Hydrophilicity modification of MCM-41 with zirconia and supported ruthenium-lanthanum for benzene hydrogenation to cyclohexene

Article abstract of DOI:10.1080/15533174.2012.756905

Zirconia modified mesoporous molecular sieve MCM-41 supports were prepared by hydrothermal synthesis method, in situ synthesis method and precipitation method. Ruthenium and lanthanum supported on MCM-41 and zirconia modified MCM-41 catalysts were prepared via two solvents impregnation method. The catalysts were characterized by X-ray diffraction, transmission electron microscopy, nitrogen adsorption-desorption, and water/benzene static adsorptions techniques. It has been found that Ru-La supported on MCM-41 modified with zirconia by hydrothermal synthesis method (Ru-La/ZrO₂-MCM-41-HS) leads to the biggest increase of the hydrophilicity. Ru-La/ZrO₂-MCM-41-HS catalyst with the highest hydrophilicity shows the best performance in liquid phase hydrogenation of benzene to cyclohexene. Copyright Taylor & Francis Group, LLC.

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Hydrophilicity Modification of MCM-41 With Zirconia
and Supported Ruthenium-Lanthanum for Benzene
Hydrogenation to Cyclohexene
Hongguang Liao a , Jing Zhang a , Pingle Liu a , Fang Hao a , Kuiyi You a & He′an Luo a
a College of Chemical Engineering , Xiangtan University , Xiangtan , P. R. China
Accepted author version posted online: 17 Apr 2013.Published online: 14 May 2013.
To cite this article: Hongguang Liao , Jing Zhang , Pingle Liu , Fang Hao , Kuiyi You & He′an Luo (2013) Hydrophilicity
Modification of MCM-41 With Zirconia and Supported Ruthenium-Lanthanum for Benzene Hydrogenation to
Cyclohexene, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:9, 1206-1211, DOI:
10.1080/15533174.2012.756905
To link to this article: http://dx.doi.org/10.1080/15533174.2012.756905
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:1206–1211, 2013
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.756905
Hydrophilicity Modification of MCM-41 With Zirconia
and Supported Ruthenium-Lanthanum for Benzene
Hydrogenation to Cyclohexene
Hongguang Liao, Jing Zhang, Pingle Liu, Fang Hao, Kuiyi You, and Heꢁan Luo
College of Chemical Engineering, Xiangtan University, Xiangtan, P. R. China
catalyst for benzene hydrogenation to cyclohexene. It has been
found that ruthenium metal is recorded as the most active com-
ponent on synthesizing cyclohexene from benzene hydrogena-
tion.[5] Numerous literature reports liquid phase hydrogenation
of benzene to cyclohexene over unsupported ruthenium based
alloy catalyst[6–11] or supported ruthenium based catalyst.[12–25]
It has also been found that La, Cu, Zn, Ce, or Fe is introduced
as promoter to improve the performance of the catalysts.[26–30]
Although there are numerous literature on selective hydrogena-
tion of benzene to cyclohexene, Asahi Chemical Industry Co. is
the only one who has succeeded in the commercialization of the
process for producing cyclohexene from benzene hydrogenation
over metallic ruthenium-zinc particles catalyst.[31]
Zirconia modified mesoporous molecular sieve MCM-41 sup-
ports were prepared by hydrothermal synthesis method, in situ
synthesis method and precipitation method. Ruthenium and lan-
thanum supported on MCM-41 and zirconia modified MCM-41
catalysts were prepared via two solvents impregnation method.
The catalysts were characterized by X-ray diffraction, trans-
mission electron microscopy, nitrogen adsorption-desorption, and
water/benzene static adsorptions techniques. It has been found
that Ru-La supported on MCM-41 modified with zirconia by hy-
drothermal synthesis method (Ru-La/ZrO2-MCM-41-HS) leads to
the biggest increase of the hydrophilicity. Ru-La/ZrO2-MCM-41-
HS catalyst with the highest hydrophilicity shows the best perfor-
mance in liquid phase hydrogenation of benzene to cyclohexene.
From the point view of thermodynamic analysis, we can
see that benzene hydrogenation is favored to produce cyclohex-
ane,[32] with smaller standard formation free-energy than that
of cyclohexene. The key point for benzene hydrogenation to
cyclohexene with high selectivity lies in promoting the des-
orption of the produced cyclohexene from the catalyst and in-
hibiting the reabsorption so as to prevent further hydrogenation
to cyclohexane. The hydrophilic supports are in favor of the
formation of a stagnant water layer on its surface which may
promote the desorption of the formed cyclohexene.[33] However,
there are very few reports on hydrophilic modified mesoporous
molecular sieve supported ruthenium catalyst used in benzene
hydrogenation to cyclohexene.
Keywords benzene hydrogenation, cyclohexene, hydrophilicity, lan-
thanum, ruthenium, zirconia modified MCM-41
INTRODUCTION
Cyclohexene can be used to produce caprolactam and adipic
acid, which are principal precursors of nylon-6 and nylon-66.[1,2]
The production route for caprolactam and adipic acid based
on cyclohexene oxidation or hydration has the advantages of
high yield, environmental friendliness, and atomic economy.
However, the conventional methods for the production of cy-
clohexene have the drawbacks of expensive raw materials, poor
efficiencies, complicated operations, or a large number of by-
products.[3] Since Hargod and Zwietering[4] first obtained a yield
of cyclohexene of 0.18% in liquid phase hydrogenation of ben-
zene over Ru catalyst in 1963, the selective hydrogenation of
benzene to cyclohexene has attracted extensive research interest.
Researchers have been focusing on the development of suitable
In this study, Ru-La supported on zirconia modified meso-
porous molecular sieve MCM-41 catalysts were used in benzene
hydrogenation in ZnSO4 solution. MCM-41 modified with zir-
conia by different methods and its effect on hydrophilic index
and catalytic performance were discussed.
EXPERIMENTAL
Received 19 November 2012; accepted 5 December 2012.
This work was supported by the NSFC (21276218), program
for New Century Excellent Talents in University (NCET-10–0168),
SRFDP (20124301110007), and Project of Hunan Provincial Science
& Technology Department (2010WK2008).
Address correspondence to Pingle Liu, College of Chemical Engi-
neering, Xiangtan University, Xiangtan, 411105, P. R. China. E-mail:
liupingle@xtu.edu.cn
Materials
RuCl3·xH2O (Ru wt% = 37.1%) and cyclohexene were
purchased from Shanghai Jiuyue Chemical Industry Corpo-
ration Limited, China. Benzene, cyclohexane, ZrOCl2·8H2O,
ZnSO4·7H2O, La(NO3)3·6H2O, tetraethoxysilane (TEOs), cetyl
trimethyl ammonium bromide (CTAB), ammonia solution
1206

ZrO2 MODIFIED MCM-41 SUPPORTED Ru-La CATALYST
1207
(25–28 wt%), and ethanol were purchased from Tianjin Guangfu a Quantachrome NOVA-2200e automated gas sorption system
Fine Chemical Research Institute, China. All reagents were an- (Boynton Beach, FL, USA). Hydrophilic index was obtained by
alytical grade. MCM-41 was purchased from Nanjing Jcnano static adsorption method and was defined as the ratio of water
Technology Corporation Limited. H2 (99.99%) was provided static adsorption value to benzene static adsorption value.
by Zhuzhou Diamond Gas Company, China.
Procedures for the Catalytic Test
Benzene hydrogenation was carried out in a 100 mL Teflon-
lined stainless-steel autoclave equipped with temperature detec-
Catalyst Preparation
The zirconia modified MCM-41 supports were prepared by
tor and pressure controller. Typically, 20 mL of 0.3 M ZnSO4
hydrothermal synthesis method, in situ synthesis method and
aqueous solution, 10 mL of benzene, and 0.2 g of catalyst were
precipitation method, which are marked as ZrO2-MCM-41-HS,
added into the autoclave. The reactor was sealed, purged with
ZrO2-MCM-41-ISS, and ZrO2-MCM-41-PS, respectively. As to
H2 to replace the air, and then it was pressurized to 4 MPa with
ZrO2-MCM-41-HS, MCM-41 powder was dispersed in 0.01 M
H2 under stirring after the desired temperature reached. After
ZrOCl2 with stirring for 30 min. Ammonia solution (25 wt%)
reaction, the organic phase was separated and the unreacted
was dropped to adjust the pH to 10. After dispersing under ul-
benzene and the products were determined by GC (GC-14C,
trasonication for 30 min, the slurry was transferred to a Teflon-
SHIMADZU, Kyoto, Japan) with a flame ionization detector
lined autoclave and kept at 453 K for 12 h. Then it was filtrated,
washed with distilled water and ethanol and dried at 333 K
(FID) and a 30 m DB-1701 capillary column.
for 12 h. As to ZrO2-MCM-41-ISS, the ammonia solution, the
TEOs and the aqueous solution of ZrOCl2 were dropped into the RESULTS AND DISCUSSIONS
aqueous solution of CTAB with stirring. The gel was transferred
Characterization of Catalysts
to a Teflon-lined autoclave and aged at 383 K for two days. Then
Figure 1 shows the XRD patterns of different samples. All the
the aged sample was filtrated and washed with distilled water
samples exhibit significant feature diffraction peak around 2θ =
and ethanol. Finally, it was dried at 363 K for 12 h and calci-
nated at 823 K for 5 h in air with a heating rate of 1 K/min.
22◦ corresponding to amorphous silica. MCM-41 shows excel-
lent dispersion due to the high specific surface area (Table 1)
As to ZrO2-MCM-41-PS, MCM-41 powder was dispersed in
and uniform mesoporous structure. There are not any observ-
15 mL 0.025 M ZrOCl2 with stirring for 30 min. 20 mL 0.05 M
able peaks attributed to zirconia and ruthenium in the XRD pat-
ammonia solution was dropped into the previous aqueous solu-
terns of zirconia modified MCM-41 supports and Ru-La/MCM-
tion. After aging for 1 h, the slurry was filtrated, washed with
41catalyst, which testifies that zirconia and ruthenium particles
distilled water and ethanol. Finally, it was dried at 373 K for
are uniformly dispersed on the surface of MCM-41. There is
12 h and calcinated at 773 K for 4 h in air with a heating rate of
5 K/min.
only a broad diffraction peak around 2θ = 44◦ assigned to the
(101) crystalline plane of ruthenium in the XRD pattern of Ru-
Ru-La/ZrO2-MCM-41 catalysts were prepared by two sol-
La/ZrO2-MCM-41-HS. Theresults of XRDpatterns suggest that
vents impregnation method. Typically, 1.0 g of ZrO2-MCM-41
the modification of zirconia decreases the dispersion of ruthe-
was dispersed in 24 mL of cyclohexane with stirring for 15 min.
nium particles a little on Ru-La/ZrO2-MCM-41-HS catalyst. As
2 mL of aqueous solution containing 0.2696 g of RuCl3·xH2O
and 0.0438 g of La(NO3)3·6H2O was dropped into the above
solution and stirred for 10 min. After the decantation of the
supernatant, the remanent black solid was dried at 373 K for
12 h, and then reduced at 573 K for 4 h under 40 mL/min of
25 vol.% H2/N2. Ru-La/MCM-41 catalyst was prepared by the
similar method except that the support changed.
Catalyst Characterization
Powder X-ray diffraction (XRD) patterns were determined
under a D/max2500 TC diffractometer (Rigaku, Tokyo, Japan)
using Cu Kα radiation (λ = 1.542 Å). The tube voltage was
40 kV, the current was 30 mA, and the scan range was 2θ =
5–90◦ with a scanning rate of 1◦ min–1. The microstructures
of the samples were observed by transmission electron mi-
croscopy (TEM) on a JEM-2100 electron microscope (JEOS,
Tokyo, Japan) working under 200 kV. The samples were de-
posited on a copper grid coated with a holey carbon film. Spe-
cific surface area, pore volume and pore size distribution of the
FIG. 1. The XRD patterns of different samples.
samples were obtained by the nitrogen adsorption-desorption on

1208
H. LIAO ET AL.
TABLE 1
the ruthenium nanoparticles images on the surface of MCM-41
Textural properties of different samples
and ZrO2-MCM-41-HS. Figure 2 shows the HRTEM images
of ruthenium nanoparticles and the lattice fringes are identified
with an average spacing of 2.1 Å corresponding well to the
(101) crystalline plane of ruthenium. As shown in Figure 2, the
ruthenium nanoparticles are uniformly dispersed on the surface
of MCM-41 with the particle size of 1–3 nm. It can be seen
from Figure 2 that ruthenium particles also disperse well on Ru-
La/ZrO2-MCM-41-HS catalyst with the particle size of about
2–4 nm.
Figure 3 displays the N2 adsorption-desorption isotherms and
BJH pore size distributions of different samples and the textu-
ral properties are shown in Table 1. The BET surface area, pore
diameter, and pore volume decrease evidently as MCM-41 mod-
ified with zirconia by hydrothermal synthesis method. The BET
surface areas of Ru-La/ZrO2-MCM-41-ISS, and Ru-La/ZrO2-
MCM-41-PS are much bigger than that of Ru-La/ZrO2-MCM-
41-HS, whiletheporediameterandporevolumeofRu-La/ZrO2-
MCM-41-ISS and Ru-La/ZrO2-MCM-41-PS are little smaller
than those of Ru-La/ZrO2-MCM-41-HS.
BET
surface
area
Pore
diameter
(nm)
Pore
volume
(cm3·g−1
Sample
(m2·g−1
)
)
MCM-41
814
88
731
592
683
84
2.8
2.2
2.5
2.3
2.8
3.4
0.84
0.39
0.69
0.66
0.65
0.45
ZrO2-MCM-41-HS
ZrO2-MCM-41-PS
ZrO2-MCM-41-ISS
Ru-La/MCM-41
Ru-La/ZrO2-
MCM-41-HS
Ru-La/ZrO2-
MCM-41-PS
Ru-La/ZrO2-
560
413
2.6
2.3
0.44
0.40
MCM-41-ISS
shown in Figure 1, the diffraction peaks of ruthenium around
2θ = 44◦ on Ru-La/ZrO2-MCM-41-ISS, and Ru-La/ZrO2-
MCM-41-PS are more evident than that on Ru-La/ZrO2-MCM-
41-HS, which declares that the ruthenium particles are dispersed
more uniformly on ZrO2-MCM-41-HS.
The results of water and benzene static adsorption for dif-
ferent samples are shown in Table 2. The hydrophilic index is
defined as the ratio of water static adsorption value to benzene
static adsorption value. The hydrophilic index of Ru-La/MCM-
41 catalyst is about the same as the MCM-41 support. While
the hydrophilic indexes of Ru-La supported on zirconia mod-
ified MCM-41 catalysts have somewhat increase. Especially,
The TEM images of Ru-La/MCM-41 and Ru-La/ZrO2-
MCM-41-HS are shown in Figure 2. The dark dots represent
FIG. 2. (a–c) The TEM images of Ru-La/MCM-41 and (d–f) Ru-La/ZrO2-MCM-41-HS.

ZrO2 MODIFIED MCM-41 SUPPORTED Ru-La CATALYST
1209
TABLE 3
The results of benzene hydrogenation over different catalysts
Selectivity (%)
Conversion
Catalyst
(%)
Cyclohexene
Cyclohexane
Ru-La/MCM-
41
44.2
44.9
55.1
Ru-La/ZrO2-
MCM-41-
HS
Ru-La/ZrO2-
MCM-41-
PS
Ru-La/ZrO2-
MCM-41-
ISS
45.6
52.3
49.2
59.6
42.6
42.2
40.3
57.4
57.8
FIG. 3. N2 adsorption-desorption isotherms and BJH pore size distributions
(inset) of different samples.
Reaction conditions: stirring rate, 1000 rpm; PH2 = 4.0 MPa; T =
423 K; 20 mL of 0.3 M ZnSO4 aqueous solution; 10 mL of benzene;
0.2 g of catalyst; mole ratio La/Ru = 0.1; mass ratio ZrO2/MCM-41 =
0.05.
the hydrophilic index of Ru-La/ZrO2-MCM-41-HS increases
17.4% to Ru-La/MCM-41 and 18.2% to MCM-41. These sug-
gest that MCM-41 modified by zirconia is helpful to improve
the hydrophilic property.
index, which is more favorable to the formation of a stagnant
water layer and the desorption of the produced cyclohexene.
As a result, with the hydrophilic modification of zirconia, the
yield of cyclohexene increases from 19.8% over Ru-La/MCM-
41 catalyst to 27.2% catalyzed by Ru-La/ ZrO2-MCM-41-HS
at the similar conversion of benzene. Although the hydrophilic
property of MCM-41 modified with zirconia by in situ synthesis
method and precipitation method improves on a certain degree,
Ru-La/ZrO2-MCM-41-ISS and Ru-La/ZrO2-MCM-41-PS cat-
alysts do not exhibit good performance. The reason may be that
the relative higher BET surface areas and smaller pore sizes of
ZrO2-MCM-41-ISS and ZrO2-MCM-41-PS counterbalance the
advantage of the desorption of cyclohexene due to the increment
of hydrophilic property.
Based on the previous results and discussions, Ru-La/ZrO2-
MCM-41-HSisselectedforfurtherresearch. Firstly, theeffectof
mass ratio of zirconia to MCM-41 on catalytic performance was
investigated. The results are recorded in Table 4. Ru-La/MCM-
41 catalyst without being modified by zirconia gives a very low
cyclohexene selectivity of 44.9% at the benzene conversion of
44.2%. By contrast, with the hydrophilic modification of zir-
conia, the selectivity of cyclohexene over Ru-La/ZrO2-MCM-
41-HS catalyst is 14.7% higher than that of Ru-La/MCM-41
catalyst at almost the same benzene conversion. The selectiv-
ity and the yield of cyclohexene increase with the increment
of the mass ratio of zirconia to MCM-41 from 0.01 to 0.05,
but they will decrease if the mass ratio of zirconia to MCM-41
continues to increase. The reason may be that the mesoporous
of MCM-41 was blocked by the excessive additive amount of
zirconia. The influence of reaction temperature on benzene hy-
drogenation over Ru-La/ZrO2-MCM-41-HS catalyst is shown
Catalytic Performance
Table 3 shows the performance of different catalysts in ben-
zene hydrogenation to cyclohexene in ZnSO4 aqueous solution.
The Ru-La/ZrO2-MCM-41-HS catalyst exhibits the best perfor-
mance with the benzene conversion of 45.6% and the cyclo-
hexene selectivity of 59.6%. It has been reported that water is
essential in selective hydrogenation of benzene to cyclohexene
and the hydrophilicity of the Ru-based catalyst influences the se-
lectivity of cyclohexene greatly.[20,34] Struijk et al.[33] found that
benzene hydrogenation in the absence of water leads to the di-
rect contact between catalyst surface and the organic phase and
the cyclohexene yield never exceed more than 1.0%. The cata-
lyst prepared from hydrophilic support can be easily surrounded
by a stagnant water layer, which is helpful to the desorption of
the formed cyclohexene and increases its selectivity. It can be
seen from Table 2 that zirconia modified MCM-41 supported
ruthenium and lanthanum catalyst has the highest hydrophilic
TABLE 2
Results of water/benzene static adsorption for different samples
Ru-La/
Ru-
Ru-
Ru-
MCM- La/MCM- MCM-
ZrO2- La/ZrO2- La/ZrO2-
MCM-
41-ISS
MCM-
41-HS
Sample
41
41
41-PS
Hydrophilic1.1842 1.1924
Indexes
1.2190
1.2882
1.4001

1210
H. LIAO ET AL.
TABLE 4
TABLE 6
The effect of mass ratio of ZrO2 to MCM-41 on benzene
hydrogenation over Ru-La/ZrO2-MCM-41-HS catalyst
The effect of reaction time on benzene hydrogenation over
Ru-La/ZrO2-MCM-41-HS catalyst
ZrO2/MCM-
41 mass
ratio
Selectivity (%)
Selectivity (%)
Conversion
(%)
Time (min) Conversion (%) Cyclohexene Cyclohexane
Cyclohexene
Cyclohexane
2
5
10
15
20
25
36.0
45.6
57.2
63.8
69.0
78.6
55.8
59.6
51.9
47.9
45.7
38.9
44.2
40.3
48.1
52.1
54.3
61.1
0
44.2
45.3
54.3
45.6
45.5
49.1
47.2
44.9
53.6
49.1
59.6
55.6
51.9
46.8
55.1
46.5
50.9
40.3
44.4
48.1
53.0
0.01
0.03
0.05
0.75
0.5
1
Reaction conditions: stirring rate, 1000 rpm; PH2 = 4.0 MPa; T =
423 K; 20 mL of 0.3 M ZnSO4 aqueous solution; 10 mL of benzene;
0.2 g of catalyst; mole ratio La/Ru = 0.1; mass ratio ZrO2/MCM-41 =
0.05.
Reaction conditions: stirring rate, 1000 rpm; PH2 = 4.0 MPa; T =
423 K; 20 mL of 0.3 M ZnSO4 aqueous solution; 10 mL of benzene;
0.2 g of catalyst; mole ratio La/Ru = 0.1.
modification of zirconia, the best result was obtained at benzene
conversion of 69.0% and cyclohexene yield of 31.5%.
in Table 5. Struijk et al.[33] found that the higher temperature
promotes the desorption of cyclohexene and decreases the hy-
drogen concentration in liquid phase, both of which inhibit the
further hydrogenation of cyclohexene to cyclohexane. As shown
in Table 5, the yield of cyclohexene increases with the incre-
ment of temperature from 403 to 423 K. However, much higher
temperature will cause negative effects, as the solubilities of cy-
clohexene and benzene in water increase concurrently under the
condition of much higher temperature, and then the coverage of
Ru with cyclohexene increases and cyclohexene hydrogenation
accelerates as well.[16] The effect of reaction time on benzene hy-
drogenation over Ru-La/ZrO2-MCM-41-HS catalyst is shown
in Table 6. With the extending of reaction time, the conversion
of benzene has been increasing while the cyclohexene selec-
tivity increases firstly and then decreases. With the hydrophilic
CONCLUSIONS
Zirconia modified mesoporous molecular sieve MCM-41
supports were prepared by hydrothermal synthesis method, in
situ synthesis method and precipitation method. Ruthenium and
lanthanum supported on zirconia modified MCM-41 catalysts
were prepared via two solvents impregnation method. The per-
formances of the catalysts were carried out in benzene hydro-
genation. It has been found that MCM-41 modified by zirconia
is helpful to improve the hydrophilic property. As a result, zir-
conia modified MCM-41 by hydrothermal synthesis method
supported ruthenium-lanthanum catalyst with the highest hy-
drophilicity shows the best performance in benzene hydrogena-
tion to cyclohexene.
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