Pd-非贵金属/C顺酐加氢制四氢呋喃催化剂的研究

【作者】 张建国；

【导师】 阮济之； 王海京；

【作者基本信息】 石油化工科学研究院 ， 化学工艺， 2000， 硕士

【摘要】 以γ-丁内酯(GBL)及顺酐(MA)为原料，在固定床反应器中，考察了非贵金属元素M对Pd／C系MA加氢催化剂用于中压加氢制备四氢呋喃(THF)的影响，发现其中Cu、Zn、Mn、Al四种非贵金属组元对Pd／C催化剂的加氢性能有显著影响，利用这四种组元制得的Pd-M／C催化剂，对MA中压加氢有良好效果。 对Cu、Zn、Mn、A1四种非贵金属组元，在Pd-M／C中与贵金属Pd的协同催化作用进行了细致的考察，发现Mn和Al有利于提高催化剂的加氢活性，Zn和Cu有利于提高催化剂对THF的选择性，四种组元组合在一起，对Pd的催化协同作用增强。 探讨了以Pd-M／C为催化剂，MA直接加氢的反应特性，证明在Pd-M／C催化体系中，MA加氢反应基本符合Massimo Messori等人的MA加氢反应网络，但在Pd-M／C催化体系中，THF的主要生成途径是：MA→GBL→BDO→THF。 采用TEM、XPS、XRD和SEM等技术分析了Pd-M／C催化剂的结构特点，考察了影响催化剂结构的主要因素，讨论了催化剂结构与性能的关系。发现催化剂组分在活性炭上高度分散的微球状结构有利于催化剂催化性能的提高，焙烧温度是影响催化剂活性组分在活性炭载体表面分布的主要因素，合适的焙烧温度范围是450～550℃，催化剂后期氨化处理能够促进活性组分在活性炭表面形成高度分散的微球状结构。更多还原

【Abstract】 The effect of non-noble metal component M (herein M represents one or more non-noble metal elements) on the performance of Pd-M/C catalyst for the hydrogenation of maleic anhydride (MA) to tefrahydroftiran (ThF) was investigated under moderate pressure (2.O-8.OMpa) in a fixed-bed microreactor ’~’ -butyrolactone (GBL) or maleic anhydride as a feedstock. It is found that the performance of the Pd-M1C catalyst for the hydrogenation of MA was significantly improved when the Pd-M/C catalyst was prepared by impregnating the Pd/C with a mixed salt solution containing four non-noble metal Cu, Zn, Mn, and Al.The concerted catalysis between copper, zinc, manganese, aluminum and palladium was investigated carefully. The addition of manganese and aluminum to Pd/C catalyst increases the activity of hydrogenation, the addition of zinc and copper improves the selectivity of THF.When the Pd-M/C catalyst was used for hydrogenation of MA, the reaction pathway was in accord with that hypothesis of Massimo Messori. In the Pd-M1C catalyst system, the most of THF was from form the pathway of MA-GBL- BDO-THF.The structure of Pd-M/C catalyst was examined by using techniques of SEM, TEM, XPS and XRD. The main factors influencing the catalyst structure were investigated. The effect of catalyst structure on catalyst performance was discussed. The spherical particles of catalyst active components highly dispersed on the support of active carbon are advantageous to improving the performance of Pd-M/C catalyst Calcining temperature is an important factor of affecting catalyst stmcture, and it is preferably in the range from 4OO-5OOC. The ammoniation of Pd-M1Ccatalyst can improve the catalyst active components to form highly dispersed spherical particles on active carbon.更多还原