Performance of Pt/Al2O3-Cl catalysts for C5/C6 paraffin isomerization

doi:10.16085/j.issn.1000-6613.2015.01.026

Abstract

Abstract: Pt/Al₂O₃ catalyst was prepared by impregnation. The Pt/Al₂O₃-Cl catalyst was derived from Pt/Al₂O₃, and chlorided by CCl₄ at 300℃ for one hour. The characterization techniques, such as FT-IR, XRD, TEM, CO-IR, Py-IR and TPD, were employed. The performance of Pt/Al₂O₃-Cl catalyst was compared with that of RISO catalyst. The experimental results show that the OH groups are replaced by chorine in the process of chlorination, leading to a great decrease in the range of high wavenumbers (3000—3800cm^-1). The structure of alumina does not appear modified upon chlorination. The chlorinated Pt/Al₂O₃ catalyst exhibits a broad particle size distribution with a larger mean particle size, leading to very low metal dispersion. Simultaneously, platinum is oxidized to platinum chloride, which reacts with AlCl₃ to produce the volatile PtCl₂·2AlCl₃ complex, so a loss of platinum is observed. Only Lewis acid sites are detected on the fresh catalyst. However, both Lewis and Bronsted acid sites are detected on used catalyst. The chlorinated Pt/Al₂O₃ catalyst is quite unstable, as shown by continuous release of three kinds of Cl species during TPD measurement. The performance of Pt/Al₂O₃-Cl catalyst is better than that of RISO catalyst. The n-hexane conversion and 2, 2-DMB selectivity are 88.17% and 29.68%, respectively. The hydrogenolysis and hydrocracking of hexane are very limited.

Key words: isomerization, Pt/Al₂O₃-Cl, chlorination, hexane, particle

摘要： 采用浸渍法制备了Pt/Al₂O₃,在300℃、CCl₄氯化1h,制备出Pt/Al₂O₃-Cl催化剂。采用FT-IR、XRD、TEM、CO-IR、Py-IR和TPD等方法表征了催化剂,并与中温型RISO催化剂的催化性能进行比较。结果表明,在氯化处理过程中氯取代了氧化铝的表面羟基,导致3000～3800cm^-1红外吸收峰强度大幅度减小,但催化剂的晶相不发生改变;氯化使Pt粒子的平均粒径增大,粒径分布变宽,金属分散度降低;氯化后金属Pt主要以+2价的PtCl₂的形式出现,其中一部分生成了易升华的PtCl₂·2AlCl₃,从而导致Pt含量降低;氯化后的催化剂上只有L酸,评价后既有L酸,又有B酸;氯化后的催化剂热稳定不高,随着温度升高,3种类型的氯化物相继脱出;Pt/Al₂O₃-Cl相对于中温型RISO催化剂表现出较好的异构化性能,正己烷转化率达88.17%,2,2-二甲基丁烷选择性达29.68%,裂化和氢解几乎没有发生。

关键词: 异构化, Pt/Al₂O₃-Cl, 氯化, 正己烷, 粒子

CLC Number:

TQ426.95

LI Yong, ZHANG Kongyuan, ZHU Hongwei, YANG Kang, LIU Chenguang. Performance of Pt/Al₂O₃-Cl catalysts for C₅/C₆ paraffin isomerization[J]. Chemical Industry and Engineering Progree, 2015, 34(1): 150-155.

李勇, 张孔远, 朱红伟, 杨康, 刘晨光. C₅/C₆烷烃异构化Pt/Al₂O₃-Cl催化剂的性能[J]. 化工进展, 2015, 34(1): 150-155.

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Performance of Pt/Al₂O₃-Cl catalysts for C₅/C₆ paraffin isomerization

C₅/C₆烷烃异构化Pt/Al₂O₃-Cl催化剂的性能

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