Korean J. Chem. Eng.

, 30(12), 2178-2185 (2013) pISSN: 0256-1115

DOI: 10.1007/s11814-013-0182-9 eISSN: 1975-7220
INVITED REVIEW PAPER

Statistical optimization for oxidation of ethyl benzene over Co-Mn/SBA-15

catalyst by Box-Behnken design
Vahid Mahdavi† and Ali Monajemi

Department of Chemistry, Surface Chemistry and Catalysis Division, Faculty of Sciences,

Arak University, Arak 38156-8-8349, Iran
(Received 10 July 2013 • accepted 17 September 2013)

Abstract−A series of cobalt and manganese catalysts supported on SBA-15 with different loading of Mn+2 and Co+2
were synthesized. These samples were characterized by SEM and XRD techniques. The catalytic activity of these sam-
ples was evaluated in the oxidation of ethylbenzene (EB) to produce acetophenone (AP) and benzoic acid (BA) in the
liquid phase using tert-butylhydroperoxide (TBHP) as an oxidant. The effects of Co-Mn loading, TBHP : EB molar
ratio and temperature on acetophenone and benzoic acid yields were studied by Box-Behnken experimental design
to optimize the production of acetophenone and benzoic acid in liquid system.
Key words: Benzoic Acid, Acetophenone, SBA-15, Cobalt-manganese Catalyst, Box-Behnken Design

INTRODUCTION cations, such as molecular adsorption, ion-exchange, catalysis, elec-

trochemistry and magnetism, because of the structural flexibility
The scrutiny of molecules confined in porous media is an impor- with novel chemical and physical properties [13,14]. Co-Mn mixed
tant subject that for decades has attracted extensive experimental and oxides have also been reported as catalysts and also used in the com-
theoretical research, and there is a large amount of literature dealing bustion of volatile organic compounds (VOC) [15].
with these problems and some examples are given in reference [1]. The purpose of the present study is to investigate the use of meso-
Thus, the realizing of geometrical and spatial restriction effects porous silica, SBA-15, as support for Co and Mn bimetallic cata-
demands the study of porous materials under conditions of con- lysts for liquid phase selective oxidation of ethyl benzene. To our
finement where the pore structure, surface properties, dimensionality knowledge, the use of SBA-15 as support for bimetallic Co-Mn
and size, are well controlling the recent discovery of highly ordered systems and their application to liquid phase selective oxidation of
SBA-15 mesoporous materials [2]. Mesoporous material based sup- ethylbenzene have not been reported previously. Furthermore, it
ported catalysts have been proven to be the most ideal catalysts due was stated that the catalytic selective oxidation efficiency of this
to high surface area, high porosity, high stability, large and uniform process is dependent on numerous parameters such as cobalt and
channel size [3,4]. It was found that the support’s porosity modi- manganese loading over SBA-15, reaction temperature and TBHP :
fied and improved the catalytic properties through its effect on cobalt Ethyl benzene molar ratio and these parameters need to be care-
particle dispersion and reducibility [5,6]. Heterogeneous catalysts fully optimized.
have many intrinsic advantages such as easy recovery and recy- Using a one-factor-at-a-time optimization method is an intricate
cling of the catalyst as well as suitability for sequential processing approach to evaluating the effects of different variables on an experi-
[7]. In addition, the chemical and structure properties of the support mental outcome. In addition, this method is time consuming, expen-
influenced the catalytic activity and product selectivity of cobalt sive and often leads to misinterpretation of results when interactions
catalysts through their modifications on the reducibility and disper- between different components are present. Another approach to exact-
sion of cobalt or the formation of desired phases. Sometimes it might ly evaluating the impact of the variables on the oxidation process is
be more affordable to modify or change the support properties than to change all the factors simultaneously in a systematic manner. This
to increase the number of active sites [8]. Recently, it has been shown approach is referred to as response surface methodology (RSM).
that mesoporous silicas are promising supports for cobalt oxides RSM is a statistical technique which can address the present sce-
and cobalt metal catalysts [9-11] .The large surface area of the meso- nario under consideration [16-18], and it can be used to establish
porous SBA-15 ensures higher metal dispersion at cobalt loading relationships between multiple independent variables and one or
up to 20 wt% compared to the conventional SiO2 [10]. Usually cobalt more dependent variables. Developing a first-degree polynomial
nitrate precursor is used, as it is relatively well investigated and is model can be performed by using statistical experimental designs.
known not to produce strong interaction with the support during Also RSM optimizes multiple variables by systematic variation of
the impregnation and under mild calcination treatment [12]. Man- all variables in a well-designed experiment with a minimum num-
ganese oxides have presented considerable importance in many appli- ber of experiments. The RSM optimization process involves the
following steps: (1) performing statistically designed experiments;
†
To whom correspondence should be addressed. (2) estimating the coefficients of a mathematical model using regres-
E-mail: v-mahdavi@araku.ac.ir, vmahdavius@yahoo.com sion analysis technique; and (3) predicting the response and check-
Copyright by The Korean Institute of Chemical Engineers. ing the adequacy and accuracy of the models [16,17].
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 Statistical optimization for oxidation of ethyl benzene over Co-Mn/SBA-15 catalyst by Box-Behnken design 2179

In this study, the effects of temperature, cobalt and manganese

loading and TBHP:Ethyl benzene molar ratio to produce acetophe-
none and benzoic acid from ethyl benzene over SBA-15 catalyst
were investigated. Box-Behnken design was used to obtain the opti-
mum values of variables and studying the interactions between vari-
ables. Analysis of variance (ANOVA) was used to investigate the
effects of main factors and their interactions. A quadratic model Fig. 1. Oxidation of ethylbenzene.
was proposed for responses (yield of acetophenone and benzoic
acid) as a function of temperature, Co and Mn loading and TBHP :
EB molar ratio. Results were used to obtain the optimum condi- tions at 530 oC for 6 h.
tions for producing high quality products. 3. Catalyst Characterization
The structure of these samples was studied by X-ray diffraction
EXPERIMENTAL (XRD) experiments. A Philips model PW 1800 diffractometer with
Cu Kα radiation and Ni filter was used to collect the X-ray data.
1. Materials The scanning electron microscopy (SEM) images were obtained
All materials were of commercial reagent grade. The ethyl ben- with a Philips XL30 instrument.
zene substrate and cobalt and manganese were obtained from cobalt 4. Experimental Design and Catalytic Reaction
chloride [Co(Cl)2·6H2O] and manganese chloride [Mn(Cl)2·4H2O] We used the Box-Behnken design of experiment to find the opti-
and tert-butylhydroperoxide (TBHP) 70% solution in water were mal conditions for benzoic acid and acetophenone production. The
purchased from Merck chemical company. SBA-15 was prepared effects of temperature (X1), Co loading (X2), Mn loading (X3) and
using tetraethyl orthosilicate (TEOS, Aldrich Co.) as the silica source, TBHP : EB molar ratio (X4) were investigated, then the percentage
poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(eth- of benzoic acid (y1) and acetophenone (y2) yield (%wt) were cal-
ylene glycol) (Pluronic P123, EO20PO70EO20, average molecular culated in the final product.
weight=5800, BASF Co.) as the template and HCl as the pH con- Oxidation reactions of ethyl benzene were performed in a round
trolling agent. Acetonitrile as the solvent was supplied from Merck bottom flask fitted with a water condenser using tert-butylhydrop-
Company and used without further purification. eroxide (TBHP, 70 wt%) as an oxidant.
2. Catalyst Preparation A mixture of 0.2 g catalyst with the grain size of 200-230 mesh
2-1. Preparation of SBA-15 containing, 15 mL solvent (acetonitrile) and 30 mmol of ethylben-
Mesoporous silica SBA-15 was synthesized according to a litera- zene was stirred under nitrogen atmosphere at 50 oC for 30 min.
ture procedure [2]. The stirring rate of the solution was set at 750 cycle/min. Then TBHP
In a typical synthesis, 4 g of block copolymer P123 was dis- was added to the solution and the mixture was heated at different
solved in 30 g distilled water and 120 ml aqueous acidic solution temperatures (65-95 oC) under nitrogen atmosphere (Fig. 1). After
of 2 M HCl, which was stirred at 35 oC for 3 h to get a transparent reaction, the reaction mixture was cooled to room temperature. The
solution. Then, 8.5 g of TEOS was added to the above solution under products were analyzed by gas chromatograph GC (Perkin Elmer
vigorous stirring. This gel was continuously stirred for 24 h and then Model 8500) equipped with a flame ionization detector (FID) con-
the solid product was collected by ltration, washed with distilled nected to a 3% OV-17 column with length of 2.5 m and diameter
water, and dried at 100 oC overnight in air. The resulting powder of 1/8 in.
was calcined at 530 oC for 6 h to remove surfactant. 5. Response Surface Exploration
2-2. Preparation of the Cobalt Containing SBA-15 Catalysts (Co/ Several preliminary tests were performed to evaluate the param-
SBA-15) eters’ effect on oxidation of ethyl benzene over Co-Mn/SBA-15;
In the first, the Co/SBA-15 catalysts with 5, 10, 15, 20 and 25 temperature (X1), Co loading (X2), Mn loading (X3) and TBHP:EB
wt% Co were prepared by impregnation method. In a typical syn- molar ratio (X4) were regarded as the important factors. To investi-
thesis, 1.0 g of calcined and outgassed SBA-15 was impregnated gate the optimum levels of those variables and to study their rela-
with an aqueous solution of the cobalt chloride precursor, using the tionship, Box-Behnken experimental design was found to be more
needed concentration to achieve the desired Co content assuming suitable. One of the advantages of Box-Behnken design (BBD) is
total incorporation. The wet solid was then dried at 80 oC overnight that they are all spherical design; the sample combinations are pro-
under vacuum and calcined in air under static conditions at 530 oC cessed such that they are located at midpoints of edges constituted
for 6 h. by any two factors and require factors to be run at only of three levels
2-3. Preparation of the Cobalt-manganese Containing SBA-15 Cat- that is represented by (−1, 0, 1) [19]. To minimize the number of
alysts (Co-Mn/SBA-15) variables, reaction time and amount of catalysts for the reaction were
The Co/SBA-15 catalysts containing manganese with 1, 2, 4, kept constant at 8 h and 0.2 g for all experiments, respectively. The
and 5 wt% Mn were prepared by impregnation method. In a typical effects of the temperature (X1) Co loading (X2), Mn loading (X3)
synthesis, 1.0 g of calcined and outgassed Co/SBA-15 was impreg- and TBHP : EB molar ratio (X4) on %yield of the final product were
nated with an aqueous solution of the manganese chloride precur- studied.
sor, using the needed concentration to achieve the desired Mn con- The parameters should be normalized before analyzing the regres-
tent assuming total incorporation. The wet solid was then dried at sion. The variables were coded as +1, −1 and 0 for three level, high,
80 oC overnight under vacuum and calcined in air under static condi- low and central, respectively. The actual variables (Xi) were coded
Korean J. Chem. Eng.(Vol. 30, No. 12)