同型H-SAPO-5和H-SSZ-24上的乙烯和丁烯齐聚反应:动力学和机理

doi:10.1016/S1872-2067(19)63426-1

催化学报 ›› 2019, Vol. 40 ›› Issue (11): 1766-1777.DOI: 10.1016/S1872-2067(19)63426-1

同型H-SAPO-5和H-SSZ-24上的乙烯和丁烯齐聚反应:动力学和机理

Christian Ahoba-Sam, Marius Westgard Erichsen, Unni Olsbye

奥斯陆大学化学系, 材料科学和纳米技术中心, N-0315 奥斯陆, 挪威

收稿日期:2019-06-17 修回日期:2019-06-20 出版日期:2019-11-18 发布日期:2019-09-06
通讯作者: Unni Olsbye

Ethene and butene oligomerization over isostructural H-SAPO-5 and H-SSZ-24: Kinetics and mechanism

Christian Ahoba-Sam, Marius Westgard Erichsen, Unni Olsbye

SMN Centre for Materials Science and Nanotechnology, Department of Chemistry, University of Oslo, N-0315 Oslo, Norway. aCurrent address:Matriks AS, Gaustadallèen 21, 0349 Oslo, Norway

Received:2019-06-17 Revised:2019-06-20 Online:2019-11-18 Published:2019-09-06
Contact: Unni Olsbye

摘要/Abstract

摘要： B酸型分子筛和分子筛型材料是乙烯转化为高级烯烃的潜在催化剂.本文在C3-C5烯烃形成热力学优于高碳氢化合物的条件下（673-823 K，1 atm），研究了两种具有AFI结构但酸强度不同的H-SAPO-5和H-SSZ-24催化剂上乙烯、顺式-2-丁烯和乙烯-丁烯混合物的转化反应.乙烯和顺式-2-丁烯分压分别在9-60和0.9-8.1 kpa范围内变化，接触时间分别在3.78-756和0.573-76.4 s.μmol H⁺/cm₃范围内变化.在用于计算速率常数的条件范围内，乙烯转化率小于1%，丁烯转化率小于10%.在酸性较强的H-SSZ-24上乙烯转化率比H-SAPO-5高一个数量级（748 K时为6.5对0.3 mmol/mol H+.S，戊烯=33 KPa），乙烯中相应的反应级数较低（673 K时为1.5对2.0），表观活化能较低（698-823 K时52对80 kJ/mol）.两种催化剂上顺式-2-丁烯转化率以及乙烯和顺式-2-丁烯共进料的表观反应速率存在相似的差异.然而，顺式-2-丁烯转化为C3-C5烯烃受热力学限制的影响很大，妨碍了详细的动力学分析，并导致在最高温度下主要生成异丁烯.

关键词: 乙烯齐聚, 丁烯齐聚, 动力学, 分子筛, 酸强度, H-SAPO-5, H-SSZ-24

Abstract: Brønsted-acidic zeolite and zeotype materials are potential catalysts for the conversion of ethene to higher alkenes. In this study, two materials with AFI structure but different acid strength, H-SAPO-5 and H-SSZ-24, were subject to studies of ethene, cis-2-butene and ethene-butene mixture conversion under conditions where C₃-C₅ alkene formation is thermodynamically favoured over higher hydrocarbons (673-823 K, 1 atm). Ethene and cis-2-butene partial pressures were varied in the range 9-60 and 0.9-8.1 kPa, respectively, and contact times were varied in the range 3.78-756 and 0.573-76.4 s.μmol H+/cm³ over H-SAPO-5 and H-SSZ-24, respectively. Less than 1% conversion of ethene and less than 10% conversion of butene was obtained in the range of conditions used for elucidation of rate parameters.
The ethene conversion rates were more than an order of magnitude higher over the more acidic H-SSZ-24 than over H-SAPO-5 (6.5 vs. 0.3 mmol/mol H⁺.s at 748 K, P_ethene=33 kPa), with corre-sponding lower reaction order in ethene (1.5 vs. 2.0 at 673 K) and lower apparent activation energy (52 vs. 80 kJ/mol at 698-823 K). Propene selectivity was substantially higher over H-SSZ-24 than over H-SAPO-5 (68% vs. 36% at 0.5% ethene conversion). A similar difference in apparent reaction rates was observed for cis-2-butene conversion over the two catalysts, and for co-feeds of ethene and cis-2-butene. However, the cis-2-butene conversion to C₃-C₅ alkenes was found to be severely influenced by thermodynamic limitations, impeding a detailed kinetic analysis, and leading predominantly to isobutene formation at the highest temperatures.

Key words: Ethene oligomerization, Butene oligomerization, Kinetics, Zeolite, Acid strength, H-SAPO-5, H-SSZ-24

Christian Ahoba-Sam, Marius Westgard Erichsen, Unni Olsbye. 同型H-SAPO-5和H-SSZ-24上的乙烯和丁烯齐聚反应:动力学和机理[J]. 催化学报, 2019, 40(11): 1766-1777.

Christian Ahoba-Sam, Marius Westgard Erichsen, Unni Olsbye. Ethene and butene oligomerization over isostructural H-SAPO-5 and H-SSZ-24: Kinetics and mechanism[J]. Chinese Journal of Catalysis, 2019, 40(11): 1766-1777.

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同型H-SAPO-5和H-SSZ-24上的乙烯和丁烯齐聚反应:动力学和机理

Ethene and butene oligomerization over isostructural H-SAPO-5 and H-SSZ-24: Kinetics and mechanism

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