Nitrogen functional groups on an activated carbon surface to effect the ruthenium catalysts in acetylene hydrochlorination

Article abstract of DOI:10.1039/c5ra18851b

To improve the activity and stability of Ru-based catalysts with a carbon support for acetylene hydrochlorination, activated carbon (AC) was consecutively modified by nitration, amination and pyridine, and the effect of the different carbon supports on the Ru-based catalysts for acetylene hydrochlorination was investigated. The results of the FT-IR studies confirmed that -NO₂, -NH₂ and -N-H-N groups were separately grafted onto the surface of the AC. Under the same reaction conditions, the modified catalysts exhibited better catalytic activity compared with the original Ru/AC catalyst. Moreover, the catalyst Ru/AC-NHN showed the best catalytic performance with a slight decrease after 48 h from 93.2% to 91.8%. The increase in catalytic activity indicates that the modification with nitrogen functional groups is beneficial for acetylene hydrochlorination.

Full text of DOI:10.1039/c5ra18851b

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PAPER
Nitrogen functional groups on an activated carbon
surface to effect the ruthenium catalysts in
acetylene hydrochlorination†
Cite this: RSC Adv., 2015, 5, 86172
a
ab
ac
Haiyang Zhangab and Bin Daiab
*
*
Na Xu, Mingyuan Zhu,
Jinli Zhang,
To improve the activity and stability of Ru-based catalysts with a carbon support for acetylene
hydrochlorination, activated carbon (AC) was consecutively modified by nitration, amination and pyridine,
and the effect of the different carbon supports on the Ru-based catalysts for acetylene
hydrochlorination was investigated. The results of the FT-IR studies confirmed that –NO2, –NH2 and
–N–H–N groups were separately grafted onto the surface of the AC. Under the same reaction
conditions, the modified catalysts exhibited better catalytic activity compared with the original Ru/AC
catalyst. Moreover, the catalyst Ru/AC-NHN showed the best catalytic performance with a slight
decrease after 48 h from 93.2% to 91.8%. The increase in catalytic activity indicates that the modification
with nitrogen functional groups is beneficial for acetylene hydrochlorination.
Received 14th September 2015
Accepted 24th September 2015
DOI: 10.1039/c5ra18851b
www.rsc.org/advances
stable acetylene conversion at 96.5% for 48 h at 170 ꢀC and
1. Introduction
a C2H2 gas hourly space velocity (GHSV) of 180 hꢁ1
.
4
In the eld of acetylene hydrochlorination, activated carbon
is the best catalyst carrier. According to the previous report, the
functional groups on an activated carbon surface will affect its
catalytic activity. Recently, Zhao et al. successfully demon-
strated that the doping of nitrogen can efficiently enhance the
catalytic performance of Au/AC and Au-Cs/AC.5,6 Wang et al.
reported that a P-doped carbon support can also signicantly
enhance the catalytic activity of a Au/SAC catalyst for acetylene
hydrochlorination.7 Previous literature also reported that
amino-functionalized metal–organic frameworks adsorbed
pyridine via hydrogen bonding.8 According to this under-
standing of previous work, there are no reports of the amination
of activated carbon with pyridine adsorbed via hydrogen
bonding for acetylene hydrochlorination.
Therefore, in this work, we prepared Ru-based catalysts
supported on activated carbon, which was modied with –NO2,
–NH2 and –N–H–N groups, and assessed their catalytic activity
for acetylene hydrochlorination, aiming to improve the activity
and stability of the acetylene hydrochlorination catalysts. In
combination with characterization using TEM, TPR, XPS and
FT-IR, etc., it was indicated that Ru-based catalysts deposited on
activated carbon modied by –N–H–N exhibited the highest
catalytic activity for acetylene hydrochlorination.
The acetylene hydrochlorination reaction is an important
process to synthesize vinyl chloride in industry. However, the
catalyst used in the reaction is HgCl2, which is highly toxic and
causes serious environmental pollution. Therefore, it is imper-
ative to explore non-mercury catalysts with high activity and
long stability for acetylene hydrochlorination.
The pioneering works of Hutchings suggested that the
activity of metal catalysts was associated with the standard
electrode potentials of the related metal ions.1 Accordingly, the
AuCl3 catalyst is the optimal catalyst with its high activity. In
fact, although Ru is also a precious metal, it is low-cost
compared to Au, and Ru-based catalysts have caused extensive
research. However, the catalytic activity and stability of Ru-
based catalysts still need to be further improved in the acety-
lene hydrochlorination process. Bimetallic Ru-Co/SAC resulted
in good catalytic activity and coking inhibition capability.2 Li
et al. reported that Ru catalysts deposited inside CNT channels
exhibited optimal catalytic activity, with an acetylene conver-
sion of 95.0% and a selectivity to VCM of 99.9%.3 Additionally,
Pu et al. reported that the original Ru/SAC catalyst was oxidized
under air at 300 ꢀC for 1 h with the catalytic performance of
aSchool of Chemistry and Chemical Engineering of Shihezi University, Shihezi,
Xinjiang, 832000, PR China. E-mail: zhuminyuan@shzu.edu.cn; zhangjinli@tju.edu.
cn; Fax: +86 993 2057210; +86-22-27890643; Tel: +86 993 2057270; +86-22-27890643
bKey Laboratory for Green Processing of Chemical Engineering of Xinjiang, Bingtuan,
Shihezi, Xinjiang, 832000, PR China
2. Experimental
2.1. Materials
cSchool of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072,
Activated carbon (neutral, coconut carbon) was purchased from
Tangshan United Carbon Technology Co., Ltd; RuCl3 (with
48.7% Ru content) and nitric acid (AR, 65.0–68.0%) were
PR China
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c5ra18851b
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purchased from Tianjin Fengchuan Chemical Reagent Tech- was 100 mg. Prior to each test, the samples were treated with N2
nology Co., Ltd; acetic anhydride (AR, $98.5%) was purchased gas at 60 ꢀC for 1 h. Aer cooling, the temperature was increased
from Tianjin Yongsheng Chemical Reagent Co., Ltd; pyridine from 30 to 800 ꢀC at a heating rate of 10 ꢀC minꢁ1 with a 10.0%
(AR, $99.5%) was purchased from Tianjin Fuyu Fine Chemical H2/Ar atmosphere owing at
a .
rate of 40 mL minꢁ1
Co., Ltd; aqua ammonia (AR, 25.0–28.0%) and sodium boro- Temperature-programmed desorption (TPD) was also analyzed
hydride (AR, $97.0%) were purchased from Chengdu Kelong using TPDRO 1100 apparatus at a temperature ramp of 25–400
ꢁ1
ꢀ
Chemical Reagent Company. All the other materials and ꢀC with a ramp rate of 10 C min and a ow rate of 45 mL
chemicals were commercially available and were used without minꢁ1. The nal temperature of 400 C was maintained for 20
ꢀ
further purication.
min. X-ray photoelectron spectroscopy (XPS) data were recorded
using an Axis Ultra spectrometer equipped with a mono-
chromatized Al-Ka X-ray source (225 W).
2.2. Modication of AC samples
According to the previously reported method,9 nitration modi-
cation of the AC sample was performed as follows: 30 mL of
nitric acid was slowly dripped into a suspension of AC and 40
mL of acetic anhydride in a three-neck round bottom ask at
room temperature. Aer stirring at this temperature for 24 h,
the solid sample was ltrated and washed until the ltrate was
neutral. The sample was dried at 110 ꢀC for 14 h, and labeled as
AC-NO2.
Amination of the AC-NO2 sample was carried out as follows:
AC-NO2 was mixed with 10 mL of ammonia solution and 20 mL
of deionized water. Aer adding 0.75 g of sodium borohydride,
the suspension was kept at room temperature for 24 h under
stirring. The solid was ltrated, washed with deionized water
until the ltrate was neutral, and then dried at 110 ꢀC for
another 24 h. The obtained sample was labeled as AC-NH2.
2.5. Catalytic performance tests
The catalytic performance tests for acetylene hydrochlorination
were carried out in the xed-bed reactor (i.d., 10 mm). A purge
pipeline with nitrogen was used prior to the catalytic reaction to
remove any water and air in the system. Then the catalyst (2 mL)
was activated with hydrogen chloride (gas, 99%) at a ow rate of
20 mL minꢁ1. Aer the reactor was heated to 180 ꢀC, acetylene
(11.8 mL minꢁ1) and hydrogen chloride (13.5 mL minꢁ1) were
fed through the heated reactor to achieve a GHSV (C2H2) of 360
hꢁ1, which contained 2 mL of catalyst. The reaction products
were analyzed by gas chromatography (GC-2014C).
Then 20 mL of pyridine was dripped into AC-NH2 in a three- 3. Results and discussion
neck round bottom ask at room temperature. Aer stirring at
The catalytic performance of the catalysts and the supports are
this temperature for 24 h, the solid samples were ltrated and
shown in Fig. 1. It can be seen that the supports (AC, AC-NO2,
AC-NH2 and AC-NHN) exhibit relatively low activity for the
acetylene hydrochlorination (Fig. 1a). Compared with the orig-
inal Ru/AC catalyst, the catalytic activity and stability of the Ru-
based catalysts (Ru/AC-NO2, Ru/AC-NH2 and Ru/AC-NHN) are
greatly enhanced when the AC is modied with nitrogen func-
tional groups, and the initial acetylene conversion increases as
the activated carbon is decorated consecutively, achieving the
highest value of 93.2% over the Ru/AC-NHN catalyst with no
obvious decline aer 48 hours of reaction. All of these related
catalysts show the selectivity to VCM at above 99.0% at 48 h
(Fig. 1b and d). This result indicates that the presence of
nitrogen functional groups, especially –NHN, promotes the
initial catalytic activity of the Ru-based catalysts and signi-
ꢀ
washed until the ltrate was neutral, and then dried at 110 C
for 14 h. The obtained sample was labeled as AC-NHN.
2.3. Preparation of Ru-based catalysts
The Ru-based catalysts were prepared via the incipient wetness
impregnation method.10 A RuCl3 aqueous solution was quanti-
tatively mixed with a modied carbon support under stirring to
prepare the catalyst with a Ru loading content of 1 wt%. Then
the catalyst was desiccated at 140 ꢀC for 18 h. The obtained
catalysts were labeled as Ru/AC, Ru/AC-NO2, Ru/AC-NH2 and
Ru/AC-NHN.
2.4. Catalyst characterization
Low temperature N2 adsorption–desorption experiments were cantly enhances the catalyst stability.
performed with a Micromeritics ASAP 2020 instrument to
The FT-IR spectra of the supports AC, AC-NO2, AC-NH2 and
investigate the surface area and porosity. Fourier-transform AC-NHN are shown in Fig. 2. Compared with AC, AC-NO2 shows
infrared spectroscopy (FT-IR) was used to judge the functional a characteristic peak at 1328 cmꢁ1, which is assigned to the
group changes with Harrick’s Praying Mantis diffuse reection fundamental vibration of the –NO2 group.11 However, the peak
attachment. Transmission electron microscopy (TEM) was per- disappears aer further amination of the AC-NO2 support, and
formed with a JEM2010 electron microscope at an accelerating for the AC-NH2 support, the peaks at 3744 and 1521 cmꢁ1 are
voltage of 200 kV. X-ray diffraction (XRD) patterns were assigned to the vibrations of NH2 and NH in the amine groups,
collected using a Bruker D8 advanced X-ray diffractometer with respectively.12 Further, the characteristic peak of NH has shied
Cu-Ka irradiation (l ¼ 1.5406 A) at 40 kV and 40 mA at wide to a lower wavelength (1508 cmꢁ1) and a new peak at 2987 cmꢁ1
˚
angles (10–90ꢀ in 2q). Temperature-programmed reduction has appeared in the AC-NHN spectrum. This is probably due to
(TPR) measurements were performed using a TPDRO 1100 the action of hydrogen bonding, formed from pyridine accept-
(Thermo-Finnigan) instrument equipped with
conductivity detector (TCD). The weight of the tested samples the FT-IR results conrm that the nitrogen functional groups
a
thermal ing a proton from NH2 to give a strong hydrogen bond.13 Thus,
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Fig. 1 Acetylene conversion (a and c) and selectivity (b and d) to VCM over the supports and the catalysts. Reaction conditions: temperature (T) ¼
180 ꢀC, GHSV (C2H2) ¼ 360 hꢁ1 and V(HCl)/V(C2H2) ¼ 1.15.
Table 1 Elemental analysis for the supports
Element composition (%)
Samples
C
H
N
AC
85.99
78.77
80.88
82.57
3.36
3.59
3.82
3.51
0.21
0.73
1.05
1.67
AC-NO2
AC-NH2
AC-NHN
Table 2 Physical properties of the different AC samplesa
V
Samples
SBET (m2 gꢁ1
)
(cm3 gꢁ1
)
D (nm)
AC
1030
871
933
924
0.57
0.44
0.52
0.51
2.20
2.01
2.25
2.21
AC-NO2
AC-NH2
AC-NHN
a
SBET: surface area; V: total pore volume; D: average pore diameter.
Fig. 2 FT-IR spectra of: (a) AC, (b) AC-NO2, (c) AC-NH2 and (d) AC-
(–NO2, –NH2 and –NHN) were successfully graed onto the
surface of the AC in the consecutive modication steps.
NHN.
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Table 3 Estimated Ru element dispersion in the catalysts determined
by CO chemisorption
CO uptake (mmol
CO per g)
Ru dispersion
(%)
Catalysts
Ru/AC
76.54
63.95
50.12
43.70
80.58
68.04
51.17
45.53
Ru/AC-NO2
Ru/AC-NH2
Ru/AC-NHN
Fig. 3 X-ray diffraction patterns of (a) the AC support, and the fresh
catalysts (b) Ru/AC, (c) Ru/AC-NO2, (d) Ru/AC-NH2 and (e) Ru/AC-
NHN.
Fig. 5 TGA curves of the fresh and used catalysts of Ru/AC-NHN.
Table 4 Carbon deposition of the Ru-based catalysts
Content of carbon
Catalysts
deposition (%)
Ru/AC
13.2
6.8
3.2
1.9
Ru/AC-NO2
Ru/AC-NH2
Ru/AC-NHN
consecutively modied, indicating the presence of nitrogen-
containing functional groups. Table 2 shows the specic
surface area and total pore volume of the AC support before and
aer surface modication. The BET surface areas for AC, AC-
Fig. 4 TEM images of the fresh catalysts: (a) Ru/AC, (b) Ru/AC-NO2, (c)
Ru/AC-NH2, and (d) Ru/AC-NHN.
NO2, AC-NH2 and AC-HNH are 1030, 871, 933 and 924 m2 gꢁ1
,
respectively. The pore volumes of AC, AC-NO2, AC-NH2 and AC-
HNH are 0.57, 0.44, 0.52 and 0.51 cm3 gꢁ1, respectively. The
decrease in the BET surface areas and pore volumes may also
indicate that the functional groups were successfully graed on
the surface of the AC and that the pores were occupied by these
groups aer surface modication.15,16
Elemental analysis was carried out to determine the amount
of nitrogen-containing groups graed onto the activated carbon
surface, the results are listed in Table 1. Only a trace amount of
nitrogen is detected on AC, which possibly originates from
weakly physisorbed nitrogen impurities on the surface.14 Then
the content of nitrogen increases gradually from 0.73% for AC-
NO2 to 1.67% for AC-HNH as the activated carbon was
Fig. 3 shows the XRD patterns of the AC, and the fresh
catalysts Ru/AC, Ru/AC-NO2, Ru/AC-NH2 and Ru/AC-NHN. As
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Fig. 6 TPR profiles of the supports: (a) AC, (b) AC-NO2, (c) AC-NH2 and (d) AC-NHN, and the catalysts: (a) Ru/AC, (b) Ru/NH2, (c) Ru/AC-NHN,
and (d) Ru/AC-NO2.
Table 5 The relative areas of the H2 consumption peaks for the
catalysts
functional groups, with a lowest dispersion of 45.53% achieved
for the Ru/AC-NHN catalyst, followed by Ru/AC-NH2 (51.17%)
and Ru/AC-NO2 (68.04%). Thus, the modication of activated
carbon is not benecial to improve the dispersion of the
H2 consumption
peaks (%)
Catalysts
catalyst.
TGA analysis was carried out to measure the amount of
Ru/AC
4.16
68.60
6.64
Ru/AC-NO2
Ru/AC-NH2
Ru/AC-NHN
carbon deposition, and the results are shown in Fig. 5. In the
case of the Ru/AC-HNH catalyst, both the fresh and the used
20.60
ꢀ
catalysts have a slight weight loss before 150 C owing to the
desorption of adsorbed water (Table S1†). In the temperature
range of 150–400 ꢀC, there is an obvious weight loss (10.0%,
Table S1†) for the used catalyst. When the temperature exceeds
400 ꢀC, there appears to be a rapid weight loss mainly due to the
combustion of the activated carbon. Thus, the coke burning
may occur in the temperature range of 150–400 ꢀC. Taking into
account that the AC support can lose its weight by reacting with
oxygen to emit CO2, the amount of carbon deposition is calcu-
lated by the difference in the weight loss between the fresh and
shown in Fig. 3, apart from the two obvious diffraction peaks at
23.4ꢀ and 43.5ꢀ originating from the (002) and (101) planes of
AC, no discernible reection of metallic Ru or anhydrous
tetragonal RuO2 is detected for any of the catalysts,17 indicating
a high dispersion of active species or a small particle size (< 4
nm).18 In addition, the TEM images in Fig. 4 show that it is
difficult to distinguish the homogeneous dispersion of small
and uniform Ru particles. This may be due to a high dispersion
of the Ru particles, which is consistent with the XRD results.
Moreover, the dispersion of the Ru elements was estimated by
CO chemisorption experiments.19 As listed in Table 3, the Ru
dispersion is 80.58% for the Ru/AC catalyst. However, the Ru
dispersion decreases aer modication with the nitrogen
the used catalysts in the temperature range of 150–400 C.20–22
ꢀ
Based on Fig. 5, the amount of carbon deposition on the used
Ru/AC-HNH catalyst is calculated to be 1.9%.
Similarly, the carbon deposition on the other used catalysts
was also calculated via the corresponding TG and DTG curves
(Fig. S1†). As listed in Table 4, for the Ru-based catalysts, the
Table 6 The relative content and binding energy of ruthenium species in the fresh and used catalysts
Binding energy (eV), (Area%)
Samples
Ru
RuCl3
RuO2
RuOx
Fresh Ru/AC
461.86(14.44)
461.53(3.95)
462.10(13.32)
461.67(9.96)
461.31(21.10)
461.45(31.88)
462.85(24.70)
462.15(17.69)
463.52(50.52)
463.22(40.24)
463.43(47.30)
463.13(35.04)
463.18(46.51)
463.14(33.66)
463.78(40.38)
463.30(33.27)
465.04(18.69)
464.83(31.19)
465.08(30.37)
464.71(40.22)
464.72(17.44)
464.48(28.50)
465.15(24.09)
464.65(35.03)
466.45(16.35)
466.70(24.62)
466.66(9.01)
467.03(14.78)
466.59(14.95)
466.16(5.96)
466.88(10.83)
466.12(14.01)
Fresh Ru/AC-NO2
Fresh Ru/AC-NH2
Fresh Ru/AC-NHN
Used Ru/AC
Used Ru/AC-NO2
Used Ru/AC-NH2
Used Ru/AC-NHN
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Fig. 7 TPD evolution profiles of the Ru-based catalysts for the desorption of (a) HCl- and (b) C2H3Cl-.
amount of carbon deposition increases in the order: Ru/AC- four peaks at 461.86 eV, 463.52 eV, 465.04 eV and 466.45 eV,
NHN (1.9%) < Ru/AC-NH2 (3.2%) < Ru/AC-NO2 (6.8%) < Ru/AC corresponding to the species of metallic Ru, RuCl3, RuO2 and
(13.2%). This clearly indicates that the AC support modied RuOx, respectively.27–29 Table 6 shows the ruthenium species
by nitrogen functional groups can greatly prevent the coking and their relative amounts in the fresh and used Ru-based
deposition of the Ru catalyst.
catalysts. The fresh Ru/AC catalyst consists of 50.52% RuCl3,
Fig. 6 displays the TPR proles of the supports and Ru-based 18.69% RuO2, 16.35% RuOx and 14.44% metallic Ru. For the
catalysts. The broad peak in the range of 500–700 ꢀC for all the fresh Ru-based catalysts deposited on activated carbon modi-
samples is attributed to the reduction of oxygenated groups in ed by nitrogen functional groups, the content of RuO2 is
the carbon support. For the AC-NO2 support, a weak reduction clearly higher than that of the fresh Ru/AC. The previous work
ꢀ
peak appeared in the temperature range of 350–480 C, which demonstrated that RuO2 is an important active ingredient in
corresponds to the characteristic reduction band of –NO2. acetylene hydrochlorination. The carbon modied by nitrogen
However, no obvious peaks appeared in the same temperature functional groups can inuence the performance of the resul-
range for the other modied carriers. Obviously, there are some tant catalysts, due to enhanced p bonding in the framework,
H2 consumption peaks in the temperature range of 100–400 ꢀC and promote their electron donor–acceptor properties.
for all of the Ru-based catalysts, which are due to the reduction However, the detailed reaction mechanism is yet to be explored
of ruthenium species involving the ruthenium oxides and in future work.
ruthenium chloride in the catalysts. Specically, for the Ru/AC
Fig. 7 shows the HCl- and C2H3Cl-TPD proles of the Ru-
catalyst, the peak at 138 ꢀC is attributed to the reduction of based catalysts. The desorption area corresponds to the
RuCl3.23 The Ru/AC-NO2 catalyst exhibits a shoulder peak at 299 amount of adsorbed species on the catalysts, and the desorp-
ꢀ
ꢀC and a strong peak at 323 C attributed to the reduction of tion temperature reects the adsorption strength. As seen in
Run+ (n $ 4) species.24 While for the Ru/AC-NH2 catalyst, there Fig. 7a, the HCl desorption peak areas on the Ru-based catalysts
ꢀ
ꢀ
are two peaks at 202 C and 293 C, which correspond to the loaded on modied activated carbon are larger than those on
reduction peaks of RuCl3 and RuO2, respectively.25,26 The cata- Ru/AC, while the corresponding desorption temperatures are
lyst Ru/AC-NHN shows a broad peak corresponding to RuO2 at slightly higher. Fig. 7b shows the desorption of C2H3Cl on the
ꢀ
291 C. Through comparing the TCD signals with a standard, Ru-based catalysts. The peak area on Ru/AC-NHN is the smallest
the fraction of different Ru species existing in these fresh compared with the other catalysts, which is benecial for the
catalysts can be estimated. Calculated from the peak area of acetylene hydrochlorination reaction. This indicates that the
TPR, it is worth mentioning that the relative areas of the H2 catalysts loaded on the modied activated carbon show
consumption peaks reduce in the order: Ru/AC (4.16%) < Ru/ enhanced adsorption of hydrogen chloride and waning
AC-NH2 (6.64%) < Ru/AC-NHN (20.60%) < Ru/AC-NO2 (68.60%) adsorption of vinyl chloride, which promotes higher catalytic
(Table 5). This suggests that there may exist an interaction activities for the acetylene hydrochlorination reaction (Fig. 1c).
between the active species and the supports to inuence the
ruthenium species content.
4. Conclusion
To explore the amount and kind of ruthenium species, the
Ru-based catalysts with different supports were prepared using
the incipient wetness impregnation method. To study the
change of the AC modied with nitrogen function groups and
the effects on the Ru-based catalysts, the characterization
techniques XRD, BET, TEM, FT-IR, TPD, TPR and XPS were
XPS deconvolution of Ru 3p3/2 (Fig. S2 and S3 in ESI†) was used
to distinguish the different species, including their binding
energy and relative quantity. For both the fresh and used Ru-
based catalysts, the Ru XPS spectra were deconvoluted into
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Acknowledgements
This work is supported by the National Basic Research Program
of China (973 Program, 2012CB720302), National Natural
Science Funds of China (NSFC, U1403294, 21366027), Young
Scientic and Technological Innovation Leader of Bingtuan
(2015BC001), and the Foundation of Young Scientist in Shihezi
University (No. 2013ZRKXJQ03).
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