Technological advances in the production of high value oxygen-containing chemicals from coal via dimethyl oxalate
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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。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.
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Key words:
- coal /
- dimethyl oxalate /
- selective hydrogenation /
- oxygen-containing chemicals /
- copper-based catalysts
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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)
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 5Ag1Ni0.20/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] 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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