WO2001021262A1 - Catalyseurs pour la destruction de composes d'organophosphonate - Google Patents

Catalyseurs pour la destruction de composes d'organophosphonate Download PDF

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Publication number
WO2001021262A1
WO2001021262A1 PCT/US2000/025815 US0025815W WO0121262A1 WO 2001021262 A1 WO2001021262 A1 WO 2001021262A1 US 0025815 W US0025815 W US 0025815W WO 0121262 A1 WO0121262 A1 WO 0121262A1
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catalyst
composition
catalyst composition
recited
manganese oxide
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PCT/US2000/025815
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English (en)
Inventor
Lixin Cao
Sunita Satyapal
Steven L. Suib
Xia Tang
James D. Freihaut
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Carrier Corporation
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Priority to AU73851/00A priority Critical patent/AU7385100A/en
Priority to EP00961975A priority patent/EP1214124A1/fr
Publication of WO2001021262A1 publication Critical patent/WO2001021262A1/fr

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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/40—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by heating to effect chemical change, e.g. pyrolysis
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/02—Chemical warfare substances, e.g. cholinesterase inhibitors
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/04—Pesticides, e.g. insecticides, herbicides, fungicides or nematocides
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/26—Organic substances containing nitrogen or phosphorus

Definitions

  • the present invention relates generally to compositions effective for destroying hazardous compounds and, more particularly, to compositions effective to catalyzing the oxidation of organophosphorus compounds, including chemical warfare agents, pesticides and solvents. .
  • US Patent 5,451,738 discloses the plasma arc decomposition of hazardous wastes into vitrified solids and non-hazardous gasses.
  • US Patent 5,545,799 describes the chemical destruction of toxic organic compounds by means of an oxidizing reaction between, for example a chlorine-containing or arsenic-containing compound, and an oxidizing agent, for example hydrogen peroxide at a temperature of 50-90 °C, and at specific pHs.
  • US Patent 5,760,089 discloses a chemical warfare agent decontaminant solution using quaternary ammonium complexes.
  • WO Patent 9718858 describes a method and apparatus for destroying chemical warfare agents based on reaction with a nitrogenous base containing solvated electrons.
  • US Patent 4,871,526 describes the heterogeneous catalytic oxidation of organophosphonate esters using a molybdenum catalyst. As disclosed therein, the reaction results in the production of carbon monoxide and phosphorus oxide(s) without the undesired accumulation of carbonaceous or phosphorus overlayers on the molybdenum surface. In fact, molybdenum is one of the only species shown to be resistant to poisoning by phosphorus compounds.
  • European Patent 0501364 discloses a low chromium activated charcoal for destroying chemical warfare agents. As disclosed therein, the amount of active metal, such as chromium VI, in the activated charcoal or ASC whetlerite charcoal catalyst is reduced by as much as 50% via a freeze-drying technique without reducing the activity of the charcoal. These materials are used in providing protection against chemical warfare agents but because chromium VI is a known carcinogen, disposal of the spent charcoal is a problem.
  • the proposed catalyst may be doped with Mo in order to enhance sustained catalytic activity and to reduce degradation.
  • the use of an oxygen or air purge may be employed.
  • destruction means the chemical decomposition or conversion to relatively non-toxic products.
  • destruction means the chemical decomposition or conversion to relatively non-toxic products.
  • a catalyst composition comprising a catalyst material selected from the group consisting of vanadium oxide or manganese oxide deposited upon a catalyst support selected from the group consisting of alumina or silica.
  • a method for decomposing volatile organic compounds contacting the volatile organic compounds with a manganese oxide catalyst composition in the presence of visible light is provided.
  • a method for decomposing organophosphonate compounds comprising contacting the organophosphonate compounds with a catalyst composition heated to a temperature of at least 300 C, said catalyst composition containing a catalyst selected from the group consisting of manganese oxide, vanadium, vanadium oxide, activated carbon or diphosphorus pentaoxide.
  • the catalyst may be heated to at least 350 C and most advantageously to at least 400 C.
  • a method is provide for regenerating a spent catalyst composition for decomposing volatile organic compounds comprising washing the spent catalyst composition with distilled deionized water.
  • Figure 1 is a schematic diagram illustrating the experimental system used to evaluate the activity of various compositions as catalysts for the destruction of organophosphorus compounds
  • Figure 2 is a graph showing the DMMP conversion activity of various compositions over time
  • Figure 3 is a graph showing the DMMP conversion activity of various vanadium based catalyst compositions over time
  • Figure 4 is a graph showing the DMMP conversion activity of various vanadium based catalyst compositions over time
  • Figure 5 is a graph showing the DMMP conversion activity of a vanadium based catalyst composition reacting at temperatures of 350 C, 400 C and 450 C over time;
  • FIG. 6 is a schematic diagram illustrating a photocatalytic reactor system for the destruction of organophosphorus compounds. Description of the Invention
  • Various metal-oxide and carbon based catalysts were synthesized using impregnation methods and their effectiveness for the destruction of dimethyl methyl phosphonate (DMMP), a simulant for nerve gas, evaluated at various operating conditions.
  • DMMP dimethyl methyl phosphonate
  • a support material was impregnated with a soluble salt of the catalyst metal.
  • the support materials employed were ⁇ -Al 2 O 3 , amorphous SiO 2 and P- 25 TiO 2
  • the precursor salts for the preparation of catalysts were: Ni(NO 3 ) 2 -6H 2 O; Fe(NO 3 ) 2 -9H 2 O; Cu(NO 3 ) 2 -2.5H 2 O; NH 4 VO 3 . and Pt(acac) 2 . With the exception of Pt(acac) 2 , each salt was dissolved in distilled deionized water to form a solution.
  • Pt(acac) 2 was dissolved in ethanol. Support material was then added to the solutions and stirred at room temperature for 12 hours. The solutions were then evaporated and dried at 393 K. Chunks of samples were recovered, ground and then calcined at 723 K for 6 hours. Powdered samples were pelleted and sieved into 28-48 mesh particles for catalytic tests.
  • Example I Approximately 5 grams of a catalyst (catalyst plus catalyst support) consisting of nickel supported on alumina (Al 2 O 3 ), with the nickel constituting 10% of the total supported catalyst weight, was synthesized as follows. First, 2.478 grams of
  • Ni(NO 3 ) 2 -6H 2 O was dissolved in 100 ml deionized water. Then, 4.364 grams of ⁇ - Al 2 O 3 was added into the solution. After stirring at room temperature for 12 hours, the solution was slowly allowed to evaporate until the formation of a slurry occurred, which was subsequently dried at 120°C for 12 hours. The sample was then calcined at 450°C for 6 hours. The powder-like sample was ground, pelleted and sieved into 28- 48 mesh particles for catalytic tests.
  • the ultra high purity air was passed at a rate of 50 ml/min through a saturator or bubbler 40 filled with 100% liquid DMMP at a room temperature of 20-22 °C in order to create a DMMP vapor/air stream containing of 1300 ppm DMMP in room temperature air.
  • the DMMP vapor/air stream flows through a catalyst bed 30 in reactor 50, which is heated by a tubular furnace 60 equipped with a temperature controller 80.
  • the reactor products pass through gas chromatographs 90 and 91 for on-line analysis. A mass of 100 milligrams of catalyst was used for each test.
  • the mechanism resulting in high activity may be based on the formation of phosphoric acid or phosphorus pentoxide (P2O5), which have been used as activating agents for carbon activation.
  • Phosphoric acid is generally impregnated in carbon materials and then pyrolyzed between 350-500 °C. Upon calcination, the impregnated chemicals dehydrate the carbon materials, which results in charring and aromatization of the carbon skeleton and the creation of a porous structure.
  • the P2O5 and coke formed during the decomposition of the organophosphonates may create a porous structure similar to active carbon at the reactor temperature we have employed (300-450 °C).
  • P2O5 is accumulated in the catalytic bed or downstream along the reactor walls during the protection period during which the original catalyst shows 100% conversion of DMMP (to our detection limit of roughly 0.1%).
  • DMMP to our detection limit of roughly 0.1%).
  • the apparent conversion of DMMP at this time is still very high (close to 100%). However, the prerequisite for this continued conversion is that an adequate amount of P2O5 be deposited in the reactor.
  • Figure 2 shows the duration of DMMP conversion at 400 ° C for different metal oxides supported on ⁇ -Al 2 O 3 .
  • the loading contents of Ni, Fe, Cu, and V were 10% by weight. Protection time or protection period is defined as the initial period during which substantially 100% conversion of DMMP is maintained, and is a very important parameter for evaluation of a catalyst's effectiveness.
  • the sequence of protection times obtained on these catalysts compositions were: 10%V/A1 2 O 3 (12.5 hours) > l%Pt/Al 2 O 3 (8.5 hours) > 10%Cu/Al 2 O 3 (7.5 hours) > Al 2 O 3 (4.0 hours) >
  • the protection time of 4 hours obtained on bare ⁇ -Al 2 O 3 could be due to the stoichiometric reaction between Al 2 O 3 and DMMP.
  • the protection times for nickel catalysts (curve B) and iron catalysts (curve C) were shorter than those for bare Al 2 O 3 .
  • the explanation for this observation is that the bulk Al 2 O 3 was covered by the phosphorus-poisoned iron, or nickel compounds (such as FePO 4 , or Ni 3 (PO 4 ) 2 ), which hindered the further exposure of Al 2 O 3 to DMMP.
  • FIG. 3 shows the initial protection periods of vanadium catalyst compositions with different loading contents ranging from 1% to 10%) by weight.
  • the initial protection periods on these catalysts were: 10%V (curve A) - 12.5 hours; 5%V (curve B) - 11.5 hours; 1%V (curve C)- 9.5 hours; and 15%V (curve D)- 8 hours.
  • the initial protection period for 10%V/A1 2 O 3 increased by only one hour although the contents of vanadium were doubled.
  • Figure 4 shows the conversion of DMMP on vanadium (10 wt %) based catalyst compositions with the vanadium catalyst supported on SiO 2 (curve A), Al 2 O 3 (curve B), and TiO 2 (curve C), respectively.
  • the disadvantage for the utilization of ⁇ -Al 2 O 3 as a support is that ⁇ -Al 2 O 3 has a degree of basicity and is able to react with acidic P 2 O 5 to form AlPO 4 , which can give rise to a drastic loss of surface area.
  • the relatively acidic supports, such as SiO 2 and TiO 2 were evaluated.
  • the SiO 2 was amo ⁇ hous and the commercially available P-25 TiO 2 was a mixture of anatase and rutile with a ratio of 75:25.
  • the catalytic activity was markedly enhanced using SiO 2 for the support material on which a protection time of 25 hours was obtained.
  • the SiO 2 catalyst composition was actually run for 100 hours with no significant deactivation. After passing through the protection time, the 10%V/SiO 2 catalyst deactivated slightly and the conversion of DMMP fluctuated within 99-100%. However, 10%N/TiO 2 catalyst deactivated very quickly.
  • the low surface area of this catalyst (29.9 m 2 /g) may be the explanation of poor activity. Therefore, 10% vanadium supported on SiO 2 was the best catalyst for the decomposition of DMMP.
  • the oxidation of DMMP with the vanadium based catalyst compositions is a temperature sensitive reaction primarily because P 2 O 5 , a decomposing product, has a high sublimation point (350 °C). At low temperatures, P 2 O 5 decomposes on the catalyst surfaces.
  • temperature dependence experiments were conducted on 10%V/SiO 2 catalyst. As seen in Fig. 5, the protection times at 350 °C (curve C), 400 °C (curve B) and 450 °C (curve A) were 5 hours, 25 hours and over 100 hours, respectively.
  • vanadium based catalysts and platinum catalyst appear to be the most active, with vanadium, at a level of 10%, by weight, being the only catalyst exhibiting the ability to maintain 100% DMMP conversion, with no indication of deactivation, over extended periods of time.
  • Vanadium based catalyst compositions having vanadium present in amounts greater than about 5% are preferred, with alumina and silica being the preferred support materials.
  • Manganese oxide, in either an amo ⁇ hous or crystalline form, based compositions also proved effective for the decomposition of DMMP and other hazardous.
  • Compositions comprising amo ⁇ hous manganese oxide (AMO) supported on a substrate also show high activity for photo-assisted catalytic oxidation applications.
  • AMO (amo ⁇ hous manganese oxide) catalyst compositions were prepared by the reduction of KMnO in distilled deionized water with oxalic acid. The precipitated materials were washed with water and dried in vacuum at room temperature.
  • the resultant brown materials are amo ⁇ hous and different from crystalline Mn(C2 ⁇ 4)3, Mn(C2 ⁇ 4)OH and similar to isolated transition metal oxalate complexes in color, structural properties, and composition.
  • non-stoichiometric amounts of oxalic acid were added in order to obtain intermediate (Mn4+ — > Mn ⁇ +) mixed valent manganese oxide compositions.
  • Infrared experiments showed only traces of oxalic acid in the resultant materials. After photolysis, the trace of oxalate or oxalic acid was present. Potassium was present to accommodate the reduced manganese (IV) ions.
  • the heterogeneous photocatalytic reactor system 70 depicted schematically in Figure 6 was used to evaluate the effectiveness of the manganese oxide based catalyst compositions.
  • Power supply (Kratos, Schoeffel Instruments, model LPS 255HR) 71 was used to power the 1000 W Xe arc lamp 72 which was used as a source of light. As no filters were used, the radiation from the lamp spanned over the entire ultraviolet and visible range (-200-800 nm). Water bottle 73 was placed in between the light source and the reactor 75 to remove heat and infrared radiation.
  • the flow rate of air was maintain at 30 mL/min. Under these conditions, the inlet DMMP concentration is 0.13 mol % or 1300 ppm.
  • Reactants and products were analyzed using gas chromatograph 92 equipped with an automatic gas-sampling valve.
  • a Carbowax 20M capillary column with flame ionization detection was used to analyze for DMMP and methanol.
  • CO 2 was analyzed using a GSC Gas Pro capillary column with thermal conductivity detection.
  • the reaction of DMMP with AMO under dark and irradiated conditions was studied. In the absence of AMO, no decomposition of DMMP occurs. In the first approximately 130 minutes of the test run, the reaction was performed under dark conditions to allow the outlet DMMP concentration to equal the inlet DMMP concentration. The long times required for equilibration indicate that AMO can also be used as an effective adsorbent for DMMP. After the initial roughly 130 minutes, the lamp was turned on and the reaction was allowed to continue for another couple of hours. Under dark conditions, the concentration of DMMP initially decreases to approximately 17 % of the original concentration, then climbs slowly back to the inlet concentration after 2 h.
  • CO 2 Another product that formed during the DMMP reactions was CO 2 .
  • no CO 2 was formed under dark conditions.
  • Some CO 2 peaks were observed towards the beginning of the reaction; presumably from noise or trace amounts of CO 2 remaining in the AMO.
  • the concentration of CO 2 then quickly dropped to 170 ppm, where it remained fairly steady.
  • the manganese oxide based catalyst compositions of the present invention may also be doped with iron and/or using an iron oxide support.
  • Other dopants such as Ce, Mo, Pt, and V for example, may also be included.
  • Magnesium oxide and siicon dioxide may also be used as supports for the manganese oxide catalyst.
  • the present invention contemplates catalytic activity regeneration via washing of the spent catalyst composition.
  • catalysts poison relatively rapidly (with the exception of some of the vanadium-based catalysts discussed previously)
  • degraded catalyst compositions may be rejuvenated by washing the water-soluble phosphate-type species that are formed as products upon the catalyst composition thereby poisoning the catalyst material.
  • AMO was collected (-90 mg) and placed in 100 mL of DDW and stirred for approximately 1 h. The sample was filtered and washed with DDW several times. The AMO sample was dried overnight in air at 110 °C, and the following day was re-tested as a catalyst in reactions of DMMP. Only DMMP and MeOH were analyzed in these experiments. The results were similar to those obtained when using fresh AMO. At the beginning of the reaction under dark conditions, the DMMP concentration decreases, although not as dramatically as in fresh AMO samples. The DMMP concentration then slowly increases to the inlet level.
  • MeOH When the lamp was turned on, the DMMP concentration increases significantly as with fresh AMO, then levels off after several hours to concentrations near the inlet concentration.
  • the formation of MeOH also follows similar trends as fresh AMO. Under dark conditions, small amounts of MeOH (50 ppm) are formed, starting after 30 min. The MeOH concentration decreases slightly until the light is switched on. After the light is turned on, a large amount of MeOH (400 ppm) is initially observed. This corresponds to approximately the same amount of MeOH seen with fresh AMO samples. The production of MeOH then decreases as was observed for fresh AMO.
  • washing of the catalyst may be used to regenerate any of the catalyst compositions mentioned previously.
  • the catalytic activity with DMMP of titania photocatalyst,TiO2 was evaluated to verify washing would regenerate spent titania catalyst material. It was found that a deactivated titania catalyst may be easily regenerated not only by washing with water, but also by subjecting the catalyst in situ to UV light in the absence of DMMP. This rejuvenation by exposure to UV light likely resulted from oxidation of adsorbed DMMP and photodeso ⁇ tion of the adsorbed intermediates during the reconditioning period. The presence of adsorbed intermediates has been suspected to be a root cause of titania catalyst deactivation. The water wash strategy was found to completely rejuvenate the catalyst, while a 2-hour exposure to UV irradiation was found to partially, but not completely, rejuvenate the catalyst.
  • the AMO based catalyst compositions of the present invention may be used to decompose organophosphonates either at room temperature via photocatalytic reaction or via thermal reaction at elevated temperatures above 300 °C and preferably above 350 °C.
  • the most common photocatalyst in use which requires UV light for initiation, the AMO based catalyst compositions of the present invention require only visible light at approximately 425 nm.
  • the metal-oxide catalyst compositions may be regenerated by heating, washing with water or other solvents, treating with light, purging with oxygen (or other purge gas) and/or treating with microwave radiation to desorb surface species.
  • the catalysts of the present invention may also be used to decompose VOCs (volatile organic compounds) and be inco ⁇ orated into an air quality control system for indoor, outdoor and vehicular environments. More specifically, the AMO photoactive catalyst compositions of the present invention may be applied as a thin coating on a support such that it may be effectively irradiated by visible light.
  • the catalyst compositions in combination with light generating or light directing devices may be inco ⁇ orated into an air cleaner system.
  • light generating or light directing devices e.g., mirrors, reflectors, lenses, fibers
  • the coated surfaces will permit photocatalytic decomposition of pollutants.
  • AMO the primary advantage of using AMO is that visible light is sufficient to activate the photocatalytic mechanism as opposed to the UV light required for TiO2 activation.
  • Such an air cleaning system may be used in a building, outdoors, in space life support systems, or in aircraft air-cleaning systems.
  • the AMO and vanadium based catalyst compositions of the present invention may also be used in a refrigerant disposal system, that may or may not be a part of a refrigerant recovery system for the on-site destruction of recovered refrigerants. These catalyst compositions may also be used to thermo-catalytically destroy other chlorinated species such as solvent, degreasing agents, and other hazardous compounds.
  • the AMO and vanadium/vanadium oxide based catalyst compositions, as well as activated carbon and P2O5, are useful for the destruction of organophosphorus compounds, specifically chemical warfare agents and pesticides.
  • These catalysts may be used in such applications as gas masks, in vehicular and aerospace filtration systems, and in building filtration/ventilation systems.
  • a reactor comprised of either a packed bed of catalyst or catalyst coating on a porous substrate (for low pressure drop operation) may be used.
  • photoactive catalysts light may be directed into the reactor.
  • the catalysts may be heated resistively, directly in situ; or by microwave radiation, or by external means such as by a furnace. Once the catalyst is activated and as gas passes through the reactor, the organophosphorus parent species will be decomposed to relatively benign byproducts.
  • catalyst compositions of the present invention may also be inco ⁇ orated into sensors as part of the detection system for organophosphorus compounds.

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Abstract

La présente invention concerne une composition de catalyseur utilisé efficacement pour catalyser la destruction de composés organophosphoreux renfermant des agents chimiques de combat, des pesticides, et des solvants. Cette composition de catalyseur comprend un matériau catalyseur choisi dans le groupe constitué par oxyde de vanadium ou oxyde de manganèse ou des mélanges de ceux-ci déposés sur un support de catalyseur choisi dans le groupe constitué par alumine, silice, ou titane ou des mélanges de ceux-ci. En outre, cette invention concerne un procédé permettant de décomposer les composés organiques volatils, notamment des composés organophosphoreux comprenant des agents chimiques de combat, des pesticides, et des solvants, en mettant en contact les composés organiques volatils avec une composition de catalyseur d'oxyde de manganèse en présence de lumière visible ou avec une composition de catalyseur chauffée à 300 °C minimum et plus avantageusement à 450 °C minimum, la composition de catalyseur contenant un catalyseur choisi dans le groupe constitué par oxyde de manganèse, vanadium, oxyde de vanadium, charbon actif ou pentaoxyde diphosphoreux. En vue de décomposer des composés organiques volatils, la composition de catalyseur utilisée peut être régénérée avec de l'eau désionisée distillée.
PCT/US2000/025815 1999-09-22 2000-09-20 Catalyseurs pour la destruction de composes d'organophosphonate WO2001021262A1 (fr)

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Application Number Priority Date Filing Date Title
AU73851/00A AU7385100A (en) 1999-09-22 2000-09-20 Catalysts for destruction of organophosphonate compounds
EP00961975A EP1214124A1 (fr) 1999-09-22 2000-09-20 Catalyseurs pour la destruction de composes d'organophosphonate

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US15543099P 1999-09-22 1999-09-22
US15552499P 1999-09-22 1999-09-22
US60/155,430 1999-09-22
US60/155,524 1999-09-22

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CN115624710A (zh) * 2022-09-30 2023-01-20 洪湖市一泰科技有限公司 一种光催化降解处理草铵膦废盐中有机膦的方法

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EP0818239A1 (fr) * 1996-01-22 1998-01-14 Petroleum Energy Center Photocatalyseur, procede de production de ce photocatalyseur, et procede de reaction photocatalytique
DE19757496A1 (de) * 1997-12-23 1999-06-24 Studiengesellschaft Kohle Mbh Hochporöse Photokatalysatoren zur Verwertung von sichtbarem Licht

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WO1997012672A1 (fr) * 1995-10-06 1997-04-10 Kansas State University Research Foundation Adsorbants composites a base d'oxydes metalliques
EP0818239A1 (fr) * 1996-01-22 1998-01-14 Petroleum Energy Center Photocatalyseur, procede de production de ce photocatalyseur, et procede de reaction photocatalytique
DE19757496A1 (de) * 1997-12-23 1999-06-24 Studiengesellschaft Kohle Mbh Hochporöse Photokatalysatoren zur Verwertung von sichtbarem Licht

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115624710A (zh) * 2022-09-30 2023-01-20 洪湖市一泰科技有限公司 一种光催化降解处理草铵膦废盐中有机膦的方法
CN115624710B (zh) * 2022-09-30 2023-09-15 洪湖市一泰科技有限公司 一种光催化降解处理草铵膦废盐中有机膦的方法

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