Mesoporous carbon with controllable pore sizes as a support of the AuCl3 catalyst for acetylene hydrochlorination

Article abstract of DOI:10.1039/c4cy01172d

Mesoporous carbon materials with controllable pore sizes within the range of 5.6-40.5 nm were successfully synthesized using colloidal silica as hard templates and boric acid as the pore expanding agent. The catalytic properties of the 0.5% AuCl₃ loaded mesoporous carbon catalysts towards acetylene hydrochlorination were tested in a fixed-bed reactor. Under reaction conditions of 180 °C, C₂H₂ hourly space velocity = 720 h^-1 and HCl/C₂H₂ feed volume ratio = 1.15, it was found that larger mesoporous carbon supports could accelerate the reaction rate, resulting in higher acetylene conversion. The AuCl₃ catalyst supported on mesoporous carbon with a pore size of about 40.5 nm displayed excellent catalytic activity (acetylene conversion was above 83%). The dependence of regular catalytic performance on pore size is important for acetylene hydrochlorination because large pore sizes enable fast molecular diffusion, thus suppressing coke formation.

Full text of DOI:10.1039/c4cy01172d

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Controlled mesoporous carbon as support of AuCl3 catalyst for acetylene
hydroclorination
Kun Chen a, Lihua Kang a,b, Mingyuan Zhu a, b *, Bin Dai a, b *
aSchool of Chemistry and Chemical Engineering of Shihezi University, Shihezi,
Xinjiang, 832000, P. R. China.
bKey Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan,
Shihezi, Xinjiang, 832000, P. R. China.
*Corresponding author. Tel.: +86 9932057270; Fax: +86 9932057210.
E-mail address: zhuminyuan@shzu.edu.cn (M. Zhu)
db_tea@shzu.edu.cn (B. Dai)
1

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Abstract: Mesoporous carbon materials with controllable pore sizes within the
range of 5.6–40.2 nm were successfully synthesized using colloidal silica as hard
templates and boric acid as the pore expanding agent. The catalytic properties of the
0.5% AuCl3 loaded mesoporous carbon catalysts towards acetylene hydrochlorination
o
were tested in a fixedꢀbed reactor. Under reaction conditions of 180 C, C2H2 hourly
space velocity = 720 hꢀ1 and the feed HCl/C2H2 volume ratio = 1.15, it was found that
larger mesoporous carbon supports could accelerate reaction rate, resulting in higher
acetylene conversion. Supported AuCl3 catalyst on mesoporous carbon with pore size
about 40.2 nm displayed excellent catalytic activity (acetylene conversion above
83%). The dependence of regular catalytic performance on pore size is important for
acetylene hydrochlorination because it provides fast molecular diffusion, thus
suppressing coke formation.
Keywords: mesoporous carbon, controlled pore size, acetylene hydrochlorination,
coke formation
2

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1. Introduction
Acetylene hydrochlorination is the main method for synthesizing vinyl chloride
monomer (VCM) in domestic industrial production of polyvinyl chloride from
calcium carbide.1 Currently, acetylene hydrochlorination is primarily performed with
a mercuric chloride catalyst supported on activated carbon (HgCl2/AC). However, the
active component of toxic HgCl2 causes serious environmental problem and causes
damage to human health. Therefore, replacing poisonous HgCl2 with an
environmentꢀfriendly catalyst for acetylene hydrochlorination has received increasing
attention.2
Hutchings et al.3–6 found a positive relationship between the catalytic activity of
metal chlorides and the standard electrode potential of cations. Accordingly, metal
catalysts, such as Au,7 Bi,8,9 and Pt,10 have been intensely investigated to obtain
prominent reactivity toward acetylene hydrochlorination. AuCl3 demonstrates optimal
catalytic activity, and its initial catalytic activity is higher than that of the HgCl2
catalyst. However, the stability of AuCl3 remains inadequate for industrial application.
The deactivation mechanism of Auꢀbased catalysts in the acetylene hydrochlorination
reaction has been investigated.11,12 The deposition of carbonaceous materials on the
catalyst dominates the deactivation process at temperatures lower than 100 °C,
whereas the reduction of Au3+ to Au0 is the deactivation pathway at temperatures
higher than 120 °C. Improving the stability of gold catalyst by introducing other
metals to inhibit the reduction of Au3+ species has received significant attention. In
our previous study, adding La3+ to an Au3+ catalyst improves the stability of the Au3+
3

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catalyst and prolongs its lifetime.13 Additionally, an Au–Co catalyst can be used for 50
h without obvious deactivation to obtain an acetylene conversion of 91.6% under a
gas hourly space velocity (GHSV, C2H2) of 360 h−1 at 150 °C.14 Moreover,
TiO2–AuCl3/AC catalyst15 shows outstanding stability in acetylene hydrochlorination;
adding TiO2 species partially inhibits the reduction of Au3+ to Au0.
The coke formation of carbonaceous materials leads to catalyst deactivation; hence,
the physicochemical properties of supports have an important role in acetylene
hydrochlorination.16,17 SiO2 and TiO2 with surface areas lower than 200 m2/g have
been used as supports of Au catalyst for acetylene hydrochlorination; a negligible
acetylene conversion was obtained compared with that of the carbon supports.18,19
However, activated carbons contain micropores (< 2 nm) only and have no
interconnected porous network; moreover, activated carbons have no sufficient
openꢀpore windows for reactant molecular diffusion and rapid reaction product
transport. Therefore, mesoporous carbons with regularly interconnected mesopores
(2–50 nm) may function as an excellent catalyst support for acetylene
hydrochlorination; the mesoporous channels and a noticeable volume of mesopores
can provide a large space for dispersion of active sites, and thus, may favor the
transportation of substances.20–22 However, the effect of different mesoporous carbons
on Auꢀbased catalysts for acetylene hydrochlorination remains unknown; determining
such effects is fundamental to develop highly efficient and environmentꢀfriendly
nonꢀmercuric catalysts for industrial VCM production.
To investigate the relationship between the pore sizes of carbon supports and the
4

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catalytic properties of AuCl3/C catalysts, we synthesized mesoporous carbon materials
with controllable pore sizes within the range of 5.6–40.2 nm. The synthesized carbon
material was used to support AuCl3 catalyst. The catalytic activity of the obtained
AuCl3/C catalysts was evaluated under the same conditions. A reasonable catalytic
activity was explained through coke deposition.
2. Experimental
2.1. Materials
Sucrose (99.0%, J&K Chemical), boric acid (H3BO3, 99.5%, J&K Chemical), silicon
(IV) oxide (4 nm, 15% in H2O colloidal dispersion, Alfa Aesar), Ludox HSꢀ40 (12 nm,
Sigma Aldrich), silicon (IV) oxide (20 nm, 15% in H2O colloidal dispersion, Alfa
Aesar), C2H2 (gas, 98%), and HCl (gas, ≥ 99%) were used in the present study.
2.2. Catalyst preparation
The synthesis of Cꢀx carbon with tunable pore sizes was performed using the
23
previous method reported by Ji Man Kim et al, where x represents the different
average pore sizes of carbon. In the synthesizing process, sucrose was used as the
carbon precursor, and colloidal silica with different particle sizes was used as hard
template and boric acid was used as pore expanding agent to achieve the various pore
sizes of carbon material. To synthesize Cꢀ5 materials, we added 13.72 g of 4 nm
colloidal silica solution to sucrose (6.25 g), sulfuric acid (0.71 g), H2O (50 mL), and
boric acid solutions (5.65 g). The mixtures were dried at 100 °C for 6 h and at 160 °C
for another 6 h in an oven. The brown powder was carbonized at 900 °C with N2 flow
and heating rate of 5 °C/min for 3 h. The carbonized powder was then etched with
5

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hydrofluoric acid solution to remove silica and boron species. The Cꢀ20/30/40
materials were synthesized by the same method using different silica with larger
colloid particle sizes as the template and increasing the amount of boric acid.
AuCl3/Cꢀx catalysts were prepared through an incipient wetness impregnation
technique using aqua regia as solvent, as described in the literature.24 A solution of
HAuCl4 · 4 H2O (Strem, 31.98 mg) in aqua regia (3.2 mL, 0.5wt. % Au) was added
dropꢀwise to the Cꢀx materials (3.0 g), which were then stirred at room temperature
for 1 h. AuCl3/Cꢀx catalysts were soaked for 24 h and dried at 140 °C for 14 h.
2.3. Catalytic reaction
Catalyst performance in acetylene hydrochlorination was evaluated using a
fixedꢀbed microreactor (i.d. of 10 mm). Before initiating the reaction, the reactor was
purged with nitrogen to remove water and air in the system. HCl gas was passed
through the pipeline at a flow rate of 20 mL/min to activate the catalyst (0.8 g).
Subsequently, the microreactor was heated at 180 °C. Afterward, acetylene and
hydrogen chloride were fed through the microreactor, thus producing a GHSV (C2H2)
of 720 h−1. The exit gas mixture was passed through an absorption bottle containing
clean water and then injected into a Shimadzu GCꢀ2014C chromatograph for analysis.
2.4. Characterization
Physical characterization of the sample was performed using a transmission
electron microscope (TEM, JEOL, JEM 2010 operating at 200 kV) forits
morphological features. Brunauer–Emmett–Teller (BET) surface area data were
collected using a Micromeritics ASAP 2020 instrument by obtaining nitrogen
6

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adsorption isotherms at 77 K. The micropore surface area was estimated using the
tꢀplot method. The pore size distribution was analyzed with the adsorption branch
using the BarrettꢀJoynerꢀHalenda (BJH) algorithm. The total pore volume was
calculated from the amount adsorbed at a relative pressure of 0.99. Thermo
gravimetric analysis (TGA) was conducted with TGA/DTA system (SDT Q600,
America) at room temperature to 900 ºC with air flow of 10 mL/min.
3. Results and discussion
N2 adsorption–desorption isotherms and the corresponding pore size distributions
determined from the adsorption branches of Cꢀx materials are shown in Fig. 1. All
porous carbon samples exhibited type IV nitrogen adsorption isotherm with a broad
intermediate hysteresis loop between H1 and H2; this isotherm is typically attributed to
the adsorption in mesoporous pores. A capillary condensation step occurred at a
relative pressure that ranged from 0.62 to 0.99，which is consistent with the results of
previous studies.25,26 With the increase in the diameter of colloidal silica particles and
the boron content in the carbon precursor, the step gradually shifted to higher relative
pressures. This result implies that pore size increased, which is also confirmed by the
narrow pore size distribution curves shown in Fig. 1b. The structural properties of Cꢀx
materials are summarized in Table 1. The representative structures of mesoporous
carbon with 5.8, 19.6, 29.2, and 40.5 nm pore diameter were also demonstrated. The
results indicated that the pore size of carbon support could be successfully controlled
using boric acid as a poreꢀexpanding agent and colloidal silica as templates. The TEM
images shown in Fig. 2 represent the pore morphologies of Cꢀx after AuCl3 catalyst
7

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loading. Structural integrity, namely, roughly spherical and closely packed structure,
was conserved after catalyst loading, further indicating that pore size increased.
However, distinguishing the homogeneous dispersions of small, spherical, and
uniform dark spots, which correspond to Au nanoparticles, in TEM images is difficult
because of the active components in the state of Au3+ in the supported catalysts.
Table 1 Physical properties of Cꢀx materials
Samples Dp (nm) (a) SBET (m2/g) (b) Vtot (cm3/g) (c) Vmicro (cm3/g) (d) Vmeso ×100 (%)
Cꢀ5
5.6
949.3
866.5
763.1
658.8
1.08
1.08
1.21
1.30
0.32
0.26
0.21
0.15
70.37
75.93
82.64
88.46
Cꢀ20
Cꢀ30
Cꢀ40
19.6
29.2
40.5
(a) Mesopore diameters calculated from the N2 adsorption branches using BJH method. (b)
Surface areas calculated using BET method. (c) Total pore volumes estimated from the N2 sorption
isotherms at p/p0 = 0.99. (d) Micropore volume with diameters less than 2 nm calculated at p/p0 =
0.16 using the Horvath–Kawazoe formula.
Fig. 1 (a) The corresponding pore size distribution curves of the obtained Cꢀx materials, and (b) N2
adsorption–desorption isotherms. Pore size distribution curves were calculated from adsorption
branches using BJH method.
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Fig. 2 TEM and HRTEM images of fresh catalyst: (a) AuCl3/Cꢀ5, (b) AuCl3/Cꢀ20, (c) AuCl3/Cꢀ30,
and (d) AuCl3/Cꢀ40.
To investigate the effect of pore size on the catalytic performance of AuCl3 catalyst
for acetylene hydrochlorination, we prepared four mesoporous carbons with different
pore sizes (5.9, 19.6, 29.2, and 40.5 nm) to support 0.5% AuCl3. Catalytic activity was
evaluated under the same conditions, and the results are presented in Fig. 3. In general,
acetylene conversion systematically increases with increasing pore sizes. Initial
acetylene conversion increased from 10.2% to 36.6% as the pore sizes of the carriers
increased from 5.9 nm to 40.5 nm. Furthermore, the catalysts exhibited a sequential
increase in their catalytic performances during acetylene hydrochlorination. For the
AuCl3/Cꢀ5 catalyst, the initial acetylene conversion is relatively low and after 8 h
reaction it becomes 46.7%. For AuCl3/Cꢀ20 and AuCl3/Cꢀ30 catalysts, the final
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acetylene conversion increases to 59.0% and 69.8%, respectively. AuCl3/Cꢀ40
catalyst shows the best catalytic performance for acetylene hydroclorination in our
experiments (maximum acetylene conversion of 84.7%). Fig. 4 shows the effect of the
carriers’ pore sizes on acetylene conversion. The final acetylene conversion of
AuCl3/Cꢀx catalysts significantly increased from 46.7% to 84.7% as pore sizes
increased. Thus, using larger mesoporous carbon to support 0.5% AuCl3 would be
favorable in catalysis because it could provide high pore accessibility and facilitate
molecular diffusion. With timeꢀonꢀstream, pore expansion can accelerate the initial
activity; the consequential fast reaction rate can result in high acetylene conversion.
100
90
80
70
60
50
40
AuCl
3
/C-5
/C-20
/C-30
30
20
10
0
AuCl
AuCl
AuCl
3
3
3
/C-40
0
1
2
3
4
5
6
7
8
Reaction Time (h)
Fig. 3 Acetylene conversion of 0.5% AuCl3/Cꢀx catalysts in acetylene hydrochlorination. Reaction
conditions: temperature (T) = 180 °C, C2H2 gas hourly space velocity (GHSV) = 720 h−1, feed
volume ratio VHCl/VC2H2= 1.15.
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90
80
70
60
50
40
0
10
20
30
40
50
Pore Size (nm)
Fig. 4 Effect of the pore sizes of 0.5% AuCl3/Cꢀx catalysts on acetylene conversion.
These findings correspond to the catalytic behavior of AuCl3/Cꢀx catalysts and
confirm that pore entrance size is relatively significant. However, different pore sizes
have fundamentally different catalytic properties. As HCl and C2H2 molecules flow
into the catalyst pore through diffusion, the collision of the pore wall and other
molecules in the active sites produces a reaction. In particular, HCl and C2H2 are
catalyzed by AuCl3 to produce C2H3Cl. The deep transport of the reactant gas into the
AuCl3 active sites and the inefficient transport of organic products, namely, C2H3Cl,
from the reaction zones within a very short distance could accelerate coke formation.
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Fig. 5 TGA curves of different 0.5% AuCl3/Cꢀx catalysts before and after acetylene
hydrochlorination.
6.0
5.5
5.0
4.8
4.5
4.0
3.5
3.3
3.0
2.5
2.0
1.7
1.5
1.0
0.5
0.5
0.0
AuCl3/C-40
AuCl3/C-5
AuCl3/C-20
AuCl3/C-30
Fig. 6 The coke contents of different 0.5% AuCl3/Cꢀx catalysts after acetylene hydrochlorination.
Fig. 5 shows TGA analysis of different 0.5% AuCl3/Cꢀx catalysts before and after
acetylene hydrochlorination, being used to evaluate the degree of coke deposition on
the surface of catalysts. Both fresh and spent AuCl3/Cꢀx catalysts had a visible mass
o
loss before 100 C, indicating that there is miner water adsorption on the surface of
o
catalyst. Whereas there have very little weight loss in the range of 100–250 C, when
the temperature continues to rise from 250 to 458 °C, the AuCl3/Cꢀx catalysts exhibit
a slow weight loss, mainly due to the burning of carbon deposition and carbon carrier
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begin to be oxidized. When the temperature exceeds 458 °C, the AuCl3/Cꢀx catalysts
rapidly decrease in weight indicating that carbon is burned off. Fig. 6 presents the
coke deposition content on porous catalysts; the content was based on previous
reported calculation method.14 Therefore, the amount of coke deposition can be
calculated by the difference of the mess loss between the fresh and spent AuCl3/Cꢀx
catalysts in the temperature range of coke burning (250ꢀ458 °C). It is obvious that the
order of carbon deposition is AuCl3/Cꢀ5 (4.8%) > AuCl3/Cꢀ20 (3.3%) > AuCl3/Cꢀ30
(1.7%) > AuCl3/Cꢀ40 (0.5%). Moreover, the interconnected pore system in larger
mesoporous carbon can favor efficient acetylene conversion better compared with that
in the porous carbons with smaller pore size. Hence, larger and open mesoporous
networks can facilitate the rapid diffusion of organic products from the reaction zones,
resulting in suppressed coke formation and improved catalytic activity.
Table 2 Textural properties of catalysts
Samples
Dp (nm) SBET (m2/g) Vtot (cm3/g) Vmicro (cm3/g) Vmeso×100 (%)
AuCl3/Cꢀ5 (fresh)
5.8
949.3
763.1
658.8
727.4
670.0
546.9
1.10
1.09
1.30
0.97
1.04
1.21
0.34
0.25
0.19
0.17
0.12
0.09
69.09
77.06
85.38
82.47
88.46
93.56
AuCl3/Cꢀ20 (fresh) 19.6
AuCl3/Cꢀ40 (fresh) 40.5
AuCl3/Cꢀ5 (spent)
6.1
AuCl3/Cꢀ20 (spent) 21.8
AuCl3/Cꢀ40 (spent) 44.2
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Fig. 7 (a) The corresponding pore size distribution curves of fresh and spent AuCl3/Cꢀx catalysts,
and (b) N2 adsorption–desorption isotherms.
Porosity should be considered to verify coke formation. The BET results listed in
Table 2 provide an indirect evidence for the coke formation on AuCl3/Cꢀx catalysts.
The specific surface area and total pore volume of AuCl3/Cꢀx catalysts were
moderately reduced after acetylene hydrochlorination. Interestingly, the mesoporosity
of the spent AuCl3/Cꢀx catalysts significantly increased compared with that of the
fresh catalysts. For AuCl3/Cꢀ5, AuCl3/Cꢀ20 and AuCl3/Cꢀ40 catalysts, the increasing
degree of mesoporosity are 13.38%, 11.40% and 8.18% after 8 h reaction, respectively.
It is indicated that there is significant difference among the AuCl3/Cꢀx catalysts for
variation of mesoprosity. The increasing of mesoporosity further proved that
micropores, which are the key components, were filled or blocked, and the coke
formation increased with decreasing pore sizes of mesoporous carbon support.
Therefore, the mesopore in AuCl3/Cꢀx catalysts is an important fraction that functions
as an efficient catalyst support to produce better molecule diffusion. Micropores can
be identified as voids where some pore channels may become inaccessible, thereby
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expanding coke formation. These findings are in good agreement with the N2 sorption
curves and the pore size distribution curves shown in Fig. 7. All N2 adsorption
isotherms are maintained as type IV isotherms with hysteresis loops for mesoporous
adsorption; moreover, wellꢀdefined steps appear in the adsorption–desorption curves
without significant shift in relative pressure. Remarkably, Fig. 7b shows that the BJH
pore size distribution curves of different AuCl3/Cꢀx catalysts narrow down and
sharpen after acetylene hydrochlorination. Thus, the systematic increase in
mesoporosity is mainly due to the fraction of the micropores blocked in
mesostructural supports; hence, the total volume for the coke formation in the carbon
framework decreases, resulting in more dense packing mesopores. This finding is
consistent with the catalytic behavior aforementioned, which exhibited a relatively
constant acetylene conversion after a period of activation that originated from the
active component. AuCl3 in the mesoporous networks exhibited maximum catalytic
performance even when the micropores were plugged.
4. Conclusions
In summary, Cꢀx mesoporous carbon materials with systematic controllable pore
sizes within the range of 5.6–40.2 nm were successfully prepared using boric acid as
poreꢀexpanding agent and different colloidal silica as templates. Loading 0.5% AuCl3
in Cꢀx mesoporous carbon materials were assessed for acetylene hydrochlorination.
Moreover, the effect of pore sizes on catalytic activity was investigated. Pore size
variation significantly affects the initial activity. Larger mesoporous carbon supports
could accelerate the reaction rate, resulting in higher acetylene conversion. In addition,
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the analysis on coke deposition in catalyst supports revealed that catalytic reaction
mainly relies on mesopores even if the micropores are blocked to some extent. The
dependence of regular catalytic performance on pore sizes will be beneficial for
acetylene hydrochlorination, which requires fast molecular diffusion to suppress coke
formation.
Acknowledgments
This work was supported by the National Basic Research Program of China
(973Program, 2012CB720302), the Program for Changjiang Scholars and Innovative
Research Teams in University (PCSIRT, IRT1161), and National Natural Science
Funds of China (NSFC, 21366027).
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