Investigations of thermochemical upgrading of biomass and its model compounds: Opportunities for methane utilization

doi:10.1016/j.fuel.2019.03.015

Fuel

Volume 246, 15 June 2019, Pages 443-453

https://doi.org/10.1016/j.fuel.2019.03.015 Get rights and content

Abstract

Biomass utilization is an attractive option for production of fuels and chemicals in the wake of global concern over continuing use of fossil fuels. Biomass can be thermochemically upgraded via gasification, liquefaction or pyrolysis to obtain fuel and/or valuable chemicals. Overall, gasification occurs at high temperature and results in a predominantly gas product. Liquefaction requires relatively low temperature and quite high pressure, and gives a high-quality liquid product. Pyrolysis takes place at moderate temperatures and produces the crude bio-oil. However, the resulting bio-crude is highly oxygenated while containing multiple impurities and disadvantageous to be used as a fuel. Due to the complex and expensive reactor systems associated with liquefaction, pyrolysis is the preferred method for biomass conversion. Hydrotreating or catalytic cracking for the crude oil upgrading either requires large consumption of expensive hydrogen or suffers from low H/C ratios without H₂ supply. A novel process named methanolysis allows pyrolysis and catalytic conversion to occur simultaneously under a methane environment, which has shown promise. Due to the original complexity of biomass and the resulting bio-oil, biomass-derived model compounds are extensively employed to investigate the involved reaction mechanisms. This article reviews the current technologies and the progress regarding methane upgrading of biomass based on model compound studies. Through catalyst development, better understanding of methane upgrading mechanisms, and kinetics investigations, biomass valorization with methane could become a viable alternative to the formation of fuels and valuable chemicals widely practiced in industries nowadays.

Graphical abstract

Thermochemical upgrading of biomass with natural gas for the production of biofuels and valuable chemicals.

Introduction

With increasing concern regarding climate change, renewable energy sources are becoming increasingly attractive alternatives to traditional fossil fuels. Biomass has been gaining attraction lately due to its low cost, topographical independence and net carbon neutrality. Biomass is a low-cost carbon source referring to all biologically produced matter including, but not limited to, wood, algae and organic waste. It can be used for heating or electricity generation via direct combustion or converted into a liquid or gas fuel via thermochemical or biochemical transformation. Biological processes typically involve anaerobic bacterial digestion while thermochemical processes usually refer to decomposition at elevated temperature [1]. The resulting products from the thermochemical processes are highly oxygenated and require further upgrading before use as a fuel. Hydrodeoxygenation or hydrogen treatment is commonly employed to reduce the oxygen content and improve the quality under the facilitate of H₂ or H donors. These hydrogen sources are not naturally available, which makes these processes unpractical and uneconomical on a large scale. It is desirable to develop a process for the conversion of biomass to fuel grade bio-oil which can provide an economically and environmentally beneficial alternative to traditional fuels. This article will review the current thermal upgrading technologies and discuss an emerging technology being used for biomass conversion.

Section snippets

Current upgrading technologies

There are a wide range of processes for the upgrading of biomass, including biological and thermal processes. Biological processes tend to have high selectivity, but low yield and lengthy reaction time, while thermal processes tend to have very short reaction time with high yield and can be coupled with catalysts to obtain high selectivity and are thus most commonly used [1]. Gasification, liquefaction and pyrolysis are the main thermal processes for biomass upgrading. A general overview of

Methane activation

Methane is the principal constituent of natural gas, which is an abundant natural resource with a low price. Due to its chemical inertness and low volumetric energy density, natural gas is mainly used for residential heating and electricity generation, but not valuable for fuel transportation or chemical production applications. Despite of intensive studies concentrated on the utilization of natural gas for several decades, real breakthrough is still limited. Therefore, it is promising and

Model compounds investigation

Generally, biomass derived products consist of a plethora of constituents, and can be roughly defined as a mixture of carboxylic acids (acetic and propanoic acid), alcohols (methanol, ethylene glycol, ethanol), aldehydes (acetaldehyde, formaldehyde, ethanedial), esters (methyl formate, butyrolactone, angelica lactone), miscellaneous oxygenates (glycolaldehyde, acetol), ketones (acetone), furans (furfurol, furfural), sugars (1,6-anhydroglucose, acetol), along with some aromatic species (phenol,

Future direction

Biomass valorization with methane is a promising future direction. However, there are some challenges that needs to be addressed effectively. High affinity to form the char/coke or oligomers during the reaction is one of the limitations, which leads to low carbon utilization efficiency. Balancing the catalytic performance and coke/char resistance for stability enhancement would be a critical future work.

Another big challenge for methane utilization for biomass upgrading is methane activation at

Conclusion

Renewable biomass has attracted significant attention as a sustainable feedstock for production of value-added chemicals and fuels. The critical problems facing catalytic fast conversion of real biomass are low yield of desired products, significant coking, and limited recycling and recovery rate. Of the three common types of thermal upgrading processes for biomass, pyrolysis and liquefaction produce a higher yield of liquid bio-oil while gasification produces higher yields of gaseous products.

Acknowledgements

We gratefully acknowledge the financial support from Natural Sciences and Engineering Research Council of Canada (NSERC) Discovery Grant Program (RGPIN/04385-2014).

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Review articleInvestigations of thermochemical upgrading of biomass and its model compounds: Opportunities for methane utilization

Abstract

Graphical abstract

Introduction

Section snippets

Current upgrading technologies

Methane activation

Model compounds investigation

Future direction

Conclusion

Acknowledgements

Biomass Bioenergy

J Energy Chem

Fuel Process Technol

Renew Sustain Energy Rev

J Anal Appl Pyrol

Int J Hydrogen Energy

Bioresour Technol

Renew Energy

J Catal

Prog Polym Sci

Bioresour Technol

Energy

Energy

J Catal

Renew Sustain Energy Rev

Fuel Process Technol

Energy

Prog Energy Combust Sci

Org Geochem

Fuel Process Technol

J Catal

Catal Commun

Catal Today

Bioresour Technol

Appl Energy

Waste Manage

Bioresour Technol

Biomass Bioenergy

J Catal

J Catal

Appl Catal A

J Ind Eng Chem

Appl Catal B

Fuel

Chin J Catal

Int J Hydrogen Energy

Appl Catal A

J Mol Catal A:Chem

Biomass Bioenergy

Fuel

J Catal

Appl Catal A

Procedia Eng

Catalytic steam gasification of biomass: catalysts, thermodynamics and kinetics

Chem Rev

An overview of advances in biomass gasification

Energy Environ Sci

Catalytic conversion of biomass to monofunctional hydrocarbons and targeted liquid-fuel classes

Science

Catalytic conversion of glucose micropyrolysis vapors in methane-using isotope labeling to reveal reaction pathways

Energy Technol

Secondary reactions of tar during thermochemical biomass conversion

Direct liquefaction of biomass

Chem Eng Technol

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Trans ASAE

Review article
Investigations of thermochemical upgrading of biomass and its model compounds: Opportunities for methane utilization