摘要
以四乙基溴化铵(TEABr)、偏铝酸钠、氢氧化钠和硅溶胶为原料,十二烷基苯磺酸钠(SDBS)为软模板剂,采用无溶剂法制备了梯级孔丝光沸石(MOR)催化剂,通过XRD、BET、NH_(3)-TPD、吡啶红外(Py-IR)对其进行了表征。考察了SDBS添加量(以硅溶胶中SiO_(2)质量为基准,下同)对梯级孔MOR催化剂催化二甲醚(DME)羰基化反应性能的影响。结果表明,SDBS的添加可以提高梯级孔MOR催化剂的相对结晶度、比表面积、介孔孔容和总孔容;在反应温度200℃、反应压力0.5 MPa、气时空速(GHSV)2000 mL/(g·h)、n(DME)∶n(CO)=97.5∶2.5的条件下,SDBS添加量为4%的梯级孔MOR催化剂(4%-SDBS)具有最佳的催化DME羰基化反应活性,DME转化率最高为88.9%,主产物乙酸甲酯的选择性接近100%。在梯级孔MOR催化剂的制备过程中,SDBS能够诱导Al原子优先进入八元环孔道形成强酸和中强酸中心,从而增加DME羰基化反应的活性中心数量。
Mesoporous composite mordenite(MOR)catalysts were prepared by solvent-free method using tetraethyl ammonium bromide(TEABr),sodium metaaluminate,sodium hydroxide as well as silica sol as raw materials,and sodium dodecyl benzene sulfonate(SDBS)as soft template agent.The MOR was characterized by XRD,BET,NH_(3)-TPD and pyridine infrared(Py-IR),and the effect of SDBS additive amount(based on the mass of SiO_(2)in silica sol,the same below)on the catalytic performance of MOR for dimethyl ether(DME)carbonylation was analyzed.The results indicated that the addition of SDBS enhanced the relative crystallinity,specific surface area,mesoporous pore volume,and total pore volume of the mesoporous composite MOR catalyst.Under the conditions of reaction temperature 200℃,reaction pressure 0.5 MPa,gas hourly space velocity(GHSV)2000 mL/(g·h),and n(DME)∶n(CO)=97.5∶2.5,the MOR catalyst with a SDBS additive amount of 4%(4%-SDBS)exhibited the best catalytic activity for DME carbonylation,with the DME conversion rate of 88.9%and the selectivity of the principal product,methyl acetate(MA),close to 100%.During the MOR preparation process,SDBS induced Al atoms to preferentially enter the 8-membered ring channel to form strong acid and medium strong acid centers,thereby increasing the number of active centers for the DME carbonylation reaction.
作者
王鸿晶
刘少铎
张扬扬
王晓胜
李然家
余长春
WANG Hongjing;LIU Shaoduo;ZHANG Yangyang;WANG Xiaosheng;LI Ranjia;YU Changchun(College of New Energy and Materials,China University of Petroleum,Beijing 102249,China)
出处
《精细化工》
北大核心
2025年第10期2208-2213,2314,共7页
Fine Chemicals
基金
国家自然科学基金项目(22008260)
中石油-中国石油大学(北京)战略合作专项(ZLZX2020-04)
中国氢能联盟2022政研项目(CHA2022RP002)。
关键词
十二烷基苯磺酸钠
丝光沸石分子筛
介孔
二甲醚
羰基化
催化技术
sodium dodecyl benzene sulfonate
mordenite
mesopore
dimethyl ether
carbonylation
catalytic technology
