Supercritical water chemical synthesis

Supercritical water (SCW) presents a unique combination of aqueous and non-aqueous character, thus being able to replace an organic solvent in certain kinds of chemical synthesis. In order to allow for a better understanding of the particular properties of SCW and of its influence on the rate of chemical reactions, molecular dynamics computer simulations were used to determine the free energy of the SN2 substitution reaction of Cl- and CH3C1 in SCW as a function of the reaction coordinate [216]. The free energy surface of this reaction was compared with that for the gas-phase and ambient water (AW) [248], In the gas phase, an ion-dipole complex and a symmetric transition... 

Superheated and supercritical water are used in several applications. Supercritical water is most often used in the destruction of organic wastes, including some chemical warfare agents, as an alternative to incineration (Katritzky et al., 1996 Sherman et al., 1998). Recent reports describe the use of both forms as a solvent and as a reactant in synthetic chemistry (Katritzky et al., 1996 An et al., 1997). Some of the reactions investigated include metal-mediated alkyne cyclizations, Pd-catalyzed al-kene arylations, aldol reactions, the Fischer indole synthesis, and hydrolysis reactions. Waterborne coatings and the destruction of wastes in supercritical water are fully... 

More polymerization reactions carried out at supercritical conditions, select biomass conversion supercritical fluid technologies for hydrogen production, wider use of supercritical water oxidation processes, portfolio of self-assembly applications, a spate of opportunities in process intensification, many supercritical fluid aided materials synthesis applications, and numerous reactions for synthesis of specialty chemicals are expected for years to come. 

A variety of chemical and biological reactions involving supercritical fluid technology are being explored and developed. They include polymerization reactions, biomass conversion, hydrogen production, applications of supercritical water oxidation, self-assembly applications, synthesis of specialty chemicals, manufacture of materials with tailored properties, and much more. These developments and new ones are expected to mature and be commercially deployed in years to come. 

This chapter focuses on reactions that take advantage of the special properties or the tunability of properties of near- and supercritical water. These are on the one hand, synthesis reactions near the critical temperature of water, and on the other, decomposition reactions at higher temperatures. First of all, the properties of near-and supercritical water and their influence on chemical reactions will be discussed. 

Supercritical or.near-critical water has found technical applications for hydrothermal syntheses, as discussed in detail in Chapter 4.1. Another more recent industrid application of chemical reactions in SCFs is the oxidative destruction of chemical wastes in SCH2O (SCWO, supercritical water oxidation). A detailed coverage of the large and prolific field of SCWO is outside the scope of this book on chemical synthesis. The extensive pilot plant activity, primarily by MODAR (now General Atomics) and Eco Waste Technologies, has recently been sununarized by Schmieder [171]. The first commercial plant was opened by Huntsman Chemical in collaboration with Eco Waste. 

The use of supercritical fluids as alternatives to organic solvents is revolutionising a huge number of important science areas (24). Scientific applications vary from established processes, such as the decaffeination of coffee and the extraction and synthesis of active compounds, to the destruction of toxic waste in supercritical water, the production of nanoparticles and new materials, to novel emerging clean technologies for chemical reactions and extraction. 

Methanation. The formation of methane and CO2 from biomass is a classical example of chemical disproportionation of the zero-valence carbon in biomass. The reaction is mildly exothermic and is the natural decomposition reaction of wet biomass in the absence of oxygen (anaerobic digestion of biomass). The reaction also proceeds at elevated temperatures (up to 400 °C) in supercritical water as a reaction medium [29]. Alternatively the reaction can be carried out in a two-stage process ofgasification ofbiomass to synthesis gas, followed by catalytic methanation at T < 400°C (BioUaz). 

In this chapter, first the ionic reaction equilibrium, phase behavior, and solubility of metal oxides in supercritical water are discussed. Next, the specific features of hydrothermal synthesis under supercritical conditions are discussed based on the experimental results. The supercritical hydrothermal crystallization method was applied to the production of functional materials, barium hexaferrite (BaFei20i9), metal-doped oxide [Al5(Y- -Tb)30i2, YAG Tb], and Li ion battery cathode material (LiC02O4). The importance of understanding the chemical reaction equilibrium and phase behavior is discussed. 

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