定向调控Ga改性沸石用于聚烯烃高效化学回收制备芳烃

doi:10.1016/S1872-2067(26)65139-X

摘要/Abstract

摘要：

面对全球塑料废弃物污染加剧与碳资源高效利用的双重挑战, 化学回收技术已成为实现聚烯烃塑料高值化转化的关键途径. 本研究聚焦于通过结构设计与Ga改性协同调控沸石分子筛的酸性位点性质, 以实现聚烯烃向高价值芳烃的高效定向转化. 首先将商业ZSM-5重塑为具有壳层结构(HZ5@s1)、镂空结构(HZ5-hol)及介孔结构(HZ5-meso)的不同形貌, 并进一步通过浸渍法引入Ga物种, 系统构筑了Ga-沸石催化剂体系. 实验结果表明, 经四丙基氢氧化铵(TPAOH)处理(含或不含正硅酸乙酯(TEOS))制备的中空或核壳型沸石酸性有所降低, 进而导致乙烯产率下降而丁烯产率上升, 并使C₂-C₄烯烃总产率提高2-6 wt%; 相比之下, NaOH诱导产生的介孔结构在相同条件下对产物分布的影响较小. Ga的加入强化了催化剂的脱氢环化能力, 使得单环芳烃(MAH)的收率提升至63 wt%. 催化剂性能的变化趋势突出了材料微观结构和Ga负载之间的协同效应. 连续运行100次后, 具有镂空结构的Ga-HZ5-hol催化剂展现出最佳的综合产物收率(30 wt% MAH+51 wt%轻质烯烃), 凸显了其优异的传质效率与活性位点可及性. 在反应过程中, 尽管Ga物种会逐渐失活, 但沸石的质子酸中心仍保持稳定, 导致产物选择性随时间推移从芳烃向烯烃及1,3-环戊二烯偏移. 催化剂氧化再生处理降低了其芳构化能力, 但可促进产物选择性向烯烃转移, 而形成的低还原性GaO_x物种不利于芳烃生成. 机理研究表明, 丁烯/丙烯的转化是MAH生成的关键控速步骤; 乙烯收率与酸位密度的关系在Ga负载前后发生逆转: 未改性催化剂中二者呈正相关, 而Ga的引入则使其转为负相关, 这揭示了Ga物种对反应路径的深度调控作用.
综上所述, 本研究通过精确的“结构-酸性-金属”三位一体设计, 阐明了Ga改性沸石催化剂在聚烯烃催化升级中的构效关系与反应机制, 不仅为理解复杂反应网络中的竞争与协同路径提供了新见解, 也为开发下一代高效、稳定的塑料升级回收催化剂奠定了坚实的理论与实验基础.

关键词: 沸石, 塑料, 芳香烃, 催化热解, 构性关系

Abstract:

Chemical recycling of plastics is emerging as a powerful strategy to tackle global plastic waste while generating high-value chemicals. In this study, we unlock the potential of Ga-promoted, structurally engineered zeolites to convert polyolefins into aromatics by tailoring acid-site properties. Commercial ZSM-5 was reimagined into shell-layer (HZ5@s1), hollow (HZ5-hol), and mesoporous (HZ5-meso) architectures, followed by Ga incorporation. Our experiments reveal how structural tuning boosts olefin production, while Ga dramatically enhances monocyclic aromatic hydrocarbons (MAH) yields—up to 63 wt% for Ga-HZ5. Catalyst performance trends highlight the synergy between architecture and Ga loading, with Ga-HZ5-hol delivering the highest combined yield (30 wt% MAH + 51 wt% light olefins) after 100 consecutive runs. Despite Ga deactivation, acid sites remain robust, shifting product selectivity toward olefins and 1,3-cyclopentadiene. Regeneration slightly reduces aromatization but improves olefin output, while less reducible GaO_x species suppress aromatic formation. Mechanistic insights reveal that butene/propylene conversion governs MAH formation, and ethylene yield correlates with acid site density—positively for Ga-free catalysts, inversely after Ga loading. These findings pave the way for the design of next-generation zeolite catalysts for efficient plastic upcycling.

Key words: Zeolite, Plastics, Aromatics, Catalytic pyrolysis, Structure-performance correlation

何清, Oğuzhan Akin, Parviz Yazdani, 翁仁贵, Devanshu Sajwan, 李凌峰, Mozhdeh Amanati, Robin J. Varghese, Kevin M. Van Geem. 定向调控Ga改性沸石用于聚烯烃高效化学回收制备芳烃[J]. 催化学报, 2026, 88: 408-421.

Qing He, Oğuzhan Akin, Parviz Yazdani, Rengui Weng, Devanshu Sajwan, Lingfeng Li, Mozhdeh Amanati, Robin J. Varghese, Kevin M. Van Geem. Tailored Ga-modified zeolites for efficient chemical recycling of polyolefins into aromatics[J]. Chinese Journal of Catalysis, 2026, 88: 408-421.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65139-X

https://www.cjcatal.com/CN/Y2026/V88/I9/408

图/表 10

Fig. 1. XRD patterns (A), pyridine-FT-IR spectra (B), NH3-TPD profiles (C), and H2-TPR profiles (D) of the zeolites used in this study.

Table 1 Pore structure characteristics of the zeolites used in this work.

Sample	Specific surface area (m²/g)			Pore volume (cm³/g)
Sample	S_BET^a	S_micro^b	S_external^b	S_Total^c	V_micro^d	V_meso^e
HZ5	401.9	384.6	17.3	0.186	0.154	0.024
HZ5@s1	325.5	303.3	22.3	0.158	0.122	0.029
HZ5-hol	418.3	394.0	24.4	0.234	0.154	0.057
HZ5-meso	333.6	321.4	12.2	0.194	0.125	0.034
Ga-HZ5	361.0	350.5	10.5	0.170	0.134	0.02
Ga-HZ5@s1	277.7	254.9	22.9	0.145	0.103	0.033
Ga-HZ5-hol	377.5	372.4	5.0	0.184	0.144	0.034
Ga-HZ5-meso	331.5	329.0	2.5	0.177	0.125	0.029

Table 2 Acid site and metal site parameters of the catalysts used in this work.

Sample	Acidity^a (Pyridine-IR, mmol/g)			Acidity^b (NH₃-TPD, mmol/g)				Reducible species^c (mmol/g)
Sample	BAS	LAS	BAS/LAS	A₁	A₂	A₃	A_total	M₁	M₂	M₃	M_total
HZ5	1.029	0.224	4.59	0.413	0.141	0.418	0.972	—	—	—	—
HZ5@s1	0.592	0.176	3.36	0.239	0.082	0.099	0.420	—	—	—	—
HZ5-hol	0.438	0.381	1.15	0.242	0.085	0.053	0.380	—	—	—	—
HZ5-meso	0.963	0.428	2.25	0.313	0.086	0.225	0.623	—	—	—	—
Ga-HZ5	0.776	0.472	1.64	0.348	0.383	0.28	1.011	0.075	0.039	0.007	0.121
Ga-HZ5@s1	0.625	0.464	1.35	0.333	0.118	0.076	0.527	0.01	0.043	0.100	0.152
Ga-HZ5-hol	0.377	0.294	1.28	0.349	0.157	0.033	0.539	0.023	0.030	0.186	0.239
Ga-HZ5-meso	0.515	0.256	2.01	0.379	0.219	0.218	0.815	0.032	0.107	0.015	0.167

Fig. 2. Main product yields of LDPE catalytic pyrolysis. (A) Ga-free zeolite; (B) Ga-loaded zeolite.

Fig. 3. Evolution of product distribution during catalytic pyrolysis as a function of pulse feeding: aliphatic hydrocarbons (A) and aromatic hydrocarbons (B).

Fig. 4. Relative activity (RA1) based on MAH selectivity (A) and MAH/(LO + MAH) (B) during catalyst deactivation, and relative activity (RA2) (C) of catalysts after regeneration at 600 and 700 °C using LDPE as the feedstock.

Fig. 5. (A) GC×GC chromatogram of catalytic pyrolysis products over Ga-HZ5-meso after 100 consecutive runs using LDPE as the feedstock. (B) Variation in 1,3-cyclopentadiene yield with the number of runs.

Fig. 6. Correlation between LDPE catalytic pyrolysis product and catalyst structure. (A) Ga-free catalyst; (B) Ga-loaded catalyst.

Fig. 7. Correlation analysis of pyrolysis products.

Fig. 8. Schematic representation of the competitive dual-hydrocarbon pool mechanism governing polyolefin catalytic pyrolysis.

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