WO2000003764A1 - Procede pour la decomposition materielle de materiaux composites renfermant une resine synthetique - Google Patents

Procede pour la decomposition materielle de materiaux composites renfermant une resine synthetique Download PDF

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Publication number
WO2000003764A1
WO2000003764A1 PCT/EP1998/004467 EP9804467W WO0003764A1 WO 2000003764 A1 WO2000003764 A1 WO 2000003764A1 EP 9804467 W EP9804467 W EP 9804467W WO 0003764 A1 WO0003764 A1 WO 0003764A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
components
synthetic resin
printed circuit
circuit boards
Prior art date
Application number
PCT/EP1998/004467
Other languages
German (de)
English (en)
Inventor
Frank Detlef
Original Assignee
Frank Detlef
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 Frank Detlef filed Critical Frank Detlef
Priority to DE59802480T priority Critical patent/DE59802480D1/de
Priority to EP98941357A priority patent/EP1077747B1/fr
Priority to PCT/EP1998/004467 priority patent/WO2000003764A1/fr
Priority to AU89767/98A priority patent/AU8976798A/en
Priority to JP2000559898A priority patent/JP2002520196A/ja
Priority to AT98941357T priority patent/ATE210482T1/de
Publication of WO2000003764A1 publication Critical patent/WO2000003764A1/fr

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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
    • A62D3/32—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by treatment in molten chemical reagent, e.g. salts or 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
    • 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
    • A62D3/36—Detoxification by using acid or alkaline reagents
    • 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

Definitions

  • a printed circuit board is usually equipped with numerous components, from which particularly problematic ones such as batteries, capacitors, rectifiers and mercury switches are removed before refurbishment. This also happens with particularly valuable components such as gold-plated connector strips.
  • the partial denitrification is absolutely necessary for an environmentally compatible recycling or disposal, since at least one coarse shredder is connected upstream in all processes that have been carried out to date. Otherwise it would ner distribution of pollutants and recyclables, which both makes recovery difficult and possible. Chen pollutant release leads. The risk of pollutant emissions could only be reduced by carrying out all process stages in hermetically sealed devices, which is of course expensive.
  • a denatured printed circuit board mainly consists of metal (30% by weight), glass fiber (50% by weight) and polymer resin (20% by weight), so far only the metals have been considered as valuable materials. To recover them, they first have to be enriched and separated from the residues as much as possible. There are several methods for this, which can also be combined with one another.
  • the circuit board is mechanically roughly shredded (shredded) for better handling and freed from ferromagnetic parts by means of a magnetic separator. This is followed by fine grinding, which can be carried out in various ways:
  • PBDD polybrominated aromatic dibenzodioxins
  • PBDF polybrominated dibenzofurans
  • the composite material is broken up by means of ultrasound, whereby material-specific grain size distributions occur. This method is very expensive, but allows the isolation of up to four different metal fractions.
  • the components After crushing, the components are separated according to density, grain size or magnetic or electrical properties. For this purpose, screening and classifying systems as well
  • Magnetic separators eddy current separators and electrostatic separators are used. Loss of valuable materials cannot be prevented because the fine metal particles are distributed over all fractions. The heavy metal-containing dusts, which accumulate in considerable quantities, are particularly problematic because they sometimes reach the lungs and cause health damage.
  • moist printed circuit boards are ground, which both protects the regrind from thermal stress and avoids dust formation.
  • the subsequent recycling is usually carried out using a flotation-like process followed by drying.
  • the metal-rich fraction is further processed by chemical or thermal means. If the precious metal content is above 0.02%, it is worthwhile to refurbish it for precious metal refineries. H ⁇ erb.e ⁇ the precious metals are either leached out with a weakly alkaline cyanide solution and then recovered reductively or thermometallurgically at 1000-
  • the material is introduced into the second stage of the copper production process.
  • the raw copper is removed from the iron in a rotary tube furnace (Peirce Smith converter) with the addition of silicate, forming an iron silicate slag which permanently encloses other heavy metals and is used as a building material (headstemoflaster).
  • the copper is then cleaned electrolytically, the precious metals being found in the anode sludge.
  • the material must be crushed very finely in order to be able to separate the individual components; however, the finer the powder becomes, the more difficult it becomes to separate, since surface effects level out the material differences.
  • the purity of a fraction inevitably affects the yield.
  • the low metal fraction has to be disposed of together with the dust fraction and comprises more than 2/3 of the total. This is usually done by depositing in a normal depot never, although their powder form and the remaining heavy metal contamination actually make disposal at a special, waste landfill or through a special waste incineration plant necessary.
  • Contamination of the metal fraction with polymer and glass poses a problem in all of the workup processes mentioned. As a result, a complex digestion of the material is necessary before the metal can be cleaned electrolytically. In addition, the metal content of the residual fraction prevents its further use or complicates its disposal.
  • US Pat. No. 5,580,905 describes a process for the hydrolytic cleavage of polyesters, specifically polyalkylene terephthalates by means of caustic solutions of alkali metal hydroxides, in which the mixture is heated and the polyester is broken down into the underlying salt and polyol.
  • the reaction basically takes place at temperatures up to the boiling point of the polyol, ie up to approx. 200 ° C, in order to evaporate and separate it.
  • DE-OS 4 001 897 discloses a process for dissolving printed circuit boards (printed circuit boards), in which these are introduced into a melt of alkali hydroxide and alkali oxide with the exclusion of oxygen at temperatures above 400 ° C. By adding oxygen, the alkali oxide is converted into peroxide, which is then converted into the Melt diffused and degrades oxidizable components such as carbon fabric or hydrogen-containing compounds from the boards ⁇ .
  • the melt of alkali hydroxide and alkali oxide is used as a matrix for the oxidation in this working method (column 1 / 25-32) and prevents the occurrence of toxic gases, which would be generated by combustion. As disclosed in column 1 / 29-34, raw material recovery and use is neither possible for the synthetic resin nor for the glass fibers.
  • the object of the invention is now to develop a method that dissolves the material bond between metal, glass and polymer.
  • Metal, glass and polymer fractions to processing their further on ⁇ and thus a significant reduction or substantial avoidance be allowed to be disposed of residual fractions.
  • the invention now relates to a process for the material digestion of composite materials containing synthetic resin, in which the high molecular structure of the synthetic resin is broken down by chemical reaction in melts of alkali metal hydroxides at temperatures above 250.degree.
  • the hydroxides of the alkali metals are preferably NaOH or KOH and particularly preferably mixtures of NaOH and KOH.
  • the proportion of potassium hydroxide is, for example, 3 to 60% by weight, preferably 5 to 20% by weight.
  • the relatively small amount of potassium hydroxide is partly due to the higher price of this substance.
  • the reaction temperatures are generally in the range between 260 and 400 ° C, preferably in the range between 280 and 370 ° C and particularly preferably in the range between 300 and 350 ° C.
  • the choice of the most suitable temperature depends naturally on the type and composition of the starting materials, whereby it should be borne in mind that at higher temperatures both the reaction rate and the risk of thermal formation of undesired degradation products are increased. In general, it is also possible to work at a lower temperature when using potassium hydroxide than when using sodium hydroxide, and when using mixtures of sodium and potassium hydroxide at even lower temperatures.
  • reaction auxiliaries which improve the wettability of the composite material by alkali metal hydroxides, lower the melting point of the alkali metal hydroxides or, under the reaction conditions, have a solvent or swelling capacity for the synthetic resin or its degradation products.
  • Reaction aids that improve the wettability of the composite material include, for example, the
  • Reaction temperatures resistant surfactants into consideration are e.g. B. inorganic salts of alkali, alkaline earth or earth metals or of metals of the fourth group of the periodic table or of metals of the subgroups with strong or weak inorganic acids.
  • B. inorganic salts of alkali, alkaline earth or earth metals or of metals of the fourth group of the periodic table or of metals of the subgroups with strong or weak inorganic acids The use of salts of metals that are already contained in the starting materials can also support the reaction. This also has the advantage that no foreign elements are introduced into the system. As a reaction aid, the one
  • Solvent or swelling capacity for the synthetic resin or its degradation products come, for. B. oligomeric fragments or base of the synthetic resin into consideration, which are stable under the reaction conditions.
  • the synthetic resins are crosslinked or uncrosslinked polymers which contain chemically cleavable functional groups in the main chain, such as polyesters, polyamides, polyethers, polyurethanes, but preferably polyimides such as polyphthalimides and polybimalinimides, polyaramides and polycyanate esters, in particular but epoxy resins.
  • These usually consist of condensation products of bisphenols, such as bisphenol A and bisphenol F, and epichlorohydrin. This list is exemplary and should not be understood as restrictive. Restrictions result from the type of chemical digestion and are obvious to the person skilled in the art.
  • the amount of alkali metal hydroxide used for the digestion can be varied within wide limits. Of course, the amount used in practice must be at least sufficient to ensure that the process is carried out. For example, 50% by weight, based on the proportion of synthetic resin, is sufficient. However, a significantly larger amount of alkali metal hydroxide is expediently used for easier handling.
  • the process is very simple, it can easily be transferred to other composites. It is particularly advantageous to apply the method to composite materials containing metallic components that are common in electrical engineering, such as, for example, but not exclusively, in printed circuit boards, components or production waste in the production of printed circuit boards and components.
  • Components are understood to mean in particular all components that are or can be used on printed circuit boards, such as processors, memory chips, resistors and capacitors. This list is to be understood as an example and not as restrictive. It is useful, but not necessary, that the printed circuit boards and the components thereon are separated before the reaction and, if necessary, completely or partially worked up separately, which can be done by customary methods. The separation can e.g. B.
  • Standard shredder systems can be used to shred composite materials such as printed circuit boards. Since no fine comminution is necessary, no high demands are placed on this sub-process. For the person skilled in the art, the maximum tolerable piece size results from the process requirements of the subsequent stages.
  • the dry comminution of the composite materials according to the prior art also produces dust-like fractions which are separated off and disposed of as filter dusts.
  • the process according to the invention now has the advantage that such dusts can be subjected to digestion by themselves or in combination with the comminuted reaction material. It is a particular advantage of the invention that it is also suitable for working up such dusts which contain flame retardants and / or metals such as are obtained in particular in the comminution of composite materials customary in electrical engineering.
  • reactors can be used for the chemical degradation of the synthetic resin. These are essentially stirred tanks and stirred tank cascades in the case of discontinuous operation, or extruders and extruder cascades, for example a twin-screw extruder in the case of continuous operation.
  • the main advantage of the extruder is the short and defined reaction time. The risk of the formation of thermal degradation products (dioxins and charring) is therefore significantly lower than when using a stirred tank.
  • long dwell times with an extruder cannot be achieved or only with complex extruder cascades.
  • reaction times Examples 1 to 3 which can be achieved with an extruder.
  • the extrusion process is preferred, the twin-screw extruder being particularly suitable on account of the better mixing.
  • the constituents of the composite materials they have to be "separated" from one another after the digestion has taken place, which can be done in the usual way, for example by dry (air sifting / electrostatics) or wet (flotation) methods.
  • dry (air sifting / electrostatics) or wet (flotation) methods In both cases
  • the advantage of the dry process is above all the lower water and energy consumption, while the wet process makes it easier to avoid the emission of dusts.
  • Extraction processes are used to separate the degradation products of the synthetic resin and to recover excess reagent with organic and aqueous solvents. Commercial systems can also be used here. The selection of suitable extraction methods and extraction agents is possible without difficulty for the person skilled in the art.
  • FR-4 class epoxy-based circuit board laminate i.e. i. a flame-retardant product was roughly crushed, the resulting fragments having a size of 20x20 mm and a thickness of 1.6 mm.
  • the shredded laminate was mixed with the same proportion by weight of alkali hydroxide and reacted in a tempered metal bath.
  • the reaction was carried out with NaOH at 340 ° C, according to Example 2 with KOH at 320 ° C and according to Example 3 with a mixture of equal parts by weight of NaOH and KOH at 300 ° C.
  • the reaction was complete in less than 5 minutes with evolution of gas.
  • the resulting gas could be condensed as water.
  • the reaction mixture was cooled and washed with cold water until the wash water was approximately neutral. After separating the degraded polymer and then drying it, the metal and glass fraction could easily be separated from one another.

Landscapes

  • 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)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un procédé pour la décomposition matérielle de matériaux composites renfermant une résine synthétique, caractérisé en ce que la structure à haut poids moléculaire de la fraction de résine synthétique est décomposée au moyen d'une réaction chimique avec des hydroxydes de métaux alcalins à des températures supérieures à 250 DEG C, et éventuellement retraitée totalement ou en partie.
PCT/EP1998/004467 1998-07-17 1998-07-17 Procede pour la decomposition materielle de materiaux composites renfermant une resine synthetique WO2000003764A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE59802480T DE59802480D1 (de) 1998-07-17 1998-07-17 Verfahren zum stofflichen aufschluss von kunstharz enthaltenden verbundwerkstoffen
EP98941357A EP1077747B1 (fr) 1998-07-17 1998-07-17 Procede pour la decomposition materielle de materiaux composites renfermant une resine synthetique
PCT/EP1998/004467 WO2000003764A1 (fr) 1998-07-17 1998-07-17 Procede pour la decomposition materielle de materiaux composites renfermant une resine synthetique
AU89767/98A AU8976798A (en) 1998-07-17 1998-07-17 Method for the material decomposition of composites containing artificial resin
JP2000559898A JP2002520196A (ja) 1998-07-17 1998-07-17 合成樹脂を含有する複合材料を分解する方法
AT98941357T ATE210482T1 (de) 1998-07-17 1998-07-17 Verfahren zum stofflichen aufschluss von kunstharz enthaltenden verbundwerkstoffen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP1998/004467 WO2000003764A1 (fr) 1998-07-17 1998-07-17 Procede pour la decomposition materielle de materiaux composites renfermant une resine synthetique

Publications (1)

Publication Number Publication Date
WO2000003764A1 true WO2000003764A1 (fr) 2000-01-27

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ID=8167006

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/004467 WO2000003764A1 (fr) 1998-07-17 1998-07-17 Procede pour la decomposition materielle de materiaux composites renfermant une resine synthetique

Country Status (6)

Country Link
EP (1) EP1077747B1 (fr)
JP (1) JP2002520196A (fr)
AT (1) ATE210482T1 (fr)
AU (1) AU8976798A (fr)
DE (1) DE59802480D1 (fr)
WO (1) WO2000003764A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1437378A1 (fr) * 2003-01-09 2004-07-14 Electricité de France Procédé de valorisation de déchets de materiaux à base de résine époxyde

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010050153B4 (de) * 2010-11-02 2012-10-25 Adam Handerek Reaktor und Verfahren zum zumindest teilweisen Zersetzen und/oder Reinigen von Kunststoffmaterial
DE102010050152B4 (de) * 2010-11-02 2016-02-11 Adam Handerek Reaktor und Verfahren zum zumindest teilweisen Zersetzen, insbesondere Depolymerisieren, und/oder Reinigen von Kunststoffmaterial

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0070789A2 (fr) * 1981-07-20 1983-01-26 CIRTA Centre International de Recherches et de Technologies Appliquées Procédé de destruction de produits à base de matières organiques contenant du soufre et/ou des halogènes et/ou des métaux toxiques et applications de celui-ci
DE4001897A1 (de) * 1990-01-21 1991-07-25 Atp Arbeit Tech Photosynthese Verfahren zur umweltfreundlichen aufloesung von platinen
EP0554761A1 (fr) * 1992-02-04 1993-08-11 MENGES, Georg, Prof. Dr.-Ing. Procédé de recyclage de matières polymères
EP0693305A1 (fr) * 1994-07-21 1996-01-24 Rockwell International Corporation Destruction par sel fondu de matériaux composites

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0070789A2 (fr) * 1981-07-20 1983-01-26 CIRTA Centre International de Recherches et de Technologies Appliquées Procédé de destruction de produits à base de matières organiques contenant du soufre et/ou des halogènes et/ou des métaux toxiques et applications de celui-ci
DE4001897A1 (de) * 1990-01-21 1991-07-25 Atp Arbeit Tech Photosynthese Verfahren zur umweltfreundlichen aufloesung von platinen
EP0554761A1 (fr) * 1992-02-04 1993-08-11 MENGES, Georg, Prof. Dr.-Ing. Procédé de recyclage de matières polymères
EP0693305A1 (fr) * 1994-07-21 1996-01-24 Rockwell International Corporation Destruction par sel fondu de matériaux composites

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1437378A1 (fr) * 2003-01-09 2004-07-14 Electricité de France Procédé de valorisation de déchets de materiaux à base de résine époxyde

Also Published As

Publication number Publication date
ATE210482T1 (de) 2001-12-15
AU8976798A (en) 2000-02-07
JP2002520196A (ja) 2002-07-09
EP1077747B1 (fr) 2001-12-12
EP1077747A1 (fr) 2001-02-28
DE59802480D1 (de) 2002-01-24

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