Waste treatment, supercritical water reactions

Supercritical Water Oxidation (SCWO) has been proved to be a suitable process for treatment of several toxic and hazardous organic wastes due to its high removal efficiency. SCWO requires of hard reaction conditions (22.1 MPa and over 374°C). Special reactors are needed to support these conditions. An original reactor design is presented here wich has been tested in the treatment of alcohols+ammonia solutions in water. Performance results are presented here for ammonia and alcohols. Destruction efficiency greater than 99.9% are reached for both compounds, probing the correct performance of the reactor. 

Like supercritical carbon dioxide, supercritical water is a very interesting substance that has strikingly different properties from those of liquid water. For example, recent experiments have shown that supercritical (superfluid) water can behave simultaneously as both a polar and a nonpolar solvent. While the reasons for this unusual behavior remain unclear, the practical value of this behavior is very clear It makes superfluid water a very useful reaction medium for a wide variety of substances. One extremely important application of this idea involves the environmentally sound destruction of industrial wastes. Most hazardous organic (nonpolar) substances can be dissolved in supercritical water and oxidized by dissolved 02 in a matter of minutes. The products of these reactions are water, carbon dioxide, and possibly simple acids (which result when halogen-containing compounds are reacted). Therefore, the aqueous mixture that results from the reaction often can be disposed of with little further treatment. In contrast to the incinerators used to destroy organic waste products, a supercritical water reactor is a closed system (has no emissions). 

Residence time for supercritical water oxidation systems may be as short as several minutes at temperatures of 600 to 650°C. More than 99.9 percent conversion of EPA priority pollutants such as chlorinated solvents has been achieved in a pilot-scale plant with retention time less than 5 minutes. The system is limited to treatment of liquid wastes or solids less than 200 microns in diameter. Char formation during reaction may impact the oxidation time of the organics, while separation of inorganic salts during the process may be a problem. Typical materials for the reactor are Hastelloy C-276 and Iconel 625 (high nickel alloys), which can withstand high temperatures and pressmes and the corrosive conditions. 

Other possible oxidative treatments for the feedstock recycling of plastic and rubber wastes include partial oxidation with organic peroxides and decomposition by reaction with oxygen by thermooxidation or under supercritical water conditions. However, these latter alternatives have so far not been widely investigated. 

With respect to dense phase fluids, supercritical water has been shown to be a very effective reaction medium for oxidation reactions [8, 9]. Despite extensive research efforts, however, corrosion and investment costs form major challenges in these processes because of the rather extreme operation conditions required (above 647 K and 22.1 MPa) [10]. StiU, several oxidation processes for waste water treatment in chemical industries are based on supercritical water technology (see, e.g., [11]). 

BDF is produced currently by a chemical process with an alkaline catalyst, which has some drawbacks, such as the energy-intensive nature of the process, the interference of the reaction by free fatty acids (FFAs) and water, the need for removal of alkaline catalyst from the product, the difficulty in recovering glycerol, and the treatment of alkaline wastewater. To overcome these problems, the processes using ion-exchange resins (Shibasaki-Kitakawa et al., 2007), supercritical MeOH (Kusdiana and Saka, 2004), MeOH vapor (Ishikawa et al, 2005), and immobilized lipases (Mittelbach, 1990 Nelson et al, 1996 Selmi and Thomas, 1998) have been proposed. In this paper, enzyme processes for production of BDF from waste edible oil, waste FFAs, and acid oil recovered from soapstock are described. In addition, applications of the element reactions to the oil and fat industry are introduced. 

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