锡负载量对PtSn/Al2O3催化丙烷脱氢性能的影响

doi:10.7503/cjcu20180545

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (2): 326.doi: 10.7503/cjcu20180545

锡负载量对PtSn/Al₂O₃催化丙烷脱氢性能的影响

马占华¹(), 李帅¹, 姜爱晶¹, 李军¹, 孙兰义¹, 魏桂涓^1,², 安长华^1,²()

1. 中国石油大学化学工程学院, 重质油国家重点实验室, 青岛 266580
2. 天津理工大学化学化工学院, 天津市有机太阳能电池与光化学转换重点实验室, 天津 300384

收稿日期:2018-08-03 出版日期:2019-02-10 发布日期:2018-11-26
作者简介:
联系人简介: 马占华, 女, 博士, 副教授, 主要从事催化材料的开发和性质方面的研究. E-mail: mzh_1999@126.com; 安长华, 男, 博士, 教授, 主要从事材料科学方面的研究. E-mail: anchh@163.com
基金资助:
国家自然科学基金(批准号: 21506255)资助

Effects of Sn Loading on Catalytic Performance of PtSn/Al₂O₃ in Propane Dehydrogenation^†

MA Zhanhua^1,^*(), LI Shuai¹, JIANG Aijing¹, LI Jun¹, SUN Lanyi¹, WEI Guijuan^1,², AN Changhua^1,^2,^*()

1. State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum, Qingdao 266580, China
2. Tianjin Key Laboratory of Organic Solar Cells and Photochemical Conversion, School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384, China

Received:2018-08-03 Online:2019-02-10 Published:2018-11-26
Contact: MA Zhanhua,AN Changhua E-mail:mzh_1999@126.com;anchh@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.21506255)

摘要/Abstract

摘要：

采用羰基合成-浸渍法制备了不同Pt/Sn摩尔比(3:1, 1:1, 1:2和1:3)的PtSn/Al₂O₃催化剂, 利用N₂吸附-脱附实验、 X射线衍射(XRD)、透射电子显微镜(TEM)、吡啶吸附红外光谱(Py-IR)和热重-差热分析(TG-DTA)等手段对其进行了表征, 研究了Sn负载量对PtSn/Al₂O₃的结构性质及催化丙烷脱氢性能的影响. 结果表明, 制备的PtSn/Al₂O₃具有较高的丙烯选择性和稳定性. 当Pt/Sn摩尔比为3:1和1:1时, 铂和锡在催化剂上主要以Pt₃Sn和PtSn合金形式存在, 合金的形成明显改善了催化剂的脱氢性能, 可抑制金属颗粒的高温烧结; 当Pt/Sn摩尔比为1:2和1:3时, 铂主要以金属形式存在. 随着Sn负载量的增加, 催化剂上L酸性位逐渐减少, 丙烷转化率降低, 丙烯选择性增加, 同时促使反应积炭从金属表面向载体迁移, 改善了催化剂的稳定性.

关键词: 丙烷脱氢, PtSn催化剂, Sn负载量

Abstract:

PtSn/Al₂O₃ catalysts with different Pt/Sn molar ratios(3:1, 1:1, 1:2 and 1:3) were prepared by carbonylation-impregnation method. The catalysts were characterized by means of nitrogen adsorption-desorption, X-ray diffraction(XRD), transmission electron microscopy(TEM), infrared spectra of pyridine adsorption(Py-IR), and thermogravimetric-differential thermal analysis(TG-DTA). The effect of Sn loading on the catalytic properties of PtSn/Al₂O₃ in the propane dehydrogenation was studied. The results showed that the PtSn/Al₂O₃ catalyst had high propylene selectivity and catalytic stability. Platinum and tin were mainly in the form of Pt₃Sn and PtSn alloys with Pt/Sn ratios of 3:1 and 1:1. With the formation of the alloy, the dehydrogenation performance of the catalyst was improved significantly, and the high temperature sintering of metal particles was effectively suppressed. When the Pt/Sn ratio was 1:2 and 1:3, the metallic Pt was mainly resulted. With the increase of Sn loading, the Lewis acid sites on the catalyst gradually decreased, and the propylene selectivity increased associated with the propane conversion decreased. At the same time, the addition of Sn promoted the migration of carbon deposition from the metal surface to support, and improved the stability of the catalyst.

Key words: Propane dehydrogenation, PtSn catalyst, Sn loading

中图分类号:

O643.38

TrendMD:

马占华, 李帅, 姜爱晶, 李军, 孙兰义, 魏桂涓, 安长华. 锡负载量对PtSn/Al₂O₃催化丙烷脱氢性能的影响. 高等学校化学学报, 2019, 40(2): 326.

MA Zhanhua,LI Shuai,JIANG Aijing,LI Jun,SUN Lanyi,WEI Guijuan,AN Changhua. Effects of Sn Loading on Catalytic Performance of PtSn/Al₂O₃ in Propane Dehydrogenation^†. Chem. J. Chinese Universities, 2019, 40(2): 326.

图/表 8

Table 1 Texture properties of Al2O3 support and PtSn/Al2O3 catalysts with different Pt/Sn ratios

Sample	Specific area/(m²·g^-1)	Average pore diameter/nm	Pore volume/(cm³·g^-1)
Al₂O₃	239.5	7.02	0.53
PtSn(3:1)/Al₂O₃	204.3	6.23	0.45
PtSn(1:1)/Al₂O₃	198.3	6.64	0.46
PtSn(1:2)/Al₂O₃	204.0	6.81	0.50
PtSn(1:3)/Al₂O₃	194.5	6.79	0.47

Fig.1 N2 adsorption-desorption isotherms(A) and pore size distribution(B) of Al2O3(a), PtSn(3:1)/Al2O3(b), PtSn(1:1)/Al2O3(c), PtSn(1:2)/Al2O3(d) and PtSn(1:3)/Al2O3(e)

Fig.2 XRD patterns of PtSn/A2O3(A) and unsupported PtSn(B) samples

Fig.3 HRTEM images and corresponding FFTs(inset) of PtSn(3:1)/Al2O3(A), PtSn(1:1)/Al2O3(B), PtSn(1:2)/Al2O3(C) and PtSn(1:3)/Al2O3(D)

Fig.4 IR spectra of pyridine adsorbed on Al2O3(a), PtSn(3:1)/Al2O3(b), PtSn(1:1)/Al2O3(c), PtSn(1:2)/Al2O3(d) and PtSn(1:3)/Al2O3(e)。

Fig.5 Catalytic performance of PtSn/Al2O3 catalysts with different Pt/Sn ratios in the propane dehydrogenation

Fig.6 TG-DTA analysis of PtSn(3:1)/Al2O3(a), PtSn(1:1)/Al2O3(b), PtSn(1:2)/Al2O3(c) and PtSn(1:3)/Al2O3(d)

Fig.7 TEM images(A1, B1) and particle size distribution(A2, B2) of fresh(A1, A2) and reacted(B1, B2) PtSn(3:1)/Al2O3 catalyst

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锡负载量对PtSn/Al₂O₃催化丙烷脱氢性能的影响

Effects of Sn Loading on Catalytic Performance of PtSn/Al₂O₃ in Propane Dehydrogenation^†

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