Recent progress on hydrodeoxygenation of biomass-derived oxygenates over transition metal carbides

doi:10.11949/0438-1157.20210048

Abstract

Abstract:

Transition metal carbides (TMCs) are formed by carburizing reaction of parent metal compounds. They have variable structure and noble metal like electronic properties. They are a kind of inexpensive but important materials in heterogeneous catalysis, providing great potential for large-scale industrial applications. Integrating carbon atoms into the parent metals leads to the expansion of metal lattice and structural rearrangement, which then broadens the metal d band with a greater density of state and alters the electronic properties. They are used in catalytic hydrogenation, hydrodeoxygenation(HDO) and hydrogenolysis and other important catalytic reactions showed excellent performance. In recent years, significant progress has been achieved in developing efficient and highly-stable TMCs in catalytic reactions. However, it remains great challenging to investigate the surface properties and understand the structure-activity relationship in these materials due to their inherent complexity of carbides involving phase purity, surface defects, surface termination and surface oxides. In this review, we firstly give a brief introduction on the current status and then summarize the recent progress in the development of TMCs towards HDO of representative oxygenates in pyrolysis bio-oil. Based on the analysis of the reaction pathway of representative oxygenates in pyrolysis bio-oil, the design and preparation strategy of TMCs, and the relationship between their structure and HDO catalytic performance are emphatically discussed. Finally, the R&D direction and prospect of TMCs as catalytic materials for HDO of biomass-derived oxygenates are proposed.

Key words: transition metal carbide, biomass, oxygenate, C—O bond, hydrodeoxygenation

摘要：

过渡金属碳化物由母体金属化合物经渗碳反应而形成，具有多变的结构组成和类贵金属的电子性质，是一类具有广泛应用前景的廉价催化材料，在催化加氢、加氢脱氧（hydrodeoxygenation，简写为HDO）和氢解等诸多重要催化反应中表现出优异的性能。近年来，对过渡金属碳化物的研究及其催化应用取得显著进展，但由于其固有的复杂性如相组成、表面缺陷与物种等导致构效关联等科学问题尚不清晰，仍有待进一步研究。本文综述了近年来过渡金属碳化物在生物质热解油中代表性含氧化合物HDO制备燃料和高附加值化学品中的研究进展，在分析了代表性含氧化合物反应路径的基础上，重点介绍了过渡金属碳化物的设计与合成策略及其结构与HDO催化性能关联，并展望了过渡金属碳化物作为生物质基含氧化合物HDO催化材料的研发方向与发展前景。

关键词: 过渡金属碳化物, 生物质, 含氧化合物, C—O键, 加氢脱氧

CLC Number:

TQ 028.8

FANG Huihuang, WU Lijie, CHEN Weikun, YUAN Youzhu. Recent progress on hydrodeoxygenation of biomass-derived oxygenates over transition metal carbides[J]. CIESC Journal, 2021, 72(7): 3562-3575.

方辉煌, 吴历洁, 陈伟坤, 袁友珠. 生物质基含氧化合物在过渡金属碳化物上加氢脱氧研究进展[J]. 化工学报, 2021, 72(7): 3562-3575.

Figures/Tables 14

Fig.1 Production of bio-fuels and value-added chemicals by transformation lignocellulose

Table 1 Major components in typical pyrolysis bio-oil［29-31］

组分	主要化合物	含量/%（质量）
不饱和醛和酮化合物	丙烯醛、苯甲醛、丁烯醛等	3.37
羟基酮醛化合物	羟基丙醛、乙醇醛、羟基丁酮等	9.27
醇和二醇类化合物	甲醇、乙醇、丁二醇等	3.50
饱和酮化合物	丙酮、丁酮、丁二酮、环己酮等	1.13
酸类和酯类化合物	甲酸、乙酸、丙烯酸、乙酸甲酯等	19.78
呋喃类和呋喃酮化合物	糠醛、（烷基）呋喃、呋喃酮等	8.50
氢化呋喃化合物	（烷基）四氢呋喃等	3.18
苯酚和烷基酚	苯酚、甲酚、二甲酚等	10.27
愈创木基化合物	愈创木酚、二甲氧基苯酚等	26.40
烷基愈创木酚化合物	乙基愈创木酚、苯甲醚等	7.77
未知产物	—	6.83

Table 2 Typical biomass based C—O bonds and their dissociation energies［36］

键型	解离能/(kJ·mol^-1)
Ar—OR	422
Ar—OH	468
ArO—R	247
R—OR	339
R—OH	385
R $? ??????$ O	799

Table 2 Typical biomass based C—O bonds and their dissociation energies［36］

键型	解离能/(kJ·mol^-1)
Ar—OR	422
Ar—OH	468
ArO—R	247
R—OR	339
R—OH	385
R $? ??????$ O	799

Fig.2 Crystal structure of transition metal carbides and the normal metal carbides in Group Ⅳ—Ⅷ

Fig.3 Preparation methods of transition metal carbides

Fig.4 Reaction pathway of guaiacol and anisole hydrodeoxygenation

Table 3 Hydrodeoxygenation of aromatic ethers and phenols

反应物	催化剂	反应条件	产物和收率	文献
愈创木酚	W₂C/CNF	釜式反应器；350℃；4 h；5.5 MPa H₂	苯酚，30.4%	[58]
愈创木酚	Mo₂C/CNF	釜式反应器；350℃；4 h；5.5 MPa H₂	苯酚，45%	[58]
愈创木酚	Mo₂C/CNF	釜式反应器；350℃；2 h；3.0 MPa H₂	酚基化合物，91.8%	[70]
愈创木酚	Mo₂C@C Mo₂C core/shell	釜式反应器；340℃；4 h；2.8 MPa H₂	酚基化合物，71.3%	[71]
愈创木酚	MoC_1-_x/CNF	釜式反应器；350℃；4 h；4.0 MPa H₂	苯酚，49%	[72]
愈创木酚	α-MoC_1-_x/AC	釜式反应器；340℃；4 h；0.1 MPa H₂	苯酚和烷基酚，74%	[73]
愈创木酚	W_xC@CS	固定床；300℃；3.0 MPa H₂；WLHSV = 3.0 h^-1	苯酚，92.5%	[74]
2-甲氧基苯酚	Mo₂C/AC	釜式反应器；350℃；3.4 MPa H₂；6 h	苯酚，>90%	[77]
间甲酚	Mo₂C	固定床；150℃；0.1 MPa；H₂/间甲酚=2800	甲苯，选择性>90%	[78]
苯酚	Mo₂C/TiO₂	固定床；350℃；2.5 MPa H₂	苯，>90%	[79]
苯甲醚	Mo₂C	固定床；247℃；H₂/苯甲醚=713；0.1 MPa	苯，选择性>90%	[79]
苯酚	MoC_x/HCS	釜式反应器；350℃；3.0 MPa H₂；2 h	苯，57.8%	[80]
苯甲醚	Mo₂C	固定床；150℃；约0.01到约0.1 MPa H₂	苯，94%	[81]
苯甲醚	MoC_x/FAU	固定床；250℃;	酚类化合物，>70%	[82]
香豆酮	W₂C nanorod	固定床；340℃；4.0 MPa H₂	主要是乙苯	[53]
香兰素	Mo₂C/AC	釜式反应器；100℃；3 h；0.6 MPa H₂	对甲酚，60%~70%	[83]
2-（2-甲氧基苯氧基）-1-苯基乙醇	W₂C/AC	釜式反应器；280℃；2 h；0.69 MPa H₂	乙苯，91.9%	[75-76]

Table 4 Hydrodeoxygenation of simple oxygenates

反应物	催化剂	反应条件	产物和收率	文献
乙酸	Mo₂C	程序升温反应，350℃；0.1 MPa；H₂/反应物=4	乙醛和乙烯	[84]
乙酸	NP-MoC_1-_x/mSBA	程序升温反应，350℃；0.1 MPa；H₂/反应物=4	乙烯	[85]
丙酮	Mo₂C	流动反应器；96℃；81 kPa	丙烷	[86]
丙酮	O^*-Mo₂C	流动反应器；96℃；81 kPa	丙烯	[86]
丙酮	Mo₂C	流动反应器；300℃；0.1 MPa；H₂/反应物=10	C₃碳氢化合物（主要是丙烯），40%~50%	[87]
丙醛	Mo₂C	流动反应器；300℃；0.1 MPa；H₂/反应物=10	C₃碳氢化合物（丙烯），30%~40%	[87]
丙醛	porous Mo₂C	流动反应器；常压；300℃	丙烯，>60%	[87]
丙醇	WC	流动反应器；380℃；0.1 MPa；H₂/反应物=10	丙烯，>73%	[88]
糠醛	Mo₂C	固定床；250℃；0.1 MPa H₂；H₂/反应物=80	甲基呋喃，80%~90%	[89]
糠醛	NiMoC-SiO₂	釜式反应器；150℃；40 min；6 MPa H₂	甲基呋喃，约100%	[90]
糠醛	β-Mo₂C	流动反应器；常压；150℃	2-甲基呋喃，50%~60%	[91]
1-辛醇	Mo₂C/ZrO₂	固定床；380℃；10.0 MPa H₂；WHSV= 4.0 h^-1	辛烯，>90%	[92]
4-甲基-3-环己烯-1-羰基醛	W₂C/AC	固定床；350℃；0.1 MPa H₂；LHSV= 1 ml·g^-1·h^-1	对二甲苯，95%	[93]

Fig.5 Hydrodeoxygenation of biomass-derived bio-oil over integrated dual catalysts

Fig.6 Activation and dissociation mechanism of hydrogen on the surface of transition metal carbides

Fig. 7 Hydrogenolysis mechanism of guaiacol on the surface of transition metal carbides

Fig.8 Hydrogenolysis mechanism of simple oxygenates on the surface of transition metal carbides

Fig.9 Possible mechanism of deactivation of transition metal carbides in catalytic reaction

Fig.10 Schematic diagram of structural control for carbide catalysts

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