Ni-P/HZSM-5催化木质素降解制备酚类化学品

doi:10.16085/j.issn.1000-6613.2019-1444

化工进展 ›› 2020, Vol. 39 ›› Issue (5): 1792-1802.DOI: 10.16085/j.issn.1000-6613.2019-1444

Ni-P/HZSM-5催化木质素降解制备酚类化学品

郑云武¹^,²(), 王继大¹^,², 刘灿¹^,², 卢怡¹^,², 林旭¹^,², 李文斌¹^,², 郑志锋¹^,³()

^1.西南林业大学林业生物质资源高效利用技术国家地方联合工程研究中心，云南昆明 650224
^2.西南林业大学材料科学与工程学院，云南昆明 650224
^3.厦门市现代农业生物质高值化技术重点实验室（厦门大学），福建省生物质高值化技术工程研究中心（厦门大学），厦门大学能源学院，福建厦门 361102

出版日期:2020-05-05 发布日期:2020-05-25
通讯作者: 郑志锋
作者简介:郑云武（1983—），男，博士，副教授，硕士生导师，主要从事生物质能源方面的研究。E-mail: zyw85114@163.com。
基金资助:
云南省科技厅项目(2018FG001-054);云南省教育厅教师类项目(2018JS325);国家自然科学基金(31670599)

Selectivity catalytic depolymerization of the hydrolyzed lignin to produce phenolic chemicals over nickel phosphides supported onHZSM-5 catalysts

Yunwu ZHENG¹^,²(), Jida WANG¹^,², Can LIU¹^,², Yi LU¹^,², Xu LIN¹^,², Wenbin LI¹^,², Zhifeng ZHENG¹^,³()

^1.National Joint Engineering Research Center for Highly-Efficient Utilization Technology of Forest Biomass Resources, Southwest Forestry University, Kunming 650224, Yunnan, China
^2.College of Materials Science & Engineering, Southwest Forestry University, Kunming 650224, Yunnan, China
^3.Xiamen Key Laboratory for High-valued Conversion Technology of Agricultural Biomass (Xiamen University), Fujian Provincial Engineering and Research Center of Clean and High-valued Technologies for Biomass, College of Energy, Xiamen University, Xiamen 361102, Fujian, China

Online:2020-05-05 Published:2020-05-25
Contact: Zhifeng ZHENG

摘要/Abstract

摘要：

采用Ni-P复合改性HZSM-5催化剂催化木质素降解制备高附加值的单酚类化学品，探讨了催化剂种类、金属负载量、反应温度、反应时间以及溶剂种类对木质素催化降解制备酚类化合物的影响。同时采用X射线衍射仪（XRD）、比表面积和孔径分析仪（BET）、化学吸附仪（NH₃-TPD）、热重分析仪（TG）以及气相色谱质谱联用仪（GC/MS）对催化剂以及液相产物进行分析表征，同时探讨其催化失活以及再生机制。结果表明：Ni、P高度分散在HZSM-5催化剂的表面，Ni的添加有效地弱化了C－C键，致使β-O-4和α-O-4发生断裂，有效地提高了木质素加氢解聚的活性，减少了焦炭的生成，但催化剂的再生水热稳定性较差，重复使用性较低。当采用甲醇为供氢试剂，在反应温度为220℃，氢气压力为2MPa，反应时间为8h，催化剂负载量为10%，NaOH为共催化剂时，其木质素的转化率为98.6%，酚类化合物的含量达到74.97%。产物以苯酚、愈创木酚和紫丁香酚为主，低温促进了紫丁香酚的产生。

关键词: 木质素, Ni-P/HZSM-5催化剂, 降解, 酚类化合物, 失活

Abstract:

Catalytic conversion was an important approach to obtain high-value mono phenolic chemicals from lignin and Ni-P composite modified HZSM-5 mesoporous catalyst was prepared. The effects of catalyst type, metal loading, reaction temperature, reaction time and hydrogen-donor solvent on the catalytic degradation of lignin to prepare phenolic compounds were investigated. The catalysts and liquid products were characterized by X-ray diffraction (XRD), specific surface area and pore size distribution analysis (BET), chemical adsorption analysis (NH₃-TPD), thermogravimetric analysis(TG) and gas chromatography-mass spectrometry(GC/MS). The deactivation mechanism and regeneration properties of the catalysts were also discussed. The results showed that P and Ni were highly dispersed on the surface of HZSM-5. The addition of Ni effectively weakened the bond of CC bond, resulting in the cracking of β-O-4 and α-O-4 bonds, and effectively improved the activity of lignin hydrodepolymerization and reduced the formation of coke. However, the thermal stability of the regenerated catalyst was poor and the reusability was unsatisfactory. When methanol was used as hydrogen donor, the reaction temperature was 220℃, hydrogen pressure was 2MPa, reaction time was 8h, catalyst loading was 10%, and NaOH was used as co-catalyst, the conversion of lignin was 98.6%, and the content of phenolic compounds reached 74.97%. Phenol, guaiacol and syringol were the main products, and low temperature promoted the formation of syringol.

Key words: lignin, Ni-P/HZSM-5 catalyst, degradation, phenolic monomers, deactivation

中图分类号:

TQ35

郑云武, 王继大, 刘灿, 卢怡, 林旭, 李文斌, 郑志锋. Ni-P/HZSM-5催化木质素降解制备酚类化学品[J]. 化工进展, 2020, 39(5): 1792-1802.

Yunwu ZHENG, Jida WANG, Can LIU, Yi LU, Xu LIN, Wenbin LI, Zhifeng ZHENG. Selectivity catalytic depolymerization of the hydrolyzed lignin to produce phenolic chemicals over nickel phosphides supported onHZSM-5 catalysts[J]. Chemical Industry and Engineering Progress, 2020, 39(5): 1792-1802.

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Ni-P/HZSM-5催化木质素降解制备酚类化学品

Selectivity catalytic depolymerization of the hydrolyzed lignin to produce phenolic chemicals over nickel phosphides supported onHZSM-5 catalysts

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