NL2016039A - Method for recycling EPS foams. - Google Patents
Method for recycling EPS foams. Download PDFInfo
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- NL2016039A NL2016039A NL2016039A NL2016039A NL2016039A NL 2016039 A NL2016039 A NL 2016039A NL 2016039 A NL2016039 A NL 2016039A NL 2016039 A NL2016039 A NL 2016039A NL 2016039 A NL2016039 A NL 2016039A
- Authority
- NL
- Netherlands
- Prior art keywords
- eps
- particles
- flame retardant
- bromine
- foams
- Prior art date
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Classifications
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
-
- 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
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0052—Organo-metallic compounds
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- 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
- B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
- B29K2025/04—Polymers of styrene
- B29K2025/06—PS, i.e. polystyrene
-
- 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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
- B29K2105/048—Expandable particles, beads or granules
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/03—Extrusion of the foamable blend
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/30—Polymeric waste or recycled polymer
-
- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- 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
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The present invention relates to a method for recycling EPS foams comprising halogen containing flame retardants, wherein said EPS foams in the presence of other starting materials are extruded, cooled and further reduced to particles. The present invention furthermore relates to the use of such a method. Such a method is characterized in that the step of extrusion is carried out in the presence of at least a halogen scavenger.
Description
Title: Method for recycling EPS foams Description
The present invention relates to a method for recycling EPS foams comprising halogen containing flame retardants, wherein said EPS foams in the presence of other starting materials are extruded, cooled and further reduced to particles. The present invention furthermore relates to the use of such a method.
Expandable Polystyrene (EPS) foam has been widely used as insulation material in building and construction and for protection in packaging applications for over 60 years. In insulation applications EPS has long service life and in some cases the material can be recycled. However, presently, incineration with energy recovery is the preferred EPS end of life (EOL) management option in Europe while in other areas like the United States it is more common to be sent to landfill. New regulatory and commercial focus on creating a circular economy is encouraging the development of alternative EOL strategies.
More than 80% of EPS production goes into the insulation of buildings. The majority of this material is flame retarded to reduce the risk of ignition and to reduce flame spread in the event of a fire. Historically, hexabromocyclododecane (HBCD) has been used as the flame retardant of choice for Expanded Polystyrene (EPS). HBCD was a unique brominated flame retardant (BFR) solution as the chemical substance uniquely satisfied both EPS processing needs and fire safety performance requirements.
In recent years HBCD came under regulatory scrutiny and will be no longer used in EPS applications. HBCD is defined as a Substance of Very High Concerns (SVHC) under REACH and as Persistent Organic Pollutant (POP). As such, waste material containing HBCD should be handled according to the Basel Convention Technical Guideline. Based on this UNEP covered convention, the European POP legislation defines limits for POPs in waste and in products. While for the waste containing HBCD, a limit of 1000 ppm is under final discussion, several different proposals have been made for HBCD limits in EPS products, ranging from 10-1000 ppm. Depending on the limit that will ultimately be set, these rules significantly impact the methods and choices for potential material recovery of valuable materials from EPS insulation.
Mechanical recycling for packaging EPS products is a very well organised set-up with well-established collection and logistics systems. Since it is never possible to recycle all EPS mechanically (due to dirt etc.), a percentage of this waste stream is going to incineration with an excellent energy recovery value (40 MJ/Kg). In the case of insulation foams, mechanical recycling is not practical or not allowed due to the HBCD content of these materials. Therefore, incineration with energy recovery was the best solution for these waste streams. Initially, the halogen content of these materials created concerns about the creation of hazardous incineration by-products, e.g. dioxins, during treatment of mixed waste materials. US Patent 8,609,778 relates to a process for recycling post consumer recycled (PCR) material comprising: providing post-consumer recycle polystyrene (PCR PS) and monovinylarene monomer to a dissolver; mixing the PCR PS and monovinylarene monomer within the dissolver to dissolve the PCR PS in the monovinylarene monomer so as to produce a first mixture; providing the first mixture to a filter system comprising a self-cleaning filter to remove polymeric contaminants from the first mixture to produce a filtered mixture; producing a reaction mixture comprising the filtered mixture; and subjecting the reaction mixture to free-radical solution polymerization conditions to produce the styrenic resin.
European publication EP 1 438 351 relates to a method for producing re-expandable polystyrene by material reprocessing of expanded polystyrene waste, comprising the following steps: (a) dissolving the expanded polystyrene waste in a solvent, b) precipitating the dissolved polystyrene with the help of a precipitant, the polarity of which is less than that of the solvent used and which simultaneously is a foaming agent for expanded polystyrene.
Japanese publication JP200-0198875 relates to a method for the separation of a thermoplastic resin composition into the flame retardant and the thermoplastic resin. This method thus covers a method for treating a flame retardant-containing thermoplastic resin composition comprising the following steps: dispersing a thermoplastic styrenic polymer composition containing a bromine-based flame retardant in a solvent, such as d-limonene, l-limonen and dipentene to dissolve at least a portion of the thermoplastic resin, successively removing at least a portion of the flame retardant or the thermoplastic resin from the solution in which the resin is dissolved and further, removing at least a portion of the thermoplastic resin or the flame retardant from the solution from which the retardant or the thermoplastic resin has been removed.
Japanese publication JP2000-290424 relates to a method for recycling a thermoplastic resin composition containing a bromine-based flame retardant, wherein the method comprises the following steps: bringing the resin composition into contact with water or an alcohol to accelerate of the debromination reaction of the flame retardant to remove the bromine. This Japanese method for recycling the thermoplastic resin composition containing the bromine-based flame retardant also comprises bringing the resin composition into contact with a metal hydroxide, a metal carbonate or octyl alcohol to produce the corresponding bromide salts or octyl bromide, and then separating the produced bromides or octyl bromide from the resin. US patent 6,388,050 relates to method for treating a styrene type resin composition containing a flame retardant comprising a dissolving or dispersing step (a) of bringing a styrene type resin composition containing a bromide flame retardant into contact with a single solvent to dissolve or disperse at least one portion of said flame retardant into said solvent, a separating step (b) of separating a solution or a dispersion of said flame retardant after said step (a), a drying step (c) of drying said styrene type resin composition from which said flame retardant is separated after said step (b). US patent publication 2002-099253 relates to a dehalogenation treatment method of a halogen-containing flame-retardant resin composition comprising a step of bringing the halogen-containing flame-retardant resin composition into contact with a material mixture containing a dehalogenation material and a dehalogenation promoting material at a temperature lower than the thermal decomposition temperature of the resin composition, by kneading the mixture while applying shear force by a biaxial kneading extruder, a kneader, or rotation rolls. The dehalogenation material is at least one substance selected from the group consisting of tetralin, sodium hypophosphite, sodium thiosulfate, ascorbic acid, hydrazine, dimide, formic acid, an aldehyde, a saccharide, hydrogen sulfide, lithium, calcium, magnesium, zinc, iron, titanium, aluminum lithium hydride, lithium hydride, hydrogenated diisobutylaluminum, alcoholic potassium, a metal alkoxide, an amine, and potassium iodide.
Japanese publication JP 2006-009033 relates to a method for extracting flame retardant from a thermoplastic resin containing the flame retardant by using an extractor comprising an extractant-introducing part through which an extractant for extracting the flame retardant is introduced into a thermoplastic resin containing the flame retardant to be extracted, a kneading part in which the extractant introduced is mixed with the thermoplastic resin, and an extractant discharging part through which the extractant is discharged from the thermoplastic resin containing the given extractant mixed therewith. As the kind of the thermoplastic resins the following may be mentioned: vinyl acetate resins, polyoxymethylene, acryl-based resin, polyamide resin, polyphenylene ether resin, polystyrene resin, ABS resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, and a polyolefin resin. Suitable extractants only capable to dissolve extracts additive ingredients contained without these resins are ethylene glycol, propylene glycol, ethyl lactate and dipropylene glycol.
An aspect of the above mentioned methods for treating a styrene type resin composition containing a flame retardant is that these methods result in a by product that has to be treated further or incinerated. Another aspect is that the product obtained contains additional components that affect the physical properties of the product.
An object of the present invention is to provide a method for recycling EPS foams comprising halogen containing flame retardants wherein the product obtained fulfils the legal requirements regarding the content of the halogen containing flame retardants.
Another object of the present invention is to provide a method for recycling EPS foams comprising halogen containing flame retardants wherein the halogen containing flame retardants are chemically converted into environmental stabile compounds.
Another object of the present invention is to provide a method for recycling EPS foams comprising halogen containing flame retardants wherein a product is obtained that can be reused in EPS foam applications, i.e. as an insulation material in building and construction and for protection in packaging applications.
The present invention thus relates to a method for recycling EPS foams comprising halogen containing flame retardants, wherein said EPS foams in the presence of other starting materials are extruded, cooled and further reduced to particles, characterized in that said step of extrusion is carried out in the presence of at least a halogen scavenger.
The present inventor found that by such a method one or more of the mentioned objects can be achieved.
Examples of the halogen containing flame retardant comprise at least one brominated flame retardant, in particular selected from the group comprising polybrominated diphenylether, polybrominated biphenyls, bis-[dibromopropoxydibromophenyl]propane, hexabromodecane, bis- (tribromophenoxy)ethane and hexabromocyclododecane (HBCD) and brominated butyl rubber (FR-122P).
The figure below is brominated butyl rubber (FR-122P). FR-122P chemical designation is benzene, ethenyl-, polymer with 1,3-butadiene, brominated.
Fig. : Brominated Polybutadiene rubber FR-122P
In the present method the at least a halogen scavenger preferably comprises a bromine scavenger, especially a compound containing at least one member chosen from the group of Ca, Ba, Mg, Sr and Zn. This selected group of alkaline earth elements are metallic elements found in the second group of the periodic table and have shown an acceptable reactivity against the present halogen containing flame retardant, especially the aforementioned brominated flame retardants.
The bromine scavenger according to the invention is preferably an oxide, hydroxide or a combination of oxide and hydroxide. Non limited examples thereof are CaO, BaO, SrO, Ca(0H)2, Ba(OH)2, MgO, Mg(OH)2 and ZnO. Without being held to a particular theory, it is believed that the alkaline earth element or other element as mentioned above reacts with the Br atom present in the brominated flame retardant thereby forming a bromine compound that is highly stabile. This means that the Br atom is no longer present in the brominated flame retardant. The formation of a highly stabile bromine compound is a benefit because the release of Br during the extrusion process will negatively influence the molecular chain length. For example, the addition of CaO has resulted in the formation of CaBr2.
According to another preferred embodiment the present bromine scavenger is a mono stearate, di stearate or a combination of a mono stearate and a di stearate. Metallic stearates are compounds of long-chain fatty acids with metals of different valencies. Its fatty part (depending on the specific metal, 1-3 parts) is based on stearate, oleate, laurate and behenate. Its metal part is based on calcium, aluminium, magnesium and zinc. A preferred embodiment is calcium mono hydroxy stearate.
The present method is especially suitable for EPS foams which originate from EPS containing discarded construction materials. In another embodiment the EPS foams originate from EPS containing discarded packaging materials.
The present inventor found that by using the present method foam particles can be obtained wherein the brominated flame retardant has been neutralised or inactivated by reaction with a bromine scavenger as mentioned above. For example, the foam particles thus obtained comprise CaBr2.
According to an embodiment the EPS foams are mixed with virgin EPS foam particles, a blowing agent and at least a thermal insulation component, wherein said mixture is extruded, cooled and further reduced to particles.
According to another embodiment the EPS foams are mixed with virgin EPS foam particles and at least a thermal insulation component, wherein said mixture is extruded, cooled and further reduced to particles, wherein said particles are subsequently subjected to an impregnation treatment with a blowing agent.
The present invention furthermore relates to the use of a bromine scavenger comprising a compound containing at least one member chosen from the group of Ca, Ba, Mg, Sr and Zn for the manufacture of recycled EPS foam containing particles, wherein the brominated flame retardant has been neutralised or inactivated by reaction with said bromine scavenger.
Hereinafter, an embodiment of the present invention will be described. In the table below Lips is low Impact Polystyrene.
Claims (12)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL2016039A NL2016039B1 (en) | 2015-12-24 | 2015-12-24 | Method for recycling EPS foams. |
DE102016125506.8A DE102016125506A1 (en) | 2015-12-24 | 2016-12-22 | Process for the recycling of EPS foams |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL2016039A NL2016039B1 (en) | 2015-12-24 | 2015-12-24 | Method for recycling EPS foams. |
Publications (2)
Publication Number | Publication Date |
---|---|
NL2016039A true NL2016039A (en) | 2017-06-29 |
NL2016039B1 NL2016039B1 (en) | 2017-07-21 |
Family
ID=59010798
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NL2016039A NL2016039B1 (en) | 2015-12-24 | 2015-12-24 | Method for recycling EPS foams. |
Country Status (2)
Country | Link |
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DE (1) | DE102016125506A1 (en) |
NL (1) | NL2016039B1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20230212368A1 (en) | 2020-06-10 | 2023-07-06 | Basf Se | Flame retardant styrene polymer composition and process for recycling styrene polymer-containing scrap |
EP4229124A1 (en) | 2020-10-19 | 2023-08-23 | INEOS Styrolution Group GmbH | Method for depolymerizing polymer masses while degrading organic halogen compounds |
DE102022001442A1 (en) | 2022-04-26 | 2023-10-26 | Styrotec GmbH | Destruction of brominated flame retardants during the recycling of foamed polystyrene insulation material |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3752101B2 (en) | 1998-04-09 | 2006-03-08 | 松下電器産業株式会社 | Method for treating thermoplastic resin composition containing flame retardant |
JP2000290424A (en) | 1999-04-07 | 2000-10-17 | Matsushita Electric Ind Co Ltd | Recycling treatment of thermoplastic resin composition containing bromine-based flame retardant |
JP3736237B2 (en) | 1999-09-17 | 2006-01-18 | 松下電器産業株式会社 | Method for treating thermoplastic resin composition containing flame retardant |
US6903242B2 (en) | 2000-07-03 | 2005-06-07 | Matsushita Electric Industrial Co., Ltd. | Method for dehalogenation treatment of halogen containing non-combustible resin composition |
ATE348855T1 (en) | 2001-10-24 | 2007-01-15 | Fraunhofer Ges Forschung | RECYCLING WASTE EXPANDED POLYMER FOAM INTO RE-EXPANDABLE PRODUCTS |
US8609778B1 (en) | 2012-08-09 | 2013-12-17 | Americas Styrenics, LLC | Styrenic resin incorporating recycled polystyrene |
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2015
- 2015-12-24 NL NL2016039A patent/NL2016039B1/en not_active IP Right Cessation
-
2016
- 2016-12-22 DE DE102016125506.8A patent/DE102016125506A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
DE102016125506A1 (en) | 2017-06-29 |
NL2016039B1 (en) | 2017-07-21 |
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MM | Lapsed because of non-payment of the annual fee |
Effective date: 20200101 |