无溶剂研磨法合成杂原子分子筛对费托合成产物调控的研究  

Solvent-free synthesis method of heteroatom zeolite for tuning Fischer-Tropsch synthesis product distribution

作　　者：孙旭[1,2] 王佳元 李明权 吕鹏 杨瑞芹[2] 李文泽[1] 邢闯[2] SUN Xu;WANG Jia-yuan;LI Ming-quan;Lü Peng;YANG Rui-qin;LI Wen-ze;XING Chuang(College of Science,Shenyang University of Chemical Technology,Shenyang 110142,China;College of Biology and Chemical Engineering,Zhejiang University of Science and Technology,Hangzhou 310023,China)

机构地区：[1]沈阳化工大学理学院,辽宁沈阳110142 [2]浙江科技学院生物与化学工程学院,浙江杭州310023

出　　处：《应用化工》2020年第S02期82-90,共9页Applied Chemical Industry

基　　金：浙江省自然科学基金(LY19B060001);浙江科技学院青年基金会(2019QN18,2019QN23)。

摘　　要：分子筛因具有特殊的酸性和孔道尺寸而被广泛应用在石油化工领域。利用无溶剂法成功合成了具有MFI拓扑结构的Silicalite-1(S1)、ZSM-5和杂原子S1分子筛(MgS1)。联合浸渍法制备Fe和Al负载型分子筛催化剂,并通过XRD、BET、NH_(3)-TPD、H_(2)-TPR、SEM和FTIR等手段对催化剂进行表征分析,探究上述催化剂在费托合成反应中的催化性能。结果表明,杂原子和浸渍Al改性后的催化剂孔结构和酸中心发生明显改变。在2.0 MPa、300℃、H_(2)/CO=2和W/F=10 g·h/mol的条件下进行费托合成反应,10%Al-Fe/S1催化剂上汽油(C_(5-11))选择性高达70.9%,且具有最低的CH_(4)和CO_(2)的选择性,分别为6.2%和12.0%。Fe/ZSM-5催化剂表现出较高汽油和异构选择性分别为70.4%和48.1%。此外,Fe/MgS1催化剂结果显示产物分布从C_(5)-C_(11)向低碳烷烃C_(2)-C_(4)移动,其中C_(2)-C_(4)选择性为40.6%。采用无溶剂方法合成杂原子分子筛对固体酸催化领域具有一定的借鉴意义。Zeolites with special acidity and pore size,have been applied widely in the field of the petrochemical industry.Silicalite-1,ZSM-5 and heteroatom silicalite-1 zeolite (MgS1)with MFI framework were successfully synthesized by solvent-free method.Fe and Al were loaded on as-synthesized zeolites by incipient wetness impregnation.The prepared catalysts were characterized by XRD,BET,NH 3-TPD,H_(2)-TPR,SEM and FTIR analysis,which were evaluated Fischer-Tropsch synthesis.The characterizations revealed that the pore structure,and acid sites of the modified catalyst were changed obviously.Fischer-Tropsch synthesis reaction was carried out under the conditions of 2.0 MPa,300℃,H_(2)/CO=2 and W/F=10g·h/mol,exhibiting the highest gasoline selectivity of 70.9%for 10%Al-Fe/S1 catalyst with low CH_(4) and CO_(2)selectivity of 6.2%and 12.0%respectively.Fe/ZSM-5 also showed high gasoline selectivity and isoparaffin selectivity(70.4%and 48.1%,respectively).Moreover,Fe/MgS1 catalyst showed a really high selectivity of 40.6%for light hydrocarbon(C_(2)-C_(4)),with the product selectivity of C_(5)-C_(11) move to C_(2)-C_(4).Therefore,the solvent-free synthesis method of heteroatom zeolite can be applied for reference in the field of solid acid catalysis.

关 键 词：无溶剂法 杂原子分子筛 费托合成 汽油 异构烷烃 

分 类 号：TQ517.2[化学工程] TQ032