塑料热解耦合等离子体催化重整制氢

doi:10.16085/j.issn.1000-6613.2023-1619

摘要/Abstract

摘要：

将废塑料转化为可用的能源或燃料，可以缓解塑料废弃物增加和化石能源减少带来的环境问题。为实现塑料高效热转化制备氢能，本文提出一种塑料热解耦合等离子体催化重整制氢的新路线。采用嵌有同轴介质阻挡放电（DBD）等离子体区的两段式固定床反应器，探索低温时高密度聚乙烯（HDPE）、聚丙烯（PP）和聚苯乙烯（PS）在单独加热、单独等离子体重整、单独催化重整和等离子体催化重整模式4种重整模式下的产物分布。结果表明：相较于单独加热模式，单独等离子体和单独催化重整模式均可提高气体产率，尤其是H₂；等离子体和催化剂具有协同作用，等离子体催化重整模式可大幅提高气体产率，其中高密度聚乙烯的H₂选择性最高（66.44%）；催化剂上的碳沉积和孔隙堵塞导致催化剂烧结严重程度顺序：HDPE>PP>PS。等离子体放电可以改善催化剂表面的碳沉积和金属相聚集问题，增加催化剂的比表面积和孔体积，减小平均孔径。因此，热解耦合等离子体催化重整系统为优化塑料能源生产提供了有效的参考方案。

关键词: 塑料, 等离子体催化, 制氢, 催化, 热解

Abstract:

Converting waste plastics into usable energy or fuel can alleviate the problems caused by increasing plastic waste and decreasing fossil energy. An integrated pyrolysis and plasma-catalysis reforming system was proposed for hydrogen production from plastics. The product distribution from different plastics [e.g. high-density polyethylene (HDPE), polypropylene (PP) and polystyrene (PS)] was explored under four different reforming modes (heating-alone, catalytic-alone, plasma-alone and plasma-catalysis). The experiments were carried out in a two-stage fixed-bed reactor embedded with a coaxial dielectric blocking discharge (DBD) plasma zone. Comparing heating-alone mode, plasma-alone and catalysis-alone reforming modes promoted hydrocarbon cracking and increased gas yields, especially for H₂. Plasma-catalysis reforming mode significantly increased the total gas and H₂ yields from three plastics, and H₂ selectivity of HDPE was the highest (66.44%). Characterisation of used catalysts revealed that the severity of catalyst sintering due to carbon deposition and pore blockage on the catalysts was in the following order: HDPE > PP > PS. The plasma discharge could improve the carbon deposition and metal phase aggregation problems on the catalyst surface, increase the specific surface area and pore volume of the catalysts, and reduce the average pore size. Therefore, the integrated pyrolysis and plasma-catalysis reforming system provided an effective reference solution for the optimization of energy production from plastic resources and supported the commercial application of the process.

Key words: plastics, plasma-catalysis, hydrogen production, catalysis, pyrolysis

中图分类号:

X705

马艳, 高宁博, 孙安邦, 全翠. 塑料热解耦合等离子体催化重整制氢[J]. 化工进展, 2024, 43(10): 5901-5912.

MA Yan, GAO Ningbo, SUN Anbang, QUAN Cui. Integrated plastics pyrolysis and plasma-catalysis reforming for H₂ production[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5901-5912.

图/表 14

表1 塑料的元素分析结果

塑料	质量分数/%
塑料	C	H
HDPE	85.71	14.29
PP	85.71	14.29
PS	92.31	7.69

图1 热解耦合等离子体催化重整实验示意图

图2 塑料的TG-FTIR结果分析

图3 不同重整模式对气体组分产率和选择性的影响（反应条件是重整温度为200℃、等离子体放电功率为15W、蒸汽流速为4mL/h）H—加热模式；H+C—热辅助催化剂重整模式；H+P—热辅助等离子体重整模式；H+C+P—热辅助等离子体催化重整模式

图4 等离子体和热量对气体产率的贡献

图5 不同重整模式对液相产物的影响（重整温度为200℃，等离子体放电功率为15W，蒸汽流速为4mL/h）

图6 催化剂的结构特性分析（C为催化重整模式；P-C表示等离子体催化重整模式）

表2 催化剂的物理特性

催化剂	比表面积/m²·g^-1	平均孔容/cm³·g^-1	平均孔径/nm
新鲜Ni-Ce/γ-Al₂O₃	133	0.35	8
C（HDPE）	8	0.06	15
P-C（HDPE）	50	0.21	10
C（PP）	36	0.17	12
P-C（PP）	68	0.25	9
C（PS）	106	0.32	8
P-C（PS）	123	0.33	7

图7 催化剂的XRD谱图

图8 新鲜催化剂的FE-SEM图像及EDS图像

图9 反应后催化剂的FE-SEM图像

图10 反应后催化剂的积炭分析

表3 反应后催化剂积碳情况

反应后催化剂	积碳量（质量分数）/%	积碳速率/g·（g cat）^-1·h^-1	I_G/I_D
C（HDPE）	24.61	0.123	0.37
P-C（HDPE）	19.19	0.096	0.51
C（PP）	13.76	0.069	0.28
P-C（PP）	13.16	0.066	0.55
C（PS）	6.15	0.031	0.53
P-C（PS）	6.09	0.030	0.64

图11 新鲜催化剂和改性催化剂NH3-TPD谱图

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