Zr-Al复合氧化物负载Pt催化甘油氢解制正丙醇

doi:10.1016/S1872-2067(18)63068-2

催化学报 ›› 2018, Vol. 39 ›› Issue (6): 1121-1128.DOI: 10.1016/S1872-2067(18)63068-2

Zr-Al复合氧化物负载Pt催化甘油氢解制正丙醇

李闯^a, 何博^a, 凌雨^a, 曾志荣^b, 梁长海^a

a 大连理工大学化工学院先进材料和催化工程实验室, 辽宁大连 116024;
b 香港高等教育科技学院, 科技学院, 香港 50011

收稿日期:2018-01-29 修回日期:2018-03-22 出版日期:2018-06-18 发布日期:2018-05-16
通讯作者: 梁长海
基金资助:
国家自然科学基金（21573031，21373038）；大连市优秀人才支持计划（2016RD09）；辽宁省博士启动基金（20170520395）.

Glycerol hydrogenolysis to n-propanol over Zr-Al composite oxide-supported Pt catalysts

Chuang Li^a, Bo He^a, Yu Ling^a, Chi-Wing Tsang^b, Changhai Liang^a

a Laboratory of Advanced Materials and Catalytic Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;
b Faculty of Science and Technology, Technological and Higher Education Institute of Hong Kong, Hong Kong 50011, China

Received:2018-01-29 Revised:2018-03-22 Online:2018-06-18 Published:2018-05-16
Contact: 10.1016/S1872-2067(18)63068-2
Supported by:
This work was supported by the National Natural Science Foundation of China (21573031, 21373038), the Program for Excellent Talents in Dalian City (2016RD09), and the Doctoral Scientific Research Foundation of Liao Ning Province (20170520395).

摘要/Abstract

摘要：

近年来，甘油氢解的研究主要集中在生成1，2-丙二醇和1，3-丙二醇二元醇.与二元醇相比，正丙醇也是一种昂贵的化学品，用过量的甘油直接氢解合成高选择性的正丙醇将是一个非常好的生产途径.因为铂金属具有较强的断C-O键的能力，所以甘油氢解制正丙醇的催化剂主要采用铂作为活性组分.本文以铂为活性组分，采用浸渍法将其负载到不同Zr/Al比的Zr-Al复合氧化物上制得2.5% Pt/Zr_xAl_1-xO_y催化剂，并将其应用到甘油氢解反应中，探讨了Zr/Al比对甘油氢解制正丙醇反应性能的影响.
表征结果发现，锆铝混合氧化物经过400℃焙烧后为无定形态的复合金属氧化物，载体中无单相氧化锆或氧化铝存在.随着锆含量增加，催化剂酸性位点向强酸方向移动.不同Zr/Al比的锆铝混合氧化物负载铂催化剂的评价结果发现，甘油转化率随催化剂中铝含量增加而增大；锆铝比大于5：5时，丙醇（正丙醇+异丙醇）的选择性很高，普遍大于87%；锆铝比至7：3时，正丙醇选择性最高.通过X射线衍射、CO化学吸附、H₂程序升温还原、吡啶吸附、氨气程序升温脱附等方法对催化剂进行了表征，发现随着锆铝混合氧化物中锆含量的增加，催化剂的酸性位点向强酸方向移动，调变Zr/Al比促进了铂颗粒的分散，实现了催化剂表面酸量和强酸位点的定向调控.当锆铝比增加至7：3时，催化剂的强酸位点占总酸含量的91.2%.对比催化剂酸性分析和反应结果可知，催化剂表面的总酸含量高有助于甘油转化；强酸位点有助于甘油深度脱水生成丙醇；正丙醇的选择性则可能与NH₃脱附温度在580℃处的强酸位和较大的Pt颗粒有关.当Zr/Al比为7：3时，催化剂表面强酸位点占91.2%，而强酸位点的增加有助于甘油的深度脱水形成正丙醇.因此，以10%甘油水溶液为原料，在240℃和6.0MPa初始氢气压力条件下反应8h，甘油转化率和正丙醇的选择性分别达到81.2%和86.3%.催化剂经过5次循环使用后，甘油转化率和丙醇（正丙醇+异丙醇）选择性几乎不变，但正丙醇的选择性略有降低.使用5次后的催化剂表面的总酸量变化不大，但酸分布变化较大，即强酸比例下降.可见，催化剂活性变化小是由于其表面酸量变化不大，而正丙醇选择性下降与强酸位点比例下降有关.

关键词: 甘油氢解, 正丙醇, 铂催化剂, 锆铝复合氧化物, 锆/铝比

Abstract:

Zr-Al mixed oxide supported Pt catalysts with different Zr/Al mole ratios (2.5%Pt/Zr_xAl_1-xO_y) were synthesized by an impregnation method and used for the selective hydrogenolysis of glycerol to n-propanol in an autoclave reactor. The catalysts were fully characterized by X-ray powder diffraction, Brunauer-Emmett-Teller surface area analysis, CO chemisorption, H₂ temperature-programmed reduction, pyridine-infrared spectroscopy, and NH₃-temperature-programmed desorption. The results revealed that the Zr/Al ratio on the support significantly affected the size of the platinum particles and the properties of the acid sites on the catalysts. The catalytic performance was well correlated with the acidic properties of the catalyst; specifically, more acid sites contributed to the conversion and strong acid sites with a specific intensity contributed to the deep dehydration of glycerol to form n-propanol. Among the tested catalysts, 2.5 wt% Pt/Zr_0.7Al_0.3O_y exhibited excellent selectivity for n-propanol with 81.2% glycerol conversion at 240℃ and 6.0 MPa H₂ pressure when 10% aqueous glycerol solution was used as the substrate. In addition, the effect of various reaction parameters, such as H₂ content, reaction temperature, reaction time, and number of experimental cycles were studied to determine the optimized reaction conditions and to evaluate the stability of the catalyst.

Key words: Glycerol hydrogenolysis, n-Propanol, Pt-based catalyst, Zr-Al composite oxide, Zr/Al ratio

李闯, 何博, 凌雨, 曾志荣, 梁长海. Zr-Al复合氧化物负载Pt催化甘油氢解制正丙醇[J]. 催化学报, 2018, 39(6): 1121-1128.

Chuang Li, Bo He, Yu Ling, Chi-Wing Tsang, Changhai Liang. Glycerol hydrogenolysis to n-propanol over Zr-Al composite oxide-supported Pt catalysts[J]. Chinese Journal of Catalysis, 2018, 39(6): 1121-1128.

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Zr-Al复合氧化物负载Pt催化甘油氢解制正丙醇

Glycerol hydrogenolysis to n-propanol over Zr-Al composite oxide-supported Pt catalysts

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