WO2003104315A1 - Process for separation of multilayered films used for packagings - Google Patents
Process for separation of multilayered films used for packagings Download PDFInfo
- Publication number
- WO2003104315A1 WO2003104315A1 PCT/BR2003/000013 BR0300013W WO03104315A1 WO 2003104315 A1 WO2003104315 A1 WO 2003104315A1 BR 0300013 W BR0300013 W BR 0300013W WO 03104315 A1 WO03104315 A1 WO 03104315A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- separation
- films
- film
- packagings
- atmospheric pressure
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 30
- 238000000926 separation method Methods 0.000 title claims abstract description 28
- 238000004806 packaging method and process Methods 0.000 title description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 238000011084 recovery Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims description 23
- 239000000853 adhesive Substances 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005063 solubilization Methods 0.000 claims description 12
- 230000007928 solubilization Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- -1 polyethylene Polymers 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005026 oriented polypropylene Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229960004319 trichloroacetic acid Drugs 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
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
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0286—Cleaning means used for separation
- B29B2017/0289—Washing the materials in liquids
-
- 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
-
- 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
- B29K2067/003—PET, i.e. poylethylene terephthalate
-
- 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
- B29L2009/00—Layered products
- B29L2009/003—Layered products comprising a metal layer
-
- 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
-
- 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
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Definitions
- the invention patent refers to a process for separation and complete recovery of multilayered films, containing polymeric films joined each other or to aluminum and paper sheets, either joined each other or not, thereby allowing to reuse thereof by usual recycling processes.
- the separation is performed by introducing the multilayered films in baths of solvents, protonic carboxyl acid and water, heated, matched or not.
- the invention is based on the discovery that the separation among films is more effective if the adhesive contained among them can have their function removed, through chemical attack by solvents, acids and water.
- solvents such as chloroform, toluene, tetrahydrofuran, xylene, acetone and carbon tetrachloride and protonic carboxyl acid in general, such as acetic acid, among other ones, either matched or not, can act over polyurethane adhesives which are most commonly used in multilayered film manufacture.
- the adhesive used is polyvinylalchool, it can have its function removed by immerging the multilayered film into solvents, acid or water, either matched or not.
- cohesive energy density which especially depends on the temperature in general, the greater the cohesive energy density - the greater is the difficulty to make soluble the polymer or any type of organic molecule with lower molecular weight, as it happens with adhesives.
- Tg vitreous transition temperature
- Solubilization of polyurethane adhesive joining the polyethylene polymeric film with polyethyleneterephthalate film, polypropylene film, aluminum or paper sheet is performed in chloroform bath at atmospheric pressure with temperature which can range between 20° C and 61° C within a time between 30 seconds and 1 hour, or in a xylene bath at atmospheric pressure with temperature ranging between 20° C to 140° C within a time between 30 seconds and 1 hour and 30 minutes, or in tetrahydrofuran bath at atmospheric pressure with temperature ranging between 20° C and 66° C within a time between 30 seconds and 1 hour, or in protonic carboxyl acid bath at atmospheric pressure with temperature which may range from 20° C to 115° C within a time between 30 seconds and 2 hours or in tetrahydrofuran solution and acetic acid bath at atmospheric pressure with temperature ranging from 20° C to 66° C within a time between 30 seconds and 1 hour and 30 minutes, or further in chloroform and tetrahydrofuran solution bath at the atmospheric pressure with temperature
- Solubilization of polyvinylalcohol adhesivev joining the different polymeric films each other or to paper and/or aluminum sheets is performed in protonic carboxyl acid bath at atmospheric pressure with temperature ranging between 20° C and 115° C within a time between 30 seconds and 2 hours, or further in water bath at atmospheric pressure with temperature ranging from 15° C and 100° C within a time between 5 seconds and 1 hour.
- Solubilization of different adhesives joining bio-oriented/oriented polypropylene films with metallized bio-oriented polypropylene and/or aluminum and/or paper is performed in pure chloroform bath or in solution with protonic carboxyl acid solution, tetrahydrofuran or water at atmospheric pressure with temperature ranging from 20° C and 61° C within a time between 30 seconds and 1 hour and 30 minutes, or tetrahydrofuran in temperatures ranging from 20° C to 66° C, within times between 30 seconds and 2 hours, or further in protonic carboxyl acid bath at atmospheric pressure with temperature ranging from 20° C and 115° C within a time between 30 seconds and 2 hours.
- Solubilization of the adhesive joining the polyethyleneterephthalate polymeric film with that of aluminum and/or paper is performed in tetrahydrofuran bath at atmospheric pressure with temperature ranging from 20° C and 66° C within a time between 30 seconds and 1 hour and 30 minutes .
- organic solvent among which, acetone, carbon tetrachloride and toluene is indicated in polymeric systems which are different from those mentioned above.
- the present invention is directly associated with equipment to perform the process according to the invention, which consists in tanks with electric, gas or coil heating for obtainment and maintenance of process temperature, in addition to the accessory inside the tank which may enable the continuous agitation of the system.
- Each type of film requires a suitable number of baths for removal of every layer, each layer in first requiring a bath.
- the removal of different materials apart the tank is performed due to the difference of density, which provides individual flotation of the different materials, which are removed in stages .
- the separating means is water with different densities, which density is intermediate between densities of the two types of materials which is to be obtained separately, which can be sole or coupled materials, such as polyethylene, it being separated from a polyethylene and aluminum coupled film, or individually by separating a polyehtyleneterephthalate film from one of aluminum, such a separation being obtained by addition of both densifying and surfactant elements aiming to improve the efficiency of the flotation process.
- Films obtained after the full separation of layers are made in non-coupled materials, and can be perfectly used in recycling operations, thereby enabling to reuse previously coupled materials, whose recycling was impossible to perform as yet .
- By-products of this separation process include residues of paints composing packings and adhesives, either soluble or in separation, which must be sent, after re-improvement of chemical solution by distillation, to a suitable sanitary backfill. Such wastes weigh lower than 1% of the initial packaging.
- Separation of a multilayered film composed by polyethyleneterephtalate, aluminum and polyethylene is performed according to the process of the present invention, where a first bath in chloroform is performed in a temperature from 50 ⁇ 2° C within 3 minutes for removal of the polyethylene film. Then, a second bath is performed in the film composed by polyethyleneterephthalate and aluminum in tetrahydrofuran, in temperature from 59 ⁇ 2° C within 15 minutes for removal of the polyethyleneterephthalate film from the aluminum film, thereby separating the three components of the multilayered film.
- the separation process described in the patent US 5.230.944 is performed upon insertion of a water-soluble adhesive, of high latent delamination power, among layers constituting the film.
- the multilayered film is separated in aqueous solution by dissolution of the adhesive used; the higher the temperature is, the most spontaneous the process.
- the process consists in the reduction of the multilayered film size to small pieces, which then are cooled to. temperatures lower than the room temperature where the stressing for separation of films is performed, due to the fragility caused in the adhesive.
- One of the existing techniques proposes the insertion of an intermediate layer with delamination latent potential, however it represents a cost accretion, modification of the existing technology for manufacture and increase in the film thickness.
- the films are formed by more than one polymeric material, some stages for separation thereof are required, as well as different times in order that each solvent may act in the polymeric layer which will become soluble.
- Such problems are solved according to the present mention in a process for separation of materials from multilayered films, from pack- and decorative-typed food packagings, among other, which are composed by several layers of different types of materials (polymer, aluminum and paper) , whose surface area is indeterminate and the polymeric film thickness varies from 8 ⁇ m up to 150 ⁇ m, the aluminum film thickness varies from 5 ⁇ m up to 200 ⁇ m, and the paper film varies from 10 m up to 600 ⁇ m.
- a heated bath of commercially- available chemical solutions for adhesive solubilization is used so as to maintain the films in their original form, able to recycling.
- the invention is based in the discovery that the separation between the films is most effective if the adhesives, polyurethane, polyvinylalcohol or even other types of adhesives which can be chemically attacked by solvents, acids as described and water contained among them can have their function removed.
- solvents such as chloroform, toluene, tetrahydrofuran, xylene, acetone and carbon tetrachloride, protonic carboxylic acids, for example, acetic acid, among others and water, either matched or not, can act over adhesives which are most commonly used in the manufacture of multilayered films.
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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)
- Processing Of Solid Wastes (AREA)
- Laminated Bodies (AREA)
Abstract
The invention refers to a multilayered film separation process containing polymeric films joined each other or to aluminum and/or paper sheets either joined each other or not, whose separation is performed through th eintroduction of films into heated organic solvent, acid or water baths, with pre-established temperatures and times for each type of material to be separated, under atmospheric pressure, thereby allowing the complete recovery of each film, which can be reused in manufacture of several articles by usual recycling processes.
Description
"PROCESS FOR SEPARATION OF MULTILAYERED FILMS USED FOR PACKAGINGS"
The invention patent refers to a process for separation and complete recovery of multilayered films, containing polymeric films joined each other or to aluminum and paper sheets, either joined each other or not, thereby allowing to reuse thereof by usual recycling processes. The separation is performed by introducing the multilayered films in baths of solvents, protonic carboxyl acid and water, heated, matched or not.
The invention is based on the discovery that the separation among films is more effective if the adhesive contained among them can have their function removed, through chemical attack by solvents, acids and water.
Commercially- available solvents, such as chloroform, toluene, tetrahydrofuran, xylene, acetone and carbon tetrachloride and protonic carboxyl acid in general, such as acetic acid, among other ones, either matched or not, can act over polyurethane adhesives which are most commonly used in multilayered film manufacture.
When the adhesive used is polyvinylalchool, it can have its function removed by immerging the multilayered film into solvents, acid or water, either matched or not.
Such chemical solutions
act, in first, by making the adhesive soluble, since chemical solution solubility parameters are quite near the adhesive solubility parameter, separating from polymeric film solubility parameters. According to Hildebrand's law, the nearer the solubility parameters of species, more easily the solubilization will occur, according to the same law, if the difference of absolute values between two solubility parameters is lower than 1.7 hildebrand, the solubilization is assured.
Another parameter to be taken into consideration is the cohesive energy density which especially depends on the temperature in general, the greater the cohesive energy density - the greater is the difficulty to make soluble the polymer or any type of organic molecule with lower molecular weight, as it happens with adhesives. The higher the temperature, the greater the thermal agitation state of adhesive molecules and, therefore, the lower is its cohesive energy density, thereby enabling solubilization thereof.
As the temperature used is higher than the vitreous transition temperature (Tg) of certain polymers such as, polyethylene, in which Tg is around -10° C, the diffusion of solvent molecules by the polymeric film may occur due to an increase in the free volume of the polymer.
This results in an increase
of the useful area for adhesive' solubilization reaction. In polymers with high degree of crystalinity and/or Tg's higher than the processing temperature, this diffusion mechanism becomes difficult, the solubilization reactions occurring in the interface in which the adhesive is exposed.
Solubilization of polyurethane adhesive joining the polyethylene polymeric film with polyethyleneterephthalate film, polypropylene film, aluminum or paper sheet is performed in chloroform bath at atmospheric pressure with temperature which can range between 20° C and 61° C within a time between 30 seconds and 1 hour, or in a xylene bath at atmospheric pressure with temperature ranging between 20° C to 140° C within a time between 30 seconds and 1 hour and 30 minutes, or in tetrahydrofuran bath at atmospheric pressure with temperature ranging between 20° C and 66° C within a time between 30 seconds and 1 hour, or in protonic carboxyl acid bath at atmospheric pressure with temperature which may range from 20° C to 115° C within a time between 30 seconds and 2 hours or in tetrahydrofuran solution and acetic acid bath at atmospheric pressure with temperature ranging from 20° C to 66° C within a time between 30 seconds and 1 hour and 30 minutes, or further in chloroform and tetrahydrofuran solution bath at the atmospheric pressure with temperature ranging from 20° C and 45° C
within a time between 10 seconds and 1 hour.
Solubilization of polyvinylalcohol adhesivev joining the different polymeric films each other or to paper and/or aluminum sheets is performed in protonic carboxyl acid bath at atmospheric pressure with temperature ranging between 20° C and 115° C within a time between 30 seconds and 2 hours, or further in water bath at atmospheric pressure with temperature ranging from 15° C and 100° C within a time between 5 seconds and 1 hour.
Solubilization of different adhesives joining bio-oriented/oriented polypropylene films with metallized bio-oriented polypropylene and/or aluminum and/or paper is performed in pure chloroform bath or in solution with protonic carboxyl acid solution, tetrahydrofuran or water at atmospheric pressure with temperature ranging from 20° C and 61° C within a time between 30 seconds and 1 hour and 30 minutes, or tetrahydrofuran in temperatures ranging from 20° C to 66° C, within times between 30 seconds and 2 hours, or further in protonic carboxyl acid bath at atmospheric pressure with temperature ranging from 20° C and 115° C within a time between 30 seconds and 2 hours.
Solubilization of the adhesive joining the polyethyleneterephthalate polymeric film with that of aluminum and/or paper is performed in tetrahydrofuran bath at atmospheric pressure with temperature ranging from 20° C and 66° C
within a time between 30 seconds and 1 hour and 30 minutes .
The use of organic solvent, among which, acetone, carbon tetrachloride and toluene is indicated in polymeric systems which are different from those mentioned above.
The present invention is directly associated with equipment to perform the process according to the invention, which consists in tanks with electric, gas or coil heating for obtainment and maintenance of process temperature, in addition to the accessory inside the tank which may enable the continuous agitation of the system.
Each type of film requires a suitable number of baths for removal of every layer, each layer in first requiring a bath. The removal of different materials apart the tank is performed due to the difference of density, which provides individual flotation of the different materials, which are removed in stages .
The separating means is water with different densities, which density is intermediate between densities of the two types of materials which is to be obtained separately, which can be sole or coupled materials, such as polyethylene, it being separated from a polyethylene and aluminum coupled film, or individually by separating a polyehtyleneterephthalate film from one of aluminum,
such a separation being obtained by addition of both densifying and surfactant elements aiming to improve the efficiency of the flotation process.
Films obtained after the full separation of layers are made in non-coupled materials, and can be perfectly used in recycling operations, thereby enabling to reuse previously coupled materials, whose recycling was impossible to perform as yet . By-products of this separation process include residues of paints composing packings and adhesives, either soluble or in separation, which must be sent, after re-improvement of chemical solution by distillation, to a suitable sanitary backfill. Such wastes weigh lower than 1% of the initial packaging.
The invention is additionally explained through the following drawings :
Example and Comparative Example
Separation of a multilayered film composed by polyethyleneterephtalate, aluminum and polyethylene is performed according to the process of the present invention, where a first bath in chloroform is performed in a temperature from 50 ± 2° C within 3 minutes for removal of the polyethylene film. Then, a second bath is performed in the film composed by polyethyleneterephthalate and aluminum in
tetrahydrofuran, in temperature from 59 ± 2° C within 15 minutes for removal of the polyethyleneterephthalate film from the aluminum film, thereby separating the three components of the multilayered film. The separation process described in the patent US 5.230.944 is performed upon insertion of a water-soluble adhesive, of high latent delamination power, among layers constituting the film. The multilayered film is separated in aqueous solution by dissolution of the adhesive used; the higher the temperature is, the most spontaneous the process.
Both processes present valid solutions, however in the Example (process as per the present invention) , it is not necessary to replace the adhesive joining the film layers.
No other process similar to the process now presented is known, however we present below some processes for comparative effects and demonstration of the novelty of the invention now proposed.
It is known from U.S. Patent 4,168,199, the possibility of recovering cellulose fibers of papers used in laminated packagings, by submerging the laminated material in an aqueous means inside a closed system, thereby heating and pressurizing the system components for a time sufficient to cause fiber-fiber adhesion drop and fiber-laminate adhesion, the pressure inside the system
is reduced to a value sufficient to quickly expel the system components, by discharging the system components under influence of the remaining pressure and finally separating the cellulose fibers apart the laminate. It is known from FR Patent
2,510,428, the possibility of separating coupled films, which are composed of aluminum, paper and polymers, which is possible with the use of a mixture of acids in a solvent (92% dichloromethane, 5% trichloracetic acid and 3% hydrochloric acid) , with agitation in periods lower than 30 minutes. A subsequent vacuum treatment is necessary for separation and removal of components. Such a treatment is possible only for films with thickness lower than 100mm, whose polymeric film is from 8μm to lOOμm thick, the aluminum film is from 7μm to 80μm thick and paper density is between 23 g/m2 to 200 g/m2.
It is known from US Patent 5,230,944 the possibility of modifying the couple packing production by using a material with adhesive properties and with an inherent latent delamination potential, that is, which is able to be cleaved in its individual components, among the main films, thereby enabling delamination in water or water steam, enabling the main components to recycle. The material should be crushed as flakes.
It is known from US Patent 5,358,184 that the separation of films composed of
paper and polymers can be performed through the action of pressurized jets into the paper film, which are disintegrated into fibers and separated from the plastic blade. In order to make this process effective, the pressurized liquid must act in the paper blade surface during the most time as possible, which is solved by using different angles of attack.
It is known from ES Patent 2,087,013, the possibility of separating the film composed of polyethylene and aluminum performed in organic solvents (bi-, tri-o tetra-chlorethane, bi-, tri-o tetrachlorethylene, bi-, tri-, tetra-penta-o hexa-chloroethane) , which is able to dissolve polyethylene in temperatures from 50 to 250° C, at a pressure from 4 to 20 atm, within a time between 2 minutes and 2 hours submitted to agitation. Polyethylene is obtained as a powder after evaporation of the solvent, and aluminum is obtained as a blade.
It is known from WO Patent 9,847,681 the existence of a method for separation of aluminum paper and film from their polymeric recoverings through the immersion into a water bath with temperature between 5° C and 30° C at atmospheric pressure within a time between 6 and 24 hours, where the cellulose material (paper) is removed from the polyethylene film. In a second stage, aluminum and polyethylene blades are separated in an aqueous solution of acetic acid in a temperature between 5° C
and 30° C at atmospheric pressure for a period from 1 and 5 days, the polyethylene blades are easily separated from those of aluminum through exfoliation.
It is known from US Patent 5,647,544, the separation of multilayered film components is performed detaching the films through the action of shearing or flexural stresses .
In first, the process consists in the reduction of the multilayered film size to small pieces, which then are cooled to. temperatures lower than the room temperature where the stressing for separation of films is performed, due to the fragility caused in the adhesive.
It is known from US Patent 5,871,161 a method for recycling laminated films, mainly films containing no paper, through the action of an impact friction force. Films must be fragmented prior to applying the impact friction force which will remove the films, such films being separated through a dragging derived from a forced airflow, which due to the difference of density among films will allow the separation thereof.
It was demonstrated that all processes of the previous techniques regarding processes for separation of multilayered films are not satisfactory.
In the previously described techniques there is no possibility of recoving the
polymeric films without causing degradation.
Moreover, they are also ineffective in presenting an unique solution for recovery of all components of the final product, composed by multilayered films .
Another significant limitation is the use of pressures other than the atmospheric pressure, which requires specialized and expensive machinery, in addition to a high power demand.
One of the existing techniques proposes the insertion of an intermediate layer with delamination latent potential, however it represents a cost accretion, modification of the existing technology for manufacture and increase in the film thickness.
Processing times existing in the techniques divulged so far is in general quite long, reaching up to 72 hours. Additionally, there are some mechanical stages of friction, friction and tension, among other ones, which also require specific machinery.
As the films are formed by more than one polymeric material, some stages for separation thereof are required, as well as different times in order that each solvent may act in the polymeric layer which will become soluble.
Such problems are solved
according to the present mention in a process for separation of materials from multilayered films, from pack- and decorative-typed food packagings, among other, which are composed by several layers of different types of materials (polymer, aluminum and paper) , whose surface area is indeterminate and the polymeric film thickness varies from 8μm up to 150μm, the aluminum film thickness varies from 5μm up to 200μm, and the paper film varies from 10 m up to 600μm. For such a purpose, a heated bath of commercially- available chemical solutions for adhesive solubilization is used so as to maintain the films in their original form, able to recycling.
As already mentioned in the beginning of this report, the invention is based in the discovery that the separation between the films is most effective if the adhesives, polyurethane, polyvinylalcohol or even other types of adhesives which can be chemically attacked by solvents, acids as described and water contained among them can have their function removed. Commercially-available solvents such as chloroform, toluene, tetrahydrofuran, xylene, acetone and carbon tetrachloride, protonic carboxylic acids, for example, acetic acid, among others and water, either matched or not, can act over adhesives which are most commonly used in the manufacture of multilayered films.
Therefore, it is
demonstrated by the use of the process of the present invention that, ' without any modification of the multilayered film manufacturing process it is possible to get the separation through a chemical process, by recovering the component films in a complete manner.
For such advantages, absence of Technique State and by the effect caused, the present process gathers the necessary conditions to reach the proprietary privilege.
Claims
1. "PROCESS FOR SEPARATION OF MULTILAYERED FILMS USED FOR PACKAGINGS" , characterized by a process for separation of multilayered films, composed by polymeric materials joined each other or to aluminum and/or paper sheets, either joined each other or not, by using organic (Solvents, acids and water, either matched or not, in different temperatures, and at atmospheric pressure, thereby enabling the complete recovery of each component film, including in usual recycling processes, which makes the process unique, characterized by the solubilization of the adhesive used among layers.
2. "PROCESS FOR SEPARATION OF MULTILAYERED FILMS USED FOR PACKAGINGS", according to claim 1, characterized by the use of organic solvents, namely: tetrahydrofuran, xylene, toluene, carbon tetrachloride, acetone and chloroform, protonic carboxyl acids and water, by use of process temperatures ranging from 20° C and 140° C and times between 5 seconds and 2 hours.
3. "PROCESS FOR SEPARATION OF MULTILAYERED FILMS USED FOR PACKAGINGS", according to claim 1, characterized by the use of atmospheric pressure, use of a unique type of chemical solution for each process and by full recovery of component films without occurring depolymerization, solubilization and/or significant oxidation thereof, maintaining the dimensional integrity of the same
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003209867A AU2003209867A1 (en) | 2002-06-07 | 2003-01-30 | Process for separation of multilayered films used for packagings |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI0202303-2 | 2002-06-07 | ||
| BR0202303A BR0202303C1 (en) | 2002-06-07 | 2002-06-07 | Process for separating multilayer films used for packaging |
| BRC10202303-2 | 2002-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2003104315A1 true WO2003104315A1 (en) | 2003-12-18 |
Family
ID=29721218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/BR2003/000013 WO2003104315A1 (en) | 2002-06-07 | 2003-01-30 | Process for separation of multilayered films used for packagings |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2003209867A1 (en) |
| BR (1) | BR0202303C1 (en) |
| WO (1) | WO2003104315A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015169801A1 (en) * | 2014-05-05 | 2015-11-12 | saperatec GmbH | Method and apparatus for recycling packaging material |
| WO2019229235A1 (en) | 2018-06-01 | 2019-12-05 | saperatec GmbH | Separation fluid, method and apparatus for recycling multilayer material using a passivation agent |
| WO2020053051A1 (en) | 2018-09-12 | 2020-03-19 | Rittec Umwelttechnik Gmbh | Method, device and use for reprocessing substantially polyalkylene terephthalate |
| WO2021007510A1 (en) * | 2019-07-10 | 2021-01-14 | Engineered Floors LLC | Recycling of composites containing layers unsuitable for recycling |
| WO2021121731A1 (en) | 2019-12-20 | 2021-06-24 | Rittec Umwelttechnik Gmbh | Method, device and use for reprocessing polyalkylene terephthalate |
| EP3950799A1 (en) * | 2020-08-07 | 2022-02-09 | Apk Ag | Solvent-based recycling with a roll-to-roll processing step |
| WO2022235343A1 (en) | 2021-05-03 | 2022-11-10 | Dow Global Technologies Llc | Solvent composition |
| US11535022B2 (en) | 2016-12-15 | 2022-12-27 | saperatec GmbH | Method and apparatus for recycling packaging material |
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| JPS60212434A (en) * | 1984-04-05 | 1985-10-24 | Takeda Chem Ind Ltd | Separation and recovery of composite material |
| EP0538730A1 (en) * | 1991-10-23 | 1993-04-28 | Nordenia Verpackungswerke GmbH | Process for the conversion of polyethylene composite films to re-usable raw materials |
| DE4328016A1 (en) * | 1992-08-28 | 1994-03-03 | Alusuisse Lonza Services Ag | Packaging material which can be delaminated for recycling - contains layers of plastic, metal foil and/or cellulosic material, sepd. by layer(s) of polymer which is soluble in non-neutral aq. medium |
| DE4330889A1 (en) * | 1993-09-11 | 1995-03-16 | Basf Magnetics Gmbh | Process for the recovery of raw materials from magnetic recording media |
| US6223904B1 (en) * | 1995-08-30 | 2001-05-01 | Emtec Magnetics Gmbh | Continuous process for recovering raw materials from coated foils, device for carrying out this process and foil materials recovered thereby |
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2002
- 2002-06-07 BR BR0202303A patent/BR0202303C1/en not_active IP Right Cessation
-
2003
- 2003-01-30 AU AU2003209867A patent/AU2003209867A1/en not_active Abandoned
- 2003-01-30 WO PCT/BR2003/000013 patent/WO2003104315A1/en not_active Application Discontinuation
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|---|---|---|---|---|
| JPS60212434A (en) * | 1984-04-05 | 1985-10-24 | Takeda Chem Ind Ltd | Separation and recovery of composite material |
| EP0538730A1 (en) * | 1991-10-23 | 1993-04-28 | Nordenia Verpackungswerke GmbH | Process for the conversion of polyethylene composite films to re-usable raw materials |
| DE4328016A1 (en) * | 1992-08-28 | 1994-03-03 | Alusuisse Lonza Services Ag | Packaging material which can be delaminated for recycling - contains layers of plastic, metal foil and/or cellulosic material, sepd. by layer(s) of polymer which is soluble in non-neutral aq. medium |
| DE4330889A1 (en) * | 1993-09-11 | 1995-03-16 | Basf Magnetics Gmbh | Process for the recovery of raw materials from magnetic recording media |
| US6223904B1 (en) * | 1995-08-30 | 2001-05-01 | Emtec Magnetics Gmbh | Continuous process for recovering raw materials from coated foils, device for carrying out this process and foil materials recovered thereby |
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| Title |
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| PATENT ABSTRACTS OF JAPAN * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170080603A1 (en) * | 2014-05-05 | 2017-03-23 | saperatec GmbH | Method and Apparatus for Recycling Packaging Material |
| US10682788B2 (en) | 2014-05-05 | 2020-06-16 | saperatec GmbH | Method and apparatus for recycling packaging material |
| WO2015169801A1 (en) * | 2014-05-05 | 2015-11-12 | saperatec GmbH | Method and apparatus for recycling packaging material |
| US11535022B2 (en) | 2016-12-15 | 2022-12-27 | saperatec GmbH | Method and apparatus for recycling packaging material |
| WO2019229235A1 (en) | 2018-06-01 | 2019-12-05 | saperatec GmbH | Separation fluid, method and apparatus for recycling multilayer material using a passivation agent |
| WO2020053051A1 (en) | 2018-09-12 | 2020-03-19 | Rittec Umwelttechnik Gmbh | Method, device and use for reprocessing substantially polyalkylene terephthalate |
| DE102018122210B4 (en) | 2018-09-12 | 2023-06-29 | Rittec Umwelttechnik Gmbh | Process and use of a device for recycling waste containing polyalkylene terephthalate |
| WO2021007510A1 (en) * | 2019-07-10 | 2021-01-14 | Engineered Floors LLC | Recycling of composites containing layers unsuitable for recycling |
| WO2021121731A1 (en) | 2019-12-20 | 2021-06-24 | Rittec Umwelttechnik Gmbh | Method, device and use for reprocessing polyalkylene terephthalate |
| CN114058073A (en) * | 2020-08-07 | 2022-02-18 | Apk股份公司 | Solvent-based recycling of drum-to-drum processing steps using a drum |
| WO2022029323A1 (en) * | 2020-08-07 | 2022-02-10 | Apk Ag | Solvent-based recycling with a roll-to-roll processing step |
| EP3950799A1 (en) * | 2020-08-07 | 2022-02-09 | Apk Ag | Solvent-based recycling with a roll-to-roll processing step |
| WO2022235343A1 (en) | 2021-05-03 | 2022-11-10 | Dow Global Technologies Llc | Solvent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003209867A1 (en) | 2003-12-22 |
| BR0202303C1 (en) | 2004-06-08 |
| BR0202303A (en) | 2004-05-04 |
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