WO2002100932A1 - Procede d'extraction de pebd dans des pellicules plastiques usees - Google Patents

Procede d'extraction de pebd dans des pellicules plastiques usees Download PDF

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Publication number
WO2002100932A1
WO2002100932A1 PCT/DE2002/002051 DE0202051W WO02100932A1 WO 2002100932 A1 WO2002100932 A1 WO 2002100932A1 DE 0202051 W DE0202051 W DE 0202051W WO 02100932 A1 WO02100932 A1 WO 02100932A1
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WO
WIPO (PCT)
Prior art keywords
film
solvent
polymer
organic solvent
solution
Prior art date
Application number
PCT/DE2002/002051
Other languages
German (de)
English (en)
Inventor
Wolfgang Lindner
Andreas Thiele
Guido Gorski
Original Assignee
Der Grüne Punkt - Duales System Deutschland 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
Application filed by Der Grüne Punkt - Duales System Deutschland Ag filed Critical Der Grüne Punkt - Duales System Deutschland Ag
Priority to EP02742797A priority Critical patent/EP1392766A1/fr
Priority to JP2003503695A priority patent/JP2004532922A/ja
Publication of WO2002100932A1 publication Critical patent/WO2002100932A1/fr

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Classifications

    • 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
    • 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
    • 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
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B17/0412—Disintegrating plastics, e.g. by milling to large particles, e.g. beads, granules, flakes, slices
    • 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
    • B29B2017/001—Pretreating the materials before recovery
    • B29B2017/0015—Washing, rinsing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0293—Dissolving the materials in gases or liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0633—LDPE, i.e. low density polyethylene
    • 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
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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 invention relates to a method for obtaining LDPE from used plastic films.
  • Plastic films used as packaging materials consist predominantly of LDPE (low density polyethylene), as well as HDPE (high density polyethylene), PP (polypropylene), residual plastics and contaminants. So far, such films have been processed wet and processed into regranulate, but regranulate of inferior and not constant quality is obtained. This is due to the fact that the additives used in the production of plastics, such as stabilizers, lubricants, antistatic agents, pigments, fillers and the like, as well as externally applied printing inks, are not separated from the used plastic films. In addition, co-extruded and multilayer films cause reduced quality. Furthermore, a proportion of contaminants is always obtained through the processing.
  • DE 41 22 277 describes a process for removing additives, such as antistatic agents, lubricants, stabilizers and waxes, that is to say degraded polymers, and also externally applied printing inks from film chips.
  • additives such as antistatic agents, lubricants, stabilizers and waxes, that is to say degraded polymers, and also externally applied printing inks from film chips.
  • the films to be recycled are first mechanically crushed, then washed with water so that dirt is separated, whereupon extraction takes place with organic solvent.
  • the film Schnitzel be freed of water beforehand and dried.
  • the solvent is first removed from the film chips by pressing out the film chips and then by evaporation.
  • the polyethylene film chips obtained in this way can be processed into new films.
  • the solvent becomes contaminated with water, which makes the process considerably more expensive.
  • the color pigments contained in the film chips are not removed in the known method.
  • DE 43 42 848 presents a method for avoiding speck formation in film chips cleaned by a method according to DE 41 22 277.
  • the film chips present after the extraction ie after removal of the degraded polymers, removal of the externally applied printing inks and removal of the degradation products of the additives, are mixed with water, so that the solvent present in the film chips evaporates and at the same time the adhering residues of the adhesion promoter, in consisting essentially of nitrocellulose, are removed.
  • To safely remove the finest dirt particles remaining on the film chips rinse with clear water.
  • the disadvantage here is the resulting three-phase mixture of solvent, water and nitrocellulose, which is separated again with great effort must become.
  • the rinse water must also be cleaned with ultra-fine filters, which again causes costs.
  • the processing of mixed inhomogeneous films from the "films" fraction from the Green Dot collections, which often contain pigmented and heavily printed films, and increasingly multilayer films from up to five or more layers, to produce high-quality polyethylene regranulates is possible with the above-mentioned processes
  • the dry-processed fraction contains 80 to 85% by weight LDPE, 10 to 15% by weight HDPE, the rest are PP and other plastics as well as contaminants.
  • the invention is based on the object of producing a preliminary stage for regranulate from this inhomogeneous and not further purified mixture of ground film, which consists of at least 90% LDPE and, in particular, has the same mechanical and physical properties as new goods.
  • This object is achieved by a process for obtaining LDPE from used plastic films, which has at least the following steps:
  • the fall temperature of LDPE is 70 to 80 ° C for hexane, 100 to 110 ° C for HDPE and 80 to 110 ° C for PP.
  • the LDPE obtained can then be granulated in the usual way.
  • wet-processed film ground material or agglomerate of wet-processed film ground material can be used as the starting material.
  • the invention has particular advantages if, for example, dry-processed ground film is used as the starting material, for example according to the procedure described above. Then the step
  • Another problem with recycling is the fluctuating composition of the polyolefins in the starting material for the film preparation.
  • Shear precipitation is used to solve this problem. This is preferably carried out while simultaneously lowering the temperature to a temperature which is in the range of the falling temperature of the interfering polyolefin for the selected solvent.
  • the organic solvents for the suspension washing, the extraction and the selective solution can be chemically the same or different, but it has turned out to be advantageous to use the same organic solvent for the extraction and the selective solution of the polyolefins, with hexane, in particular technical hexane , is a particularly preferred selection.
  • Technical hexane always contains a proportion of branched components and is therefore inexpensive to obtain.
  • Technical hexane should also preferably be used for shear precipitation.
  • Other aliphatic solvents are suitable, such as EXXSOL ® D30.
  • the extraction is more preferably carried out under the boiling conditions of the solvent used.
  • the extraction can take place in countercurrent, crosscurrent or cocurrent.
  • a preferred temperature range is between 60 and 70 ° C.
  • a pressure range between 0.9 and 1.2 bar, with a residence time of 20 to 60 minutes, preferably 30 to 40 minutes.
  • the prepared film grist is preferably dissolved in stages in one or more dissolving kettles in the step of selective dissolution, with the grinded film being placed in the first dissolving kettle and then the solvent being added. In the subsequent dissolving kettle, ground film is again placed and the polymer solution from the previous dissolving kettle is added. This is repeated until the desired concentration increases Polymer is present in the solution. Values for the desired polymer concentration are between 1 and 25% by weight, preferably between 10 and 25% by weight, particularly preferably between 10 and 20% by weight and more preferably between 15 and 20% by weight.
  • the same solvent as in the extraction can be used in the dissolving vessel or in the dissolving vessels, but also a different solvent.
  • the polyolefinic constituents of the ground material or the agglomerate are selectively dissolved under a defined temperature and pressure.
  • the result is a polymer solution in which undissolved constituents, such as, for example, pigments, binders, printing inks, adhesion promoters, labels, non-polyolefinic polymers made from laminated films and contaminants such as aluminum and paper, are still present.
  • undissolved constituents such as, for example, pigments, binders, printing inks, adhesion promoters, labels, non-polyolefinic polymers made from laminated films and contaminants such as aluminum and paper
  • the insoluble constituents and the fibers previously produced during the shear precipitation are separated from the polymer solution.
  • the insoluble components and fibers are disposed of.
  • the polymer solution is concentrated using conventional spiral tube and thin-weight evaporation or by methods known per se for static vacuum degassing. The material obtained can then be granulated.
  • FIG. 1 shows a flow chart for the dry processing of used films for the method according to the present invention
  • Figure 2 is a block diagram of an embodiment according to the method of the invention together with the procedural alternatives that wet processed film or film agglomerate is used as the starting material.
  • the dry preparation of the foils is preferably used for preparation, as is shown in table is shown in Figure 1.
  • the bales of film are first separated and sieved.
  • the first coarse contaminants are removed during sieving.
  • the pieces of film pass through the heavy goods separation and arrive at the pre-shredder, for example a shredder, where the films, e.g. B. crushed to about 10 cm x 10 cm.
  • the so-called ground film is sieved and the top grain shredded again.
  • the shredded pieces of film are now subjected to a metal deposition in which the ferrous and non-ferrous metals are separated before they are finely ground.
  • the fine material is first bunkered in a first buffer and then subjected to paper separation.
  • the typical dry-processed film regrind from the collections of the Duales System GmbH consists of approx. 84% LDPE, approx. 11% HDPE, approx. 1% PP, approx. 0.4% residual plastics and approx. 3% residual contaminants.
  • Figure 2 shows how the prepared film material is treated further. If this film material comes from the dry preparation according to FIG. 1, it is subjected to a suspension wash with a first solvent, while the printing inks adhering to the surface are washed off. The solvent is then discharged and worked up and returned to the suspension step. Subsequent to the discharge of the first solvent, the extraction takes place with a second solvent, in which low-molecular components are extracted from the film material. As before, the solvent is then discharged, worked up and returned to the extraction step. The second solvent can also be used for the selective dissolving step, alternatively a third solvent is used. Subsequent to the selective dissolution, a coarse material separation can optionally be carried out by customary methods of solid-liquid separation.
  • the actual polymer separation then takes place by shear crystallization, where fibers which consist mainly of HDPE and PP are precipitated under the influence of shear and temperature reduction.
  • the insoluble components of the printing inks, stabilizers, lubricants, antistatic agents, dyes, fillers and binders serve as crystallization nuclei.
  • these insoluble constituents and the fibers produced are separated from the polymer solution.
  • the remaining polymer solution is evaporated and optionally granulated.
  • the result is an LDPE blend with at least 95% by weight LDPE, which has a low intrinsic color and has physical and mechanical properties similar to that of new goods.
  • Table I shows the comparison of some properties of LDPE blends (PRL-PE-LD blend) obtained by the process according to the invention with new goods.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

L'invention concerne un procédé d'extraction de PEBD dans des pellicules plastiques usées consistant à extraire des constituants de faible poids moléculaire dans le matériau de pellicule dissout dans un deuxième solvant organique ; à dissoudre sélectivement le matériau de pellicule ainsi traité dans au moins un troisième solvant organique, une solution polymère de concentration définie étant produite ; à faire précipiter au moins un polymère parasite dans la solution polymère par application de forces de cisaillement dans la solution ; et, à extraire le PEBD dans la solution polymère restante. Le matériau initial peut se présenter sous la forme d'une composition de pellicule provenant du traitement sec ou humide. Si ladite composition de pellicule provient du traitement sec, on effectue d'abord l'étape de lavage du matériau de pellicule dans un premier solvant organique, au cours de laquelle une suspension est créée et des colorants d'impression adhérant à la surface sont lavés.
PCT/DE2002/002051 2001-06-08 2002-06-06 Procede d'extraction de pebd dans des pellicules plastiques usees WO2002100932A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP02742797A EP1392766A1 (fr) 2001-06-08 2002-06-06 Procede d'extraction de pebd dans des pellicules plastiques usees
JP2003503695A JP2004532922A (ja) 2001-06-08 2002-06-06 Ｌｄｐｅを使用済みプラスチックフィルムから得る方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10127875.6 2001-06-08
DE2001127875 DE10127875A1 (de) 2001-06-08 2001-06-08 Verfahren zur Gewinnung von LDPE aus gebrauchten Kunststofffolien

Publications (1)

Publication Number Publication Date
WO2002100932A1 true WO2002100932A1 (fr) 2002-12-19

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PCT/DE2002/002051 WO2002100932A1 (fr) 2001-06-08 2002-06-06 Procede d'extraction de pebd dans des pellicules plastiques usees

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EP (1) EP1392766A1 (fr)
JP (1) JP2004532922A (fr)
DE (1) DE10127875A1 (fr)
WO (1) WO2002100932A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2687975C1 (ru) * 2015-06-30 2019-05-17 Дзе Проктер Энд Гэмбл Компани Способ очистки загрязненных полимеров
RU2752416C2 (ru) * 2016-10-10 2021-07-27 Фраунгофер-Гезельшафт Цур Фёрдерунг Дер Ангевандтен Форшунг Э.Ф. Способ переработки содержащих полиолефин отходов
WO2022129309A1 (fr) * 2020-12-16 2022-06-23 Alpla Werke Alwin Lehner Gmbh & Co. Kg Procédé de recyclage pour polyoléfines contaminées

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9284431B2 (en) * 2012-02-14 2016-03-15 Clariant International Ltd. Method for recycling floor coverings
DE102013009138A1 (de) 2013-05-31 2014-12-04 Rainer Pommersheim Verfahren und technischer Prozess zur Rückgewinnung von Rohstoffen aus papierhaltigen Abfällen mittels lonischer Flüssigkeiten
EP3112406A1 (fr) * 2015-06-30 2017-01-04 The Procter and Gamble Company Procédé de purification de polyoléfines contaminées
WO2018118575A1 (fr) * 2016-12-20 2018-06-28 The Procter & Gamble Company Procédé de purification de polypropylène recyclé
CA3045910C (fr) * 2016-12-20 2022-12-06 The Procter & Gamble Company Procede de purification de polymeres recuperes
DE102016015198A1 (de) * 2016-12-21 2018-06-21 Apk Ag Lösungsmittel sowie Verfahren zum Lösen eines Kunststoffes von einem Feststoff innerhalb einer Suspension
KR102090018B1 (ko) * 2017-11-14 2020-03-17 한국과학기술연구원 폴리올레핀계 플라스틱을 이용한 탄소 소재 제조 방법 및 이로부터 얻어진 탄소 소재
DE102021203708B3 (de) 2021-04-14 2022-08-04 Thyssenkrupp Ag Verfahren und Vorrichtung für das Recycling von Low Density Polyethylene (LDPE)

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US4048429A (en) * 1972-04-22 1977-09-13 Stamicarbon B.V. Process for the preparation of polymer fibers
US5368796A (en) * 1991-07-05 1994-11-29 Nordenia Verpackungswerke Gmbh Process and apparatus for regenerating used articles of polyolefin to reusable raw material
DE19744436A1 (de) * 1997-10-08 1999-04-15 Lindner Wolfgang Verfahren zur Gewinnung von polyolefinischen Kunststoffen
DE19905029A1 (de) * 1999-01-29 2000-11-16 Bgb Ges Tu Berlin Verfahren zur Trennung vermischter Polyolefine
DE19927523A1 (de) * 1999-06-16 2000-12-21 Wolfgang Lindner Verfahren zur Trennung von polyolefinischen Kunststoffgemischen

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US3119801A (en) * 1964-01-28 Recovery of olefin polymers fkom
DE19822234A1 (de) * 1998-05-07 1999-11-18 Stefan Bosewitz Verfahren zur Trennung von Kunststoffen und deren Mischungen durch selektives Fällen aus Lösungen

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
US4048429A (en) * 1972-04-22 1977-09-13 Stamicarbon B.V. Process for the preparation of polymer fibers
US5368796A (en) * 1991-07-05 1994-11-29 Nordenia Verpackungswerke Gmbh Process and apparatus for regenerating used articles of polyolefin to reusable raw material
DE19744436A1 (de) * 1997-10-08 1999-04-15 Lindner Wolfgang Verfahren zur Gewinnung von polyolefinischen Kunststoffen
DE19905029A1 (de) * 1999-01-29 2000-11-16 Bgb Ges Tu Berlin Verfahren zur Trennung vermischter Polyolefine
DE19927523A1 (de) * 1999-06-16 2000-12-21 Wolfgang Lindner Verfahren zur Trennung von polyolefinischen Kunststoffgemischen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2687975C1 (ru) * 2015-06-30 2019-05-17 Дзе Проктер Энд Гэмбл Компани Способ очистки загрязненных полимеров
RU2752416C2 (ru) * 2016-10-10 2021-07-27 Фраунгофер-Гезельшафт Цур Фёрдерунг Дер Ангевандтен Форшунг Э.Ф. Способ переработки содержащих полиолефин отходов
WO2022129309A1 (fr) * 2020-12-16 2022-06-23 Alpla Werke Alwin Lehner Gmbh & Co. Kg Procédé de recyclage pour polyoléfines contaminées
CH718174A1 (de) * 2020-12-16 2022-06-30 Alpla Werke Alwin Lehner Gmbh & Co Kg Recycling-Verfahren für verunreinigte Polyolefine.

Also Published As

Publication number Publication date
DE10127875A1 (de) 2003-01-30
EP1392766A1 (fr) 2004-03-03
JP2004532922A (ja) 2004-10-28

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