Tugas Katalis
Tugas Katalis
Tugas Katalis
Combustion of volatile organic compounds over CuMn based mixed oxide type
catalysts supported on mesoporous Al2 O3 , TiO2 and ZrO2
Pradeep Doggali a , Y. Teraoka b , P. Mungse a , Irfan K. Shah c , S. Rayalu a , Nitin Labhsetwar a,
a
b
c
National Environmental Engineering Research Institute(CSIR-NEERI), Nehru Marg, Nagpur 440020, India
Department of Energy and Material Sciences, Faculty of Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816-8580, Japan
Department of Civil Engineering, Indian Institute of Technology (IIT) Delhi, Hauz Khas, New Delhi 16, India
a r t i c l e
i n f o
Article history:
Received 2 August 2011
Received in revised form 29 January 2012
Accepted 6 February 2012
Available online 28 February 2012
Keywords:
Mesoporous Al2 O3
TiO2 and ZrO2
CuMn catalyst
Acetaldehyde combustion
Benzene combustion
H2 -TPR
O2 -TPD
a b s t r a c t
A series of supported CuMn based catalysts have been synthesized using three different supports
mesoporous Al2 O3 , mesoporous TiO2 and mesoporous ZrO2 . CuMn precursors were incorporated on
mesoporous supports using wet impregnation method. These catalyst supports were prepared by templating method using a natural biopolymer namely, chitosan. The catalytic activity for benzene and
acetaldehyde combustion was studied for these catalysts. The synthesized catalysts have been characterized by XRD, BET-SA, O2 -TPD and H2 -TPR in a view of material characterization, as well as to investigate
the mechanistic aspects of catalytic reactions. The bimetallic supported catalysts follow the activity
sequenceCuMn/TiO2 > CuMn/ZrO2 > CuMn/Al2 O3 for both the reactions studied. These results interestingly show, that the catalytic activity is dependent on the support used, however, quite independent
of the surface area of these supports. The better activity of TiO2 and ZrO2 based catalysts is likely due to
their redox properties. The existence of low temperature peaks in both O2 -TPD and H2 -TPR explain better
redox properties as well as catalytic performance of TiO2 and ZrO2 supported catalysts as compared to
those Al2 O3 supported mixed oxides.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Volatile organic compounds (VOCs) have high vapour pressure
under normal atmospheric conditions and therefore, can be easily
vaporized [1]. VOCs include a variety of different organic compounds including alcohols, ethers, esters, aromatics, chlorinated
hydrocarbons and odorous compounds containing sulphur [2]. The
major sources of VOCs are the paint industry, building materials,
automobile exhaust, combustion exhaust, industrial off gases, personal care products as well as a range of other sources [3]. VOCs
are often toxic [4] and also responsible for the formation of photochemical ozone [5] as well as secondary aerosols in urban air
[6]. Therefore, removal of VOCs from ambient air and controlling VOC emission at source has now been deemed as crucial for
environmental and health point of view. Although various types
of air purication techniques such as adsorption and combustion
processes have been developed and widely used for hazardous
air pollutant removal, they are often not suitable for the removal
of diluted pollutants [7]. The use of catalytic combustion allows
decreasing the temperatures (<600 C) to obtain complete combustion of organic compounds as compared to thermal processes
Corresponding author. Tel.: +91 712 2247828; fax: +91 712 2247828.
E-mail address: nk labhsetwar@neeri.res.in (N. Labhsetwar).
1381-1169/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2012.02.004
24
2.3. Characterization
XRD patterns were recorded on a Rigaku Rint-220HF diffractometer, operated at 40 kV and 50 mA with monochromator, and
using Cu K radiation ( = 0.15418 nm). Indexing of XRD peaks was
done, by using the JCPDS database for the respective phases. Surface area was measured by nitrogen adsorption using the automatic
gas adsorption apparatus BELSORP 28SA (produced by Nippon Bell
Co.) and evaluated by following BET method. The samples were
pre-treated at 300 C before the nitrogen adsorption experiments.
Elemental analysis of the catalytic materials was carried out using
PerkinElmer ICP-OES 4100 BV instrument to assess the content
of copper and manganese present. The H2 -TPR and O2 -TPD analysis were performed in a Thermo-Quest TPD/R/O 1100 analyzer,
equipped with a TCD detector. For H2 -TPR test, the quartz tube
reactor was loaded with100 mg sample in powder form. It was
pre-treated in He ow by heating the catalyst from room temperature to 400 C for 30 min (10 mL/min, STP) and cooled to ambient
under helium ow (10 mL/min, STP). The reduction was performed
by owing 5% hydrogen diluted in helium. The sample temperature
was raised at 10 C/min till 400 C under 5% H2 /He (10 mL/min, STP)
ow. The amount of hydrogen consumed in TPR was quantitatively
measured by a thermal conductivity detector (TCD). In the similar way, temperature-programmed oxygen desorption (TPD) was
performed. Prior to each run, the catalyst was heated up to 400 C
under the helium ow (30 N mL/min). After 30 min of isothermal
heating at this temperature, the sample was cooled to 25 C in air
ow. Afterwards, helium was fed to the reactor at 10-mL/min-ow
rate for 1 h at room temperature, in order to purge out any excess
oxygen. The catalyst was then heated up to 400 C at a constant
heating rate of 10 C/min under the same helium ow, and O2 desorbed during the heating was determined to study the TPD pattern.
CHN analysis was carried out on a Shimadzu Elementer. The copper and manganese contents of materials were determined using
ICP-OES technique (PerkinElmer, Model Optima 4100DV). Blank
experiments were conducted throughout the studies and majority of the experiments were repeated thrice and it was observed
that the experimental error was within 2%. The samples were
dissolved in acid before the analysis.
2.1. Materials
All the reagents used for experimental work were of analytical
reagent grade. Acetic acid, ammonia, aluminium nitrate, zirconyl
nitrate, cupric acetate and manganese acetate were obtained from
Merck India Ltd. Chitosan was procured from Chemchito India. Titanium isopropoxide was obtained from Acros India Ltd.
2.2. Methods
Mesoporous Al2 O3 was synthesized following a similar procedure as reported elsewhere [29] and later applied for the synthesis
of TiO2 and ZrO2 in our group [2830]. The supports thus obtained
were ground into powder, homogenised and used for the synthesis of supported catalysts. Aqueous equimolar solutions of the
stoichiometric quantity of Cu(CH3 COO)2 and Mn(CH3 COO)2 were
used to prepare mixed metal solution in deionized water. Catalysts were synthesized by targeted loading of 8 wt% Cu and 8 wt%
25
Table 1
ICP analysis results for Cu and Mn content of mesoporous Al2 O3 , mesoporous TiO2
and mesoporous ZrO2 .
Sample
mg of metal/g of support
CuMn/Al2 O3
CuMn/TiO2
CuMn/ZrO2
78 Cu77 Mn/Al2 O3
77 Cu78 Mn/ZrO2
78 Cu77 Mn/TiO2
Table 2
Surface area pore size and pore volume results for mesoporous Al2 O3 , CuMn/Al2 O3 ,
mesoporous TiO2 , CuMn/TiO2 , mesoporous ZrO2 and CuMn/ZrO2 .
Sample
BET-surface
area (m2 /g)
Pore diameter
(nm)
Pore volume
(cm3 /g)
Mesoporous Al2 O3
CuMn/Al2 O3
Mesoporous TiO2
CuMn/TiO2
Mesoporous ZrO2
CuMn/ZrO2
312
150.9
130
92.5
34.9
28.5
4.2
3.4
3.2
2.9
3.5
2.4
0.36
0.28
0.23
0.10
0.11
0.05
26
27
Table 3
Summary of the % CHN of CuMn/Al2 O3 , CuMn/TiO2 , CuMn/ZrO2 .
Sample
%C
%H
%N
CuMn/Al2 O3
CuMn/TiO2
CuMn/ZrO2
0.58
0.4
0.33
2.2
1.1
0.9
0.1
0.84
0.2
Fig. 5. Benzene combustion over CuMn/Al2 O3 , CuMn/TiO2 and CuMn/ZrO2 catalysts (feed composition: benzene = 900 ppm, O2 = 10% balance He, at approximately
30,000 h1 space velocity).
28
29
as SiO2 MgO, SiO2 ZrO2 , SiO2 Al2 O3 and TiO2 ZrO2 . Among the
studied catalysts only TiO2 ZrO2 catalysts show enhanced activity,
though the other catalyst studied were also of acidic nature.
Clearly the present work infers that TiO2 and ZrO2 are better
supports for transition metal based oxide and mixed oxide type catalysts and their physical properties can be signicantly enhanced
through template synthesis.
3.2. O2 -TPD studies
O2 -TPD (temperature programmed oxygen desorption) experiments were performed to understand the oxygen desorption
properties of CuMn/Al2 O3 , CuMn/ZrO2 and CuMn/TiO2 . Two
different types of oxygen species known as and were dened in
our previous O2 -TPD studies on mixed oxide materials for soot oxidation reaction [38]. The peaks at low temperatures are supposed
to be desorbed oxygen species, which are weakly chemisorbed
supercial oxygen species. Fig. 7 shows the O2 -TPD curves for
CuMn/Al2 O3 , CuMn/TiO2 and CuMn/ZrO2 . The -oxygen desorption temperatures are observed around 180, 135 and 120 C
for CuMn/Al2 O3 , CuMn/TiO2 and CuMn/ZrO2 , respectively. The
lower temperature -oxygen desorption further support the better catalytic activity results for CuMn impregnated ZrO2 and TiO2
as compared to CuMn impregnated Al2 O3 . The high activity of
CuMn/TiO2 catalyst also correlates very well with the oxygen
species of peak , i.e. larger area of peak corresponds to higher
combustion activity of the catalyst. From the results it can also
be seen that oxygen releasing temperature of the CuMn/ZrO2
is low, which represents the oxygen desorption properties of
CuMn/ZrO2 at lower temperatures as compared to CuMn/TiO2 .
However, the smaller surface area of this catalyst could also be
responsible for smaller oxygen content of this catalyst. Hence this
catalyst shows slightly inferior activity than that of CuMn/TiO2 .
The catalyst support interaction leading to improved redox properties is the likely cause for the enhanced catalytic activity of
CuMn/TiO2 and CuMn/ZrO2 .
3.3. H2 -TPR studies
Fig. 8 depicts the H2 -TPR (temperature programmed reduction with hydrogen) proles of CuMn/Al2 O3 , CuMn/TiO2 and
CuMn/ZrO2 catalysts. The obtained H2 -TPR proles show two
reduction peaks for CuMn/TiO2 and CuMn/ZrO2 , whereas
CuMn/Al2 O3 shows the single reduction peak. It has been reported
that the low temperature peak/peaks is/are due to highly dispersed
metal oxide particles on supports and the second reduction peak
30
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