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Al-MCM-41分子筛的制备及其催化合成聚甲氧基二甲醚
Preparation of Al-MCM-41 zeolite and its catalytic performance in the synthesis of polymethoxy dimethyl ether
【摘要】 采用水热合成法制备了不同Al含量的Al-MCM-41介孔分子筛,考察了分子筛催化甲醇和多聚甲醛合成聚甲氧基二甲醚(PODEn,n为聚合度)的性能;采用XRD、FTIR、N2吸附-脱附、ICP-OES、SEM、NH3-TPD等方法分析了分子筛的孔结构和酸性质对产物分布的影响,并对PODEn的合成工艺条件进行了优化。实验结果表明,制备的Al-MCM-41分子筛具有二维六方有序介孔结构;Al的掺入导致分子筛的比表面积、孔体积和孔径出现不同程度的减小,但有效提高了分子筛的中强酸量,进而促进高聚合度产物的生成;硅铝比为40的Al-MCM-41(40)分子筛的催化性能最优。PODEn最佳合成条件为:135℃、5 h、甲醇与多聚甲醛的摩尔比为1.5、催化剂的用量为2%(w),在此条件下,甲醇转化率达74.5%,PODE3~5选择性达31.3%。Al-MCM-41(40)分子筛重复使用5次仍具有较好的催化活性。
【Abstract】 Al-MCM-41 mesoporous zeolite with different Al contents were synthesized by the hydrothermal method.The catalytic performances of Al-MCM-41 zeolite in the synthesis of polyoxymethylene dimethyl ethers(PODEn,n represents degree of polymerization) with methanol and paraformaldehyde were investigated.XRD,FTIR,N2 adsorption-desorption,ICP-OES,SEM,and NH3-TPD techniques were used to analyze the pore structure and acid properties of Al-MCM-41,whose influence on the product distribution was discussed.The synthesis process conditions of PODEn were further optimized.The results show that the prepared Al-MCM-41 has an ordered two-dimensional hexagonal mesoporous structure.The doping of Al causes the specific surface area,pore volume and pore size of the zeolite decrease,while effectively increases the amount of medium-strong acid in zeolite which promotes the formation of high polymerization products.When the molar ratio of Si/Al is 40,the Al-MCM-41(40) zeolite shows the best catalytic performance.The optimal synthesis condition for PODEn is that the reaction temperature being 135℃,reaction time being 5 h,the ratio molar of methanol to paraformaldehyde being 1.5,and the amount of catalyst being 2%(w).Under the optimal condition,the conversion of methanol reaches 74.5%and the selectivity to PODE3-5 is up to 31.3%.Al-MCM-41(40) zeolite catalyst exhibited good catalytic activity after being reused for 5 times.
【Key words】 MCM-41 zeolite; polymethoxy dimethyl ether; alumina modification; acid catalysis; paraformaldehyde;
- 【文献出处】 石油化工 ,Petrochemical Technology , 编辑部邮箱 ,2021年02期
- 【分类号】TE624.81
- 【被引频次】3
- 【下载频次】339