催化裂化条件下噻吩与改性Y分子筛的作用机制

祖运; 秦玉才; 高雄厚; 莫周胜; 张磊; 张晓彤; 宋丽娟

催化裂化条件下噻吩与改性Y分子筛的作用机制

1.
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;
2.
中国石油天然气股份有限公司石油化工研究院兰州化工研究中心, 甘肃兰州 730060;
3.
中国石油大学(华东) 化学化工学院, 山东青岛 266555

基金项目: 国家自然科学基金(21076100, 21376114); 中国石油天然气股份有限公司炼油催化剂重大专项(10-01A-01-01-01)。

详细信息

通讯作者:
宋丽娟

中图分类号: TE626.21
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出版历程
- 收稿日期: 2015-05-30
- 修回日期: 2015-06-30
- 刊出日期: 2015-07-30

Mechanisms of thiophene conversion over the modified Y zeolites under catalytic cracking conditions

1.
Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning Province, Liaoning Shihua University, Fushun 113001, China;
2.
Lanzhou Petrochemical Research Center, Petrochemical Research Institute, Petro China Company Limited, Lanzhou 730060, China;
3.
College of Chemistry & Chemical Engineering, China University of Petroleum (East China), Qingdao 266555, China

摘要

摘要: 以HY、NiY和稀土离子改性的Y分子筛(REY)为研究对象,采用固定床装置评价噻吩模拟油催化裂化性能;运用气相色谱-氢火焰离子发光检测器(GC-FID)、气相色谱-硫化学发光检测器(GC-SCD)和原位红外光谱技术分析产物,关联分子筛的酸性,研究催化裂化条件下噻吩与改性Y分子筛的作用机制。实验结果表明,催化裂化条件下,噻吩与分子筛的作用机制差异主要取决于与B酸或L酸相关的非骨架铝物种或金属离子物种的存在形式。其中,NiY分子筛中,噻吩主要是吸附在与NiOH⁺物种相关的L酸中心,而Ni₄AlO₄³⁺等物种减弱B酸性中心从而降低其裂化性能。对HY来说,噻吩易在与AlO⁺等物种相邻的B酸中心上聚合形成三联噻吩,并发生一定的氢转移和裂化反应;而对REY而言,分子筛中与RE物种相关的L酸位会促进噻吩在与非骨架铝羟基等物种(如Al(OH)₂⁺、Al(OH)²⁺等)相邻的B酸中心形成的二联噻吩发生氢转移和裂化反应。
- 噻吩 /
- 改性Y分子筛 /
- 催化裂化 /
- 酸性 /
- 作用机制
Abstract: The mechanisms of thiophene conversion over various Y zeolites, viz., HY, Ni-modified NiY and rare earths metal-modified REY, were investigated under catalytic cracking conditions in a fix-bed reactor. The final products of thiophene conversion were analyzed by using a gas chromatography with flame ionization detector (GC-FID), a gas chromatography with sulfur chemiluminescence detector (GC-SCD) and an in situ infrared spectrometer. The results were then correlated with the acidic properties of the zeolites, which indicated that the mechanisms of thiophene interacting with these Y zeolites are dependent on the state and occurrence mode of the modified metallic cation and/or the extraframework aluminum species, which can modulate the Brnsted and Lewis acidities in the zeolites. For the NiY zeolites, the thiophene molecules are mainly adsorbed on the Lewis acidic sites associated with the NiOH⁺ species; the species of Ni₄AlO₄³⁺ and those generated from the Ni²⁺ and the extraframework aluminum can weaken the Brnsted acidity and then reduce the cracking activity of the zeolite. Polymerization and cracking reactions are observed for the conversion of thiophene over the HY and REY zeolites. For the HY zeolites, 2,2',5',2''-terthiophene can be found, which is ascribed to the Brnsted acid sites adjacent to extraframework aluminum species (AlO⁺ or so on); some subsequent reactions of hydrogen transfer and cracking can also be detected. Over the REY zeolite, hydrogen transfer and cracking reactions of thiophene oligomer species derived on the Brnsted acid sites adjacent to extraframework aluminum species (Al(OH)₂⁺, Al(OH)²⁺ and so on) can be promoted by the Lewis acid center related to the RE species.
- thiophene /
- modified Y zeolite /
- catalytic cracking /
- acidity /
- reaction mechanism

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参考文献(25)

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