DE19618663A1 - Decontaminating plastics mat - Google Patents

Decontaminating plastics mat

Info

Publication number
DE19618663A1
DE19618663A1 DE1996118663 DE19618663A DE19618663A1 DE 19618663 A1 DE19618663 A1 DE 19618663A1 DE 1996118663 DE1996118663 DE 1996118663 DE 19618663 A DE19618663 A DE 19618663A DE 19618663 A1 DE19618663 A1 DE 19618663A1
Authority
DE
Germany
Prior art keywords
mercury
plastic
plastics
contaminated
decontaminating
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.)
Withdrawn
Application number
DE1996118663
Other languages
German (de)
Inventor
Detlef Fender
Juergen Ziemann
Gunter Dr Feix
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.)
Dow Olefinverbund GmbH
Original Assignee
Buna Sow Leuna Olefinverbund GmbH
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 Buna Sow Leuna Olefinverbund GmbH filed Critical Buna Sow Leuna Olefinverbund GmbH
Priority to DE1996118663 priority Critical patent/DE19618663A1/en
Publication of DE19618663A1 publication Critical patent/DE19618663A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • 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
    • A62D2101/24—Organic substances containing heavy metals
    • 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
    • A62D2101/40—Inorganic substances
    • A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0293—Dissolving the materials in gases or liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/06—PVC, i.e. polyvinylchloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/065—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts containing impurities
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Landscapes

  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Decontaminating plastics materials contaminated with Hg or Hg compounds comprises treating the comminuted contaminated plastics material with excess of an oxidising agent which has an electrochemical potential of greater than 0.85 V and which does not decompose the plastics matrix, to convert the Hg or Hg compounds into a dissolved form, and separating this from the plastics matrix.

Description

Die Erfindung betrifft ein Verfahren zur Dekontaminierung von mit Quecksilber und seinen Verbindungen belasteten Kunststoffen.The invention relates to a method for the decontamination of mercury and its connections contaminated plastics.

Es ist bekannt, daß mit Quecksilber belastete Kunststoffe, bei denen eine mecha­ nische Trennung nicht möglich ist, durch Deponierung entsorgt werden. Die sich daraus ergebenden Probleme sind hinreichend bekannt.It is known that mercury-contaminated plastics in which a mecha African separation is not possible to be disposed of by landfill. Which problems resulting therefrom are well known.

Die Erfindung in der DE 23 34 879 betrifft die Verwendung einer Polythiurampoly­ sulfidverbindung oder einer Mischung dieser Verbindungen zum Entfernen von Schwermetallen. Anwendungszweck dieser Erfindung ist die Entfernung von Schwermetallen aus der Umwelt.The invention in DE 23 34 879 relates to the use of a polythiuram poly sulfide compound or a mixture of these compounds for removing Heavy metals. The purpose of this invention is to remove Heavy metals from the environment.

Die DE 37 03 922 bezieht sich auf ein Verfahren zum Entfernen von in Böden ent­ haltenen Schwermetallen wie Blei, Cadmium und Quecksilber durch Zugabe eines sauren Lösungsmittels.DE 37 03 922 relates to a method for removing ent in soils heavy metals such as lead, cadmium and mercury by adding a acidic solvent.

Aus der DE 42 33 600 ist bekannt, daß Kunststoff-Restmaterialien in einer wäßrigen, alkoholischen Lösung, deren ph-Wert über 12 liegt, in verdünnter Natronlauge oder in einer wäßrigen Suspension aus Calciumhydroxid gewaschen werden, wobei sich die metallischen Verunreinigungen unter Wasserstoffbildung auflösen.From DE 42 33 600 it is known that plastic residual materials in an aqueous, alcoholic solution, the pH value of which is above 12, in dilute sodium hydroxide solution or in an aqueous suspension of calcium hydroxide, the Dissolve metallic contaminants with the formation of hydrogen.

Beim bekannten Verfahren der Deponierung entsteht ein großer finanzieller Aufwand für die Einlagerung in Sondermülldeponien. Desweiteren gehen bei dieser Vorge­ hensweise sowohl der Kunststoff als auch das entsprechend zurückzugewinnende Schwermetall, beispielsweise Quecksilber, als Wertstoff verloren.The known method of depositing involves a great deal of financial effort for storage in hazardous waste landfills. Furthermore go with this Vorge Both the plastic and the one to be recovered accordingly Heavy metal, such as mercury, is lost as a valuable substance.

Bei anderen Verfahren wird der Kunststoff häufig zersetzt, was ebenfalls den Verlust des Wertstoffes zur Folge hat. Insbesondere bei thermischen Verfahren, wie der Pyrolyse oder der Verbrennung, ist das Herausfiltern des gasförmigen Quecksilbers technologisch schwierig und kostenintensiv.In other processes, the plastic is often decomposed, which is also a loss of the recyclable material. Especially in thermal processes such as the Pyrolysis, or combustion, is the filtering out of the gaseous mercury technologically difficult and expensive.

Der Erfindung liegt das Problem zugrunde, den mit ionischem und metallischem Quecksilber sowie seinen Verbindungen belasteten Kunststoffen vor ihrem stofflichen Recycling zu dekontaminieren.The invention is based on the problem with ionic and metallic Mercury and its compounds contaminate plastics before their material Decontaminate recycling.

Das Problem wird erfindungsgemäß durch das in den Patentansprüchen dargestellte Verfahren gelöst. Der vorsortierte und zerkleinerte kontaminierte Kunststoff wird mit einem Oxidationsmittel behandelt, dessen elektrochemisches Potential größer 0,85 V ist, dessen Oxydationspotential aber nicht ausreicht, um die Kunststoffmatrix aufzu­ schließen bzw. zu einer Veränderung der Kunststoffmatrix führt. Für die Lösung dieses Problems eignet sich insbesondere Natriumhypochlorit in Form einer Lösung. Diese dringt in die Porenstruktur der Kunststoffmatrix ein, das Oxydationsmittel Natriumhypochlorit reagiert mit dem Kontaminaten entsprechend der Nernst′schen Gleichung, wobei im Ergebnis alle Kontaminate ionisiert vorliegen. Durch das Wasser werden die Schwermetallionen in das Eluat überführt. Der dekontaminierte Kunststoff wird anschließend gewaschen und dann dem stofflichen Recycling zugeführt. Zur Abtrennung des in Lösung vorliegendem Quecksilbers aus dem Oxydationsmittel wird eine Fällungsreaktion in bekannter Weise oder eine Anreicherung mittels Permeation durchgeführt.The problem is solved according to the invention by the one presented in the claims Procedure solved. The pre-sorted and shredded contaminated plastic is included treated with an oxidizing agent whose electrochemical potential is greater than 0.85 V. whose oxidation potential is not sufficient to open up the plastic matrix close or leads to a change in the plastic matrix. For the solution This problem is particularly suitable for sodium hypochlorite in the form of a solution. This penetrates into the pore structure of the plastic matrix, the oxidizing agent Sodium hypochlorite reacts with the contaminants according to the Nernst's Equation, with the result that all contaminants are ionized. Through the water the heavy metal ions are transferred into the eluate. The decontaminated plastic is then washed and then recycled. For The mercury in solution is separated from the oxidizing agent a precipitation reaction in a known manner or an enrichment by means of permeation carried out.

Solche mit Quecksilber oder Quecksilberverbindungen kontaminierte Kunststoffe können beispielsweise Polyvinylchlorid, Polyäthylen oder Polypropylen darstellen. Das erfindungsgemäße Verfahren ist aber auch bei Kunststoffverbunden zur Dekontamination anwendbar.Such plastics contaminated with mercury or mercury compounds can represent, for example, polyvinyl chloride, polyethylene or polypropylene. However, the method according to the invention is also used for plastic composites Decontamination applicable.

Der mit der Erfindung erreichte Vorteil besteht insbesondere darin, daß der mit Quecksilber verunreinigte Kunststoff nicht mehr auf Sondermülldeponien eingelagert werden muß. In der dekontaminierten Form ist es möglich, z. B. durch einen Pyrolyse­ prozeß, aus dem Kunststoff den Grundstoff HCl zu gewinnen.The advantage achieved by the invention is in particular that the Mercury contaminated plastic is no longer stored in hazardous waste landfills must become. In the decontaminated form it is possible e.g. B. by pyrolysis process to obtain the basic material HCl from the plastic.

Anhand eines Ausführungsbeispiels wird die Erfindung im folgenden näher erläutert. Quecksilberkontaminierter Kunststoff mit 160 mg metallischem Quecksilber pro kg PVC wird durch eine Schneidmühle in Granulatgröße zerkleinert und 24 h auf einem Überkopfschüttler in einem Eluat aus Natriumhypochlorit mit einem aktiven Chlor­ gehalt von 150 g/l gewälzt. Durch die Oxydationswirkung des Natriumhypochlorits sinkt der Quecksilberanteil im Kunststoffgranulat auf einen Gehalt von unter 50 mg/kg. Bei der nachfolgenden Elution des entkontaminierten Kunststoffgranulats werden im Eluat weniger als 0,1 mg/l Gesamtquecksilber vorgefunden. Als Elutionsmittel wird destilliertes Wasser verwendet.The invention is explained in more detail below using an exemplary embodiment. Mercury-contaminated plastic with 160 mg metallic mercury per kg PVC is shredded by a granulate-size cutting mill and placed on one for 24 hours Overhead shaker in an eluate of sodium hypochlorite with an active chlorine content of 150 g / l rolled. Due to the oxidation effect of sodium hypochlorite  the proportion of mercury in the plastic granulate drops to a level below 50 mg / kg. In the subsequent elution of the decontaminated plastic granulate in the Eluate less than 0.1 mg / l total mercury found. As an eluent distilled water used.

Die Elution quecksilberkontaminierter Kunststoffe ist temperaturabhängig. So erhöhte sich der Gesamtquecksilbergehalt im Eluat im Temperaturintervall 20 bis 60°C unter gleichen Bedingungen von 1,55 mg/l (20°C) über 2,35 mg/l (40°C) auf die Endkon­ zentration von 3,05 mg/l (60°C). Die Restkonzentration Gesamtquecksilber im Kunststoff nach der Elution betrug 34 mg/kg.The elution of mercury-contaminated plastics is temperature-dependent. So increased the total mercury content in the eluate falls below 20 to 60 ° C in the temperature range same conditions of 1.55 mg / l (20 ° C) over 2.35 mg / l (40 ° C) on the final con concentration of 3.05 mg / l (60 ° C). The residual concentration of total mercury in Plastic after the elution was 34 mg / kg.

Nachdem das Quecksilber mittels Natriumhypochlorit in die ionische Form überführt wurde, liegt dieses in komplexer Form vor. Diese Form weist eine sterische Hinderung beim Ausfällen mit Sulfid-Ionen auf. Durch die Zugabe eines Reduktionsmittels wird dieser Komplex zerstört, so daß ein Ausfällen mit Na₂S unter die geforderte Grenz­ wertkonzentration von 0,1 mg Hg/l führt. Die dabei entstehenden unlöslichen Queck­ silberverbindungen können aus dem Prozeß entnommen werden.After the mercury is converted into the ionic form using sodium hypochlorite this is in a complex form. This form shows steric hindrance when precipitating with sulfide ions. By adding a reducing agent this complex destroyed, so that a failure with Na₂S below the required limit concentration of 0.1 mg Hg / l. The resulting insoluble mercury silver compounds can be removed from the process.

Claims (2)

1. Verfahren zur Behandlung von mit Quecksilber oder Quecksilberverbindungen kontaminierten Kunststoffen durch Überführung des Quecksilbers oder der Quecksilberverbindungen in eine gelöste Form und Abtrennung vom Kunststoff, dadurch gekennzeichnet, daß der kontaminierte Kunststoff in zerkleinerter Form mit einem Oxidationsmittel im Überschuß behandelt wird, wobei das Oxidationsmittel durch ein elektrochemisches Potential größer 0,85 V gekennzeichnet ist und die Kunststoffmatrix nicht aufschließt.1. A method of treating plastics contaminated with mercury or mercury compounds by converting the mercury or the mercury compounds into a dissolved form and separating them from the plastic, characterized in that the contaminated plastic is treated in excess with an oxidizing agent, the oxidizing agent being treated by an electrochemical potential greater than 0.85 V is marked and does not unlock the plastic matrix. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Oxidationsmittel ein wäßriges Hypochlorit, vorzugsweise ein wäßriges Natriumhypochlorit, verwendet wird.2. The method according to claim 1, characterized in that as an oxidizing agent aqueous hypochlorite, preferably an aqueous sodium hypochlorite, is used.
DE1996118663 1996-05-09 1996-05-09 Decontaminating plastics mat Withdrawn DE19618663A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE1996118663 DE19618663A1 (en) 1996-05-09 1996-05-09 Decontaminating plastics mat

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Application Number Priority Date Filing Date Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19801321C2 (en) * 1998-01-16 2003-07-03 Brz Bodenreinigungszentrum Her Process for the decontamination of solids contaminated with mercury
US6997407B1 (en) * 2000-05-02 2006-02-14 Plastic Technologies, Inc. Decontamination of RPET through particle size reduction

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3705956A1 (en) * 1987-02-25 1988-09-08 Dornier System Gmbh Simultaneous depletion of heavy metals and oxidizable pollutants from waste water
DE4304735A1 (en) * 1993-02-12 1994-08-18 Guenther Spitzl Method for cleaning contaminated pipes, especially those polluted with heavy metal

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3705956A1 (en) * 1987-02-25 1988-09-08 Dornier System Gmbh Simultaneous depletion of heavy metals and oxidizable pollutants from waste water
DE4304735A1 (en) * 1993-02-12 1994-08-18 Guenther Spitzl Method for cleaning contaminated pipes, especially those polluted with heavy metal

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19801321C2 (en) * 1998-01-16 2003-07-03 Brz Bodenreinigungszentrum Her Process for the decontamination of solids contaminated with mercury
US6997407B1 (en) * 2000-05-02 2006-02-14 Plastic Technologies, Inc. Decontamination of RPET through particle size reduction

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