非贵金属催化生物质加氢脱氧制备烃基生物燃料的研究进展

doi:10.16085/j.issn.1000-6613.2024-0725

化工进展 ›› 2024, Vol. 43 ›› Issue (S1): 225-242.DOI: 10.16085/j.issn.1000-6613.2024-0725

非贵金属催化生物质加氢脱氧制备烃基生物燃料的研究进展

李帅哲¹^,²^,³(), 聂懿宸¹^,²^,³, PHIDSAVARD Keomeesay¹, 顾雯¹^,²^,³, 张伟¹^,²^,³^,⁴, 刘娜¹^,²^,³^,⁴, 徐高翔¹^,²^,³^,⁴, 刘莹¹^,²^,³^,⁴, 李兴勇¹^,²^,³^,⁴(), 陈玉保¹^,²^,³^,⁴()

^1.云南师范大学能源与环境科学学院，云南昆明 650500
^2.云南省教育厅生物质绿色能源与平台化合物重点实验室，云南昆明 650500
^3.云南省低碳农业绿色发展技术国际研发中心，云南昆明 650500
^4.云南省农村能源工程重点实验室，云南昆明 650500

收稿日期:2024-04-30 修回日期:2024-07-04 出版日期:2024-11-20 发布日期:2024-12-06
通讯作者: 李兴勇,陈玉保
作者简介:李帅哲（1999—），男，硕士研究生，研究方向为生物质热化学催化转化。E-mail：l2461965521@163.com。
基金资助:
云南省基础研究计划重点项目(202301AS070011);云南省低碳发展引导专项(云财资环[2021]135号);云南省科技人才与平台计划(202105AC160058);云南省教育厅重点实验室项目(云教发[2024]5号);云南省国际联合创新平台项目(202407AH170008);云南省院士专家工作站项目(202205AF150024);2024年云南省国际科技特派员（个人）认定工作(202403AK140049)

Research progress on non-precious metal-catalyzed hydrogenation and deoxygenation of biomass to produce hydrocarbon-based biofuels

LI Shuaizhe¹^,²^,³(), NIE Yichen¹^,²^,³, PHIDJAVARD Keomeesay¹, GU Wen¹^,²^,³, ZHANG Wei¹^,²^,³^,⁴, LIU Na¹^,²^,³^,⁴, XU Gaoxiang¹^,²^,³^,⁴, LIU Ying¹^,²^,³^,⁴, LI Xingyong¹^,²^,³^,⁴(), CHEN Yubao¹^,²^,³^,⁴()

^1.School of Energy and Environmental Sciences, Yunnan Normal University, Kunming 650500, Yunnan, China
^2.Key Laboratory of Biomass Green Energy and Platform Compounds, Yunnan Provincial Department of Education, Kunming 650500, Yunnan, China
^3.Yunnan International Research and Development Center for Low Carbon Agriculture Green Development Technology, Kunming 650500, Yunnan, China
^4.Key Laboratory of Rural Energy Engineering in Yunnan Province, Kunming 650500, Yunnan, China

Received:2024-04-30 Revised:2024-07-04 Online:2024-11-20 Published:2024-12-06
Contact: LI Xingyong, CHEN Yubao

摘要/Abstract

摘要：

烃基生物液体燃料在生物质应用中扮演重要角色。传统第一代生物柴油即脂肪酸甲酯存在含氧量高、热值低并且与化石能源混合比例有限等不足，因此采用光热催化生物质加氢脱氧异构工艺制备的第二代烃基生物柴油备受关注，其中催化剂的开发至关重要。催化剂主要由金属活性组分和载体组成，由于贵金属催化剂成本高、不易大规模应用于工业化生产，因此在生产第二代烃基生物柴油时着重研发既具有高转化率、高选择性又兼备良好稳定性的非贵金属催化剂。本文围绕生物质催化加氢脱氧工艺，重点阐述了非贵金属（Ni、Mo、W、Co等）催化剂催化生物质制备烃基燃料过程中催化活性、转化机理及失活原因等，同时对后续非贵金属催化剂在油脂加氢脱氧催化方面的研究进行了展望。

关键词: 烃基生物柴油, 加氢脱氧, 非贵金属催化剂, 催化机理, 光热催化

Abstract:

Alkyl-based bio-liquid fuels play an important role in biomass applications. The first generation of biodiesel (fatty acid methyl ester) has high oxygen content, low calorific value, and limited mixing ratio with fossil fuels, so the second generation of hydrocarbon-based biodiesel,which is mainly prepared by thermal catalytic hydrogenation and deoxygenation isomerization process, has attracted much attention, and the study of catalysts is crucial. The composition of catalysts mainly includes metal active components and carriers. Due to the high cost of precious metal catalysts, they are not easily applied on a large scale in industrial production. Therefore, in the production and research of second-generation hydrocarbon-based biodiesel, emphasis is placed on developing non-precious metal catalysts with high conversion rates, high selectivity, good stability, and low cost. This paper expounds on the catalytic hydrogenation and deoxygenation process, focusing on the catalytic activity, catalytic conversion mechanism, catalyst deactivation reasons, and other catalytic characteristics of non-precious metal (Ni, Mo, W, Co, etc.) catalysts in the preparation of hydrocarbon fuels from biomass. At the same time, prospects for future research on non-precious metal catalysts in oil and fat hydrogenation and deoxygenation catalysis are proposed.

Key words: alkyl biodiesel, hydrodeoxygenation, non-precious metal catalysts, catalytic mechanism, photothermal catalysis

中图分类号:

李帅哲, 聂懿宸, PHIDSAVARD Keomeesay, 顾雯, 张伟, 刘娜, 徐高翔, 刘莹, 李兴勇, 陈玉保. 非贵金属催化生物质加氢脱氧制备烃基生物燃料的研究进展[J]. 化工进展, 2024, 43(S1): 225-242.

LI Shuaizhe, NIE Yichen, PHIDJAVARD Keomeesay, GU Wen, ZHANG Wei, LIU Na, XU Gaoxiang, LIU Ying, LI Xingyong, CHEN Yubao. Research progress on non-precious metal-catalyzed hydrogenation and deoxygenation of biomass to produce hydrocarbon-based biofuels[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 225-242.

图/表 22

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燃料	碳数	主要成分	性能	热值 /MJ∙kg^-1
汽油	5~12	异构烷烃	高辛烷值	40~45
柴油	10~22	支链烷烃	高十六烷值，低冷滤点	45~50
航空燃油	8~14	支链烷烃	低冷滤点	42~46
生物航油	8~16	直链烷烃支链烷烃	油脂黏度低	40~45
生物柴油	16~18	支链烷烃	十六烷值高于化石柴油	43~47

燃料	碳数	主要成分	性能	热值 /MJ∙kg^-1
汽油	5~12	异构烷烃	高辛烷值	40~45
柴油	10~22	支链烷烃	高十六烷值，低冷滤点	45~50
航空燃油	8~14	支链烷烃	低冷滤点	42~46
生物航油	8~16	直链烷烃支链烷烃	油脂黏度低	40~45
生物柴油	16~18	支链烷烃	十六烷值高于化石柴油	43~47

催化剂	催化原料	反应条件	主要产物	转化率/%	选择性/%	参考文献
Pd/Al₂O₃	油酸	325℃、2MPa	C₁₇烷烃	100	95	[12]
Pd/CeZrO₂	油酸	300℃、2MPa	C₁₇烷烃	100	37	[13]
Pt/ZSM-22	大豆油	300℃、3MPa	C₇~C₁₄烷烃	100	84.3	[14]
Pt/SPAO-11	大豆油	357℃、4MPa	C₇~C₁₄烷烃	100	63.3	[14]
Pt/TiO₂	麻疯树油	100℃、0.4MPa	C₈~C₁₇烷烃	93.20	54.92	[15]
Pt/TiO₂-ZSM-5	麻疯树油	100℃、0.4MPa	C₈~C₁₇烷烃	99.71	71.37	[16]

催化剂	催化原料	反应条件	主要产物	转化率/%	选择性/%	参考文献
Pd/Al₂O₃	油酸	325℃、2MPa	C₁₇烷烃	100	95	[12]
Pd/CeZrO₂	油酸	300℃、2MPa	C₁₇烷烃	100	37	[13]
Pt/ZSM-22	大豆油	300℃、3MPa	C₇~C₁₄烷烃	100	84.3	[14]
Pt/SPAO-11	大豆油	357℃、4MPa	C₇~C₁₄烷烃	100	63.3	[14]
Pt/TiO₂	麻疯树油	100℃、0.4MPa	C₈~C₁₇烷烃	93.20	54.92	[15]
Pt/TiO₂-ZSM-5	麻疯树油	100℃、0.4MPa	C₈~C₁₇烷烃	99.71	71.37	[16]

催化剂	催化原料	反应条件	主要产物	转化率 /%	裂化率 /%	参考文献
NiC	废咖啡油	400℃、2MPa	C₁₅~C₁₈烷烃	78.9	—	[12]
NiP	废咖啡油	400℃、2MPa	C₁₅~C₁₈烷烃	77.4	—	[12]
NiS	废咖啡油	400℃、2MPa	C₁₅~C₁₈烷烃	71.5	—	[12]
Mo₂C/AC	脂肪酸甲酯	370℃、3MPa	C₁₅~C₁₈烷烃	100	21	[13]
MoO/AC	脂肪酸甲酯	370℃、3MPa	C₁₅~C₁₈烷烃	56.05	18.55	[13]
MoO/Al₂O₃	脂肪酸甲酯	370℃、3MPa	C₁₅~C₁₈烷烃	85.64	25.79	[13]
MoS₂/Al₂O₃	脂肪酸甲酯	370℃、3MPa	C₁₅~C₁₈烷烃	83.46	11.88	[13]

非贵金属催化生物质加氢脱氧制备烃基生物燃料的研究进展

Research progress on non-precious metal-catalyzed hydrogenation and deoxygenation of biomass to produce hydrocarbon-based biofuels

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活性组分	载体	原料	温度 /℃	氢压/MPa	脱氧率 /%	选择性 /%	参考文献
3Ni/2P	SBA-15	油酸甲酯	250	0.3	79.5	—	[26]
Ni/P	—	甲酚	350	4	83.4	—	[27]
Ni/3P	ZrO₂	甲酚	340	4	88	—	[28]
Ni₃P	HZSM-5	苯酚	250	4	64.5	47.4	[25]
Ni₂P	SiO₂	二苯并呋喃	300	3	79.6	90.0	[24]

活性组分	载体	原料	温度 /℃	氢压 /MPa	转化率 /%	选择性 /%	参考文献
NiMo	SiO₂	苯甲醚	300	6	>90	90	[38]
NiMo	SiO₂	苯酚	410	0.1	99.3	99.3	[39]
NiMo	SiO₂	茴香醚	410	0.1	99.4	98.6	[39]
NiMo	Al₂O₃	愈创木酚	350	8	100	65.0	[40]
MoO₃-NiO	SBA-15	愈创木酚	300	0.1	20	30	[41]
MoO₃-NiO	MAS	愈创木酚	300	0.1	74	80	[41]

活性组分	温度/℃	氢压/MPa	转化率/%	烷烃选择性/%	不饱和烃选择性/%
Cu-Mo	280	2.5	98.8	56.7	40.2
Ni-Mo	280	2.5	100	99.9	—
Gr-Mo	280	2.5	79.7	62.1	32.5
Zn-Mo	280	2.5	44.8	53.8	23.5
Fe-Mo	280	2.5	38.9	45.5	24.3
Co-Mo	280	2.5	37.1	60.3	21.8

活性组分	载体	原料	温度 /℃	氢压 /MPa	转化率 /%	选择性 /%	参考文献
Au	WO₃	愈创木酚	225	3	94.2	98.3	[64]
Co-W-B	—	环戊酮	300	4	96.6	57.3	[65]
Cu-WO _x	Al₂O₃	油酸	300	3	100	93	[66]
NiW	Al₂O₃	脂肪酸酯	300	0.25	84	74	[67]
NiW	SiO₂	油酸	320	4	100	—	[58]
NiWPB	—	对甲酚	225	4	99.6	92.6	[68]

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