炼油技术与工程 ›› 2022, Vol. 52 ›› Issue (6): 27-30.

• 催化剂和助剂 • 上一篇    下一篇

天然气脱硫工艺羰基硫水解催化剂失活研究

刘剑利1,朱春蕾2,刘爱华1,刘增让1,徐翠翠1,宋宛霖1,王国玮2    

  1. 1.中国石油化工股份有限公司齐鲁分公司研究院; 2.中国石油大学(华东)重质油国家重点实验室
  • 收稿日期:2022-03-04 出版日期:2022-06-15 发布日期:2022-06-17
  • 作者简介:刘剑利，高级工程师，1999年毕业于抚顺石油学院工业催化专业，主要从事硫磺回收技术及催化剂研发。联系电话：0533-7511297,E-mail:liujianli.qlsh@sinopec.com。

Study on deactivation of carbonyl sulfide hydrolysis catalyst in natural gas desulfurization process

Liu Jianli1,Zhu Chunlei2,Liu Aihua1,Liu Zengrang2,Xu Cuicui1,Song Wanlin1,Wang Guowei2   

  1. 1.Research Institute of SINOPEC Qilu Petrochemical Company; 2.State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)
  • Received:2022-03-04 Online:2022-06-15 Published:2022-06-17

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摘要：

为研究羰基硫水解催化剂的失活机理，对PG新剂及旧剂进行了表征。低温氮气吸脱附实验表明：PG新剂比表面积大于330 m2/g,使用后催化剂比表面积降低20%以上，平均孔径增大，孔体积略有减小。SEM(扫描电子显微镜)照片表明：新鲜剂表面颗粒形貌均匀，失活催化剂比表面积减小，孔体积减小，孔道变大。XRD(X射线衍射)结果表明：PG新剂主要由AlO(OH)和Al2O3两种晶相构成，使用后催化剂除AlO(OH)相外，均新增Al(OH)3相，且随床层高度下移，Al(OH)3衍射峰强度逐渐削弱。XRF(X射线荧光法)结果表明：PG新剂主要组成为氧化铝和少量氧化钠，反应后催化剂上积聚了一定量的含碳、氮和硫的物质，且氧化钠的含量有所降低。CO2-TPD(CO2程序升温脱附)结果表明：PG新剂上存在丰富的弱碱性中心，而反应后催化剂上硫等杂质的沉积导致弱碱性中心数量显著减少。

关键词: 天然气脱硫工艺, 羰基硫水解, 催化剂失活, 低温氮气吸脱附, SEM, XRD, XRF, CO2-TPD

Abstract:

In order to study the deactivation mechanism of carbonyl sulfide hydrolysis catalyst, the new and old PG catalyst were characterized. Low temperature nitrogen adsorption and desorption experiments show that the specific surface area of PG new agent is greater than 330 m2/g, and the specific surface area of used catalyst is reduced by more than 20%, the average pore size increased and the pore volume decreased slightly. SEM results show that the surface particle morphology of the fresh agent is uniform, the specific surface area of the deactivated catalyst decreases, the pore volume decreases and the pore channel becomes larger.XRD results show that the PG new agent is mainly composed of two crystalline phases of AlO(OH) and Al2O3, Al(OH)3 phase is added to the used catalyst except for AlO(OH) phase, and the diffraction peak intensity of Al(OH)3 decreases gradually with the height of the bed moving down. XRF results show that the PG new agent is mainly composed of Al2O3 and a small amount of Na2O, a certain amount of species containing carbon, nitrogen and sulfur are accumulated on the catalyst, and the content of Na2O decreased. The results of CO2-TPD show that there are abundant weak alkaline centers on the PG new agent, and the deposition of sulfur and other impurities on the catalyst after the reaction results in a significant reduction in the number of weak alkaline centers.

Key words: natural gas desulfurization process, carbonyl sulfide hydrolysis, catalyst deactivation, low temperature nitrogen adsorption and desorption, SEM, XRD, XRF, CO2-TPD