Upgrading of derived pyrolysis vapors for the production of biofuels from corncobs
Liaoyuan Mao, Yanxin Li, Z. Conrad Zhang()
State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
A bubbling fluidized bed pyrolyzer was integrated with an in-situ honeycomb as a catalytic upgrading zone for the conversion of biomass to liquid fuels. In the upgrading zone, zeolite coated ceramic honeycomb (ZCCH) catalysts consisting of ZSM-5 (Si/Al=25) were stacked and N2 or recycled non-condensable gas was used as a carrier gas. Ground corncob particles were fast pyrolyzed in the bubbling bed using fine sand particles as a heat carrier and the resulting pyrolysis vapors were passed on-line over the catalytic upgrading zone. The influence of carrier gas, temperature, and weight hourly space velocity (WHSV) of catalyst on the oil product properties, distribution and mass balance were studied. Using ZCCH effectively increased the hydrocarbon yield and the heating value of the dry oil, especially in the presence of the recycled noncondensable gas. Even a low usage of zeolite catalyst at WSHV of 180 h−1 was effective in upgrading the pyrolysis oil and other light olefins. The highest hydrocarbon (≥C2) and liquid aromatics yields reached to 14.23 and 4.17 wt-%, respectively. The undesirable products including light oxygenates, furans dramatically decreased in the presence of the ZCCH catalyst.
. [J]. Frontiers of Chemical Science and Engineering, 2018, 12(1): 50-58.
Liaoyuan Mao, Yanxin Li, Z. Conrad Zhang. Upgrading of derived pyrolysis vapors for the production of biofuels from corncobs. Front. Chem. Sci. Eng., 2018, 12(1): 50-58.
Huber G W, Chheda J N, Barrett C J, Dumesic J A. Production of liquid alkanes by aqueous-phase processing of biomass-derived carbohydrates. Science, 2005, 308(5727): 2075–2078 https://doi.org/10.1126/science.1111166
2
Cortright R D, Davda R R, Dumesic J A. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water. Nature, 2002, 418(6901): 964–967 https://doi.org/10.1038/nature01009
3
Huber G W, Dumesic J A. An overview of aqueous-phase catalytic processes for production of hydrogen and alkanes in a biorefinery. Catalysis Today, 2006, 111(1-2): 119–132 https://doi.org/10.1016/j.cattod.2005.10.010
4
Czernik S, Bridgwater A V. Overview of applications of biomass fast pyrolysis oil. Energy & Fuels, 2004, 18(2): 590–598 https://doi.org/10.1021/ef034067u
5
Huber G W, Ibarra S, Corma A. Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering. Chemical Reviews, 2006, 106(9): 4044–4098 https://doi.org/10.1021/cr068360d
6
Bridgwater A V, Bridge S A. A review of biomass pyrolysis and pyrolysis technologies. In: Bridgwater A V, Grassi G, eds. Biomass Pyrolysis Liquids Upgrading and Utilisation. London: Elsevier Applied Science, 1991, 11–92
7
Zhang H, Carlson T R, Xiao R, Huber G W. Catalytic fast pyrolysis of wood and alcohol mixtures in a fluidized bed reactor. Green Chemistry, 2012, 14(1): 98–110 https://doi.org/10.1039/C1GC15619E
8
Elliott D C, Beckman D, Bridgwater A V, Diebold J P, Gevert S B, Solantausta Y. Developments in direct thermochemical liquefaction of biomass: 1983‒1990. Energy & Fuels, 1991, 5(3): 399–410 https://doi.org/10.1021/ef00027a008
Valle B, Gayubo A G, Atutxa A, Alonso A, Bilbao J. Integration of thermal treatment and catalytic transformation for upgrading biomass pyrolysis oil. International Journal of Chemical Reactor Engineering, 2007, 5(1): 1–13 https://doi.org/10.2202/1542-6580.1559
11
Gayubo A G, Valle B, Aguayo A T, Olazar M, Bilbao J. Olefin production by catalytic transformation of crude bio-oil in a two-step process. Industrial & Engineering Chemistry Research, 2010, 49(1): 123–131 https://doi.org/10.1021/ie901204n
12
Srinivas S T, Dalai A K, Bakhshi N N. Thermal and catalytic upgrading of a biomass-derived oil in a dual reaction system. Chemical Engineering Journal, 2000, 78(2): 343–354
13
Valle B, Atutxa A, Aguayo A T, Olazar M, Gayubo A G. Effect of nickel incorporation on the acidity and stability of HZSM-5 zeolite in the MTO process. Catalysis Today, 2005, 106(1-4): 118–122 https://doi.org/10.1016/j.cattod.2005.07.132
Gayubo A G, Aguayo A T, Atutxa A, Aguado R, Olazar M, Bilbao J, Olazar M, Bilbao J. Transformation of oxygenate components of biomass pyrolysis oil on a HZSM-5 zeolite. II. Aldehydes, ketones, and acids. Industrial & Engineering Chemistry Research, 2004, 43(11): 2619–2626 https://doi.org/10.1021/ie030792g
16
Aho A, Kumar N, Eränen K, Salmi T, Hupa M, Murzin D Y. Catalytic pyrolysis of woody biomass in a fluidized bed reactor: Influence of the zeolite structure. Fuel, 2008, 87(12): 2493–2501 https://doi.org/10.1016/j.fuel.2008.02.015
17
Alaitz A, Roberto A, Ana G G, Martin O, Javier B. Kinetic description of the catalytic pyrolysis of biomass in a conical spouted bed reactor. Energy & Fuels, 2005, 19(3): 765–774 https://doi.org/10.1021/ef040070h
18
Lappas A A, Samolada M C, Iatridis D K, Voutetakis S S, Vasalos I A. Biomass pyrolysis in a circulating fluid bed reactor for the production of fuels and chemicals. Fuel, 2002, 81(16): 2087–2095 https://doi.org/10.1016/S0016-2361(02)00195-3
Renaud M, Grandmaison J L, Roy C, Kaliaguine S. Low-Pressure Upgrading of Vacuum-Pyrolysis Oils from Wood. Pyrolysis Oils from Biomass. Washington DC: ACS, 1988, 290–310
Chantal P D, Kaliaguin S, Grandmaison J L, Mahay A. Production of hydrocarbons from aspen poplar pyrolytic oils over H-ZSM5. Applied Catalysis, 1984, 10(3): 317–332 https://doi.org/10.1016/0166-9834(84)80127-X
23
Carlson T R, Cheng Y T, Jaea J, Huber G W. Production of green aromatics and olefins by catalytic fast pyrolysis of wood sawdust. Energy & Environmental Science, 2011, 4(1): 145–161 https://doi.org/10.1039/C0EE00341G
24
Williams P T, Horne P A. The influence of catalyst type on the composition of upgraded biomass pyrolysis oils. Journal of Analytical and Applied Pyrolysis, 1995, 31(2): 39–61 https://doi.org/10.1016/0165-2370(94)00847-T
25
Aho A, Kumar N, Eränen K, Hupa M, Salmi T, Murzin D Y. Zeolite-bentonite hybrid catalysts for the pyrolysis of woody biomass. Studies in Surface Science and Catalysis, 2008, 174(1): 1069–1074 https://doi.org/10.1016/S0167-2991(08)80071-7
26
Aho A, Kumar N, Lashkul A V, Eränen K, Murzin D. Catalytic upgrading of woody biomass derived pyrolysis vapours over iron modified zeolites in a dual-fluidized bed reactor. Fuel, 2010, 89(8): 1992–2000 https://doi.org/10.1016/j.fuel.2010.02.009
27
Adama J, Antonakoub E, Lappasb A, Stöckerc M, Nilsenc M H, Bouzgac A, Hustada J E, Øyed G. In situ catalytic upgrading of biomass derived fast pyrolysis vapours in a fixed bed reactor using mesoporous materials. Microporous and Mesoporous Materials, 2006, 96(1-3): 93–101 https://doi.org/10.1016/j.micromeso.2006.06.021
28
Zhang Q, Chang J, Wang T, Xu Y. Review of biomass pyrolysis oil properties and upgrading research. Energy Conversion and Management, 2007, 48(1): 87–92 https://doi.org/10.1016/j.enconman.2006.05.010
29
Diebold J P, Chum H L, Evans R J, Milne T A, Reed T B, Scahill J W. In: Klass D L. ed. Energy from Biomass and Wastes X. London: IGT Chicago and Elsevier Applied Sciences Publishers, 1987, 801
30
Diebold J, Scahill J. Biomass to gasoline: Upgrading pyrolysis vapors to aromatic gasoline with zeolites catalysis at atmospheric pressure. In: Soltes E J, Milne T A, eds. Pyrolysis Liquids from Biomass. Washington DC: ACS, 1988, 264–276
31
Diebold J P, Beckman D, Bridgwater A V, Elliott D C, Solantausta Y. IEA technoeconomic analysis of the thermochemical conversion of biomass to gasoline by the NREL process. In: Bridgwater A V, ed. Advances in Thermochemical Biomass Conversion. Berlin: Springer Netherlands, 1994, 1325–1342
32
Evans R, Milne T. Molecular-beam, mass spectrometric studies of wood vapor and model compounds over an HSZM-5 catalyst. In: Soltes E J, Milne T A, eds. Pyrolysis Liquids from Biomass. Washington DC: ACS, 1988, 311–327
Zhang Q, Chang J, Wang T, Xu Y. Review of biomass pyrolysis oil properties and upgrading research. Energy Conversion and Management, 2007, 48(1): 87–92 https://doi.org/10.1016/j.enconman.2006.05.010
35
Stefanidis S D, Kalogiannis K G, Iliopoulou E F, Lappas A A, Pilavachi P A. In-situ upgrading of biomass pyrolysis vapors: Catalyst screening on a fixed bed reactor. Bioresource Technology, 2011, 102(17): 8261–8267 https://doi.org/10.1016/j.biortech.2011.06.032
36
Cybulski A, Moulijn J. Monoliths in heterogeneous catalysis. Catalysis Reviews. Science and Engineering, 1994, 36(2): 179–270 https://doi.org/10.1080/01614949408013925
37
Evans R J, Milne T A. In: Soltes E J, Milne T A, eds. Pyrolysis Oils from Biomass, Producing, Analysing and Upgrading. ACS Symposium Series 376. Washington DC: American Chemical Society, 1988, 328–341
38
Huber G W, Iborra S, Corma A. Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering. Chemical Reviews, 2006, 106(9): 4044–4098 https://doi.org/10.1021/cr068360d
39
Kharas K C, Robota H J, Liu D J. Deactivation in Cu-ZSM-5 lean-burn catalysts. Applied Catalysis B: Environmental, 1993, 2(2-3): 225–237 https://doi.org/10.1016/0926-3373(93)80050-N
40
Vitolo S, Bresci B, Seggiani M, Gallo M G. Catalytic upgrading of pyrolytic oils over HZSM-5 zeolite: Behaviour of the catalyst when used in repeated upgrading-regenerating cycles. Fuel, 2001, 80(1): 17–26 https://doi.org/10.1016/S0016-2361(00)00063-6
41
Foster A J, Jae J, Cheng Y T, Huber G W, Lobo R F. Optimizing the aromatic yield and distribution from catalytic fast pyrolysis of biomass over ZSM-5. Applied Catalysis A, General, 2012, 423-424: 154–161 https://doi.org/10.1016/j.apcata.2012.02.030
42
Li J, Li X, Zhou G, Wang W, Wang C, Komarneni S, Wang Y. Catalytic fast pyrolysis of biomass with mesoporous ZSM-5 zeolites prepared by desilication with NaOH solutions. Applied Catalysis A, General, 2014, 470(2): 115–122
