WO1997034660B1 - Method for hot and supercritical water oxidation of material using specific reactants - Google Patents
Method for hot and supercritical water oxidation of material using specific reactantsInfo
- Publication number
- WO1997034660B1 WO1997034660B1 PCT/US1997/004443 US9704443W WO9734660B1 WO 1997034660 B1 WO1997034660 B1 WO 1997034660B1 US 9704443 W US9704443 W US 9704443W WO 9734660 B1 WO9734660 B1 WO 9734660B1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compounds
- sodium carbonate
- specific reactant
- reaction
- oxidant
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract 19
- 239000000376 reactant Substances 0.000 title claims abstract 13
- 238000009284 supercritical water oxidation Methods 0.000 title claims 3
- 238000000034 method Methods 0.000 claims abstract 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract 18
- 238000006243 chemical reaction Methods 0.000 claims abstract 15
- 239000007800 oxidant agent Substances 0.000 claims abstract 11
- 230000001590 oxidative Effects 0.000 claims abstract 11
- 150000001875 compounds Chemical class 0.000 claims abstract 9
- 239000001187 sodium carbonate Substances 0.000 claims abstract 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract 9
- 150000002894 organic compounds Chemical class 0.000 claims abstract 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000001301 oxygen Substances 0.000 claims abstract 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 7
- 238000000354 decomposition reaction Methods 0.000 claims abstract 6
- 230000015556 catabolic process Effects 0.000 claims abstract 4
- 230000004059 degradation Effects 0.000 claims abstract 4
- 238000006731 degradation reaction Methods 0.000 claims abstract 4
- 239000007864 aqueous solution Substances 0.000 claims abstract 2
- 230000000593 degrading Effects 0.000 claims abstract 2
- 239000002002 slurry Substances 0.000 claims abstract 2
- -1 sodium carbonate Chemical compound 0.000 claims abstract 2
- 239000007787 solid Substances 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims 5
- GZUXJHMPEANEGY-UHFFFAOYSA-N Bromomethane Chemical class BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 4
- 230000035484 reaction time Effects 0.000 claims 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-Trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims 2
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N Bromoethane Chemical class CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 2
- 239000007789 gas Substances 0.000 claims 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- 229940102396 methyl bromide Drugs 0.000 claims 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 2
- XNNBBCRKZSYVFA-UHFFFAOYSA-N 2,3,5,6-tetrachloro-1,4-benzodioxine Chemical compound ClC1=CC=C2OC(Cl)=C(Cl)OC2=C1Cl XNNBBCRKZSYVFA-UHFFFAOYSA-N 0.000 claims 1
- 229960003563 Calcium Carbonate Drugs 0.000 claims 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L Calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N Dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 claims 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L Magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L Magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000003570 air Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims 1
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 1
- 229940099364 dichlorofluoromethane Drugs 0.000 claims 1
- 150000002484 inorganic compounds Chemical class 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims 1
- 239000002370 magnesium bicarbonate Substances 0.000 claims 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims 1
- 239000001095 magnesium carbonate Substances 0.000 claims 1
- 239000011776 magnesium carbonate Substances 0.000 claims 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims 1
- 229960001708 magnesium carbonate Drugs 0.000 claims 1
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229960001407 sodium bicarbonate Drugs 0.000 claims 1
- 229940001593 sodium carbonate Drugs 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract 2
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000011780 sodium chloride Substances 0.000 abstract 2
- NTBPHHXYEGRAGC-UHFFFAOYSA-N 3-chloro-1,4-benzodioxine Chemical compound C1=CC=C2OC(Cl)=COC2=C1 NTBPHHXYEGRAGC-UHFFFAOYSA-N 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
Abstract
This invention relates to a process for the decomposition of material selected from halogenated organic compounds, to compounds which are environmentally acceptable, or are amenable to further degradation by conventional disposal systems to produce environmentally acceptable products, which process comprises: (a) conveying an aqueous solution or an aqueous slurry of material into a reaction zone capable of withstanding the temperatures and pressures of decomposition of the material; (b) contacting the material in the reaction zone with aqueous sodium carbonate as a reactant in an amount effective to decompose the material under hydrothermal oxidation conditions of between about 300 and 600 °C and a pressure of between about 10 and 400 atmospheres for between 0.01 and 120 min wherein the specific reactant, a carbonate such as sodium carbonate, at the reaction conditions is present at about 10 % or less as a water-soluble salt as compared to the solubility of the salt at ambient conditions wherein the specific reactant is essentially present as a solid and the oxidation occurs under heterogeneous conditions, wherein the process occurs in the presence of a gaseous oxidant wherein said oxidant is present in an amount of between about 0.01 and 50 % by weight of the material; (c) producing about 99 % or greater of the decomposition of the material, or 99 % or greater conversion of the material to compounds which are environmentally acceptable or to compounds which are amendable to further degradation; and (d) optionally degrading further the compounds produced in step (c) by reaction to environmentally acceptable products. Preferably, the specific reactant is sodium carbonate and the oxidant is oxygen or air. Preferably, the halogenated organic compound is selected from polychlorobiphenyl, polybromobiphenyl mono-chlorobenzodioxin or poly-chlorobenzodioxin compounds.
Claims
33
AMENDED CLAIMS
[received by the International Bureau on 18 September 1997 (18.09.97); original claims 7, 9 and 14 cancelled; original claims 1-4, 8, 10, 12, 13, 15, 17 and 19-21 amended; new claims 22 and 23 added; remaining claims unchanged (3 pages)]
1 . A process for the decomposition of material selected from the group consisting of organic compounds, inorganic compounds, and combinations thereof, to compounds which are environmentally acceptable, or which are amenable to further degradation by conventional disposal systems to produce environmentally acceptable products, which process comprises:
(a) conveying an aqueous solution or an aqueous slurry of the material to be decomposed into a reaction zone capable of withstanding the temperatures and pressures of the decomposition; and
(b) contacting the material, in the presence of water, with a specific reactant present as a solid in an amount effective to decompose the material under hot or supercritical water oxidation conditions, said conditions including a reaction temperature of between about 300 and 600 °C and a reaction pressure of between about 10 and 400 atmospheres, wherein the specific reactant is at least about 90% insoluble in an aqueous medium at said hot or supercritical water oxidation conditions, and reacts to neutralize any acid gases produced in the decomposition, and wherein the process occurs in the presence of a gaseous oxidant, said contacting being carried out for a reaction time sufficient to convert about 99% or greater of the material τo compounds which are environmentally acceptable, or to conversion compounds which are amendable to further degradation.
2. The process of claim 1 , wherein the material is selected from halogenated organic compounds, and said conditions include a reaction temperature of between about 300 and 400°C.
3. The process of claim 1 , wherein the specific reactant is selected from the group consisting of sodium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, calcium bicarbonate, magnesium bicarbonate, and combinations thereof.
34
4. The process of claim 1 , wherein the gaseous oxidant is selected from the group consisting of air, oxygen, hydrogen peroxide, ozone and combinations thereof.
5. The process of claim 2, wherein the halogenated organic compounds are selected from the group consisting of tetrachlorobenzodioxin, polychlorobiphenyls, polybromobiphenyls, methylenedichloride, chloroform, carbon tetrachloride, dichloroethylene, methylchloroform, polychlorinatβd benzene, polychlorohexane, chlorinated olefins, methyl bromide, ethyl bromide, dichlorofluoromethanβ, 1 ,2- dichloro-1 ,1 ,2,2-tetrafluoroethane, and combinations thereof.
6. The process of claim 3, wherein the specific reactant is sodium carbonate.
8. The process of claim 2, wherein said halogenated organic compounds are present in at least about 90 weight percent of the total material.
10. The process of claim 1 , wherein in step (b) the temperature is between about 373° and 400°C and the pressure is between about 220 and 300 atmospheres.
1 1 . The process of claim 10, wherein the specific reactant is sodium carbonate.
12. The process of claim 1 , further comprising the step of
(c) further degrading the compounds produced in step (b) by subsequent reaction to environmentally acceptable products.
13. The process of claim 2, wherein in step (bl, the specific reactant is sodium carbonate, the reaction temperature is between about 374 and 400°C, the gaseous oxidant is air or oxygen, and the reaction time is between about 0.1 and 60 min.
1 5. The process of claim 4, wherein the gaseous oxidant is oxygen or air.
16. The process of claim 1 5, wherein the oxidant is oxygen.
17. The process of claim 2, wherein in step (b), the specific reactant is sodium carbonate, the reaction temperature is between about 300 and 374° C, the reaction pressure is maintained to keep the water present as a gas, and the reaction time is between about 1 and 60 min.
1 8. The process of claim 17, wherein the oxidant is oxygen or air.
19. The process of claim 18, wherein the halogenated organic compounds are selected from the group consisting of ehlorobenzodioxins, polyibromobiphenyls, polychlorobiphenyls, methylene dichloride, chloroform, carbon tetrachloride, dichloroethylene, methylchloroform, polychlohnated benzene, polychiorohexaπe, methyl bromide, ethyl bromide, dichlorofluoromethane, 1 ,2-dichloro-1 , 1 ,2,2- tetrafluoroethane, and combinations thereof.
20. The process of claim 2, wherein the material is selected from polychlorobiphenyls .
21 . The process of claim 20, wherein in step (b) the specific reactant is sodium carbonate, the reaction temperature is about 375 °C to 385 °C, and the gaseous oxidant is oxygen or air.
22. The process of claim 20, wherein said polychlorobiphenyls are present in at least about 90 weight percent of the total material.
23. The process of claim 1 , wherein the oxidant is present in an amount of between about 0.1 and 50% by weight of the material.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97916849A EP0888153B1 (en) | 1996-03-22 | 1997-03-19 | Method for hot and supercritical water oxidation of material using specific reactants |
| AT97916849T ATE194503T1 (en) | 1996-03-22 | 1997-03-19 | PROCESS FOR WARM AND SUPERCRITICAL WATER OXIDATION OF MATERIALS USING SPECIFIC REACTANTS |
| DE69702503T DE69702503T2 (en) | 1996-03-22 | 1997-03-19 | METHOD FOR WARM AND SUPERCRITICAL WATER OXIDATION OF SPECIFIC REACTANTS USING MATERIALS |
| JP53368797A JP3346773B2 (en) | 1996-03-22 | 1997-03-19 | A method for high temperature and supercritical water oxidation of materials using special reactants. |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/621,746 US5837149A (en) | 1996-03-22 | 1996-03-22 | Method for hot and supercritical water oxidation of material with addition of specific reactants |
| US08/621,746 | 1996-03-22 | ||
| US08/632,604 | 1996-04-15 | ||
| US08/632,604 US5746926A (en) | 1996-03-22 | 1996-04-15 | Method for hydrothermal oxidation of halogenated organic compounds with addition of specific reactants |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/632,604 Continuation-In-Part US5746926A (en) | 1996-03-22 | 1996-04-15 | Method for hydrothermal oxidation of halogenated organic compounds with addition of specific reactants |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/069,892 Continuation-In-Part US6010632A (en) | 1996-03-22 | 1998-04-29 | Hydrothermal oxidation of organic compounds with heterogenous neutralizing reagent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO1997034660A1 WO1997034660A1 (en) | 1997-09-25 |
| WO1997034660B1 true WO1997034660B1 (en) | 1997-10-30 |
Family
ID=27089042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1997/004443 WO1997034660A1 (en) | 1996-03-22 | 1997-03-19 | Method for hot and supercritical water oxidation of material using specific reactants |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5746926A (en) |
| EP (1) | EP0888153B1 (en) |
| JP (1) | JP3346773B2 (en) |
| AT (1) | ATE194503T1 (en) |
| CA (1) | CA2249404A1 (en) |
| DE (1) | DE69702503T2 (en) |
| WO (1) | WO1997034660A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6010632A (en) * | 1996-03-22 | 2000-01-04 | Sri International | Hydrothermal oxidation of organic compounds with heterogenous neutralizing reagent |
| JP3482306B2 (en) * | 1996-09-04 | 2003-12-22 | オルガノ株式会社 | Supercritical water oxidation method and apparatus for organic chlorine compounds |
| US5992326A (en) * | 1997-01-06 | 1999-11-30 | The Ensign-Bickford Company | Voltage-protected semiconductor bridge igniter elements |
| JP3649572B2 (en) * | 1997-04-15 | 2005-05-18 | 三菱重工業株式会社 | PCB decomposition method and PCB decomposition apparatus |
| DE19747696C2 (en) * | 1997-10-29 | 1999-09-23 | Karlsruhe Forschzent | Process for carrying out chemical reactions in supercritical aqueous systems |
| JP3664867B2 (en) * | 1998-03-13 | 2005-06-29 | 三菱重工業株式会社 | PCB decomposition reaction vessel |
| JP3546136B2 (en) * | 1998-03-13 | 2004-07-21 | 三菱重工業株式会社 | PCB decomposition method |
| JP3057250B2 (en) * | 1998-11-18 | 2000-06-26 | 財団法人石炭利用総合センター | Organic waste treatment method |
| EP1076041A3 (en) * | 1999-08-09 | 2001-12-12 | Nippon Shokubai Co., Ltd. | Method for decomposing or oxidizing dioxins and/or poly chlorinated biphenyls contained in liquid |
| US6416682B1 (en) | 1999-11-04 | 2002-07-09 | Ceramic Oxides International B.V. | Method of producing minerals under near-critical, critical and supercritical conditions |
| WO2001096247A1 (en) * | 2000-06-12 | 2001-12-20 | Auburn University | Supercritical water oxidation with reduced corrosion and enhanced oxidation rate |
| US6533499B2 (en) * | 2001-03-13 | 2003-03-18 | Boyd Breeding | Soil and groundwater remediation system |
| US6709602B2 (en) * | 2001-04-23 | 2004-03-23 | General Atomics | Process for hydrothermal treatment of materials |
| SE528840C2 (en) * | 2004-11-15 | 2007-02-27 | Chematur Eng Ab | Reactor and process for supercritical water oxidation |
| US8242323B2 (en) * | 2007-10-31 | 2012-08-14 | Ravi Jain | Detoxification of chemical agents |
| CO6150041A1 (en) * | 2008-12-19 | 2010-04-20 | Univ Del Valle | PROCESS FOR THE DISTRIBUTION OF TOXIC WASTE BY OXIDATION IN THE PRESENCE OF WATER AND OXYGEN AND CONTINUOUS UNIT FOR THE TREATMENT OF HAZARDOUS COMPOUNDS |
| JP6445836B2 (en) * | 2014-10-27 | 2018-12-26 | 原嶋 文子 | Decomposition method of organochlorine compounds |
| CN107055743B (en) * | 2017-05-27 | 2020-04-21 | 南京工业大学 | Catalytic purification method for rectification residual liquid in benzaldehyde preparation by toluene chlorination hydrolysis method |
| CA3105642A1 (en) | 2018-07-06 | 2020-01-09 | Beyond The Dome, Inc. | Supercritical oxidation of waste |
| CA3141768A1 (en) | 2019-06-28 | 2020-12-30 | Battelle Memorial Institute | Destruction of pfas via an oxidation process and apparatus suitable for transportation to contaminated sites |
| CN110723804A (en) * | 2019-10-24 | 2020-01-24 | 北京纬纶华业环保科技股份有限公司 | Equipment and method for treating polychlorinated biphenyl-containing substances by supercritical water oxidation method |
| CN113578935A (en) * | 2021-08-13 | 2021-11-02 | 中国天楹股份有限公司 | Resourceful treatment method for kitchen waste |
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| US4113446A (en) * | 1975-07-22 | 1978-09-12 | Massachusetts Institute Of Technology | Gasification process |
| US4380960A (en) * | 1978-10-05 | 1983-04-26 | Dickinson Norman L | Pollution-free low temperature slurry combustion process utilizing the super-critical state |
| JPS55160091A (en) * | 1979-05-30 | 1980-12-12 | Osaka Gas Co Ltd | Purification of gas and treatment of waste water |
| WO1981000854A1 (en) * | 1979-09-27 | 1981-04-02 | Modar Inc | Treatment of organic material in supercritical water |
| US4543190A (en) * | 1980-05-08 | 1985-09-24 | Modar, Inc. | Processing methods for the oxidation of organics in supercritical water |
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-
1996
- 1996-04-15 US US08/632,604 patent/US5746926A/en not_active Expired - Lifetime
-
1997
- 1997-03-19 DE DE69702503T patent/DE69702503T2/en not_active Expired - Fee Related
- 1997-03-19 JP JP53368797A patent/JP3346773B2/en not_active Expired - Fee Related
- 1997-03-19 AT AT97916849T patent/ATE194503T1/en not_active IP Right Cessation
- 1997-03-19 WO PCT/US1997/004443 patent/WO1997034660A1/en active IP Right Grant
- 1997-03-19 EP EP97916849A patent/EP0888153B1/en not_active Expired - Lifetime
- 1997-03-19 CA CA002249404A patent/CA2249404A1/en not_active Abandoned
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