摘要
为了合成对汽油段、柴油段产物有高选择性的催化剂载体,以多种有机硅烷为模板剂原位合成了高结晶度介孔Y型分子筛,考察了硅烷剂浓度以及有机硅烷剂中的取代基对Y型分子筛性能的影响,并以合成的介孔分子筛为载体通过浸渍法负载钴制备了催化剂,考察了催化剂的费托反应性能;采用X射线衍射、比表面积测试、扫描电子显微镜等测试手段分析了介孔分子筛及催化剂的物性特征,分别使用气相色谱质谱联用仪、气相色谱对反应产物进行了定性和定量分析。结果表明:有机硅烷剂中的硅与硅凝胶中的硅摩尔比为1∶30时达到饱和,继续提高硅烷剂浓度将导致分子筛结晶度下降,且大量的微孔损失,粒径明显减小。通过改变有机硅烷剂的取代基链长,分子筛的平均介孔尺寸可在4.9~9.0 nm进行调控。极性有机硅烷剂更有利于合成高结晶度与大比表面积的介孔分子筛,其中最大比表面积达到683.7 m^(2)/g,且相较于相同链长的非极性有机硅烷剂合成的分子筛其微孔孔容增加了约30%,而介孔孔容几乎相同。在以合成气为原料气的费托合成实验中,极性有机硅烷剂合成的分子筛催化剂对柴油段C_(10-20)产物具有较高选择性,最高达31.1%;非极性有机硅烷剂合成的分子筛催化剂对汽油段C_(5-12)产物具有较高选择性,最高达39.7%。
In order to synthesize a catalyst support with high selectivity for the production of gasoline and diesel fractions,a high-crystallinity mesoporous Y-type molecular sieve was synthesized in situ using various organosilanes as template agents.The effects of silane concentration and substituents on organosilane on the properties of Y-type zeolite were investigated.Zeolite Y was used as catalyst support,cobalt was loaded by impregnation method and the Fischer-Tropsch reaction performance of catalysts was investigated.The samples were analyzed with XRD,BET and SEM,GC-MS and GC were used for qualitative and quantitative analysis of reaction products respectively.The results show that the chemical anchorage of organosilane and siloaluminum species reaches saturation when the ratio of silicon is 1∶30,and further increase in the concentration of silane agent lead to a decrease in the crystallinity of the molecular sieve,a large number of microporous losses,and a significant decrease in particle size.When changing the substituent chain length of organosilanes,the average mesoporous size of molecular sieve can be regulated in the range of 4.9~9.0 nm.In addition,polar organosilanes are more inclined to synthesis of mesoporous zeolite with high crystallinity and high specific surface area.The highest specific surface area reaches 683.7 m^(2)/g.The micropore volume of the polar organosilane group with the same chain length is 30%higher than that of the non-polar organosilane group,while the mesoporous volume is almost the same.In Fischer-Tropler reaction synthesis with syngas as feed gas,the catalyst synthesized with polar organosilane has the highest product selectivity of 31.1%for C_(10-20),and the catalyst synthesized with non-polar organosilane has the highest product selectivity of 39.7%for C_(5-12).
作者
白净
林溢琦
何正
胡俊豪
李攀
常春
BAI Jing;LIN Yiqi;HE Zheng;HU Junhao;LI Pan;CHANG Chun(School of Mechanical and Power Engineering,Zhengzhou University,Zhengzhou 450001,China;CAS Key Laboratory of Renewable Energy,Guangzhou 510640,China;School of Chemical Engineering,Zhengzhou University,Zhengzhou 450001,China;Henan Center for Outstanding Overseas Scientists,Zhengzhou 450001,China)
出处
《广西大学学报（自然科学版）》
CAS
北大核心
2024年第1期178-192,共15页
Journal of Guangxi University（Natural Science Edition）
基金
中国科学院可再生能源重点实验室开放基金项目(E129kf1001)
国家自然科学基金项目(51906082)
生物质资源加工与高效利用杰出外籍科学家工作室项目(GZS2022007)。
关键词
有机硅烷
介孔分子筛
费托合成
钴基催化剂
organosilane
mesoporous molecular sieve
Fischer-Tropsch synthesis
cobalt-based catalyst
作者简介
通信作者:胡俊豪(1989-),男,河南长葛人,讲师,博士,E-mail:junhaohu_hust@163.com。
