王 帅1， 杨学松1， 王家兴1,2， 刘 辉1
（1. 哈尔滨工业大学 能源科学与工程学院， 黑龙江 哈尔滨 150001；2.烟台龙源电力技术股份有限公司， 山东 烟台 264006）
引用格式:
王帅， 杨学松， 王家兴， 等. 甲烷裂解双分散孔催化剂颗粒积碳行为模拟［J］. 中国粉体技术， 2024， 30（1）： 14-22.
WANG S, YANG X S, WANG J X, et al. Simulation of carbon deposition behaviors of bi-disperse pore catalytic particles in methane cracking［J］. China Powder Science and Technology， 2024， 30（1）： 14-22.
DOI:10. 13732/j. issn. 1008-5548. 2024. 01. 002
收稿日期： 2023-08-16，修回日期：2023-10-19，上线日期：2023-11-21。
基金项目：国家自然科学基金项目，编号：52076060。
第一作者简介：王帅（1985—），男，教授，博士，博士生导师，黑龙江自科优秀青年基金获得者，研究方向为催化颗粒制备与表征。E-mail： shuaiwang@ hit. edu. cn。
摘要：【目的】为了更好地理解催化剂颗粒的积碳行为，分析积碳效应下催化剂颗粒界面反应传质特性，实现对催化剂颗粒的优化设计与调控。【方法】采用颗粒解析模型，考虑积碳引起的孔隙结构动态演变以及反应性能的衰减，分别探讨单分散孔和双分散孔颗粒积碳形成及所引起的孔隙结构演变规律。【结果】积碳失活从多孔颗粒表层向内部核心移动，扩散主导机制转向反应主导机制；相较于单分散孔颗粒，双分散孔颗粒具备更强的抗积碳性能；固定床反应器中催化剂颗粒分布影响积碳行为，壁面处积碳更加严重，更容易导致失活。【结论】选择双分散孔催化剂颗粒对于积碳行为具有改善作用，同时应选择合适的长径比反应器，削弱壁面效应对积碳行为的影响。
关键词： 积碳； 甲烷； 裂解； 双分散孔； 孔隙结构
Abstract
Objective When methane contacts with the catalyst, cokeis easily deposited on the catalyst surface. Carbon behaviors on the catalyst surface can cause a decrease in the intrinsic activity, leading to a reduction in the reaction rate. At the same time, carbon deposition can also cause the evolution of catalyst pore structure, further affecting the efficiency of mass transfer and reaction. However,few studies about the relationship between dynamic evolution of pore structure and reaction deactivation can be available. In this work, considering the dynamic evolution of pore structure caused by carbon deposition, a particle-scale model is established. The impact of carbon deposition on the performance of monodisperse pore and bidisperse catalysts is analyzed, which provides a theoretical foundation for the optimization design of porous catalyst.
Methods In this paper, the catalyst wasfirst regarded as theporous media. Based on the transport model of porous media, a particle-scale model coupling mass transfer and reaction activitywas constructed, where the decay of reaction performance and the dynamic evolution of pore structure caused by carbon deposition were considered. Secondly, the simulation of methane cracking was carried out. The evolution of pore structure and diffusion-reaction performance of monodisperse and bidisperse catalysts were evaluated. Finally, the catalysts were packed in a fixed bed, and the reaction performance and carbon deposition distribution of bidisperse catalysts were analyzed.
Results and Discussion Basedontheparticle-scale model coupling the mass transfer andreactivity,the instantaneous variations of hydrogen concentration inside the catalyst are shown in Fig. 3. Compared to the monodisperse particle, the bidisperse particle has a lower diffusion resistance, leading to enhanced uniformity of hydrogen concentration distribution. The instantaneous variations of carbon deposition and reaction rate are shown in Fig. 4 and Fig. 5. The maximum carbon deposition mass of bidisperse particleis also significantly increased, and carbon deposition continue to occur at around 10 000 s. In contrast, the decay rate of monodisperse particle is faster. Fig.6 shows the instantaneous change of effective diffusion rate. The effective diffusion rate of the bidisperse particle is always higher than that of themonodisperse particle. As the carbon deposition proceeds, the diffusion rate distribution of thebidisperse particle is also less inhomogeneous than that of themonodisperse particle. This indicates that the introduction of macropores in the catalyst promotes the gas diffusion from the shell to the core, and inhibits the catalyst deactivation. Fig.7 shows the instantaneous contour plot of velocity and coke deposition. When the gas flows through the pore channels, the region with locally high velocity is formed, resulting in ahigh coke deposition area. Fig.8 shows the radial distribution of bed porosity, activity factor and coke accumulation in a fixed bed reactor. The wall effect leads to an increase in local porosity, enhancing the local flow velocity and producing more coke.
Conclusion In this paper, carbon deposition behaviors of porous catalyst particles in the methane cracking are numerically investigated based on a particle-scale model coupling with the reaction kinetics model.The results reveal that coke deactivation moves from the surface of porous particles to the inner core. In the early stage of deactivation, the reaction rate in the shell region is relatively high. Ascoke is continuously generated, the reaction rate in the core region dominates, with opposite reaction ratesbetween the shell and the core region.In contrast to the monodisperse catalyst, the bidisperse particle has a stronger coke resistance. Monodisperse porous particles tend to become inactive after about 5 000 s, while bi-disperse porous particles continue to react after about 10 000 s. In addition, a high mass transfer coefficient near the walls ofthefixed-bed reactor leads tomore severe deactivation of catalyst.
Keywords: carbon deposition； methane； cracking; bi-disperse pore； pore structure
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