摘要
使用来源广泛的甲醇为原料制取丙烯,是对石油路线生产丙烯的重要补充.尽管以ZSM-5分子筛为催化剂的固定床甲醇制丙烯(MTP)技术已经实现了工业应用,但进一步提高催化剂的寿命和丙烯的选择性一直是学术界和工业界的研究热点.MTP过程作为典型的酸催化反应,积碳是催化剂失活的主要原因,由于ZSM-5分子筛十元环孔道的空间限制作用,积碳主要分布在外表面.因此,消除外表面的酸性位点对延长催化剂的寿命至关重要,但修饰外表面酸性位点的同时往往会改变样品的其他性质,如孔径、整体酸量等.本文分别使用Na_2H_2EDTA和H_3PO_4处理高硅ZSM-5分子筛原粉(微孔内含有机模板剂)来选择性地减小或消除外表面的酸密度,而不影响分子筛内部的性质,并考察了处理后样品的MTP性能.使用N_2物理吸附、SEM和^(27)Al MAS NMR表征样品的织构性质、形貌和Al原子的化学环境,XPS和三异丙苯裂解实验表征外表面的硅铝比和酸密度.表征结果表明,Na_2H_2EDTA处理虽然可以选择性的脱除表面Al原子,但会在外表面产生新的酸点(可能是硅巢).H_3PO_4处理虽然不能脱除表面的Al原子,但外表面残留的P物种能够有效的减小酸密度.MTP评价结果表明,H_3PO_4处理能够有效的延长催化剂的寿命和维持丙烯的选择性,这是因为H_3PO_4处理既提高了外表面的容碳能力,也抑制了积碳沉积的速率.Na_2H_2EDTA处理仅能增加外表面的容碳能力,所以其只能延长催化寿命.通过进一步优化H_3PO_4后处理的条件,处理后的ZSM-5样品的催化寿命可以延长至前体的1.5倍,同时,丙烯的选择性也略有提高。
Post-synthetic treatment of high-silica as-made ZSM-5 with organic template in the micropores was explored to reduce/remove the external surface acid density of ZSM-5. It is found that Na_2H_2 EDTA treatment can selectively remove the surface Al atoms, but generates new acid sites(likely silanol nests) on the external surface. H_3PO_4 treatment is unable to remove surface Al atoms, while small amount of P is left on the external surface, which effectively decreases the acid density. The catalytic performance of the resultant materials is evaluated in the methanol conversion reaction. H_3PO_4 treatment can effectively improve both the catalytic lifetime and the stability of propene selectivity.This occurs due to a combination of the increased tolerance to the external coke deposition and the depressed coking rate(reduced side reactions). Na_2H_2 EDTA treatment only prolongs the catalytic lifetime, resulting from the improved tolerance to the external coke deposition. Under the optimized H_3PO_4 treatment condition, the resultant ZSM-5 gives a catalytic lifetime of about 1.5 times longer than the precursor. Moreover, the propene selectivity is improved, showing a slight increasing trend until the deactivation.
作者
赵学斌
洪杨
王林英
樊栋
闫娜娜
刘晓娜
田鹏
郭新闻
刘中民
Xuebin Zhao;Yang Hong;Linying Wang;Dong Fan;Nana Yan;Xiaona Liu;Peng Tian;Xinwen Guo;Zhongmin Liu(State Key Laboratory of Fine Chemicals,PSU-DUT Joint Center for Energy Research,School of Chemical Engineering,Dalian University of Technology,Dalian116024,Liaoning,China;National Engineering Laboratory for Methanol to Olefins,State Energy Low Carbon Catalysis and Engineering R&D Center,Dalian National Laboratory for Clean Energy,Collaborative Innovation Center of Chemistry for Energy Materials(iChEM),Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian116023,Liaoning,China;University of Chinese Academy of Sciences,Beijng100049,China)
基金
国家自然科学基金(21676262)
中国科学院前沿科学重点研究计划(QYZDB-SSW-JSC040).
关键词
甲醇制丙烯
ZSM-5分子筛
改性
磷酸
乙二胺四乙酸
Methanol to propene ZSM‐5 zeolite
Modification Phosphoric acid
Ethylenediamine tetraacetic acid