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      • KCI등재

        A kinetic study of Pd–Au catalyzed synthesis of vinyl acetate from oxidation of ethylene and acetic acid in heterogeneous gas reaction

        Kazem Motahari,Hossein Atashi,Farhad Fazlollahi,Farshad F. Tabrizi,Majid Sarkari 한국공업화학회 2012 Journal of Industrial and Engineering Chemistry Vol.18 No.1

        While qualitative interpretation of the experimental results is often limited to the identification of global mechanistic phenomena, kinetic modeling is a more powerful tool for the identification of the chemical reaction network that can describe the experimental results. In this paper, kinetic study of vinyl acetate (VA) synthesis was performed in a fixed bed reactor with oxidation of ethylene and acetic acid in gaseous phase over Pd/Au/SiO2 catalyst under the industrial relevant reaction condition as follows: temperature of 120–165 8C, at constant pressure of 8 bar and the ratio of catalyst mass to the feed (W/F) was maintained at 70 g/mol min. Variation in partial pressure and concentration of reactants have led us to determine the rate limiting step and therefore proposing a new rate low based on Langmuir-Hinshelwood–Hougen–Watson (LHHW) approached consistent with experimental observation while adapted through mathematical formulation with high reliance. So, the kinetic parameters were determined by the Levenberg–Marquardt algorithm. Effect of temperature has also been surveyed showing a decreased in selectivity due to the difference in reaction constants of main and side reaction rate and an increase rate due to the increase in apparent activation energy.

      • KCI등재

        Effect of Acetate Promotor on the Pd-Au/SiO2-catalyzed Synthesis of Vinyl Acetate from the Reaction of Ethylene with Acetic Acid

        Hossein Atashi,Kazem Motahari,Farshad Farshchi Tabrizi,Farhad Fazlollahi,Majid Sarkari 대한화학회 2011 대한화학회지 Vol.55 No.1

        The effect of Group I alkali acetate promoters on vinyl acetate (VA) synthesis was evaluated. Catalyst product selectivity and ethylene conversion are compared to the unpromoted catalyst in the fixed-bed reactor with oxidation reaction of ethylene and acetic acid in gaseous phase over Pd-Au/SiO_2 catalyst. It was found that: a) the promoters were stabilized on the catalyst surface, b) common effect for the alkali promoted Pd-Au catalysts increaseed in product selectivity and ethylene conversion compared to unpromoted catalyst (these effects increase from top to the bottom of Group I). These promoting effect is due to the common-ion effect of acetate, present in the reaction, resulting in an increase in the activity of the catalyst. In addition a complementary theory for the effect of Au in the structure of the catalyst is proposed the imposition of distribution of palladium particles through decreasing the particle’s diameter.

      • SCOPUSKCI등재

        Effect of Acetate Promotor on the Pd-Au/SiO<sub>2</sub>-catalyzed Synthesis of Vinyl Acetate from the Reaction of Ethylene with Acetic Acid

        Atashi, Hossein,Motahari, Kazem,Tabrizi, Farshad Farshchi,Sarkari, Majid,Fazlollahi, Farhad Korean Chemical Society 2011 대한화학회지 Vol.55 No.1

        비닐 아세트산염 합성에 대한 1족 알칼리금속 아세트산염의 촉진 효과를 조사하였다. Pd-Au/$SiO_2$ 촉매를 사용한 경우와 사용하지 않은 경우에 대해 에틸렌과 아세트산 간의 기체상 반응에 대해 생성물 선택성과 에틸렌 전환을 비교하였다. 촉진제가 촉매 표면을 안정화시켰으며, 생성물 선택성과 에틸렌 전환을 촉진하였다. 이 촉매 효과는 1족에서 위에서 아래로 내려갈수록 증가하였다. 이것은 아세트산염의 공통이온효과 때문이다. The effect of Group I alkali acetate promoters on vinyl acetate (VA) synthesis was evaluated. Catalyst product selectivity and ethylene conversion are compared to the unpromoted catalyst in the fixed-bed reactor with oxidation reaction of ethylene and acetic acid in gaseous phase over Pd-Au/$SiO_2$ catalyst. It was found that: a) the promoters were stabilized on the catalyst surface, b) common effect for the alkali promoted Pd-Au catalysts increaseed in product selectivity and ethylene conversion compared to unpromoted catalyst (these effects increase from top to the bottom of Group I). These promoting effect is due to the common-ion effect of acetate, present in the reaction, resulting in an increase in the activity of the catalyst. In addition a complementary theory for the effect of Au in the structure of the catalyst is proposed the imposition of distribution of palladium particles through decreasing the particle's diameter.

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