《厦门大学学报（自然科学版）》

可生物降解聚酯单体乙醇酸甲酯的催化合成研究进展

段新平,赵威,叶林敏,袁友珠^*

(厦门大学化学化工学院,固体表面物理化学国家重点实验室,能源材料化学协同创新中心,醇醚酯化工清洁生产国家工程实验室,福建厦门 361005)

关键词：煤基合成气转化; 生物降解塑料; 聚酯单体; 聚乙醇酸; 乙醇酸甲酯; Cu基催化剂; Ag基催化剂

Progresses in catalytic synthesis of methyl glycolate as biodegradable polyester monomer

DUAN Xinping,ZHAO Wei,YE Linmin,YUAN Youzhu^*

(State Key Laboratory of Physical Chemistry of Solid Surfaces,Collaborative Innovation Center of Chemistry for Energy Materials,National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China)

Keywords：coal-based syngas transformation; biodegradable plastic; polyester monomer; polyglycolic acid; methyl glycolate; copper-based catalyst; silver-based catalystdoi:10.6043/j.issn.0438-0479.202006036

DOI: 10.6043/j.issn.0438-0479.202006022

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生物降解塑料是指一类可在自然界存在的微生物和藻类作用下进行降解的塑料.理想的生物降解塑料是一种具有优良使用性能,废弃后可被环境微生物完全分解,最终被无机化而成为自然界中碳素循环的一个组成部分的高分子材料.乙醇酸甲酯经缩聚反应可制得新一代生物降解塑料聚乙醇酸,而合成气(CO和H2混合气)转化的草酸二甲酯选择性加氢可实现乙醇酸甲酯的大规模制备.鉴于我国富煤的能源结构、国际原油市场的变幻波动以及环保要求提高等因素,开发煤基合成气化学路线的可降解塑料单体乙醇酸甲酯的生产技术不仅符合国家层面的战略技术需求,也适应绿色化学发展的理念,同时极具商业价值.本文概述了国内外催化合成可降解塑料单体乙醇酸甲酯的最新进展,重点讨论了基于我国日渐成熟的“煤制乙二醇”技术路线中催化合成乙醇酸甲酯的研究现状,并展望该体系中可能存在的问题和可期的发展趋势.

Biodegradable plastics are a kind of plastics degraded by microorganisms and algae in nature.The ideal biodegradable plastic is a kind of polymer material with excellent property,in terms of that it can be completely decomposed by environmental microorganisms after being discarded,and finally become an integral part of the carbon cycle in nature.A new generation of biodegradable plastic polyglycolic acid can be prepared with polycondensation of methyl glycolate.In contrast,large-scale production of methyl glycolate can be achieved via selective hydrogenation of dimethyl oxalate converted from syngas(CO and H2).Considering the energy structure of China with rich coals,the fluctuation in the international crude oil market and the improvement of environmental protection requirements,developing the technology to produce degradable plastic monomer methyl glycolate via coal-based syngas chemical route not only meets the strategic and technological demands in the national level,but also fits the concept of green chemistry development,and is of great commercial value.In this review,the latest progresses in the catalytic synthesis of degradable plastic monomer methyl glycolate at home and abroad are summarized,with emphasis on the research status of the catalytic synthesis of methyl glycolate with the increasingly mature technology of "coal to ethylene glycol" in China.The potential problems in the system and future aspects are discussed.

引言
1 PGA的物化性能、市场及应用
2 MG的合成
3 煤基化学DMO加氢催化剂
4 总结与展望

图1 不同聚合物合成来源及煤基化学可降解聚酯示意图<br/>Fig.1 Schematic illustration of different synthetic sources of polymers and diagrams of coal-based chemical degradable polyesters

图1 不同聚合物合成来源及煤基化学可降解聚酯示意图
Fig.1 Schematic illustration of different synthetic sources of polymers and diagrams of coal-based chemical degradable polyesters

图2 煤基路线合成可降解聚酯单体的催化合成路线示意图<br/>Fig.2 Schematic diagram of catalytic synthesis of degradable polyester monomers by coal-based route

图2 煤基路线合成可降解聚酯单体的催化合成路线示意图
Fig.2 Schematic diagram of catalytic synthesis of degradable polyester monomers by coal-based route

图3 Ru基催化剂对DMO加氢制MG(和/或EG)的催化过程示意图(a)、催化剂X射线晶体结构图(b,c)和DMO加氢催化性能与催化剂结构的关联(d)[31]<br/>Fig.3 Schematic illustration of catalytic process of liquid-phase for DMO hydrogenation to MG over Ru-based catalysts(a),X-ray crystal structures of catalysts(b,cand relationship between catalytic performance and structure of DMO hydrogenation catalyst(d)[31]

图3 Ru基催化剂对DMO加氢制MG(和/或EG)的催化过程示意图(a)、催化剂X射线晶体结构图(b,c)和DMO加氢催化性能与催化剂结构的关联(d)[31]
Fig.3 Schematic illustration of catalytic process of liquid-phase for DMO hydrogenation to MG over Ru-based catalysts(a),X-ray crystal structures of catalysts(b,cand relationship between catalytic performance and structure of DMO hydrogenation catalyst(d)[31]

表1 不同催化剂上DMO加氢制MG的对比<br/>Tab.1 Comparison of DMO hydrogenation to MG over different catalysts

表1 不同催化剂上DMO加氢制MG的对比
Tab.1 Comparison of DMO hydrogenation to MG over different catalysts

图4 Cu原子被等离子体“轰击”冷冻图示(a)及其不同Cu基催化剂表面的DMO加氢制MG性能(b)和反应机理(c)[40]<br/>Fig.4 Schematic illustration of

图4 Cu原子被等离子体“轰击”冷冻图示(a)及其不同Cu基催化剂表面的DMO加氢制MG性能(b)和反应机理(c)[40]
Fig.4 Schematic illustration of "freezing" copper species(a)and performances of DMO hydrogenation to MG(b)as well catalytic reaction mechanism(c)over surfaces of different copper-based catalysts surfaces[40]

图5 Na2SiO3修饰的高选择性Cu基催化剂用于DMO加氢制MG[39]<br/>Fig.5 Highly selective copper-based catalysts modified by Na2SiO3 for hydrogenation of DMO to MG[39]

图5 Na2SiO3修饰的高选择性Cu基催化剂用于DMO加氢制MG[39]
Fig.5 Highly selective copper-based catalysts modified by Na2SiO3 for hydrogenation of DMO to MG[39]

图6 限域Ag活性物种在CNT孔道中构筑DMO加氢制MG催化剂示意图(a)、电镜图(b～d)及其催化性能(e)[52]<br/>Fig.6 Schematic description of confined Ag active species in CNT for MG production via hydrogenation of DMO(a),TEM images(b-d)and catalytic performances(e)[52]

图6 限域Ag活性物种在CNT孔道中构筑DMO加氢制MG催化剂示意图(a)、电镜图(b～d)及其催化性能(e)[52]
Fig.6 Schematic description of confined Ag active species in CNT for MG production via hydrogenation of DMO(a),TEM images(b-d)and catalytic performances(e)[52]

图7 不同Au/Ag比的Au-Ag/SBA-15催化剂上DMO加氢制MG的性能(a)及8Au-1.5Ag/SBA-15催化剂上的催化稳定性(b)[51]<br/>Fig.7 Performances of DMO hydrogenation to MG over Au-Ag/SBA-15 catalysts with different Au/Ag atomic ratios(a)and time-dependent catalytic performances over 8Au-1.5Ag/SBA-15(b)[51]

图7 不同Au/Ag比的Au-Ag/SBA-15催化剂上DMO加氢制MG的性能(a)及8Au-1.5Ag/SBA-15催化剂上的催化稳定性(b)[51]
Fig.7 Performances of DMO hydrogenation to MG over Au-Ag/SBA-15 catalysts with different Au/Ag atomic ratios(a)and time-dependent catalytic performances over 8Au-1.5Ag/SBA-15(b)[51]

图8 高效N-改性碳基材料负载Ag催化剂用于DMO加氢制MG催化过程[53]<br/>Fig.8 Efficient silver-based catalysts supported on nitrogen-modified carbon materials for DMO hydrogenation to MG process[53]

图8 高效N-改性碳基材料负载Ag催化剂用于DMO加氢制MG催化过程[53]
Fig.8 Efficient silver-based catalysts supported on nitrogen-modified carbon materials for DMO hydrogenation to MG process[53]

图9 Ag基合金催化剂在DMO加氢制MG中的应用[54]<br/>Fig.9 Illustration of alloying Ag-based catalysts for DMO hydrogenation to MG[54]

图9 Ag基合金催化剂在DMO加氢制MG中的应用[54]
Fig.9 Illustration of alloying Ag-based catalysts for DMO hydrogenation to MG[54]

图10 负载型Ru-NH2-SiO2催化剂在80 ℃低温下用于DMO加氢制MG的示意图[56]<br/>Fig.10 Schematic description of the heterogeneous Ru-NH2-SiO2 catalyst employed for DMO hydrogenation to MG[56]

图10 负载型Ru-NH2-SiO2催化剂在80 ℃低温下用于DMO加氢制MG的示意图[56]
Fig.10 Schematic description of the heterogeneous Ru-NH2-SiO2 catalyst employed for DMO hydrogenation to MG[56]

图11 基于微观动力学分析方法研究不同金属表面的DMO加氢反应机理[73]<br/>Fig.11 Based on micro-dynamical analysis for illustration of catalytic mechanism for DMO hydrogenation on various metal surfaces[73]

图11 基于微观动力学分析方法研究不同金属表面的DMO加氢反应机理[73]
Fig.11 Based on micro-dynamical analysis for illustration of catalytic mechanism for DMO hydrogenation on various metal surfaces[73]

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学报简介

《厦门大学学报（自然科学版）》于1931年创刊，是由教育部主管，厦门大学主办，国内外公开发行的综合性学术期刊（双月刊），是我国自然科学核心期刊。本刊以印刷版、网络版的方式同时出版。主要刊载自然科学各学科的最新研究成果，包括自然科学基础理论研究、应用基础研究、高新技术方面的学术论文。所刊载的论文分三大类型：（1）“快讯”：报道某前沿领域具有突破性的最新研究成果。（2）“研究论文”：刊载理工科基础理论研究与实验研究学术论文。（3）“研究简报”：刊载内容新颖、实用（或阶段性）的成果。更多>>

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引言

1 PGA的物化性能、市场及应用

2 MG的合成

3 煤基化学DMO加氢催化剂

4 总结与展望

学报简介