Quartz capillary microreactor for studies of oxidation in supercritical water

An inexpensive, low-power quartz capillary flow reactor was designed to investigate the global reaction rate for the supercritical water oxidation of acetic acid. The effluent from the ∼0.1 cm dia. quartz microreactor is such that it is easily incorporated into an online spectroscopic or vacuum mass spectrometer detection system. The reactor is capable of operating up to 28 MPa and 530°C. Standard HPLC sample injection valves permit the rapid change of reactant composition. This reactor is a nonisothermal design and requires a heat-transfer calculation that involves coupling the transport equations for momentum, mass, and heat with the chemical kinetics equations. A numerical calculation presented includes a rigorous treatment of the equation of state and the transport properties of pure water. With this design, the global rate data was fitted to the following form: r A =-9.3±0.7x10 10 exp(-(172.2±1.7)/RT)[C HOAc ] 0.89±0.07 [C Peroxide ] 0.2±0.1 (M/s).

[1]  P. Savage,et al.  Kinetics of acetic Acid oxidation in supercritical water. , 1995, Environmental science & technology.

[2]  J. Syage.  Real-time detection of chemical agents using molecular beam laser mass spectrometry , 1990 .

[3]  M. Myrick,et al.  In situ fiber-optic Raman spectroscopy of organic chemistry in a supercritical water reactor , 1994 .

[4]  Michael Jerry Antal,et al.  A critical evaluation of the plug-flow idealization of tubular-flow reactor data , 1988 .

[5]  J. Tester,et al.  Fundamental Kinetics and Mechanisms of Hydrogen Oxidation in Supercritical Water , 1993 .

[6]  J. Fenn,et al.  Microjet burners for molecular-beam sources and combustion studies , 1988 .

[7]  A. L. Wahrhaftig,et al.  Direct coupling of a dense (supercritical) gas chromatograph to a mass spectrometer using a supersonic molecular beam interface , 1981 .

[8]  M. Abraham,et al.  An economic evaluation of catalytic supercritical water oxidation: Comparison with alternative waste treatment technologies , 1998 .

[9]  David A. Lustig,et al.  A continuous flow probe method for on-line introduction of liquid samples for detection by laser desorption with resonant two-photon ionization in supersonic beam mass spectrometry , 1991 .

[10]  B. W. Wright,et al.  Performance of capillary restrictors in supercritical fluid chromatography , 1986 .

[11]  F. Cansell,et al.  Hydrothermal oxidation of model molecules and industrial wastes , 1998 .

[12]  T. Fujii,et al.  Forced convective heat transfer to supercritical water flowing in tubes , 1972 .

[13]  D. S. Lee,et al.  Efficiency of H2O2 and O2 in supercritical water oxidation of 2,4-dichlorophenol and acetic acid , 1990 .

[14]  Jefferson W. Tester,et al.  Acetic acid oxidation and hydrolysis in supercritical water , 1995 .

[15]  Lixiong Li,et al.  Generalized kinetic model for wet oxidation of organic compounds , 1991 .

[16]  S. F. Rice,et al.  Raman spectroscopic measurement of oxidation in supercritical water. 1. Conversion of methanol to formaldehyde , 1996 .

[17]  J. Abeln,et al.  Supercritical Water Oxidation: State of the Art , 1999 .

[18]  S. F. Rice,et al.  Oxidation rates of common organic compounds in supercritical water , 1998 .

[19]  A. L. Wahrhaftig,et al.  Dense gas chromatograph/mass spectrometer interface , 1978 .

[20]  Richard R. Steeper,et al.  CO2-Based Thermometry of Supercritical Water Oxidation , 1991 .

[21]  T. Imasaka,et al.  Supercritical fluid for sample introduction in supersonic jet spectrometry , 1986 .