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Recently, catalytic oxidation in supercritical water (SCW) has received considerable research attention. The major thrust of this current research effort is attributable to the rapid development of supercritical water oxidation (SCWO) as an innovative wastewater treatment technology. The incentives of catalyst-enhanced processes may include increased reaction rates, reduced residence times and temperatures, and optimized reaction pathways that are otherwise difficult to achieve through noncatalytic processes. However, the databases associated with the use of catalysts in SCWO are limited. The purpose of this paper is to (1) review catalytic enhancement and technology as related to SCWO; (2) analyze effects of SCW on catalysts and catalytic SCWO processes; and (3) present a catalyst development strategy for SCWO-related applications. Catalyst activity and stability (in terms of reaction kinetics, surface phenomena, and phase behavior of catalysts in SCW) are emphasized. The paper presents a useful database, provides guidelines for catalyst selection, and illustrates how effective use of catalyst may enhance SCWO process development.

Catalytic oxidation of ammonia in supercritical water (SCW) was studied using a continuous-flow, packed-bed reactor at temperatures ranging from 410 to 470 °C, a nominal pressure of 27.6 MPa, and reactor residence times of less than 1 s. The kinetics and catalyst performance of MnO2/CeO2 for oxidation of ammonia in SCW was evaluated. In this reaction environment, ammonia was predominantly converted into molecular nitrogen (N2), and the rate of ammonia conversion was enhanced by MnO2/CeO2. For example, 40% of the ammonia was converted when using the MnO2/CeO2 catalyst at a temperature of 450 °C and a reactor residence time of 0.8 s. It was reported that, without a catalyst, essentially no ammonia conversion was observed below 525 °C (Helling, R. K.; Tester, J. W. Environ. Sci. Technol. 1988, 22 (11), 1319) and 10% of the ammonia was converted at a temperature of 680 °C, a pressure of 24.6 MPa, and a reactor residence time of 10 s (Webley, P. A.; Tester, J. W.; Holgate, H. R. Ind. Eng. Chem. Res. 1991, 30 (8), 1745). Kinetic models developed for the gas-phase catalytic oxidation of ammonia were adopted and proven to be adequate for catalytic oxidation of ammonia in supercritical water. The best-fit global rate expression for catalytic supercritical water oxidation of ammonia by MnO2/CeO2 was obtained as follows:  r = 1.14 × 1014 exp(−189 kJ/mol/RT) [NH3]0.63[O2]0.71. The BET surface area and X-ray diffraction analyses of the exposed catalyst indicated a significant reduction of surface area and changes in the crystalline structure of the catalyst.

This paper describes a catalytic hydrothermolysis (CH) process aimed at converting triglycerides to nonester biofuels. The CH conversion was carried out at temperatures ranging from 450 to 475 °C and a pressure of 210 bar in the presence of water with and without a catalyst. The organic phase (biocrude) from the CH process underwent post-treatment involving decarboxylation and hydrotreating. Results derived from soybean oil, jatropha oil, and tung oil show that certain biofuel fractions met JP-8 specifications and Navy distillate specifications. One of the CH biofuel characteristics is their high levels of cyclics and aromatics. Tung-oil-based biofuels derived from the CH process contain up to 60% aromatics, which can be a desirable ingredient for fuel blends involving biofuels derived from other processes or feedstocks. Results from these crop oils also suggest that the CH process can be adapted to a variety of other triglyceride feedstocks.

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