能源化学(英文版)

能源化学(英文) ›› 2002, Vol. 11 ›› Issue (1): 51-56.

• Articles • 上一篇    下一篇

Synthesis of Acetic Acid on Pd-H4SiW12O40-Based Catalysts by Direct Oxidation of

Xinping Wang, Kegong Fang, Jianlu Zhang, Tianxi Cai   

  1. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, China
  • 出版日期:2002-03-30 发布日期:2002-03-30

Synthesis of Acetic Acid on Pd-H4SiW12O40-Based Catalysts by Direct Oxidation of

Xinping Wang, Kegong Fang, Jianlu Zhang, Tianxi Cai   

  • Online:2002-03-30 Published:2002-03-30

PDF

1923

摘要： Synthesis of acetic acid by direct oxidation of ethylene on Pd-H4SiW12O40-based catalysts was studied in a fixed-bed integral reactor and a pulse di erential reactor. From the performance of the catalysts with different compositions and configurations, it is proposed that acetic acid is predominantly produced via an intermediate of acetaldehyde. This can be easily confirmed by comparing the product distributions in the integral and the di erential reactors. The active sites for acetic acid formation are considered to exist mainly at the boundaries between the H4SiW12O40 and the Pd particles. The Pd-based catalysts reduced by H2/N2 have higher activities than those reduced by hydrazine, as explained by the degree of Pd dispersion obtained from the characteristics of hydrogen chemical adsorption. It was found that the Pd-Se-SiW12/SiO2 catalyst with selenium tetrachloride as a precursor was more active than that with potassium selenite, and that the acetic acid yield can be greatly increased by adding a suitable amount of dichloroethane (C2H4Cl2/C2H4 mole ratio=0.03) to the reactants.

关键词: acetic acid, synthesis, ethylene, Pd-H4SiW12O40/SiO2, dichloroethane

Abstract: Synthesis of acetic acid by direct oxidation of ethylene on Pd-H4SiW12O40-based catalysts was studied in a fixed-bed integral reactor and a pulse di erential reactor. From the performance of the catalysts with different compositions and configurations, it is proposed that acetic acid is predominantly produced via an intermediate of acetaldehyde. This can be easily confirmed by comparing the product distributions in the integral and the di erential reactors. The active sites for acetic acid formation are considered to exist mainly at the boundaries between the H4SiW12O40 and the Pd particles. The Pd-based catalysts reduced by H2/N2 have higher activities than those reduced by hydrazine, as explained by the degree of Pd dispersion obtained from the characteristics of hydrogen chemical adsorption. It was found that the Pd-Se-SiW12/SiO2 catalyst with selenium tetrachloride as a precursor was more active than that with potassium selenite, and that the acetic acid yield can be greatly increased by adding a suitable amount of dichloroethane (C2H4Cl2/C2H4 mole ratio=0.03) to the reactants.

Key words: acetic acid, synthesis, ethylene, Pd-H4SiW12O40/SiO2, dichloroethane