B⁃MFI分子筛可控合成及丁烯双键异构化应用

Controlled Synthesis of B⁃MFI Zeolite and Application for Butene Double Bond Isomerization

张景威 惠宇 杨野 李强 秦玉才 宋丽娟 李晟闻

Jingwei ZHANG Yu HUI Ye YANG Qiang LI Yucai QIN Lijuan SONG Shengwen LI

辽宁石油化工大学 辽宁省石油化工催化科学与技术重点实验室，辽宁 抚顺 113001 中国石油大学（华东）;化学工程学院，山东 青岛 266555 中国航油集团辽宁石油有限公司，辽宁 沈阳 110000

Liaoning Provincial Key Laboratory of Petrochemical Catalysis Science and Technology，Liaoning Petrochemical University，Fushun Liaoning 113001，China School of Chemical Engineering，China University of Petroleum，Qingdao Shandong 266555，China China Aviation Oil Group Liaoning Petroleum Company Limited，Shenyang Liaoning 110000

采用无溶剂法，以四丙基氢氧化铵(TPAOH)为模板剂，合成了一系列B?MFI分子筛，采用XRD、SEM、N2吸附?脱附、原位红外光谱及吡啶吸附红外光谱等方法，表征了TPAOH添加量对B?MFI分子筛物化性质的影响，并考察了1?丁烯双键异构化反应性能。结果表明，TPAOH添加量显著影响B?MFI分子筛的晶粒尺寸和骨架硼物种含量，当TPAOH添加量为4.500 g（n（SiO2）/n（TPAOH）=11.6）时，所制得的B?MFI分子筛粒径最小，且具有最大量的硅硼羟基窝，可提供更多高活性反应位点。反应评价结果证实，采用B?MFI分子筛催化剂进行1?丁烯双键异构化反应时，1?丁烯的转化率高达70.00%，2?丁烯的选择性大于99%，且催化剂稳定性优异，评价周期内无失活迹象。

A series of B?MFI zeolites were synthesized using a solvent?free method using tetrapropylammonium hydroxide (TPAOH) as a template. XRD, SEM, N2 adsorption desorption, in situ infrared spectroscopy, and pyridine adsorption infrared spectroscopy were used to characterize the effect of template agent addition on the physicochemical properties of B?MFI zeolites, and the performance of 1?butene double bond isomerization reaction was investigated. The results showed that the addition of template significantly affected the grain size and skeleton boron species content of B?MFI zeolites. When the template agent addition was 4.500 g (n（SiO2）/n（TPAOH)=11.6）, the B?MFI zeolites obtained had the smallest particle size and the largest number of silicon boron hydroxyl pits, providing more highly active reaction sites. The reaction evaluation results confirmed that when using B?MFI molecular sieve catalyst for the double bond isomerization of 1?butene, the conversion rate of 1?butene was as high as 70.00%, and the selectivity of 2?butene was greater than 99%. The catalyst had excellent stability and showed no signs of deactivation during the evaluation period.

国家自然科学基金项目(U20A20120)

10.12422/j.issn.1006-396X.2023.05.004