非均相催化剂催化5-羟甲基糠醛氢解制备2,5-二甲基呋喃研究进展

doi:10.16085/j.issn.1000-6613.2020-0710

摘要/Abstract

摘要：

随着化石能源的日益短缺，清洁可再生生物质资源的利用，尤其是制备高品质生物燃料逐渐成为研究热点。2,5-二甲基呋喃（DMF）具有优良的物理化学性质，被认为是最有前途的液体生物燃料之一，可通过生物质平台分子5-羟甲基糠醛（HMF）选择性氢解制备。HMF化学性质非常活泼，可以转化成多种下游产品，因此设计制备高选择性催化剂对于靶向合成DMF至关重要。本文依据贵金属和非贵金属对催化剂进行分类，详细综述了非均相催化剂在HMF氢解制备DMF反应中的研究新进展；针对目前研究中存在的局限性和问题，提出了催化剂和反应体系的研究方向。此外，指出以生物质为原料直接制备DMF及建立有效的分离技术是实现DMF工业化生产的重要途径。

关键词: 生物质, 5-羟甲基糠醛, 催化, 氢解, 生物燃料, 2,5-二甲基呋喃

Abstract:

With the increasing shortage of fossil energy, the utilization of clean and renewable biomass resources, especially the preparation of high-quality biofuels has become a research hotspot. 2,5-Dimethylfuran (DMF) is regarded as one of the most promising liquid biofuels due to its excellent physical and chemical properties. DMF can be synthesized by selective hydrogenolysis of 5-hydroxymethylfurfural (HMF). However, HMF is chemically active and can be converted into various downstream products, so it is critical to develop catalysts with high selectivity for DMF production. In this review, recent advances of noble and non-noble metal-based catalysts are reviewed in detail for the hydrogenolysis of HMF to DMF. The limitations and problems in current researches, potential research trends of the catalysts and reaction systems were proposed. In addition, it is pointed out that the direct preparation of DMF from biomass and the establishment of effective separation technology are important for realizing the industrial production of DMF.

Key words: biomass, 5-hydroxymethylfurfural, catalysis, hydrogenolysis, biofuel, 2,5-dimethylfuran

中图分类号:

王彤, 安华良, 李芳, 薛伟, 王延吉. 非均相催化剂催化5-羟甲基糠醛氢解制备2,5-二甲基呋喃研究进展[J]. 化工进展, 2021, 40(2): 824-834.

Tong WANG, Hualiang AN, Fang LI, Wei XUE, Yanji WANG. Research progress of the heterogeneous catalysts for 2,5-dimethylfuran synthesis via hydrogenolysis of 5-hydroxymethylfufural[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 824-834.

图/表 7

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催化剂	氢供体	温度/℃	反应时间/h	HMF转化率/%	DMF产率/%	参考文献
Ru/C+RuO₂	异丙醇	190	6	100	72	[17]
r-Ru₂@MSC-30	H₂(0.5MPa)	125	1	100	69.52	[18]
Ru-ZrO₂-MCM-41	H₂(1.5MPa)	160	1	100	90	[19]
Ru@Mg(Al)O	异丙醇	220	5	—	14	[20]
Ru-MoO_x/C	H₂(1.5MPa)	180	1	100	79.8	[21]
RuCo/CoO_x	H₂(0.5MPa)	200	2	100	96.5	[22]
Pt-Co/MWCNTs	H₂(1MPa)	160	8	100	92.3	[23]
Pt₃Co₂	H₂(3.3MPa)	160	—	100	98	[24]
Pt₃Ni/C	H₂(3.3MPa)	200	—	100	98	[25]
PtCu/C	H₂(3.3MPa)	200	—	100	96	[25]
Pt₂Zn/C	H₂(3.3MPa)	200	—	100	97	[25]
PtCo/HCS	H₂(1MPa)	180	2	100	98	[26]
Pd/Fe₂O₃	异丙醇	180	24	100	72	[27]
Pd/C	H₂(1MPa)	80	2	100	100	[28]
Pd/C	H₂(2MPa)	120	15	95	85	[29]
Pd-Co₉S₈/S-CNT	H₂(0.3MPa)	120	13	96	83.7	[30]
Pd₅₀Au₅₀/C	H₂(0.1MPa)	60	6	>99	>99	[31]
PdAu₄/GC800	H₂(1MPa)	150	4	86.8	81.9	[32]
Pd-Cs_2.5H_0.5PW₁₂O₄₀/K-10	H₂(1MPa)	90	2	98	79	[33]
Pd/C/Zn	H₂(0.8MPa)	150	8	>99	85	[34]
Cu-Pd@C	H₂(1.5MPa)	120	7	100	96	[35]
Pd/Co-CoO_x@NC	H₂(1.5MPa)	180	2	100	97.8	[36]
Raney Ni	H₂(1.5MPa)	180	15	100	88.5	[37]
Ni-Al₂O₃	H₂(1.2MPa)	180	4	100	91.5	[38]
NiSi-PS	H₂(1.5MPa)	130	3	100	72.9	[39]
7Ni-30W₂C/AC	H₂(4MPa)	180	3	100	96	[40]
2%Ni-20%Co/C	甲酸	210	24	99	90	[41]
Ni-OMD3	H₂(3MPa)	200	6	>99.9	98.7	[42]
Ni/ZrP	H₂(3MPa)	240	20	100	68.1	[43]
Ni/ZSM-5	H₂(0.25MPa)	180	7	91.2	96.2	[45]
Ni/TiO₂	H₂(3MPa)	220	2	100	85	[46]
Ni/C	H₂(4.5MPa)	180	2	100	75	[47]
Ni@SAZn-PC	H₂(0.6MPa)	150	1	56	50	[48]
NiCu₃/C	H₂(3.3MPa)	180	—	100	98.7	[49]
Ni₂-Fe₁/CNTs	H₂(3MPa)	200	3	100	91.3	[50]
Cu-PMO	甲醇	260	3	100	48	[52]
Cu20-Ru2-PMO	H₂(5MPa)	220	1	100	62.6	[53]
Cu/Al₂O₃	甲醇	240	6	>99.9	73.9	[54]
NC-Cu/MgAlO	环己醇	220	0.5	100	96.1	[55]
Co@Cu/3CoAlO_x	H₂(1.5MPa)	180	5	>99	98.5	[56]
CuZn	H₂(2MPa)	200	6	100	89	[57]
CnZn-2	H₂(1.5MPa)	220	5	100	91.8	[58]
CuZnO(P)	H₂(3MPa)	220		100	79	[59]
CuCo?/NGr/α-Al₂O₃	H₂(2MPa)	180	6	100	>99	[60]
Cu-Co@C(Cu∶Co=1∶3)	H₂(5MPa)	180	8	100	99.4	[61]
CuZnCo_x	乙醇	210	5	100	99	[62]
FeN_x/C	H₂(4MPa)	240	5	100	86.2	[63]
Fe-N-C	H₂(4MPa)	240	3	100	85.7	[64]
Fe-Co-Ni/h-BN	H₂(2MPa)	180	4.5	100	94	[65]
Co-CoO_x	H₂(1MPa)	170	12	100	83.3	[66]
Co@NGs	H₂(2MPa)	200	6	99.9	94.7	[67]
20Co/β-DAC723R	H₂(1.5MPa)	150	3	100	83.1	[68]
Co-(ZnO-ZnAl₂O₄)	H₂(0.7MPa)	130	6	100	74.2	[69]

催化剂	氢供体	温度/℃	反应时间/h	HMF转化率/%	DMF产率/%	参考文献
Ru/C+RuO₂	异丙醇	190	6	100	72	[17]
r-Ru₂@MSC-30	H₂(0.5MPa)	125	1	100	69.52	[18]
Ru-ZrO₂-MCM-41	H₂(1.5MPa)	160	1	100	90	[19]
Ru@Mg(Al)O	异丙醇	220	5	—	14	[20]
Ru-MoO_x/C	H₂(1.5MPa)	180	1	100	79.8	[21]
RuCo/CoO_x	H₂(0.5MPa)	200	2	100	96.5	[22]
Pt-Co/MWCNTs	H₂(1MPa)	160	8	100	92.3	[23]
Pt₃Co₂	H₂(3.3MPa)	160	—	100	98	[24]
Pt₃Ni/C	H₂(3.3MPa)	200	—	100	98	[25]
PtCu/C	H₂(3.3MPa)	200	—	100	96	[25]
Pt₂Zn/C	H₂(3.3MPa)	200	—	100	97	[25]
PtCo/HCS	H₂(1MPa)	180	2	100	98	[26]
Pd/Fe₂O₃	异丙醇	180	24	100	72	[27]
Pd/C	H₂(1MPa)	80	2	100	100	[28]
Pd/C	H₂(2MPa)	120	15	95	85	[29]
Pd-Co₉S₈/S-CNT	H₂(0.3MPa)	120	13	96	83.7	[30]
Pd₅₀Au₅₀/C	H₂(0.1MPa)	60	6	>99	>99	[31]
PdAu₄/GC800	H₂(1MPa)	150	4	86.8	81.9	[32]
Pd-Cs_2.5H_0.5PW₁₂O₄₀/K-10	H₂(1MPa)	90	2	98	79	[33]
Pd/C/Zn	H₂(0.8MPa)	150	8	>99	85	[34]
Cu-Pd@C	H₂(1.5MPa)	120	7	100	96	[35]
Pd/Co-CoO_x@NC	H₂(1.5MPa)	180	2	100	97.8	[36]
Raney Ni	H₂(1.5MPa)	180	15	100	88.5	[37]
Ni-Al₂O₃	H₂(1.2MPa)	180	4	100	91.5	[38]
NiSi-PS	H₂(1.5MPa)	130	3	100	72.9	[39]
7Ni-30W₂C/AC	H₂(4MPa)	180	3	100	96	[40]
2%Ni-20%Co/C	甲酸	210	24	99	90	[41]
Ni-OMD3	H₂(3MPa)	200	6	>99.9	98.7	[42]
Ni/ZrP	H₂(3MPa)	240	20	100	68.1	[43]
Ni/ZSM-5	H₂(0.25MPa)	180	7	91.2	96.2	[45]
Ni/TiO₂	H₂(3MPa)	220	2	100	85	[46]
Ni/C	H₂(4.5MPa)	180	2	100	75	[47]
Ni@SAZn-PC	H₂(0.6MPa)	150	1	56	50	[48]
NiCu₃/C	H₂(3.3MPa)	180	—	100	98.7	[49]
Ni₂-Fe₁/CNTs	H₂(3MPa)	200	3	100	91.3	[50]
Cu-PMO	甲醇	260	3	100	48	[52]
Cu20-Ru2-PMO	H₂(5MPa)	220	1	100	62.6	[53]
Cu/Al₂O₃	甲醇	240	6	>99.9	73.9	[54]
NC-Cu/MgAlO	环己醇	220	0.5	100	96.1	[55]
Co@Cu/3CoAlO_x	H₂(1.5MPa)	180	5	>99	98.5	[56]
CuZn	H₂(2MPa)	200	6	100	89	[57]
CnZn-2	H₂(1.5MPa)	220	5	100	91.8	[58]
CuZnO(P)	H₂(3MPa)	220		100	79	[59]
CuCo?/NGr/α-Al₂O₃	H₂(2MPa)	180	6	100	>99	[60]
Cu-Co@C(Cu∶Co=1∶3)	H₂(5MPa)	180	8	100	99.4	[61]
CuZnCo_x	乙醇	210	5	100	99	[62]
FeN_x/C	H₂(4MPa)	240	5	100	86.2	[63]
Fe-N-C	H₂(4MPa)	240	3	100	85.7	[64]
Fe-Co-Ni/h-BN	H₂(2MPa)	180	4.5	100	94	[65]
Co-CoO_x	H₂(1MPa)	170	12	100	83.3	[66]
Co@NGs	H₂(2MPa)	200	6	99.9	94.7	[67]
20Co/β-DAC723R	H₂(1.5MPa)	150	3	100	83.1	[68]
Co-(ZnO-ZnAl₂O₄)	H₂(0.7MPa)	130	6	100	74.2	[69]

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