Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J11/00—Recovery or working-up of waste materials
  • C08J11/04—Recovery or working-up of waste materials of polymers
  • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
  • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
• • 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
  • C08J11/18—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 organic material
  • C08J11/22—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 organic material by treatment with organic oxygen-containing compounds
  • C08J11/24—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 organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
• • 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
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• the invention relates to a method and an apparatus for removing colorants from PET-flake which can be obtained by shredding commercially available used PET bottles.
• PET is the common abbreviation for "polyethylene terephthalate” or more precisely “polyethylene terephthalate)” (CAS: 25038-59-9).
• PET is a thermoplastic polyester and widely used for food containers and bottles, e.g. for water, carbonated soft drinks, beer or the like. Pure PET is transparent for visible light with wavelengths between 380 nm and 780 nm and thus colourless. For aesthetic reasons and as well as to protect the liquids to be handled by PET bottles from degrading when subjected to light, the bottles are often coloured by organic colorants and/or pigments. Large amounts of used bottles are to be recycled.
• Various chemical recycling techniques are known, in particular glycolysis, methanolysis, hydrolysis, and saponification. However, according to the Petcore PET knowledge centre these methods are unable to remove colours from the PET feedstreams
• EP 1 153 070 Bl suggests to contact PET with a glycol, e.g. ethylene glycol (briefly "EG”) to thereby obtain oligomers and monomers of the PET, in particular bis- (2- hydroxyethyl) terephthalate (briefly "BHET", CAS: 959-26-2) in an agitated reactor vessel at a temperature of about 150°C to 300°C and an absolute pressure of 0.5 to 3.0 bars.
• the ratio of EG to dicarboxylic acid is greater than 1 to 5 total glycol units to total dicarboxylic acid units.
• Lower density contaminants form a distinct top layer in the reactor vessel and are separated from a lower layer con- taining a remainder of a glycolysis reaction mixture. Remaining immiscible contaminants are removed by filtration or straining.
• PET bottle recycling is addressed by the European Patent EP 1 437 377 Bl.
• First PET bottles are unpacked, steel and aluminium residues are removed and the bottles are shredded. Subsequently, non PET polymers are separated by winnowing and float-sink separation.
• the such obtained PET-flake are depolymerized by charging them into EG at 175-190°C at 0.1- 0.5 MPa to thereby obtain BHET which is later subjected to an ester interchange reaction for forming crude dimethyl terephthalate (briefly "DMT", CAS: 120-61-6) and EG. DMT and EG can be separated, purified and again used as monomers in the polymer industry.
• DMT crude dimethyl terephthalate
• EP 1 914 270 suggest to recover colorants from dyed polyester fiber as used in PET-fabric by a dye extraction using ethylene glycol.
• the invention is based on the observation, that the prior art methods for PET- recycling require transparent PET-flake or PET-flake of the same colour i.e. include a colour sorting step to obtain high quality recycling products.
• the problem to be solved by the invention is to provide a method and apparatuses for the recycling of PET-flake without colour sorting.
• the method of the invention can be used for pre-processing PET-flake in particular prior to depolymerisation.
• the PET-flake can be obtained for example by shredding PET bottles.
• PET-flake are preferably devoid of metal, paper and residues of beverages and other compounds previously stored in the bottles. This can be obtained by known prior art sorting and washing techniques, which are commercially available.
• the PET-flake may be of any colour and may comprise a mixture of colours, e.g. brown PET-flake as well as blue, green, red, or black PET- flake.
• the colour removal process preferably comprises at least two process steps. 1) PET-flake are pre-treated in a hot organic liquid and (optional) and
• Colorant extraction and simultaneous embrittlement of the PET-flake is obtained by contacting the PET-flake with hot EG in a contacting vessel (step 2). Only for brevity this is subsequently summarized by referring only to "extraction”. Extraction (and thus simultaneous embrittlement) is performed preferably at or slightly below the boiling temperature of EG (satp) at about ambient pressure.
• the extraction temperature T ext is preferably about 197.5°C (192°C ⁇ T ext ⁇ 205°C, pref- erably 195°C ⁇ T ext ⁇ 200°C, more preferably 196°C ⁇ T ext ⁇ 199°C, particularly preferred 197.0° ⁇ T ext ⁇ 197.6°C) at preferably ambient pressure p a (typically 850 hPa ⁇ p a ⁇ 1100 hPa).
• the EG extracts the organic colorants and embrittles the PET-flake, however without significant depolymerisation. There is no need to add a catalyst to embrittle the PET, because in commercially produced PET, as used for the bottles from which the PET-flake preferably origin, catalysts used for pol- ycondensation of the PET are embedded in the polymer matrix.
• the extraction step and as well the optional pre-treatment step are performed at least approximately at ambient pressure (+-200hPa).
• used EG i.e. EG loaded with organic colorants is preferably continuously removed from the PET-flake and/or at least from the extraction vessel, i.e. the contacting vessel, containing the PET-flake.
• Fresh, i.e. colourless or at least less loaded EG is added to the PET-flake, preferably continuously.
• Extraction of the PET-flake is preferably completed once the PET-flake are colourless.
• the mean colour distance ⁇ of the PET-flake when re- moving from the EG is preferably less or equal to 20, more preferably less or equal to 10.
• Total depolymerisation of the PET to BHET is avoided by the preferred temperature and pressure range and by limiting the contact time between PET and EG, respectively the residence time of PET under extraction conditions.
• the extrac- tion process removes organic colorants from PET-flake.
• pigments like titanium dioxide (Ti0 2 , CAS: 13463-67-7) remain in the solid PET. These pigments migrate very slowly in the amorphous phase of solid-state PET and can be removed by an optional downstream depolymerisation process of PET to DMT or any other PET monomer.
• the mechanism of organic colorants removal is still not fully understood.
• the working hypothesis is that the organic colorants are extracted from a preferably pre-treated amorphous polymer matrix by molecular diffusion and film diffusion.
• PET-flake embrittle in the course of the extraction process This could be explained by a reduction of the degree of polymerisation of PET-flake.
• PET-flake are not fully depolymerized to PET monomers during the extraction step.
• the degree of polymerizations (Pn) is solely reduced from initially typically 134 to a Pn of about 50 to 25.
• the extraction is preferably completed as soon as the PET-flake are sufficiently decolourized as explained above.
• the time to obtain sufficient colorant extraction depends on the residence time, i.e. the time the PET-flake are in contact with EG, the flow velocity of the liquid EG, the flake particle size, flake particle shape and the temperature. Apart from sufficient colorant extraction, the process should preferably be completed before the flake soften. Criteria for completing the extraction step can in addition or alternatively to the degree of de- colourization as defined above be an intrinsic viscosity of IV ⁇ 0.20 dL/g and/or a molar mass Mn ⁇ 4000 g/mol and/or a degree of polymerization Pn ⁇ 20 ( ⁇ 5).
• Extracting the organic colourants is preferably obtained by conveying the PET- flake in a conveying direction and simultaneously contacting the PET-flake with liquid EG.
• extraction is obtained by establishing a counter-current flow of EG directed against the PET conveying direction.
• Such counter-current flow can be realized by conveying the PET-flake in a conveyor, e.g. a screw-conveyor, in a PET conveying or flow direction.
• Extraction liquid i.e. liquid EG can be fed to the screw conveyor via an EG inlet downstream of the PET-flake inlet.
• the EG is removed from the screw conveyor upstream of the EG inlet.
• the EG flows in the opposite direction of the PET-flake flow, to which upstream and downstream refers.
• the EG flows through the voids of the PET-flake bulk.
• the PET-flake and the EG are in close contact and the PET- flake are extracted by a counter-current flow of EG.
• the PET-flake are heated by heat transfer from condensing EG vapour while being extracted.
• at least a part of the EG being used for extraction of colorants from the PET-flake condenses from a gaseous phase into a liquid phase on the PET-flake and/or in already liquid EG.
• the optimum temperature for colorant extraction can be obtained easily, which turned out to be only slightly below the boiling temperature of EG (197.3°C at 1013 hPa).
• EG provided to the EG inlet or at least one of multiple EG inlets of the conveyor is at least partially in vapour phase and condenses in the conveyor. Additional heat can also be provided to the conveyor by heat transfer media at its shell or by electric heating devices via the shell or any other means.
• the PET-flake Prior to extracting organic colorants from the PET-flake by contacting them with hot EG, the PET-flake are preferably pre-treated in a pre-treating liquid, referred to as pre-processing by pre-treatment.
• the pre-treatment liquid may at least comprise one of the following compounds: benzophenone (Ci 3 Hi 0 O, CAS: 119- 61-9) and/or polyethylene glycol 600 ("PEG", HO(C 2 H 4 0) n , CAS: 25322-68-3) and/or 1,2-dichlorobenzene (C 6 H 4 CI 2 , CAS: 95-50-1) and/or limonene (Ci 0 Hi 6 , CAS: 5989-27-5) and/or 1,4-dioxane (C 4 H 8 0 2 , CAS: 123-91-1) and/or ethylene glycol (C 2 H 6 0 2 , CAS: 107-21-1) and/or triethylene glycol
• the PET-flake are brought in close contact with the pre-treatment liquid.
• the PET-flake can be immersed in a pre- treatment vessel containing the pre-treatment liquid
• the pre-treatment temperature T pre should be above the glass transition temperature (Tgi) of the PET-flake and below the melting temperature (T me
• the glass transition temperature together with the melting point of the bottle grade PET-flake differs with the PET-flake and depends on the PET specification (i.e. the kind and amount of PET co-monomers).
• a typical glass transition temperature of "bottle grade PET” is about 80°C ( ⁇ 5 K).
• the melting temperature of "bottle grade PET” is about 240°C to 255°C.
• the pre-treatment temperature T pre is below the temperature where significant softening of the PET-flake can be observed (T SO ft), to thereby avoid that the PET-flake get "sticky” and agglomerate while pre-treated. This happens typically above 220°C ( ⁇ 5 K).
• the pre-treatment temperature interval can be chosen as Tgi ⁇ T pre ⁇ T me it, more preferred T g i ⁇ T pre ⁇ T soft .
• Typical values for T pre are between 120°C and 180°C. It has been observed that the PET-flake shrink and the wall thickness increases while pre-treated. It was shown experimentally that the PET relaxes above the glass transition temperature.
• the mass ratio of PET-flake to liquid for pre-treating PET-flake in e.g. EG is preferably at least about 1:2 (possible 1:1 to 1:5).
• a pre-treatment vessel may be used to immerse the PET-flake in the pre-treatment liquid, e.g. EG.
• the pre- treatment vessel may be heated to T pre with T g ⁇ T pre ⁇ T me
• a blanket of gaseous nitrogen (N 2 ) may be used on top of the pre-treatment liquid/PET-flake slurry to avoid contamination of the PET-flake with moisture and/or oxygen. Agitation, e.g. by stirring is preferred.
• a condenser e.g.
• the pre-treatment liquid can be provided, preferably continuously to the pre-treatment vessel, e.g. via a tube.
• the tube's outlet is preferably below the fluid level in the pre- treatment vessel.
• the pre-treatment liquid can be removed, preferably continuously from the pre-treatment vessel for example by an overflow.
• a mesh may ensure that the PET-flake remain in the pre-treatment vessel.
• the PET-flake can be removed using a conveyor means, e.g. a screw conveyor with its lower end inside the pre-treatment vessel.
• the pre-treatment has two advantages: firstly, the PET is dried. PET is hygroscopic and PET-flake being subjected to ambient air have typical moisture (water, H 2 0) content of up to 10,000 ppm by weight (typically 3000 ppm to 6000 ppm) and already small amounts of water may affect the boiling temperature of the extracting liquid and thus have an impact on extracting temperature T ext . Secondly, the subsequent colourant extraction is enhanced. It is assumed that pre- treating the PET-flake somehow affects the amorphous part of the solid PET matrix by a kind of "swelling" effect. However, a profound microscopic understanding is still missing. During the pre-treatment step only minor colour extraction is noticed.
• the pre-treatment time t pre depends on the pre-treatment liquid and the pre- treatment temperature T pre .
• T pre 130°C
• a higher pre-treatment temperature requires a lower residence time, but a non-linear relation between temperature and time is noticed.
• An apparatus for extracting organic colorants from PET-flake preferably comprises a conveyor as extracting vessel for conveying a flow of PET-flake from a PET- flake inlet in a conveying direction to a PET-flake outlet.
• the conveyor can be for example a screw-conveyor with a screw housing and a conveyor screw for con- veying PET-flake via the screw housing from at least one PET-flake inlet in a PET conveying direction to at least one PET-flake out-let.
• the conveyor has at least one EG inlet, i.e. an extraction liquid inlet in the screw housing.
• the EG inlet is downstream of said PET-flake inlet.
• an extraction fluid outlet is upstream of the EG inlet for providing a counter-current flow.
• Upstream and downstream refer to the PET flow, i.e. the PET conveying direction.
• the apparatus may be used in particular for pre-processing PET-flake prior to depolymerization of PET-flake with an extraction fluid, in particular EG.
• the counter-current EG flow in opposite direction to the PET-flake flow can be obtained if the PET conveying direction is inclined against the horizontal or in other words sloped (including a vertical PET-flake conveying direction).
• the extraction fluid pours or flows downwards in the conveyor through voids between the PET-flake, whereas the PET-flake are conveyed upwards.
• the screw axis may be sloped.
• the EG can of course be provided to the extraction vessel at its lower end and removed at the top, while the PET-flake are conveyed in the opposite direction.
• the apparatus may further comprise at least one EG vapour source being connected to the screw housing for providing gaseous EG, i.e. EG vapour, to the screw housing.
• the conveyor housing may comprise at least one condenser, for example being attached to its screw housing. This arrangement ensures that vapour from the extraction apparatus (which consists at least mainly of EG) is condensed, thus ensuring ambient (or slightly above ambient) pressure in the extraction apparatus.
• the extraction apparatus which consists at least mainly of EG
• the condensing chamber has at least one drain for removing condensed EG vapour, i.e. liquid EG.
• the drain may be connected to at least one ex- traction fluid-inlet of the screw housing and/or at least one vapour generator for providing a liquid to said at least one vapour generator.
• the apparatus further comprises at least a pre-treatment vessel for immersing PET-flake in one of the above specified a pre-treatment liquids at a temperature T pre of T g ⁇ T pre ⁇ T SO ft- Such immersing is subsequently referred to as pre-treatment (optional step 1).
• the pre-treatment vessel and/or pre- treatment liquid is preferably heated.
• the pre-treatment vessel contains the pre-treatment liquid.
• pre-treating the PET-flake e.g. in liquid EG water can be removed from the PET. Further, pre-treatment enhances colour extraction in the second step as explained above. In the pre-treatment step no significant colour extraction or embrittlement is observed. The colour of the pre- treatment liquid remains almost unchanged.
• the pre-treatment vessel comprises a PET strainer for removing PET from the pre-treatment vessel and feeding the PET-flake inlet of the screw conveyor, handling of large amounts of PET-flake is facilitated.
• pre-treatment vessel has been explained above with respect to EG as pre- treatment liquid.
• pre-treatment liquids may as well be used for pre-treatment of PET-flake, e.g. in said pre-treatment vessel.
• the apparatus further comprises a rectification apparatus for rectifying liquid EG drained at the screw-conveyor's EG outlet to thereby obtain a colourless fraction and an a fraction comprising organic colorants and other high boiling residues.
• the colourless fraction may be reused for pre-treating and extracting PET-flake.
• PET-flake denotes the singular and the plural, i.e. a single PET-flake as well as a multitude of PET-flake. In an industrial scale process, only the plural is relevant.
• extractions vessel and contacting vessel are used interchangeably throughout this application, as the colour extraction and PET-flake embrittlement is obtained by contacting the PET-flake with hot EG.
• the pre-treatment vessel for immersing the PET-flake prior to the extraction step could thus as well be referred to as immersing vessel.
• Figure 1 shows a process flow diagram of a method for extracting organic colorants from coloured PET-flake.
• FIG. 2 shows an apparatus for extracting PET-flake with hot EG.
• PET-flake are supplied by PET-flake supply 400.
• the PET-flake are typically provided in so called bigbags and thus unpacked as indicated by Symbol 405.
• the PET-flake may pass an optional separator 460 for removing foreign material or PET-flake with a size out of a given specification and stored in a PET-flake reservoir 410.
• the PET-flake reservoir 410 is a PET-flake source for the pre-processing PET-flake.
• Other bulk transport means can as well be used for providing the PET-flake.
• Required is only a preferable continuous PET-flake stream to the pre-treatment vessel 340.
• PET-flake from a PET-flake source i.e. reservoir 410
• a pre-treatment vessel 340 In the pre-treatment vessel 340 the PET-flake are immersed in EG.
• EG is preferably continuously provided from an EG-source, in this case an EG-reservoir 110.
• the EG is heated to a pre-treatment temperature T pre of typically 150°C (preferred: T g ⁇ T pre ⁇ T SOft ).
• T pre typically 150°C
• EG is pumped from the pre-treatment vessel 340 by pump 124, fed to a heater 134 and fed back to the pre-treatment vessel 340.
• Other possibilities for obtaining the required temperature are as well suitable, for example an electrical pre- treatment vessel heating.
• EG is preferably continuously removed from the pre- treatment vessel, e.g. via line 345 and may be provided to an EG treatment device, e.g. a filtration and/or rectification unit. Purified EG may be used again, e.g. by providing it to the EG reservoir 110.
• an EG treatment device e.g. a filtration and/or rectification unit.
• Purified EG may be used again, e.g. by providing it to the EG reservoir 110.
• Pre-treated PET-flake are drained from the pre-treatment vessel and transported via a separator 360 to an extraction vessel 370. Transporting may be obtained e.g. by use of a rotary feeder 350.
• Most EG may be removed from the PET-flake flow using the separator 360 and then fed to a PET-flake inlet 374 of a conveyor 370 used as extraction vessel.
• a screw-conveyer as shown in Fig. 2 may be used as extraction vessel 370.
• the PET-flake are conveyed by rotation of the screw from the PET-flake inlet 374 to a PET-flake outlet 375.
• EG is provided in a counter-current flow (with respect to the PET-flake flow) to the conveyor.
• EG is provided from the reservoir 110 and may be split on two lines: In a first line 111 the EG is heated using a first heater 132 and fed as liquid EG to the downstream end of the conveyor.
• of the liquid EG provided to the extraction vessel should be adjusted to the extraction temperature T ext j.e. to:
• the EG is vaporized at least partially by an EG-vapour generator 130, symbolized by two heaters 133; the number of heaters 133 is of course not essential, nor the energy source for heating the EG.
• the vapourized EG i.e. gaseous EG is as well fed downstream of the PET-flake inlet to the conveyor. The gaseous EG thereby heats the PET-flake by condensation preferably to about 197°C, i.e. just below the boiling temperature of EG at ambient pressure.
• an EG outlet from which EG is removed to thereby obtain a counter-current flow of EG and PET-flake.
• the removed EG can be provided to an EG treatment (indicated by arrow 361) for purification and reuse.
• Organic colorants are extracted from the PET-flake in the conveyor 370 by contacting the PET-flake with a counter-current EG flow.
• the PET-flake are preferably at least almost colourless when leaving the conveyor 370 via the PET-flake outlet 375.
• the PET-flake are not only at least almost colourless but as well brit- tie after passing the conveyor 370.
• EG leaving the conveyor via the PET-flake outlet 375 can be separated using a strainer 380.
• PET-flake from the outlet 375 can be further processed, e.g. by milling.
• the colourless brittle PET-flake (line 490) can be subjected to depolymerisation, e.g. by methanolysis as indicated by arrow 499.
• Fig. 2 shows a simplified screw-conveyor 500 for pre-processing PET-flake, in particular for extracting organic colorants from PET-flake.
• the screw conveyor is a possible extraction vessel for extracting organic colorants from PET-flake while simultaneously obtaining an embrittlement of the PET- flake, as referred to as step 2.
• the screw-conveyor as shown in Fig. 2 can be used as conveyor 370 in the scheme of Fig. 1.
• the screw- conveyor 500 has a tubular screw housing 510, the latter housing a conveyor screw 520, briefly referred to as screw 520.
• the screw 520 is preferably motor driven.
• the longitudinal axis 515 of the screw 520 and accordingly as well of the screw housing 510 is sloped.
• the screw housing 510 has a PET-flake inlet 374, being connected to a down pipe 511 for feeding PET-flake to the PET-flake inlet 374.
• the down pipe 511 is optional.
• the screw 520 conveys the PET-flake to a PET-flake outlet 375 at the upper end of the screw housing 510.
• a further optional down pipe 519 is attached to PET-flake outlet.
• the screw housing 510 has nozzles 530 as EG inlets 372 for injecting vaporous EG into the screw housing and thereby heating the PET-flake to a temperature slightly below the boiling temperature of EG.
• the vaporous EG thus condenses inside the screw housing.
• the condensed, i.e. liquid, EG flows downwards through the voids in the PET-flake bulk to an EG outlet 373.
• the EG is removed from the screw- conveyor.
• liquid EG may as well be injected into the screw housing 510 for example via EG inlet 371.
• the temperature in the conveyor can thus be adjusted by adjusting the amount of EG vapour provided to the extraction vessel.
• the crew conveyor may have an additional shell for heat transfer by a heat transfer medium and/or other heating means like an electrical heater.
• 350 feeder e.g. star feeder
• 405 cleaning means PET-flake reservoir / PET-flake source

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• Sustainable Development (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
• Polyesters Or Polycarbonates (AREA)
• Extraction Or Liquid Replacement (AREA)

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• 2013
  • 2013-06-12 EP EP13171754.8A patent/EP2784110B1/en active Active
• 2014
  • 2014-03-26 KR KR1020157030844A patent/KR101812198B1/ko not_active Expired - Fee Related
  • 2014-03-26 WO PCT/EP2014/056053 patent/WO2014154745A1/en not_active Ceased
  • 2014-03-26 CN CN201480018097.7A patent/CN105051097A/zh active Pending
  • 2014-03-26 JP JP2016504656A patent/JP6214754B2/ja not_active Expired - Fee Related
• 2015
  • 2015-09-23 US US14/862,584 patent/US9890261B2/en active Active

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