JZUS - Journal of Zhejiang University SCIENCE

Journal of Zhejiang University SCIENCE A

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Hole-growth phenomenon during pyrolysis of a cation-exchange resin particle

Author(s): Zheng-liang HUANG, Yun-bo YU, Qi SONG, Yao YANG, Jing-yuan SUN, Jing-dai WANG, Yong-rong YANG
Affiliation(s): Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China; more
Corresponding email(s): yao_yang@zju.edu.cn
Key Words: Non-catalytic gas-solid reaction; Cation-exchange resin; Pyrolysis; Central-hole expansion; Temperature difference; Transformation

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Abstract: A novel central hole-expansion phenomenon is identified, in which the cation-exchange resin is pyrolyzed in a mixed atmosphere of nitrogen and oxygen at 400‍–‍500°C. In this reaction, the reaction path is predictable and always starts from the center of the resin particle to form a central hole, then continues and expands around the hole, finally forming a uniformly distributed hole group; the particle surface remains intact. Analysis shows that this formation mode is due to the different reaction paths of sulfonic groups between the surface and interior of the particle, caused by the temperature difference. On the surface, transformation reactions happen at high temperatures (410‍–‍500°C) to form stable organic sulfur structures, while decomposition occurs inside the particle at a relatively low temperature (<410 °C) and promotes complete pyrolysis of the copolymer matrix to form holes.

阳离子交换树脂颗粒热解过程中的孔增长现象

作者：黄正梁¹，余云波¹，宋琦¹，杨遥¹，孙靖元¹，王靖岱²，阳永荣²
机构：¹浙江大学，化学与生物工程学院,浙江省先进化学工程制造技术重点实验室,中国杭州,310027；²浙江大学，化学与生物工程学院，化学工程国家重点实验室,中国杭州，310027
目的：传统非催化气固反应模型无法用于解释离子交换树脂的热解过程。本文旨在探讨不同条件下管式炉反应器中阳离子交换树脂的热解模式，并研究反应气氛、反应温度和树脂结构对新型热解模式的影响规律。希望提出的中心孔扩展模式为非催化气固反应模型的验证和开发提供指导。
创新点：1.确定一种新的非催化气固反应，且该反应遵循中心孔膨胀模式；2.厘清中心空穴扩展模式的形成机理。
方法：1.通过实验分析及相关表征测试，研究反应气氛、反应温度和树脂结构对新型热解模式的影响规律；2.通过数值模拟和动力学角度（Flynn-Ozawa方法），分析磺酸基团的分解和转化动力学，厘清中心空穴扩展模式的形成机理；3.通过仿真模拟（COMSOL Multiphysics），初步模拟树脂颗粒在初始反应阶段的温度变化，为阳离子交换树脂热解新模式提供间接验证。
结论：1.确定了一种新的非催化气固反应，且该反应遵循中心孔膨胀模式；2.厘清了中心空穴扩展模式的形成机理，发现其主要与磺酸基团的反应路径有关；3.中心孔扩展模式因其规律的反应过程和可预测的反应位点，可为非催化气固反应模型的验证和开发提供指导。

关键词组：非催化气固反应；阳离子交换树脂；热解；中心扩孔；温差；转化

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阳离子交换树脂颗粒热解过程中的孔增长现象

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