Recent advances in heterogeneous catalysts for bio-oil upgrading via “ex situ catalytic fast pyrolysis”: catalyst development through the study of model compounds

Ruddy, Daniel A.; Schaidle, Joshua A.; Ferrell, Jack R.; Wang, Jun; Moëns, Luc; Hensley, Jesse E.

doi:10.1039/c3gc41354c

Cited by 443 publications

(431 citation statements)

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“…The chemical transformations targeted during ex situ catalytic fast pyrolysis are hydrogenation, deoxygenation, and C-C coupling [12]. Some examples of these reactions are shown in Table 4 (a more thorough description of these reactions can be found in [12]).…”

Section: Reaction Chemistry and Catalyst Optionsmentioning

confidence: 99%

“…Some examples of these reactions are shown in Table 4 (a more thorough description of these reactions can be found in [12]). The H/C molar ratio for raw pyrolysis bio-oil ranges from 0.9 to 1.5 [13][14][15], thus hydrogen incorporation is required to produce finished fuels similar to gasoline, diesel, and jet fuel (H/C molar ratio of 1.9-2.2).…”

Section: Reaction Chemistry and Catalyst Optionsmentioning

confidence: 99%

“…The lower operating pressure of the ex situ upgrading reactors, chosen to maintain the pyrolysis products in the vapor phase, will also limit the extent of hydrogenation, as compared to typical hydrotreating conditions (50-100 bar) [17,18]. Deoxygenation can be achieved through decarbonylation (removal of oxygen as CO), decarboxylation (removal of oxygen as CO 2 ), hydrodeoxygenation (encompassing both direct hydrogenolysis and hydrogenation-dehydration; removal of oxygen as H 2 O), and certain C-C coupling reactions (discussed below) [12,17,18]. Decarbonylation and decarboxylation proceed through cleavage of C-C bonds, thus reducing oxygen content at the expense of carbon efficiency, with decarboxylation being preferred as two oxygen atoms are removed per carbon atom.…”

Section: Reaction Chemistry and Catalyst Optionsmentioning

confidence: 99%

“…Research is ongoing to develop catalysts that can perform these transformations under the process conditions outlined in this study. Accordingly, a number of excellent reviews have been published in the last 3-4 years discussing potential catalysts for biomass pyrolysis vapor upgrading, highlighting the key advantages and disadvantages of the different materials, and identifying reaction mechanisms [12,17,18,48,49]. As the scope of this work is to evaluate a process design for ex situ catalytic fast pyrolysis incorporating hot gas filtration and fixed bed systems, a thorough discussion of catalyst types and functionalities is not included; however, a few catalyst types/formulations are highlighted as they are explicitly considered in the process design (Table 3).…”

Section: Reaction Chemistry and Catalyst Optionsmentioning

confidence: 99%

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Conceptual Process Design and Techno-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A Fixed Bed Reactor Implementation Scenario for Future Feasibility

Dutta

Schaidle

Humbird³

et al. 2015

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103

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Ex situ catalytic fast pyrolysis of biomass is a promising route for the production of fungible liquid biofuels. There is significant ongoing research on the design and development of catalysts for this process. However, there are a limited number of studies investigating process configurations and their effects on biorefinery economics. Herein we present a conceptual process design with techno-economic assessment; it includes the production of upgraded bio-oil via fixed bed ex situ catalytic fast pyrolysis followed by final hydroprocessing to hydrocarbon fuel blendstocks. This study builds upon previous work using fluidized bed systems, as detailed in a recent design report led by the National Renewable Energy Laboratory (NREL/ TP-5100-62455); overall yields are assumed to be similar, and are based on enabling future feasibility. Assuming similar yields provides a basis for easy comparison and for studying the impacts of areas of focus in this study, namely, fixed bed reactor configurations and their catalyst development requirements, and the impacts of an inline hot gas filter. A comparison with the fluidized bed system shows that there is potential for higher capital costs and lower catalyst costs in the fixed bed system, leading to comparable overall costs. The key catalyst requirement is to enable the effective transformation of highly oxygenated biomass into hydrocarbons products with properties suitable for blending into current fuels. Potential catalyst materials are discussed, along with their suitability for deoxygenation, hydrogenation and C-C coupling chemistry. This chemistry is necessary during pyrolysis vapor upgrading for improved bio-oil quality, which enables efficient downstream hydroprocessing; C-C coupling helps increase the proportion of diesel/jet fuel range product. One potential benefit of fixed bed upgrading over fluidized bed upgrading is catalyst flexibility, providing greater control over chemistry and product composition. Since this study is based on future projections, the impacts of uncertainties in the underlying assumptions are quantified via sensitivity analysis. This analysis indicates that catalyst researchers should prioritize by: carbon efficiency [ catalyst cost [ catalyst lifetime, after initially testing for basic operational feasibility.

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Section: Reaction Chemistry and Catalyst Optionsmentioning

confidence: 99%

Section: Reaction Chemistry and Catalyst Optionsmentioning

confidence: 99%

Section: Reaction Chemistry and Catalyst Optionsmentioning

confidence: 99%

Section: Reaction Chemistry and Catalyst Optionsmentioning

confidence: 99%

See 2 more Smart Citations

Conceptual Process Design and Techno-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A Fixed Bed Reactor Implementation Scenario for Future Feasibility

Dutta

Schaidle

Humbird³

et al. 2015

Top Catal

Self Cite

103

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“…The high oxygen content of bio-oil, usually 20 to 50 wt%, changes its physical and chemical properties which directly affect its combustion behavior (Ruddy et al, 2014).…”

Section: Introductionmentioning

confidence: 99%

Hydrodeoxygenation of furfuryl alcohol over Cu/MgAl and Cu/ZnAl catalysts derived from hydrotalcite-like precursors: A reaction for bio-oil upgrading

Pino¹,

Hincapié²,

López³

2017

ing.inv.

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The aqueous phase hydrodeoxygenation (HDO) of furfuryl alcohol over Cu/MgAl and Cu/ZnAl catalysts with different Mg/Al and Zn/ Al molar ratios, were investigated. Mg-Al and Zn-Al mixed oxides derived from hydrotalcites precursors were used as supports, which were impregnated with an aqueous solution of copper nitrate by incipient wetness impregnation. The HDO reaction was carried out in a typical batch reactor at 5 MPa of H 2 and 200 °C for 4 h. Among the catalysts studied, the Cu/MgAl-0.5 catalyst exhibited the higher furfuryl alcohol conversion (86 %) and yield of cyclopentanol (35 %), which is the reaction product with the highest hydrogencarbon (H/C) ratio. With the Cu/MgAl-3 catalyst a high cyclopentanone yield (67 %) was achieved. The results obtained, showed that copper supported on mixed oxides catalysts derived from hydrotalcite precursors are a promising alternative to improve the bio-oil quality.Keywords: Hydrotalcites, cyclopentanol, furfuryl alcohol, copper, bio-oil upgrading. RESUMENSe investigó la hidrodesoxigenación(HDO) del furfuril alcohol sobre catalizadores de Cu/MgAl y Cu/ZnAl con diferentes relaciones molares Mg/Al y Zn/Al. Óxidos mixtos de Mg-Al y Zn-Al derivados de precursores tipo hidrotalcitas se usaron como soporte, los cuales fueron impregnados con una solución acuosa de nitrato de cobre, mediante el método de impregnación húmeda. La reacción de hidrodesoxigenación (HDO) se realizó en un reactor tipo batch a 5 MPa de H 2 y 200 °C por 4 h. Entre los catalizadores estudiados, el catalizador de Cu/MgAl-0.5 exhibió la más alta conversión del furfuril alcohol (86 %) y rendimiento hacia ciclopentanol (35 %), el cual es el producto de reacción con mayor relación hidrógeno-carbono (H/C). Con el catalizador de Cu/MgAl-3 se logró un alto rendimiento hacia ciclopentanona (67 %). Los resultados obtenidos, mostraron que los catalizadores de óxidos mixtos derivados de precursores tipo hidrotalcitas son una alternativa prometedora para mejorar las características del bio-oil.Palabras clave: Hidrotalcitas, ciclopentanol, furfuril alcohol, cobre, mejora del bio-aceite.

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Valorization of Agricultural Byproducts Through Conversion to Biochar and Bio‐Oil

Guo

Xiao

Hong

2019

Byproducts From Agriculture and Fisheries

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Recent advances in heterogeneous catalysts for bio-oil upgrading via “ex situ catalytic fast pyrolysis”: catalyst development through the study of model compounds

Cited by 443 publications

References 256 publications

Conceptual Process Design and Techno-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A Fixed Bed Reactor Implementation Scenario for Future Feasibility

Conceptual Process Design and Techno-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A Fixed Bed Reactor Implementation Scenario for Future Feasibility

Hydrodeoxygenation of furfuryl alcohol over Cu/MgAl and Cu/ZnAl catalysts derived from hydrotalcite-like precursors: A reaction for bio-oil upgrading

Valorization of Agricultural Byproducts Through Conversion to Biochar and Bio‐Oil

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