Biomass has the potential to serve as a sustainable source of energy and organic carbon for our industrialized society. The focus of this Review is to present an overview of chemical catalytic transformations of biomass-derived oxygenated feedstocks (primarily sugars and sugar-alcohols) in the liquid phase to value-added chemicals and fuels, with specific examples emphasizing the development of catalytic processes based on an understanding of the fundamental reaction chemistry. The key reactions involved in the processing of biomass are hydrolysis, dehydration, isomerization, aldol condensation, reforming, hydrogenation, and oxidation. Further, it is discussed how ideas based on fundamental chemical and catalytic concepts lead to strategies for the control of reaction pathways and process conditions to produce H(2)/CO(2) or H(2)/CO gas mixtures by aqueous-phase reforming, to produce furan compounds by selective dehydration of carbohydrates, and to produce liquid alkanes by the combination of aldol condensation and dehydration/hydrogenation processes.

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Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals.

Hydrothermal technologies are broadly defined as chemical and physical transformations in high-temperature (200–600 °C), high-pressure (5–40 MPa) liquid or supercritical water. This thermochemical means of reforming biomass may have energetic advantages, since, when water is heated at high pressures a phase change to steam is avoided which avoids large enthalpic energy penalties. Biological chemicals undergo a range of reactions, including dehydration and decarboxylation reactions, which are influenced by the temperature, pressure, concentration, and presence of homogeneous or heterogeneous catalysts. Several biomass hydrothermal conversion processes are in development or demonstration. Liquefaction processes are generally lower temperature (200–400 °C) reactions which produce liquid products, often called “bio-oil” or “bio-crude”. Gasification processes generally take place at higher temperatures (400–700 °C) and can produce methane or hydrogen gases in high yields.

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Thermochemical biofuel production in hydrothermal media: A review of sub- and supercritical water technologies

Innovative valorization of naturally abundant and renewable lignocellulosic biomass is of great importance in the pursuit of a sustainable future and biobased economy. Ionic liquids (ILs) as an important kind of green solvents and functional fluids have attracted significant attention for the catalytic transformation of lignocellulosic feedstocks into a diverse range of products. Taking advantage of some unique properties of ILs with different functions, the catalytic transformation processes can be carried out more efficiently and potentially with lower environmental impacts. Also, a new product portfolio may be derived from catalytic systems with ILs as media. This review focuses on the catalytic chemical conversion of lignocellulose and its primary ingredients (i.e., cellulose, hemicellulose, and lignin) into value-added chemicals and fuel products using ILs as the reaction media. An outlook is provided at the end of this review to highlight the challenges and opportunities associated with this interes...

Catalytic Transformation of Lignocellulose into Chemicals and Fuel Products in Ionic Liquids

The concept of a biorefinery that integrates processes and technologies for biomass conversion demands efficient utilization of all components. Hydrothermal processing is a potential clean technology to convert raw materials such as lignocellulosic materials and aquatic biomass into bioenergy and high added-value chemicals. In this technology, water at high temperatures and pressures is applied for hydrolysis, extraction and structural modification of materials. This review is focused on providing an updated overview on the fundamentals, modelling, separation and applications of the main components of lignocellulosic materials and conversion of aquatic biomass (macro- and micro- algae) into value-added products.

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Hydrothermal processing, as an alternative for upgrading agriculture residues and marine biomass according to the biorefinery concept: A review

A wide variety of commodity chemicals can be produced from the catalytic oxidation of carbohydrates or carbohydrate derived molecules including formic acid, acetic acid, glycolic acid, gluconic acid, glucaric acid, malonic acid, oxalic acid, 2,5-diformylfuran (DFF), 5-hydroxymethyl-2-furancarboxylic acid (HFCA), 5-formyl-2-furancarboxylic acid (FFCA), and 2,5-furandicarboxylic acid (FDCA). This review will highlight the recent research progress in the development of new routes for the production of organic acids and furan compounds via catalytic oxidation reactions. Particular attention will be paid to these one-pot reactions with the requirements of an acidic site and a metal site. For the one-pot transformation of cellobiose or lignocellulose into gluconic acid, these reactions were performed via a one-step strategy using a single catalyst containing an acidic site and a metal site. However, a two-step strategy was adopted for the oxidative transformation of carbohydrates into DFF or FDCA in order to avoid the oxidation of the carbohydrates. The first step was performed for the dehydration of carbohydrates into 5-hydroxylmethylfuran (HMF) in the presence of an acid catalyst, and the second step was performed for the oxidation of HMF into DFF or FDCA with a metal catalyst.

Catalytic oxidation of carbohydrates into organic acids and furan chemicals

A two-step hydrothermal process to improve the production of acetic acid was discussed. The first step was to accelerate the formation of 5-hydroxymethyl-2-furaldehyde (HMF), 2-furaldehyde (2-FA), and lactic acid (LA), and the second step was to further convert the furans (HMF, 2-FA) and LA produced in the first step to acetic acid by oxidation with newly supplied oxygen. The acetic acid obtained by the two-step process had not only a high yield but also better purity. The contribution of two pathways via furans and LA in the two-step process to convert carbohydrates into acetic acid was roughly estimated as 85−90%, and the ratio of the contributions of furans and LA to yield acetic acid was estimated as 2:1. The fact that WO of carbohydrates is not capable of producing a large amount of acetic acid, while the two-step process can enhance the acetic acid yield, can be explained because formic acid is a basic product of direct oxidation of carbohydrate, and acetic acid in WO of carbohydrates may come from ...

Controlling hydrothermal reaction pathways to improve acetic acid production from carbohydrate biomass.

The conversion mechanism of cellulosic biomass to lactic acid in subcritical water without the addition of any alkaline catalyst is discussed. Results showed that this conversion mechanism appears ...

Conversion Mechanism of Cellulosic Biomass to Lactic Acid in Subcritical Water and Acid–base Catalytic Effect of Subcritical Water

To increase the acetic acid yield in a wet oxidation of lignocellulosic wastes, a new two-step reaction process is proposed. The first step produces 5-hydroxymethyl-2-furaldehyde (HMF) and 2-furaldehyde (2-FA) by dehydration of monosaccharides which are formed by hydrolysis of polysaccharides under the condition of non-supply of oxygen. In the second step, HMF and 2-FA are oxidized to acetic acid with oxygen newly added. The yield increased about twofold.

Hisao Higashijima

Papers

Controlling hydrothermal reaction pathways to improve acetic acid production from carbohydrate biomass.

Conversion Mechanism of Cellulosic Biomass to Lactic Acid in Subcritical Water and Acid–base Catalytic Effect of Subcritical Water

Hydrothermal process for increasing acetic acid yield from lignocellulosic wastes