WO2018118578A1 - Method for purifying reclaimed polyethylene - Google Patents
Method for purifying reclaimed polyethylene Download PDFInfo
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- WO2018118578A1 WO2018118578A1 PCT/US2017/066082 US2017066082W WO2018118578A1 WO 2018118578 A1 WO2018118578 A1 WO 2018118578A1 US 2017066082 W US2017066082 W US 2017066082W WO 2018118578 A1 WO2018118578 A1 WO 2018118578A1
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- Prior art keywords
- polyethylene
- mpa
- psig
- another embodiment
- fluid solvent
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Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
-
- 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
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- 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
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- 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
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0032—Pigments, colouring agents or opacifiyng agents
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- 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 generally relates to a method for purifying contaminated polymers through the use of a pressurized solvent and solid media. More specifically, this invention relates to a method for purifying recycled polymers, such as post-consumer and post-industrial recycled plastics, to produce a colorless or clear, odor free, virgin-like polymer. It is particularly useful for the purification of polyethylene.
- Synthetic plastics are ubiquitous in daily life due to their relatively low production costs and good balance of material properties. Synthetic plastics are used in a wide variety of applications, such as packaging, automotive components, medical devices, and consumer goods. To meet the high demand of these applications, tens of billions of pounds of synthetic plastics are produced globally on an annual basis. The overwhelming majority of synthetic plastics are produced from increasingly scarce fossil sources, such as petroleum and natural gas. Additionally, the manufacturing of synthetic plastics from fossil sources produces CO2 as a by-product.
- Plastics recycling has emerged as one solution to mitigate the issues associated with the wide-spread usage of plastics. Recovering and re-using plastics diverts waste from landfills and reduces the demand for virgin plastics made from fossil-based resources, which consequently reduces greenhouse gas emissions. In developed regions, such as the United States and the European Union, rates of plastics recycling are increasing due to greater awareness by consumers, businesses, and industrial manufacturing operations. The majority of recycled materials, including plastics, are mixed into a single stream which is collected and processed by a material recovery facility (MRF). At the MRF, materials are sorted, washed, and packaged for resale.
- MRF material recovery facility
- Plastics can be sorted into individual materials, such as high-density polyethylene (HDPE) or poly(ethylene terephthalate) (PET), or mixed streams of other common plastics, such as polypropylene (PP), low- density polyethylene (LDPE), poly(vinyl chloride) (PVC), polystyrene (PS), polycarbonate (PC), and polyamides (PA).
- HDPE high-density polyethylene
- PET poly(ethylene terephthalate)
- PP polypropylene
- LDPE low- density polyethylene
- PVC poly(vinyl chloride)
- PS polystyrene
- PC polycarbonate
- PA polyamides
- recycled plastics are sorted into predominately uniform streams and are washed with aqueous and/or caustic solutions, the final reprocessed pellet often remains highly contaminated with unwanted waste impurities, such as spoiled food residue and residual perfume components.
- recycled plastic pellets except for those from recycled beverage containers, are darkly colored due to the mixture of dyes and pigments commonly used to colorize plastic articles. While there are some applications that are insensitive to color and contamination (for example black plastic paint containers and concealed automotive components), the majority of applications require non-colored pellets.
- the need for high quality, "virgin-like" recycled resin is especially important for food and drug contact applications, such as food packaging.
- many recycled resin products are often heterogeneous in chemical composition and may contain a significant amount of polymeric contamination, such as recycled polypropylene contamination in polyethylene and vice versa.
- U.S. Patent No. 7,935,736 describes a method for recycling polyester from polyester-containing waste using a solvent to dissolve the polyester prior to cleaning.
- the '736 patent also describes the need to use a precipitant to recover the polyester from the solvent.
- U.S. Patent No. 6,555,588 describes a method to produce a polypropylene blend from a plastic mixture comprised of other polymers.
- the '588 patent describes the extraction of contaminants from a polymer at a temperature below the dissolution temperature of the polymer in the selected solvent, such as hexane, for a specified residence period.
- the '588 patent further describes increasing the temperature of the solvent (or a second solvent) to dissolve the polymer prior to filtration.
- the '588 patent yet further describes the use of shearing or flow to precipitate polypropylene from solution.
- the polypropylene blend described in the '588 patent contained polyethylene contamination up to 5.6 wt%.
- European Patent Application No. 849,312 (translated from German to English) describes a process to obtain purified polyolefins from a polyolefin-containing plastic mixture or a polyolefin-containing waste.
- the '312 patent application describes the extraction of polyolefin mixtures or wastes with a hydrocarbon fraction of gasoline or diesel fuel with a boiling point above 90°C at temperatures between 90°C and the boiling point of the hydrocarbon solvent.
- the '312 patent application further describes contacting a hot polyolefin solution with bleaching clay and/or activated carbon to remove foreign components from the solution.
- the '312 patent yet further describes cooling the solution to temperatures below 70°C to crystallize the polyolefin and then removing adhering solvent by heating the polyolefin above the melting point of the polyolefin, or evaporating the adhering solvent in a vacuum or passing a gas stream through the polyolefin precipitate, and/or extraction of the solvent with an alcohol or ketone that boils below the melting point of the polyolefin.
- U.S. Patent No. 5,198,471 describes a method for separating polymers from a physically commingled solid mixture (for example waste plastics) containing a plurality of polymers using a solvent at a first lower temperature to form a first single phase solution and a remaining solid component.
- the '471 patent further describes heating the solvent to higher temperatures to dissolve additional polymers that were not solubilized at the first lower temperature.
- the '471 patent describes filtration of insoluble polymer components.
- U.S. Patent No. 5,233,021 describes a method of extracting pure polymeric components from a multi-component structure (for example waste carpeting) by dissolving each component at an appropriate temperature and pressure in a supercritical fluid and then varying the temperature and/or pressure to extract particular components in sequence.
- a multi-component structure for example waste carpeting
- the '021 patent only describes filtration of undissolved components.
- U.S. Patent No. 5,739,270 describes a method and apparatus for continuously separating a polymer component of a plastic from contaminants and other components of the plastic using a co-solvent and a working fluid.
- the co-solvent at least partially dissolves the polymer and the second fluid (that is in a liquid, critical, or supercritical state) solubilizes components from the polymer and precipitates some of the dissolved polymer from the co-solvent.
- the '270 patent further describes the step of filtering the thermoplastic-co-solvent (with or without the working fluid) to remove particulate contaminants, such as glass particles.
- a method for purifying a reclaimed polyethylene involves:
- the second fluid solvent may have either the same chemical composition or a different chemical composition than the first fluid solvent.
- the polyethylene is separated from the third solution at a temperature from about 0°C to about 220°C and a pressure from about 0 psig (0 MPa) to 2,000 psig (13.79 MPa).
- the reclaimed polyethylene is dissolved in the fluid solvent, or fluid solvent mixture, at a mass percent concentration of at least 0.5%.
- the reclaimed polyethylene is dissolved in the fluid solvent, or fluid solvent mixture, at a mass percent concentration of at least 1%.
- the reclaimed polyethylene is dissolved in the fluid solvent, or fluid solvent mixture, at a mass percent concentration of at least 2%.
- the reclaimed polyethylene is dissolved in the fluid solvent, or fluid solvent mixture, at a mass percent concentration of at least 3%. In another embodiment, the reclaimed polyethylene is dissolved in the fluid solvent, or fluid solvent mixture, at a mass percent concentration of at least 4%. In yet another embodiment, the reclaimed polyethylene is dissolved in the fluid solvent, or fluid solvent mixture, at a mass percent concentration of at least 5%.
- the reclaimed polyethylene is dissolved in the fluid solvent, or fluid solvent mixture, at a mass percent concentration up to 20%. In another embodiment, the reclaimed polyethylene is dissolved in the fluid solvent, or fluid solvent mixture, at a mass percent concentration up to 18%. In yet another embodiment, the reclaimed polyethylene is dissolved in the fluid solvent, or fluid solvent mixture, at a mass percent concentration up to 16%. In one embodiment, the reclaimed polyethylene is dissolved in the fluid solvent, or fluid solvent mixture, at a mass percent concentration up to 14%. In another embodiment, the reclaimed polyethylene is dissolved in the fluid solvent, or fluid solvent mixture, at a mass percent concentration up to 12%.
- the reclaimed polyethylene is post-consumer recycle derived polyethylene.
- the reclaimed polyethylene is a polyethylene homopolymer or a primarily polyethylene copolymer.
- the fluid solvent has a standard boiling point less than about 0°C and greater than about -45°C and a standard enthalpy change of vaporization of less than about +25 kJ/mol.
- the fluid solvent is selected from the group consisting of olefinic hydrocarbons, aliphatic hydrocarbons, and mixtures thereof.
- the aliphatic hydrocarbon is selected from the group consisting of Ci-C 6 aliphatic hydrocarbons and mixtures thereof.
- the aliphatic hydrocarbons and mixtures thereof is comprised of primarily C 4 aliphatic hydrocarbons.
- the fluid solvent consists essentially of C 4 liquefied petroleum gas.
- the fluid solvent is n-butane, butane isomers, or mixtures thereof.
- the temperature in the contacting, dissolving, settling and purification steps is from about 110°C to about 170°C.
- the pressure in the contacting step is from about 1,100 psig (7.58 MPa) to about 5,500 psig (37.92 MPa). In another embodiment, the pressure in the contacting step is less than about 1,100 psig (7.58 MPa). In yet another embodiment, the pressure in the dissolving, settling, and purification steps is greater than about 4,500 psig (31.03 MPa). In one embodiment, the pressure in the dissolving, settling, and purification steps is greater than about 5,500 psig (37.92 MPa).
- the solid media is selected from the group consisting of inorganic substances, carbon-based substances, and mixtures thereof.
- the inorganic substances are selected from the group consisting of oxides of silicon, oxides of aluminum, oxides of iron, aluminum silicates, amorphous volcanic glasses, and mixtures thereof.
- the inorganic substances are selected from the group consisting of silica gel, diatomite, sand, quartz, alumina, perlite, fuller' s earth, bentonite, and mixtures thereof.
- the carbon-based substances are selected from the group consisting of anthracite coal, carbon black, coke, activated carbon, cellulose, and mixtures thereof.
- the contacting of the polyethylene solution with said solid media is done in a packed bed of said solid media.
- the packed bed is greater than 20 cm in length.
- FIG. 1 is a block flow diagram showing the major steps of one embodiment of the present invention.
- reclaimed polymer refers to a polymer used for a previous purpose and then recovered for further processing.
- reclaimed polyethylene refers to a polyethylene polymer used for a previous purpose and then recovered for further processing.
- post-consumer refers to a source of material that originates after the end consumer has used the material in a consumer good or product.
- PCR post-consumer recycle
- post-industrial refers to a source of a material that originates during the manufacture of a good or product.
- fluid solvent refers to a substance that may exist in the liquid state under specified conditions of temperature and pressure.
- the fluid solvent may be a predominantly homogenous chemical composition of one molecule or isomer, while in other embodiments, the fluid solvent may be a mixture of several different molecular compositions or isomers.
- the term “fluid solvent” may also apply to substances that are at, near, or above the critical temperature and critical pressure (critical point) of that substance. It is well known to those having ordinary skill in the art that substances above the critical point of that substance are known as "supercritical fluids" which do not have the typical physical properties (i.e. density) of a liquid.
- thermodynamic stability of the solute/solvent solution can be described by the following equation 1 :
- standard boiling point refers to the boiling temperature at an absolute pressure of exactly 100 kPa (1 bar, 14.5 psia, 0.9869 atm) as established by the International Union of Pure and Applied Chemistry (IUPAC).
- standard enthalpy change of vaporization refers to the enthalpy change required to transform a specified quantity of a substance from a liquid into a vapor at the standard boiling point of the substance.
- polyethylene solution refers to a solution of polyethylene dissolved in a solvent.
- the polyethylene solution may contain undissolved matter and thus the polyethylene solution may also be a "slurry" of undissolved matter suspended in a solution of polyethylene dissolved in a solvent.
- the terms “sedimentation” and “settling” refer to the tendency of particles within a suspension to separate from a liquid in response to a force (typically a gravitational force) acting upon the particles.
- the term "suspended contaminants" refers to unwanted or undesired constituents that are present throughout the bulk of medium of a heterogeneous mixture.
- solid media refers to a substance that exists in the solid state under the conditions of use.
- the solid media may be crystalline, semi-crystalline, or amorphous.
- the solid media may be granular and may be supplied in different shapes (i.e. spheres, cylinders, pellets, etc.). If the solid media is granular, the particle size and particle size distribution of solid media may be defined by the mesh size used to classify the granular media.
- An example of standard mesh size designations can be found in the American Society for Testing and Material (ASTM) standard ASTM El 1 "Standard Specification for Woven Wire Test Sieve Cloth and Test Sieves.”
- the solid media may also be a non-woven fibrous mat or a woven textile.
- purer polyethylene solution refers to a polyethylene solution having fewer contaminants relative to the same polyethylene solution prior to a purification step.
- extraction refers to the practice of transferring a solute species from a liquid phase (or solid matrix) across a phase boundary to a separate immiscible liquid phase.
- the driving force(s) for extraction are described by partition theory.
- the term “extracted” refers to a material having fewer solute species relative to the same material prior to an extraction step.
- extracted reclaimed polyethylene refers to a reclaimed polyethylene having fewer solute species relative to the same reclaimed polyethylene prior to an extraction step.
- the term "virgin-like” means essentially contaminant-free, pigment-free, odor-free, homogenous, and similar in properties to virgin polymers.
- primarily polyethylene copolymer refers a copolymer with greater than 70 mol% of ethylene repeating units.
- any reference to international units of pressure refers to gauge pressure.
- This process comprises 1) obtaining a reclaimed polyethylene (step a in FIG. 1), followed by 2) extracting the polyethylene with a fluid solvent at an extraction temperature (TE) and at an extraction pressure (PE) (step b in FIG. 1), followed by 3) dissolution of the polyethylene in a fluid solvent at a dissolution temperature (TD) and at a dissolution pressure (PD) (step c in FIG.
- step 1) followed by 4) sedimentation of the polymer solution at a dissolution temperature (TD) and at a dissolution pressure (PD) (step d in FIG. 1), followed by 5) contacting the dissolved polyethylene solution with solid media at a dissolution temperature (TD) and at a dissolution pressure (PD) (step e in FIG. 1), followed by separation of the polyethylene from the fluid solvent (step f in FIG. 1).
- TD dissolution temperature
- PD dissolution pressure
- the purified polyethylene which may be sourced from post-consumer waste streams, is essentially contaminant-free, pigment-free, odor- free, homogenous, and similar in properties to virgin polymers.
- the physical properties of the fluid solvent of the present invention may enable more energy efficient methods for separation of the fluid solvent from the purified polyethylene.
- a method for purifying reclaimed polyethylene includes obtaining reclaimed polyethylene.
- the reclaimed polyethylene is sourced from post-consumer, post-industrial, post-commercial, and/or other special waste streams.
- post-consumer waste polyethylene can be derived from curbside recycle streams where end-consumers place used polymers from packages and products into a designated bin for collection by a waste hauler or recycler.
- Post-consumer waste polymers can also be derived from in-store "take-back" programs where the consumer brings waste polymers into a store and places the waste polymers in a designated collection bin.
- An example of post- industrial waste polymers can be waste polymers produced during the manufacture or shipment of a good or product that are collected as unusable material by the manufacturer (i.e. trim scraps, out of specification material, start up scrap).
- An example of waste polymers from a special waste stream can be waste polymers derived from the recycling of electronic waste, also known as "e- waste.”
- Another example of waste polymers from a special waste stream can be waste polymers derived from the recycling of automobiles.
- Another example of waste polymers from a special waste stream can be waste polymers derived from the recycling of used carpeting and textiles.
- the reclaimed polyethylene is a homogenous composition of an individual polymer or a mixture of several different polyethylene compositions.
- polyethylene compositions are homopolymers and copolymers of ethylene, such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), copolymers of ethylene and alpha-olefins, and other dissolvable polyethylene polymers that may be apparent to those having ordinary skill in the art.
- the reclaimed polyethylene may also contain various pigments, dyes, process aides, stabilizing additives, fillers, and other performance additives that were added to the polymer during polymerization or conversion of the original polymer to the final form of an article.
- pigments are organic pigments, such as copper phthalocyanine, inorganic pigments, such as titanium dioxide, and other pigments that may be apparent to those having ordinary skill in the art.
- a non- limiting example of an organic dye is Basic Yellow 51.
- process aides are antistatic agents, such as glycerol monostearate and slip-promoting agents, such as erucamide.
- a non-limiting example of a stabilizing additive is octadecyl-3-(3,5-di- tert.butyl-4-hydroxyphenyl)-propionate.
- Non-limiting examples of fillers are calcium carbonate, talc, and glass fibers.
- the fluid solvent of the present invention has a standard boiling point less than about 70°C. Pressurization maintains solvents, which have standard boiling points below the operating temperature range of the present invention, in a state in which there is little or no solvent vapor.
- the fluid solvent with a standard boiling point less than about 70°C is selected from the group consisting of carbon dioxide, ketones, alcohols, ethers, esters, alkenes, alkanes, and mixtures thereof.
- Non-limiting examples of fluid solvents with standard boing points less than about 70°C are carbon dioxide, acetone, methanol, dimethyl ether, diethyl ether, ethyl methyl ether, tetrahydrofuran, methyl acetate, ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, branched isomers of pentene, 1-hexene, 2-hexene, methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isomers of isohexane, and other substances that may be apparent to those having ordinary skill in the art.
- a method for purifying polyethylene includes contacting reclaimed polyethylene with a fluid solvent at a temperature and at a pressure wherein the polymer is essentially insoluble in the fluid solvent.
- the extractable contamination may be residual processing aides added to the polymer, residual product formulations which contacted the polymer, such as perfumes and flavors, dyes, and any other extractable material that may have been intentionally added or unintentionally became incorporated into the polymer, for example, during waste collection and subsequent accumulation with other waste materials.
- the controlled extraction may be accomplished by fixing the temperature of the polymer/fluid solvent system and then controlling the pressure below a pressure, or pressure range, where the polymer dissolves in the fluid solvent.
- the controlled extraction is accomplished by fixing the pressure of the polymer/solvent system and then controlling the temperature below a temperature, or temperature range where the polymer dissolves in the fluid solvent.
- the temperature and pressure-controlled extraction of the polymer with a fluid solvent uses a suitable pressure vessel and may be configured in a way that allows for continuous extraction of the polymer with the fluid solvent.
- the pressure vessel may be a continuous liquid-liquid extraction column where molten polymer is pumped into one end of the extraction column and the fluid solvent is pumped into the same or the opposite end of the extraction column.
- the fluid containing extracted contamination is removed from the process.
- the fluid containing extracted contamination is purified, recovered, and recycled for use in the extraction step or a different step in the process.
- the extraction may be performed as a batch method, wherein the reclaimed polyethylene is fixed in a pressure vessel and the fluid solvent is continuously pumped through the fixed polymer phase.
- the extraction time or the amount of fluid solvent used will depend on the desired purity of the final purer polymer and the amount of extractable contamination in the starting reclaimed polyethylene.
- the fluid containing extracted contamination is contacted with solid media in a separate step as described in the "Purification" section below.
- a method for purifying reclaimed polyethylene includes contacting reclaimed polyethylene with a fluid solvent at a temperature and at a pressure wherein the polymer is molten and in the liquid state.
- the reclaimed polyethylene is contacted with the fluid solvent at a temperature and at a pressure wherein the polymer is in the solid state.
- a method for purifying reclaimed polyethylene includes contacting polyethylene with a fluid solvent at a temperature and a pressure wherein the polyethylene remains essentially undissolved.
- a method for purifying reclaimed polyethylene includes contacting polyethylene with n-butane at a temperature from about 80°C to about 220°C.
- a method for purifying reclaimed polyethylene includes contacting polyethylene with n-butane at a temperature from about 100°C to about 200°C.
- a method for purifying reclaimed polyethylene includes contacting polyethylene with n-butane at a temperature from about 130°C to about 180°C.
- a method for purifying reclaimed polyethylene includes contacting polyethylene with n-butane at a pressure from about 150 psig (1.03 MPa) to about 6,500 psig (44.82 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes contacting polyethylene with n-butane at a pressure from about 3,000 psig (20.68 MPa) to about 6,000 psig (41.37 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes contacting polyethylene with n-butane at a pressure from about 4,500 psig (31.03 MPa) to about 5,500 psig (37.92 MPa).
- a method for purifying reclaimed polyethylene includes contacting polyethylene with propane at a temperature from about 80 °C to about 220 °C. In another embodiment, a method for purifying reclaimed polyethylene includes contacting polyethylene with propane at a temperature from about 100°C to about 200°C. In another embodiment, a method for purifying reclaimed polyethylene includes contacting polyethylene with propane at a temperature from about 130°C to about 180°C. In another embodiment, a method for purifying reclaimed polyethylene includes contacting polyethylene with propane at a pressure from about 1 ,000 psig (6.89 MPa) to about 15,000 psig (103.42 MPa).
- a method for purifying reclaimed polyethylene includes contacting polyethylene with propane at a pressure from about 2,000 psig (13.79 MPa) to about 10,000 psig (68.95 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes contacting polyethylene with propane at a pressure from about 5,000 psig (34.47 MPa) to about 9,000 psig (62.05 MPa).
- a method for purifying reclaimed polyethylene includes dissolving the reclaimed polyethylene in a fluid solvent at a temperature and at a pressure wherein the polymer is dissolved in the fluid solvent.
- the temperature and pressure can be controlled in such a way to enable thermodynamically favorable dissolution of the reclaimed polymer in a fluid solvent.
- the temperature and pressure can be controlled in such a way to enable dissolution of a particular polymer or polymer mixture while not dissolving other polymers or polymer mixtures. This controllable dissolution enables the separation of polymers from polymer mixtures.
- a method for purifying polymers includes dissolving contaminated reclaimed polyethylene in a solvent that does not dissolve the contaminants under the same conditions of temperature and pressure.
- the contaminants may include pigments, fillers, dirt, and other polymers. These contaminants are released from the reclaimed polyethylene upon dissolution and then removed from the polymer solution via a subsequent solid-liquid separation step.
- a method for purifying reclaimed polyethylene includes dissolving polyethylene in a fluid solvent at a temperature and at a pressure wherein the polyethylene is dissolved in the fluid solvent.
- a method for purifying reclaimed polyethylene includes dissolving polyethylene in n-butane at a temperature from about 90°C to about 220°C.
- a method for purifying reclaimed polyethylene includes dissolving polyethylene in n-butane at a temperature from about 100°C to about 200°C. In another embodiment, a method for purifying reclaimed polyethylene includes dissolving polyethylene in n-butane at a temperature from about 130°C to about 180°C. In another embodiment, a method for purifying reclaimed polyethylene includes dissolving polyethylene in n-butane at a pressure from about 1,000 psig (6.89 MPa) to about 12,000 psig (82.74 MPa).
- a method for purifying reclaimed polyethylene includes dissolving polyethylene in n-butane at a pressure from about 2,000 psig (13.79 MPa) to about 10,000 psig (68.95 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes dissolving polyethylene in n-butane at a pressure from about 4,000 psig (27.58 MPa) to about 6,000 psig (41.37 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes dissolving polyethylene in n-butane at a mass percent concentration of at least 0.5%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 1%.
- the polyethylene is dissolved at a mass percent concentration of at least 2%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 3%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 4%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 5%. In another embodiment, a method for purifying reclaimed polyethylene includes dissolving polyethylene in n-butane at a mass percent concentration up to 20%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 18%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 16%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 14%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 12%.
- a method for purifying reclaimed polyethylene includes dissolving polyethylene in propane at a temperature from about 90°C to about 220°C. In another embodiment, a method for purifying reclaimed polyethylene includes dissolving polyethylene in propane at a temperature from about 100°C to about 200 °C. In another embodiment, a method for purifying reclaimed polyethylene includes dissolving polyethylene in propane at a temperature from about 130°C to about 180°C. In another embodiment, a method for purifying reclaimed polyethylene includes dissolving polyethylene in propane at a pressure from about 3,000 psig (20.68 MPa) to about 20,000 psig (137.90 MPa).
- a method for purifying reclaimed polyethylene includes dissolving polyethylene in propane at a pressure from about 5,000 psig (34.47 MPa) to about 15,000 psig (103.42 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes dissolving polyethylene in propane at a pressure from about 8,000 psig (55.16 MPa) to about 11,000 psig (75.84 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes dissolving polyethylene in propane at a mass percent concentration of at least 0.5%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 1%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 2%.
- the polyethylene is dissolved at a mass percent concentration of at least 3%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 4%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 5%. In another embodiment, a method for purifying reclaimed polyethylene includes dissolving polyethylene in propane at a mass percent concentration up to 20%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 18%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 16%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 14%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 12%.
- a method for purifying polyethylene includes separating the undissolved contaminants from the polyethylene solution via a sedimentation (also known as settling) step at a temperature and at a pressure wherein the polymer remains dissolved in the fluid solvent.
- the settling step causes the undissolved contaminants to experience a force that uniformly moves the undissolved contaminants in the direction of the force.
- the applied settling force is gravity, but can also be a centrifugal, centripetal, or some other force.
- the amount of applied force and duration of settling time will depend upon several parameters, including, but not limited to: particle size of the contaminant particles, contaminant particle densities, density of the fluid or solution, and the viscosity of the fluid or solution.
- Equation 2 is a relationship between the aforementioned parameters and the settling velocity, which is a measure of the contaminant sedimentation rate: Equation 2
- ⁇ 9 ⁇
- v is the settling velocity
- p p is the density of the contaminant particle
- p j is the density of the fluid or solution
- g is the acceleration due to the applied force (typically gravity)
- r is the radius of the contaminant particle
- ⁇ is the dynamic viscosity of the fluid or solution.
- a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/fluid solvent solution at a temperature and at a pressure wherein the polyethylene remains dissolved in the fluid solvent.
- a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/n-butane solution at a temperature from about 90°C to about 220°C.
- a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/n-butane solution at a temperature from about 100°C to about 200°C.
- a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/n-butane solution at a temperature from about 130°C to about 180°C.
- a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/n-butane solution at a pressure from about 1,000 psig (6.89 MPa) to about 12,000 psig (82.74 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/n-butane solution at a pressure about 2,000 psig (13.79 MPa) to about 10,000 psig (68.95 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/n-butane solution at a pressure from about 4,000 psig (27.58 MPa) to about 6,000 psig (41.37 MPa).
- a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/n-butane solution wherein the polyethylene is dissolved at a mass percent concentration of at least 0.5%.
- the polyethylene is dissolved at a mass percent concentration of at least 1%.
- the polyethylene is dissolved at a mass percent concentration of at least 2%.
- the polyethylene is dissolved at a mass percent concentration of at least 3%.
- the polyethylene is dissolved at a mass percent concentration of at least 4%.
- the polyethylene is dissolved at a mass percent concentration of at least 5%.
- a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/n-butane solution where in the polyethylene is dissolved at a mass percent concentration up to 20%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 18%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 16%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 14%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 12%.
- a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/propane solution at a temperature from about 90°C to about 220°C. In another embodiment, a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/propane solution with at a temperature from about 100°C to about 200°C. In another embodiment, a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/propane solution at a temperature from about 130°C to about 180°C.
- a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/propane solution at a pressure from about 3,000 psig (20.68 MPa) to about 20,000 psig (137.90 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/propane solution at a pressure from about 5,000 psig (34.47 MPa) to about 15,000 psig (103.42 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/propane solution with at a pressure from about 8,000 psig (55.16 MPa) to about 11,000 psig (75.84 MPa).
- a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/propane solution wherein the polyethylene is dissolved at a mass percent concentration of at least 0.5%.
- the polyethylene is dissolved at a mass percent concentration of at least 1%.
- the polyethylene is dissolved at a mass percent concentration of at least 2%.
- the polyethylene is dissolved at a mass percent concentration of at least 3%.
- the polyethylene is dissolved at a mass percent concentration of at least 4%.
- the polyethylene is dissolved at a mass percent concentration of at least 5%.
- a method for purifying reclaimed polyethylene includes settling contaminants from a polyethylene/propane solution where in the polyethylene is dissolved at a mass percent concentration up to 20%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 18%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 16% . In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 14% . In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 12%
- a method for purifying polyethylene includes contacting a contaminated polymer solution with solid media at a temperature and at a pressure wherein the polymer remains dissolved in the fluid solvent.
- the solid media of the present invention is any solid material that removes at least some of the contamination from a solution of reclaimed polyethylene dissolved in the fluid solvent of the present invention.
- the applicants believe that the solid media removes contamination by a variety of mechanisms. Non-limiting examples of possible mechanisms include adsorption, absorption, size exclusion, ion exclusion, ion exchange, and other mechanisms that may be apparent to those having ordinary skill in the art.
- the pigments and other contaminants commonly found in reclaimed polyethylene may be polar compounds and may preferentially interact with the solid media, which may also be at least slightly polar.
- the polar- polar interactions are especially favorable when non-polar solvents, such as alkanes, are used as the fluid solvent.
- the solid media is selected from the group consisting of inorganic substances, carbon-based substances, or mixtures thereof.
- inorganic substances include oxides of silicon, oxides of aluminum, oxides of iron, aluminum silicates, magnesium silicates, amorphous volcanic glasses, silica, silica gel, diatomite, sand, quartz, reclaimed glass, alumina, perlite, fuller's earth, bentonite, and mixtures thereof.
- Useful examples of carbon-based substances include anthracite coal, carbon black, coke, activated carbon, cellulose, and mixtures thereof.
- the solid media is recycled glass.
- the solid media is contacted with the polymer in a vessel for a specified amount of time while the solid media is agitated.
- the solid media is removed from the purer polymer solution via a solid- liquid separation step.
- solid-liquid separation steps include filtration, decantation, centrifugation, and settling.
- the contaminated polymer solution is passed through a stationary bed of solid media.
- the height or length of the stationary bed of solid media is greater than 5 cm.
- the height or length of the stationary bed of solid media is greater than 10 cm.
- the height or length of the stationary bed of solid media is greater than 20 cm.
- the solid media is replaced as needed to maintain a desired purity of polymer.
- the solid media is regenerated and re-used in the purification step.
- the solid media is regenerated by fluidizing the solid media during a backwashing step.
- a method for purifying reclaimed polyethylene includes contacting a polyethylene/fluid solvent solution with solid media at a temperature and a pressure wherein the polyethylene remains dissolved in the fluid solvent.
- a method for purifying reclaimed polyethylene includes contacting a polyethylene/n-butane solution with solid media at a temperature from about 90°C to about 220°C.
- a method for purifying reclaimed polyethylene includes contacting a polyethylene/n-butane solution with solid media at a temperature from about 100°C to about 200°C.
- a method for purifying reclaimed polyethylene includes contacting a polyethylene/n-butane solution with solid media at a temperature from about 130°C to about 180°C. In another embodiment, a method for purifying reclaimed polyethylene includes contacting a polyethylene/n-butane solution with solid media at a pressure from about 1,000 psig (6.89 MPa) to about 12,000 psig (82.74 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes contacting a polyethylene/n- butane solution with solid media at a pressure from about 2,000 psig (13.79 MPa) to about 10,000 psig (68.95 MPa).
- a method for purifying reclaimed polyethylene includes contacting a polyethylene/n-butane solution with solid media at a pressure from about 4,000 psig (27.58 MPa) to about 6,000 psig (41.37 MPa).
- a method for purifying reclaimed polyethylene includes contacting a polyethylene/n-butane solution with solid media wherein the polyethylene is dissolved at a mass percent concentration of at least 0.5%.
- the polyethylene is dissolved at a mass percent concentration of at least 1%.
- the polyethylene is dissolved at a mass percent concentration of at least 2%.
- the polyethylene is dissolved at a mass percent concentration of at least 3%.
- the polyethylene is dissolved at a mass percent concentration of at least 4%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 5%. In another embodiment, a method for purifying reclaimed polyethylene includes contacting a polyethylene/n-butane solution with solid media wherein the polyethylene is dissolved at a mass percent concentration up to 20%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 18%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 16%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 14%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 12%.
- a method for purifying reclaimed polyethylene includes contacting a polyethylene/propane solution with solid media at a temperature from about 90°C to about 220°C. In another embodiment, a method for purifying reclaimed polyethylene includes contacting a polyethylene/propane solution with solid media at a temperature from about 100°C to about 200°C. In another embodiment, a method for purifying reclaimed polyethylene includes contacting a polyethylene/propane solution with solid media at a temperature from about 130°C to about 180°C.
- a method for purifying reclaimed polyethylene includes contacting a polyethylene/propane solution with solid media at a pressure from about 3,000 psig (20.68 MPa) to about 20,000 psig (137.90 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes contacting a polyethylene/propane solution with solid media at a pressure from about 5,000 psig (34.47 MPa) to about 15,000 psig (103.42 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes contacting a polyethylene/propane solution with solid media at a pressure from about 8,000 psig (55.16 MPa) to about 11,000 psig (75.84 MPa).
- a method for purifying reclaimed polyethylene includes contacting a polyethylene/propane solution with solid media wherein the polyethylene is dissolved at a mass percent concentration of at least 0.5%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 1%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 2%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 3%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 4%. In another embodiment, the polyethylene is dissolved at a mass percent concentration of at least 5%.
- a method for purifying reclaimed polyethylene includes contacting a polyethylene/propane solution with solid media wherein the polyethylene is dissolved at a mass percent concentration up to 20%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 18%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 16%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 14%. In another embodiment, the polyethylene is dissolved at a mass percent concentration up to 12%.
- a method for purifying reclaimed polyethylene includes separating the purer polymer from the fluid solvent at a temperature and at a pressure wherein the polymer precipitates from solution and is no longer dissolved in the fluid solvent.
- the precipitation of the purer polymer from the fluid solvent is accomplished by reducing the pressure at a fixed temperature.
- the precipitation of the purer polymer from the fluid solvent is accomplished by reducing the temperature at a fixed pressure.
- the precipitation of the purer polymer from the fluid solvent is accomplished by increasing the temperature at a fixed pressure.
- the precipitation of the purer polymer from the fluid solvent is accomplished by reducing both the temperature and pressure.
- the solvent can be partially or completely converted from the liquid to the vapor phase by controlling the temperature and pressure.
- the precipitated polymer is separated from the fluid solvent without completely converting the fluid solvent into a 100% vapor phase by controlling the temperature and pressure of the solvent during the separation step.
- the separation of the precipitated purer polymer is accomplished by any method of liquid-liquid or liquid-solid separation. Non-limiting examples of liquid-liquid or liquid-solid separations include filtration, decantation, centrifugation, and settling.
- a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/fluid solvent solution at a temperature and a pressure wherein the polyethylene precipitates from solution.
- a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/n-butane solution at a temperature from about 0°C to about 220°C.
- a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/n-butane solution at a temperature from about 50°C to about 175°C.
- a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/n-butane solution at a temperature from about 100°C to about 160°C. In another embodiment, a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/n-butane solution at a pressure from about 0 psig (0 MPa) to about 4,000 psig (27.58 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/n-butane solution at a pressure from about 50 psig (0.34 MPa) to about 2,000 psig (13.79 MPa).
- a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/n-butane solution at a pressure from about 75 psig (0.52 MPa) to about 1,000 psig (6.89 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/propane solution at a temperature from about -42°C to about 220°C. In another embodiment, a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/propane solution at a temperature from about 0°C to about 150°C.
- a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/propane solution at a temperature from about 50°C to about 130°C. In another embodiment, a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/propane solution at a pressure from about 0 psig (0 MPa) to about 15,000 psig (103.42 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/propane solution at a pressure from about 50 psig (0.34 MPa) to about 5,000 psig (34.48 MPa). In another embodiment, a method for purifying reclaimed polyethylene includes separating polyethylene from a polyethylene/propane solution at a pressure from about 75 psig (0.52 MPa) to about 1,000 psig (6.89 MPa).
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CA3045907A CA3045907C (en) | 2016-12-20 | 2017-12-13 | Method for purifying reclaimed polyethylene |
JP2019530405A JP6853359B2 (en) | 2016-12-20 | 2017-12-13 | A method for purifying the recovered polyethylene |
MX2019007026A MX2019007026A (en) | 2016-12-20 | 2017-12-13 | Method for purifying reclaimed polyethylene. |
BR112019012859-0A BR112019012859B1 (en) | 2016-12-20 | 2017-12-13 | METHOD FOR THE PURIFICATION OF RECOVERED POLYETHYLENE |
RU2019113530A RU2721005C1 (en) | 2016-12-20 | 2017-12-13 | Purification method of regenerated polyethylene |
CN201780076812.6A CN110062788B (en) | 2016-12-20 | 2017-12-13 | Process for purifying regenerated polyethylene |
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JP2021526576A (en) * | 2018-06-20 | 2021-10-07 | ザ プロクター アンド ギャンブル カンパニーThe Procter & Gamble Company | Methods for Purifying Regenerated Polymers |
CN114133618A (en) * | 2021-10-28 | 2022-03-04 | 金发科技股份有限公司 | Method for purifying cyclic olefin copolymer from plastic reclaimed materials |
US12102940B2 (en) | 2020-04-15 | 2024-10-01 | The Procter & Gamble Company | Reducing surface and bulk contamination in plastic |
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WO2018118579A1 (en) * | 2016-12-20 | 2018-06-28 | The Procter & Gamble Company | Method for purifying reclaimed polymers |
US10941269B2 (en) * | 2018-06-20 | 2021-03-09 | The Procter & Gamble Company | Method for purifying reclaimed polyethylene |
KR20230072490A (en) | 2020-12-07 | 2023-05-24 | 도요세이칸 그룹 홀딩스 가부시키가이샤 | How to remove impurities from plastics |
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BR112019012859A2 (en) | 2019-12-10 |
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CN110062788A (en) | 2019-07-26 |
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