多级孔NiMo负载Beta沸石催化剂的制备及加氢脱氧性能  

Preparation and hydrodeoxygenation performances of multi-stage hole NiMo loaded Beta zeolite catalyst

作　　者：刘玉珂 顾宇飞 王伟[1] 李福威 黄雪 李志霞[1] LIU Yuke;GU Yufei;WANG Wei;LI Fuwei;HUANG Xue;LI Zhixia(School of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,Guangxi,China)

机构地区：[1]广西大学化学化工学院,广西南宁530004

出　　处：《精细化工》2025年第4期849-857,共9页Fine Chemicals

基　　金：国家自然科学基金项目(22078076);广西自然科学基金项目(2020GXNSFAA159174)。

摘　　要：以廉价的硅藻土和偏铝酸钠为原料,采用水热法制备Beta沸石。通过软模板法、有机碱(尿素)处理法、无机碱(NaOH)处理法对沸石的酸性和孔结构进行了调节,合成了多级孔Beta分子筛,通过超声辅助浸渍法负载非贵金属Ni、Mo制备了双金属负载Beta沸石(NiMo/Beta)催化剂。利用XRD、SEM、N2吸附-脱附、NH3-TPD、H2-TPR对催化剂晶体结构、微观形貌、孔结构、酸性和金属还原性进行了表征。考察了改性处理方式和工艺条件(反应温度、H2压力、溶剂正十二烷用量、反应时间)对催化剂催化愈创木酚加氢脱氧反应性能的影响。结果表明,在300℃、H2压力4 MPa、反应时间3 h、溶剂正十二烷20 mL的条件下,在6.0 g硅藻土中加入3.0 g十六烷基三甲基溴化铵(CTAB)改性后的NiMo/Beta-3.0CB表现出最佳的催化活性,愈创木酚转化率为99.8%,环己烷选择性为92.7%。NiMo/Beta-3.0CB循环使用3次后,愈创木酚转化率为85.7%。Beta zeolite was prepared from hydrothermal reaction of cheap diatomite and sodium meta-aluminate,and the acidity and pore structure was modified by soft template method,organic alkali(urea)treatment and inorganic alkali(NaOH)treatment to synthesize multi-stage hole Beta molecular sieve,which was further loaded with non-noble metals Ni and Mo via ultrasound-assisted impregnation method to obtain bimetallic-loaded Beta zeolite catalyst(NiMo/Beta).The crystal structure,micromorphology,pore structure,acidity and metal reducibility of the catalyst were characterized by XRD,SEM,N2 adsorption-desorption,NH3-TPD and H2-TPR,while the effects of modified treatment methods and process conditions(reaction temperature,H2 pressure,solvent n-dodecane dosage,reaction time)on the catalytic performance in hydrodeoxygenation of guaiacol were analyzed.The results showed that under the conditions of 300℃,H2 pressure 4 MPa,reaction time 3 h and solvent n-dodecane 20 mL,NiMo/Beta-3.0CB modified with 3.0 g cetyl trimethyl ammonium bromide(CTAB)in 6.0 g diatomite exhibited the best catalytic activity,with the guaiacol conversion of 99.8%and the cyclohexane selectivity of 92.7%.After three times of recycling of NiMo/Beta-3.0CB,the conversion of guaiacol was still maintained at 85.7%.

关 键 词：多级孔Beta 硅藻土 木质素 加氢脱氧 愈创木酚 环己烷 催化技术 

分 类 号：TQ426.94[化学工程]