EP4114633A1 - Procédé de séparation de matériaux polymères d'un assembalge d'éléments - Google Patents
Procédé de séparation de matériaux polymères d'un assembalge d'élémentsInfo
- Publication number
- EP4114633A1 EP4114633A1 EP21714930.1A EP21714930A EP4114633A1 EP 4114633 A1 EP4114633 A1 EP 4114633A1 EP 21714930 A EP21714930 A EP 21714930A EP 4114633 A1 EP4114633 A1 EP 4114633A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- thermoplastic polymer
- support
- temperature
- polymer
- process according
- 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.)
- Pending
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
-
- 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
-
- 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
- B29B2017/0203—Separating plastics from plastics
-
- 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
- B29B2017/0217—Mechanical separating techniques; devices therefor
-
- 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
- B29B2017/0255—Specific separating techniques using different melting or softening temperatures of the materials to be separated
-
- 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
- B29B2017/0416—Cooling the plastics before disintegration, e.g. freezing
-
- 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
- B29B2017/0424—Specific disintegrating techniques; devices therefor
- B29B2017/0428—Jets of high pressure fluid
-
- 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
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
- B29K2027/16—PVDF, i.e. polyvinylidene fluoride
-
- 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
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
- B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
-
- 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
- B29L2031/00—Other particular articles
- B29L2031/14—Filters
-
- 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 process for separating polymeric materials from elements of an assembly.
- One field of application envisaged is in particular that of recycling liquid filtration modules. These each comprise a framework made of first polymeric materials and a filter membrane made of a second polymeric material having a porous structure.
- PVDF poly (vinylidene fluoride)
- PVDF has the advantage of being resistant to a wide range of chemical compounds and this is one reason it is popular for use as a filter.
- the membranes of tubular shape can in certain cases be coated with a support, for example braided PET threads.
- the water is thus filtered radially from the outside to the inside of the membrane, then it flows longitudinally along the support wires.
- tubular membranes associated with the other frame elements thus constitute filtration modules allowing in particular, the realization of a stage of clarification, or even disinfection, on water treatment installations and processes.
- these filtration modules cease to be effective, in particular because of the irreversible clogging, or the degradation of the polymers which constitute them, they are interchanged, and the modules at the end of their life or at the end of their life are then, either buried or incinerated, which, in the case of fluorinated polymers such as PVDF, releases hydrofluoric acid which should be neutralized.
- a problem which then arises and which the present invention aims to solve is to provide an inexpensive and efficient process which makes it possible to recover the polymer materials with high added value from assembled elements.
- thermoplastic polymer having a temperature of glass transition T g given; b) the temperature of said thermoplastic polymer is lowered to a temperature T inf lower than said glass transition temperature T g of said thermoplastic polymer; c) said thermoplastic polymer is mechanically treated at said temperature Ti nt to detach said thermoplastic polymer from said support; and, d) recovering said detached thermoplastic polymer.
- a characteristic of the invention lies in taking into account the glass transition temperature T g of the polymer material, in order to bring the temperature of the polymer material to a temperature below this before subjecting it to mechanical processing.
- T g glass transition temperature
- the polymer becomes more brittle and it can then more easily break into pieces when subjected to the mechanical treatment.
- a membrane comprising a braided support, in particular made of PET, coated at least partially with polymer material
- said polymer material can be easily detached from the support and recovered by means of the process according to the invention, as is done. will explain below.
- “Thermoplastic polymers” are well known to those skilled in the art.
- fluorinated polymers such as PVDF or PTFE are more particularly envisaged, but also polyethersulfone (PES) or polypropylene (PP).
- the "support” is generally itself a polymer material.
- a "mechanical treatment” means an interaction by contact with the polymer in order to be able to separate it from its support.
- said temperature Ti nt is less than 240 K. In this way, the temperature of the thermoplastic polymer is for example lowered to 230 K .
- step b) said support coated with said thermoplastic polymer is immersed in liquid nitrogen.
- the boiling point of nitrogen in the liquid state being 77.36 K
- the thermoplastic polymer when the thermoplastic polymer is immersed therein, its temperature drops suddenly below its glass transition temperature.
- the temperature T inf is between 240 K and 100 K, preferably between 220 K and 195 K.
- the immersion time must make it possible to rapidly lower the temperature of the polymer directly exposed to liquid nitrogen, without however lowering the temperature of the support material too much if the latter is a polymer material, at the risk that he himself becomes more fragile.
- thermoplastic polymers do not all exhibit the same behavior when their temperature is lower than that of their glass transition and that some are more resistant to it than others. In addition to their nature, polymers exhibit behaviors which also vary depending on the additives they contain and their method of use.
- step c) said support coated with said thermoplastic polymer is crushed to detach said thermoplastic polymer from said support.
- the material of the support when it is a polymer, does not behave in the same way as the thermoplastic polymer in order to be able to detach the first from the second and easily separate the two materials.
- the support is made of braided threads, its morphology is different from the porous layer of PVDF which covers it.
- thermoplastic polymer breaks at the level of the bond with the support and comes off easily.
- said support coated with said thermoplastic polymer is crushed between two rollers.
- the two rollers bear tangentially along a common generatrix, and the coated support is engaged between the two rotating rollers.
- the coated supports extend longitudinally, for example, when they are threads coated with the thermoplastic polymer to be recovered.
- a plurality of pairs of successive rollers can be used to detach the polymer material from the support.
- dry ice is projected against said thermoplastic polymer to simultaneously lower the temperature and mechanically treat said thermoplastic polymer according to steps b) and c).
- dry ice is used, that is to say C0 2 in solid form, typically in the form of granules or sticks, the sublimation temperature of which is 195, 6 K.
- the dry ice, in the form of granules or sticks, is then projected at high speed against the coated support, which provides the double advantage of cooling the thermoplastic polymer covering the support, and moreover of striking the polymer then cooled with high kinetic energy, to detach it from its support.
- dry ice makes it possible to lower the temperature of the thermoplastic polymer undergoing the impact, below its glass transition temperature, and hence the impacts of the dry ice themselves cause the detachment and separation of the material. polymer of its support.
- steps b) and c) are simultaneous.
- Another advantage of dry ice is that it leaves no residue in the thermoplastic polymer, since it turns into gaseous carbon dioxide and escapes into the atmosphere when the materials return to room temperature.
- dry ice is projected against said thermoplastic polymer at a speed greater than 200 ms 1 .
- the speed of the granules or rods is close to 300 ms 1 , which produces a high kinetic energy of impact.
- the speed of the projected dry ice is less than 340 ms 1 , preferably less than 320 ms 1 .
- a support comprising a plurality of wire braids respectively coated with said thermoplastic polymer.
- Braided supports for example made of PET, are covered with a porous tubular filter layer constituting the membrane. These coated supports thus constitute the hollow fibers.
- the support comprises a plurality of films or multilayer plates.
- a support comprising a plurality of braids of poly (ethylene terephthalate) yarns.
- said thermoplastic polymer which covers it is poly (vinylidene fluoride). It will be observed that this thermoplastic polymer can cover other wire supports to form filtration membranes.
- thermoplastic polymer material can also be used on flat supports to form filtration membranes.
- the method according to the invention is implemented to collect the PVDF from the “backsheets” of photovoltaic panels.
- a layer of PVDF then covers a flat support, typically of PET. By lowering the temperature of the PVDF to a temperature below its glass transition temperature, it causes cracking and detachment from the PET support.
- said thermoplastic polymer is poly (difluoromethylene). In other words, the thermoplastic polymer is PTFE.
- FIG. 1 is a schematic front view of an organ capable of being treated according to a method according to the invention
- FIG. 2 is a detailed schematic view of the member illustrated in the figure [Fig. 1];
- FIG. 3 is a schematic view of a device for implementing the method according to the invention in accordance with a first variant embodiment
- FIG. 4 is a detailed schematic view of the device illustrated in FIG. [FIG. 3] in operation;
- FIG. 5 is a flowchart illustrating the steps for implementing the method according to the invention in accordance with the first variant embodiment.
- FIG. 6 is a flowchart illustrating the steps for implementing the method according to the invention in accordance with a second variant embodiment.
- the process for separating polymeric materials according to the invention applied to the recycling of filtration modules will be described in detail. In particular, these are end-of-life water filtration modules, or defective filtration modules intended for disposal.
- the beams 12 extend longitudinally in parallel between two heads, one upper 14, the other lower 16, over a length of between 1.50 m and 3 m, for example 2 m.
- Figure [Fig. 2] shows in a straight section one of the hollow fibers 15. It comprises a braid 18 of son of poly (ethylene terephthalate), commonly referred to as PET according to its ISO code.
- the wire braid 18 is covered with a tubular layer 20 of Poly (vinylidene fluoride) or PVDF, which tubular layer 20 forms a porous and filtering membrane. It will be observed that the tubular layer 20 and the braid of threads 18 are more or less interpenetrated into one another.
- the diameter d of the wire braid 18 is of the order of 2 mm while the thickness ⁇ of the tubular layer 20 is of the order of ten micrometers.
- the ends of the hollow fibers 15 including the support 18 and the tubular layer 20 forming a membrane, are respectively engaged in the upper 14 and lower 16 heads, and are connected in a sealed manner to collectors not shown.
- the heads 14, 16 include different polymer materials, and in particular acrylonitrile butadiene styrene, or ABS, polyurethane or ethylene-vinyl acetate, or EVA, or even PVC or l epoxy.
- PVDF which is of very particular interest, even if it represents only a small percentage of the total mass of the module, for example between 5% and 15 %, and that it should be possible to separate it from other polymer materials in order to recover it.
- the fibers represent for example between 40% and 50% of the weight of the module and the remainder to 100% corresponds to the materials of the two heads.
- PVDF is a semi-crystalline thermoplastic polymer whose glass transition temperature T g is 233 K.
- T g glass transition temperature
- one of the merits of the invention is to have imagined lowering the temperature of the PVDF of the modules filtration to better detach it and thus recover it. This is because, in fact, when a thermoplastic polymer is brought to a temperature below that of its glass transition, it is generally made more fragile and brittle so that it breaks easily. And in this case, this is indeed the case with PVDF as will be illustrated in the examples below.
- dry ice is projected against the bundles 12 of hollow fibers 15 and therefore directly against the tubular layer 20 of PVDF. Dry ice indeed has a sublimation temperature of 195.6 K.
- a suitable projection device as shown in the figure [Fig. 3]. It comprises a dry ice reservoir 22 inside which the dry ice is stored in the form of sticks with a diameter of 3 mm for example.
- the tank ends with a conical bottom, and a The metering mechanism delivers the ice cream sticks into a flow of compressed air supplied by a compressor 24.
- the flow of compressed air thus loaded with dry ice is guided through a projection duct 26 terminated by a projection nozzle 28.
- the dry ice sticks reach at the outlet of nozzle 28 a speed of 300 m / s.
- the two heads are kept parallel to each other in the same substantially horizontal plane so as to extend the bundles 12 of hollow fibers 15 in a chain above a recovery tank.
- the projection nozzle 28 is applied and maintained from above towards the bundles of hollow fibers and it is maintained substantially perpendicular to the bundle at a distance of between 20 cm and 50 cm for example.
- the bundles of hollow fibers are extended in a vertical direction. And in the same way, the projection nozzle 28 is applied and maintained perpendicular to the beams.
- the projection nozzles are used simultaneously against the two opposite surfaces of said module 10. Also, such a variant embodiment is easily implemented when the bundle of hollow fibers is extended. in a vertical direction.
- the chips of the polymer material are recovered in the recovery tank in order to be able to repackage it into usable polymer.
- the recovery tank also contains organic and inorganic impurities, in particular earth and sand, which inevitably adhered to the tubular membranes. However, they easily detach from the membranes upon impact of dry ice. And in addition, these impurities and these polymer material chips can then be easily separated. Furthermore, such a separation process can easily be automated, either by means of a robot equipped with a movable arm supporting the nozzle, or by means of movable tables and nozzles maintained substantially perpendicular to said movable tables, in fixed position.
- the temperature of the PVDF of the tubular layer forming a membrane is lowered and its mechanical treatment is carried out in two successive steps.
- the module 10 is dismembered as shown in the figure [Fig. 1] so as to detach the bundles 12 of hollow fibers 15 from the two heads 14, 16. In other words, the hollow fibers 15 are separated from the rest of the module 10.
- an immersion step 46 the bundles of coated fiber son are immersed in liquid nitrogen.
- the boiling point of liquid nitrogen is 77.36 K. Consequently, the PVDF quickly reaches, after a few seconds of immersion, a temperature below that of its glass transition, for example 210 K. And hence , it becomes brittle and crumbly.
- a mechanical processing step 48 the bundles of coated son are then driven, in the longitudinal direction of the son, through a pair of rollers.
- a drip tray is installed under the pair of rollers.
- the pair of rollers comprises two rollers bearing tangentially against one another along a common generatrix.
- the rollers are initially in contact with one another and they move away substantially from one another as the hollow fibers of the bundles pass, while maintaining a bearing pressure on these fibers.
- the rollers are rotated in opposite directions to each other so as to drive the hollow fibers of the bundles in translation as they crush them. Thanks to the pair of rollers through which the wires of the bundles pass, the tubular membrane of the support wire braids bursts and is detached from the braids.
- the fragments of the polymer material then travel by gravity into the recovery tank.
- the fragments of the polymer are thus recovered, just as in the first embodiment, in order to be able to recondition it.
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR2002092A FR3107658B1 (fr) | 2020-03-02 | 2020-03-02 | Procédé de séparation de matériaux polymères d‘un assemblage d’éléments |
PCT/FR2021/050350 WO2021176174A1 (fr) | 2020-03-02 | 2021-03-02 | Procédé de séparation de matériaux polymères d'un assembalge d'éléments |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4114633A1 true EP4114633A1 (fr) | 2023-01-11 |
Family
ID=70614175
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP21714930.1A Pending EP4114633A1 (fr) | 2020-03-02 | 2021-03-02 | Procédé de séparation de matériaux polymères d'un assembalge d'éléments |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP4114633A1 (fr) |
FR (1) | FR3107658B1 (fr) |
WO (1) | WO2021176174A1 (fr) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2050752A5 (en) * | 1969-06-24 | 1971-04-02 | Air Liquide | Removing rubber coating from wire |
US4483488A (en) * | 1981-06-30 | 1984-11-20 | Air Products And Chemicals, Inc. | Method and apparatus for recovering thermoplastic from coated fabric scrap |
BE1004619A3 (nl) * | 1990-10-18 | 1992-12-22 | Mefag Finanz Ag | Werkwijze en inrichting voor het scheiden van verschillende komponenten van een produkt. |
DE10000566A1 (de) * | 2000-01-08 | 2001-07-26 | Messer Griesheim Gmbh | Verfahren zur Wiederverwertung eines eine Oberflächenbeschichtung aufweisenden Kunststoffbauteils |
US7087655B2 (en) * | 2002-12-16 | 2006-08-08 | Kimberly-Clark Worldwide, Inc. | Separation process for multi-component polymeric materials |
GB0820342D0 (en) * | 2008-11-06 | 2008-12-17 | Haydale Ltd | Processing of waste materials |
CN103752190A (zh) * | 2013-12-26 | 2014-04-30 | 江南大学 | 一种废旧聚偏氟乙烯平板膜的回收再利用方法 |
CN108312388A (zh) * | 2018-04-18 | 2018-07-24 | 北京星和众维科技股份有限公司 | 分离装置及分离方法 |
-
2020
- 2020-03-02 FR FR2002092A patent/FR3107658B1/fr active Active
-
2021
- 2021-03-02 EP EP21714930.1A patent/EP4114633A1/fr active Pending
- 2021-03-02 WO PCT/FR2021/050350 patent/WO2021176174A1/fr unknown
Also Published As
Publication number | Publication date |
---|---|
FR3107658A1 (fr) | 2021-09-03 |
FR3107658B1 (fr) | 2023-03-10 |
WO2021176174A1 (fr) | 2021-09-10 |
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