Alternative Processing Technology for Converting Vegetable Oils and Animal Fats to Clean Fuels and Light Olefins

Abstract

Abstract: Since the production cost of biodiesel is now the main hurdle limiting their applicability in some areas, catalytic cracking reactions represent an alternative route to utilization of vegetable oils and animal fats. Hence, catalytic transformation of oils and fats was carried out in a laboratory-scale two-stage riser fluid catalytic cracking (TSRFCC) unit in this work. The results show that oils and fats can be used as FCC feed singly or co-feeding with vacuum gas oil (VGO), which can give high yield (by mass)of liquefied petroleum gas (LPG), C₂-C₄ olefins, for example 45% LPG, 47% C₂-C₄ olefins, and 77.6% total liquid yield produced with palm oil cracking. Co-feeding with VGO gives a high yield of LPG (39.1%) and propylene (18.1%). And oxygen element content is very low (about 0.5%) in liquid products, hence, oxygen is removed in the form of H₂O, CO and CO₂. At the same time, high concentration of aromatics (C₇-C₉ aromatics predominantly) in the gasoline fraction is obtained after TSRFCC reaction of palm oil, as a result of large amount of hydrogen-transfer, cyclization and aromatization reactions. Additionally, most of properties of produced gasoline and diesel oil fuel meet the requirements of national standards, containing little sulfur. So TSRFCC technology is thought to be an alternative processing technology leading to production of clean fuels and light olefins.

Key words: vegetable oil, animal fat, renewable resource, biodiesel, two-stage riser fluid catalytic cracking technology

摘要： Since the production cost of biodiesel is now the main hurdle limiting their applicability in some areas, catalytic cracking reactions represent an alternative route to utilization of vegetable oils and animal fats. Hence, catalytic transformation of oils and fats was carried out in a laboratory-scale two-stage riser fluid catalytic cracking (TSRFCC) unit in this work. The results show that oils and fats can be used as FCC feed singly or co-feeding with vacuum gas oil (VGO), which can give high yield (by mass)of liquefied petroleum gas (LPG), C₂-C₄ olefins, for example 45% LPG, 47% C₂-C₄ olefins, and 77.6% total liquid yield produced with palm oil cracking. Co-feeding with VGO gives a high yield of LPG (39.1%) and propylene (18.1%). And oxygen element content is very low (about 0.5%) in liquid products, hence, oxygen is removed in the form of H₂O, CO and CO₂. At the same time, high concentration of aromatics (C₇-C₉ aromatics predominantly) in the gasoline fraction is obtained after TSRFCC reaction of palm oil, as a result of large amount of hydrogen-transfer, cyclization and aromatization reactions. Additionally, most of properties of produced gasoline and diesel oil fuel meet the requirements of national standards, containing little sulfur. So TSRFCC technology is thought to be an alternative processing technology leading to production of clean fuels and light olefins.

关键词: vegetable oil, animal fat, renewable resource, biodiesel, two-stage riser fluid catalytic cracking technology

TIAN Hua, LI Chunyi, YANG Chaohe, SHAN Honghong. Alternative Processing Technology for Converting Vegetable Oils and Animal Fats to Clean Fuels and Light Olefins[J]. , 2008, 16(3): 394-400.

田华, 李春义, 杨朝合, 山红红. Alternative Processing Technology for Converting Vegetable Oils and Animal Fats to Clean Fuels and Light Olefins[J]. , 2008, 16(3): 394-400.

References

1 Dandik, L., Aksoy, H.A., Erdem-Senatalar, A., “Catalytic conversion of used oil to hydrocarbon fuels in a fractionating pyrolysis reactor”, Energy Fuels, 12, 1148-1152(1998).
2 Ma, F.R., Hanna, M.A., “Biodiesel production:A review”, Bioresource Technol., 70, 1-15(1999).
3 Idem, R.O., Katikaneni, S.P.R., Bakhshi, N.N., “Catalytic conversion of canola oi1 to fuels and chemicals:Roles of catalyst acidity, basicity and shape selectivity on product distribution”, Fuel Process. Technol., 51, 101-125(1997).
4 Deng, L., Nie, K.L., Wang, F., Tan, T.W., “Studies on production of biodiesel by esterification of fatty acids by a lipase preparation from Candida sp. 99-125”, Chin. J. Chem. Eng., 13, 529-534(2005).
5 Min, E.Z., Du, Z.X., Hu, J.B., “An exploratory study on developing biorefinery based on vegetable oils”, Science & Technology Review, 23(5), 15-17(2005).(in Chinese)
6 Kubiková, I., Snåre, M., Er nen, K., M ki-Arvela, P., Murzin, D.Y., “Hydrocarbons for diesel fuel via decarboxylation of vegetable oils”, Catal. Today, 106, 197-200(2005).
7 Demirba , A., “Biodiesel fuels from vegetable oils via catalytic and non-catalytic supercritical alcohol transesterifications and other methods:A survey”, Energy Convers. Manage., 44, 2093-2109(2003).
8 Maher, K.D., Bressler, D.C., “Pyrolysis of triglyceride materials for the production of renewable fuels and chemicals”, Bioresource Technol., 98, 2351-2368(2007).
9 Weisz, P.B., Haag, W.O., Rodewald, P.G., “Catalytic production of high-grade fuel(gasoline) from biomass compounds by shape selective catalysts”, Science, 206, 57-58(1979).
10 Katikaneni, S.P.R., Adjaye, J.D., Bakhshi, N.N., “Performance of aluminophosphate molecular sieve catalysts for the production of hydrocarbons from wood-derived and vegetable oils”, Energy Fuels, 9, 1065-1078(1995).
11 Tian, H., Li, C.Y., Yang, C.H., Shan, H.H., “Conversion of animal fat over various catalysts”, Chinese Journal of Catalysis, 29, 69-74(2008).(in Chinese)
12 Katikaneni, S.P.R., Adjaye, J.D., Idem, R.O., Bakhshi, N.N., “Performance studies of various cracking catalysts in the conversion of canola oil to fuels and chemicals in a fluidized-bed reactor”, J. Am. Oil Chem. Soc., 75, 381-391(1998).
13 Dupain, X., Costa, D.J., Schaverien, C.J., Makkee, M., Moulijn, J.A., “Cracking of a rapeseed vegetable oil under realistic FCC conditions”, Appl. Catal. B, 72, 44-61(2007).
14 Bhatia, S., Leng, C.T., Tamunaidu, P., “Modeling and simulation of transport riser reactor for catalytic cracking of palm oil for the production of biofuels”, Energy Fuels, 21, 3076-3083(2007).
15 Zhang, J.F., Shan, H.H., Li, Z., Niu, G.L., Sun, Y.D. “New development of FCC through two-staged riser in series I. The reactor of two-staged riser”, Acta Petrol. Eng. Sinica(Petrol. Process. Sect.), 16(5), 66-69(2000).(in Chinese)
16 Shan, H.H., Dong, H.J., Zhang, J.F., Niu, G.L., “Experimental study of two-stage riser FCC reactions”, Fuel, 80, 1179-1185(2001).
17 Yang, C.H., Shan, H.H., Zhang, J.F., “Two-stage riser FCC technologies”, Petroleum Refinery Engineering, 35(3), 28-33(2005).(in Chinese)
18 Li, C.Y., Yang, C.H., Shan, H.H., “Maximizing propylene yield by two-stage riser catalytic cracking of heavy oil”, Ind. Eng. Chem. Res., 46, 4914-4920(2007).
19 Tian, H., Li, C.Y., Yang, C.H., Sun, W., Shan, H.H., Zhang, J.F.,“Application of blending vegetable oils and animal fats in fluid catalytic cracking unit”, Petrochem. Technol. Appl., 25, 425-428(2007).(in Chinese)
20 Shan, H.H., “Fundamental Studies on the technology of fluid catalytic cracking with two-stage risers”, Ph. D. Thesis, China University of Petroleum, China(2004).(in Chinese)
21 Lima, D.G., Soares, V.C.D., Ribeiro, E.B., Carvalho, D.A., Cardoso, é.C.V., Rassi, F.C., Mundima, K.C., Rubima, J.C., Suarez, P.A.Z., “Diesel-like fuel obtained by pyrolysis of vegetable oils”, J. Anal. Appl. Pyrolysis, 71, 987-996(2004).
22 Wang, A.M., Zou, X.H., Li, X., “Comparative study of nutria, bullfrog and other animal fats”, Journal of Economic Animal,(2), 10-16(1996).(in Chinese)
23 Sun, W., Li, X.H., Chang, Z.M., Li, C.Y., “Application of catalyst LTB-2 for maximizing propylene production in two-stage riser FCC unit”, Petroleum Refinery Engineering, 36, 5-7(2006).(in Chinese)
24 Shan, H.H., Li, C.Y., Niu, G.L., Yang, C.H., Zhang, J.F., “Research progress in fluid catalytic cracking technology”, Journal of China University of Petroleum, 29, 135-150(2005).(in Chinese)
25 Xiang, Y.D., Zhang, J.L., Shan, J.W., Wang, L., “Optimizing the production of two-stage riser fluid catalytic cracking”, Petroleum Processing and Petrochemicals, 37, 16-19(2006).(in Chinese)
26 Twaiq, F.A., Zabidi, N.A.M., Bhatia, S., “Catalytic conversion of palm oil to hydrocarbons:Performance of various zeolite catalysts”, Ind. Eng. Chem. Res., 38, 3230-3237(1999).
27 Katikaneni, S.P.R., Adjaye, J.D., Idem, R.O., Bakhshi, N.N., “Catalytic conversion of Canola oil over potassium-impregnated HZSM-5 catalysts:C 2 -C 4 olefin production and model reaction studies”, Ind. Eng. Chem. Res., 35, 3332-3346(1996).
28 Yarlagadda, P.S., Hu, Y.L., Bakhshi, N.N., “Effect of hydrothermal treatment of HZSM-5 catalyst on its performance for the conversion of canola and mustard oils to hydrocarbons”, Ind. Eng. Chem. Prod. Res. Dev., 25, 251-257(1986).
29 Wang, F., Wang, W.C., Huang, S.P., Teng, J.W., Xie, Z.K., “Experiment and modeling of pure and binary adsorption of n-butane and butene-1 on ZSM-5 zeolites with different Si/Al ratios”, Chin. J. Chem. Eng., 15, 376-386(2007).
30 Ke, M., Wang, X.Q., Zhang, F.M., “Physicochemical features of phosphorousmodified ZSM-5 zeolite and its performance on catalytic pyrolysis to produce ethylene”, Chin. J. Chem. Eng., 11, 671-676(2003).
31 Kong, C.H., Xu, X.H., Separation and Structure Identification of Organic Compound, Chemical Industry Press, Beijing, 220(2003).(in Chinese)

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