Preparation, Characterization of Dawson-type Heteropoly Acid Cerium (III) Salt and Its Catalytic Performance on the Synthesis of n-Butyl Acetate

doi:10.1016/S1004-9541(13)60493-0

Chinese Journal of Chemical Engineering ›› 2013, Vol. 21 ›› Issue (5): 500-506.DOI: 10.1016/S1004-9541(13)60493-0

• 催化、动力学与反应工程 • 上一篇下一篇

Preparation, Characterization of Dawson-type Heteropoly Acid Cerium (III) Salt and Its Catalytic Performance on the Synthesis of n-Butyl Acetate

曹小华^1,2, 任杰¹, 徐常龙², 张康华², 占昌朝^1,2, 蓝健²

1 College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, China;
2 College of Chemical and Environmental Engineering, Jiujiang University, Jiujiang 332005, China

收稿日期:2012-08-13 修回日期:2012-12-19 出版日期:2013-05-28 发布日期:2013-05-31
通讯作者: REN Jie
基金资助:
Supported by the National Natural Science Foundation of China (21161009), the Natural Science Foundation of Jiangxi Province (20122BAB213001, 20114BAB213002) and the Science and Technology Foundation of Jiangxi Province (GJJ11613).

Preparation, Characterization of Dawson-type Heteropoly Acid Cerium (III) Salt and Its Catalytic Performance on the Synthesis of n-Butyl Acetate

CAO Xiaohua^1,2, REN Jie¹, XU Changlong², ZHANG Kanghua², ZHAN Changchao^1,2, LAN Jian²

1 College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, China;
2 College of Chemical and Environmental Engineering, Jiujiang University, Jiujiang 332005, China

Received:2012-08-13 Revised:2012-12-19 Online:2013-05-28 Published:2013-05-31
Supported by:
Supported by the National Natural Science Foundation of China (21161009), the Natural Science Foundation of Jiangxi Province (20122BAB213001, 20114BAB213002) and the Science and Technology Foundation of Jiangxi Province (GJJ11613).

摘要/Abstract

摘要： A novel cerium (III) salt of Dawson type tungstophosphoric acid (Ce₂P₂W₁₈O₆₂·16H₂O) was prepared by doping cerous nitrate in H₆P₂W₁₈O₆₂·13H₂O powder and characterized by thermogravimetry and differential thermal analyses (TG/DTA), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), pyridine infrared spectroscopy (Py-IR) and scanning electron microscopy (SEM). Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol. The effects of various parameters such as molar ratio of n-butanol to acetic acid, reaction temperature, reaction time, and catalyst amount have been studied by single factor experiment. The results show that Ce₂P₂W₁₈O₆₂·16H₂O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate. The optimum synthetic conditions were determined as follows:molar ratio of n-butanol to acetic acid at 2.0:1.0, mass of the catalyst being 1.44% of the total reaction mixture, reaction temperature of 120 ℃ and reaction time of 150 min. Under above conditions, the conversion of acetic acid was above 97.8％. The selectivity of n-butyl acetate based on acetic acid was, in all cases, nearly 100%. The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction. It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products. Compared with using sulfuric acid as catalyst, the present procedure with Ce₂P₂W₁₈O₆₂·16H₂O is a green productive technology due to simple process, higher yield, catalyst recycling and no corrosion for the production facilities.

关键词: cerous phosphotungstate, Dawson structure, catalyst, esterification, n-butyl acetate

Abstract: A novel cerium (III) salt of Dawson type tungstophosphoric acid (Ce₂P₂W₁₈O₆₂·16H₂O) was prepared by doping cerous nitrate in H₆P₂W₁₈O₆₂·13H₂O powder and characterized by thermogravimetry and differential thermal analyses (TG/DTA), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), pyridine infrared spectroscopy (Py-IR) and scanning electron microscopy (SEM). Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol. The effects of various parameters such as molar ratio of n-butanol to acetic acid, reaction temperature, reaction time, and catalyst amount have been studied by single factor experiment. The results show that Ce₂P₂W₁₈O₆₂·16H₂O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate. The optimum synthetic conditions were determined as follows:molar ratio of n-butanol to acetic acid at 2.0:1.0, mass of the catalyst being 1.44% of the total reaction mixture, reaction temperature of 120 ℃ and reaction time of 150 min. Under above conditions, the conversion of acetic acid was above 97.8％. The selectivity of n-butyl acetate based on acetic acid was, in all cases, nearly 100%. The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction. It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products. Compared with using sulfuric acid as catalyst, the present procedure with Ce₂P₂W₁₈O₆₂·16H₂O is a green productive technology due to simple process, higher yield, catalyst recycling and no corrosion for the production facilities.

Key words: cerous phosphotungstate, Dawson structure, catalyst, esterification, n-butyl acetate

曹小华, 任杰, 徐常龙, 张康华, 占昌朝, 蓝健. Preparation, Characterization of Dawson-type Heteropoly Acid Cerium (III) Salt and Its Catalytic Performance on the Synthesis of n-Butyl Acetate[J]. Chinese Journal of Chemical Engineering, 2013, 21(5): 500-506.

CAO Xiaohua, REN Jie, XU Changlong, ZHANG Kanghua, ZHAN Changchao, LAN Jian. Preparation, Characterization of Dawson-type Heteropoly Acid Cerium (III) Salt and Its Catalytic Performance on the Synthesis of n-Butyl Acetate[J]. Chin.J.Chem.Eng., 2013, 21(5): 500-506.

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Preparation, Characterization of Dawson-type Heteropoly Acid Cerium (III) Salt and Its Catalytic Performance on the Synthesis of n-Butyl Acetate

Preparation, Characterization of Dawson-type Heteropoly Acid Cerium (III) Salt and Its Catalytic Performance on the Synthesis of n-Butyl Acetate

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