Hydrochlorination of acetylene using expanded multilayered vermiculite (EML-VMT)-supported catalysts

Article abstract of DOI:10.1016/j.cclet.2015.05.020

Catalyst supports have very important effects on catalyst performance. A novel expanded multilayered vermiculite (EML-VMT) is successfully used as the catalyst support for the acetylene hydrochlorination. By mixing carbon on the surface of EML-VMT (i.e., EML-VMT-C), the HgCl2/EML-VMT-C achieved a high acetylene conversion of 97.3%, a vinyl chloride selectivity of 100% and a turn over frequency (TOF) value 8.83*10-3s-1 a temperature of 140 8C, an acetylene gas hourly space velocity (GHSV) of 108 h-1, and a feed volume ratio V(HCl)/V(C2H2) of 1.15. Moreover, the HgCl2/EML-VMT-C shows good stability. The EML-VMT also shows potential in the preparation of other EML-VMT-supported catalysts.

Full text of DOI:10.1016/j.cclet.2015.05.020

G Model
CCLET 3324 1–4
Chinese Chemical Letters xxx (2015) xxx–xxx
Contents lists available at ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
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Original article
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Hydrochlorination of acetylene using expanded multilayered
vermiculite (EML-VMT)-supported catalysts
a
a
a
*
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Q1 Xin-Huang a, Feng Yu a,b,c, , Ming-Yuan Zhu , Fei-Hong Ouyang , Bin Dai ,
Jian-Ming Dan a,b,c,
*
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a Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University,
Shihezi 832003, China
b Engineering Research Center of Materials-Oriented Chemical Engineering of Xinjiang Production and Construction Corps, Shihezi 832003, China
c Key Laboratory of Materials-Oriented Chemical Engineering of Xinjiang Uygur Autonomous Region, Shihezi 832003, China
A R T I C L E I N F O
A B S T R A C T
Article history:
Catalyst supports have very important effects on catalyst performance. A novel expanded multilayered
vermiculite (EML-VMT) is successfully used as the catalyst support for the acetylene hydrochlorination.
By mixing carbon on the surface of EML-VMT (i.e., EML-VMT-C), the HgCl2/EML-VMT-C achieved a high
acetylene conversion of 97.3%, a vinyl chloride selectivity of 100% and a turn over frequency (TOF) value
Received 27 March 2015
Received in revised form 20 April 2015
Accepted 5 May 2015
Available online xxx
of 8.83 ꢀ 10ꢁ3 sꢁ1 at a temperature of 140 8C, an acetylene gas hourly space velocity (GHSV) of 108 hꢁ1
,
and a feed volume ratio V(HCl)/V(C2H2) of 1.15. Moreover, the HgCl2/EML-VMT-C shows good stability.
The EML-VMT also shows potential in the preparation of other EML-VMT-supported catalysts.
ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.
Keywords:
Acetylene hydrochlorination
Vermiculite
Catalyst support
Acetylene conversion
Vinyl chloride selectivity
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1. Introduction
surface area, high electrical conductivity and thermal conductivity, 29
which enhances the active components on the surface of AC and 30
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Vinyl chloride monomer (VCM) is mainly used in the synthesis
of polyvinyl chloride (PVC), which is one of the world’s five major
engineering plastics and widely used in all walks of life. The
acetylene hydrochlorination reaction was the earliest process for
the industrial production of vinyl chloride [1,2]. Up to date, China
has been the world’s largest PVC production country, which
produces 20,000,000 t of PVC annually, accounting for 41% of total
world production capacity. It is worth noting that more than 70% of
the PVC is prepared by the acetylene hydrochlorination method
in China [3,4].
Catalyst supports have very important effects on the perfor-
mance of catalysts and strongly affect the catalytic activity for the
acetylene hydrochlorination. Generally, carbon-supported cata-
lysts (especially for the HgCl2-supported activated carbon (AC), i.e.,
HgCl2/AC) are employed for the acetylene hydrochlorination
reaction [5]. The AC as a catalyst support possesses high specific
gives good catalytic efficiency [6]. However, AC is easily crushed 31
under reaction conditions, resulting in loss of the active 32
components HgCl2 and eventual deactivation of the catalyst. 33
HgCl2 erosion can be toxic and a source of pollution [3,7]. In 34
addition, the AC-supported catalysts are difficult to owing to their 35
the low mechanical strength and pulverization [8]. These Q236
liabilities, along with the essential demands to incorporate special 37
features, lead scientists toward: (a) low-cost and environmentally 38
friendly mercury-free catalysts; (b) advanced catalyst supports 39
with high mechanical strength and adsorption ability, which 40
reduce the loss of mercury and enhance the acetylene hydro- 41
chlorination reaction [9–11].
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Herein, we employed expanded multilayered vermiculite (EML- 43
VMT) as a catalyst support for acetylene hydrochlorination. VMT is 44
a natural clay mineral (aluminosilicate) and possesses a layered 45
structure, high mechanical strength, good thermal stability and 46
low cost [12]. Moreover, the vermiculite has considerable 47
adsorption capacity to mercury [13]. Recently, EML-VMT has been 48
used as catalyst supports, such as in the modified-VMT-supported 49
Ni catalysts for CO2 methanation to syngas (SG) [14], VMT- 50
supported TiO2 as efficient photocatalysts for water decontamina- 51
tion [15] and methylene blue photocatalytic degradations [16]. To 52
*
Corresponding authors at: Key Laboratory for Green Processing of Chemical
Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering,
Shihezi University, Shihezi 832003, China.
E-mail addresses: yufeng05@mail.ipc.ac.cn (F. Yu), djm_tea@shzu.edu.cn
(J.-M. Dan).
http://dx.doi.org/10.1016/j.cclet.2015.05.020
1001-8417/ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: . , et al., Hydrochlorination of acetylene using expanded multilayered vermiculite (EML-VMT)-
supported catalysts, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.05.020

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date, vermiculite as a catalyst support in the acetylene hydro-
chlorination has not been reported. We have successfully prepared
EML-VMT and employed EML-VMT as a catalyst support for the
acetylene hydrochlorination. The as-obtained HgCl2/EML-VMT and
HgCl2/EML-VMT-C achieved good acetylene conversions of 90.6%
and 97.3%, respectively. The selectivity of vinyl chloride is 93.7%
and 100%, respectively, corresponding to turnover frequency (TOF)
values of 7.03 ꢀ 10ꢁ3 sꢁ1 and 8.83 ꢀ 10ꢁ3 sꢁ1, respectively at a
temperature of 140 8C, an acetylene gas hourly space velocity of
108 hꢁ1, and a feed volume ratio V(HCl)/V(C2H2) of 1.15.
system. Then, hydrogen chloride gas was passed through the
reactor with a flow rate of 20 mL/min to activate the catalyst (1.0 g)
[19]. When the reactor was heated to 140 8C, acetylene and
hydrogen chloride were fed through the heated reactor at a gas
hourly space velocity (GHSV) of 108 hꢁ1. The exit gas mixture was
passed through a Dreschel bottle containing water to remove
hydrogen chloride. Compositions of the product were analyzed
using GC-2014C gas chromatography (Shimadzu International
Trading Ltd. Company). The data were collected every 40 min (i.e.,
10 min, 50 min, 90 min, . . ., etc.). Acetylene conversion (XA) and
VCM selectivity (SVC) were defined by the following equations.
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2. Experimental
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fAO
fAO
ꢁ
fA
2.1. Pretreatment of raw VMT
XA
¼
ꢀ 100%
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Raw VMT was purchased from Xinjiang Yuli Xinlong Vermicu-
lite Co., Ltd., Xinjiang, China. The VMT is composed of 38.76% SiO2,
24.05% MgO, 20.04% Al2O3, 6.22% K2O, 4.93% Fe2O3, 3.03% CaO,
2.02% Na2O, 0.94% TiO2. The EML-VMT was prepared by adding
VMT (5 g) into 50 mL of 25% H2O2 aqueous solution with heating
in a water bath (80 8C) for 2 h. After the treatment, the hydrated
VMC was dried quickly by microwave radiation (700 W for 1 min).
The dried EML-VMT was ground and sieved to a size fraction of
0.25–0.42 mm (passed through 40–60 sieve).
In order to obtain carbon-mixing EML-VMT (EML-VMT-C), the
EML-VMT (2 g) was transferred to a clear and dense solution of
pure glucose (22.4 g) in deionized water (80 mL). The mixture was
placed in a 100 mL Teflon-sealed autoclave and maintained at
180 8C in an oven for 3 h, since glucose is carbonized at 180 8C
under hydrothermal conditions. The as-prepared product was
centrifuged and washed with deionized water and ethanol five
times sequentially, and then dried at 80 8C for 5 h. Finally the
powder was further annealed at 850 8C for 4 h in flowing nitrogen.
1223
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fVC
1 ꢁ fA
SVC
¼
ꢀ 100%
In the above equations,
fAO was defined as the volume fraction
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of acetylene in the raw gas, and fA was defined as the volume
fraction of remaining acetylene in the product gas. fVC was the
volume fraction of vinyl chloride in product gas.
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3. Results and discussion
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To understand the formation mechanism of EML-VMT-C
catalyst support, a schematic illustration is proposed in Fig. 1a.
It mainly consists of two steps. Firstly, the raw VMT is immersed in
a H2O2 aqueous solution, which can effectively exfoliate VMT and
lead to EML-VMT. The excess water is then removed by microwave
irradiation-assisted heat treatment, which can rapidly heat the
materials [20–22]. The corresponding SEM images of the as-
obtained VMT and EML-VMT are shown in Fig. 1b and c. The raw
VMT could be expanded more than 40 times via soaking in a H2O2
aqueous solution and the subsequent microwave treatment.
Secondly, the EML-VMT-C is formed from the glucose degradation
and carbonization using a hydrothermal synthesis and subsequent
heattreatmentat850 8Cfor4 h. AsshowninFig. 1dandc, thesurface
of EML-VMT was coated by carbon layer and deposited by carbon
nanospheres due to the glucose degradation and carbonization.
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2.2. Catalyst preparation
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In order to achieve 10 wt% HgCl2 loading, HgCl2/EML-VMT and
HgCl2/EML-VMT-C catalysts were prepared using an incipient
wetness impregnation technique. A solution of HgCl2 (222 mg) in
deionized water (7 mL) was added drop wise to the EML-VMT (2 g)
and EML-VMT-C (2 g) respectively, while stirring for 1 h at room
temperature. The samples were soaked for 12 h and dried at 105 8C
for 12 h.
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2.3. Catalyst characterization
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The chemical compositions of raw vermiculite were deter-
mined by X-ray fluorescence (XRF, Panalytical Axios-mAX). X-ray
diffraction (XRD) patterns were determined using a Bruker D8
advanced X-ray diffractometer to evaluate the crystal structure of
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97
the as-obtained samples, using monochromatic Cu K
˚
(l = 1.5406 A) in the range 2u = 108–908. The carbon deposition on
a radiation
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used catalysts was analyzed by a thermogravimetric analysis (TGA,
Netzsch STA449F3). The samples of 10–15 mg were heated at a
rate of 10 K/min from room temperature to 1223 K in an oxygen
flow (50 mL/min). Scanning electron microscopy (SEM, JEOL JSM-
6490LV) and transmission electron microscope (TEM, Hitachi H-
600) were performed to observe the morphologies of the catalysts.
The real HgCl2 content was determined by an atomic fluorescence
spectrometer (AFS-810, Titan Instruments Co., Beijing).
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2.4. Catalytic performance evaluation
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Catalytic performance was measured in a fixed bed reactor
according to our previous paper [17,18]. At first, the reactor was
purged with nitrogen to remove water and air in the reacting
Fig. 1. (a) Schematic illustration of the synthesis process of EML-VMT-C. SEM
images of (b) VMT, (c) EML-VMT, (d) EML-VMT-C and (e) TEM image of EML-VMT-C.
Please cite this article in press as: . , et al., Hydrochlorination of acetylene using expanded multilayered vermiculite (EML-VMT)-
supported catalysts, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.05.020

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V: vermiculite
M: mica
C: carbon
C/M
Used HgCl2/EML-VMT-C
Fresh HgCl2/EML-VMT-C
Used HgCl2/EML-VMT
Fresh HgCl2/EML-VMT
C/V
M
M/V
M/V
V
V
V
M/V
M/V
EML-VMT-C
M/V
M/V
M/V
M/V
M/V
M
V
M/V
M/V
M/V
M/V
M/V
V
EML-VMT
M
M/V
V
V
M/V
M/V
M/V
M/V
V
M/V
M
M
VMT
V
V
10
20
30
40
50
60
70
80
90
10
20
30
40
50
2θ (o)
60
70
80
90
2θ (degree)
Fig. 2. The XRD patterns of VMT, EML-VMT and EML-VMT-C.
Fig. 4. XRD patterns of HgCl2/EML-VMT and HgCl2/EML-VMT-C before and after
reaction.
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Fig. 2 shows the XRD patterns of the as-obtained products. The
reflections of VMT and EML-VMT can be mainly attributed to the
VMT crystal layer (PDF#74-1732) and mica (1M-phlogopite,
PDF#10-0495) [23–25]. The carbon in the EML-VMT-C is detected
in the XRD pattern, and the corresponding diffraction peaks appear
at 2u = 26.68 and 31.38, respectively. Moreover, a thermogravi-
metric analysis (TGA) confirmed the presence of carbon and gave a
carbon content value of 21.8%.
conversion of 97.3% at 250 min. Even after 810 min, the HgCl2/ 171
EML-VMT-C exhibited a value of 86.7%. Moreover, the VCM 172
selectivity for the HgCl2/EML-VMT-C catalyst was easy to reach a 173
value of 100%, while that of the HgCl2/EML-VMT catalysed at about Q3174
92.0%. Additionally, it can be easily found that the calculated 175
turnover frequency (TOF) values of HgCl2/EML-VMT-C catalyst 176
were much higher than those of the HgCl2/EML-VMT catalyst (e.g., 177
reaction time at 90, 250, 330, 410 min, respectively). Compared 178
with the HgCl2/EML-VMT, the HgCl2/EML-VMT-C gave the highest 179
TOF value of 8.83 ꢀ 10ꢁ3 sꢁ1. All results indicated that the catalytic 180
performance of the HgCl2/EML-VMT-C catalyst is much better than 181
The HgCl2/EML-VMT and HgCl2/EML-VMT-C catalysts were
evaluated under a fixed reaction condition at a temperature of
140 8C, an acetylene gas hourly space velocity (GHSV) of 108 hꢁ1
,
and a feed volume ratio V(HCl)/V(C2H2) of 1.15. The real contents
of HgCl2 in HgCl2/EML-VMT and HgCl2/EML-VMT-C were 9.73 wt%
and 9.89 wt%, respectively. As shown in Fig. 3, theHgCl2/EML-VMT
and HgCl2/EML-VMT-C exhibited initial acetylene conversions of
85.7% and 94.8% respectively, corresponding to initial VCM
selectivities of 89.3% and 99.8% respectively. Unfortunately, the
acetylene conversion for the HgCl2/EML-VMT started to decrease
at the reaction time of 250 min. Then, the acetylene conversion
showed continued slowdown and reached the value of 17.1% at
810 min. This is principally because there was much carbon
deposition onto the surface of HgCl2/EML-VMT, which easily
resulted in the dehydrogenation of hydrocarbons. Unlike the
HgCl2/EML-VMT, the HgCl2/EML-VMT-C gave a high acetylene
that of the HgCl2/EML-VMT catalyst.
182
From the XRD patterns in Fig. 4, it can be seen that there are no 183
significant variations from fresh HgCl2/EML-VMT-C to used HgCl2/ 184
EML-VMT-C. Unlike the pattern of the fresh HgCl2/EML-VMT, the 185
used HgCl2/EML-VMT significantly changed at 26.68 due to carbon 186
deposition in the acetylene hydrochlorination process. The amount 187
of solid carbon deposited on the used HgCl2/EML-VMT was up 188
to 5.48%, which indicated that hydrocarbon dehydrogenation 189
occurred severely on the surface of HgCl2/EML-VMT in the 190
acetylene gas flowing process [26]. It is worth noting that only 191
0.78% solid carbon deposited on the used HgCl2/EML-VMT-C, 192
which strongly favored the acetylene hydrochlorination process. 193
Fig. 3. (a) Acetylene conversion in acetylene hydrochlorination of HgCl2/EML-VMT and HgCl2/EML-VMT-C under
GHSV = 108 hꢁ1 and reaction temperature = 140 8C). (b) VCM selectivity and the corresponding TOF values (inset).
a fixed reaction condition (C2H2/HCl = 1:1.15,
Please cite this article in press as: . , et al., Hydrochlorination of acetylene using expanded multilayered vermiculite (EML-VMT)-
supported catalysts, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.05.020

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A novel expanded multilayered vermiculite (EML-VMT) is
successfully used as a catalyst support for the acetylene hydro-
chlorination. The as-obtained HgCl2/EML-VMT catalyst exhibits an
initial acetylene conversion of 85.7% and the corresponding
selectivity of vinyl chloride is 89.3% at a temperature of 140 8C,
an acetylene gas hourly space velocity of 108 hꢁ1, and a feed
volume ratio V(HCl)/V(C2H2) of 1.15. However, the HgCl2/EML-
VMT catalyst was deactivated after 300 min of use. Owing to the
mixing carbon, the as-obtained HgCl2/EML-VMT-C achieved a
high acetylene conversion of 97.3% and showed good stability.
The corresponding selectivity of vinyl chloride was100% and the
turnover frequency (TOF) value was 8.83 ꢀ 10ꢁ3 sꢁ1. We believe
that this EML-VMT represents a new way to prepare the catalysts
for the acetylene hydrochlorination and can potentially be
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Acknowledgments
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This work was financially supported by National Natural
Science Foundation of China (Nos. 21163015, 21366027), the
Doctor Foundation of Bingtuan (No. 2014BB004), the National
Basic Research Program of China (973Program, No.
2012CB720300), the Program for Changjiang Scholars, Innovative
Research Team in University (No. IRT1161), the Program of Science
and Technology Innovation Team in Bingtuan (No. 2011CC001).
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Please cite this article in press as: . , et al., Hydrochlorination of acetylene using expanded multilayered vermiculite (EML-VMT)-
supported catalysts, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.05.020