Biomass is an important feedstock for the renewable production of fuels, chemicals, and energy. As of 2005, over 3% of the total energy consumption in the United States was supplied by biomass, and it recently surpassed hydroelectric energy as the largest domestic source of renewable energy. Similarly, the European Union received 66.1% of its renewable energy from biomass, which thus surpassed the total combined contribution from hydropower, wind power, geothermal energy, and solar power. In addition to energy, the production of chemicals from biomass is also essential; indeed, the only renewable source of liquid transportation fuels is currently obtained from biomass.

The Catalytic Valorization of Lignin for the Production of Renewable 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.

/pdf/thermochemical-biofuel-production-in-hydrothermal-media-a-57itjyvhnt.pdf

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

Hydrothermal liquefaction of biomass: A review of subcritical water technologies

Hydrothermal carbonization can be defined as combined dehydration and decarboxy lation of a fuel to raise its carbon content with the aim of achieving a higher calorific value. It is realized by applying elevated temperatures (180–220°C) to biomass in a suspension with water under saturated pressure for several hours. With this conversion process, a lignite-like, easy to handle fuel with well-defined properties can be created from biomass residues, even with high moisture content. Thus it may contribute to a wider application of biomass for energetic purposes. Although hydrothermal carbonization has been known for nearly a century, it has received little attention in current biomass conversion research. This review summarizes knowledge about the chemical nature of this process from a process design point of view. Reaction mechanisms of hydrolysis, dehydration, decarboxylation, aromatization, and condensation polymerization are discussed and evaluated to describe important operational parameters qualitatively. The results are used to derive fundamental process design improvements. Copyright © 2010 Society of Chemical Industry and John Wiley & Sons, Ltd

Hydrothermal carbonization of biomass: A summary and discussion of chemical mechanisms for process engineering

Roles of water for chemical reactions in high-temperature water

http://en.xtbg.ac.cn/ns/es/200811/W020090810605874044736.pdf

Reaction chemistry and phase behavior of lignin in high-temperature and supercritical water

The decomposition of lignin was examined in supercritical water with and without phenol at 673 K. In the absence of phenol, the yield of tetrahydrofuran (THF)-insoluble (TIS) products decreased and the molecular weight distribution of THF-soluble (TS) products shifted toward lower molecular weights as the water density increased. The increase in water density enhanced the lignin conversion. In the presence of phenol, the yield of TIS products was lower and the molecular weight distribution of TS products shifted toward lower molecular weights than those in the absence of phenol. Some alkylphenols were obtained only in the presence of phenols, because of the reaction of phenol with the decomposition products. These results show that the reaction of phenol with reactive sites occurred in supercritical water and suppressed cross-linking reactions among reactive sites of large fragments. This promoted the decomposition of lignin to lower-molecular-weight compounds.

Conversion of Lignin with Supercritical Water−Phenol Mixtures

Chemical Reactions of C1 Compounds in Near-Critical and Supercritical Water

Lignin and cellulose were gasified at 400 °C with gas yields of 30% and 70%, respectively, in supercritical water with a ruthenium catalyst. In both cases, the main gas product was CH4 and no solid product was formed. Without water or catalyst, lignin and cellulose were gasified slightly and a brown solid product was formed. The decomposition of formaldehyde was also demonstrated in supercritical water. Formaldehyde was rapidly decomposed to gases such as CH4, CO2, and H2 with ruthenium, whereas formaldehyde was converted into methanol and CO2 without catalyst. The catalytic conversion of biomass with ruthenium in supercritical water is an efficient method for biomass gasification at temperatures of ∼400 °C.

Takafumi Sato

Papers

Reaction chemistry and phase behavior of lignin in high-temperature and supercritical water

Conversion of Lignin with Supercritical Water−Phenol Mixtures

Chemical Reactions of C1 Compounds in Near-Critical and Supercritical Water

Low-Temperature Catalytic Gasification of Lignin and Cellulose with a Ruthenium Catalyst in Supercritical Water

Catalytic effects of NaOH and ZrO2 for partial oxidative gasification of n-hexadecane and lignin in supercritical water