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CA2492180A1 - Method for treating waste materials containing halogen - Google Patents

Method for treating waste materials containing halogen Download PDF

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Publication number
CA2492180A1
CA2492180A1 CA002492180A CA2492180A CA2492180A1 CA 2492180 A1 CA2492180 A1 CA 2492180A1 CA 002492180 A CA002492180 A CA 002492180A CA 2492180 A CA2492180 A CA 2492180A CA 2492180 A1 CA2492180 A1 CA 2492180A1
Authority
CA
Canada
Prior art keywords
polyolefin
waste materials
bromine
halogen
materials containing
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.)
Abandoned
Application number
CA002492180A
Other languages
French (fr)
Inventor
Andreas Hornung
Aliaksandr Balabanovich
Susanne Donner
Helmut Seifert
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.)
Karlsruher Institut fuer Technologie KIT
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
Publication of CA2492180A1 publication Critical patent/CA2492180A1/en
Abandoned legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/09Bromine; Hydrogen bromide
    • C01B7/093Hydrogen bromide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/70Chemical treatment, e.g. pH adjustment or oxidation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention relates to a method for treating waste materials containing halogen, especially containing bromine, wherein useful material and/or energ y can be recycled and no other harmful halogenated substances arise. This is achieved by means of a method for treating waste materials containing haloge n, comprising the following steps: a) the waste materials containing halogen ar e mixed with a melted, substituted or un-substituted polyolefin in an inert ga s atmosphere, b) the hydrogen halogenide arising during melting is separated.< /SDOAB>

Description

' K 235 Can METHOD FOR TREATING WASTE MATERIALS CONTAINING HALOGEN
The invention relates to a method for treating waste mate-rials containing halogen, in accordance with the first claim.
Electrical and electronic waste materials contain a number of toxic compounds. Among these toxic compounds are mainly halogenated hydrocarbons, especially brominated hydrocarbons.
Brominated hydrocarbons are often used in fire protection medi-ums. The bromine content may be 20 to 40 wto. In many cases, tetrabrominebiphenol A is used in fire-retarding agents. Other often used bromine-containing compounds are polybrominated di-phenyl ether and Bis (Tribrominephenoxy)ethane. But also chlo-rine containing hydrocarbons and hydrocarbons which contain chlorines as well as bromine, are important.
A common method for treating waste materials containing toxic compounds is to subject them to a pyrolysis process.
Compared with other decontamination processes such as combus-tion or deposition, pyrolisis has the advantage that chemical compounds and energy can be recuperated. However, in connec-tion with waste material containing halogens and particularly bromine and chlorine, this method is problematic since a wide spectrum of additional compounds is generated. For example, tetrabrominebisphenol A forms toxic mono- and di-bromine phe-nols. Other typical pyrolysis products are halogenated p-dibenzodioxines (PBDD) and p-dibenzofuranes (PBDF). The advan-tage of energy generation and material recuperation is there-fore counterbalanced by the toxicity of the pyrolysis products.
DE 44 25 658 Cl discloses that the polyhalogenated com-pounds can be removed from the exhaust gas of a combustion plant by contact with polyolefins, particularly polyethylene and polypropylene. However, in that case, the polyhalogenated compounds are adsorbed in the polyolefins only reversibly so that they can again be desorbed under suitable conditions. For a long-term immobilization of these halogenated toxic compounds polyolefins are not suitable as adsorption materials under the limit conditions as described in the cited patent.
It is the object of the present invention to provide a method for the treatment of waste materials containing halo-genated, particular bromine-containing compounds, wherein valu-able compounds and/or energy can be recuperated as it is gener-ally possible with pyrolysis methods and the waste materials are destroyed at least to a large extent, whereby essentially no additional halogenated hazardous materials are generated.
The object is solved by the method described in the first claim. The additional claims define preferred embodiments of the method.
Under halogenated waste materials, particularly waste ma-terials from the manufacture of components of the electrical and electronic industry, but also electrical and electronic ap-paratus as such or the components thereof are to be understood.
The most important application of the method is its application to halogenated, preferably brominated hydrocarbons which are used in the industry for electrical insulations and/or fire protection. The mixing with the halogen containing waste mate-rial occurs with a molten polyolefin, whose temperature corre-sponds at least to the melting temperature of the waste mate-rial.
The method is performed in all its variants under an inert gas atmosphere since otherwise the polyolefin may burn at the processing temperature. For establishing the inert gas atmos-phere the usual protective gases may be used. In any case, it is important that no oxygen is present. The method can be per-formed under normal pressure but also under an increased pres-sure for example up to 10 bar.
Some polyolefins melt also under an inert gas atmosphere only while, at the same time, being decomposed. The decomposi-tion may occur already at the melting point. Where, in the de-scription of the method, reference is made to a melting point, the transition from the solid phase to the liquid phase is meant wherein a chemical decomposition is negligible. The be-ginning of the decomposition of the polyolefin during melting does not detrimentally affect the method.
Basically, the halogen-containing waste materials can be mixed with the molten polyolefin in a solid and not pretreated form. The results however are less satisfactory if, at the temperature at wh~_ch the polyolefin is melted, the waste mate-rials remain solid. For example, it is less advantageous to subject to the method according to the invention solid compo-nents, such as transformers without additional pre-treatment.
Rather the waste materials should be separated to such an ex-tent that, at the temperature at which the polyolefin is melted, the materials to be treated are at least liquid but preferably gaseous. In practice, this means that, before the start of the procedure, metals such as housing parts or support structures should be separated at least roughly from the chemi-cal compounds for electrical insulation and fire protection.
For waste materials containing halogens which are gaseous at the melting point of the polyolefin melt, a method variant is particularly suitable according to which molten polyolefin is provided and the gaseous halogen containing waste material is conducted through the liquid polyolefin and, consequently, mixed with the polyolefin melt. In this way, a particularly intense mixture of polyolefin and waste material is obtained whereby substantially higher yields can be achieved then with other variants of the method.
The two most simple polyolefins, polyethylene and polypro-pylene are particularly suitable for the method according to the invention. Their melting point is in the area of about 200°C. The method can therefore be performed - depending on the nature of the waste material - in a temperature range be-tween 200°C, which is the melting point of the olefin, and 500°C. If no materials are used which are difficult to con-vert, a temperature range slightly over the melting tempera-ture, that is, about 50°C to maximally 200°C above the melting temperature is preferred.
In place of the un-substituted polyolefins, polyethylene and polypropylene also substituted polyolefins may be used. As substituted polyolefin polyvinyl alcohol is particularly suit-able.
During the reaction of the halogen-containing waste mate-rial with the polyolefin, the halogen content is removed from the waste material whereby hydrogen halides are formed. Since - as initially mentioned - in the electrical and electronic area, many bromine-containing compounds are used, hydrogen bro-mide is formed during the execution of the method. Hydrogen bromide is of substantial value and is therefore preferably separated during processing from the other start-out and reac-tion products and is collected. This can be done without dif-ficulties since hydrogen bromide is gaseous under reaction con-ditions and, if at all, needs to be separated only from the gaseous halogen containing waste materials.
The thermal treatment of bromine-containing hydrocarbons without the use of reaction partners results at temperatures above 270°C in the splitting of the carbon - bromine bond.
With aromates, then phenyl- and bromine radicals are formed.
The stabilization of phenyl radicals can be achieved for exam-ple by radical recombination with another aromatic compound.
This reaction path leads to the formation of biphenyl deriva-tives, to carbonization and to the formation of PBDD and PBDF
(Eiton J.C. Borojowich, Zeev Aizenshtat, ~~Thermal behavior of brominated and polybrominated compounds II. Pyroproducts of brominated phenols as mechanistic tools", Journal of Analytical and Applied Pyrolysis 63 (2002) 129 - 145).
It has been found that the formation of PBDD and PBDF can be effectively suppressed if the pyrolysis occurs in the pres-ence of polyolefins, particularly polyethylene and polypropyl-ene. In that case, the phenyl- and bromine radicals appear to attack the macromolecules of the polyolefin with hydrogen ab-straction, so that, in this way, a de-brominization occurs.
Starting out for example with bromine phenol and polypropylene, phenol and hydrogen bromide are obtained as the main products.
As by-products, alkyl phenols and alkyl bromides are formed.
An addition of polyethylene or polypropylene causes the radi-cals to form stable molecules whereby the formation of PBDD and PBDF is avoided.
The reaction can be performed in a conventional way. The volume rates between the halogen containing waste material and the polyolefin to be used can be calculated based on the knowl-edge of the halogen content. The optimal process temperature can be determined by a few tests. In a usable method, polyole-fin is continuously melted in a reactor and a gaseous flow of the halogen containing waste material is conducted through the molten polyolefin. The hydrogen bromide formed in this way is separated continuously from the remaining waste material. The remaining waste material can be recycled.
Below the invention will be explained in greater detail on the basis of an exemplary embodiment.
Example:
Various stoichiometric mixtures of substituted or un-substituted polyolefins were converted with bromine containing compounds in closed and open reaction systems. Among several possible test settings, a suitable setup is described by the following specifications: 80 mg tetrabrominebiphenol A or 2, 4-dibromine phenol are introduced under a nitrogen cover atmos-phere together with 15 mg polypropylene into a glass ampulla of 6.5 cm length and 6 mm diameter. The ampulla is then melted closed and pyrolized at 350°C for 20 minutes.
A gas chromatography/mass spectrometry examination of the pyrolysis products shows that phenol, alkyl phenol and hydrogen bromide are the main products. Bromine-containing compounds, particularly polybrominated dibenzodioxene and furons are not detectable.

Claims (6)

claims
1. Method for the treatment of halogen containing waste materials comprising the steps:
a) Mixing the halogen containing waste materials with a molten substituted or non-substituted polyolefin in an inert gas atmosphere, b) Separating the hydrogen halogenide formed upon melting.
2. Method according to claim 1, with polyvinyl alcohol, polyethylene and/or polypropylene as polyolefin.
3. Method according to claim 1 or 2, wherein the molten polyolefin has a temperature of between the melting point of the polyolefin and 500°C.
4. Method according to claim 1, 2, or 3, wherein the halo-gen containing waste materials include bromine.
5. Method according to claim 4, with such bromine contain-ing waste materials which are gaseous at a temperature above the melting point of the polyolefin.
6. Method according to claim 5, wherein the halogen con-taining waste materials are mixed with the polyolefin in that the gaseous waste products are conducted through the molten polyolefin.

Method according to claims 4, 5, or 6, wherein hydrogen bromide formed in the process is collected and isolated.
CA002492180A 2002-07-31 2003-06-18 Method for treating waste materials containing halogen Abandoned CA2492180A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10234837A DE10234837A1 (en) 2002-07-31 2002-07-31 A process for handling halogens, especially bromine containing waste material useful for non-toxic processing of waste material from the electrical and electronics industry
DE10234837.5 2002-07-31
PCT/EP2003/006425 WO2004014491A1 (en) 2002-07-31 2003-06-18 Method for treating waste materials containing halogen

Publications (1)

Publication Number Publication Date
CA2492180A1 true CA2492180A1 (en) 2004-02-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
CA002492180A Abandoned CA2492180A1 (en) 2002-07-31 2003-06-18 Method for treating waste materials containing halogen

Country Status (7)

Country Link
EP (1) EP1525032B1 (en)
AT (1) ATE489142T1 (en)
AU (1) AU2003246550A1 (en)
BR (1) BR0305685A (en)
CA (1) CA2492180A1 (en)
DE (2) DE10234837A1 (en)
WO (1) WO2004014491A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009531340A (en) * 2006-03-29 2009-09-03 フォルシュングスツェントルム カールスルーエ ゲゼルシャフト ミット ベシュレンクテル ハフツング Equipment for heating dehalogenation of halogen-containing materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019118560A1 (en) 2019-07-09 2021-01-14 Karlsruher Institut für Technologie Pyrolysis reactor and process for the chemical processing of plastics

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1983004259A1 (en) * 1982-06-02 1983-12-08 The Franklin Institute Improved method for the solvent extraction of polychlorinated biphenyls
BE903383A (en) * 1985-10-07 1986-04-07 Desemberg Richard Eliminating poly:chloro:bi:phenyl or prods. from electrical appts. - using chlorinated and/or fluorinated ethane deriv. pref. with a liquid aliphatic hydrocarbon
DE3602041C2 (en) * 1986-01-24 1996-02-29 Rwe Entsorgung Ag Improved process for processing carbon-containing waste
IT1223802B (en) * 1988-09-07 1990-09-29 Tecnocolor Sas Di Celebrano A SOLIDIFICATION TREATMENT SYSTEM INERTIZATION AND STABILIZATION OF TOXIC HARMFUL WASTE THROUGH RESIN SWITCHING
EP0554761A1 (en) * 1992-02-04 1993-08-11 MENGES, Georg, Prof. Dr.-Ing. Process for recycling of polymeric materials
DE4300860A1 (en) * 1993-01-15 1994-07-21 Rwe Entsorgung Ag Process for the removal of chlorine from synthetic, organic waste
US5744117A (en) * 1993-04-12 1998-04-28 Molten Metal Technology, Inc. Feed processing employing dispersed molten droplets
US5688335A (en) * 1995-09-05 1997-11-18 General Electric Company Contaminant removal from material
DE19547259A1 (en) * 1995-12-06 1997-06-12 Uve Inst Fuer Tech Chemie Und Production of hydrocarbon(s) from thermoplastic waste plastic
US6030549A (en) * 1997-08-04 2000-02-29 Brookhaven Science Associates Dupoly process for treatment of depleted uranium and production of beneficial end products

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009531340A (en) * 2006-03-29 2009-09-03 フォルシュングスツェントルム カールスルーエ ゲゼルシャフト ミット ベシュレンクテル ハフツング Equipment for heating dehalogenation of halogen-containing materials

Also Published As

Publication number Publication date
BR0305685A (en) 2004-10-19
DE50313281D1 (en) 2011-01-05
DE10234837A1 (en) 2004-02-19
EP1525032A1 (en) 2005-04-27
AU2003246550A1 (en) 2004-02-25
EP1525032B1 (en) 2010-11-24
WO2004014491A1 (en) 2004-02-19
ATE489142T1 (en) 2010-12-15

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EEER Examination request
FZDE Discontinued