高分子及表面活性剂对ZSM-5分子筛形貌调控  

Regulation of ZSM-5 zeolite morphology with polymers and surfactants

作　　者：李贵生[1] 史静 何万仁 赵国良 滕加伟 LI Guisheng;SHI Jing;HE Wanren;ZHAO Guoliang;TENG Jiawei(Sinopec Zhongyuan Petrochemical Co.,Ltd.,Puyang 457000,China;State Key Laboratory of Green Chemical Engineering and Industrial Catalysis,Sinopec Shanghai Research Institute of Petrochemical Technology,Shanghai 201208,China)

机构地区：[1]中原石油化工有限责任公司,河南濮阳457000 [2]中国石化上海石油化工研究院绿色化工与工业催化国家重点实验室,上海201208

出　　处：《石油化工》2023年第1期20-28,共9页Petrochemical Technology

摘　　要：采用高通量水热合成设备,在分子筛合成过程中使用水溶性高分子(甲基纤维素、淀粉和聚乙二醇400)及表面活性剂(十二烷基磺酸钠、十二烷基苯磺酸钠)作为特殊添加剂,对ZSM-5分子筛形貌进行调控;采用XRD和SEM方法对分子筛的尺寸和形貌进行表征,探索了不同添加剂对晶体生长的作用以及对分子筛形貌的影响;研究了不同粒径分子筛对苯分子的吸附性能及其在C4烯烃催化裂解反应中的性能。实验结果表明,加入不同添加剂会制备出不同形貌及粒径大小的分子筛,使用十二烷基苯磺酸钠可以得到小粒径纳米级分子筛。TG和吸附结果表明,小粒径分子筛中有机模板剂或添加剂含量更高,失重更明显,具有更高的苯饱和吸附量。同时纳米分子筛会暴露出更多的外表面活性位,与反应物/中间体/产物产生过强的吸附作用力,扩散速率较低。在C4烯烃裂解反应中,纳米分子筛催化剂由于具有更多的活性位而表现出较高的初始转化率及优良的稳定性。In this paper,water-soluble polymers(methylcellulose,starch and polyethylene glycol 400) and surfactants(sodium dodecyl sulfonate,sodium dodecyl benzene sulfonate) were applied as special additives to control the morphology of ZSM-5 zeolite with high throughput hydrothermal synthesis equipment. The size and morphology of the obtained samples were characterized by XRD and SEM. The promotion or inhibition role of different additives on the growth of crystal and their effects on the morphology were explored. Adsorption of benzene on the zeolites with different particle sizes and their performance in catalytic cracking of C4 olefins were studied. Nano-sized zeolite can be obtained with sodium dodecyl benzene sulfonate as additive. The results of TG and benzene adsorption behavior of nano-sized zeolite showed that the content of organic template or additive was higher than zeolite with micro-size. The weight loss was more obvious,and the adsorption capacity of benzene saturation was greater. At the same time,zeolite with small particle size exposed more active sites on the external surface,resulting in too strong adsorption force and low diffusion rate. In the C4 olefin cracking reaction,nano-sized zeolite catalyst has more active sites and shows higher initial conversion and excellent stability.

关 键 词：ZSM-5分子筛 形貌 添加剂 晶体生长 烯烃裂解反应 

分 类 号：TQ612.2[化学工程—精细化工]