生物油脂催化重构与加氢精制集成工艺制取生物喷气燃料技术研究

摘要/Abstract

摘要： 生物喷气燃料作为未来有望替代石油基喷气燃料的可再生资源，其对航空业的重要性日益凸显。针对现有较为成熟的HEFA工艺存在着原料预处理复杂、喷气燃料组分单一等系列问题，基于生物油脂分子结构特征，在专用分子筛催化剂上，对脂肪酸甲酯分子结构进行催化重构，使其部分转化为芳烃和环烷烃，以催化重构指数（CRI）作为衡量氢转移与环化反应发生的程度，进行小型探索试验研究，取得富含芳烃和环烷烃的中间馏分，对此中间馏分进行加氢精制，可获得富含环状分子结构的生物喷气燃料。结果表明：脂肪酸甲酯经催化重构与加氢精制集成工艺加工后，可制取生物喷气燃料，收率约为70.78%，其喷气燃料净热值可达45 MJ/kg，冰点低于-65 ℃，其密度与石油基喷气燃料接近，具有良好工业应用前景。

关键词: 生物油脂, 脂肪酸甲酯, 催化重构, 加氢精制, 生物喷气燃料

Abstract: As a renewable resource that is expected to completely replace petroleum based jet fuel in the future, bio-jet fuel has become increasingly important to the aviation industry. At present, the production of jet fuel from bio-oil via HEFA technology has achieved industrial application. Aiming at the problems of complex pretreatment of raw materials and single component of jet fuel in the existing HEFA technology, based on the molecular structure characteristics of bio-oils, the molecular structure of fatty acid methyl ester was catalytically reformed on a special molecular sieve catalyst, so that it was partially converted into aromatics and naphthenes. The catalytic reforming index (CRI) was used to measure the degree of hydrogen transfer and cyclization reactions. Small scall experiments were carried out to obtain the middle distillate rich in aromatics and naphthenes. The middle distillate was hydrotreated to obtain the bio-kerosene rich in aromatics and naphthenes. The experimental results showed that after the fatty acid methyl ester was treated by the integrated technology of catalytic reforming and hydrofining, the yield of bio-jet fuel was more than 65%, the yield of light olefins was about 10%, the net calorific value of bio-jet fuel was 45 MJ/kg, the freezing point was less than -65 ℃, and its density was close to that of petroleum based jet fuel.

Key words: bio-oils, fatty acid methyl esters, catalytic reforming, hydrofining, bio-jet fuel

许友好王启飞汪燮卿鞠雪艳邬仕平陶志平刘鸿洲. 生物油脂催化重构与加氢精制集成工艺制取生物喷气燃料技术研究[J]. 石油炼制与化工, 2026, 57(5): 1-9.

参考文献

[1]Peters M A, Alves C T, Onwudili J A.A review of current and emerging production technologies for biomass-derived sustainable aviation fuels: Energies[J]. 2023: 16.[J].Energies, 2023, 16(16):/-/ [2]王圣, 杨鹤, 闫瑞, 等.生物航煤生产技术的发展现状[J].生物工程学报, 2022, 38(07):2477-2488 [3]孙克乙, 陈伟, 管育林, 等.生物航煤产业发展现状与建议[J].油气与新能源, 2024, 36(04):49-56 [4]周建华, 葛泮珠, 黄爱斌, 等.油脂加氢生产生物喷气燃料技术及工业应用[J].石油炼制与化工, 2023, 54(12):1-5 [5]Zahid I, Nazir M H, Chiang K, et al.Current outlook on sustainable feedstocks and processes for sustainable aviation fuel production[J]. Current Opinion in Green and Sustainable Chemistry, 2024, 49:100959.[J].Current Opinion in Green and Sustainable Chemistry, 2024, 49(/):/-/ [6]聂红, 习远兵, 葛泮珠, 等.可持续航空燃料生产路线与展望——以中石化石科院为例[J].化工进展, 2025, 44(05):2529-2534 [7]Long F, Liu W, Jiang X, et al.State-of-the-art technologies for biofuel production from triglycerides: a review[J]. Renewable and Sustainable Energy Reviews, 2021, 148:111269.[J].Renewable and Sustainable Energy Reviews, 2021, 148(/):/-/ [8]聂红, 孟祥堃, 张哲民, 等.适应多种原料的生物航煤生产技术的开发[J].中国科学:化学, 2014, 44(01):46-54 [9]Stummann M Z, H?j M, Hansen A B, et al.Deactivation of a CoMo catalyst during catalytic hydropyrolysis of biomassPart 1. Product distribution and composition[J].Energy & Fuels, 2019, 33(12):12374-12386 [10]Nejadmoghadam E, Achour A, ?hrman O, et al.Understanding catalyst deactivation in an industrial green hydrotreater and its correlation with catalyst composition[J]. Fuel Processing Technology, 2025, 276:108260.[J].Fuel Processing Technology, 2025, 276(/):/-/ [11]Laurent E, Delmon B.Influence of water in the deactivation of a sulfided nimoγ-al2o3 catalyst during hydrodeoxygenation[J].Journal of Catalysis, 1994, 146(1):281-291 [12]Shahinuzzaman M, Yaakob Z, Ahmed Y.Non-sulphide zeolite catalyst for bio-jet-fuel conversion[J]. Renewable and Sustainable Energy Reviews, 2017, 77:1375-1384.[J].Renewable and Sustainable Energy Reviews, 2017, 77(/):1375-1384 [13]Cordero-Lanzac T, Palos R, Hita I, et al.Revealing the pathways of catalyst deactivation by coke during the hydrodeoxygenation of raw bio-oil[J]. Applied Catalysis B: Environmental, 2018, 239:513-524.[J].Applied Catalysis B: Environmental, 2018, 239(/):513-524 [14]田胜龙, 强倩, 杨华美, 等.过渡金属硫化物催化木质素定向合成航空煤油范围环烷烃和芳烃[J].中国科学:化学, 2025, 55(01):3-17 [15]Balster L M, Corporan E, DeWitt M J, et al.Development of an advanced,thermally stable,coal-based jet fuel[J].Fuel Processing Technology, 2008, 89(4):364-378 [16]Munzar J D, Akih-Kumgeh B, Denman B M, et al.An experimental and reduced modeling study of the laminar flame speed of jet fuel surrogate components[J]. Fuel, 2013, 113:586-597.[J].Fuel, 2013, 113(/):586-597 [17]Andrésen J M, Strohm J J, Sun L, et al.Relationship between the formation of aromatic compounds and solid deposition during thermal degradation of jet fuels in the pyrolytic regime[J].Energy & Fuels, 2001, 15(3):714-723 [18]Zhang X, Lei H, Zhu L, et al.Development of a catalytically green route from diverse lignocellulosic biomasses to high-density cycloalkanes for jet fuels[J].Catalysis Science & Technology, 2016, 6(12):4210-4220 [19]Graham J L, Striebich R C, Myers K J, et al.Swelling of nitrile rubber by selected aromatics blended in a synthetic jet fuel[J].Energy & Fuels, 2006, 20(2):759-765 [20]Liu G, Yan B, Chen G.Technical review on jet fuel production[J]. Renewable and Sustainable Energy Reviews, 2013, 25:59-70.[J].Renewable and Sustainable Energy Reviews, 2013, 25(/):59-70 [21]Yang J, Xin Z, He Q S, et al.An overview on performance characteristics of bio-jet fuels[J]. Fuel, 2019, 237:916-936.[J].Fuel, 2019, 237(/):916-936 [22]Chen D, Tracy N I, Crunkleton D W, et al.Comparison of canola oil conversion over MFI,BEA,and FAU[J].Applied Catalysis A: General, 2010, 384(1):206-212 [23]Twaiq F A, Zabidi N A M, Mohamed A R, et al.Catalytic conversion of palm oil over mesoporous aluminosilicate MCM-41 for the production of liquid hydrocarbon fuels[J].Fuel Processing Technology, 2003, 84(1):105-120 [24]Ooi Y, Zakaria R, Mohamed A R, et al.Catalytic cracking of used palm oil and palm oil fatty acids mixture for the production of liquid fuel:? kinetic modeling[J].Energy & Fuels, 2004, 18(5):1555-1561 [25]Pacheco J G A, Padilha J F, Santos B L, et al.Hydrogen-free deoxygenation of oleic acid on acidic and basic ZSM-5 and Y-zeolites: products for biofuel and reaction pathways[J]. Catalysis Today, 2025, 445:115094.[J].Catalysis Today, 2025, 445(/):/-/ [26]Pinho A D R, de Almeida M B B, Mendes F L, et al.Co-processing raw bio-oil and gasoil in an FCC unit[J]. Fuel Processing Technology, 2015, 131:159-166.[J].Fuel Processing Technology, 2015, 131(/):159-166 [27]Padilha J F, Frety R, Santos A P, et al.Deoxygenation of oleic acid methyl ester in FCC process conditions over protonated and sodium exchanged y and zsm-5 zeolites[J].Waste and Biomass Valorization, 2022, 13(1):185-194 [28]Chen X, An Z, Wang Y, et al.Green btx production from methyl oleate over hierarchical HZSM-5 zeolites prepared by NaOH treatment[J]. Fuel, 2021, 290:119798.[J].Fuel, 2021, 290(/):/-/ [29]Li G, Mao Q, Lu J, et al.Synergistic catalysis effect of micro-mesoscopic channel for enhanced methyl oleate catalytic cracking to BTX: a molecular simulation study[J]. Chemical Engineering Science, 2024, 295:120183.[J].Chemical Engineering Science, 2024, 295(/):/-/ [30]许友好著.催化裂化化学与工艺[M].催化裂化化学与工艺, 2013. [31]许友好, 王启飞, 汪燮卿, 等.一种制备生物航空煤油组分的方法: 中国, CN202510464593.5[P]. 2025-04-14 [32]许友好, 王启飞, 汪燮卿, 等.一种利用生物质原料催化制取生物航空煤油组分的方法: 中国, CN202510464594.X [P]. 2025-04-14 [33]汪燮卿, 王启飞, 刘鸿洲, 等.一种利用生物质原料催化生产生物航空煤油组分的方法: 中国, CN202510464599.2 [P]. 2025-04-14 [34]许友好, 王启飞, 汪燮卿, 等.一种制备生物航空燃料的方法: 中国, CN202511414153.5 [P]. 2025-09-29 [35]王启飞, 许友好, 刘凌涛, 等.一种生产生物航空燃料的方法: 中国, CN202511414453.3 [P]. 2025-09-29 [36]田华.脂肪酸酯的催化裂化研究[D].中国石油大学, 2008. [37]王萌.基于非食用油脂的生物液体燃料制备工艺研究[D].北京化工大学, 2016. [38]田华, 李春义, 杨朝合, 等.动物油在不同催化剂上的转化[J].催化学报, 2008, 01(/):69-74 [39]蔡文静, 闫昊, 冯翔, 等.不同碳链长度脂肪酸甲酯的催化裂化产物分布规律[J].化工学报, 2017, 68(05):2057-2065 [40]Vonghia E, Boocock D G B, Konar S K, et al.Pathways for the deoxygenation of triglycerides to aliphatic hydrocarbons over activated alumina[J].Energy & Fuels, 1995, 9(6):1090-1096 [41]Leung A, Boocock D G B, Konar S K.Pathway for the catalytic conversion of carboxylic acids to hydrocarbons over activated alumina[J].Energy & Fuels, 1995, 9(5):913-920 [42]Wang Y, Zeng Y, Fan L, et al.Pyrolysis of different types of waste cooking oil in the presence/absence hzsm-5 catalyst: influence of feedstock characteristics on aromatic formation[J]. Fuel, 2023, 351:128937.[J].Fuel, 2023, 351(/):/-/ [43]李瑞英.脂肪酸酯在ZSM-5分子筛上催化裂解机理的密度泛函理论研究[D].中国石油大学(华东), 2020. [44]Li R, Yan H, Dang Y, et al.Deoxygenation mechanism of methyl butyrate on HZSM-5: a density functional theory study[J]. Molecular Catalysis, 2019, 479:110588.[J].Molecular Catalysis, 2019, 479(/):/-/ [45]Laurent E, Delmon B.Study of the hydrodeoxygenation of carbonyl,carboxylic and guaiacyl groups over sulfided comoγ-al2o3 and nimoγ-al2o3 catalysts: iCatalytic reaction schemes[J].Applied Catalysis a: General, 1994, 109(1):77-96 [46]Laurent E, Delmon B.Study of the hydrodeoxygenation of carbonyl,carboxylic and guaiacyl groups over sulfided comoγ-al2o3 and nimoγ-al2o3 catalyst: iiInfluence of water,ammonia and hydrogen sulfide[J].Applied Catalysis a: General, 1994, 109(1):97-115 [47]DeWitt M J, West Z, Zabarnick S, et al.Effect of aromatics on the thermal-oxidative stability of synthetic paraffinic kerosene[J].Energy & Fuels, 2014, 28(6):3696-3703 [48]Sharma S, Singh P, Bhardwaj C, et al.Investigations on combustion and emissions characteristics of aromatic fuel blends in a distributed combustor[J].Energy & Fuels, 2021, 35(4):3150-3163 [49]Cheng F, Brewer C E.Producing jet fuel from biomass lignin: potential pathways to alkyl-benzenes and cycloalkanes[J]. Renewable and Sustainable Energy Reviews, 2017, 72:673-722.[J].Renewable and Sustainable Energy Reviews, 2017, 72(/):673-722 [50]范曦, 申海平, 侯焕娣, 等.芳烃催化加氢反应机理的研究进展[J].化工进展, 2019, 38(S1):133-138