晶种导向合成MOR分子筛及其催化应用  

Seed directed synthesis of mordenite zeolite and its catalytic application

作　　者：张宇[1,2] 王亚男 刘稳 安杰 徐仕睿[3,4] 李秀杰 石磊[1,2] 朱向学[3] ZHANG Yu;WANG Yanan;LIU Wen;AN Jie;XU Shirui;LI Xiujie;SHI Lei;ZHU Xiangxue(Key Laboratory on Resources Chemicals and Materials of Ministry of Education,Shenyang University of Chemical Technology,Shenyang 110142,Liaoning,China;Institute of Industrial Chemistry and Energy Technology,Shenyang University of Chemical Technology,Shenyang 110142,Liaoning,China;Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,Liaoning,China;Fushun Dongke Fine Chemical Co.,Ltd.,Fushun 113116,Liaoning,China)

机构地区：[1]沈阳化工大学资源化工与材料教育部重点实验室,辽宁沈阳110142 [2]沈阳化工大学能源与化工产业技术研究院,辽宁沈阳110142 [3]中国科学院大连化学物理研究所,辽宁大连116023 [4]抚顺东科精细化工有限公司,辽宁抚顺113116

出　　处：《天然气化工—C1化学与化工》2022年第2期54-60,68,共8页Natural Gas Chemical Industry

基　　金：国家自然科学基金(No.22008229,U20A20120);兴辽英才计划(XLYC1901006&XLYC1908010);大连市重点领域创新团队(2020RT06)。

摘　　要：具有8元环与12元环孔道结构的丝光沸石(MOR)分子筛因其独特的孔道结构和酸性被广泛应用到烷基化、异构化和羰基化等反应过程,通过晶种辅助无胺绿色合成MOR分子筛一直是人们关注的热点,但添加的晶种类型对产物的影响鲜有研究。借助XRD、IR和SEM在内的多种表征手段详细考察了同晶MOR晶种及异晶(FER)晶种在MOR无胺绿色合成路线中的导向作用。实验结果表明,因合成体系碱度过高,添加MOR分子筛晶种并未显著加速晶化。当MOR分子筛作晶种合成得到纺锤形的MOR纳米团聚体,尺寸在1μm左右,样品性质与无晶种添加路线相似。以FER为晶种可导向合成棒束状形貌的MOR分子筛,跟踪晶化过程发现,FER晶种首先诱导形成了FER晶相,随后薄片状FER晶体溶解转晶生成了MOR晶相。上述结果为分子筛无胺转晶路线制备棒束状MOR沸石提供了新的合成思路。在异丁烯齐聚反应中,通过添加MOR晶种制得的纺锤形MOR纳米团聚体因其丰富的晶间介孔呈现较佳的反应稳定性。Mordenite(MOR) molecular sieve with 8-membered ring and 12-membered ring channel structure is widely applied in alkylation,isomerization, carbonylation and other reaction processes because of its unique pore structure and acidity. The amine-free green synthesis of MOR molecular sieve assisted by crystal seed has always been a hot spot, but the effect of added seed types on the products is rarely studied.The guide role of MOR seed and ferrierite(FER) seed for MOR synthesis in MOR amine-free green synthesis route was investigated in detail by means of XRD, IR and SEM. The experimental results show that due to the high alkalinity of the synthesis system, the addition of MOR molecular sieve seed do not accelerate the crystallization significantly. When MOR molecular sieves are applied as seed, spindleshaped MOR nano-agglomerates with a size of about 1 μm are synthesized which are similar to those of the no seed route. When FER molecular sieves are introduced as seed, MOR molecular sieves with rod beam morphology are obtained. On basis of the crystallization process tracking, it is found that FER seed induce the formation of FER crystal phase at first, and then the thin flake FER crystal dissolve and transform into MOR crystal phase. These results provide a new route for the preparation of rod-bundle MOR zeolite by amine-free transformation of molecular sieve. In the isobutene oligomerization reaction, the spindle-shaped MOR nano-aggregates prepared by the addition of MOR seeds, have better reaction stability due to the abundance of intergranular mesopore.

关 键 词：MOR分子筛 晶种诱导 转晶路线 无胺绿色合成 

分 类 号：TE09[石油与天然气工程] O643.36[理学—物理化学]