A perspective on catalytic conversion of glycerol to olefins

Biomass and Bioenergy

Volumn 55, Issue , 2013, Pages 370-385

  Zakaria, Zaki Y ^a   Amin, Nor Aishah Saidina ^a   Linnekoski, Juha ^b  

^a UNIVERSITI TEKNOLOGI MALAYSIA   (Malaysia)

^b VTT TECHNICAL RESEARCH CENTRE OF FINLAND   (Finland)

Author keywords

Catalytic glycerol conversion; Glycerol to olefins; Hydrocarbons; Propane 1,2,3 triol; ZSM 5 zeolite

Indexed keywords

BIODIESEL PRODUCTION; CATALYTIC CONVERSION; ENVIRONMENTAL-FRIENDLY TECHNOLOGY; ETHANOL CONVERSION; GLYCEROL CONVERSIONS; PROPANE-1,2,3-TRIOL; RENEWABLE RESOURCE; ZSM-5 ZEOLITES;

ALCOHOL FUELS; ENVIRONMENTAL TECHNOLOGY; ETHANOL; GLYCEROL; HYDROCARBONS; INDICATORS (CHEMICAL); METHANOL; SUSTAINABLE DEVELOPMENT;

OLEFINS;

ALCOHOL; BIOFUEL; CATALYSIS; OXYGENATION; REACTION KINETICS; RENEWABLE RESOURCE;

EID: 84879417656     PISSN: 09619534     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.biombioe.2013.02.014     Document Type: Review

References (121)

1. Pagliaro M., Rossi M. The future of glycerol new usages of a versatile raw material 2008, RSC Green Chemistry Book Series, UK.
2. Zakaria Z.Y., Linnekoski J., Amin N.A.S. Catalyst screening for conversion of glycerol to light olefins. Chem Eng J 2012, 207-208:803-813.
3. Pessoa M.N., Danielle C.D.S., José B.D. Process to transform glycerol and/or biomass into products of greater aggregate value 2009 Jun 18, WO/2009/073938.
4. Corma A., Huber G.W., Sauvanaud L., O'Connor P. Biomass to chemicals: catalytic conversion of glycerol/water mixtures into acrolein, reaction network. J Catal 2008, 257(1):163-171.
5. Murata K., Takahara I., Inaba M. Propane formation by aqueous-phase reforming of glycerol over Pt/H-ZSM5 catalysts. React Kinet Catal Lett 2008, 93(1):59-66.
6. Wolfson A., Dlugy C., Shotland Y. Glycerol as a green solvent for high product yields and selectivities. Environ Chem Lett 2007, 5(2):67-71.
7. Brady J.E. General chemistry: principles and structure 1990, John Wiley & Sons, New York. 5th ed.
8. Perry R.H., Green D. Perry's chemical engineers' handbook 2007, McGraw-Hill, Singapore. 6th ed.
9. Pathak K., Reddy K.M., Bakhshi N.N., Dalai A.K. Catalytic conversion of glycerol to value added liquid products. Appl Catal A 2010, 372(2):224-238.
10. Mohammad Fauzi A.H., Amin N.A.S. An overview of ionic liquids as solvents in biodiesel synthesis. Renew Sust Energ Rev 2012, 16(8):5770-5786.
11. Huber G.W., Corma A. Synergies between bio- and oil refineries for the production of fuels from biomass. Angew Chem Int Ed 2007, 46(38):7184-7201.
12. Knothe G., Gerpen J.V. The biodiesel handbook 2010, AOCS Press, Champaign, IL. 2nd ed.
13. McCoy M. Wacker holds own in chemical world. Chem Eng News 2007, 83(19):15-17.
14. Claude S. Research of new outlets for glycerol - recent developments in France. Eur J Lipid Sci Technol 1999, 101(3):101-104.
15. Hoang T., Danuthai T., Lobban L.L., Resasco D.E., Mallinson R.G. Catalytic conversion of glycerol to fuel 2007.
16. Guzman Dd Oleochemicals rebound but outlook cautious for 2011 19 January 2011, [accessed 08.11.12.]. http://www.icis.com/Articles/2011/01/24/9427112/oleochemicals-rebound-but-outlook-cautious-for-2011.html.
17. Zheng S., Kates M., Dubé M.A., McLean D.D. Acid-catalyzed production of biodiesel from waste frying oil. Biomass Bioenerg 2006, 30(3):267-272.
18. Bender M. Economic feasibility review for community-scale farmer cooperatives for biodiesel. Bioresour Technol 1999, 70(1):81-87.
19. da Silva G.P., Mack M., Contiero J. Glycerol: a promising and abundant carbon source for industrial microbiology. Biotechnol Adv 2009, 27(1):30-39.
20. Yang G., Tian J., Li J. Fermentation of 1,3-propanediol by a lactate deficient mutant of Klebsiella oxytoca under microaerobic conditions. Appl Microbiol Biotechnol 2007, 73(5):1017-1024.
21. Zhou C.-H., Beltramini J.N., Fan Y.-X., Lu G.Q. Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals. Chem Soc Rev 2008, 37(3):527-549.
22. Gätgens C., Degner Ursula, Bringer-Meyer Stephanie, Herrmann U. Biotransformation of glycerol to dihydroxyacetone by recombinant Gluconobacter oxydans DSM 2343. Appl Microbiol Biotechnol 2007, 76(3):553-559.
23. Song H., Lee S.Y. Production of succinic acid by bacterial fermentation. Enzyme Microb Technol 2006, 39(3):352-361.
24. Imandi S.B., Bandaru V.R., Somalanka S.R., Garapati H.R. Optimization of medium constituents for the production of citric acid from byproduct glycerol using Doehlert experimental design. Enzyme Microb Technol 2007, 40(5):1367-1372.
25. Solaiman Daniel K.Y., Ashby Richard D., Foglia Thomas A., Marmer W.N. Conversion of agricultural feedstock and coproducts into poly(hydroxyalkanoates). Appl Microbiol Biotechnol 2006, 71(6):783-789.
26. Prati L., Porta F. Oxidation of alcohols and sugars using Au/C catalysts: part 1. Alcohols. Appl Catal A 2005, 291(1-2):199-203.
27. Dimitratos N., Porta F., Prati L. Au, Pd (mono and bimetallic) catalysts supported on graphite using the immobilisation method: synthesis and catalytic testing for liquid phase oxidation of glycerol. Appl Catal A 2005, 291(1-2):210-214.
28. Schlaf M., Ghosh P., Fagan P.J., Hauptman E., Bullock R.M. Metal-catalyzed selective deoxygenation of diols to alcohols. Angew Chem Int Ed 2001, 40(20):3887-3890.
29. Montassier C., Giraud D., Barbier J. Polyol conversion by liquid phase heterogeneous catalysis over metals. Stud surf sci catal 1988, 165-170. Elsevier, Amsterdam. M. Guisnet, J. Barrault, C. Bouchoule, D. Duprez, C. Montassier, G. Pérot (Eds.).
30. Nimlos M.R., Blanksby S.J., Qian X., Himmel M.E., Johnson D.K. Mechanisms of glycerol dehydration. JPhys Chem A 2006, 110(18):6145-6156.
31. Ramayya S., Brittain A., DeAlmeida C., Mok W., Antal M.J. Acid-catalysed dehydration of alcohols in supercritical water. Fuel 1987, 66(10):1364-1371.
32. Melero J.A., van Grieken R., Morales G., Paniagua M. Acidic mesoporous silica for the acetylation of glycerol: synthesis of bioadditives to petrol fuel. Energy Fuels 2007, 21(3):1782-1791.
33. Plasman V., Caulier T., Boulos N. Polyglycerol esters demonstrate superior antifogging properties for films. Plast Addit Compd 2005, 7(2):30-33.
34. 2 in the presence of zeolites and ion exchange resins. Catal Lett 1998, 56(4):245-247.
35. Stein Y.S., Antal M.J., Jones M. A study of the gas-phase pyrolysis of glycerol. J Anal Appl Pyrolysis 1983, 4(4):283-296.
36. Xu X., Matsumura Y., Stenberg J., Antal M.J. Carbon-catalyzed gasification of organic feedstocks in supercritical water†. Ind Eng Chem Res 1996, 35(8):2522-2530.
37. Wang K., Hawley M.C., DeAthos S.J. Conversion of glycerol to 1,3-propanediol via selective dehydroxylation. Ind Eng Chem Res 2003, 42(13):2913-2923.
38. Soares R.R., Simonetti D.A., Dumesic J.A. Glycerol as a source for fuels and chemicals by low-temperature catalytic processing. Angew Chem Int Ed 2006, 45(24):3982-3985.
39. Jalinski T.J. Bio-diesel fuel and manufacture of same 2006 Aug 10, WO2006084048 A1.
40. Puche J.D. Procedure to obtain biodiesel fuel with improves properties at low temperature 2003 Sep 11, US 0167681 A1.
41. Karinen R.S., Krause A.O.I. New biocomponents from glycerol. Appl Catal A 2006, 306(0):128-133.
42. Gupta V.P., Berwyn P. Glycerine ditertiary butyl ether preparation 1995 Dec 19, US 5476971.
43. Noureddini H. System and process for producing biodiesel fuel with reduced viscosity and a cloud point below thirty-two (32) degrees fahrenheit 2001 Jan 16, US 6174501.
44. Bradin Biodiesel Fuel 1996 Nov 26, US 5578090.
45. Moss G.P., PAS S., Tavernier D. Glossary of class names of organic compounds and reactive intermediates based on structure. Pure Appl Chem 1995, 67(8-9):1307-1375.
46. Morrison R.T., Boyd R.N. Organic chemistry 1992, Prentice Hall, New York. 6th ed.
47. Wade L.G. Organic chemistry 2005, Prentice Hall, New Jersey. 6th ed.
48. Xieqing W., Chaogang X., Zaiting L., Genquan Z. Catalytic processes for light olefin production. Practical advances in petroleum processing 2006, 149-168. Springer, New York. C.S. Hsu, P.R. Robinson (Eds.).
49. Li X., Shen B., Guo Q., Gao J. Effects of large pore zeolite additions in the catalytic pyrolysis catalyst on the light olefins production. Catal Today 2007, 125(3-4):270-277.
50. Bellussi G., Pollesel P. Industrial applications of zeolite catalysis: production and uses of light olefins. Stud surf sci catal 2005, 1201-1212. Elsevier. J. Čejka, N. Žilková, P. Nachtigall (Eds.).
51. Kadolph S.J., Langford A.L. Textiles 2001, Prentice Hall, New Jersey. 9th ed.
52. Yaw C.S. Make hay while the sun shines 2005, Titan Chemicals Corporation Bhd: TA Securities Holdings Berhad.
53. 2009 world light olefins analysis 2008, ChemGuide, Available from:, [accessed 02.11.12.]. http://chemguide.asia/news/2008/11/26/2009-world.html.
54. Lyondell Basell to shutter Terni, Italy PP facility 2010, PlasticsToday, Available from:, [accessed 02.11.12.]. http://www.plasticstoday.com/articles/lyondellbasell-shutter-terni-italy-pp-facility.
55. Hopkins T.E., Wagener K.B. Bio-olefins via condensation metathesis chemistry. J Mol Catal A: Chem 2004, 213(1):93-99.
56. Wurzel T. Olefins from syngas - potential for bio-based applications 2010, New Biofuels 2010. Berlin, Germany.
57. Hoang T.Q., Zhu X., Danuthai T., Lobban L.L., Resasco D.E., Mallinson R.G. Conversion of glycerol to alkyl-aromatics over zeolites. Energy Fuels 2010, 24(7):3804-3809.
58. Stöcker M. Methanol-to-hydrocarbons: catalytic materials and their behavior. Micropor Mesopor Mater 1999, 29(1-2):3-48.
59. Takahara I., Saito M., Inaba M., Murata K. Dehydration of ethanol into ethylene over solid acid catalysts. Catal Lett 2005, 105(3):249-252.
60. Phillips C.B., Datta R. Production of ethylene from hydrous ethanol on H-ZSM-5 under mild conditions. Ind Eng Chem Res 1997, 36(11):4466-4475.
61. Aguayo A.T., Gayubo A.G., Atutxa A., Olazar M., Bilbao J. Catalyst deactivation by coke in the transformation of aqueous ethanol into hydrocarbons. kinetic modeling and acidity deterioration of the catalyst. Ind Eng Chem Res 2002, 41(17):4216-4224.
62. de las Pozas C., Lopez-Cordero R., Gonzalez-Morales J.A., Travieso N., Roque-Malherbe R. Effect of pore diameter and acid strength in ethanol dehydration on molecular sieves. J Mol Catal 1993, 83(1-2):145-156.
63. Inaba M., Murata K., Saito M., Takahara I. Ethanol conversion to aromatic hydrocarbons over several zeolite catalysts. React Kinet Catal Lett 2006, 88(1):135-141.
64. Ivanova S., Vanhaecke E., Dreibine L., Louis B., Pham C., Pham-Huu C. Binderless HZSM-5 coating on β-SiC for different alcohols dehydration. Appl Catal A 2009, 359(1-2):151-157.
65. Haw J.F., Song W., Marcus D.M., Nicholas J.B. The mechanism of methanol to hydrocarbon catalysis. Acc Chem Res 2003, 36(5):317-326.
66. Meisel S.L. Fifty years of research in catalysis. Stud surf sci catal 1988, 17-37. Elsevier, New York. D.M. Bibby, C.D. Chang, R.F. Howe, S. Yurchak (Eds.).
67. Matar S., Hatch L.F. Chemistry of petrochemical processes 2001, Gulf Professional Publishing, Houston Texas. 2nd ed.
68. Chang C.D., Hellring S.D., Pearson J.A. On the existence and role of free radicals in methanol conversion to hydrocarbons over HZSM-5: I. Inhibition by NO. J Catal 1989, 115(1):282-285.
69. Froment G.F., Dehertog W.J.H., Marchi A.J. Zeolite catalysis in the conversion of methanol into olefins. Catalysis 1992, 1-64. The Royal Society of Chemistry, London. J.J. Spivey (Ed.).
70. Hutchings G.J., Themistocleous T., Copperthwaite R.G. Methanol conversion to hydrocarbons using modified clinoptilolite catalysts: investigation of catalyst lifetime and reactivation. Appl Catal 1988, 43(1):133-140.
71. Mole T. Methane conversion via methanol. Stud surf sci catal 1988, 145-156. Elsevier, New York. D.M. Bibby, C.D. Chang, R.F. Howe, S. Yurchak (Eds.).
72. Dahl I.M., Kolboe S., Rønning P.O. Methanol conversion to hydrocarbons over ZSM-5. Use of isotopes for mechanism studies. Stud surf sci catal 1995, 176-177. Elsevier, New York. H.G. Karge, J. Weitkamp (Eds.).
73. Dahl I.M., Kolboe S. On the reaction mechanism for propene formation in the MTO reaction over SAPO-34. Catal Lett 1993, 20(3-4):329-336.
74. Cormerais F.X., Perot G., Guisnet M. Selectivity of the dimethylether to hydrocarbons conversion on various zeolites. Zeolites 1981, 1(3):141-144.
75. Gayubo A.G., Aguayo A.T., Atutxa A., Aguado R., Bilbao J. Transformation of oxygenate components of biomass pyrolysis oil on a HZSM-5 zeolite. I. Alcohols and phenols. Ind Eng Chem Res 2004, 43(11):2610-2618.
76. Tavares F., Marreiros A. Biomass: new feedstock for the plastic industry 2009, Available from:, [accessed 03.11.12.]. http://biomassmagazine.com/articles/3195/biomass-new-feedstock-for-the-plastic-industry.
77. Zaidi H.A., Pant K.K. Catalytic conversion of methanol to gasoline range hydrocarbons. Catal Today 2004, 96(3):155-160.
78. Chang C.D., Silvestri A.J. The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts. J Catal 1977, 47(2):249-259.
79. Givens E.N., Plank C.J., Rosinski E.J. Manufacture of light olefins 1978 Mar 14, US 4079096.
80. Wunder F.A., Leupold E.I. A selective pathway from methanol to ethylene and propene. Angew Chem Int Ed 1980, 19(2):126-127.
81. Marchi A.J., Froment G.F. Catalytic conversion of methanol to light alkenes on SAPO molecular sieves. Appl Catal 1991, 71(1):139-152.
82. Zaidi H.A., Pant K.K. Catalytic activity of copper oxide impregnated HZSM-5 in methanol conversion to liquid hydrocarbons. Can J Chem Eng 2005, 83(6):970-977.
83. Patcas F.C. The methanol-to-olefins conversion over zeolite-coated ceramic foams. J Catal 2005, 231(1):194-200.
84. Ivanova S., Louis B., Madani B., Tessonnier J.P., Ledoux M.J., Pham-Huu C. ZSM-5 coatings on β-SiC monoliths: possible new structured catalyst for the methanol-to-olefins process. J Phys Chem C 2007, 111(11):4368-4374.
85. Park J.W., Kim S.J., Seo M., Kim S.Y., Sugi Y., Seo G. Product selectivity and catalytic deactivation of MOR zeolites with different acid site densities in methanol-to-olefin (MTO) reactions. Appl Catal A 2008, 349(1-2):76-85.
86. Sano T., Suzuki K., Okado H., Fujisawa K., Kawamura K., Ikai S., et al. High steam stability of ZSM-5 type zeolites containing alkaline earth metals. Stud surf sci catal 1987, 613-624. Elsevier, Amsterdam. B. Delmon, G.F. Froment (Eds.).
87. Corma A., Huber G.W., Sauvanaud L., O'Connor P. Processing biomass-derived oxygenates in the oil refinery: catalytic cracking (FCC) reaction pathways and role of catalyst. JCatal 2007, 247(2):307-327.
88. Chen N.Y., Lucki S.J. Nonregenerative catalytic cracking of gas oils. Ind Eng Chem Process Des Dev 1986, 25(3):814-820.
89. Zhang H., Cheng Y.T., Vispute T.P., Xiao R., Huber G.W. Catalytic conversion of biomass-derived feedstocks into olefins and aromatics with ZSM-5: the hydrogen to carbon effective ratio. Energy Environ Sci 2011, 4(6):2297-2307.
90. Simonetti DA, Kunkes EL, Rass-Hansen J, Soares RR, Dumesic JA. Production of liquid fuels via catalytic glycerol processing coupled with Fischer-Tropsch synthesis. In: Catalytic biofuel and chemical refining: the preliminary program for 2007 annual meeting; 2007.
91. Melero J.A., Vicente G., Morales G., Paniagua M., Moreno J.M., Roldán R., et al. Acid-catalyzed etherification of bio-glycerol and isobutylene over sulfonic mesostructured silicas. Appl Catal A 2008, 346(1-2):44-51.
92. Lu J., Zhao Z., Xu C., Duan A., Zhang P. CrHZSM-5 zeolites - highly efficient catalysts for catalytic cracking of isobutane to produce light olefins. Catal Lett 2006, 109(1):65-70.
93. Hardy S. Olefins market report 2009, Available from:, [accessed 01.11.12.]. http://www.chemsystems.com/about/cs/news/items/PPE%20PCMD%20Olefins%202009.cfm.
94. Yoshimura Y., Kijima N., Hayakawa T., Murataa K., Suzuki K., Mizukami F., et al. Catalytic cracking of naphtha to light olefins. Catal Surv Jpn 2000, 4(2):157-167.
95. Ren T., Patel M., Blok K. Olefins from conventional and heavy feedstocks: energy use in steam cracking and alternative processes. Energy 2006, 31(4):425-451.
96. Dillon T., London R.Y. Crude oil falls help to push spot naphtha lower 2010, ICIS Chemical Business, p. 24.
97. UOP/HYDRO MTO process - methanol to olefins conversion 2004, UOP, Process Technology and Equipment.
98. Soundararajan S., Dalai A.K., Berruti F. Modeling of methanol to olefins (MTO) process in a circulating fluidized bed reactor. Fuel 2001, 80(8):1187-1197.
99. Business area biomass chemicals - ethylene from ethanol 2010, Chematur EEG, Chematur Engineering AB.
100. Ethanol prices and pricing information 2011, ICIS, Available from:, [accessed 10.04.11.]. http://www.icis.com/v2/chemicals/9075312/ethanol/pricing.html.
101. Methanol price 2012, Methanex, Available from:, [accessed 01.07.12.]. http://www.methanex.com/products/methanolprice.html.
102. Reisch M. Dow issues methane challenge - call for proposals targets direct conversion of methane into feedstocks. Chem Eng News 2007, 85(12):12.
103. Podkolzin S.G., Stangland E.E., Jones M.E., Peringer E., Lercher J.A. Methyl chloride production from methane over lanthanum-based catalysts. J Am Chem Soc 2007, 129(9):2569-2576.
104. Global K. Natural gas prices set for gains 2010, Available from:, [accessed 04.11.12.]. http://www.thestreet.com/story/10851133/1/natural-gas-prices-set-for-gains.html%3fcm_ven%3dGOOGLEN.
105. Assis C. Natural gas prices hold steady after EIA data 2010, Available from:, [accessed 05.11.12.]. http://www.marketwatch.com/story/natural-gas-prices-hold-steady-after-eia-data-2010-09-02.
106. Burridge E. Looming excess methanol could marginalize China production 2010, ICIS Chemical Business, p. 17.
107. Plotkin J.S., Coleman H.J. PERP program - cole to olefins 2007, Nexant Chem System.
108. Maher K. Chinese slowdown idles U.S 2012, Coal Mines, Available from:, [accessed 17.11.12.]. http://online.wsj.com/article/SB10000872396390443890304578010472748244256.html.
109. Indonesian coal reference price 2012, COALspot.com, Available from:, [accessed 17.11.12.]. http://www.coalspot.com/.
110. Lerner I. Coal-to-olefins technology leaps forward in China - China's Coal Plan 2010, [accessed 02.11.12.]. http://www.icis.com/Articles/2010/02/22/9336493/coal-to-olefins-technology-leaps-forward-in-china.html.
111. Seng S. Asia glycerine prices poised to rise on tight supply in Q1 2010, Available from:, [accessed 02.11.12.]. http://www.icis.com/Articles/2010/01/29/9329895/asia-glycerine-prices-poised-to-rise-on-tight-supply-in-q1.html.
112. ICIS pricing - 2nd May 2012-glycerine (US Gulf) 2012, ICIS, Available from:, [accessed 03.11.12.]. http://www.icispricing.com/il_shared/Samples/SubPage170.asp.
113. Scott S.A., Davey M.P., Dennis J.S., Horst I., Howe C.J., Lea-Smith D.J., et al. Biodiesel from algae: challenges and prospects. Curr Opin Biotechnol 2010, 21(3):277-286.
114. Campbell P.K., Beer T., Batten D. Life cycle assessment of biodiesel production from microalgae in ponds. Bioresour Technol 2011, 102(1):50-56.
115. Demirbas A., Fatih Demirbas M. Importance of algae oil as a source of biodiesel. Energy Convers Manage 2011, 52(1):163-170.
116. Doan T.T.Y., Sivaloganathan B., Obbard J.P. Screening of marine microalgae for biodiesel feedstock. Biomass Bioenerg 2011, 35(7):2534-2544.
117. Tan J., Seng L.P. Exxon explores algae biofuels as alternative energy 2010, Available from:, [accessed 07.06.12.]. http://www.reuters.com/article/2010/06/07/us-exxonmobil-petchem-biofuels-aogc-idUSTRE6562XK20100607.
118. Kumar Tiwari A., Kumar A., Raheman H. Biodiesel production from jatropha oil (Jatropha curcas) with high free fatty acids: an optimized process. Biomass Bioenerg 2007, 31(8):569-575.
119. Chongkhong S., Tongurai C., Chetpattananondh P., Bunyakan C. Biodiesel production by esterification of palm fatty acid distillate. Biomass Bioenerg 2007, 31(8):563-568.
120. Hughes K. Honeywell's UOP wins third license for breakthrough methanol-to-olefins technology 2012, Available from:, [accessed 16.11.12.]. http://www.equities.com/news/headline-story%3fdt%3d2012-11-13%26val%3d703341%26cat%3dmaterial.
121. Thompson J.C., He B.B. Characterization of crude glycerol from biodiesel production from multiple feedstocks. Appl Eng Agric 2006, 22(2):261-265.