Recent advances in preparing biomass-based 2,5-bis(hydroxymethyl)furan by catalytic transfer hydrogenation
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摘要: 生物质基2,5-呋喃二甲醇(BHMF)可从廉价易得的糖类出发,经催化转化-选择性氢化制取,并作为一种用途广泛的化工中间体及燃料前体,尤其在改善传统聚酯性能以及合成绿色可降解的生物基聚酯新材料方面具有独特优势。BHMF制取过程中,传统的氢化方式消耗了大量高品位能源氢气,且高压氢气存在安全隐患并导致基础设施投入多。本工作立足于催化转移氢化的优势,综述了甲酸、醇类及其他类型氢供体通过催化转移氢化的方式选择性加氢制取BHMF的研究进展;并针对催化转移氢化过程中不同类型氢供体、催化剂和反应工艺的特点及存在的问题,分析了反应条件、强化手段等对BHMF选择性和收率的影响以及反应体系的优劣。在此基础上,提出了转移氢化制取BHMF新型催化体系的研究方向,并对清洁高效、本质安全BHMF制取工艺的发展进行了展望,为生物质转化中特定催化体系的研发提供科学参考。Abstract: Biomass-based 2,5-bis(hydroxymethyl)furan (BHMF) is one of the important high value-added chemicals, which can be prepared from inexpensive and renewable carbohydrates through the way of catalytic conversion and selective hydrogenation, and as a widely used chemical intermediate and fuel precursor, it has unique advantages in improving the performance of traditional polyesters and synthesizing new biodegradable bio-based polyesters. In recent years, the research on the production of high value-added chemicals such as BHMF from carbohydrate has been attracting much attention from both academia and industry. However, cleanliness, high efficiency, high selectivity and low-cost remain key challenges in this area, especially for practical applications. In the process of BHMF production, the traditional hydrogenation method consumed a large amount of high-grade energy of hydrogen, and an excessive investment in infrastructure would be generated due to the security risks of higher pressure of hydrogen. On account of the advantages of catalytic transfer hydrogenation, the advances in selective hydrogenation to prepare BHMF using formic acid, alcohols and other types of hydrogen donors by the approach of catalytic transfer hydrogenation is systematically discussed in this review. In view of the features and problems of different types of hydrogen donors, catalysts and reaction processes during the catalytic transfer hydrogenation process, the effects of reaction conditions and process intensifications on the selectivity and yield of BHMF, and the merits and demerits of the reaction system were all investigated. On this basis, the future directions of new catalytic systems for preparation of BHMF by transfer hydrogenation is proposed, and the cleaner, more efficient and essential safety technologies for the production of BHMF is predicted, which will provide some scientific reference for the research and development of related catalytic systems in biomass conversion.
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表 1 不同醇类化合物的还原电势
Table 1 Reduction potential of different alcohol compounds
No. Alcohol Reduction potential/(kJ·mol−1) 1 Methanol 130.1 2 Propanol 87.3 3 Ethanol 85.4 4 1-Butanol 79.7 5 Isopropanol 70.0 6 2-Butanol 69.3 表 2 以乙醇为溶剂和氢供体催化HMF选择性氢化效果
Table 2 Results of selective catalytic hydrogenation of HMF to BHMF using ethanol as the solvent and hydrogen donor
表 3 以异丙醇为溶剂和氢供体催化HMF选择性氢化效果
Table 3 Results of selective catalytic hydrogenation of HMF to BHMF using isopropanol as the solvent and hydrogen donor
No. Catalyst Temperature/℃ Time/h HMF conversion rate/% BHMF yield/% Ref. 1 Pd/Fe2O3 150 − 50 35 [45] 2 Ru/Co3O4 190 6 100 82.8 [46] 3 RuCu@NFC 210 12 97 91.5 [47] 4 ZrBa-SBA 150 2.5 98.3 90.6 [48] 5 ZrCa@CNS 190 10 91.2 84.2 [49] 6 Zr/NC 130 2.5 99.9 99.9 [42] 7 Zr-DTPA 140 4 98.7 95.2 [50] 8 Zr-HTC 120 4 100 99.2 [44] 9 Zr-PN 140 2 99 98 [51] 10 m-PhP-Zr 120 2 99 93 [52] 11 Zr-FDCA 140 8 100 87 [53] 12 Zr-MOF-808 82 2 98.2 96.2 [54] 13 DUT-69(Zr) 130 6 97.2 86.2 [55] 14 Zr-tannin 100 5 95 89.3 [56] 15 Zr-LS 100 2 98 89 [57] 16 Hf-LigS 100 2 97.3 89.8 [58] 17 Hf-H3IDC-T 100 4 94 92 [59] 18 FDCA-Hf 100 5 98 95 [60] 19 Hf-MOF-808 100 1.5 − 98 [61] 20 Co/UiO-66-NH2 100 4 92.6 88.8 [62] 21 UiO-66 180 4 87 82 [63] 22 Co3O4/MC 140 12 100 97 [64] 23 MnO@C-N 170 21 98 93 [65] 表 4 以丁醇为氢供体和溶剂HMF选择性加氢反应效果
Table 4 Results of selective catalytic hydrogenation of HMF to BHMF using different butanols as the solvent and hydrogen donor
表 5 催化转移氢化制BHMF不同氢供体的优劣
Table 5 Advantages and disadvantages of different hydrogen donors in catalytic transfer hydrogenation for the synthesis of BHMF
Hydrogen donor Advantage Disadvantage Formic acid or formate salts High atomic utilization rate, high safety and environmental friendliness, ideal liquid hydrogen storage material Stronger acidity and corrosiveness, special requirements of catalyst structure Methanol Renewable, lower price, high hydrogen density Higher reduction potential, harsher reaction conditions Ethanol Renewable, economical efficiency Higher reduction potential Isopropanol Lower reduction potential, small steric-hinerance, and strong hydrogen supply ability Higher cost and equipment corrosion Butanol More sources of hydrogen, high value-added by-product γ- butyrolactone Toxic and cost-effective compared to methanol, ethanol, etc Benzyl alcohol Low price and low volatility Flammable, toxic, irritating Cyclohexanol Higher boiling point, continuous hydrogen-supply, by-product cyclohexanone Higher cost, less research NaBH4 High hydrogen storage capacity, high energy density, safety and reliability Expensive and not easy to be separated NaH2PO2 No obvious toxicity, stable to air and water, easy to handle, and large-scale application Releasing heat, leading to flammability and corrosiveness PMHS It is a byproduct of the silicon industry, which is stable, inexpensive, and low toxic to water and air The overall price is relatively expensive, which in turn leads to higher production costs Ph2SiH2 Non toxic, biodegradable, and stable for air and water Hydrogen production requires activation by metal containing catalysts HMF No additional hydrogen donors need to be added Strong alkaline condition, complicated separation pathways Water or protons Electrocatalysis can be carried out at lower temperatures and pressures, HMF can simultaneously undergo hydrogenation and oxidation to obtain different types of high value-added chemicals Lower efficiency -
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