工业催化: 选择性提升策略

doi:10.1016/S1872-2067(20)63578-1

摘要/Abstract

摘要： 工业催化直接或间接贡献了世界GDP的20%-30%,推动了产业变革和社会进步.对于工业催化,开发高活性、高选择性和高稳定性的多相催化剂至关重要,而选择性是最主要的挑战.因为实现催化选择性的精确控制是绿色化学的重要概念之一,更是工业催化可持续发展的重要驱动力;而且,选择性不仅决定了催化过程的原子经济性,也影响到后续分离过程的能耗.针对多数工业催化反应存在“活性越高、选择性越低”的相互制约与矛盾问题,本文以若干能源化工催化反应为例,试图总结催化选择性提升的一般策略,以期为有关工业应用的催化新过程提供科学参考.
多相催化一般经历与反应物有关的步骤(反应物的外扩散、内扩散和化学吸附)、与反应有关的步骤(活化和表面反应)、以及与产物相关的步骤(产物脱附、内扩散和外扩散).本文依此归纳并举例说明提高选择性的一般策略.在汽油催化吸附脱硫中,主要利用了催化剂中零价镍-氧化锌耦合活性中心的选择吸附策略,使零价镍优先吸附含硫化合物,从而实现选择性脱硫而不饱和烯烃.在甲苯和甲醇侧链烷基化反应中,主要利用了特定空间分布的酸碱吸附位,实现吸附甲苯和稳定甲醛中间体的协同匹配.在乙苯脱乙基型二甲苯异构化反应中,主要利用了双床层对催化剂功能的分离策略,在不同的择形催化剂床层中分别进行乙苯脱乙基反应和二甲苯异构化反应,从而提高对二甲苯的产量.在苯选择加氢制环己烯反应中,主要利用强化产品脱附的策略,促进环己烯产品从亲水改性的催化剂表面脱附,实现环己烯选择性的提升.
这些炼油与化工研究案例中同时存在多个连串-平行反应,主要是利用吸附中心、反应中心在时间或空间上的耦合、解耦或限域策略,调控不同途径的扩散能垒、反应能垒,实现了催化剂选择性的提升.多相催化多是复杂过程,基于提高选择性的初步认识,还要结合具体复杂催化过程,系统研究单策略以及多策略组合作用下的选择催化过程,实现在合理时间尺度、空间尺度上设计高选择性的催化剂,而这本质上是一种介尺度催化.

关键词: 工业催化, 选择性, 热力学平衡, 吸附, 脱附

Abstract: Precise control of catalytic selectivity is a key concept of green chemistry, and also an important driving force for the sustainable development of catalytic industry. Selectivity not only determines the atomic economy of the catalytic process, but also affects the energy consumption of subsequent separation process. The objective of this review is to illustrate successful catalyst design strategies to enhance selectivity, by using several important catalytic cases of petroleum refining and petrochemicals. These industrial applications and cutting-edge research cases mainly use the strategies of coupling, decoupling or confinement of adsorption sites and active sites to tune the diffusion barrier and activation energy barrier in different routes, so as to improve the selectivity of catalyst. Based on the preliminary understanding of selectivity improvement, it is necessary to systematically investigate the selective catalytic processes using combination of multiple strategies, thereby realizing the design of highly selective catalyst over reasonable time scales and space scales.

Key words: Industrial catalysis, Selectivity, Thermodynamic equilibrium, Adsorption, Desorption

郑仁垟, 刘志成, 王仰东, 谢在库. 工业催化: 选择性提升策略[J]. 催化学报, 2020, 41(7): 1032-1038.

Renyang Zheng, Zhicheng Liu, Yangdong Wang, Zaiku Xie. Industrial catalysis: Strategies to enhance selectivity[J]. Chinese Journal of Catalysis, 2020, 41(7): 1032-1038.

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