煤经草酸酯制高价值含氧化学品的技术进展

张红旭; 刘蝈蝈; 俞佳枫; 孙剑

doi:10.19906/j.cnki.JFCT.2023044

煤经草酸酯制高价值含氧化学品的技术进展

doi: 10.19906/j.cnki.JFCT.2023044

张红旭^{1, 2,},
刘蝈蝈^1,,
俞佳枫^2, ,,
孙剑^2, ,

1.
沈阳化工大学, 辽宁沈阳 110142
2.
中国科学院大连化学物理研究所, 辽宁大连 116023

基金项目: 国家自然科学基金（2022JJ12GX037）资助

详细信息

通讯作者:
E-mail: yujf@dicp.ac.cn

sunj@dicp.ac.cn

中图分类号: TQ225.24
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出版历程
- 收稿日期: 2023-04-10
- 修回日期: 2023-05-04
- 录用日期: 2023-05-16
- 网络出版日期: 2023-05-24
- 刊出日期: 2023-11-13

Technological advances in the production of high value oxygen-containing chemicals from coal via dimethyl oxalate

ZHANG Hong-xu^{1, 2
,},
LIU Guo-guo^1
,,
YU Jia-feng^{2
, ,},
SUN Jian^{2
, ,}

1.
Shenyang University of Chemical Technology, Shenyang 110142, China
2.
Dalian Institute of Chemical Physics, Dalian 116023, China

Funds: The project was supported by the Natural Science Foundation of China (2022JJ12GX037)

摘要

摘要: 中国的能源结构是富煤少油，开发煤炭资源的高效清洁利用是中国重点发展方向。煤经合成气羰基化后可以合成草酸酯（DMO），进一步加氢可获得具有高附加值的含氧化学品：如乙醇酸甲酯（MG）、乙二醇（EG）、乙醇（EO）等。其中，MG可以制备可降解材料聚乙醇酸（PGA），EG可以合成聚乙二醇（PEG），EO可以合成醋酸乙酯（EAC），应用前景十分广泛。本工作围绕DMO加氢反应展开，分析了各个加氢过程中所使用催化剂的研究状况，重点归纳了催化剂的组成调控、催化作用机理以及新催化剂制备技术，分析了DMO加氢催化剂研发过程存在的问题和挑战，指出了加氢产物以及下游产品的应用瓶颈及未来发展趋势。
- 煤 /
- 草酸二甲酯 /
- 选择性加氢 /
- 含氧化学品 /
- 铜基催化剂
Abstract: Chinese energy structure is rich in coal and less in oil, and the development of efficient and clean utilization of coal resources is a key development direction in China. Coal can be used to synthesize dimethyl oxalate (DMO) after carbonylation by synthesis gas, and DMO can further be hydrogenated to obtain oxygen-containing chemicals with high added value, such as methyl glycolate (MG), ethylene glycol (EG), ethanol (EO), etc. Among them, MG can prepare degradable materials polyglycolic acid (PGA), EG can synthesize polyethylene glycol (PEG), and EO can synthesize ethyl acetate (EAC), which have wide application prospects. This paper focuses on DMO hydrogenation reactions, analyzes the research status of catalysts used in each hydrogenation process, focuses on the regulation of catalyst composition, catalytic mechanism and new catalyst preparation technology, analyzes the problems and challenges in the development of DMO hydrogenation catalysts, and points out the application bottlenecks and future development trends of hydrogenation products and downstream products.
- coal /
- dimethyl oxalate /
- selective hydrogenation /
- oxygen-containing chemicals /
- copper-based catalysts

HTML全文

FIG. 2760. FIG. 2760.

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图 1 煤经草酸酯制高价值含氧化学品技术路线图

Figure 1 Technology roadmap for high value oxygen-containing chemicals from coal via dimethyl oxalate

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图 2 冷冻铜催化剂（a）旋转溅射制备方法示意图；（b）Cu原子电子结构重构原理图；（c）冷冻铜的抗氧化性质；（d）冷冻铜催化剂在DMO加氢反应中的产物分布^[32]

Figure 2 Catalyst of freezing copper: (a) Schematic diagram of rotation sputtering preparation method; (b) Principle diagram of electronic structure reconstruction of Cu atoms; (c) The resistance properties of freezing copper; (d) Product distrib ution of freezing copper catalyst in DMO hydrogenation reaction^[32] (with permission from Science Advances)

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图 3 Cu原子迁移到CeO₂上形成亚纳米团簇示意图^[39]

Figure 3 Schematic diagram of the migration of Cu atoms onto CeO₂ to form sub-nanoclusters^[39] (with permission from Nature Communication)

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图 4 DMO加氢制MG过程机理示意图^[45]

Figure 4 Mechanism of DMO hydrogenation to MG process^[45] (with permission from Catalysis Science & Technology)

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图 5 Ag颗粒尺寸与催化性能^[48]

Figure 5 Relationship between particle size and catalytic performance^[48] (with permission from Journal of Catalysis)

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图 6 Cu-Zr/SiO₂协同作用^[65]

Figure 6 Schematic diagram of Cu-Zr/SiO₂ cooperation^[65] (with permission from Journal of Energy Chemistry)

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图 7 C₆₀-Cu/SiO₂催化剂上组分与性能^[67]

Figure 7 Relationship to Component and performance on C₆₀-Cu/SiO₂ catalysts^[67] (with permission from Science)

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图 8 C₆₀与Cu之间的电子转移示意图^[67]

Figure 8 Schematic diagram of the electron transfer between C₆₀ and Cu^[67] (with permission from Science)

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图 9 Cu⁰、Lewis酸和中强碱位协同效应示意图^[70]

Figure 9 Schematic diagram of the synergistic effect of Cu⁰, Lewis acid and medium-strong base sites^[70] (with permission from Applied Catalysis B: Environment)

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图 10 Fe@C催化剂用于DMO加氢合成EO示意图^[78]

Figure 10 Schematic diagram of Fe@C catalyst for DMO hydrogenation to EO^[78] (with permission from ACS Publications)

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图 11 Cu@CNTs催化剂用于DMO加氢反应示意图^[79]

Figure 11 Schematic diagram of Cu@CNTs catalyst for DMO hydrogenation reaction^[79] (with permission from ChemCatChem)

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图 12 不同Cu含量的Cu/ZrO₂催化剂的SEM照片^[80]

Figure 12 SEM images of Cu/ZrO₂ catalysts with different Cu contents^[80] (a): 10%; (b): 20%; (c): 32%; (d): 40%; (e): 50%; (f): 58% (with permission from Chemical Engineering)

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图 13 Cu镶嵌介孔Al₂O₃合成乙醇过程^[81]

Figure 13 Process of synthesizing ethanol from Cu-encrusted mesoporous Al₂O₃^[81] (with permission from ACS publications)

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表 1 Ag催化剂用于DMO转化为MG的催化

Table 1 Ag catalyst for DMO to MG conversion

Entry	Catalyst	Conv._DMO /%	Selec._MG /%	p /MPa	t /℃	H₂ /DMO	LHSV /h⁻¹	Lifetime /h	Ref.
1	10Ag/SiO₂	54.4	99.8	0.5	180	150	0.5	120	[22]
2	15Ag/SiO₂	100.0	99.8	2.5	220	100	0.2	−	[23]
3	4.5Ag/SBA-15	99.9	95.6	3.0	235	100	0.6	110	[24]
4	15Ag/KCC-1	97.8	92.2	3.0	200	100	1.75	100	[25]
5	10Ag/0.02Ti-KCC	~ 98.0	~ 95.0	3.0	200	100	1.75	200	[26]
6	Ag-in/hCNT	100.0	>97.0	3.0	220	80	0.6	150	[27]
7	Ag/AC-N-3	100.0	~ 95.0	3.0	220	80	0.6	100	[28]
8	5Ag₁Ni_0.20/SBA-15	97.6	92.8	3.0	200	80	1.0	140	[29]
9	Ag-B₂O₃/SiO₂	98.9	97.2	0.5	180	150	0.5	260	[22]

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表 2 Cu用于DMO转化为MG的催化性能

Table 2 Cu catalyst for DMO to MG conversion

Entry	Catalyst	Conv._DMO /%	Selec._MG /%	p /MPa	t /℃	H₂ /DMO	LHSV /h⁻¹	Lifetime /h	Ref.
1	Cu/SiO₂-u	26.5	87	3.0	180	80	4.0	200	[31]
2	SP-Cu-SiO₂	20	87.0	3.0	240	150	0.5	~ 30	[32]
3	6Cu/SBA-15	75.4	60.8	3.0	180	80	0.6	−	[33]
4	Cu/AC-673	91.6	88.9	2.5	220	120	0.18	120	[20]
5	Cu-ZrO₂-SiO₂	90	90	2.0	200	150	0.3	100	[34]
6	Raney Cu-40	80.0	80.0	2.5	210	100	2.0	100	[35]
7	20Cu-HAP	85.0	75.0	2.5	210	150	0.4	120	[36]
8	Cu/MgO	~ 60.0	88.0	2.5	210	200	0.257	300	[37]
9	Cu/RGO	100.0	98.8	2.5	210	200	0.257	264	[38]
10	Cu/SiO₂-CeO₂	100	95	−	200	80	6	100	[39]

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