WO2001002105A1 - Soil and/or groundwater remediation process - Google Patents

Soil and/or groundwater remediation process Download PDF

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Publication number
WO2001002105A1
WO2001002105A1 PCT/US2000/017231 US0017231W WO0102105A1 WO 2001002105 A1 WO2001002105 A1 WO 2001002105A1 US 0017231 W US0017231 W US 0017231W WO 0102105 A1 WO0102105 A1 WO 0102105A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxidizing agent
source
situ environment
reagent
contaminants
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2000/017231
Other languages
English (en)
French (fr)
Inventor
Richard S. Greenberg
Thomas Andrews
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to DE60041772T priority Critical patent/DE60041772D1/de
Priority to JP2001507588A priority patent/JP3793084B2/ja
Priority to AU57593/00A priority patent/AU780219B2/en
Priority to CA002370097A priority patent/CA2370097C/en
Priority to EP00943068A priority patent/EP1212149B1/en
Priority to DK00943068T priority patent/DK1212149T3/da
Publication of WO2001002105A1 publication Critical patent/WO2001002105A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate

Definitions

  • the present invention is directed to methods and systems for converting
  • the methods and systems include treatment of the contaminants with a
  • PCDD polychlorinated dibenzo-p-dioxins
  • PCDF polychlorinated dibenzofurans
  • the preferred metal catalysts include metal salts, iron oxyhydroxides, iron chelates,
  • reaction product complex is highly acidic with a pH in the range of 2 to 4, which is
  • AOPs in ex situ advanced oxidation processes
  • the metal catalyst can travel from the injection point throughout the aerial extent of the
  • turnover rate of the metal catalyst is moderated in order to promote more efficient
  • the present invention is directed to reagents and methods for treating
  • treating contaminants in an in situ environment comprising adding a source of an
  • oxidizing agent preferably a stabilized source of oxidizing agent, capable of oxidizing
  • a reagent comprising an aqueous solution of a metal catalyst having a pH in the
  • the present method is applicable to all areas of the in situ environment
  • the stabilized oxidizing agent in accordance with a further aspect of the invention, the stabilized oxidizing
  • the capillary fringe is that portion of the
  • oxidizing agent and the catalytic reagent are injected into an area of the subsurface
  • the saturated unconsolidated zone environment known as the saturated unconsolidated zone.
  • unconsolidated zone is that portion of the contamination at a site which lies within the
  • the catalytic reagent are injected at elevated pressures into the fractured bedrock to
  • catalytic reagent are injected into an situ environment to enhance the operation and
  • the present invention enhances these conventional systems that
  • the present invention is generally directed to methods and systems for removing
  • PCBs polychorinated biphenyls
  • PCP pentachlorophenol
  • remediation of a contaminated environment in situ is performed by providing a reagent
  • an oxidizing agent such as a peroxide and preferably hydrogen
  • reagent reacts in situ to form a reactive species (e.g. hydoxyl radical), as hereinafter
  • stabilized source of the oxidizing agent are alternately injected (i.e. in cycles) into the
  • catalytic reagent and the stabilized source of the oxidizing agent are continuously
  • the catalytic reagent is the first injection in the
  • stabilized source of the oxidizing agent is the first injection in the soil and/or
  • the catalytic reagent is injected into the in situ environment in at
  • substantially pH neutral catalytic reagent provides better dispersion of reagents in the
  • the present catalytic reagent moderates the catalytic turnover rate
  • the oxidation efficiency of the reagent of the present invention is
  • the sources of oxidizing agents employed in the present invention are those that
  • calcium peroxide can be used as an effective source of oxidizing agent for
  • Hydrogen peroxide is the
  • Ozone Another suitable source of the oxidizing agent is ozone. Ozone has previously
  • Ozone under well known conditions can generate hydroxyl
  • radicals which is a preferred oxidizing agent.
  • oxidizing agent be capable of generating hydroxyl radicals in sufficient quantity to
  • the source of the oxidizing agent e.g. peroxide
  • the source of the oxidizing agent is preferably
  • stabilized peroxide is used at a
  • Suitable stabilizers include acids and salts thereof.
  • the catalytic reagent employed in the present invention is obtained by mixing an
  • the resulting solution may be neutralized with a pH modifying agent
  • Suitable catalysts include metal
  • Preferred metal salts include iron (II) and (III) salts, copper (II) salts and
  • manganese (II) salts are selected from the group consisting of
  • ferric nitrate Preferred iron oxyhydroxides include goethite, hematite and magnetite.
  • chelates i n include , for exa mple , Fe(l l/l 11 )-EDTA, Fe( I l/l 11 )-NTA, Fe(ll/III)-hydroxyethyliminodiaceticacid (HEIDA), Fe(ll/III)-mucicacid, Fe(ll/lll)-malonic
  • Fe(ll/lll)-oxalic acid Fe(ll/lll)-gallicacid, Fe(ll/lll)-picolinicacid, Fe(ll/lll)-dipicolinicacid,
  • Fe(ll/lll)-hexaketocyclohexane (HKCH).
  • the most preferred catalyst is iron sulfate or
  • pH modifying agents include strong bases such as alkali metal hydroxides (e.g.
  • weak bases such as salts of weak acids (e.g. sodium acetate
  • the in situ environment for most soil and/or groundwater sites includes a water
  • the capillary fringe is that portion of the
  • vadose region which lies just above the water table.
  • the capillary fringe is formed by contact between the water table and the dry
  • LNAPLs having a density less than water (e.g. BTEX contamination) due to the
  • water table elevation may deposit additional contamination in the capillary fringe and/or
  • reagent can be administered to the in situ environment by any method considered
  • administration can be directly into the
  • the capillary fringe constitutes the in situ environment for treatment
  • DNAPLs mostly resides at or near the bottom of the saturated zone due to its tendency to sink in water (e.g. chlorinated solvents).
  • water e.g. chlorinated solvents
  • the saturated zone constitutes the in situ environment for treatment of the
  • oxidizing agent and catalytic reagent are administered into the bottom layers of the
  • the saturation depth or depth of the saturated zone is very high at some
  • source of the oxidizing agent and catalytic reagent are administered.
  • source of the oxidizing agent and catalytic reagent are administered.
  • injection wells with adjustable depth injectors are utilized at sites with high saturation
  • the depth variation is performed after each
  • the reagents of the present invention can be any suitable reagents of the present invention.
  • the reagents of the present invention can be any suitable reagents of the present invention.
  • the reagents are then injected into the fractures at applied elevated
  • pressures typically in the range of from about 20 to 100 psi.
  • bedrock fractures under elevated pressures can be accomplished either alone or in
  • Such systems include pump and
  • the stabilized source of the oxidizing agent and the metal found in many subsurface environments. As indicated above, the stabilized source of the oxidizing agent and the metal
  • catalyst reagent can be administered directly into the in situ environment.
  • catalyst reagent can be administered directly into the in situ environment.
  • the concentration of the contaminants of interest e.g. hydrocarbons.
  • Typical sample weights can be in the range of from
  • a catalyst such as a chelated iron (II) salt is premixed with water
  • a pH adjusting agent such as a base
  • the metal catalyst reagent within a pH range of from about 5 to 8.
  • a control sample is set up for each type of sample undergoing the study to
  • reagent may be performed under both applied and hydrostatic pressure into the in situ
  • the stabilized source of the oxidizing agent and metal catalyst e.g. clays and/or silts.
  • reagent may be injected into the subsurface and allowed to disperse over a period of
  • period may vary depending, in part, on the soil type.
  • injection procedures are preferably associated with a
  • a typical system involves injection wells installed with screens set
  • the pumping system can include a low horsepower pump at
  • source of the oxidizing agent and catalytic reagent may be pumped in short pulse
  • the injection efficiency into less permeable soils is improved by subjecting the less
  • the stabilized source of the oxidizing agent and metal catalyst is less dense than water, the stabilized source of the oxidizing agent and metal catalyst
  • reagent are injected directly into the capillary fringe, located just above the water table.
  • the stabilized source of the oxidizing agent As previously indicated, the stabilized source of the oxidizing agent and the
  • catalytic reagent are alternately injected (i.e. in cycles) into the in situ environment.
  • the stabilized source of the oxidizing agent and the catalytic reaction is another embodiment, the stabilized source of the oxidizing agent and the catalytic reaction.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Soil Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Catalysts (AREA)
  • Cultivation Of Plants (AREA)
  • Road Paving Structures (AREA)
PCT/US2000/017231 1999-07-01 2000-06-22 Soil and/or groundwater remediation process Ceased WO2001002105A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE60041772T DE60041772D1 (de) 1999-07-01 2000-06-22 Verfahren zur boden- und/oder grundwassersanierung
JP2001507588A JP3793084B2 (ja) 1999-07-01 2000-06-22 土壌及び／又は地下水の改善方法
AU57593/00A AU780219B2 (en) 1999-07-01 2000-06-22 Soil and/or groundwater remediation process
CA002370097A CA2370097C (en) 1999-07-01 2000-06-22 Soil and/or groundwater remediation process
EP00943068A EP1212149B1 (en) 1999-07-01 2000-06-22 Soil and/or groundwater remediation process
DK00943068T DK1212149T3 (da) 1999-07-01 2000-06-22 Fremgangsmåde til jord- og/eller grundvandsoprydning

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/345,922 US6319328B1 (en) 1999-07-01 1999-07-01 Soil and/or groundwater remediation process
US09/345,922 1999-07-01

Publications (1)

Publication Number Publication Date
WO2001002105A1 true WO2001002105A1 (en) 2001-01-11

Family

ID=23357109

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/017231 Ceased WO2001002105A1 (en) 1999-07-01 2000-06-22 Soil and/or groundwater remediation process

Country Status (10)

Country Link
US (2) US6319328B1 (enExample)
EP (1) EP1212149B1 (enExample)
JP (1) JP3793084B2 (enExample)
AT (1) ATE424942T1 (enExample)
AU (1) AU780219B2 (enExample)
CA (1) CA2370097C (enExample)
DE (1) DE60041772D1 (enExample)
DK (1) DK1212149T3 (enExample)
ES (1) ES2322540T3 (enExample)
WO (1) WO2001002105A1 (enExample)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002254062A (ja) * 2001-02-28 2002-09-10 Shimizu Corp 有機物汚染土壌の原位置修復法と修復装置
WO2011042884A1 (fr) 2009-10-09 2011-04-14 Total S.A. Procédé d'oxydation de composes organiques
EP1647529B1 (en) * 2003-08-22 2015-09-30 Peroxychem Spain, S.L.U. Method for purifying wastewaters
AU2020203659B2 (en) * 2018-10-15 2021-04-08 Anthony Doherty Method of treating contaminated groundwater

Families Citing this family (43)

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US7338563B2 (en) * 1996-10-16 2008-03-04 Clark Steve L Process for cleaning hydrocarbons from soils
US6923914B2 (en) * 1996-12-17 2005-08-02 Global Biosciences, Inc. Remediation of metal contaminants with hydrocarbon-utilizing bacteria
US7270499B2 (en) * 1998-04-20 2007-09-18 Greenberg Richard S Soil and/or groundwater remediation process
RS49639B (sr) * 1998-05-14 2007-08-03 Soll, Peter, Primena peroksida alkalnozemnih metala za imobilisanje fosfata u vodama, tlu, talozima i/ili mulju
FR2806939B1 (fr) * 2000-03-30 2002-12-06 Patrice Jean Albert Stengel Procede et dispositif de depollution des sables ou des terres souilles par des hydrocarbures ou des germes infectieux
US6630105B1 (en) * 2000-09-27 2003-10-07 The United States Of America As Represented By The United States Department Of Energy Method and apparatus for the gas phase decontamination of chemical and biological agents
DE10114177A1 (de) * 2001-03-23 2002-09-26 Degussa Verfahren zur Aufbereitung schadstoffhaltiger Wässer
US7329532B2 (en) 2001-07-27 2008-02-12 Global Biosciences, Inc. Remediation of sulfur-containing pollutants with hydrocarbon-utilizing bacteria
US7928277B1 (en) 2002-02-11 2011-04-19 Cox Jr Henry Wilmore Method for reducing contamination
AU2003215360A1 (en) * 2002-02-22 2003-09-09 University Of Utah Research Foundation Remediation with ozone of sediments containing organic contaminants
WO2004002902A1 (en) * 2002-06-26 2004-01-08 Fmc Corporation Oxidation of organic compounds
AUPS329702A0 (en) * 2002-07-01 2002-07-18 Sdp Pty Ltd Method of soil geochemistry analysis prospecting
US6960330B1 (en) 2002-07-12 2005-11-01 Cox Jr Henry Wilmore Method for reducing H2S contamination
US7074959B2 (en) 2002-08-01 2006-07-11 New Mexico Highlands University Methods and systems for remediating hydrazine-contaminated equipment and/or surfaces
US7175770B2 (en) * 2003-03-17 2007-02-13 Groundwater And Environmental Services, Inc. Methods and systems for groundwater remediation
US7264419B2 (en) * 2003-03-19 2007-09-04 Applied Process Technology, Inc. System and method for remediating contaminated soil and groundwater in situ
US20040197150A1 (en) * 2003-04-04 2004-10-07 Xpert Design And Diagnostics, Llc Chemical oxidation of organic and inorganic contaminants by chelated transition metals catalyzed persulfate
US7160471B2 (en) * 2003-05-06 2007-01-09 Westinghouse Savannah River Company, Llc In-situ generation of oxygen-releasing metal peroxides
US7662294B1 (en) 2004-02-02 2010-02-16 Cox Jr Henry Wilmore Method for reducing organic contamination
HUE035667T2 (en) * 2004-05-27 2018-05-28 Solvay Combined chemical oxidation / facilitated bioremediation of contaminants
US7833423B2 (en) * 2004-06-01 2010-11-16 Regenesis Bioremediation Products Enhanced oxidation process for removal of water and soil contaminants
JP4596524B2 (ja) * 2004-10-08 2010-12-08 オルガノ株式会社 汚染土壌浄化方法
US7481974B2 (en) * 2005-02-17 2009-01-27 Charles Sizer Method and apparatus for sterilizing containers
WO2006123574A1 (ja) * 2005-05-19 2006-11-23 Mitsubishi Gas Chemical Company, Inc. 土壌及び／又は地下水の浄化方法
ITMI20051559A1 (it) * 2005-08-10 2007-02-11 Eni Spa Procedimento per la rimozione di barriere impermeabili presenti nei pozzi petroliferi
EP2059483A4 (en) * 2006-08-17 2012-03-28 Dowling College WATER DETOXIFICATION METHODS, CATALYSTS THEREFOR AND CATALYST PRODUCTION PROCESS
US8609926B1 (en) 2006-11-21 2013-12-17 Henry Wilmore Cox, Jr. Methods for managing sulfide in wastewater systems
US7846408B1 (en) 2006-11-21 2010-12-07 Cox Jr Henry Wilmore Compositions, methods, and systems for managing total sulfide
ITMI20080995A1 (it) * 2008-05-28 2009-11-29 Eni Spa Metodo per la bonifica in situ di un'area contaminata da composti organici
US8293696B2 (en) * 2009-02-06 2012-10-23 Ecolab, Inc. Alkaline composition comprising a chelant mixture, including HEIDA, and method of producing same
DK2396089T3 (da) * 2009-02-11 2017-11-20 Natural Energy Systems Inc Fremgangsmåde til omdannelse af organisk materiale til methanrig brændgas
WO2011074007A2 (en) 2009-12-18 2011-06-23 Bharat Petroleum Corporation Limited Process and composition for bioremediation of oily sludge
JP5733781B2 (ja) 2010-03-31 2015-06-10 国立研究開発法人農業・食品産業技術総合研究機構 コーヒー粕あるいは茶殻を原料とするフェントン反応触媒
TWI551551B (zh) * 2010-04-30 2016-10-01 三菱瓦斯化學股份有限公司 過氧化物活性化劑以及土壤及／或地下水之淨化方法
JP2012239952A (ja) * 2011-05-17 2012-12-10 National Agriculture & Food Research Organization 還元性有機物を原料とするフェントン反応触媒
JP5888877B2 (ja) * 2011-05-30 2016-03-22 株式会社Adeka 化学物質分解剤組成物及びそれを用いた化学物質の分解処理方法
CA2911436A1 (en) 2013-05-24 2014-11-27 Solvay Sa Non-oxidizer particles
US9771284B2 (en) * 2013-12-30 2017-09-26 Environmental Technology and Investment Corporation Situ chemical fixaton of metal contaminants
US10252303B2 (en) * 2015-06-01 2019-04-09 Michael Lindstrom Method to remediate soil and groundwater
US20170297932A1 (en) * 2016-04-14 2017-10-19 Phillips 66 Company Method of remediating groundwater
BR112020017642A2 (pt) * 2018-03-01 2020-12-22 Arkema Inc. Tratamento de solo usando peróxido
JP7267112B2 (ja) * 2019-06-04 2023-05-01 ジオテクノス株式会社 汚染土壌の浄化方法
CN112537839A (zh) * 2020-11-17 2021-03-23 同济大学 一种过氧化钙-黄铁矿修复河网地区地下水重金属污染的办法

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US5755977A (en) * 1996-07-03 1998-05-26 Drexel University Continuous catalytic oxidation process
US5789649A (en) * 1995-08-29 1998-08-04 E. I. Du Pont De Nemours And Company Method for Remediating contaminated soils

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US5741427A (en) * 1996-03-14 1998-04-21 Anesys Corp. Soil and/or groundwater remediation process
US5755977A (en) * 1996-07-03 1998-05-26 Drexel University Continuous catalytic oxidation process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002254062A (ja) * 2001-02-28 2002-09-10 Shimizu Corp 有機物汚染土壌の原位置修復法と修復装置
EP1647529B1 (en) * 2003-08-22 2015-09-30 Peroxychem Spain, S.L.U. Method for purifying wastewaters
WO2011042884A1 (fr) 2009-10-09 2011-04-14 Total S.A. Procédé d'oxydation de composes organiques
AU2020203659B2 (en) * 2018-10-15 2021-04-08 Anthony Doherty Method of treating contaminated groundwater

Also Published As

Publication number Publication date
AU780219B2 (en) 2005-03-10
CA2370097A1 (en) 2001-01-11
EP1212149A1 (en) 2002-06-12
EP1212149A4 (en) 2004-09-29
US20020002983A1 (en) 2002-01-10
JP3793084B2 (ja) 2006-07-05
CA2370097C (en) 2006-11-21
ATE424942T1 (de) 2009-03-15
US6319328B1 (en) 2001-11-20
JP2003503197A (ja) 2003-01-28
ES2322540T3 (es) 2009-06-23
DE60041772D1 (de) 2009-04-23
DK1212149T3 (da) 2009-06-08
AU5759300A (en) 2001-01-22
EP1212149B1 (en) 2009-03-11

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