EP2547452A2 - Procédé de fragmentation de déchets électroniques et de verre technique à des fins de recyclage - Google Patents

Procédé de fragmentation de déchets électroniques et de verre technique à des fins de recyclage

Info

Publication number
EP2547452A2
EP2547452A2 EP11765105A EP11765105A EP2547452A2 EP 2547452 A2 EP2547452 A2 EP 2547452A2 EP 11765105 A EP11765105 A EP 11765105A EP 11765105 A EP11765105 A EP 11765105A EP 2547452 A2 EP2547452 A2 EP 2547452A2
Authority
EP
European Patent Office
Prior art keywords
extraction
shock wave
treatment
medium
piece goods
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.)
Granted
Application number
EP11765105A
Other languages
German (de)
English (en)
Other versions
EP2547452B1 (fr
Inventor
Jörg BECKMANN
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
Publication of EP2547452A2 publication Critical patent/EP2547452A2/fr
Application granted granted Critical
Publication of EP2547452B1 publication Critical patent/EP2547452B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C19/00—Other disintegrating devices or methods
    • B02C19/18—Use of auxiliary physical effects, e.g. ultrasonic waves or irradiation, for disintegrating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C19/00—Other disintegrating devices or methods
    • B02C19/0056—Other disintegrating devices or methods specially adapted for specific materials not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C19/00—Other disintegrating devices or methods
    • B02C19/18—Use of auxiliary physical effects, e.g. ultrasonic waves or irradiation, for disintegrating
    • B02C19/186—Use of cold or heat for disintegrating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C19/00—Other disintegrating devices or methods
    • B02C19/18—Use of auxiliary physical effects, e.g. ultrasonic waves or irradiation, for disintegrating
    • B02C2019/183—Crushing by discharge of high electrical energy

Definitions

  • the invention relates to a method of shredding electronic waste, i. general electronic components, such as Circuit boards, chips and parts containing electronic components, as well as technical glass, such as picture tubes, fluorescent tubes and the like.
  • electronic waste i. general electronic components, such as Circuit boards, chips and parts containing electronic components, as well as technical glass, such as picture tubes, fluorescent tubes and the like.
  • the processing of these materials is very difficult, since different substances are present in the composite and the content of the individual materials can be very different.
  • metals various polymers, glass, semimetals and semiconductors (especially silicon), adhesives, inorganic fillers, organic chemical auxiliaries, such as. containing often bromides, oils, waxes, greases and many other possible substances.
  • the metals mainly include copper, iron, lead, zinc, tin, gold, silver, palladium and platinum.
  • the brominated flame retardants eg tetrabromobisphenol A - mass fraction up to 30%
  • these flame retardants form other brominated hydrocarbons, some of which have an even higher hazard potential.
  • Such degradation products can be stored and accumulated by organisms in adipose tissue and show partial carcinogenic effects. Since since 2006 the use of bromine-containing materials in the Federal Republic of Germany is only permitted to a limited extent, old equipment is subject to a special burden.
  • a first treatment step is generally the mechanical pre-shredding, for
  • Example a shredding From the shredder fraction or generally mechanically
  • CONFIRMATION COPY pretreated good magnetic metals can be separated with Magnettrennem, but separated depending on the degree of division not clean without additives.
  • Organic components are often broken down by thermal pyrolysis or wet-chemical oxidative.
  • the electronic scrap is also used as a surcharge in the metal extraction in metallurgy, which corresponds to a substantial recovery of the metals in pyrolytic removal of organic components.
  • the leaching of the metals is also operated.
  • One method of obtaining relatively fine debris is shock wave crushing.
  • DE 195 34 232 C2 discloses a basic apparatus for a concept developed by the Düsseldorf Research Center for the destruction of essentially non-metallic solids, such as, for example, mineral solids.
  • the shock waves are triggered by rapid discharge of an electrical energy store.
  • the material to be comminuted is located in a non-conductive or only slightly conductive process liquid.
  • DE 100 61 386 therefore deals with the provision of a special process and reactor in order to be able to handle the wet oxidation in supercritical water.
  • the process developed therein does not yet solve the problem of being able to separate the other different materials within the electronic scrap, such as glass, ceramics, metals and inorganic residues, eg mixed oxides of previous treatment stages.
  • the object of the invention is to be able to process environmentally harmful scrap from complex composite multistage systems, in this case electronic waste and used technical glass, economically and ecologically efficient. Contained hazardous substances should be isolated and destroyed or recycled. Base materials, such as metals and glass, are to be made available for recycling.
  • the invention is based on the idea to use a separation of substances by fine division on the one hand and targeted physical-chemical extractive treatment of the starting materials and / or the particles on the other hand in combination.
  • the method does not include the treatment of elastomeric, especially rubber-elastic and purely thermoplastic materials, which has been previously described. Rather, the method is directed to the treatment of composites of metals, polymers such as in particular polycarbonates, phenolic resins, phenolformaldehyde resins, polyesters, polyvinyl chloride and polyolefins, optionally glass, ceramics and other reinforcements, and organic chemical auxiliaries.
  • piece goods any lumpy source material, which may be a shredder fraction of electronic waste, but which may contain small components as such Small components may be piece goods per se and may not need to be mechanically pre-shredded the homogenization of the material are used, so that a piece goods is obtained with particles of a fairly uniform size as the starting material.
  • the process can be carried out batchwise, ie in batch mode, continuously or semicontinuously.
  • batch operation extraction of a certain amount of the starting material in an extractor is first performed, and the material is then transferred to a shock wave treatment reactor.
  • the product of the process a solid meal, is removed and separated from the process liquid or further treated in it, stored or transported for use or further utilization.
  • starting material is fed continuously to a specially designed extractor, for example a countercurrent extractor, taken off continuously and passed through the reaction space of a shock wave system, as already shown, for example, in US Pat. No. 5,758,831.
  • a specially designed extractor for example a countercurrent extractor
  • Both procedures can be combined, for example, by sequentially and separately treating larger batches of unitary starting materials in a plant designed for continuous operation.
  • the organic fraction When using supercritical water as the extraction agent, the organic fraction will also separate after relaxation of the water phase and can be further treated accordingly. It is particularly preferred to use the extractant supercritical water in combination with the shockwave medium water.
  • the subsequent work-up will comprise, for example, a rectification or adsorptive separation.
  • the shock wave treatment is then carried out preferably also in an organic solvent and more preferably with the solvent selected as the extraction agent.
  • the addition of a mild oxidizing agent is preferred.
  • the solvent used is acetylacetone in a solution which is halic acid, nitric acid or halopetonic acid and in which case N-thiobenzoyl-N-phenylhydroxylamine is added.
  • the temperature to be selected during the shock wave treatment depends on the treatment task and the fluid medium used (the dielectric and shock wave transmission medium or the process fluid).
  • the fluid dielectric medium water, an organic liquid or supercritical carbon dioxide is used.
  • the organic liquid may preferably be a hydrocarbon, a ketone such as acetone or an alcohol, preferably methanol, ethanol, propanol, isopropanol or higher alcohols.
  • the alcohol may also be a polyol, in particular a glycol such as ethylene glycol or propylene glycol, generally a diol or a triol, in the latter preferably glycerol.
  • a polyol in particular a glycol such as ethylene glycol or propylene glycol, generally a diol or a triol, in the latter preferably glycerol.
  • hydrocarbons for example hexane, heptane, cyclohexane, xylene, benzene, toluene, ethereal solvents, for example dioxane, diisopropyl ether, tetrahydrofuran or chlorinated hydrocarbons, in particular chloroform, dichloromethane, tetrachlorohydrocarbon or dichloroethylene.
  • the dielectric medium may be a liquid mixture.
  • the shock wave treatment is carried out within the inventive method at a temperature between - 80 ° C and + 50 ° C.
  • both the extraction and the shock wave treatment are carried out with supercritical carbon dioxide. This makes it possible to connect the streams of extractant and fluid shockwave medium. The use (and partial disposal) of organic liquids is avoided.
  • the piece goods are treated with acid or suspended in aqueous acid before or during the extraction. Furthermore, the process can be carried out so that an oxidizing agent is allowed to act on the piece goods at the same time as the extraction medium. Suitable are mild oxidants such as atmospheric oxygen or oxidants with a similar or lower oxidation potential than oxygen. Strong oxidizing agents, eg peroxides de, are not uncritical in handling and have a strong corrosive effect on the process apparatus. They should therefore be avoided.
  • the extraction medium and / or the dielectric medium are cleaned and recycled.
  • the cleaning processes can be connected in terms of process technology.
  • the extraction and the shockwave treatment follow one another directly. Intermediate steps are not required.
  • the process parameters (pressure, temperature) for the extractant and the shock wave medium can be set identical, so that the transfer of the substances to be treated and the connection of the process cycles between extraction and shock wave treatment is simplified.
  • a reduction in pressure takes place between extraction and shock wave treatment, for example by spontaneous relaxation after extraction.
  • the piece goods should be mechanically crushed before extraction as far as necessary.
  • Already fine-particle cargo does not need to be further pretreated.
  • pretreatment steps such as pre-cleaning or dedusting of the material, are generally not excluded.
  • the aftertreatment may include, for example, surface conditioning, e.g. a plasma treatment.
  • the aftertreatment may also consist in a screening or classification of the particles. It can be a physical or a chemical aftertreatment.
  • the aftertreatment depends on the planned reuse of the solid meal.
  • a post-treatment with a chemical functionalization of the solid-flour polymers is particularly preferred.
  • a surface functionalization of the particles is provided, as is generally known in the art.
  • the functionalization is carried out with OH groups (hydroxyl groups), amine groups, amide groups, halogen groups, oxygen groups, in particular -COOH or acid halide groups.
  • Mixed functionalizations with chemically different groups can also be performed.
  • the inventive method provides products in particulate form with a relatively uniform size distribution.
  • the energy supplied to the parameter, the duration of treatment, the degree of pre-grinding, the particle sizes obtained and the degrees of distribution can be influenced.
  • particle sizes below 30 pm are well reproducible, particle sizes of up to 100 nm are preferably set and obtained for certain applications.
  • the invention will be explained in more detail with reference to a flow chart shown in the figure.
  • the method starts in this example with a mechanical pre-shredding 1 of the piece goods, for example of used boards, for example in the form of printed circuit boards.
  • a mechanical pre-shredding 1 of the piece goods for example of used boards, for example in the form of printed circuit boards.
  • the particle size under a maximum of 5 cm in diameter, preferably less than 1 cm in diameter (or.
  • the extraction is carried out according to the invention with supercritical carbon dioxide, supercritical water or an organic solvent in a suitable extractor.
  • Preferred examples here are the extraction by means of acetylacetone from halogenated and / or nitric acid solutions and N-thiobenzoyl-N-phenylhydroxylamine.
  • the temperature can be adjusted.
  • a relaxation at position 3 takes place in this example.
  • the pressure reduction step is omitted at this point.
  • the excess pressure from the extraction stage is reduced here or reduced to atmospheric pressure.
  • the starting material still has its initial particle size in this stage of the process, but is already freed from low molecular weight substances and soluble polymers by the extraction step. Additives such as flame retardants (bromides), oils, silicones and the like are removed. Subsequently, the material thus treated is subjected to the shock wave crushing 4.
  • the shock wave treatment takes place in a fluid medium, for example, in an alcohol. The fluid is recirculated here and before returning to the
  • Treatment with shock waves produces a fine particulate flour from the treated material.
  • the grain size is of several parameters, i.a. However, depending on the type of scrap used, the degree of pre-grinding, the energy used and the duration of the treatment, it can be well adjusted to the desired range.
  • particulate products A solid particles
  • a treatment 5 is carried out, which may for example consist of additional separation operations or in which the particles are surface-functionalized. Suitable processes for the surface functionalization of the particles obtained are known to the person skilled in the art and need not be further detailed here. Refined and / or fractionated products A are obtained by way of the treatment 5.
  • the extracting agent (extraction medium) leaving the extraction stage 2 carries the substances extracted from the starting material. These are unloaded in process stage 6 in a container or reactor.
  • the CO 2 extract is residue-free with respect to the extractant and can be recycled directly or further separated. Other extractants must be separated here. By further purification, various products B can be obtained.

Landscapes

  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Processing Of Solid Wastes (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

L'invention concerne un nouveau procédé de retraitement de produits usagés se présentant sous forme de cartes de circuits imprimés, de composants électroniques ou d'éléments techniques contenant du verre, selon lequel ces déchets sont éventuellement d'abord fragmentés (1) avant de subir une extraction (2) puis un traitement par ondes de choc (4) déclenchées par une haute tension dans un milieu diélectrique fluide, le milieu des ondes de choc pouvant être notamment un liquide organique ou de l'eau. Les particules obtenues (produits A), de taille inférieure à 30 μm, sont sensiblement exemptes de produits chimiques polluants et peuvent être utilisées dans de multiples applications.
EP11765105.9A 2010-03-18 2011-03-18 Procédé de fragmentation de déchets électroniques et de verre technique à des fins de recyclage Not-in-force EP2547452B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201010011937 DE102010011937B4 (de) 2010-03-18 2010-03-18 Verfahren zum Zerkleinern von Elektronikschrott und technischem Glas für die Wiederverwertung
PCT/DE2011/000285 WO2011124195A2 (fr) 2010-03-18 2011-03-18 Procédé de fragmentation de déchets électroniques et de verre technique à des fins de recyclage

Publications (2)

Publication Number Publication Date
EP2547452A2 true EP2547452A2 (fr) 2013-01-23
EP2547452B1 EP2547452B1 (fr) 2016-09-14

Family

ID=44585322

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11765105.9A Not-in-force EP2547452B1 (fr) 2010-03-18 2011-03-18 Procédé de fragmentation de déchets électroniques et de verre technique à des fins de recyclage

Country Status (3)

Country Link
EP (1) EP2547452B1 (fr)
DE (1) DE102010011937B4 (fr)
WO (1) WO2011124195A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014070193A1 (fr) * 2012-11-02 2014-05-08 Empire Technology Development Llc Traitement de déchets électroniques par des gaz rares supercritiques
DE102014013857B4 (de) * 2014-09-24 2016-09-22 Jörg Beckmann Verwendung eines Schockwellenverfahrens
AT516381B1 (de) * 2014-12-04 2016-05-15 Andritz Ag Maschf Verfahren zur Aufbereitung elektrischer und elektronischer Bauteile zur Rückgewinnung von Wertstoffen
FR3030317B1 (fr) * 2014-12-23 2017-02-10 Brgm Procede de recyclage de dechets d'equipements electriques et electroniques
DE102015216932A1 (de) * 2015-09-03 2017-03-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zum Recycling von Kompositwerkstoffen sowie recycelte Kompositwerkstoffe

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19534232C2 (de) * 1995-09-15 1998-01-29 Karlsruhe Forschzent Verfahren zur Zerkleinerung und Zertrümmerung von aus nichtmetallischen oder teilweise metallischen Bestandteilen konglomerierten Festkörpern und zur Zerkleinerung homogener nichtmetallischer Festkörper
US5758831A (en) 1996-10-31 1998-06-02 Aerie Partners, Inc. Comminution by cryogenic electrohydraulics
JP2000246132A (ja) * 1999-02-26 2000-09-12 Kobe Steel Ltd 放電処理装置
DE10061386A1 (de) * 2000-12-09 2002-09-05 Daimler Chrysler Ag Verfahren und Vorrichtung zur überkritischen Nassoxidation

Non-Patent Citations (1)

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Title
See references of WO2011124195A2 *

Also Published As

Publication number Publication date
WO2011124195A3 (fr) 2012-06-07
DE102010011937B4 (de) 2012-02-02
EP2547452B1 (fr) 2016-09-14
DE102010011937A1 (de) 2011-09-22
WO2011124195A2 (fr) 2011-10-13

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