Research progress in catalytic hydroconversion of lipid to second-generation biodiesel

doi:10.11949/0438-1157.20220954

Abstract

Abstract:

Biodiesel is a clean and renewable energy source, and it is one of the most potential development directions to deal with problems such as greenhouse effect, environmental pollution, and energy shortage. The second-generation biodiesel is a hydrocarbon mixture prepared by the hydroconversion of lipid with the assistance of hydrogen (H₂). It has similar components to the traditional petrochemical diesel. In addition to the advantages of greenness, high cetane number and renewability, it also has the characteristics of good low-temperature fluidity, low oxygen content, high stability and high calorific value. It can be mixed with petrochemical diesel without fraction limitation. This review systematically summarizes the research progress in the preparation of second-generation biodiesel by catalytic hydroconversion of lipid in recent years. We discuss the hydroconversion mechanism, active phase of catalysts, catalyst supports and hydroconversion process, with special emphasis on the design and development of highly efficient hydroconversion catalysts. In addition, the opportunities and challenges in the field of lipid hydrogenation to produce second-generation biodiesel were analyzed, and the future development directions were prospected.

Key words: petroleum, renewable energy, hydrogenation, catalyst, support, process

摘要：

生物柴油是一种清洁的可再生能源，是应对温室效应、环境污染、能源短缺等问题最有潜力的发展方向之一。第二代生物柴油是油脂与氢气（H₂）进行加氢转化反应制得的与传统石化柴油组成类似的烃类混合物，除具有绿色环保、十六烷值高、可再生等优点外，还具有低温流动性好、含氧量低、稳定性高、热值高等特点，可与石化柴油无比例限制地混合使用。系统总结了近年来油脂催化加氢转化制备第二代生物柴油方面的研究进展，包括加氢转化机理、催化剂活性相、催化剂载体和加氢转化工艺四个方面，着重介绍高效加氢转化催化剂的设计和开发。此外，还分析了油脂催化加氢转化制备第二代生物柴油领域所面临的机遇和挑战，并对未来的发展方向进行了展望。

关键词: 石油, 再生能源, 加氢, 催化剂, 载体, 工艺

CLC Number:

TQ 028.8

Kuan HUANG, Yongde MA, Zhenping CAI, Yanning CAO, Lilong JIANG. Research progress in catalytic hydroconversion of lipid to second-generation biodiesel[J]. CIESC Journal, 2023, 74(1): 380-396.

黄宽, 马永德, 蔡镇平, 曹彦宁, 江莉龙. 油脂催化加氢转化制备第二代生物柴油研究进展[J]. 化工学报, 2023, 74(1): 380-396.

Figures/Tables 13

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催化剂	反应原料	反应器形式	反应条件	主要产物	转化率/%	选择性/%	文献
Pd/Al₂O₃	油酸	间歇式	325℃、2 MPa	C₁₇烷烃	100	95	[20]
Ru/H-ZSM-5	硬脂酸甲酯	间歇式	200℃、3 MPa	C₁₇烷烃	91	71	[21]
Rh/ZrO₂	棕榈酸甲酯	间歇式	300℃、8 MPa	C₁₅烷烃	—	—	[22]
Pd/HPS	硬脂酸	间歇式	260℃、0.18 MPa	C₁₇烷烃	—	—	[23]
Ru/TpPON	油酸、棕榈酸、肉豆蔻酸等	间歇式	180℃、3 MPa	奇数碳烷烃	—	—	[24]
Pt/C	棕榈酸	间歇式	370℃	C₁₅烷烃	68	62	[25]
PtSn/SAPO-11	棕榈酸甲酯	连续式	375℃、3 MPa	C₁₆烷烃	87	79	[26]
RuRe/TiO₂	硬脂酸乙酯	间歇式	220℃、3 MPa	C₁₈烷烃	100	70	[27]
PdFeNi/MCF	油酸	间歇式	278℃、4 MPa	C₁₈烷烃	100	—	[28]
PtNi/Al₂O₃	油酸	间歇式	275℃、6.21 MPa	C₁₇烷烃	91	—	[29]
PdCu/MN270	油酸、亚油酸	间歇式	270℃、2 MPa	C₁₇烷烃	—	99	[30]
Ni/Al₂O₃	油酸	间歇式	325℃、2 MPa	C₁₇烷烃	77	58	[20]
Ni/Al₂O₃	硬脂酸	间歇式	300℃、3 MPa	C₁₇烷烃	99	97	[31]
Ni/Al₂O₃	月桂酸甲酯	连续式	400℃、2 MPa	C₁₁烷烃	91	69	[32]
Ni/HBeta	微藻油脂	间歇式	260℃、4 MPa	C₁₈烷烃	—	—	[33]
Ni/H-Y-80	脂肪酸甲酯、动物油脂	间歇式	300℃、3 MPa	偶数碳烷烃	—	—	[34]
Ni/TS-1	棕榈酸	间歇式	260℃、3 MPa	C₁₅烷烃	100	92	[35]
Co/H-ZSM-5	硬脂酸	间歇式	270℃、3 MPa	C₁₈烷烃	100	96	[36]
Co/H-ZSM-22	棕榈酸	间歇式	260℃、2 MPa	C₁₆烷烃	100	73	[37]
Fe/SBA-15	油酸	间歇式	290℃、3 MPa	C₁₈烷烃	100	83	[38]
Fe/NC-Al₂O₃	硬脂酸	间歇式	320℃、4 MPa	C₁₈烷烃	—	—	[39]
NiCu/ZrO₂	硬脂酸	间歇式	260℃、4 MPa	C₁₇烷烃	—	—	[40]
NiFe/SiO₂	月桂酸	间歇式	300℃、3.5 MPa	C₁₁烷烃	99	87	[41]
NiMo/SAPO-11	月桂酸甲酯	连续式	375℃、3 MPa	C₁₂烷烃	100	—	[42]
CoMo/CNT	棕榈酸	间歇式	200℃、4 MPa	C₁₆烷烃	100	91	[43]
NiMo/PSi	棕榈酸甲酯	间歇式	220℃、1 MPa	C₁₅烷烃	100	71	[44]
CoMo/SG	油酸	间歇式	300℃、2 MPa	C₁₇烷烃	89	48	[45]
NiW/meso-Y	微藻油脂	连续式	255℃、2 MPa	C₁₅烷烃	97	46	[46]
NiMo/SiO₂	硬脂酸	间歇式	260℃、3 MPa	C₁₈烷烃	100	65	[47]
Ni/NbO_x	硬脂酸	间歇式	240℃、2.5 MPa	C₁₇烷烃	99	73	[48]
NiW/SiO₂	油酸	连续式	320℃、4 MPa	C₁₇烷烃	100	—	[49]
MoO₂/CNT	棕榈酸	间歇式	220℃、4 MPa	C₁₆烷烃	100	92	[50]

催化剂	反应原料	反应器形式	反应条件	主要产物	转化率/%	选择性/%	文献
Pd/Al₂O₃	油酸	间歇式	325℃、2 MPa	C₁₇烷烃	100	95	[20]
Ru/H-ZSM-5	硬脂酸甲酯	间歇式	200℃、3 MPa	C₁₇烷烃	91	71	[21]
Rh/ZrO₂	棕榈酸甲酯	间歇式	300℃、8 MPa	C₁₅烷烃	—	—	[22]
Pd/HPS	硬脂酸	间歇式	260℃、0.18 MPa	C₁₇烷烃	—	—	[23]
Ru/TpPON	油酸、棕榈酸、肉豆蔻酸等	间歇式	180℃、3 MPa	奇数碳烷烃	—	—	[24]
Pt/C	棕榈酸	间歇式	370℃	C₁₅烷烃	68	62	[25]
PtSn/SAPO-11	棕榈酸甲酯	连续式	375℃、3 MPa	C₁₆烷烃	87	79	[26]
RuRe/TiO₂	硬脂酸乙酯	间歇式	220℃、3 MPa	C₁₈烷烃	100	70	[27]
PdFeNi/MCF	油酸	间歇式	278℃、4 MPa	C₁₈烷烃	100	—	[28]
PtNi/Al₂O₃	油酸	间歇式	275℃、6.21 MPa	C₁₇烷烃	91	—	[29]
PdCu/MN270	油酸、亚油酸	间歇式	270℃、2 MPa	C₁₇烷烃	—	99	[30]
Ni/Al₂O₃	油酸	间歇式	325℃、2 MPa	C₁₇烷烃	77	58	[20]
Ni/Al₂O₃	硬脂酸	间歇式	300℃、3 MPa	C₁₇烷烃	99	97	[31]
Ni/Al₂O₃	月桂酸甲酯	连续式	400℃、2 MPa	C₁₁烷烃	91	69	[32]
Ni/HBeta	微藻油脂	间歇式	260℃、4 MPa	C₁₈烷烃	—	—	[33]
Ni/H-Y-80	脂肪酸甲酯、动物油脂	间歇式	300℃、3 MPa	偶数碳烷烃	—	—	[34]
Ni/TS-1	棕榈酸	间歇式	260℃、3 MPa	C₁₅烷烃	100	92	[35]
Co/H-ZSM-5	硬脂酸	间歇式	270℃、3 MPa	C₁₈烷烃	100	96	[36]
Co/H-ZSM-22	棕榈酸	间歇式	260℃、2 MPa	C₁₆烷烃	100	73	[37]
Fe/SBA-15	油酸	间歇式	290℃、3 MPa	C₁₈烷烃	100	83	[38]
Fe/NC-Al₂O₃	硬脂酸	间歇式	320℃、4 MPa	C₁₈烷烃	—	—	[39]
NiCu/ZrO₂	硬脂酸	间歇式	260℃、4 MPa	C₁₇烷烃	—	—	[40]
NiFe/SiO₂	月桂酸	间歇式	300℃、3.5 MPa	C₁₁烷烃	99	87	[41]
NiMo/SAPO-11	月桂酸甲酯	连续式	375℃、3 MPa	C₁₂烷烃	100	—	[42]
CoMo/CNT	棕榈酸	间歇式	200℃、4 MPa	C₁₆烷烃	100	91	[43]
NiMo/PSi	棕榈酸甲酯	间歇式	220℃、1 MPa	C₁₅烷烃	100	71	[44]
CoMo/SG	油酸	间歇式	300℃、2 MPa	C₁₇烷烃	89	48	[45]
NiW/meso-Y	微藻油脂	连续式	255℃、2 MPa	C₁₅烷烃	97	46	[46]
NiMo/SiO₂	硬脂酸	间歇式	260℃、3 MPa	C₁₈烷烃	100	65	[47]
Ni/NbO_x	硬脂酸	间歇式	240℃、2.5 MPa	C₁₇烷烃	99	73	[48]
NiW/SiO₂	油酸	连续式	320℃、4 MPa	C₁₇烷烃	100	—	[49]
MoO₂/CNT	棕榈酸	间歇式	220℃、4 MPa	C₁₆烷烃	100	92	[50]

催化剂	反应原料	反应器形式	反应条件	主要产物	转化率/%	选择性/%	文献
CoMoS _x	废弃餐饮油脂	间歇式	375℃、9 MPa	C₁₇烷烃	100	77	[17]
NiMoS _x	油酸	间歇式	280℃、6 MPa	C₁₈烷烃	100	79	[15]
NiMoS _x	棕榈酸	间歇式	320℃、7 MPa	C₁₆烷烃	95	79	[15]
NiMoS _x /Al₂O₃	菜籽油	连续式	280℃、5 MPa	C₁₈烷烃	—	—	[58]
CoMoS _x /Al₂O₃	棕榈酸甲酯	间歇式	300℃、3.5 MPa	C₁₆烷烃	100	72	[64]
NiMoS _x /Al₂O₃	油酸、油酸甲酯、三油酸甘油酯	连续式	260℃、6 MPa	C₁₇烷烃	80	60	[65]
NiMoS _x /Al₂O₃	硬脂酸	间歇式	300℃、7 MPa	C₁₈烷烃	—	—	[66]
NiWS _x /Al₂O₃	废弃植物油脂	间歇式、连续式	350℃、7 MPa	C₁₇烷烃	100	—	[67]
NiWS _x /SiO₂-Al₂O₃	废弃餐饮油脂	间歇式	350℃	C₁₇烷烃	—	—	[68]
NiMoS _x /Al₂O₃	油酸甲酯	连续式	260℃、3 MPa	C₁₈烷烃	22	60	[69]

催化剂	反应原料	反应器形式	反应条件	主要产物	转化率/%	选择性/%	文献
CoMoS _x	废弃餐饮油脂	间歇式	375℃、9 MPa	C₁₇烷烃	100	77	[17]
NiMoS _x	油酸	间歇式	280℃、6 MPa	C₁₈烷烃	100	79	[15]
NiMoS _x	棕榈酸	间歇式	320℃、7 MPa	C₁₆烷烃	95	79	[15]
NiMoS _x /Al₂O₃	菜籽油	连续式	280℃、5 MPa	C₁₈烷烃	—	—	[58]
CoMoS _x /Al₂O₃	棕榈酸甲酯	间歇式	300℃、3.5 MPa	C₁₆烷烃	100	72	[64]
NiMoS _x /Al₂O₃	油酸、油酸甲酯、三油酸甘油酯	连续式	260℃、6 MPa	C₁₇烷烃	80	60	[65]
NiMoS _x /Al₂O₃	硬脂酸	间歇式	300℃、7 MPa	C₁₈烷烃	—	—	[66]
NiWS _x /Al₂O₃	废弃植物油脂	间歇式、连续式	350℃、7 MPa	C₁₇烷烃	100	—	[67]
NiWS _x /SiO₂-Al₂O₃	废弃餐饮油脂	间歇式	350℃	C₁₇烷烃	—	—	[68]
NiMoS _x /Al₂O₃	油酸甲酯	连续式	260℃、3 MPa	C₁₈烷烃	22	60	[69]

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