Catalytic synthesis of methanethiol from methanol and carbon disulfide over KW/Al2O3 catalysts

Article abstract of DOI:10.1016/j.catcom.2015.06.001

Abstract A series of KW/γ-Al₂O₃ catalysts with varying K/W mole ratio were prepared for the synthesis of methanethiol from carbon disulfide and methanol, and characterized by N₂ adsorption-desorption, XRD and NH₃/CO₂-TPD techniques. Experimental results showed that the acidic and basic property of the catalyst plays a key role on the catalytic performance. It is shown that the conversion of CH₃OH is chiefly related to the acid sites, while the base sites of catalysts are favorable for the selectivity toward CH₃SH and hydrocarbons, but the strong base sites will restrain the selectivity toward CH₃SH. When the K/W mole ratio is K/W = 2/1 and the reaction temperature is at 603 K, the conversion of CH₃OH and the selectivity toward CH₃SH are 98.3 and 56.2%, respectively.

Full text of DOI:10.1016/j.catcom.2015.06.001

Catalytic synthesis of methanethiol from methanol and carbon disulfide over
KW/Al2O3 catalysts
Weiming Wang, Yang Li, Xiang Zhang, Weiping Fang, Yiquan Yang
PII:
DOI:
Reference:
S1566-7367(15)00228-9
doi: 10.1016/j.catcom.2015.06.001
CATCOM 4350
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
5 May 2015
1 June 2015
3 June 2015
Please cite this article as: Weiming Wang, Yang Li, Xiang Zhang, Weiping
Fang, Yiquan Yang, Catalytic synthesis of methanethiol from methanol and car-
bon disulfide over KW/Al2O3 catalysts, Catalysis Communications (2015),
0.1016/j.catcom.2015.06.001
doi:
1
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ACCEPTED MANUSCRIPT
Catalytic synthesis of methanethiol from methanol and carbon
disulfide over KW/Al O catalysts
2
3
a
a
a
a
b,
Weiming Wang , Yang Li , Xiang Zhang , Weiping Fang , Yiquan Yang *
a
Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering,
Xiamen University, Xiamen, 361005, PR China
b
Department of Chemistry, College of Chemistry and Chemical Engineering, and National Engineering
Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, Xiamen University, Xiamen, 361005,
PR China
*
Corresponding author. Tel. /fax: +865922880786. E-mail address: yyiquan@xmu.edu.cn
Abstract
A series of KW/γ-Al O catalysts with varying K/W mole ratio were prepared for
2
3
the synthesis of methanethiol from carbon disulfide and methanol, and characterized
by N adsorption-desorption, XRD and NH /CO -TPD techniques. Experimental
2
3
2
results showed that the acidic and basic property of the catalyst plays a key role on the
catalytic performance. It is shown that the conversion of CH OH is chiefly related to
3
the acid sites, while the base sites of catalysts are favorable for the selectivity toward
CH SH and hydrocarbons, but the strong base sites will restrain the selectivity toward
3
CH SH. When the K/W mole ratio is K/W=2/1 and the reaction temperature is at
3
6
5
03K, the conversion of CH OH and the selectivity toward CH SH are 98.3 and
3 3
6.2%, respectively.
Keywords: methanethiol; methanol; carbon disulfide; KW/Al O3
2
1

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1
. Introduction
Methanethiol, also referred to as methyl mercaptan (CH SH, MT), is an
3
important chemical raw material, which can be used for the synthesis of valuable
organosulfur compounds, such as pharmaceuticals, pesticides, and petrochemicals.
The most important application of methanethiol is in the manufacture of methionine,
which is widely used as an animal feed supplement. In the past 20 years, the reaction
routes for the formation of methanethiol mainly include CH OH-H S reaction method
3
2
[
1-4], H S-containing synthesis gas conversion method [5-8], CH SCH -H S
2 3 3 2
conversion method [9-11], and COS-H S-H conversion method [12, 13] and so on.
2
2
The synthesis of methanethiol from methanol and carbon disulfide, however, is
seldom reported and needs to be explored in more detail.
In recent years, the industrial process for the manufacture of methanethiol from
methanol and hydrogen sulfide is an effective process. The catalyst system, which
was applied to catalyze the synthesis of methanethiol from methanol and hydrogen
sulfide, was found to be a transition metal oxide-supported and alkali metal-promoted
γ-alumina catalyst [14-17]. But, it is worth mentioning that one of the raw materials
(
hydrogen sulfide, H S) of this method is mainly obtained by means of the
2
combustion of natural gas and sulfur in industry.
CH  4S  2H S CS
4
2
2
It is shown that large amount of carbon disulfide (about 50% in terms of sulfur atom)
is generated simultaneously as a byproduct in the process of the production of
hydrogen sulfide. At present, the market demand of CS was less in China, and CS is
2
2
environmental pollutant and very difficult to be disposed of by now. Therefore, the
method of the synthesis of methanethiol from carbon disulfide and methanol can
make up for the defect of that from methanol and hydrogen sulfide. In addition, to
develop a feed additive with regard to the places where natural gas is lack especially,
2

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the route of the synthesis of methanethiol from carbon disulfide and methanol would
be attractive and promising.
In this work, a series of KW/γ-Al O catalysts with varying K/W mole ratio were
2
3
prepared to catalyze the reaction of CH OH with CS for the synthesis of CH SH.
3
2
3
Comprehensive properties of these catalysts, including specific surface area, pore
volume, average pore diameter, phase composition, acid-base properties on the
catalysts surface and catalytic performances, were measured and discussed in detail.
2
. Experimental
2
.1 Catalysts preparation
A series of KW/γ-Al O catalysts with varying K/W mole ratio were prepared
2
3
following the incipient wetness co-impregnation method. Mixed aqueous solutions of
the required quantities of anhydrous potassium carbonate (K CO , Aldrich, 99.9%)
2
3
and ammonium metatungstate (AMT, Aldrich, 99%) were used as KW precursor
2
solutions, and γ-Al O (commercial sample, S =327m /g, Sphere: Φ3-5mm,
2
3
BET
Shandong) was used as the support. WO /γ-Al O and K O/γ-Al O catalysts were
3
2
3
2
2
3
prepared in a single impregnation step from aqueous solution of AMT and K CO ,
2
3
respectively. After impregnation, the materials were dried at 383 K for 12 h and then
treated at 673 K under atmosphere for 4 h. For the sake of brevity, the catalysts KW/γ-
Al O are denoted as K W /Al hereafter, in which x/y is the K/W molar ratio (x/y=0.5,
2
3
x
y
1
, 2, 4, 8). The catalysts γ-Al O , WO /γ-Al O and K O/γ-Al O are denoted as Al,
2 3 3 2 3 2 2 3
W/Al and K/Al, respectively.
2
.2 The evaluation of the catalysts
The activity tests of the catalysts were performed in a quartz tube fixed bed reactor
with an internal diameter of 10mm typically, in which 2.0ml of the catalyst with
0~60 mesh was filled per pass. In addition, quartz powder of 30~60 mesh was placed
3
just above the catalyst bed to mix carbon disulfide with methanol in advance in order
to maintain the uniformity of feedstock flow. Prior to activity measurement, the
3

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catalysts were activated in a flow of N at a flow rate of 50ml/min, with the
2
temperature rising up from ambient temperature to 673K at a heating rate of 5K/min
and maintaining at this temperature for 1h, then the catalyst bed was cooled to
reaction temperature. Liquid carbon disulfide and methanol were pumped into the
catalyst bed by two double-plunger precision metering pump (Beijing Satellite
Manufactory, 2ZB-1L10). The evaluation experiments were carried out under the
reaction conditions: the reaction pressure was 0.3MPa, the mole ratio of CH OH/CS
3
2
-1
was 2.2, the gas hourly space velocity (GHSV) of reactant was 1000h , the flow rate
of auxiliary gas helium was 30ml/min. All lines from the reactor to the gas sampling
valves were kept at 423K by adopting a thermostat heating belt to prevent product
from condensation, and the effluent was analyzed by an on-line gas-chromatograph
equipped with a porapak Q (2m × 3mm) column connected to a thermal conductivity
detector (TCD). The experiments were repeated at least twice to verify reproducibility
and ensure that the results obtained were within the experimental error of ±2%.
2
.3 Catalyst characterization
Nitrogen adsorption-desorption experiments were performed at 77K on the auto-
physical chemistry adsorption test apparatus Micromeritics Tristar 3000. Prior to the
measurement, all samples were degassed at 393K for 1h and then evacuated at 573K
for 3h to remove physically adsorbed impurities. The specific surface area was
determined by the Brunauer-Emmett-Teller (BET) method in the range of 0.05-0.3
P/P , and the pore size distributions were calculated by Barrett-Joyner-Halenda (BJH)
o
method according to the desorption branch of the isotherms.
XRD characterization of the fresh catalysts and the used catalysts was conducted on
a Panalytical X’pert PRO X-ray diffractometer utilizing monochromatic Cu Kα
radiation (λ=0.15418nm, tube voltage: 40kV, tube current: 30mA) with a scanning 2θ
◦
ranging from 10 to 90 . The measurements were performed by using a step length of
◦
0
.0167 and 115s as counting time per step. The XRD patterns were referenced to the
powder diffraction files (ICDD-FDP data base) for identification.
NH and CO temperature-programmed desorption (TPD) were performed on a
3
2
4

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self-constructed instrument equipped with a quadra-pole mass spectrometer model
QIC-20 (Hiden Analytical Ltd.), in which 100mg sample was filled per pass. For
NH -TPD experiment, the sample was pretreated in Ar at 673K for 1h, then cooled
3
down to 303K, at which ammonia was adsorbed for about 0.5h in an ammonia stream
of 30ml/min. Loosely bound NH was removed by Ar sweeping at 303K, and then the
3
temperature was increased to 973K at a heating rate of 10K/min under Ar flow. The
desorbed NH was monitored with a MS signal of m/e=17 in multiple ion detection
3
(
MID) mode. So did the CO -TPD experiment as NH -TPD experiment with CO
2 3 2
substituting for NH . Desorbed CO component was monitored with a MS signal of
3
2
m/e=44 in MID mode.
3
. Results and discussion
3
.1 Textural properties
The BET specific surface area, pore volume and average pore diameter of the
catalysts are compiled in Table 1. As described in Table 1, BET specific surface area
2
3
and pore volume of the pure alumina support are respectively 327m /g and 0.43cm /g,
which were found to be decreased after introducing the active ingredients to generate
KW-supported catalysts. This is mainly due to the increase in the density of the
materials, and the metal salt loading on the support block the interstitial pore volume
of the pure alumina support during the preparation procedure. The molecular weight
of tungsten is larger than that of potassium, therefore, the density of the catalysts
decreases with the increase of K/W molar ratio, resulting in increasing the volume per
unit mass. It was found that the average pore size of the catalysts increase with
increasing in the K-loading, which is most likely because the interaction between
potassium and alumina became strong, and formed a number of large particle species.
Therefore, some small pores were blocked, leading to the shift of the average pore
size to bigger values. This conclusion was confirmed by the changes observed in the
pore size distribution (see Fig. 1).
5

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Table 1 Physicochemical property of the catalysts
Specific surface area
Pore volume
Average pore diameter
(nm)
catalysts
2
3
(m /g)
(cm /g)
Al
327.2
183.5
189.2
199.0
199.6
200.3
201.1
193.4
0.43
0.24
0.26
0.28
0.30
0.36
0.37
0.37
2.18
2.31
2.32
2.32
2.35
2.66
2.83
2.93
W/Al
K W /Al
1
2
K W /Al
1
1
K W /Al
2
1
K W /Al
4
1
K W /Al
8
1
K/Al
6

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Fig. 1 Pore size distribution of the catalysts
7

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3
.2 X-ray diffraction measurements
The X-ray diffraction patterns of the fresh catalysts and the corresponding used
catalysts are presented in Fig. 2(a) and 2(b), respectively. It is known that the peaks at
°
2
θ=14.4, 28.1, 38.2, 49.3 and 67.3 may be ascribed to alumina (PDF number: 00-
0
49-0134). As is shown in Fig. 2(a), the diffraction peaks, which can be ascribed to a
mixture of K Al O (PDF number: 00-044-1009) and K O (PDF number: 01-089-
2
19 29.5
2
5
956), were detected when the K/W mole ratio was more than 4/1. And the intensity
of the reflections increased with increasing the K/W mole ratio, which indicates the
increasing size of the K Al O and K O crystallites. When the K/W mole ratio was
2
19 29.5
2
°
less than 1/1, the peaks at 2θ = 22.7 and 24.3 which can be ascribed to WO (PDF
3
number: 00-033-1387) were detected. For the K W /Al catalysts (x/y >1/1), however,
x
y
the diffraction peaks which can be ascribed to W-containing species had not been
detected from the diffraction patterns, suggesting that the W-containing species exist
as amorphous phase with high dispersion on the surface of γ-Al O or probably
2
3
because the concentration of tungsten is too low.
The XRD patterns of the used catalysts collected after the activity tests are shown
in Fig. 2(b). In addition to the diffraction peaks which can be ascribed to alumina,
weak crystalline signals corresponding to WS (PDF number: 01-084-1399) were
2
°
observed at 2θ =33.1, and 34.2 . And the reflections became more defined and intense
with higher tungsten- loading, which manifests the increasing agglomeration of the
WS phase. Furthermore, the diffraction peaks appeared at 2θ=21.3, 23.8, 29.8, 30.8,
2
°
3
7.2, 40.5 and 43.5 can be attributed to K SO (PDF number: 00-003-0608) over the
2
4
used KW/Al catalysts. In the present work, however, all the catalysts did not undergo
the pre-sulfurization process prior to activity tests, whereas the crystalline phases of
WS and K SO were also detected by the X-ray diffraction measurements from the
2
2
4
used catalysts. Accordingly, it is shown that the catalysts underwent the sulfurization
process during the catalytic synthesis of methanethiol from carbon disulfide and
methanol.
8

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Fig. 2 XRD diffraction patterns of the fresh catalysts (a) and the used catalysts (b), K Al O
2
19 29.5
(
▽), K O (○), WO (◇), WS (▼), K SO (●)
2 3 2 2 4
9

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3
.3 Surface acid-base properties
The acidic property of the catalysts was measured by NH temperature program
3
desorption (NH -TPD) tests. Fig. 3(a) shows the NH -TPD experiment results. In Fig.
3
3
3
3
(a), three NH desorption peaks were detected in the tested temperature range (from
3
00 to 973K), which manifests the presence of three different acid sites owing to
different NH absorption energies over the catalysts. The amount distribution of acid
3
sites is summarized in Table 2. The weak, medium and strong acid sites were
estimated from the NH desorption peaks in the temperature range 320-450K, 450-
3
6
50K and 650-970K, respectively. It can be found that the amount of acid sites
decreased with increasing the K/W mole ratio, which is most likely because that some
acid sites on the surface of the catalysts, to some extent, were neutralized by alkali
during the preparation procedure. For the K/Al catalyst, only two desorption peaks at
4
00 and 505K were detected, which are attributed to NH desorbed from weak and
3
moderate acid sites, respectively. This illustrates that the strong acid sites do not exist
on the K/Al catalyst. In addition, the amounts of acid sites on the catalysts were found
to vary in the sequence: W/Al > K W /Al > K W /Al > K W /Al > K W /Al >
1
2
1
1
2
1
4
1
K W /Al > K/Al.
8
1
The CO -TPD results of the catalysts are shown in Fig. 3(b). The amount
2
distribution of the week, medium and strong basic sites derived from CO -TPD curves
2
is summarized in table 2. Only small amount of desorbed CO was detected from
2
W/Al catalyst, and the amount of desorbed CO increased rapidly with increasing in
2
the K-loading. When the K/W mole ratio was more than 4/1, the CO desorption peak,
2
which can be attributed to strong basic sites, can be detected. While the amount of the
base sites varied in the sequence: K/Al > K W /Al > K W /Al > K W /Al >
8
1
4
1
2
1
K W /Al > K W /Al > W/Al.
1
1
1
2
1
0

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Table 2 The amount distribution of acid sites and basic sites of the catalysts
Acid site distribution based on
Basic site distribution based on
a
b
NH -TPD data
CO -TPD data
Catalysts
3
2
Weak Medium Strong
Total
1.55
1.31
1.12
1.00
0.91
0.60
0.43
Weak
0.01
0.12
0.31
0.98
1.05
1.09
1.32
Medium Strong Total
W/Al
0.43
0.34
0.19
0.08
0.07
0.05
0.05
0.54
0.47
0.46
0.45
0.45
0.46
0.38
0.58
0.50
0.47
0.47
0.39
0.09
-
-
-
-
0.01
0.12
0.32
1.00
1.49
1.99
2.57
K W /Al
-
1
2
K1W1/Al
K W /Al
0.01
0.02
0.33
0.48
0.52
-
-
2
1
K W /Al
0.11
0.42
0.73
4
1
K W /Al
8
1
K/Al
a, b
The amounts of acid sites and base sites of K W /Al were all assigned to be 1.0, so as to
2
1
compare with those of the other catalysts.
1
1

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Fig. 3 TPD results of the fresh catalysts, (a) NH -TPD and (b) CO -TPD
3
2
1
2

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3
.4 Catalytic activity of the catalysts
A series of KW/Al catalysts with varying K/W mole ratio was prepared to
determine the effect of K/W mole ratio on the catalytic activity. The activity
measurement of the catalysts was conducted in the temperature range from 573 to
6
53K. Based on the results of activity evaluation, the evaluation results at 603K were
chosen to illustrate the catalytic performances in order to properly contrast. Fig. 4
shows the effect of K/W mole ratio on the catalytic performances of the catalysts
under certain reaction conditions, including the conversion of methanol and the
selectivity toward products. As it can be seen from Fig. 4, the activities of the
catalysts for the conversion of methanol into methanethiol varied in the following
sequence (the conversion of methanol expressed in % is given in brackets): W/Al
(
100) > K W /Al (99.9) > K W /Al (99.7) > K W /Al (98.3) > K W /Al (96.7) >
1 2 1 1 2 1 4 1
K W /Al (95.6) > K/Al (94.6). The selectivity toward CH SH rapidly increased at
8
1
3
first, and then slightly decreased again with increasing the K/W mole ratio, and the
maximum CH SH selectivity (at 603K) was 56.2% over K W /Al catalyst. While the
3
2
1
selectivity toward CH SCH has exactly the opposite trend with that of CH SH, and
3
3
3
the minimum CH SCH selectivity (at 603K) was 7.2% over K W /Al catalyst. There
3
3
2
1
is no doubt that CH SCH is directly derived from CH SH. The selectivity to CO
2
3
3
3
remains substantially constant (about 30%) when the K/W mole ratio is more than 1/2,
which is probably because that the formation of CO was accompanied by the
2
generation of CH SH, and CO is very difficult to be converted to other products
3
2
under the reaction conditions. Furthermore, the maximum CH OCH selectivity (at
3
3
6
03K) was 6.8% over K W /Al catalyst. And the selectivity toward hydrocarbons
1 1
(
CH +C H ) started increasing at the K/W mole ratio higher than 2/1 corresponding to
4 2 6
the decline in the selectivity toward CH SH. According to the characterization results
3
of NH /CO -TPD, the acidic and basic property of the catalyst plays a key role on the
3
2
catalytic performance for the synthesis of CH SH from CS and CH OH. It is shown
3
2
3
that the conversion of CH OH is chiefly related to the acid sites, while the base sites
3
1
3

ACCEPTED MANUSCRIPT
of catalysts are favorable for the selectivity toward CH SH and hydrocarbons, but the
3
strong base sites will restrain the selectivity to CH SH.
3
According to the results above, it is shown that K W /Al catalyst has better
2
1
catalytic activity and the selectivity toward methanethiol for the synthesis of
methanethiol from carbon disulfide and methanol. Therefore, we choose K W /Al
2
1
catalyst to make further experiments in the following paragraphs, to study the effect
of reaction temperature on catalytic properties of K W /Al catalyst and the stability of
2
1
the catalyst. Fig. 5 shows the catalytic performances of the K W /Al catalyst as a
2
1
function of reaction temperature. As it can be seen from Fig. 5, the conversion of
CH OH increased rapidly with increasing the reaction temperature, and reached
3
almost 100% at the reaction temperature higher than 623K. And the selectivity toward
CH SH increased at first, and then decreased slightly with the reaction temperature
3
increasing. While the selectivity to CH SCH decreased at first, and then increased
3
3
gradually with increasing the reaction temperature. The selectivity toward CH OCH
3
3
and CO were not affected, to a significant extent, by increasing the reaction
2
temperature in the evaluated temperature range. In addition, the selectivity toward
hydrocarbons (CH +C H ) increased slightly with increasing the reaction temperature,
4
2
6
which is probably attributed to the decomposition of CH SH and CH SCH
3
3
3
themselves at high temperature.
Fig. 6 shows the conversion of CH OH and the selectivity toward CH SH over
3
3
K W /Al catalyst as a function of time on stream, which can be taken as a
2
1
measurement of stability of the catalysts. As can be seen from Fig. 6, the CH OH
3
conversion and the CH SH selectivity maintained at a high and stable level for the
3
whole 100h on stream.
Based on the discussions above, to optimize the selectivity toward CH SH, it is
3
necessary to choose the optimum K/W mole ratio and to limit the reaction
temperature in a suitable range (593~623K). For the system studied in this work, for
instance, the optimum K/W mole ratio is K/W=2/1, and the optimum reaction
temperature is 603K. Under these conditions, the conversion of CH OH and the
3
1
4

ACCEPTED MANUSCRIPT
selectivity toward CH SH were measured to be 98.3 and 56.2%, respectively. It is
3
well known that the activity and selectivity of the catalyst depends not only on active
components, additives and the preparation method used but also on the nature of the
support. The selectivity to CH SH can be further improved by modifying the catalyst
3
formulation, e.g., using high surface area supports or adding a second promoter to the
catalyst as shown in Ref. [4, 18].
1
5

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Fig. 4 Effect of K/W mole ratio on the conversion of CH OH and the product selectivity, reaction
3
-1
conditions: P=0.3MPa, CH OH/CS =2.2, GHSV=1000h , T=603K
3
2
1
6

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Fig. 5 Catalytic performances of K W /Al catalyst as a function of reaction temperature under the
2
1
-1
reaction conditions: P=0.3MPa, CH OH/CS =2.2, GHSV=1000h
3
2
1
7

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Fig. 6 Conversion of CH OH and the selectivity toward CH SH over the K W /Al catalyst as a
3
3
2
1
function of time on stream under the reaction conditions: P=0.3MPa, T=603K, CH OH/CS =2.2,
3
2
-1
GHSV=1000h
1
8

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4
. Conclusions
In the present work, the catalytic synthesis of methanethiol from carbon disulfide
and methanol over a series of KW/γ-Al O catalysts was investigated. It is shown that
2
3
potassium-promoted W-based catalysts exhibit a high activity for the CH SH
3
synthesis. XRD characterization results showed that the catalysts underwent the
sulfurization process during the reaction. According to activity evaluation and
NH /CO -TPD characterization results, the conversion of CH OH is chiefly related to
3
2
3
the acid sites, while the base sites of the catalysts are favorable for the selectivity
toward CH SH and hydrocarbons, but the strong base sites will restrain the selectivity
3
to CH SH. From this perspective, the optimum K/W mole ratio was found to be
3
K/W=2/1. When the reaction temperature is at 603K, the conversion of CH OH and
3
the selectivity toward CH SH over K W /Al catalyst are 98.3 and 56.2%, respectively.
3
2
1
Acknowledgments
This research topic is a major project of the Science and Technology Department of
Fujian Province, project number: 2012H6020. The authors gratefully acknowledge the
Science and Technology Department of Fujian Province and Fujian Xiamen
University Catalyst Co., Ltd. for financial support.
1
9

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Graphical Abstract
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ACCEPTED MANUSCRIPT
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CS instead of H S was employed as starting S precursor.
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The KW/Al Catalysts can undergo the sulfurization process.
Optimum K/W mole ratio is K/W=2/1.
K W /Al catalyst shows higher CH OH conversion and CH SH selectivity.
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