the pore structure (Benaliouche et al., 2007). After high-
temperature calcination, metal ions easily block the pores of the zeolite, Taking copper ion as the research object, the influence of anion
resulting in decreased adsorption performance of the zeolite (Wang and species on the performance of adsorption desulfurization was in-
Peng, 2010; Ates and Hardacre, 2012). vestigated. The Cu/13X adsorbent was prepared by the equal volume
impregnation method, using the solution of 0.1 mol/L of the salt at
room temperature for 24 h, followed by drying and calcined at 450 °C
3.3. Effect of calcination temperature on adsorption performance
for 5 h.
It can be seen in Fig. 5 and Table 4 that copper chloride is superior
The effective adsorption time and saturation time were compared,
to copper nitrate, and both are better than copper bromide. After the
and the results are shown in Table 3.
From the results of Fig. 4 and Table 3, it is known that the ad-
sorption performance of the modified zeolite is enhanced with the in-
crease of the calcination temperature within a certain range, and the
adsorption performance of the modified zeolite calcined at 450 °C is the
best. This is because zeolite is a type of porous material with a regular
pore structure and a large specific surface area, which is placed in the
air for a long time to adsorb water and other gases in the air. A large
amount of impurities will occupy the active sites and the pore in the
zeolite, thereby affecting the adsorption performance of the zeolite.
After a certain high temperature roasting, the zeolite can drive out
moisture and other gaseous impurities in the zeolite to re-expose the
active components on the zeolite. Moreover, the high temperature
calcination causes the metal salt solution to react to form a metal oxide

Table 3
Comparison of adsorption performance of modified zeolites for methyl sulfide.
Roasting temperature/oC 150 350 400 450 550
Effective adsorption/min 19.1 34.7 55.2 61.4 6.7
Saturation adsorption time/min 39.7 56.1 72.6 83.0 29.8
Fig. 5. The breakthrough curve for modified Cu/13X by different anion copper
Saturation adsorption capacity/mg-S/g 24.5 34.6 44.8 51.3 18.4
salt.

4
L. Zhu, et al.
Table 4
Adsorption performance comparison of different anions copper-modified Cu/
13X.
Adsorbent 13X Cu(NO3)2/ CuCl2/13X CuBr2/13X
13X
Effective adsorption/min 30.7 61.4 70.0 35
Saturation adsorption time/min 40.0 83.0 89.9 55
Saturation adsorption capacity/ 24.7 51.3 55.5 34.0
mg-S/g
zeolite is immersed in a copper salt solution of different anions, a part
of the cations are ion-exchanged with the cations on the surface of the
zeolite. The other part is adsorbed inside the zeolite pores in the form of
a salt solution. Different anions affect the surface properties of the
adsorbent during the post-treatment. During the vacuum drying pro-
cess, the water evaporates, the copper salt precipitates or hydrolyzes,
and then the bound water is lost.
At the calcination stage of 450 °C, the copper salt on the surface of
the zeolite will further chemically react. The copper salt is hydrolyzed
to form copper hydroxide, which is then decomposed to form copper
oxide. Or the copper salt is directly thermally decomposed into copper
oxide. In this process, especially in the copper salt pyrolysis process, the
leaving molecules are different and the decomposition temperature is
different due to the different anions. Therefore, the particle size of the
formed copper oxide may be different, and the adsorption performance
of the prepared modified zeolite may be different (Xue et al., 2005).
3.5. Effect of different metal ions on the adsorption performance
Metal ions are the active sites of adsorption of modified zeolites. The
type of metal ions, electronic structure and crystalline state determine
the adsorption performance. So, the adsorption properties of metals
such as Cu2+, Ni+, Ce2+ and Ag+ ions on methyl sulfide were in-
vestigated. Although the copper chloride modified zeolite is better than
copper nitrate, the metal nitrate has the advantage of solubility, and
most of the metal nitrate is easily dissolved. In order to compare the
difference of metal ions under the same conditions, the nitrates of Zn,
Ni, Ce, Ag and Cu were used to modify the 13X zeolite under optimized
conditions, impregnated by the solution of 0.1 mol/L of the salt, and
calcined at 450 °C for 5 h.
The adsorption performance of the adsorbent on methyl sulfide was
investigated in Fig. 6.
The data of the breakthrough curve are also summarized to obtain
the effective adsorption time and saturation time as shown in Table 5.
Fig. 6. The effect of metal ions on the adsorption performance of metal mod-
ified 13X
5
Journal of Natural Gas Science and Engineering 69 (2019) 102941
Table 5
The comparison of adsorption performance of 13X and modified 13X zeolite.
Adsorbent 13X Ni/13X Zn/13X Cu/13X Ce/13X Ag/13X
Atomic mass – 58.7 65.4 63.5 140 108
Metal loading (%) 0 0.939 1.046 1.016 2.240 1.728
Effective adsorption/min 25.4 54.4 57.9 61.7 71.2 82.3
Saturation adsorption 40.0 98.4 88.9 83.0 98.4 105.0
time/min
Saturation adsorption 24.7 60.8 54.9 51.3 60.8 64.8
capacity/mg-S/g
When calculating the amount of metal loading, according to the
equal volume impregnation method, all solutions are adsorbed in the
pores of the zeolite, so all metals are supported on the zeolite by de-
fault. However, during the actual operation, some of the metal will be
lost, resulting in a slightly smaller than the actual load amount.
The results from Table 5 shows that the adsorption performance of
13X zeolite modified by metal ion is obviously higher than that of blank
13X, while the adsorption performance of 13X modified by Ag+ is best
one. Compared to 13X, the adsorption amount of Ag/13X increased by
162%. According to the breakthrough time of adsorption of the same
concentration of methyl sulfide, the effective adsorption performance of
the five metal ion modified 13X from high to low is: Ag/13X > Ce/
13X > Cu/13X > Zn/13X > Ni/13X > 13X.
There are many factors affecting the adsorption performance of
metal species. It is generally believed that the adsorption performance
of metal-modified zeolite is due to the Metal-S bond between sulfide
and metal and the π-complexation of aromatic ring with metal of aro-
matic sulfide (thiophene, benzothiophene, dibenzothiophene, etc)
(Chen et al., 2017; Lee and Valla, 2017; Dehghan and Anbia, 2017;
Zhang et al., 2008). For dimethyl sulfide, since the aromatic ring is not
contained, the adsorption performance mainly depends on the strength
of the Metal-S. The different electronic orbital distribution of metals
leads to different ability to accept lone pairs of electrons on a sulfur
atom. As a result, the strength of the formed M-S is different.
In addition, studies on the liquid phase desulfurization of Ag-mod-
ified β zeolite show that the changes in Brønsted and Lewis acidity also
have an effect on the desulfurization performance (Gong et al., 2009).
For Ce modified zeolites, studies have shown that sulfur compounds in
jet fuel are adsorbed by a direct S-adsorbent (S-M) interaction but not
by π-complexation as reported recently over Cu (I) Y and AgY zeolites.
Unlike Cu and Ag cations, the cerium ions, being an f block element
with high positive charge, have a low tendency to form π-complexes
with π-bonding ligands (Cotton and Wilkinson, 1966; Velu et al., 2003).
In fact, the desulfurization capacity of the adsorbent depends on a
number of factors such as exchanged metal cation, microporous struc-
ture properties and acid-base properties which is related to the SiO2/
Al2O3 ratio of the framework (Gong et al., 2009).
3.6. Adsorption capacity of modified zeolites for different organic sulfides
The adsorption performance of Ag/13X is the best, but in view of
cost considerations, and in a lot of the study of adsorption desulfur-
ization of gasoline, the copper ions were selected as the metal for the
modification of zeolite, and good adsorption performance was ob-
tained. So the Cu modified zeolite is further studied. There are various
organic sulfides in natural gas, and representative sulfides include
methyl sulfide, ethyl sulfide, methyl mercaptan, ethyl mercaptan and
dimethyl disulfide (Satokawa et al., 2005). In order to evaluate the
performance of adsorption from natural gas, the adsorption perfor-
mance of Cu/13X to dimethyl disulfide and ethanethiol in simulated
natural gas was investigated.
According to the experimental results in Table 6, the Cu/13x has
obvious difference in adsorption capacity for different single sulfides,
and the adsorption order is ethanethiol > methyl mercaptan >
dimethyl disulfide. The adsorption capacity of ethanethiol is about
L. Zhu, et al. Journal of Natural Gas Science and Engineering 69 (2019) 102941

Table 6
Comparison of adsorption properties of different sulfides by Cu/13X.
Organic sulfur Methyl Dimethyl Ethyl mercaptan
sulfide disulfide
Effective adsorption/min 61.7 42 77.2
Saturation adsorption time/ 83.0 48 95.5
min

twice that of dimethyl disulfide. It is indicated that the metal modified

zeolite is selective for organic sulfides. This may be related to the po-
larity of the molecule. Since the sulfur atom of the thiol is at the end
and the molecule is asymmetrical, the molecular polarity is greater. The
adsorption of organic sulfur reported in the recent literature is listed in
Table 7. The Cu/13X with adsorption capacity of 51.3 mg-S/g can be
improved through further research, and it is a potential industrial ad-
sorbent.

3.7. Selective adsorption properties of modified zeolites for mixed organic

sulfur Fig. 7. The breakthrough curve for Cu/13X to mixed organic sulfur in gas.

According to the results of Fig. 7 and Table 8, when the zeolite Table 8
adsorbs the mixed sulfide, the methyl sulfide is preferentially saturated Comparison of adsorption performance of mixed organic sulfur by Cu/13X.
than the ethyl mercaptan, which indicates that the adsorption capacity
Item Adsorption time Cu/13X
of Cu/13X on the ethyl mercaptan is greater than that of the methyl
sulfide. This is consistent with the single sulfide adsorption results. dimethyl sulfide Effective adsorption/min 42.4
According to the complete breakthrough time, the adsorption break- Saturation adsorption time/min 70.0
ethyl mercaptan Effective adsorption/min 66.3
through time of ethanethiol and methyl sulfide is reduced compared
Saturation adsorption time/min 93.7
with the adsorption of one component of dimethyl sulfide or etha-
nethiol. It is considered that the pore space of the zeolite and the active
center of the metal are limited, and the competitive adsorption of Fig. 8.
ethanethiol and methyl sulfide on the zeolite makes the adsorption It can be seen from the results in Table 9 that the change in ad-
amount of the Cu/13X much lower than that of the single component. sorption performance after regeneration is small, indicating that the
When the sulfide is mixed, the sum of the adsorption time of the two high temperature treatment is a good regeneration of the adsorbent.
sulfides is 108.7 min, which is greater than the adsorption time Zeolites are inorganic porous materials with stable structure and basi-
(61.7 min and 77.2 min) in the single sulfide adsorption, but less than cally no change in structure during calcination, so they can be re-
the sum of the adsorption amounts of the two sulfides at the single generated and reused very well.
adsorption (138.9 min). This indicates that Cu/13X is selective for
different sulfides when adsorbing mixed sulfides. The active sites on the
surface of the adsorbent have size matching and activity matching for 3.9. Structural characterization of adsorbents
different sulfides. Therefore, when adsorbing mixed sulfides, the
amount of adsorption will increase. (1) Powder X-ray diffraction (XRD)

3.8. Re-use performance of modified zeolite
The Cu/13X zeolite after adsorption saturation was regenerated by
calcination at 350 °C for 2 h, and then the adsorption performance of
methyl sulfide of Cu/13X zeolite was evaluated after regeneration, and
the breakthrough curve was obtained and the results are shown in
After ion impregnation and calcination modification, the structure
of the zeolite can be characterized by XRD. Therefore, the 13X analy-
tical crystal structure modified by different anionic copper salts is
analyzed by XRD in Fig. 9.
It can be seen from the XRD pattern (Fig. 9) that the characteristic
diffraction peaks of 13X zeolite exist after the modified by different

Table 7
Summary of organic sulfur removal performance in gases reported in the literature.
Adsorbent Organic sulfur TEMP (oC) sulfide concentration (ppm) Adsorption capacity Ref.

Na-Y Pipeline natural gas 25 DMS: 1.8 TBM: 1.2 12.8 mg-S/g Satokawa et al. (2005)
Ag(18)Na-Y DMS in mixture 25 DMS: 10 TBM: 10 60.8 mg-S/g Satokawa et al. (2005)
Ag(18)Na-Y TBM in mixture 25 DMS: 10 TBM: 10 19.2 mg-S/g Satokawa et al. (2005)
AC DMS 26 1.4 2.23 mg-S/g Cui and Turn (2009)
AC-FeCl3 DMS 26 1.4 3.32 mg-S/g Cui and Turn (2009)
MIL-53(Al) TBM 35 60 220 mg/g Chen et al. (2016)
NaY TBM 35 60 140 mg/g Chen et al. (2016)
UiO-66(Zr) TBM 35 60 90 mg/g Chen et al. (2016)
Na-Y DMS RT 30 35.2 mg-S/g Wakita et al. (2001)
H-β DMS RT 30 28.5 mg-S/g Wakita et al. (2001)
AC RB1 DMS 20 5.5 mg/m3 0.43 mg/g Barelli et al. (2015)
AC RGM1 DMS 20 5.5 mg/m3 1.96 mg/g Barelli et al. (2015)
AC RGM1 + zeolite ATZ (1:1) DMS 20 5.5 mg/m3 2.29 mg/g Barelli et al. (2015)

In the table DMS is Dimethyl sulfide and TBM is tert-butyl mercaptan.

6
L. Zhu, et al. Journal of Natural Gas Science and Engineering 69 (2019) 102941

Fig. 8. The breakthrough curve for fresh adsorbent and regenerated adsorbent.
Fig. 10. The XRD pattern of 13X zeolite before and after calcination of CuCl2.

Table 9
of the zeolite, but has a certain influence on the crystallinity. Mainly
Comparison of saturation time between fresh adsorbent and regenerated ad-
sorbent. because during the roasting process, some chemical changes occur in
the pores, and it is also possible that the high temperature has a certain
Item First used Reused
influence on the crystallinity of the zeolite (Chandrasekhar, 1996).
Effective adsorption/min 61.7 51.3 From the evaluation of adsorption performance, it is known that the
Saturation adsorption time/min 83.0 74.7 adsorption capacity after modification is greatly improved, indicating
Saturation adsorption capacity/mg-S/g 51.3 46.2 that there is almost no major change in the pore structure, and the
deterioration of crystallinity has little effect on the adsorption.
The XRD analysis of the 13X modified with Ag ions and Ce ions with
good adsorption performance was also carried out to study the effects of
these two ion modifications on the crystal structure of the zeolites (in
Fig. 11).
It can be seen from Fig. 11 that the modified 13X basically retains
the original crystal structure, and the intensity of the diffraction peak of
Ag/13X and Ce/13X is basically unchanged from that of 13X, but a little
lattice collapse occurs to cause crystallization. The degree is slightly
reduced. Compared with 13X, no new characteristic peaks were ob-
served on the spectra, indicating that no metal oxides were produced on
the zeolites, and Ag ions and Ce ions were successfully exchanged onto
the zeolites.

(2) Fourier transforms infrared spectroscopy (FT-IR)

Fig. 9. The XRD pattern of modified 13X zeolite prepared after impregnation
with different anionic copper salts.

anionic copper salts. Therefore, the modification has little effect on the
crystal structure of 13X zeolite.
The calcination has a great influence on the ion dispersion and ion
state. For this reason, the XRD spectrum of 13X modified by CuCl2
before and after calcination was investigated (Fig. 10). Comparing the
XRD before and after calcination, it was found that the diffraction peaks
before calcination and untreated 13X did not change much, which in-
dicated that there was no significant change in crystal structure before
calcination. This also means that there is no effect on the structure
during the impregnation process.
Compared to the XRD pattern before roasting, the position of the
diffraction peak of 13X after calcination is basically the same as that
before calcination, but the strength is remarkably lowered. This in-
dicates that the ion modification does not damage the crystal structure Fig. 11. The XRD pattern of AG/13X and Ce/13X zeolite.

7
L. Zhu, et al.
Fig. 12. Infrared spectra of adsorbents before and after ion modification.
Fig. 13. The program temperature programmed desorption curve of adsorbent
before and after ion modification.
Presented in Fig. 12 are the IR spectra which the characteristic vi-
bration bands at 3300-3620 cm−1 region related to the O-H stretch of
the H2O located in the sodalite cage (Montanari et al., 2011), and the
1648 cm−1 for H2O bending, and 1000 cm−1 corresponding to the
asymmetrical stretch of the internal tetrahedra in the three-dimensional
silica phases (Osonio and Vasquez, 2018; Gao et al., 2010). Overall,
FTIR spectral analyses verified that the incorporation of metal treat-
ment did not alter the structure and bonds present in the 13X zeolite.
(3) Temperature programmed desorption (TPD)
In order to investigate the regeneration temperature, a temperature
programmed desorption method was used. 40 mg of the sample after
saturation was tested at a temperature rise of 10 °C/min, and the
thermal conductivity detector was used to check the composition of the
outlet gas. It can be seen from the results (Fig. 13) that, as the tem-
perature increases, the methyl sulfide is significantly desorbed. The
signal value reaches a peak at about 100–300 °C, and no dimethyl
sulfide was detected after 350 °C, indicating complete desorption.
Therefore, during the calcination treatment, the regeneration of the
adsorbent can be completely achieved by calcination at 350 °C for 2 h. It
8
Journal of Natural Gas Science and Engineering 69 (2019) 102941
can be seen from the peak area of the modified zeolite is greater than
that before the modification, indicating that the adsorption amount is
significantly improved. Comparing the temperature of desorption, it
can be seen that the temperature after ion modification is higher than
that before modification, by about 38 °C–123 °C. This indicates that the
adsorption force of the modified zeolite on the sulfide is significantly
enhanced.
4. Conclusions
The adsorptive performance of zeolite modified by different metal
ions was studied by dynamic fixed bed adsorption, in order to remove
organic sulfur in natural gas. The 13X zeolite was obviously better than
other adsorbent materials due to pore size limitation. Chloride is better
than nitrate, but its use is limited because many chlorides are insoluble.
Among the cations, the 13X zeolite modified by silver ions has the best
adsorption performance. The adsorption capacity of Cu/13X to the
mixed sulfide is better than that of the single sulfide. Moreover, the
adsorption performance was not significantly deteriorated after re-
peated use. The FT-IR and XRD analysis showed that the zeolite mod-
ified by ion impregnation did not change the crystal structure. The TPD
experiment proves that the calcination at 350 °C can completely re-
generate the adsorbent, and it also verifies that the adsorption capacity
and adsorption amount of the modified zeolite are obviously increased.
This research showed that the impregnation of metal ions can sig-
nificantly improve the adsorption capacity of zeolites for sulfides in
gases. This method can be used for deep adsorption of industrial natural
gas to remove organic sulfur sulfides.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant Nos. 21376265, U1662115), Shandong
Province Natural Science Foundation (ZR2019MB057) and the
Fundamental Research Funds for the Central Universities (Grant No.
18CX02118A).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.jngse.2019.102941.
References
Aguiar, M.F.D., Coelho, G.L.V., 2017. Adsorption of sulfur compounds from natural gas by
different adsorbents and desorption using supercritical CO 2. J. Environ. Chem. Eng.
5, 4353–4364.
Alptekin, 2004. In: Sixth Annual SECA Workshop. Pacific Grove, CA, April 21.
Ates, A., Hardacre, C., 2012. The effect of various treatment conditions on natural zeo-
lites: ion exchange, acidic, thermal and steam treatments. J. Colloid Interface Sci. 372
(1), 130–140.
Barelli, L., Bidini, G., Desideri, U., et al., 2015. Dimethyl sulfide adsorption from natural
gas for solid oxide fuel cell applications. Fuel Process. Technol. 140, 21–31.
Benaliouche, F., Boucheffa, Y., Ayrault, P., et al., 2007. NH3-TPD and FTIR spectroscopy
of pyridine adsorption studies for characterization of Ag- and Cu-exchanged X zeo-
lites. Microporous Mesoporous Mater. 111 (1), 80–88.
Chandrasekhar, S., 1996. Influence of metakaolinization temperature on the formation of
zeolite 4A from kaolin. Clay Miner. 31 (2), 253–261.
Chen, X., Shen, B.X., Sun, H., et al., 2017. Ion-exchanged zeolites Y for selective ad-
sorption of methyl mercaptan from natural gas: experimental performance evaluation
and computational mechanism explorations. Ind. Eng. Chem. Res. 56, 10164–10173.
Chen, G., Koros, W.J., Jones, C.W., 2016. Hybrid polymer/UiO-66(Zr) and polymer/NaY
fiber sorbents for mercaptan removal from natural gas. ACS Appl. Mater. Interfaces 8
(15), 9700–9709 15.
Cotton, F.A., Wilkinson, G., 1966. Advanced Inorganic Chemistry, second ed.
Interscience, New York Chapters 28 and 31.
Crespo, D., Qi, G., Wang, Y., Yang, F.H., Yang, R.T., 2008. Superior sorbent for natural gas
desulfurization. Ind. Eng. Chem. Res. 47 (4), 1238–1244.
Cui, H., Turn, S.Q., 2009. Adsorption/desorption of dimethylsulfide on activated carbon
modified with iron chloride. Appl. Catal. B Environ. 88, 25–31.
Dehghan, R., Anbia, M., 2017. Zeolites for adsorptive desulfurization from fuels: a review.
Fuel Process. Technol. 167, 99–116.
L. Zhu, et al.
Dyke, J.M., Ghosh, M.V., Kinnison, D.J., et al., 2005. A kinetics and mechanistic study of
the atmospherically relevant reaction between molecular chlorine and dimethyl
sulfide (DMS). Phys. Chem. Chem. Phys. 7 (5), 866–873.
Farrauto, R., Hwang, S., Shore, L., et al., 2003. New material needs for hydrocarbon fuel
processing: generating hydrogen for the PEM fuel cell. Annu. Rev. Mater. Res. 33,
1–27.
Gao, Y., Choudhury, N.R., Dutta, N.K., 2010. Systematic study of interfacial interactions
between clays and an ionomer. J. Appl. Polym. Sci. 117 (6), 3395–3405.
Gaylord Chemical Corporation, June 2007. Dimethyl Sulfide Overview.
Ge, S., Geng, W., He, X., et al., 2018. Effect of framework structure, pore size and surface
modification on the adsorption performance of methylene blue and Cu2+, in me-
soporous silica. Colloid. Surf. Physicochem. Eng. Asp. 539, 154–162.
Glindemann, D., Novak, J., Witherspoon, J., 2006. Dimethyl sulfoxide (DMSO) waste
residues and municipal waste water odor by dimethyl sulfide (DMS): the north-east
WPCP plant of Philadelphia. Environ. Sci. Technol. 40, 202–207.
Gong, Y., Dou, T., Kang, S., et al., 2009. Deep desulfurization of gasoline using ion-ex-
change zeolites: Cu (I)- and Ag(I)-beta. Fuel Process. Technol. 90 (1), 122–129.
Hernandez-Maldonado, A.J., Yang, R.T., 2003. Desulfurization of liquids fuels by ad-
sorption via π complexation with Cu (I) -Y and Ag-Y zeolite. Ind. Eng. Chem. Res. 42,
123–129.
Hernández-Maldonado, Arturo, J., Yang, R.T., 2004. Desulfurization of diesel fuels via π-
complexation with nickel(II)-Exchanged X- and Y-zeolites. Ind. Eng. Chem. Res. 43
(4), 1081–1089.
Israelson, G., 2004. Results of testing various natural gas desulfurization adsorbents. J.
Mater. Eng. Perform. 13 (3), 282–286.
Jian, Z., Liang, W., Bingsen, Z., et al., 2018. Sinter-resistant metal nanoparticle catalysts
achieved by immobilization within zeolite crystals via seed-directed growth. Nat.
Catal. 540–546.
Lee, K.X., Valla, J.A., 2017. Investigation of metal-exchanged mesoporous Y zeolites for
the adsorptive desulfurization of liquid fuels. Appl. Catal. B Environ. 201, 359–369.
Ma, X., Velu, S., Kim, J.H., et al., 2005. Deep desulfurization of gasoline by selective
adsorption over solid adsorbents and impact of analytical methods on ppm-level
sulfur quantification for fuel cell applications. Appl. Catal. B Environ. 56 (1–2),
137–147.
Miao, T., Ju, S., Xue, F., 2012. Selectivity adsorption of thiophene alkylated derivatives
over modified Cu+-13X zeolite. J. Rare Earths 30 (8), 807–813.
Montanari, T., Finocchio, E., Busca, G., 2011. Infrared spectroscopy of heterogeneous
catalysts: acidity and accessibility of acid sites of Faujasite-type solid acids. J. Phys.
Chem. C 115, 937.
Journal of Natural Gas Science and Engineering 69 (2019) 102941
Osonio, A.P., Vasquez, M.R., 2018. Plasma-assisted reduction of silver ions impregnated
into a natural zeolite framework. Appl. Surf. Sci. 432 (28), 156–162.
Ozaydin, Z., Yasyerli, S., Dogu, G., 2008. Synthesis and activity comparison of copper-
incorporated MCM-41-type sorbents prepared by one-pot and impregnation proce-
dures for H2S removal. Ind. Eng. Chem. Res. 47 (4), 1035–1042.
Rufford, T.E., Smart, S., Watson, G.C.Y., et al., 2012. The removal of CO2 and N2 from
natural gas: a review of conventional and emerging process technologies. J. Pet. Sci.
Eng. 94–95, 123–154.
Satokawa, S., Kobayashi, Y., Fujiki, H., 2005. Adsorptive removal of dimethylsulfide and
t-butylmercaptan from pipeline natural gas fuel on Ag zeolites under ambient con-
ditions. Appl. Catal. B Environ. 56 (1–2), 51–56.
Song, L., Bu, T., Zhu, L., et al., 2014. Synthesis of organically–inorganically functionalized
MCM-41 for adsorptive desulfurization of C4 hydrocarbons. J. Phys. Chem. C 118
(18), 9468–9476.
Strohm, J.J., Zheng, J., Song, C., 2006. Low-temperature steam reforming of jet fuel in the
absence and presence of sulfur over Rh and Rh-Ni catalysts for fuel cells. J. Catal. 238
(2), 309–320.
Sun, H.Y., Sun, L.P., Li, F., et al., 2015. Adsorption of benzothiophene from fuels on
modified NaY zeolites. Fuel Process. Technol. 134, 284–289.
Velu, S., Ma, X., Song, C., 2003. Selective adsorption for removing sulfur from jet fuel
over zeolite-based adsorbents. Ind. Eng. Chem. Res. 42 (21), 5293–5304.
Wakita, H., Tachibana, Y., Hosaka, M., 2001. Removal of dimethyl sulfide and t-bu-
tylmercaptan from city gas by adsorption on zeolites. Microporous Mesoporous
Mater. 46, 237–247.
Wang, S., Peng, Y., 2010. Natural zeolites as effective adsorbents in water and wastewater
treatment. Chem. Eng. J. 156 (1), 11–24.
Wang, S., Zhu, Z.H., 2006. Characterisation and environmental application of an
Australian natural zeolite for basic dye removal from aqueous solution. J. Hazard
Mater. 136 (3), 946–952.
Wang, H., Song, L., Jiang, H., et al., 2009. Effects of olefin on adsorptive desulfurization
of gasoline over Ce(IV)Y zeolites. Fuel Process. Technol. 90 (6), 835–838.
Xi, Chen, Benxian, Shen, Hui, Sun, Guoxiong, Zhan, 2018. Ion-exchange modified zeolites
X for selective adsorption desulfurization from Claus tail gas: experimental and
computational investigations. Microporous Mesoporous Mater. 261, 227–236.
Xue, M., Chitrakar, R., Sakane, K., et al., 2005. Selective adsorption of thiophene and 1-
benzothiophene on metal-ion-exchanged zeolites in organic medium. J. Colloid
Interface Sci. 285 (2), 487–492.
Zhang, Z.Y., Shi, T.B., Jia, C.Z., et al., 2008. Adsorptive removal of aromatic organosulfur
compounds over the modified Na-Y zeolites. Appl. Catal. B Environ. 82 (1), 1–10.