Applications of direct chemical oxidation to demilitarization

Title: Applications of direct chemical oxidation to demilitarization

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Abstract

Research is reported concerning an aqueous process for oxidative destruction of solid- and liquid organic wastes, including ongoing work relevant to demilitarization This process uses acidified ammonium- or sodium peroxydisulfate and operates at ambient pressure and at temperatures of 80- 100 C The oxidant may be regenerated by electrolysis of the sulfate by- product at Pt anodes at roughly 80% coulombic efficiency, even in the presence of inorganic contaminants (e g , nitrate, phosphate or chloride) found in the original waste and entrained in the recycle stream Integral rate constants have been determined for the oxidation of diverse organic compounds at low concentrations (50 ppm, C), with rate constants (based on equivalents) of 0 004-O 02 miri Higher concentrations generally react at a 2-4X higher rate. The process has been carried through full- scale laboratory tests and initial pilot plant tests on chlorinated solvents, using a hydrolysis pretreatment Integral rate data indicate throughput rates of about 200 kg- C/m3-day The process may benefit the demilitarization efforts in various specialized applications destruction of solvents; destruction of trace propellants and explosives in shell casings remaining after bulk removal, destruction of red and pink waters, in situ remediation of soils at open pitmore »« less

Authors:: Cooper, J.F., LLNL

Publication Date:: Mon Jun 01 00:00:00 EDT 1998

Research Org.:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

OSTI Identifier:: 310921

Report Number(s):: UCRL-JC-130803; CONF-980593-
ON: DE98058771; CNN: W-7405-Eng-48

DOE Contract Number:: W-7405-ENG-48

Resource Type:: Conference

Resource Relation:: Conference: 1998 global demilitarization symposium and exhibition, Coeur d`Alene, ID (United States), 11-14 May 1998; Other Information: PBD: 1 Jun 1998

Country of Publication:: United States

Language:: English

Subject:: 40 CHEMISTRY; 45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEFENSE; ORGANIC COMPOUNDS; SOLID WASTES; AMMONIUM SULFATES; CHEMICAL EXPLOSIVES; WASTE PROCESSING; REACTION KINETICS; OXIDATION

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                    Cooper, J.F., LLNL. Applications of direct chemical oxidation to demilitarization.  United States: N. p., 1998. 
        Web.

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                    Cooper, J.F., LLNL. Applications of direct chemical oxidation to demilitarization.  United States.

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                    Cooper, J.F., LLNL. 1998.  
        "Applications of direct chemical oxidation to demilitarization".  United States.  https://www.osti.gov/servlets/purl/310921.

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@article{osti_310921,

  title        = {Applications of direct chemical oxidation to demilitarization},

  author       = {Cooper, J.F., LLNL},

  abstractNote = {Research is reported concerning an aqueous process for oxidative destruction of solid- and liquid organic wastes, including ongoing work relevant to demilitarization This process uses acidified ammonium- or sodium peroxydisulfate and operates at ambient pressure and at temperatures of 80- 100 C The oxidant may be regenerated by electrolysis of the sulfate by- product at Pt anodes at roughly 80% coulombic efficiency, even in the presence of inorganic contaminants (e g , nitrate, phosphate or chloride) found in the original waste and entrained in the recycle stream Integral rate constants have been determined for the oxidation of diverse organic compounds at low concentrations (50 ppm, C), with rate constants (based on equivalents) of 0 004-O 02 miri Higher concentrations generally react at a 2-4X higher rate. The process has been carried through full- scale laboratory tests and initial pilot plant tests on chlorinated solvents, using a hydrolysis pretreatment Integral rate data indicate throughput rates of about 200 kg- C/m3-day The process may benefit the demilitarization efforts in various specialized applications destruction of solvents; destruction of trace propellants and explosives in shell casings remaining after bulk removal, destruction of red and pink waters, in situ remediation of soils at open pit burning/detonation sites; and as a regenerative filter for offgas carrying toxic or explosive substances.},

  doi          = {},

  url          = {https://www.osti.gov/biblio/310921},
  journal      = {},
number       = ,

  volume       = ,

  place        = {United States},

  year         = {Mon Jun 01 00:00:00 EDT 1998},

  month        = {Mon Jun 01 00:00:00 EDT 1998}

}

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Research is reported concerning a new aqueous process for oxidative destruction of solid- and liquid organic wastes. This process uses acidified ammonium peroxydisulfate and operates at ambient pressure and at 80- to 100 {degrees}C. The oxidant may be efficiently regenerated by electrolysis of the sulfate by-product at Pt anodes, even in the presence of organic and inorganic contaminants expected to be entrained in the cycle. Integral rate constants were determined for the oxidation of 25 diverse organic compounds at low (50 ppm) concentrations through fixed-time experiments with excess oxidant and a Pt wire catalyst. For high initial concentrations, uncatalyzed mineralizationmore »« less
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Direct Chemical Oxidation (DCO) is an ambient-pressure, low-temperature (<100 C), and aqueous-based process for general-purpose destruction of the organic fraction of hazardous or mixed waste. It uses the peroxydisulfate anion (S{sub 2}O{sub 8}{sup 2{minus}}) in acid or base solutions. The byproduct of the oxidation reaction, typically sodium or ammonium hydrogen sulfate, may be recycled electrolytically to produce the oxidant. The oxidation kinetic reaction is first order with respect to the peroxydisulfate concentration, expressed in equivalents. The rate constant is constant for nearly all dissolved organic compounds: k{sub a} = 0.01 {+-} 0.005 min{sup {minus}1}. This reflects a common rate-determining step,more »« less
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