利用甲醛稳定剂和木质素中甲氧基从木质素选择性制备高碳数芳烃

doi:10.1016/S1872-2067(24)60186-5

催化学报 ›› 2025, Vol. 68: 356-365.DOI: 10.1016/S1872-2067(24)60186-5

利用甲醛稳定剂和木质素中甲氧基从木质素选择性制备高碳数芳烃

董琳^a^,^b^,^c, 方志强^b, 袁乾博^a, 樊勇^a, 杨勇^d, 王平^d, 盛时雄^d^,^*(), 王艳芹^e^,^*(), 陈祖鹏^a^,^d^,^*()

^a南京林业大学化学工程学院, 林业资源高效加工利用协同创新中心, 林产化学与材料国际创新高地, 江苏南京 210037
^b华南理工大学制浆造纸工程国家重点实验室, 广东广州 510640
^c菲立化学工程(遂昌)有限公司, 浙江遂昌 323316
^d德华兔宝宝装饰新材股份有限公司, 浙江湖州 313200
^e华东理工大学化学与分子工程学院工业催化研究所, 费林加诺贝尔奖科学家联合研究中心, 结构可控分子工程国际合作联合实验室, 上海 200237

收稿日期:2024-08-30 接受日期:2024-10-22 出版日期:2025-01-18 发布日期:2025-01-02
通讯作者: * 电子信箱: 38701@qq.com (盛时雄), wangyanqin@ecust.edu.cn (王艳芹), czp@njfu.edu.cn (陈祖鹏).
基金资助:
国家重点研发项目(2023YFD2200505);国家自然科学基金(22202105);国家自然科学基金(22002043);江苏省高等学校自然科学基金(21KJA150003);江苏省双创团队(JSSCTD202345);中国博士后科学基金(2023M731703);中国博士后科学基金(2024T170415);制浆造纸工程国家重点实验室开放基金资助项目(202414)

Selective utilization of formaldehyde stabilizing additive and methoxy groups in lignin for the production of high-carbon-number arenes

Lin Dong^a^,^b^,^c, Zhiqiang Fang^b, Qianbo Yuan^a, Yong Fan^a, Yong Yang^d, Ping Wang^d, Shixiong Sheng^d^,^*(), Yanqin Wang^e^,^*(), Zupeng Chen^a^,^d^,^*()

^aJiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, Jiangsu, China
^bState Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
^cFeili Chemical Engineering (Zhejiang Suichang) Co. Ltd., Suichang 323316, Zhejiang, China
^dDehua TB New Decoration Material Co., Ltd, Huzhou 313200, Zhejiang, China
^eKey Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2024-08-30 Accepted:2024-10-22 Online:2025-01-18 Published:2025-01-02
Contact: * E-mail: 38701@qq.com (S. Sheng), wangyanqin@ecust.edu.cn (Y. Wang), czp@njfu.edu.cn (Z. Chen).
Supported by:
National Key Research and Development Program of China(2023YFD2200505);National Natural Science Foundation of China(22202105);National Natural Science Foundation of China(22002043);Natural Science Foundation of Jiangsu Higher Education Institutions of China(21KJA150003);Innovation and Entrepreneurship Team Program of Jiangsu Province(JSSCTD202345);China Postdoctoral Science Foundation(2023M731703);China Postdoctoral Science Foundation(2024T170415);State Key Laboratory of Pulp and Paper Engineering(202414)

摘要/Abstract

摘要：

高碳数芳烃是一类重要的航空煤油组分, 具有较高的沸点和熔点, 较低的挥发性, 可以显著提高油品的质量. 传统的高碳数芳烃来自于不可再生的化石能源, 常常伴随着温室气体排放和环境污染. 从可再生的生物质资源出发, 催化转化制备高碳数芳烃, 是一条清洁绿色的工艺路线. 木质素作为生物质的三大组分之一, 是由芳香族化合物通过碳-氧和碳-碳键连接而成的高聚物, 可以作为生产高碳芳烃的潜在资源. 因此, 本文利用甲醛稳定剂和木质素中的甲氧基, 提出了一条从木质素选择性制备高碳数芳烃的高效合成方法.
本文发展了以木质生物质为原料, 串联多步催化转化过程, 定向制备高碳数芳烃的反应策略. 芳烃的碳数增长来自于甲醛稳定剂和木质素本身的甲氧基, 实现了较高的原子利用率和质量收率. 首先, 探究了木质纤维素中分离木质素以及木质素还原解聚的过程. 研究结果发现, 醛类稳定剂可以显著提高木质素的质量得率, 有效避免木质素中的聚合反应, 进而提高木质素解聚产物的收率. 甲醛稳定剂不仅可以提高产品收率, 而且可以发生烷基化反应提高产物的碳数, 是本文反应路线中最优的稳定剂, 木质素质量得率可达20.4 wt%. 在木质素的还原解聚反应中, 采用Ni/C为催化剂, 可以实现木质素单体之间碳-氧键以及单体中脂肪醇的高效氢解, 单体收率最高可达46.6%. 该反应体系在不同来源的木质纤维素中均表现出较好的催化性能. 其次, 以木质素还原解聚产物为原料, 利用本身的甲氧基官能团, 通过转甲基反应, 制备得到高碳数的酚类化合物. 探究了溶剂效应和催化剂载体对反应的作用机制, 二氧六环溶剂由于其恰当的极性和溶解性, 表现出最佳的催化性能; Au/Nb₂O₅催化剂具有最佳的催化效果, 在300 °C反应10 h, 烷基化产物的总收率可达66.9%. 该催化体系适用于多种木质素解聚产物和烷基化的解聚产物. 然后, 将烷基化产物进行选择性加氢脱氧, 高选择性得到芳烃. 该反应的关键在于避免苯环的环加氢副反应的发生, 对比了钌、钯、铂负载到多种载体的催化剂的反应性能, 研究发现Ru/Nb₂O₅表现出最佳的催化活性和芳烃选择性(86.1%), 这归因于钌恰当的加氢活性以及铌基催化剂对酚类化合物的选择性吸附. 最后, 直接以木质纤维素为底物, 串联全部反应过程, 高选择性得到多种高碳数芳烃. 当以桦木为原料时, 高碳数芳烃的质量收率高达23.1 wt%.
综上, 本文以木质纤维素中的木质素组分为原料, 利用甲醛稳定剂和木质素中甲氧基官能团, 通过烷基化反应, 实现了高碳数芳烃的高选择性转化, 合成了高附加值的航空煤油添加剂. 本文发展了新的合成策略, 阐明了反应机制, 为生物质资源的高值化利用提供了新思路.

关键词: 木质素, 芳烃, 转甲基反应, 加氢脱氧, 液体燃料添加剂

Abstract:

Many strategies have been proposed to produce arenes from lignin as liquid fuel additives. However, the development of these methods is limited by the low yield of products, low atom utilization, and inefficient lignin depolymerization. Herein, we develop an energy-efficient synthetic method for the production of high-carbon-number arenes from sustainable lignin with a total yield of 23.1 wt%. Particularly, high carbon number arenes are obtained by fully utilizing the formaldehyde stabilizing additive and the methoxy group in lignin. The process begins with the reductive depolymerization of formaldehyde-stabilized lignin, followed by transmethylation between lignin monomers over Au/Nb₂O₅ catalyst, and the Ru/Nb₂O₅-catalyzed hydrodeoxygenation. This work demonstrates the potential of value-added arenes production directly from lignin.

Key words: Lignin, Arene, Transmethylation, Hydrodeoxygenation, Liquid fuel additive

董琳, 方志强, 袁乾博, 樊勇, 杨勇, 王平, 盛时雄, 王艳芹, 陈祖鹏. 利用甲醛稳定剂和木质素中甲氧基从木质素选择性制备高碳数芳烃[J]. 催化学报, 2025, 68: 356-365.

Lin Dong, Zhiqiang Fang, Qianbo Yuan, Yong Fan, Yong Yang, Ping Wang, Shixiong Sheng, Yanqin Wang, Zupeng Chen. Selective utilization of formaldehyde stabilizing additive and methoxy groups in lignin for the production of high-carbon-number arenes[J]. Chinese Journal of Catalysis, 2025, 68: 356-365.

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图/表 7

Scheme 1. Strategies employed for arenes production from lignin. (a) The traditional route for arenes production from lignin. (b) The proposed route for high-carbon-number arenes production from lignin in this work.

Fig. 1. Production of lignin monomers from birch wood under different reaction conditions. Extraction conditions: birch wood 1.0 g, dioxane 10 mL, stabilizing agent 0-1.5 mL, HCl solution 420 μL, 80 °C, 5 h; Hydrogenolysis conditions: lignin 0.2 g, catalyst 0.1 g, dioxane 20 mL, H2 4.0 MPa, 250 °C, 15 h. The extracted lignin yield was calculated based on the mass of the wood.

Fig. 2. Production of lignin monomers from different types of wood. Extraction conditions: wood 1.0 g, dioxane 10 mL, formaldehyde 1.5 mL, HCl solution 420 μL, 80 °C, 5 h; Hydrogenolysis conditions: lignin 0.2 g, 5% Ni/C 0.1 g, dioxane 20 mL, H2 4.0 MPa, 250 °C, 15 h. The extracted lignin yield was calculated based on the mass of the wood.

Fig. 3. Reaction results for the transmethylation of 2-methoxy-4-propylphenol in a batch reactor under different reaction conditions. Reaction conditions: 2-methoxy-4-propylphenol 0.5 g, catalyst 0.2 g, solvent 15 mL, H2 5.0 MPa, 300 °C, 10 h.

Fig. 4. Reaction results for the transmethylation of 2,6-dimethoxy-4-propylphenol, 2,6-dimethoxy-4-ethylphenol, and 2-methoxy-5-methyl-4-propylphenol in a batch reactor. Reaction conditions: substrate 0.5 g, Au/Nb2O5 0.2 g, dioxane 15 mL, H2 pressure 5.0 MPa, 300 °C, 10 h.

Fig. 5. Reaction results for the hydrodeoxygenation of 2-methyl-4-propylphenol for different catalysts in a batch reactor. Reaction conditions: 2-methyl-4-propylphenol 0.2 g, catalyst 0.1 g, H2O 15 mL, H2 0.5 MPa, 250 °C, 5 h.

Table 1 Results of conversion of various wood into arenes.

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利用甲醛稳定剂和木质素中甲氧基从木质素选择性制备高碳数芳烃

Selective utilization of formaldehyde stabilizing additive and methoxy groups in lignin for the production of high-carbon-number arenes

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