树脂载钯双功能催化剂的制备及其催化碳四烯烃临氢叠合反应  

Preparation and Performance of Bifunctional Resin-Supported Palladium Catalyst inHydro-Polymerization of C_(4) Olefins

作　　者：李浩东 温朗友 高永恩 夏玥穜 苏鑫 LI Haodong;WEN Langyou;GAO Yongen;XIA Yuetong;SU Xin(SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,Beijing 100083,China;SINOPEC Dalian Research Institute of Petroleum and Petrochemicals Co.,Ltd.,Dalian 116045,China)

机构地区：[1]中石化石油化工科学研究院有限公司,北京100083 [2]中石化(大连)石油化工研究院有限公司,辽宁大连116045

出　　处：《石油学报（石油加工）》2024年第3期629-636,共8页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(21808244)资助。

摘　　要：基于碳四烯烃叠合反应工艺,设计并制备了酸性树脂(KC110、Amberlyst35)载钯双功能催化剂,用于一步法催化1,3-丁二烯选择性加氢和异丁烯叠合反应。借助电子微区探针分析(EPMA)、N 2物理吸附-脱附(BET)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等手段对其物化性质进行表征,并进一步考察了双功能催化剂在碳四烯烃临氢叠合反应过程中的催化性能。结果表明:0.10%Pd/KC110双功能催化剂负载的钯纳米颗粒主要分布在树脂大孔表层结构,平均粒径为3~10 nm,且树脂载体本身的酸性和孔结构保存完好;在反应温度为25℃、压力为1.4~1.6 MPa、质量空速为2.7 h-1、氢气/丁二烯摩尔比为1.5的条件下进行0.10%Pd/KC110催化碳四烯烃临氢叠合反应,1,3-丁二烯可以完全脱除,异丁烯转化率高于81.5%,叠合产物中碳八选择性为75.1%。Based on the reaction process for C 4 olefins polymerization,a new kind of bifunctional acid resin(KC110,Amberlyst35)supported palladium catalyst was designed and prepared,which can simultaneously catalyze the selective hydrogenation of 1,3-butadiene by one-step reaction and the polymerization of isobutene.The properties of the bifunctional catalyst were respectively characterized by electron probe microanalysis(EPMA),N 2 physisorption-desorption(BET),transmission electron microscope(TEM),and X-ray photoelectron spectroscopy(XPS).Moreover,the performance of the bifunctional catalyst in the hydro-polymerization of C 4 olefins was also investigated.The results show that the palladium nanoparticles loaded on 0.10%Pd/KC110 bifunctional catalyst with an average particle diameter of 3—10 nm were mostly distributed on the macroporous surface of resin.The acidic property and the pore structure of resin were well preserved.The hydro-polymerization of C 4 olefins was performed at the reaction temperature of 25℃,the reaction pressure of 1.4—1.6 MPa,the mass hourly space velocity of 2.7 h-1,the molar ratio of hydrogen to 1,3-butadiene of 1.5,as a result of which 1,3-butadiene can be completely removed;the isobutene conversion rate is above 81.5%,and the selectivity of C 8 in polymerization products is about 75.1%.

关 键 词：阳离子交换树脂 钯纳米颗粒 双功能催化剂 碳四馏分 临氢叠合 

分 类 号：TQ241.1[化学工程—有机化工]