金属-分子筛集成催化剂调控生物质热裂解制高值化学品研究进展

doi:10.11949/0438-1157.20251284

摘要/Abstract

摘要：

生物质催化热裂解是制备可再生烃类燃料与化学品的关键途径，其技术核心在于高效催化剂的设计与开发。本文系统综述了金属-分子筛集成催化剂在生物质热裂解中的最新研究进展，重点分析了贵金属、过渡金属、碱（土）金属及稀土金属等与ZSM-5、SAPO-11等典型分子筛结合所构建催化剂的性能特点及其应用效果。文中探讨了金属位点与分子筛酸中心之间的协同作用机制，特别是在调控脱氧路径、提高芳烃选择性以及增强催化剂抗积碳稳定性等方面的重要作用。最后，针对当前该技术仍面临的金属与酸中心平衡调控、活性位稳定性及工业放大可行性等挑战，对未来的研究方向与发展前景进行了展望。

关键词: 生物质, 催化热裂解, 集成催化剂, 分子筛, 芳构化

Abstract:

Catalytic pyrolysis of biomass serves as an important technology for producing renewable hydrocarbon fuels and chemicals, with the core challenge lying in the design of high-performance catalysts. This review systematically summarizes recent advances in metal-zeolite integrated catalysts for biomass pyrolysis, focusing specifically on the performance and application effects of integrated catalysts constructed from precious metals, transition metals, alkaline earth metals, and rare-earth metals supported on typical zeolites such as ZSM-5 and SAPO-11. The synergistic mechanisms between metal sites and zeolitic acid sites are discussed, highlighting their key roles in regulating deoxygenation pathways, enhancing aromatic selectivity, and improving catalyst stability against coking. Furthermore, current challenges are addressed, including balancing metal-acid site interactions, maintaining active site stability, and scaling up the technology for industrial implementation. Prospects for future research directions are also presented.

Key words: biomass, catalytic pyrolysis, integrated catalyst, zeolite, aromatization

中图分类号:

TK 6

吴艺铃, 陈彬, 田间, 詹国武. 金属-分子筛集成催化剂调控生物质热裂解制高值化学品研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.20251284.

Yiling WU, Bin CHEN, Jian TIAN, Guowu ZHAN. Research progress on metal-zeolite integrated catalysts for regulating biomass pyrolysis toward high-value chemicals[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251284.

图/表 9

图1 （a）目标液体烃类燃料与生物油的关键性质对比；（b）生物油中典型含氧化合物的分子结构[12]

Fig. 1 (a) Comparison of key properties between target liquid hydrocarbon fuels and bio-oil; (b) Molecular structures of representative oxygenated compounds present in bio-oil

表1 木质纤维素生物质主要组分（木质素、半纤维素和纤维素）的热解途径［32］

Table 1 Pyrolysis pathways of the primary constituents of lignocellulosic biomass： lignin， hemicellulose， and cellulose

300-350 ^oC

热稳定性中等

糖苷键断裂、开环、环化

左旋葡聚糖、葡萄糖、呋喃环

产物多样性显著，以含氧化合物（如醛、酮）和轻质烯烃为主，是烯烃类的重要来源

反应路径复杂，易生成含氧小分子副产物，结焦适中

半纤维素

200-350 ^oC

热稳定性最低

解聚、脱水、支链断裂

木糖、乙酸、糠醛、小分子醛

气体产率最高，为主要不可凝气体来源，液体产物中含氧组分高

结焦量最低，但气体产物占比大

木质素

280-500 ^oC

热稳定性最高

醚键断裂、脱甲氧基、芳环缩合

酚类单体（如愈创木酚、苯酚等）

芳香族产物主导，是酚类和轻质芳烃的最主要来源，但结焦率最高，易生成多环芳烃（如萘）

结焦率最高，芳香缩合导致多环芳烃积累

图2 原位与非原位催化热裂解反应流程示意图[40]

Fig. 2 Schematic diagrams of the in-situ and ex-situ catalytic pyrolysis processes

图3 金属-分子筛集成催化剂类型、制备方法及主要性质示意图

Fig. 3 Schematic diagram of the types, preparation methods, and key properties of metal-zeolite integrated catalysts

图4 （a）不同金属（Zn, Fe, Ca, Ce, La）改性ZSM-5催化剂对生物质催化热裂解生成单环芳烃产率的影响[49]；（b）愈创木酚在三种催化剂模型表面吸附构型与静电势计算[50]

Fig. 4 (a) Yields of monocyclic aromatic hydrocarbons from catalytic pyrolysis of biomass over ZSM-5 catalysts modified with different metals (Zn, Fe, Ca, Ce, La); (b) Adsorption configurations and electrostatic potential calculations for guaiacol on three catalyst models

图5 （a）混合催化策略下竹屑催化热裂解产物中单环芳烃的相对选择性[55]；（b）湿法焙烧预处理耦合催化快速热解提升竹子热解生物芳烃产量示意图[56]

Fig. 5 (a) Relative selectivity of monocyclic aromatic hydrocarbons from catalytic pyrolysis of bamboo sawdust using a mixed catalytic strategy; (b) Schematic of wet torrefaction pretreatment coupled with catalytic fast pyrolysis for enhancing bio-aromatics production from bamboo pyrolysis

表2 单金属负载分子筛催化生物质热解制备芳烃产率

Table 2 Research on the yield of aromatics prepared by catalytic pyrolysis of biomass over single - metal loaded zeolites

催化剂	原料	生物质与催化剂的比例	热裂解温度/^oC	芳烃产率/%	参考文献
ZSM-5	牧草	10：1	600	24.5	^[61]
Ga/ZSM-5	玉米秸秆	1∶1	500	49.4	^[52]
Ca/ZSM-5	竹屑	3：10	550	31.3	^[55]
Fe/ZSM-5	柳枝稷	1∶10	550	17.0	^[62]
Pd/ZSM-5	麻疯树废弃物	1∶1	500	27.2	^[63]
Sn/ZSM-5	木粉	1∶10	450	33.0	^[64]

表3 双金属负载分子筛催化生物质热解制备芳烃产率

Table 3 Yield of aromatics prepared by catalytic pyrolysis of biomass over bimetal-loaded zeolites. zeolites

催化剂	原料	生物质与催化剂的比例	热裂解温度/^oC	芳烃产率/%	参考文献
Mo-Cu/ZSM-5	松木屑	1∶10	550	36.5	^[65]
Co-Ni/ZSM-5/MCM-41	酶解木质素	1：2	550	19.0	^[66]
Mo-Co/ZSM-5	褐煤	1：1	600	80.7	^[67]
Ni-Ce/ZSM-5	甘蔗渣	1：1	500	13.8	^[68]
Zn-Co/ZSM-5	松木粉	1：2	500	79.1	^[69]

图6 （a）Sn添加量对催化剂异构化活性的影响[70]；（b）不同金属助剂对Pt/SAPO-11催化剂性能的影响[71]；（c）酶解木质素在Co-Ni@HZSM-5/MCM-41催化剂上热解转化为单环芳烃等产物的可能路径[66]

Fig. 6 (a) Effect of Sn loading on the isomerization activity of the catalysts; (b) Influence of different metal promoters on the performance of Pt/SAPO-11 catalyst; (c) Proposed reaction pathway for the conversion of enzymatic hydrolysis lignin to monocyclic aromatic hydrocarbons and other products via pyrolysis over a Co-Ni@HZSM-5/MCM-41 catalyst

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