A review on ex situ catalytic fast pyrolysis of biomass
Shaolong WAN1(), Yong WANG2
1. Center for Biomass Refining, School of Chemical, Biological and Materials Engineering, The University of Oklahoma, Norman, OK 73019, USA 2. Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA 99164, USA
Catalytic fast pyrolysis (CFP) is deemed as the most promising way to convert biomass to transportation fuels or value added chemicals. Most works in literature so far have focused on the in situ CFP where the catalysts are packed or co-fed with the feedstock in the pyrolysis reactor. However, the ex situ CFP with catalysts separated from the pyrolyzer has attracted more and more attentions due to its unique advantages of individually optimizing the pyrolysis conditions and catalyst performances. This review compares the differences between the in situ and ex situ CFP operation, and summarizes the development and progress of ex situ CFP applications, including the rationale and performances of different catalysts, and the choices of suitable ex situ reactor systems. Due to the complex composition of bio-oil, no single approach was believed to be able to solve the problems completely among all those existing technologies. With the increased understanding of catalyst performances and reaction process, the recent trend toward an integration of biomass or bio-oil fractionation with subsequent thermo/bio-chemical conversion routes is also discussed.
. [J]. Frontiers of Chemical Science and Engineering, 2014, 8(3): 280-294.
Shaolong WAN, Yong WANG. A review on ex situ catalytic fast pyrolysis of biomass. Front. Chem. Sci. Eng., 2014, 8(3): 280-294.
Continuous auger-reactor with separate catalyst auger-reactor
ZSM-5
500
5
50.1% (17 %)
The catalytic treatment reduced the oxygen content of the organic phase of bio-oils notably. More phenols and aromatics were produced in the in situ CFP, resulting in a better quality of bio-oil.
[27]
Fixed bed reactor with separate catalyst bed
Na-faujasite, H-faujasite, Na0.2H0.8-faujasite
500
1/10
46.3–55.0
The ex situ was superior to the in situ case (mixed mode) with regard to the degree of oxygen removal. Compared to two other catalysts, Na0.2H0.8-faujasite removes the most oxygen from bio-oil, reduces amount of acids and aldehydes/ketones.
[28]
Semi-batch fixed bed reactor with separate catalyst bed
ReUS-Y Red mud ZSM-5.
400
1/20
9.3
Two-step pyrolysis (ex situ) in the presence of ReUS-Y catalyst?showed better results of the bio-oil yield and quality, which decreased the formation of water soluble compounds and increased the amount of pyrolytic lignin compounds in bio-oil.
[29]
Fluidized bed reactor with catalyst bed in the freeboard
HZSM-5
500
1.05–1.14?h−1 (WHSV)a)
5.5
Mainly aromatic hydrocarbons were produced.
[50]
Fluidized bed reactor with catalyst bed in the freeboard
HZSM-5
550
~1.0?h−1
3.4–7.2
The catalyzed oils were markedly increased in single ring and PAH.
[51]
Batch stirred reactor with catalyst bed in top
HZSM-5 Hβ
400
1/10
10.4–13.4
The highest organic liquid phase yield was attained on H-ZSM-5 zeolite which is better than H-Beta
[52]
Continued
Fixed-bed reactor with separate catalyst bed
HZSM-5, Ga/HZSM-5, Hβ,
500
1/10
42.5–46.3 (5.4–10.0)
Ga/HZSM-5 exhibited the highest selectivity for aromatics while Hβ showed better capability for decomposing levoglucosan. Oxygenates are dominant probably due to a very low catalyst/biomass ratio.
The mesoporous MFI zeolite exhibited better activity in deoxygenation and aromatization. The incorporation of gallium into the mesoporous MFI zeolite increased both the organic fraction of the bio-oil and resistance to coke deposition.
[58]
Fluidized bed reactor with catalyst bed in the side stream
ZnO
400
4.9–5.1?h−1
50
The liquid yields were not substantially reduced. It had no effect on the water-insoluble fraction (lignin-derived), but decomposed the diethyl ether-insoluble fraction (water-soluble anhydrosugars and polysaccharides). The stability of the ZnO-treated oil was greatly improved.
[74]
Fix-bed reactor with separate catalyst bed
Na2CO3/Al2O3
500
0.5, 1, 2
9
Almost completely removed acids, but higher carbonyl components in bio-oil
[78]
Continuous entrained flow reactor with separate catalyst bed
Ru/TiO2
400
6.7–10?h−1
49.9 (25.3)
Significant conversion of light oxygenates to larger, less oxygenated, molecules. Bio-oil phenolics were also converted to less oxygenated phenolics with methoxy methyl groups transferred to the ring. The organic oil from the treated vapors has a lower initial viscosity with only a small increase upon accelerated aging compared to the untreated product oil, which has a dramatic increase in viscosity after aging.
[80]
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