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芳烃装置歧化反应催化剂活性对产物选择性的影响
Impact of Catalyst Activity on Product Selectivity in the Disproportionation Reaction of an Aromatics Complex
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- DOI:
- 作者:
- 马利民，赵小林，魏军伟
Ma Limin, Zhao Xiaolin, Wei Junwei
- 作者单位:
- 浙江石油化工有限公司芳烃部
Aromatics Department, Zhejiang Petroleum & Chemical Co., Ltd.
- 关键词:
- 芳烃联合装置；Tatoray工艺；歧化反应机理；催化剂；选择性
Aromatics Complex; Tatoray Process；Disproportionation Reaction Mechanism; Catalyst; Selectivity
- 摘要:
- 某石化公司芳烃联合歧化装置采用Tatoray工艺，歧化单元含反应及分馏部分，以TA-32为催化剂。其歧化反应可将甲苯、C9芳烃转化为苯和二甲苯，流程涵盖进料混合、反应到产物分离。投用后随运行周期延长，催化剂活性与转化率降低，为保转化率，反应温度从340 ℃提至400 ℃，转化率从49%降至39%，老化速率2.6 ℃/月。进料甲苯比例不变时，随催化剂活性下降苯选择性上升、C8A选择性下降、乙苯含量上升，影响异构化，需提高异构化温度稳定乙苯的含量。通过对失活催化剂的表征分析及运行数据追溯，确认结焦沉积是导致TA-32催化剂活性衰减的主要原因，焦炭前驱体在催化剂活性中心的吸附与累积，覆盖了活性位点并堵塞了催化剂孔道结构，最终导致催化性能下降。文中通过对实际运行的工业运行数据进行系统分析，揭示了催化剂活性衰减与产物选择性变化的内在关联规律，为同类装置的工艺优化、催化剂运行维护及长周期稳定运行提供了实践参考。The disproportionation unit of the aromatics complex in a petrochemical company adopts the Tatoray process. Compris⁃ing a reaction section and a fractionation section, the disproportionation unit utilizes TA-32 as the catalyst. The disproportionationreaction converts toluene and C9 aromatics into benzene and xylene, with the process flow covering feed mixing, reaction and prod⁃uct separation.After commissioning, the catalyst activity and conversion rate decline with the extension of the operation cycle. Tosustain the conversion rate, the reaction temperature is raised from 340 ℃ to 400 ℃, yet the conversion rate still drops from 49% to39%, with a catalyst deactivation rate of 2.6 ℃ per month. When the proportion of toluene in the feed is kept constant, the degrada⁃tion of catalyst activity results in an increase in benzene selectivity, a decrease in C8 aromatics (C8A) selectivity and a rise in ethyl⁃benzene content, which impairs the isomerization process. Consequently, the isomerization temperature has to be elevated to stabi⁃lize the ethylbenzene content.Via characterization analysis of the deactivated catalyst and retrospective review of operational data,coke deposition is identified as the primary cause for the activity attenuation of the TA-32 catalyst. The adsorption and accumula⁃tion of coke precursors on the catalyst's active sites cover the active centers and block the catalyst's pore structure, ultimately lead⁃ing to the deterioration of catalytic performance.This paper systematically analyzes the actual industrial operational data, unveils theintrinsic correlation between catalyst activity attenuation and the variation of product selectivity, and provides practical referencesfor process optimization, catalyst operation and maintenance, as well as long-cycle stable operation of similar units.