甘油三酯催化转化为柴油、喷气燃料和润滑油基础油

doi:10.1016/S1872-2067(23)64617-0

摘要/Abstract

摘要：

将生物质转化为可持续燃料和化学品对于解决环境问题、减少碳排放、增强能源安全以及促进经济和社会发展至关重要. 在众多生物质原料中, 来自不同来源的甘油三酯, 如植物油、动物脂肪和微藻油, 因其低氧含量和脂肪酸单元中的高度石蜡骨架, 与石油衍生烃的结构相似, 而特别适合生产可持续的烃燃料和化学品. 这意味着通过相对简单的催化转化过程, 就能有效地将甘油三酯转化为烃类产物.

本文概述了甘油三酯通过加氢过程转化为无氧燃料(如柴油和喷气燃料)以及润滑油基础油等高附加值产品的过程. 此外, 还根据反应机理讨论了所需催化剂的重要结构性质, 以及甘油三酯的不同脂肪酸组成对催化转化过程的影响.

关键词: 甘油三酯, 脱氧, 柴油, 喷气燃料, 润滑油基础油, 加氢处理的植物油, 加氢处理的酯和脂肪酸, 可持续航空燃料

Abstract:

The conversion of biomass into sustainable fuels and chemicals is essential for addressing environmental concerns, reducing the carbon footprint of the energy sector, enhancing energy security, and promoting economic and social development. Among various biomass feedstocks, triglycerides from diverse sources, such as vegetable oils, animal fats, and microalgal oils, are particularly suitable for producing sustainable hydrocarbon fuels and chemicals due to their low oxygen contents and highly paraffinic backbone in the fatty acid units, the structures of which are already quite similar to those of petroleum-derived hydrocarbons. This implies that relatively simple catalytic conversions can effectively convert triglycerides into hydrocarbon products. In this Perspective, we will provide an overview on the hydroconversion of triglycerides into oxygen-free fuels, such as diesel and jet fuel, and value-added products such as lube base oil. In addition, we will discuss the important structural properties of the required catalysts and the effects of different fatty acid compositions of triglycerides for each conversion process in light of reaction mechanisms.

Key words: Triglycerides, Deoxygenation, Diesel, Jet fuel, Lube base oil, Hydrotreated vegetable oil, Hydrotreated esters and fatty acids, Sustainable aviation fuel

Yaejun Baik, Kyeongjin Lee, Minkee Choi. 甘油三酯催化转化为柴油、喷气燃料和润滑油基础油[J]. 催化学报, 2024, 58: 15-24.

Yaejun Baik, Kyeongjin Lee, Minkee Choi. Catalytic conversion of triglycerides into diesel, jet fuel, and lube base oil[J]. Chinese Journal of Catalysis, 2024, 58: 15-24.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64617-0

https://www.cjcatal.com/CN/Y2024/V58/I3/15

图/表 5

Fig. 1. Processes for green diesel, bio-jet fuel, and lube base oil production. (a) Common sources of triglycerides. Reaction pathways for triglyceride deoxygenation into green diesel (b) and its further hydroisomerization/cracking into bio-jet fuel (c). Reproduced with permission from Ref. [13]. Copyright 2017, American Chemical Society. (d) Reaction pathways for the ketonization/thermal oligomerization of triglycerides and subsequent hydrotreating to produce lube base oil.

Table 1 Summary of the catalytic conversion of triglycerides and related model compounds into products associated with diesel, jet fuel, and lube base oil.

Entry	Feed	Reaction	Catalyst	Reaction condition	Target product	Yield (%)	Ref.
1	soybean oil	deoxygenation by hydrotreating	Pt/γ- and θ-Al₂O₃ with varying pore sizes	fixed bed reactor, 633 K, 20 bar H₂	n-C13-C18 (green diesel)	44.3-74.9	[15]
2	palm oil	deoxygenation by hydrotreating	Pt/mesopor. γ-Al₂O₃	fixed bed reactor, 653 K, 40 bar H₂	n-C15-C18 (green diesel)	73.3-78.6	[17]
3	soybean oil	deoxygenation by hydrotreating	NiMoS_x	batch reactor, 673 K, 92 bar H₂	n-C13-C18 (green diesel)	60.3	[12]
			CoMoS_x	673 K, 92 bar H₂		45.5
			Ni	673 K, 92 bar H₂		51.0
			Pd	673 K, 92 bar H₂		39.0
4	palm oil	hydrothermal deoxygenation	PtRe/C	batch reactor, 558 K, 10 bar H₂	n-C15-C18 (green diesel)	10.1-72.0	[22]
5	palm oil	hydroisomerization/cracking of the pre-deoxygenated palm oil	Pt/Bulk-BEA	fixed bed reactor, 503 K, 20 bar H₂	n- and iso-C8-C16 (bio-jet fuel)	49.9	[13]
			Pt/Nano-BEA	508 K, 20 bar H₂		55.8
			Pt/Bulk-MFI	503 K, 20 bar H₂		38.8
			Pt/Nano-MFI	513 K, 20 bar H₂		44.5
6	palm oil	one-pot hydrocracking	Ni/NH₄-BEA	batch reactor 633 K, 30 bar H₂	C9-C21 (bio-jet fuel)	24.9	[38]
			Ni/H-BEA			26.1
			Ni/NH₄-MFI			21.0
			Ni/H-FAU			20.3
7	castor oil	one-pot hydrocracking	Pt/SAPO-11	fixed bed reactor, 673 K, 40 bar H₂	n- and iso-C8-C16 (bio-jet fuel)	49.9	[39]
			Pt-La/SAPO-11			58.2
			Pt-Ni/SAPO-11			50.0
			Pt-Zn/SAPO-11			47.9
8	jatropha oil	one-pot hydrocracking	Pt/SAPO-11	fixed bed reactor, 613 K, 30 bar H₂	n- and iso-C14-C18 (bio-jet fuel)	60.7	[40]
	jatropha oil	one-pot hydrocracking	Pt/SAPO-11 mixed with γ-Al₂O₃		n- and iso-C14-C18 (bio-jet fuel)	63.5
9	stearic acid	ketonization	TiO₂	fixed bed reactor 653 K, 1 bar He	C35 fatty ketone (lube oil precursor)	88.2	[50]
	oleic acid					70.6
	linoleic acid					44.4
10	palm oil	oligomerization at 573 K followed by deoxygenation via hydrotreating	Pt-MoO_x/TiO₂	batch reactor 593 K, 50 bar H₂	branched C30-54 (lube oil)	16.5	[52]
	soybean oil					32.6
	linseed oil					56.2

Table 1 Summary of the catalytic conversion of triglycerides and related model compounds into products associated with diesel, jet fuel, and lube base oil.

Entry	Feed	Reaction	Catalyst	Reaction condition	Target product	Yield (%)	Ref.
1	soybean oil	deoxygenation by hydrotreating	Pt/γ- and θ-Al₂O₃ with varying pore sizes	fixed bed reactor, 633 K, 20 bar H₂	n-C13-C18 (green diesel)	44.3-74.9	[15]
2	palm oil	deoxygenation by hydrotreating	Pt/mesopor. γ-Al₂O₃	fixed bed reactor, 653 K, 40 bar H₂	n-C15-C18 (green diesel)	73.3-78.6	[17]
3	soybean oil	deoxygenation by hydrotreating	NiMoS_x	batch reactor, 673 K, 92 bar H₂	n-C13-C18 (green diesel)	60.3	[12]
			CoMoS_x	673 K, 92 bar H₂		45.5
			Ni	673 K, 92 bar H₂		51.0
			Pd	673 K, 92 bar H₂		39.0
4	palm oil	hydrothermal deoxygenation	PtRe/C	batch reactor, 558 K, 10 bar H₂	n-C15-C18 (green diesel)	10.1-72.0	[22]
5	palm oil	hydroisomerization/cracking of the pre-deoxygenated palm oil	Pt/Bulk-BEA	fixed bed reactor, 503 K, 20 bar H₂	n- and iso-C8-C16 (bio-jet fuel)	49.9	[13]
			Pt/Nano-BEA	508 K, 20 bar H₂		55.8
			Pt/Bulk-MFI	503 K, 20 bar H₂		38.8
			Pt/Nano-MFI	513 K, 20 bar H₂		44.5
6	palm oil	one-pot hydrocracking	Ni/NH₄-BEA	batch reactor 633 K, 30 bar H₂	C9-C21 (bio-jet fuel)	24.9	[38]
			Ni/H-BEA			26.1
			Ni/NH₄-MFI			21.0
			Ni/H-FAU			20.3
7	castor oil	one-pot hydrocracking	Pt/SAPO-11	fixed bed reactor, 673 K, 40 bar H₂	n- and iso-C8-C16 (bio-jet fuel)	49.9	[39]
			Pt-La/SAPO-11			58.2
			Pt-Ni/SAPO-11			50.0
			Pt-Zn/SAPO-11			47.9
8	jatropha oil	one-pot hydrocracking	Pt/SAPO-11	fixed bed reactor, 613 K, 30 bar H₂	n- and iso-C14-C18 (bio-jet fuel)	60.7	[40]
	jatropha oil	one-pot hydrocracking	Pt/SAPO-11 mixed with γ-Al₂O₃		n- and iso-C14-C18 (bio-jet fuel)	63.5
9	stearic acid	ketonization	TiO₂	fixed bed reactor 653 K, 1 bar He	C35 fatty ketone (lube oil precursor)	88.2	[50]
	oleic acid					70.6
	linoleic acid					44.4
10	palm oil	oligomerization at 573 K followed by deoxygenation via hydrotreating	Pt-MoO_x/TiO₂	batch reactor 593 K, 50 bar H₂	branched C30-54 (lube oil)	16.5	[52]
	soybean oil					32.6
	linseed oil					56.2

Fig. 2. Deoxygenation of soybean oil using Pt/Al2O3 catalysts. Diesel-range paraffin yield plotted as a function of the pore size of the catalysts (a) and distributions of liquid products (b). Reaction conditions: 633 K, 20 bar, WHSV = 1 h-1, and H2/soybean oil = 50. (c) Third-order power law deactivation fitting of the normalized rate (defined as the ratio of the diesel-range paraffin yield at time (t) and that at t = 0) as a function of reaction time (reaction conditions: 653 K, 20 bar, WHSV = 1 h-1, and H2/soybean oil = 20). Reproduced with permission from Ref. [15]. Copyright 2022, Elsevier.

Fig. 3. Two-step hydroconversion of palm oil into bio-jet fuel. (a) Hydrocarbon distributions in the green diesel obtained from the deoxygenation of palm oil via hydrotreating over Pt/γ-Al2O3 (reaction conditions: 633 K, 2.0 MPa, and WHSV = 1.0 h-1). Product distributions obtained after subsequent hydrocracking of the green diesel under optimized conditions over Pt/Bulk-BEA (b) (reaction conditions: 503 K, 2.0 MPa, and WHSV = 2.0 h-1), Pt/Nano-BEA (c) (reaction conditions: 508 K, 2.0 MPa, and WHSV = 2.0 h-1), Pt/Bulk-MFI (d) (reaction conditions: 503 K, 2.0 MPa, and WHSV = 2.0 h-1), and Pt/Nano-MFI (e) (reaction conditions: 513 K, 2.0 MPa, and WHSV = 2.0 h-1). (f) Correlation between the maximum C8-C16 yields (filled symbols) and iso/n-paraffin ratios (open symbols) versus diffusion kinetics (D/L2) of 2,2,4-trimethylpentane in hydrocracking catalysts. Reproduced with permission from Ref. [13]. Copyright 2017, American Chemical Society.

Fig. 4. Ketonization of fatty acids. (a) Proposed reaction mechanism for ketonization. Product yields as a function of time-on-stream (stacked area graph) in the ketonization of stearic acid (including no C=C bond) (b), oleic acid (including one C=C bond) (c), and linoleic acid (including two C=C bonds) (d) (reaction conditions: 653 K, 1 bar, and WHSV: 0.5 g gcat-1 h-1). (e) Decomposition of unsaturated fatty ketone into methyl ketone and olefin via McLafferty rearrangement. Reproduced with permission from Ref. [50]. Copyright 2018, American Chemical Society.

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