Hydrodeoxygenation and coupling of aqueous phenolics over bifunctional zeolite-supported metal catalysts

Hong, Do‐Young; Miller, Stephen J.; Agrawal, Pradeep; Jones, Christopher W.

doi:10.1039/b918209h

Cited by 250 publications

(218 citation statements)

References 29 publications

Supporting

Mentioning

207

Contrasting

Unclassified

Order By: Relevance

“…Meanwhile, alkylation and etherification take place to form bicyclic compounds. Hong et al also reported similar reaction pathways of phenol to bicyclics over Pt/HY catalyst [27]. Studies on both aqueous-phase and vapor-phase HDO of phenol indicated that non-sulfide catalysts favor HYD route to saturate the aromatic ring.…”

Section: Propertymentioning

confidence: 71%

An Overview on Catalytic Hydrodeoxygenation of Pyrolysis Oil and Its Model Compounds

et al. 2017

View full text Add to dashboard Cite

Abstract:Pyrolysis is considered the most promising way to convert biomass to fuels. Upgrading biomass pyrolysis oil is essential to produce high quality hydrocarbon fuels. Upgrading technologies have been developed for decades, and this review focuses on the hydrodeoxygenation (HDO). In order to declare the need for upgrading, properties of pyrolysis oil are firstly analyzed, and potential analysis methods including some novel methods are proposed. The high oxygen content of bio-oil leads to its undesirable properties, such as chemical instability and a strong tendency to re-polymerize. Acidity, low heating value, high viscosity and water content are not conductive to making bio-oils useful as fuels. Therefore, fast pyrolysis oils should be refined before producing deoxygenated products. After the analysis of pyrolysis oil, the HDO process is reviewed in detail. The HDO of model compounds including phenolics monomers, dimers, furans, carboxylic acids and carbohydrates is summarized to obtain sufficient information in understanding HDO reaction networks and mechanisms. Meanwhile, investigations of model compounds also make sense for screening and designing HDO catalysts. Then, we review the HDO of actual pyrolysis oil with different methods including two-stage treatment, co-feeding solvents and in-situ hydrogenation. The relative merits of each method are also expounded. Finally, HDO catalysts are reviewed in order of time. After the summarization of petroleum derived sulfured catalysts and noble metal catalysts, transitional metal carbide, nitride and phosphide materials are summarized as the new trend for their low cost and high stability. After major progress is reviewed, main problems are summarized and possible solutions are raised.

show abstract

Section: Propertymentioning

confidence: 71%

An Overview on Catalytic Hydrodeoxygenation of Pyrolysis Oil and Its Model Compounds

et al. 2017

View full text Add to dashboard Cite

show abstract

“…have differing rates, and different catalysts will promote DDO or HYD as a primary reaction depending on the nature of the metal and the support [10]. It has been observed that noble metals favor HYD whereas sulfided catalysts preferentially undergo DDO reactions [23], [24]. In addition to facilitating multiple reactions, an ideal bifunctional catalyst should still be able to exhibit a high turnover frequency (TOF) and the capability to maintain this activity after repeated trials.…”

Section: Bifunctional Catalysismentioning

confidence: 99%

Hydropyrolysis of Lignin Using Pd/HZSM-5

Jan

Marchand

Anjos³

et al. 2015

Energy Fuels

105

View full text Add to dashboard Cite

Hydropyrolysis of Lignin using Pd/HZSM-5 Oliver D. Jan Chair of the Supervisory Committee:Dr. Fernando Resende School of Environmental and Forest SciencesThe aim of this work was to study the formation of cycloalkanes from hydropyrolysis of lignin with HZSM-5 and Pd/HZSM-5 catalysts. We observed that palladium supported on HZSM-5 catalyzed hydrogenation and deoxygenation reactions that converted phenolic compounds into aromatic hydrocarbons and cycloalkanes. This study analyzed the effect of the catalyst-to-lignin ratio, H 2 partial pressure, and temperature on the yields of hydrocarbons with HZSM-5 and Pd/HZSM-5. Pd/HZSM-5 produced 44% more aromatic hydrocarbons than HZSM-5 at a catalyst-to-lignin ratio of 20:1, 650ºC, and a constant H 2 partial pressure of 1.7 MPa. The presence of palladium led to significant difference in yields only at 1.7 MPa H 2 partial pressure.In both the in-situ and ex-situ experiments conducted, hydropyrolysis temperature played a substantial role in the equilibrium conversion of hydrogenation reactions that led to cycloalkanes directly from lignin.iv Dedication This thesis is dedicated to my family for all their love and support v Acknowledgements

show abstract

“…Hydroalkylation involves ring-coupling of phenol with cyclohexanol or cyclohexene on Brønsted acidic materials, resulting in the formation of bi-cyclic or tri-cyclic oxygenates, that can then undergo subsequent hydrodeoxygenation [30][31][32]. While most of the work on hydroalkylation of biomassderived phenolics has been performed in the aqueous liquid phase [30,32], ring coupling has been observed in the vapor phase at temperatures similar to the operating temperature of fixed bed reactor #2 [33]. Accordingly, hydroalkylation will be targeted in reactor #2.…”

Section: Reaction Chemistry and Catalyst Optionsmentioning

confidence: 99%

“…This approach combining upstream ketonization with downstream aldol condensation and hydrogenation-dehydration provides a promising route for converting carboxylic acids into diesel/jet fuel range products [22,[26][27][28]. Hydroalkylation involves ring-coupling of phenol with cyclohexanol or cyclohexene on Brønsted acidic materials, resulting in the formation of bi-cyclic or tri-cyclic oxygenates, that can then undergo subsequent hydrodeoxygenation [30][31][32]. While most of the work on hydroalkylation of biomassderived phenolics has been performed in the aqueous liquid phase [30,32], ring coupling has been observed in the vapor phase at temperatures similar to the operating temperature of fixed bed reactor #2 [33].…”

Section: Reaction Chemistry and Catalyst Optionsmentioning

confidence: 99%

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

103

View full text Add to dashboard Cite

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.

show abstract

Hydrodeoxygenation and coupling of aqueous phenolics over bifunctional zeolite-supported metal catalysts

Abstract: Pt supported on HY zeolite is successfully used as a bifunctional catalyst for phenol hydrodeoxygenation in a fixed-bed configuration at elevated hydrogen pressures, leading to hydrogenation-hydrogenolysis ring-coupling reactions producing hydrocarbons, some with enhanced molecular weight.

Cited by 250 publications

References 29 publications

An Overview on Catalytic Hydrodeoxygenation of Pyrolysis Oil and Its Model Compounds

An Overview on Catalytic Hydrodeoxygenation of Pyrolysis Oil and Its Model Compounds

Hydropyrolysis of Lignin Using Pd/HZSM-5

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

Contact Info

Product

Resources

About