CO-PROCESSING TECHNOLOGY OF CATALYTIC CRACKING OF HEAVY BIO-OIL AND VGO FOR PRODUCING GASOLINE WITH HIGH OCTANE NUMBER

Abstract

Abstract:

Heavy bio-oil, the by-product from synthesis of biodiesel using two-step process with solid acid and alkali catalysts, was characterized by infrared spectroscopy and high-resolution mass spectrometry. The heavy bio-oil is mainly composed of high boiling point alcohols, ketones, esters and ethers with oxygen atoms number ranging from 1 to 12. The oxygenated compounds in the heavy bio-oil are converted to hydrocarbon by dehydration, decarbonylation and decarboxylation reactions. Compared with the single VGO feed, more aromatics are obtained by co-processing the mixed raw material of bio-oil (20%) and VGO, resulting in higher octane number of gasoline, but a little more dry gas and coke yields. The experiments indicate that the heavy bio-oil can be a promising alternative supplemental raw material for catalytic cracking unit, and the co-processing technology can convert the by-product to hydrocarbon products with high value and expand the source of catalytic cracking feedstock with lower cost.

Key words: heavy bio-oil, oxygenated compounds, catalytic cracking, high octane number gasoline

References

[1] De Miguel Mercader F, Groeneveld M J, Kersten S R A, et al. Production of advanced biofuels: Co-processing of upgraded pyrolysis oil in standard refinery units[J]. Applied Catalysis B: Environmental, 2010,96(1-2):57-66. [2] Thegarid N, Fogassy G, Schuurman Y, et al. Second-generation biofuels by co-processing catalytic pyrolysis oil in FCC units[J]. Applied Catalysis B: Environmental, 2014,145(1):161-166. [3] Cerny R, Kubu M, Kubicka D. The effect of oxygenates structure on their deoxygenation over USY zeolite[J]. Catalysis Today, 2013,204(1):46-53. [4] Rezaei P S, Shafaghat H, Daud W M A W. Production of green aromatics and olefins by catalytic cracking of oxygenate compounds derived from biomass pyrolysis: A review[J]. Applied Catalysis, A: General, 2014,469(3):490-511. [5] Sfetsas T, Michailof C, Lappas A, et al. Qualitative and quantitative analysis of pyrolysis oil by gas chromatography with flame ionization detection and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry[J]. Journal of Chromatography A, 2011,1218(21):3317-3325. [6] Liu Y, Shi Q, Zhang Y, et al. Characterization of Red Pine Pyrolysis Bio-oil by Gas Chromatography-Mass Spectrometry and Negative-Ion Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry[J]. Energy & Fuels, 2012,26(7):4532-4539. [7] Fogassy G, Thegarid N, Toussaint G, et al. Biomass derived feedstock co-processing with vacuum gas oil for second-generation fuel production in FCC units[J]. Applied Catalysis B: Environmental, 2010,96(3-4):476-485. [8] Corma A, Huber G W, Sauvanaud L, et al. Processing biomass-derived oxygenates in the oil refinery: Catalytic cracking (FCC) reaction pathways and role of catalyst[J]. Journal of Catalysis, 2007,247(2):307-327. [9] 山红红, 刘熠斌, 陈小博, 等. 废弃油脂与减压蜡油共催化裂化技术开发及工业试验[J]. 石油学报(石油加工), 2015,31(2):460-467. [10] 杨翠定，顾侃英，吴文辉. 石油化工分析方法[M]. 北京: 科学出版社，1990.438-463 [11] Gayubo A G, Aguayo A T, Atutxa A, et al. Undesired components in the transformation of biomass pyrolysis oil into hydrocarbons on an HZSM-5 zeolite catalyst[J]. Journal of Chemical Technology & Biotechnology, 2005,80(11):1244-1251. [12] Tian H, Li C, Yang C, et al. Alternative processing technology for converting vegetable oils and animal fats to clean fuels and light olefins[J]. Chinese Journal of Chemical Engineering, 2008,16(3):394-400. [13] Idem R O, Katikaneni S P R, Bakhshi N N. Catalytic conversion of canola oil to fuels and chemicals: roles of catalyst acidity, basicity and shape selectivity on product distribution[J]. Fuel Processing Technology, 1997,51(1-2):101-125. [14] Dupain X, Costa D J, Schaverien C J, et al. Cracking of a rapeseed vegetable oil under realistic FCC conditions[J]. Applied Catalysis, B: Environmental, 2007,72(1-2):44-61. [15] Adjaye J D, Bakhshi N N. Catalytic conversion of a biomass-derived oil to fuels and chemicals I: Model compound studies and reaction pathways[J]. Biomass and Bioenergy, 1995,8(3):131-149. [16] 高永灿, 张久顺. 催化裂化过程中的热裂化与催化裂化[J]. 化工学报, 2002,53(5):469-472. [17] Wielers A F H, Vaarkamp M, Post M F M. Relation between properties and performance of zeolites in paraffin cracking[J]. Journal of Catalysis, 1991,127(1):51~66. [18] Horne P A, Williams P T. Reaction of oxygenated biomass pyrolysis model compounds over a ZSM-5 catalyst[J]. Renewable Energy, 1996,7(2):131-144.