EP0500837A1 - Procede de recuperation de metaux et de materiaux d'enduction contenus dans des materiaux composites - Google Patents

Procede de recuperation de metaux et de materiaux d'enduction contenus dans des materiaux composites

Info

Publication number
EP0500837A1
EP0500837A1 EP91914746A EP91914746A EP0500837A1 EP 0500837 A1 EP0500837 A1 EP 0500837A1 EP 91914746 A EP91914746 A EP 91914746A EP 91914746 A EP91914746 A EP 91914746A EP 0500837 A1 EP0500837 A1 EP 0500837A1
Authority
EP
European Patent Office
Prior art keywords
solvent
minutes
weight
metal
composite
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Withdrawn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
EP91914746A
Other languages
German (de)
English (en)
Inventor
Dagmar Mertens-Gottselig
Gerd Rauser
Werner Löffler
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.)
RWE Entsorgung AG
Original Assignee
RWE Entsorgung AG
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
Priority claimed from DE19904028999 external-priority patent/DE4028999A1/de
Priority claimed from DE19904037523 external-priority patent/DE4037523A1/de
Application filed by RWE Entsorgung AG filed Critical RWE Entsorgung AG
Publication of EP0500837A1 publication Critical patent/EP0500837A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D9/00—Chemical paint or ink removers
    • C09D9/005—Chemical paint or ink removers containing organic solvents
    • 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
    • B29K2031/00—Use of polyvinylesters or derivatives thereof as moulding material
    • B29K2031/04—Polymers of vinyl acetate, e.g. PVAc, i.e. polyvinyl acetate
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • 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
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • 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
    • 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
    • B29K2705/02—Aluminium
    • 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
    • B29K2705/08—Transition metals
    • 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
    • B29K2705/08—Transition metals
    • B29K2705/10—Copper
    • 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
    • B29K2711/00—Use of natural products or their composites, not provided for in groups B29K2601/00 - B29K2709/00, for preformed parts, e.g. for inserts
    • B29K2711/12—Paper, e.g. cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3425—Printed circuits
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/707—Cables, i.e. two or more filaments combined together, e.g. ropes, cords, strings, yarns
    • 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

Definitions

  • the present invention relates to a method for the recovery of metals and coatings of the metals from composite materials by treating the composite materials with certain solvents at elevated temperatures, the coating being brought into solution and recovered from this solution and the metal quantitatively and in pure form from the Solution is separated and can be reused.
  • the present invention also relates to an apparatus for performing the method.
  • Composite materials are used as packaging materials e.g. B. for coffee, tea, toothpaste, chemicals, drinks and. a. in large quantities on the market.
  • Metal foils in such composite materials are mostly made of aluminum, while the coating can be made of numerous plastic materials.
  • Called epoxy resins outside multilayer composites containing films made of various plastics are on the market. Furthermore, the metal foil with cellulose-containing materials such. B. be shrewd with paper. Paper coatings can also be combined with plastic layers.
  • the foils can be made with or without Kleoer or
  • Adhesion promoter to be connected Metal containing composite materials, however, are not only used as packaging material. Examples outside the packaging area are cables, coated wires, Closing lid, plastic-coated items such as. B. door handles or tools, further electrical devices, circuit boards and numerous other items.
  • a recovery of metals present in the composite materials is of greater interest, the more valuable the metal is, there is also considerable interest in the recovery of copper.
  • An important aspect for recovery can also be the separation of the metals for environmental reasons, since it is known that heavy metals get into the atmosphere in small quantities when the entire composite material is burned.
  • a process is described in DD-PS 218313 in which aluminum and polyvinyl chloride are recovered from an aluminum / polyvinyl chloride film by grinding and mechanical separation.
  • a mechanical separation process is also described in FR-PS 2528351 for composite materials such as power cables and wires and the like.
  • Japanese patent JP-PS 57043941 discloses a method according to which composites are subjected to pyrolysis, in which the plastic decomposes and the pyrolysis gases are used as fuel to maintain the pyrolysis temperature.
  • polyvinylchloride-laminated aluminum foils are treated with carbon tetrachloride, producing two layers of solvent, the lower one containing the aluminum and the upper one containing the polyvinyl chloride.
  • thermoplastics According to JP-PS 51020976, mixtures of aluminum foils laminated with various thermoplastics are treated with xylene at various temperatures and with phenol.
  • the laminates contain polypropylene, ethylene-vinyl 1-acetate copolymer, poly (ethylene) terephthalate, polycarbonate and polyethylenes.
  • the thermoplastics can be partially separated from one another by using the solvents under different conditions.
  • an aluminum / polyvinyl chloride laminate bonded with an ethylene / vinyl acetate copolymer adhesive is mixed with a solvent mixture of ethyl acetate, isopropanol, acetone and tol 30 ml. treated at room temperature.
  • the adhesive dissolves, so that subsequently aluminum foil and polyvinyl chloride are separated.
  • U.S. Patent 4,168,199 discloses the removal of paper from an aluminum / paper laminate. For this, the material is treated for 10 minutes at 120 ° C. with water under nitrogen pressure.
  • JP-PS 54088817 A similar method is described in JP-PS 54088817.
  • xylene is used as a solvent for the coating materials polyethylene, polypropylene, ethylene-vinyl acetate copolymer and polycarbonate, the latter two thermoplastics already at room temperature and the thermoplastics polyethylene and polypropylene at 120 ° C.
  • the investigations of the applicant have shown that under these conditions the plastic coatings do not completely detach and therefore no pure aluminum is obtained.
  • the object of the invention is to provide a method for separating and recovering aer coating materials and metals from composite materials, which allows in a simple and economical manner, as well as that To recover metal as well as the coating agent as quantitatively and in pure form as possible and to be able to reuse the solvent used.
  • the applicant has now found a process for recovering metals and coating materials from composite materials by removing the coatings on the metal with solvents, characterized in that the composite material is used to remove non-polar layers with dimethyl and / or trimethyl and / or tetramethylbenzenes and / ooer ethylbenzene and / or isopropylbenzene to 40 ° C to 280 ° C, preferably to 75 ° C to 220 ° C and particularly preferably to 138.4 ° C to 204 ° C without pressure or under pressure during a residence time of 0.5 to 360 minutes, preferably from 5 to 120 minutes and particularly preferably from 5 to 60 minutes, that the composite materials are removed to 40 with tetrahydrofuran and / or its methylated derivatives and / or dioxane and / or its methylated derivatives in order to detach polar layers ° C to 280 ° C, preferably to 60 ° C to 200 ° C without pressure or under pressure
  • the applicant has also found a process for recovering metals and coating material from composite materials by removing the coatings present on the metal with solvent, characterized in that the composite material is removed with C 3 -C 18 ketones and / or C to remove the layers 3 -C 18 polyketones at 40 ° C to 280 ° C, preferably at 75 ° C to 220 ° C and particularly preferably at 100 ° C to 220 ° C without pressure or under pressure during a residence time of 0.5 to 360 minutes, preferably from 5 heated to 120 min. and particularly preferably from 5 to 60 min.
  • the present invention now makes it possible, by using special solvents and by using special conditions, to obtain the metals in such a pure form that they can be used without further treatment for new applications or for reuse in composite materials can be set.
  • the investigations by the applicants in have shown that from the very common packaging films consisting of a metal film, in particular aluminum and a non-polar one.
  • the metal can be obtained quantitatively in a very pure form if the compounding material is heated with di-, tri-, tetramethylbenzenes, ethylbenzene and isopropylbenzene or mixtures of these hydrocarbons until the coating material has dissolved and then separating the metal and generally subjecting it to aftertreatment with at least one of the hydrocarbons mentioned. Since the boiling points of di-, tri- and tetramethylbenzenes are between 138.4 ° C and 203.2 ° C to 204 ° C, the solvent can be selected so that the solvent treatment can be carried out without pressure. This is a procedural advantage. However, according to the invention, it is also possible to work under pressure in closed vessels.
  • the xylenes are advantageously used as an industrial mixture, it being known that industrial mixtures have very different compositions, depending on the point at which the mixture is drawn in a xylene plant and the process used to obtain pure xylenes .
  • a suitable C 8 mixture consists, for example, of 1 to 4% by weight of non-aromatics, 19 to 28% by weight of ethylbenzene, 16 to 20% by weight of p-xylene, 40 to 45% by weight of m-xylene and 10 to 15 % By weight o-xylene, which add up to 100 -2- depending on the mixture.
  • two phases can occur with different plastic concentrations instead of a uniform, highly concentrated solution.
  • the individual aromatic hydrocarbons or other mixtures can also be used.
  • the individual isomers and mixtures can be used.
  • the mixtures may also contain 1,2,4,5-tetramethylbenzene, although in pure form it is solid at normal temperature and melts at 81oC to 82oC.
  • the boiling points of the aromatic hydrocarbons are 143.6 ° C for o-xylene, 139 ° C for m-xylene and 138.4 ° C for b-xylene.
  • 1.3.5-trimethyloenzene has a boiling point of 164.6 ° C
  • 1.2.4-trimethylbenzene has a boiling point of 170.2 ° C
  • 1.2.3-trimethylbenzene has a boiling point of 175.6 ° C
  • 1.2.3.5-tetramethylbenzene has a boiling point of 195 ° C to 197 ° C
  • 1.2.3.4-tetramethylbenzene has a boiling point of 203 ° C to 204 ° C
  • ethylbenzene has a boiling point of 136.1 ° C
  • isopropylbenzene nat has a boiling point of 152.5 ° C.
  • any mixtures of at least two of the hydrocarbons mentioned can also be used.
  • the xylenes or ethyloenzene or their mixtures it is not possible to work at 200 ° C. without pressure.
  • B. a xylene mixture, which is used under boiling conditions, is much better, so that relatively short residence times can be chosen.
  • a residence time of 5 to 10 minutes should generally not be undercut.
  • Another group of solvents which are very suitable according to the invention are ketones and polyketones.
  • pierper can be both open-chain and rinc-shaped ketones.
  • ketones such as B. Cyclopentanone, boiling point 129 ° C, cyclohexanone, boiling point 155.7 ° C, cycloheptanone, boiling point 179-81 ° C, cyclooctanone and higher derivatives, acetylacetone, boiling point 194 ° C, 2,7-octanedione, boiling point 114 ° C (18 mo ).
  • the dissolution temperatures can be from 40 ° C to 280 ° C, preferably from 75 ° C to 220 ° C and particularly preferably from 138.4 ° C to 204 ° C in the case of aromatic solvents and particularly preferably from 100 ° C to 220 ° C in The case of the ketone compounds, while the preferred temperature for tetrahydrofuran and dioxane and their derivatives is 60 ° C to 200 ° C.
  • the residence time during the dissolving process is 0.5 to 360 minutes, preferably 5 to 120 minutes and particularly preferably 5 to 60 minutes. In general, low temperatures are combined with longer residence times.
  • the dissolving process can take place without pressure or under pressure, but preferably without pressure, the solvents being chosen so that the boiling point is not exceeded.
  • Composite materials can be in any layering, and the layers can have any thickness according to the required applications.
  • the layers can be applied as desired, such as. B. by vapor deposition, coating, etc.
  • thermoplastics such as polyethylene - this applies to the various ethylene or polyethylene types, such as LD, HD and LLD polyethylene, polypropylene and ethylene / propylene copolymers - dissolve in the solvent, as does the adhesive or Adhesion promoter, if the composite material contains one.
  • the plastics can be recovered from the process according to the invention. This can be done in a known manner, e.g. B. cases by distilling off at least part of the solvent, cases by cooling the solution or cases by adding a solvent in which the plastic is insoluble or only slightly soluble.
  • the plastic it is possible to consider the plastic as fine-grained. obtain huge granules that can be used directly for processing into finished products.
  • thermoplastics such as. B. polyester, polycarbonate, polyvinyl chloride, ethylene-vinyl acetate copolymers or epoxy resins or others
  • tetrahydrofuran and / or dioxane depending on the polarity of the polymer building blocks, methylated as well Derivatives are suitable. Very good results can also be achieved here.
  • H. very pure metals can be obtained with a residence time of 5 minutes depending on the temperature used. Temperatures of up to 280 ° C. can be used here, it being advantageous to work with self-jerk.
  • multi-layer composites e.g. B. a packaging film made of aluminum, polyethylene and polyester films
  • the solution processes mentioned can be carried out in succession, z. B. in the case of external polyethylene film, methylbenzenes are used first and then tetrahydrofuran and / or dioxane.
  • total dwell times can be up to 360 min. In general, however, these can be significantly shorter per stage, as already explained above, e.g. E. 5 to 60 min.
  • Treatment with a mixture of the polar and non-polar solvents is also possible according to the invention.
  • composite materials can also be processed, which contain several metals, which can consist of the same metal or different metal.
  • ketone solvent has also been used for the removal of non-polar layers, depending on the structure of the ketone for polar layers, such as.
  • the plastics can often be easily obtained from these solvents by cooling them down in a pure, finely divided, granular form.
  • thermoplastics such as different types of PE and PP, polyester, polyvinyl chloride and the like.
  • Thermoplastics are particularly well suited for the process according to the invention.
  • resins such as. B. epoxy resins and elastomers processable according to the invention.
  • the amount of solvent based on the composite material used can vary within wide limits.
  • a suitable ratio is
  • Solvent content should not exceed 15 parts by weight. It has surprisingly shown that C 9 aromatics have a particularly high dissolving power for numerous thermoplastics, so that plastic concentrations of 49% by weight can easily be achieved in the solution.
  • technical C 9 aromatics fractions from platformer and xylene plants are particularly suitable.
  • Technical C 10 aromatics fractions or mixtures of technical C 9 and C 10 aromatics fractions are also very suitable.
  • the ratio of composite material to solvent may also be> 1.
  • plastic-coated reusable moldings such as. B. crush door handles. Rather, the entire composite molded part is subjected to a solvent treatment. In such cases, appropriate release containers are to be used, such as slowly curling, tumbling, draining or other dissolving devices.
  • the solvents used in the present invention can be returned to the solution container after at least partial separation from the dissolved plastic.
  • the solvent can accordingly be circulated.
  • the metal freed from the plastic foils is separated off - this can be done in a conventional manner, e.g. B. by filtering, decanting or centrifuging - and usually subjected to a washing step. To do this, use the same solvent as that used for the dissolving stage or another suitable solvent.
  • the aftertreatment serves to detach the thinnest plastic layers from the metal, such as z. B. can arise when drying solvents from the first stage.
  • the temperature in the aftertreatment stage can advantageously be between room temperature and 280 ° C., with residence times of 1 to 120 minutes. Short residence times are advantageously selected in combination with a sufficiently high temperature and pressure-free operation. However, the person skilled in the art has a wide range of temperatures and residence times available here.
  • the metal is then separated from the washing liquid, dried and is then ready for reuse.
  • the comminuted composite material is mixed with water, which also contains small amounts of additives such as e.g. B. alcohols, such as methanol or ethanol or of ketones, such as. B. acetone or methyl ethyl ketcn or other detaching additives may be heated to 100 ° C to 200 ° C.
  • the dwell time is 5 to 120 minutes.
  • these conditions can also be varied within wide limits.
  • at least a portion of the paper can result from hydrolysis of the cellulose in solution, the paper or cellulose is generally pulp, with high quality pulp that can be reused as such.
  • Post-treatment may also be necessary or advantageous here.
  • the composite material can be comminuted in a conventional manner, generally comminuting to a particle size of 1 to 50 mm. However, this area is not absolutely necessary. Depending on the treatment containers, larger particles or composite parts can also be treated according to the invention. The same applies to parts ⁇ 1 mm, although it must be taken into account that the size of the metal is favored by a size> 1 mm.
  • FIGS. 1 and 2 represent examples of greatly simplified devices for carrying out the method according to the invention.
  • apparatus 1 is used to shred the composite film material that has already been freed of paper.
  • 2 is a container in which the coating material is detached from the aluminum foil or other metal.
  • 3 the metal is separated from the solution. The metal reaches 4, where it is rinsed again with hot solvent and dried. At 5 the pure metal is removed.
  • the solvent is largely removed, for example by distillation or vacuum distillation. 7 represents an extruder from which the granulate is removed at 8. The solvent can be recycled from 6 to 2.
  • FIG. 2 shows an example of an alternative device for carrying out the method according to the invention.
  • Apparatus 1 in turn serves to shred the composite film material which has already been freed of paper.
  • 2 is the release container.
  • the metal is separated from the solution. The separated metal is rinsed in 4. At 5 the pure metal is removed. The detergent from 4 arrives at 5. In 9 wire the solvent is distilled off and returned to 2.
  • the solution from 6 geianet in container 7, where the coating material, e.g. B. polyethylene as a granular, free-flowing material by cooling or falling with one
  • FIGS. 1 and 2 are highly simplified embodiments of the present invention, which can be varied within wide limits without leaving the scope of the invention and can be equipped with additional apparatus.
  • the usual apparatuses of the prior art can be used for the various device stages, such as for comminution and for dissolving materials, that is to say stirred tanks, shaking tanks, stirred cascades, flow tanks equipped with internals and the like. Like. More are known. Numerous apparatuses are also known to those skilled in the art for flushing processes. This can be continuous countercurrent rinsing systems or rinsing cascades, stirred tanks and. a. Devices. The separation of materials need not be explained in more detail, since the person skilled in the art can use suitable devices such as centrifuges, decanders, filters and the like. Like. Are known. The same applies to apparatus for separating solvents.
  • a sample of the compound film was weighed out and the weight fraction of the aluminum in the film was determined in the atomic absorption spectrometer.
  • the metal obtained by the treatment step according to the invention was weighed out, a sample was weighed and the weight fraction of the aluminum was again determined in the atomic absorption spectrometer. In all cases, the metal samples consisted of 100% aluminum. So they were completely free of foil components. The yield of aluminum was 100%.
  • the plastic solution was then concentrated in a flash evaporator and fed into a degassing extruder via an evaporation chamber.
  • Example 1 was repeated, but a solvent mixture of C 9 and C 10 methylbenzenes was used with a boiling range of 175 ° C
  • the aluminum rinsed in this way was centrifuged in a centrifuge, rinsing at 180 ° C. using the same solvent.
  • Example 1 pure aluminum was obtained in quantitative yield, just as in Example 1, a solvent-free polyethylene granulate was obtained quantitatively.
  • Example 1 was repeated, but became proprietary at 220 ° C for 2 minutes pressure stirred. The same results as in Example 1 were obtained.
  • Example 1 was repeated, but the coating consisted of polypropylene. The results corresponded to those described in Example 1.
  • Example 1 was repeated, but the process was carried out at a weight ratio of composite materials to solvent of 1: 5.
  • Example 1 was repeated, but heating was carried out with 1000 g of 1.2.3.5-tetramethylbenzene for 0.5 min at 260 ° C. with stirring and autogenous pressure. The sieved metal was then treated for 5 minutes with 1000 g of the same tetramethylbenzene at 150 ° C. The sieved aluminum was now dried. Completely pure aluminum was obtained in quantitative yield. The polyethylene solution was worked up as described in Example 1.
  • Example 1 was repeated, but the film was wetted with 3000 g of isopropylbenzene for 120 minutes at 40 ° C.
  • the aluminum was then sieved and washed with 1000 g of isoprocylbenzene at 100 ° C.
  • a steel door handle coated with polyethylene with a layer thickness of 1.5 mm was in a tumble reactor for 15 minutes with 1000 ml of a mixture of 53% by weight of 1,2.4-trimethylbenzene and 50% by weight of 1.2.3.5-tetramethylbenzene at 170 ° C treated. The door handle was then removed from the solvent, rinsed with hot solvent and dried. The steel is completely free of polyethylene. The polyethylene was recovered as described in Example 1.
  • Example 1 400 g of an aluminum foil with a layer thickness of 0.5 mm. a polyester film with a layer thickness of 0.2 mm and an outer polyethylene slide with a thickness of 0.5 mm was treated with a technical C 9 cut as in Example 1.
  • the decanted and rinsed film which was still coated with polyester, was then wetted with 1500 ml of tetrahydrofuran for 10 minutes at 100 ° C. under autogenous pressure.
  • the aluminum was sieved and dried.
  • Example 10 was repeated with dioxane with the same result.
  • a laminate of a copper foil with a particle size of 10 mm and a layer thickness of 0.01 mm and a polypropylene layer with a thickness of 0.3 mm was 5 min. At 160 ° C with a 1: 1: 1 mixture of the three trimethylbenzene -Isomers treated.
  • 600 g of an aluminum foil crushed to 4 mm particle size, a layer thickness of 0.01 mm and a polyethylene foil with a layer thickness of 0.5 mm were mixed with 6000 g of a technical xylene mixture, consisting of 4% by weight non-aromatics, 20% by weight Ethylbenzene, 15% by weight of p-xylene, 40% by weight of m-xylene and 20% by weight of o-xylene were stirred at 140 ° C. for 20 minutes.
  • the aluminum was then sieved and stirred with 1500 g of fresh xylene added at 140 ° C for 10 minutes. Now the aluminum was sieved again and dried.
  • the aluminum was then sieved off and added with 500 g fresh tetrahydrofuran stirred at 140 ° C under pressure for 10 min. Now the aluminum was sieved and dried.
  • the tetrahydrofuran was concentrated to half.
  • the polyester was then precipitated by adding toluene and cooling to 50 ° C.
  • Example 15 was repeated, but acetylacetone was used instead of cyclohexanone. As in Example 15, a very pure aluminum could be obtained in duantitati ver yield.
  • the polyethylene was precipitated in granular form by cooling the polyethylene solution to 52 ° C.

Abstract

Selon un procédé de récupération de métaux et de matériaux d'enduction contenus dans des matériaux composites, on traite les matériaux composites avec des solvants donnés à une température élevée. Dans le cas de matériaux composites en métaux/matières plastiques, on peut dissoudre les matières plastiques et les récupérer dans la solution, alors que le métal est quantitativement séparée sous une forme purifiée de la solution et peut être réutilisé. Dans le cas de matériaux composites en métaux/papier et en métaux/matières plastiques/papier, on peut également récupérer les métaux sous forme purifiée en éliminant le papier avec de l'eau, à laquelle on ajoute le cas échéant des quantités réduites d'alcools C1 à C3 et/ou de cétones C3 à C4.
EP91914746A 1990-09-13 1991-08-29 Procede de recuperation de metaux et de materiaux d'enduction contenus dans des materiaux composites Withdrawn EP0500837A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4028999 1990-09-13
DE19904028999 DE4028999A1 (de) 1990-09-13 1990-09-13 Verfahren zur rueckgewinnung von metallen aus verbundwerkstoffen
DE19904037523 DE4037523A1 (de) 1990-11-26 1990-11-26 Verfahren und vorrichtung zur isolierung von polymeren werkstoffen und metallen aus verbundwerkstoffen
DE4037523 1990-11-26

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EP0500837A1 true EP0500837A1 (fr) 1992-09-02

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JP (1) JPH0765124B2 (fr)
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BR (1) BR9106175A (fr)
CA (1) CA2050767A1 (fr)
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WO (1) WO1992005215A1 (fr)

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DE4214527C2 (de) * 1992-05-07 1996-01-18 Linde Ag Verfahren zur Aufbereitung von Verpackungsmaterialien
EP0603434A1 (fr) * 1992-12-18 1994-06-29 Karl Fischer Industrieanlagen Gmbh Récupération de polyamide
ES2087013B1 (es) * 1993-10-25 1997-03-16 Univ Valencia Politecnica Procedimiento para recuperar polietileno y aluminio de hojas de aluminio recubiertas de polietileno de residuos de envases tipo "pack".
FR2737673B1 (fr) * 1995-08-09 1997-10-31 Europ De Dezingage Comp Procede de valorisation des dechets, constitues de toles recouvertes sur au moins une face d'une couche de zinc
FR2741826B1 (fr) * 1995-12-04 1998-01-09 Muller Michel Procede pour la separation des resines ou composite des metaux
ES2130040B1 (es) * 1996-04-29 1999-12-01 Olmos Ibanez Desamparados Procedimiento para la recuperacion de aluminio y energia a partir de envases usados tipo "tetrabrick" y horno para realizarlo.
JPH1128667A (ja) 1997-07-10 1999-02-02 Tokyo Ohka Kogyo Co Ltd サンドブラスト用プラスチック研磨材およびそれを用いたプラズマディスプレイパネル基板のサンドブラスト加工法、並びにサンドブラスト廃材の処理方法
US6419755B1 (en) * 1999-12-30 2002-07-16 Alcoa Inc. Chemical delacquering process
AU2002222386A1 (en) * 2001-12-20 2003-07-09 Virgo Manufacturing Sa Computer recycling
KR100889315B1 (ko) * 2007-11-16 2009-03-18 한국지질자원연구원 유기용액을 이용한 폐인쇄회로기판으로부터 금속을회수하는 방법
CN102166579B (zh) * 2011-01-14 2013-02-13 陕西科技大学 一种纸铝塑包装盒回收分离方法
DE102013009138A1 (de) * 2013-05-31 2014-12-04 Rainer Pommersheim Verfahren und technischer Prozess zur Rückgewinnung von Rohstoffen aus papierhaltigen Abfällen mittels lonischer Flüssigkeiten
AU2015349557B2 (en) * 2014-11-20 2019-08-08 Juarez Souza De OLIVEIRA Process for recycling by separating the constituents of aluminized and plasticized, optionally carton, containers, and respective equipment
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BR9106175A (pt) 1993-03-16
AU8337191A (en) 1992-04-15
JPH0765124B2 (ja) 1995-07-12
CA2050767A1 (fr) 1992-03-14
JPH05501134A (ja) 1993-03-04
NZ239670A (en) 1993-08-26
US5232489A (en) 1993-08-03
WO1992005215A1 (fr) 1992-04-02

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