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DE19923171A1 - Mobilization of heavy metal, metalloid and actinide elements, used for reducing pollution in soil, sediment, deposits and water-purification slurry, involves treating substrate with non-oxidizing gas in presence of water and reducing agent - Google Patents

Mobilization of heavy metal, metalloid and actinide elements, used for reducing pollution in soil, sediment, deposits and water-purification slurry, involves treating substrate with non-oxidizing gas in presence of water and reducing agent

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Publication number
DE19923171A1
DE19923171A1 DE1999123171 DE19923171A DE19923171A1 DE 19923171 A1 DE19923171 A1 DE 19923171A1 DE 1999123171 DE1999123171 DE 1999123171 DE 19923171 A DE19923171 A DE 19923171A DE 19923171 A1 DE19923171 A1 DE 19923171A1
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Germany
Prior art keywords
water
substrate
elements
substrates
oxidizing gas
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DE1999123171
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German (de)
Inventor
Rainer Haas
Franz D Oeste
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Individual
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Priority to DE1999123171 priority Critical patent/DE19923171A1/en
Publication of DE19923171A1 publication Critical patent/DE19923171A1/en
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/10Reclamation of contaminated soil microbiologically, biologically or by using enzymes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/02Extraction using liquids, e.g. washing, leaching, flotation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Soil Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biotechnology (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • Molecular Biology (AREA)
  • Mycology (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treating Waste Gases (AREA)
  • Treatment Of Sludge (AREA)

Abstract

Improving the mobility and/or mobilization of heavy metal, metalloid and actinide elements from substrates comprises treating the substrates with a non-oxidizing gas phase in the presence of moisture and reducing agent.

Description

Die Erfindung beschreibt ein Verfahren zur Freisetzung von schwerlöslichen Metalloid- und Schwermetallverbindungen aus Böden und Sedimenten.The invention describes a method for the release of sparingly soluble Metalloid and heavy metal compounds from soils and sediments.

Dabei handelt es sich um Metalloide, vorzugsweise Arsen, Antimon und Selen sowie um Schwermetalle, vorzugsweise Nickel, Cadmium, Kupfer, Blei, Quecksilber und Actiniden wie Uran und Thorium.These are metalloids, preferably arsenic, antimony and selenium as well around heavy metals, preferably nickel, cadmium, copper, lead, mercury and Actinides such as uranium and thorium.

Ein herkömmliches Verfahren zur Erdreichreinigung ist z. B. die Wäsche unter Zuhilfenahme von Tensiden. Dabei werden in der Regel die o. g. Elemente als schwerlösliche Verbindungen in der Schlammphase angereichert, die aus diesem Grunde meist als Sonderabfall behandelt oder deponiert werden muß.A conventional method for soil cleaning is e.g. B. the laundry under Using surfactants. As a rule, the above-mentioned Elements as poorly soluble compounds in the sludge phase enriched from this Basically mostly has to be treated as special waste or landfilled.

Auch geogen oder anthropogen bedingt existieren Böden und Ablagerungen, in denen Schwermetalle und Metalloide als schwerlösliche Verbindungen festgelegt sind. Geringfügige Änderungen, z. B. pH-Wert-Veränderungen durch sauren Regen, können diese Metalle oder Metalloide mobilisieren. Daher stellen diese Böden und Ablagerungen eine latente Gefahr für die Umwelt dar.Soils and deposits also exist in geogenic or anthropogenic conditions Heavy metals and metalloids are defined as poorly soluble compounds. Minor changes, e.g. B. pH changes due to acid rain mobilize these metals or metalloids. Therefore, these floors and Deposits pose a latent danger to the environment.

Das erfindungsgemäße Verfahren gemäß Anspruch 1 bis 13 stellt eine wirtschaftliche Möglichkeit zur Entfernung dieser Substanzen aus Substraten, vorzugsweise Böden, Sedimente, Ablagerungen oder Wasserreinigungsschlämme, dar.The inventive method according to claims 1 to 13 represents an economical Possibility to remove these substances from substrates, preferably soils, Sediments, deposits or water purification sludges.

Nach dem erfindungsgemäßen Verfahren werden die o. g. Zielelemente (Schwermetalle und/oder Metalloide) durch die Behandlung mit Gasphasen in Gegenwart von Reduktionsmitteln aus ihrer schwerlöslichen Bindungsform freigesetzt. Dies gelingt überraschenderweise hinreichend quantitativ.According to the inventive method, the above-mentioned. Target elements (Heavy metals and / or metalloids) by treatment with gas phases in Presence of reducing agents from their poorly soluble binding form released. Surprisingly, this is sufficiently quantitative.

Als Gasphasen können reduzierende Gase oder Gasgemische, vorzugsweise bestehend aus Wasserstoff, Methan, Kohlendioxid, Rauchgas, Wasserstoff-Stickstoff-Gemischen, Gemische von Stickstoff mit gasförmigen organischen Verbindungen, vorzugsweise Methan eingesetzt werden.Reducing gases or gas mixtures can preferably exist as gas phases from hydrogen, methane, carbon dioxide, flue gas, Hydrogen-nitrogen mixtures, mixtures of nitrogen with gaseous ones organic compounds, preferably methane.

Es können auch Inertgase, vorzugsweise Edelgase und/oder Stickstoff, eingesetzt werden, wenn das Substrat hinreichende Mengen reduzierender Komponenten, vorzugsweise Humus, Rindenmulch oder Sägespäne enthält.Inert gases, preferably noble gases and / or nitrogen, can also be used if the substrate has sufficient quantities of reducing components, preferably contains humus, bark mulch or sawdust.

Durch die Begasung der Substrate mit reduzierenden Gasen bzw. Inertgasen wird die Tätigkeit der anaeroben Mikroorganismen in den Substraten offenbar so stark aktiviert und begünstigt, daß die Zielelemente aus ihrer Bindung gelöst werden können.By gassing the substrates with reducing gases or inert gases Activity of the anaerobic microorganisms in the substrates apparently so strongly activated and favors that the target elements can be released from their binding.

Falls das Substrat leicht abbaubare Reduktionsmittel enthält oder mit solchen versetzt ist (z. B. Glucose), kann es hinreichend sein, das Substrat relativ gasdicht einzuhausen, um die Zielelemente zu mobilisieren. In diesem Fall kann auf die Anwendung zusätzlicher Gase komplett verzichtet werden: der im Porenvolumen enthaltene Gasgehalt kann hinreichend sein, genügend anaerobe Bedingungen aufrecht zu erhalten, da der für das erfindungsgemäße Verfahren störende Sauerstoff entfernt wird.If the substrate contains or contains easily degradable reducing agents (e.g. glucose), it may be sufficient to enclose the substrate relatively gas-tight, to mobilize the target elements. In this case, the application additional gases are completely eliminated: the one contained in the pore volume Gas content can be sufficient to maintain sufficient anaerobic conditions  obtained because the oxygen which is disruptive to the process of the invention is removed becomes.

Zur Durchführung des erfindungsgemäßen Verfahrens muß dafür Sorge getragen werden, daß ein Mindestwassergehalt im Substrat verbleibt. Dies geschieht vorzugsweise so, daß das behandelnde Gas befeuchtet wird. Es ist stattdessen auch möglich, das Substrat vor der Gasbehandlung zu befeuchten oder das Gas im Kreislauf zu führen. Das Wasser kann reduzierende Verbindungen enthalten.Care must be taken to carry out the method according to the invention be that a minimum water content remains in the substrate. this happens preferably so that the treating gas is humidified. Instead, it is too possible to moisten the substrate before the gas treatment or the gas in the To lead a cycle. The water can contain reducing compounds.

Unter derart anaeroben Bedingungen können Arsen, Antimon und Quecksilber als gasförmige methylierte Verbindungen flüchtig werden.Under such anaerobic conditions, arsenic, antimony and mercury can be used as gaseous methylated compounds become volatile.

Überraschenderweise wurde unter diesen Bedingungen auch Nickeltetracarbonyl aus Nickel-enthaltendem Substrat in die Gasphase freigesetzt.Surprisingly, nickel tetracarbonyl was also produced under these conditions Nickel-containing substrate released into the gas phase.

Die gasförmig freigesetzten Zielelemente werden mit einem Adsorbens, vorzugsweise mit einem Aktivkohleadsorber, aus der Gasphase entfernt.The gaseous released target elements are preferably adsorbed with an activated carbon adsorber, removed from the gas phase.

Das hinreichend lange derart in den anaeroben Zustand versetzte Substrat enthält nunmehr die Zielelemente in einer derart wasserlöslichen Form, daß sie ohne weitere Hilfsmittel wie z. B. EDTA mit einfacher Wasserwäsche aus dem Substrat extrahiert werden können.Contains the substrate which has been placed in the anaerobic state for a sufficiently long time now the target elements in such a water-soluble form that they without further Tools such as B. EDTA extracted with simple water wash from the substrate can be.

In einem anschließenden Schritt werden die im Wasser gelösten Zielelemente vorzugsweise durch Sorption oder gegebenenfalls auch durch Fällung oder andere bekannte Verfahren aus dem Wasser entfernt.In a subsequent step, the target elements dissolved in the water preferably by sorption or optionally also by precipitation or others known methods removed from the water.

Das Waschwasser wird vorzugsweise im Kreislauf geführt.The wash water is preferably circulated.

Die Behandlung der Substrate kann in situ, vorzugsweise mit Abdeckung oder auf einer vorzugsweise eingehausten Miete erfolgen.The treatment of the substrates can be in situ, preferably with cover or on a preferably rent.

Claims (13)

1. Verfahren zur Mobilitätsverbesserung und/oder Mobilisierung von Elementen aus den Gruppen der Schwermetalle, Metalloide und Actiniden aus Substraten, dadurch gekennzeichnet, daß die Substrate in der Gegenwart von Feuchtigkeit und Reduktionsmitteln mit nicht oxidierender Gasphase behandelt werden.1. Process for improving mobility and / or mobilization of elements from the groups of heavy metals, metalloids and actinides from substrates, characterized in that the substrates are treated with non-oxidizing gas phase in the presence of moisture and reducing agents. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Substrate in der Gegenwart von anaeroben Mikroorganismen behandelt werden.2. The method according to claim 1, characterized in that the substrates in the Treated in the presence of anaerobic microorganisms. 3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß dem Substrat und/oder der nicht oxidierenden Gasphase Feuchtigkeit zugesetzt wird.3. The method according to claim 1 and 2, characterized in that the substrate and / or moisture is added to the non-oxidizing gas phase. 4. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß der zugesetzten Feuchtigkeit Reduktionsmittel zugeschlagen werden.4. The method according to claim 1 to 3, characterized in that the added Moisture reducing agents can be added. 5. Verfahren nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß als Gase Methan, Wasserstoff, Stickstoff, Kohlendioxid, Edelgase, Rauchgas bzw. gasförmige organische Verbindungen als Einzelstoffe oder in Gemischen aus Kombination mehrerer Gase eingesetzt werden.5. The method according to claim 1 to 4, characterized in that methane as gases, Hydrogen, nitrogen, carbon dioxide, noble gases, flue gas or gaseous organic compounds as individual substances or in mixtures of combinations several gases can be used. 6. Verfahren nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß als Gasgemisch das bei der Umsetzung von reduzierenden Substratbestandteilen mit dem im Substratporenvolumen vorhandenen Gasgemisch entstandene Reaktionsgas eingesetzt wird.6. The method according to claim 1 to 5, characterized in that the gas mixture in the implementation of reducing substrate components with the im Existing gas mixture used in the substrate pore volume becomes. 7. Verfahren nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß die Substratbehandlung in situ oder auf einer Miete erfolgt.7. The method according to claim 1 to 6, characterized in that the Substrate treatment is done in situ or on a rental. 8. Verfahren nach Anspruch 1 bis 7, dadurch gekennzeichnet, daß Substratbehandlung eingehaust durchgeführt wird.8. The method according to claim 1 to 7, characterized in that substrate treatment is housed. 9. Verfahren nach Anspruch 1 bis 8, dadurch gekennzeichnet, daß die mobilisierten Elemente aus dem Substrat entfernt werden.9. The method according to claim 1 to 8, characterized in that the mobilized Elements are removed from the substrate. 10. Verfahren nach Anspruch 1 bis 9, dadurch gekennzeichnet, daß die Entfernung der gasförmigen mobilisierten Elemente mit einem Adsorbens vorgenommen wird.10. The method according to claim 1 to 9, characterized in that the removal the gaseous mobilized elements is carried out with an adsorbent. 11. Verfahren nach Anspruch 1 bis 10, dadurch gekennzeichnet, daß die Entfernung der gasförmigen mobilisierten Elemente mittels Aktivkohle durchgeführt wird.11. The method according to claim 1 to 10, characterized in that the removal the gaseous mobilized elements is carried out using activated carbon. 12. Verfahren nach Anspruch 1 bis 11, dadurch gekennzeichnet, daß die Entfernung der wasserlöslichen mobilisierten Elemente durch Substratbehandlung mit Wasser vorgenommen wird.12. The method according to claim 1 to 11, characterized in that the removal of the water-soluble mobilized elements by substrate treatment with water is made. 13. Verfahren nach Anspruch 1 bis 12, dadurch gekennzeichnet, daß das Verfahren auf die Substrate Erdreich, Sediment, Ablagerungen und Wasserreinigungsschlämme angewendet wird.13. The method according to claim 1 to 12, characterized in that the method on the substrates soil, sediment, deposits and water purification sludge is applied.
DE1999123171 1999-05-20 1999-05-20 Mobilization of heavy metal, metalloid and actinide elements, used for reducing pollution in soil, sediment, deposits and water-purification slurry, involves treating substrate with non-oxidizing gas in presence of water and reducing agent Withdrawn DE19923171A1 (en)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3605042A1 (en) * 1986-02-18 1987-08-20 Peter A Prof Dr Ing Wilderer process for the biological treatment of contaminated soils, and device for carrying out the process
EP0324465A1 (en) * 1988-01-15 1989-07-19 Dr. Wolman GmbH Process for the decontamination of soil contaminated with chromate
DE4227769A1 (en) * 1992-08-23 1994-02-24 Biotechnolog Forschung Gmbh Bacterial strains for mercury reduction and processes for their production
DE4304446A1 (en) * 1993-02-13 1994-08-18 Hans Dipl Ing Friedmann Process for separating off heavy metals
WO1996020797A1 (en) * 1995-01-05 1996-07-11 Ulli Bartsch Biotechnological purification of ground and water containing heavy metals
DE19505514A1 (en) * 1995-02-10 1996-08-14 Lausch Gmbh & Co Kg Umwelt Und Combined decontamination of soil polluted with difficult degradable organic pollutants and heavy metals
US5711020A (en) * 1993-04-09 1998-01-20 The United States Of America As Represented By The Environmental Protection Agency Method for remediating environmental contaminants
WO1998047820A1 (en) * 1997-03-07 1998-10-29 Budel Zink B.V. Method for in-situ immobilisation of heavy metals and/or sulphate in water-containing zones
DE19828665A1 (en) * 1997-06-26 1999-01-07 Chemical Land Holdings Inc Process for the reduction of hexavalent chromium in soils, sediments, industrial waste and other contaminated materials using ascorbic acid
US5888021A (en) * 1995-12-19 1999-03-30 Canon Kabushiki Kaisha Method and apparatus for remediation of contaminated soil

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3605042A1 (en) * 1986-02-18 1987-08-20 Peter A Prof Dr Ing Wilderer process for the biological treatment of contaminated soils, and device for carrying out the process
EP0324465A1 (en) * 1988-01-15 1989-07-19 Dr. Wolman GmbH Process for the decontamination of soil contaminated with chromate
DE4227769A1 (en) * 1992-08-23 1994-02-24 Biotechnolog Forschung Gmbh Bacterial strains for mercury reduction and processes for their production
DE4304446A1 (en) * 1993-02-13 1994-08-18 Hans Dipl Ing Friedmann Process for separating off heavy metals
US5711020A (en) * 1993-04-09 1998-01-20 The United States Of America As Represented By The Environmental Protection Agency Method for remediating environmental contaminants
WO1996020797A1 (en) * 1995-01-05 1996-07-11 Ulli Bartsch Biotechnological purification of ground and water containing heavy metals
DE19505514A1 (en) * 1995-02-10 1996-08-14 Lausch Gmbh & Co Kg Umwelt Und Combined decontamination of soil polluted with difficult degradable organic pollutants and heavy metals
US5888021A (en) * 1995-12-19 1999-03-30 Canon Kabushiki Kaisha Method and apparatus for remediation of contaminated soil
WO1998047820A1 (en) * 1997-03-07 1998-10-29 Budel Zink B.V. Method for in-situ immobilisation of heavy metals and/or sulphate in water-containing zones
DE19828665A1 (en) * 1997-06-26 1999-01-07 Chemical Land Holdings Inc Process for the reduction of hexavalent chromium in soils, sediments, industrial waste and other contaminated materials using ascorbic acid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Schwermetalle lösen. In: Umwelt, Bd.28, 1998, Nr.3, März, S.55 *

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