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EP4294892A1 - Pyrolyse d'un matériau contenant du polycarbonate pour récupérer des matières premières - Google Patents

Pyrolyse d'un matériau contenant du polycarbonate pour récupérer des matières premières

Info

Publication number
EP4294892A1
EP4294892A1 EP21843741.6A EP21843741A EP4294892A1 EP 4294892 A1 EP4294892 A1 EP 4294892A1 EP 21843741 A EP21843741 A EP 21843741A EP 4294892 A1 EP4294892 A1 EP 4294892A1
Authority
EP
European Patent Office
Prior art keywords
pyrolysis
reactor
pyrolysate
weight
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21843741.6A
Other languages
German (de)
English (en)
Inventor
Stefanie Eiden
Rainer Bellinghausen
Aurel Wolf
Erik SLUYTS
Jonas KRAUSE
Andreas Seidel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP4294892A1 publication Critical patent/EP4294892A1/fr
Pending legal-status Critical Current

Links

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
    • C08J11/10—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
    • C08J11/12—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 dry-heat treatment only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/008—Pyrolysis reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/22—General preparatory processes using carbonyl halides
    • C08G64/24—General preparatory processes using carbonyl halides and phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/307—General preparatory processes using carbonates and phenols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/14—Features of low-temperature carbonising processes
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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

  • Polycarbonate-containing material - such as polycarbonate blends, e.g. polycarbonate resin or polycarbonate composite resin - is used as a material for consumer goods.
  • Corresponding polycarbonate resins or polycarbonate composite resins are made by blending the polycarbonate with other polymers, such as by blending polycarbonate with acrylonitrile butadiene styrene (ABS). Because these polycarbonate-containing materials have excellent properties such as impact resistance, flowability, toughness, and flame retardancy, they are used in a variety of applications, such as electronic devices and automobiles.
  • the processes for recycling plastic waste can be roughly divided into 3 categories:
  • the chemical raw materials obtained from thermochemical recycling can be used to synthesize new synthetic resins or other chemical products.
  • catalysts or additives in the pyrolysis process can lead to lower operating temperature, shorten reaction time, increase degradation efficiency and restrict product distribution, making the process more efficient.
  • metal halide salts as catalysts, especially copper and iron chloride catalysts, it was possible to produce more phenolic compounds during the pyrolysis of polycarbonate at 600° C than without a catalyst (M. Blazsö, J. Anal. Appl. Pyrolysis, 1999, 51, 73-88). Furthermore, the catalytic pyrolysis of polycarbonate was optimized by using various metal chloride compounds with the aim of reducing char residues (J. Chiu et al., Waste Manage., 2006, 26, 252-259). The influence of the catalyst was determined at 400 °C (1 h), since the uncatalyzed pyrolysis proceeds very slowly at this temperature. The choice of metal chloride had a large effect on pyrolysis. NaCl, CrCb, CuCb, and AlCb did not improve pyrolysis rates, while SnCb and ZnCb degraded the polycarbonate with over 80% weight loss.
  • the product distribution of the pyrolysis of polycarbonate could also be improved by the use of metal salt catalysts. While in the non-catalytic polycarbonate pyrolysis the liquid product contained eleven different products, the mixtures with ZnCb or SnC12 as the catalyst obtained only seven main products, including bisphenol A, phenol and diphenyl ether with smaller amounts of impurities.
  • Catalysts consisting of metal oxides and zeolites with different porosities and acid/basicity are also known for the pyrolysis of polycarbonate-containing material (E. V. Antonakou et al. polym. degradation Stab., 2014, 110, 482-491. MN Siddiqui et al., Thermochim. Acta, 2019, 675, 69-76).
  • said new method for pyrolysis should deliver such a pyrolysis product in which, in addition to the cleavage products that can be reused in the polycarbonate synthesis, cleavage products of the other ingredients, e.g. styrene from polystyrene-containing material, are contained in significant quantities and good yields, which suitable for the production of said ingredients in terms of cyclic recycling.
  • cleavage products of the other ingredients e.g. styrene from polystyrene-containing material
  • step (b) decomposition of at least the material of the pyrolysis material introduced in step (a) in the reactor at a temperature of 300° C. to 700° C. to obtain product in the gas phase as pyrolysate and non-gas phase pyrolysis residue, wherein (i) during said decomposition the amount of oxygen gas in the reactor is from 0 to 2.0% by volume based on the total volume of gases in the reactor, and
  • pyrolysis material All of the substances introduced into the reactor for pyrolysis, which are thermally treated there in the absence of oxygen gas or in the presence of a reduced amount of oxygen gas, are referred to as "pyrolysis material". Before being introduced into the reactor, the pyrolysis material is preferably in solid form.
  • “Pyrolysis residue” is understood to mean all those substances formed by pyrolysis and the other residues of the pyrolysis material which are not in the gas phase of the reactor under the conditions of step (b). Those embodiments of the process which are characterized in that the pyrolysis residue in the reactor is solid are preferred.
  • a substance e.g. material, pyrolysis product, pyrolysate, pyrolysis product, pyrolysis residue
  • liquid if it is in the liquid state at 20°C and 1013 mbar.
  • solid if it is in the solid state of aggregation at 20°C and 1013 mbar.
  • a "polycarbonate-containing compound” is a polymeric compound selected from a homo- or copolymer obtained by polyreaction and wherein at least one repeating unit contains at least one *-0-C-0-* structural unit,
  • polystyrene-containing material or “polystyrene-containing compound” is understood to mean a material or a compound, preferably a polymer, containing structural units derived from styrene or styrene derivatives, in particular from styrene.
  • a “reactor” is a volume in which a chemical conversion, eg thermal decomposition of material from the pyrolysis material, takes place.
  • a chemical conversion eg thermal decomposition of material from the pyrolysis material
  • this can be the volume of a heated vessel in which the pyrolysis material is located.
  • it is advantageous to introduce the pyrolysis material into a reactor according to the method according to the invention, which is characterized in that it is selected from a continuous stirred tank reactor (CSTR), fixed bed reactor, fluidized bed reactor, screw reactor, screw conveyor reactor, entrained flow reactor, entrainment flow reactor, rotary tube reactor, fluidized bed reactor, paddle reactor.
  • CSTR continuous stirred tank reactor
  • those reactors are preferably suitable in which the pyrolysis material can be introduced continuously and are selected in particular from rotary tube reactors, continuous stirred tank reactors (CSTR), fixed bed reactors (in particular with continuous bed exchange (shaft reactor) with internal heat exchangers, preferably with internal heat exchanger tubes), screw reactors, screw conveyor reactors , entrained flow reactor, rotary tube reactor or fluidized bed reactor.
  • a very particularly preferred reactor of an embodiment of the process is selected from a screw reactor, a rotary kiln or a fluidized bed.
  • Further reactors preferred for the process according to the invention and their embodiments are described in the context of the embodiments of the device for pyrolysis according to the invention and in the context of an embodiment of the process using a catalyst (many below).
  • the pyrolysis material introduced into the reactor comprises at least one material containing a mixture of polycarbonate-containing compound and polystyrene-containing compound.
  • said material of the pyrolysis material is preferably introduced into the reactor in the form of solid particles (in particular in the form of a granular mixture).
  • a granular mixture of said material is formed from a multitude of loose, solid particles of said material, which in turn comprise so-called granules.
  • a grain is a designation for the particulate components of powders (grains are the loose, solid particles), dusts (grains are the loose, solid particles), granules (loose, solid particles are agglomerates of several grains) and other granular mixtures.
  • the flowability of a granular mixture relates to its ability to flow freely under its own weight from a flow test funnel with a 16.5 mm diameter outlet.
  • the solid particles, in particular the loose, solid particles of the granular mixture, of said material introduced into the reactor preferably have an average diameter X o (volume average) of 0.01 mm to 5 cm, preferably 0.1 mm to 5 cm. on.
  • the mean particle size diameter X50. is determined by sieving or using a particle size analyzer Camsizer from Retsch.
  • said material can be, for example, a homopolymer, a copolymer, a comb polymer, a block polymer or mixtures thereof.
  • the preparation of the aromatic polycarbonates usable as a polycarbonate-containing compound is carried out e.g. B. by reacting compounds having at least two hydroxyl groups, in particular diphenols, with carbonic acid halides, preferably phosgene and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface process, optionally using chain terminators, for example monophenols and optionally using trifunctional or more as trifunctional branching agents, for example triphenols or tetraphenols. It can also be produced using a melt polymerization process by reacting compounds having at least two hydroxyl groups, in particular diphenols, with diphenyl carbonate, for example.
  • the polycarbonate-containing compound is at least one compound which, by reacting at least the compounds (i) at least one aromatic compound having at least two hydroxyl groups, particularly preferably bisphenol A, and (ii) phosgene or diphenyl carbonate was obtained.
  • At least one aromatic compound having at least two hydroxyl groups which is selected from the general formula (I), is preferably used to prepare the polycarbonate-containing compound.
  • A is a single bond, Ci to Cs-alkylene, C2 to Cs-alkylidene, C5 to C ö -cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, C o to Ci2 -arylene, to which other aromatic rings optionally containing heteroatoms can be fused, or a radical of the formula (II) or (III)
  • aromatic compounds having at least two hydroxyl groups are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3.3.5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis(3 -Chloro-4-hydroxyphenyl)-propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)-propane or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-pro- pan.
  • 2,2-bis(4-hydroxyphenyl)propane bisphenol-A is particularly preferred.
  • the aromatic compounds having at least two hydroxyl groups can be used individually or as any mixtures.
  • the aromatic compounds having at least two hydroxyl groups are known from the literature or can be obtained by methods known from the literature.
  • Chain terminators suitable for the production of thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols such as 4-[2-(2,4,4 -Trimethylpentyl)]-phenol, 4-(1,3-tetramethylbutyl)-phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert- butyl phenol, p-iso-octyl phenol, p-tert-octyl phenol, p-dodecyl phenol and 2-(3,5-dimethylheptyl) phenol and 4-(3,5-dimethylheptyl) phenol.
  • the amount of chain terminators to be used is generally between 0.5 mole % and 10 mo
  • thermoplastic, aromatic polycarbonates that can be used have average molecular weights (weight-average M w , measured by GPC (gel permeation chromatography) with a polycarbonate standard based on bisphenol A) of preferably 20,000 to 40,000 g/mol, more preferably 24,000 to 32,000 g/mol , particularly preferably 26,000 to 30,000 g/mol.
  • the thermoplastic, aromatic polycarbonates can be branched in a known manner, preferably by incorporating from 0.05 to 2.0 mol%, based on the sum of the aromatic compound used having at least two hydroxyl groups, of trifunctional or more than trifunctional compounds, for example those with three or more phenolic groups.
  • Linear polycarbonates are preferably used.
  • Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the dicarboxylic acid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
  • Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio of between 1:20 and 20:1 are particularly preferred.
  • a carbonic acid halide preferably phosgene, is also used as a bifunctional acid derivative.
  • suitable chain terminators for the preparation of the aromatic polyester carbonates are their chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids, which may be substituted by C 1 to C 22 alkyl groups or by halogen atoms, and aliphatic C 2 to C 22 monocarboxylic acid chlorides.
  • the amount of chain terminators is in each case 0.1 to 10 mol %, based in the case of the phenolic chain terminators on moles of aromatic compound with at least two Hydroxyl groups and, in the case of monocarboxylic acid chloride chain terminators, on moles of dicarboxylic acid dichloride.
  • aromatic polyester carbonates In the production of aromatic polyester carbonates, one or more aromatic hydroxy carboxylic acids can also be used.
  • the aromatic polyester carbonates can be either linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934), preference being given to linear polyester carbonates.
  • Pyromellitic acid tetrachloride in amounts of 0.01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or trifunctional or polyfunctional phenols such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)- hept-2-ene, 4,6-dimethyl-2,4-6-tri-(4-hydroxyphenyl)-heptane, l,3,5-tri-(4-hydroxyphenyl)-benzene, l,l,l- Tri-(4-hydroxyphenyl)ethane, Tri-(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis( 4-hydroxyphenyl-isopropyl)-phenol, tetra-(4-hydroxyphenyl)-methane, 2,6-bis(2-hydroxy-5-methyl-benzyl)-4
  • the proportion of carbonate structural units in the thermoplastic, aromatic polyester carbonates can vary as desired.
  • the proportion of carbonate groups is preferably up to 100 mol %, in particular up to 80 mol %, particularly preferably up to 50 mol %, based on the sum of ester groups and carbonate groups.
  • Both the ester and the carbonate portion of the aromatic polyester carbonates can be in the form of blocks or randomly distributed in the polycondensate.
  • aromatic polycarbonates and polyester carbonates can be used alone or in any desired mixture in the said material of the process according to the invention.
  • said material of the pyrolysis material also contains at least one polystyrene-containing compound.
  • polystyrene-containing compound is therefore understood to mean a compound which contains a repeating unit derived from styrene which is optionally substituted on the aromatic ring (such as, in particular, styrene, a-methylstyrene, p-methylstyrene, p-chlorostyrene).
  • *-CR 1 Ph-CH 2 -* contains, in which * denotes a valency of the repeating unit of the polymer backbone, R 1 represents a hydrogen atom or a methyl group and Ph an optionally with at least one group selected from (Ci to C4)-alkyl group, Halogen atom (particularly chlorine) substituted phenyl group.
  • vinyl aromatic and/or nuclear-substituted vinyl aromatic such as styrene, a-methylstyrene, p-methylstyrene p-chlorostyrene.
  • the glass transition temperature is determined by means of differential scanning calorimetry (DSC) in accordance with the standard DIN EN 61006 at a heating rate of 10 K/min with definition of the T g as the midpoint temperature (tangent method).
  • the graft base B.1.2 generally has an average particle size (do value) of 0.05 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m, particularly preferably 0.2 to 1 ⁇ m.
  • the average particle size d o is the diameter above and below which 50% by weight of the particles are in each case. It can be determined by means of an ultracentrifuge measurement (W. Scholtan, H. Lange, Colloid, Z. and Z. Polymere 250 (1972), 7824796).
  • Monomers B.1.1 are preferably mixtures of
  • B.l.1.1 50 to 99, preferably 60 to 80, in particular 70 to 80 parts by weight, based on B.1.1, vinyl aromatics and/or nuclear-substituted vinyl aromatics (in particular selected from styrene, a-methylstyrene, p-methylstyrene, p-chlorostyrene or mixtures thereof), and
  • B.1.1.2 1 to 50, preferably 20 to 40, in particular 20 to 30 parts by weight, based on B.1.1, vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and/or (meth)acrylic acid (Ci-Cs )-alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and/or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide.
  • Preferred monomers Bl1.1 are selected from at least one of the monomers styrene and a-methylstyrene
  • preferred monomers Bl1.2 are selected from at least one of Monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • Particularly preferred monomers are B.1.1.1 styrene and B.1.1.2 acrylonitrile.
  • graft bases B.1.2 suitable for the graft polymers B.1 are diene rubbers, EP(D)M rubbers, ie those based on ethylene/propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene and ethylene/vinyl acetate -Rubber and silicone/acrylic composite rubber.
  • Preferred graft bases B.1.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers (e.g. according to B.1.1.1 and B.1.1.2).
  • Pure polybutadiene rubber is particularly preferred as the graft base B.1.2.
  • the graft copolymers B.1 are prepared by free-radical polymerization, for example by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization.
  • the gel fraction of the graft base B.1.2 is at least 30% by weight, preferably at least 40% by weight, in particular at least 60% by weight, based in each case on B.1.2 and measured as the insoluble fraction in toluene.
  • the gel content of the graft base B.1.2 is determined at 25° C. in a suitable solvent as the proportion insoluble in these solvents (M. Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
  • ABS polymers which are prepared by redox initiation using an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.
  • crosslinking monomers having more than one polymerizable double bond can be copolymerized.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, such as ethylene glycol dimethacrylate, allyl methacrylate ; polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least three ethylenically unsaturated groups.
  • Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
  • the amount of crosslinked monomers is preferably from 0.02 to 5% by weight, in particular from 0.05 to 2% by weight, based on the graft base B.1.2. In the case of cyclic crosslinking monomers having at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base B.1.2.
  • graft base B.1.2 examples of preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can be used to prepare the graft base B.1.2 are acrylonitrile, styrene, ⁇ -methylstyrene, acrylamide, vinyl-C 1 -C 6 -alkyl ether, methyl methacrylate, butadiene.
  • Preferred acrylate rubbers as the graft base B.1.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • graft bases according to B.1.2 are silicone rubbers with graft-active sites, as described in DE-OS 3,704,657, DE-OS 3,704,655, DE-OS 3,631,540 and DE-OS 3,631,539.
  • the rubber-free vinyl (co)polymers according to component B.2 are preferably rubber-free homo- and/or copolymers of at least one monomer from the group consisting of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth)- Acrylic acid (Ci to C 8 ) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids.
  • B.2.2 0 to 90% by weight, preferably 1 to 50% by weight, more preferably 20 to 40% by weight, in particular 20 to 30% by weight, based in each case on the total weight of the (co)polymer B .2, at least one monomer selected from the group of vinyl cyanides, such as unsaturated nitriles such as acrylonitrile and methacrylonitrile, (meth)acrylic acid (Ci-Cx) - alkyl esters, such as methyl methacrylate, n-butyl acrylate, tert. -butyl acrylate, unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids, such as maleic anhydride and N-phenylmaleimide.
  • vinyl cyanides such as unsaturated nitriles such as acrylonitrile and methacrylonitrile, (meth)acrylic acid (Ci-Cx) - alkyl esters, such as methyl methacrylate, n-butyl
  • Such (co)polymers B.2 are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co)polymers preferably have average molecular weights M w (weight average, determined by GPC using polystyrene as the standard) between 15,000 and 250,000 g/mol, preferably in the range from 80,000 to 150,000 g/mol.
  • said material of the pyrolysis material can also contain at least one polymer additive selected from flame retardants, anti-dripping agents, flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g. hydrolysis, Heat aging and UV stabilizers and transesterification inhibitors), flow promoters, phase compatibilizers, other components A and B different polymeric components (e.g. functional blend partners), fillers and reinforcing materials as well as dyes and pigments.
  • at least one polymer additive selected from flame retardants, anti-dripping agents, flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g. hydrolysis, Heat aging and UV stabilizers and transesterification inhibitors), flow promoters, phase compatibilizers, other components A and B different polymeric components (e.g. functional blend partners), fillers and reinfor
  • a proportion of 0% by weight to at most 0.5% by weight of phosphorus, preferably from 0% by weight to at most, contributed by this total amount and based on the total weight of the pyrolysis material proved to be such a defined total amount of phosphorus-containing organic compound 0.1% by weight phosphorus, more preferably from 0% by weight to at most 0.05% by weight phosphorus, particularly preferably from 0% by weight to at most 0.01% by weight phosphorus.
  • the phosphorus-containing organic compound which is limited in its amount is selected from phosphorus-containing organic compounds whose phosphorus has a formal oxidation state of +5.
  • the pyrolysis material is free from phosphorus-containing organic compounds in which at least one phosphorus atom has a formal oxidation state of +5.
  • R 1 , R 2 , R 3 and R 4 each independently optionally halogenated C 1 to C 8 alkyl, each optionally substituted by alkyl, preferably C 1 to C 4 alkyl, and/or halogen, preferably chlorine, bromine, C 5 to C 6 Cycloalkyl, C6 to C20 aryl or C7 to C12 aralkyl, n are independently 0 or 1, q 0 to 30 and
  • X is a polynuclear aromatic radical having 12 to 30 carbon atoms, or a linear or branched aliphatic radical having 2 to 30 carbon atoms, which can be OH-substituted and contain up to eight ether bonds.
  • the aforementioned phosphorus-containing organic compounds are known (cf. e.g. EP-A 0 363 608, EP-A 0 640655) or can be prepared in an analogous manner using known methods (e.g. Ullmanns Enzyklopädie der Technischen Chemie, Vol. 18, p. 301 1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p. 43; Beilstein, Vol. 6, p. 177).
  • the polycarbonate material is preferably mixed with a filler, e.g. sand, which simplifies continuous process management of the method according to the invention. In particular, sticking of said material in the reactor and in the supply of the dosing device to the reactor is avoided.
  • the filler and said material are added to the pyrolysis material as a mixture in a volume ratio of filler to said material of at least 0.1:1 to 10:1.
  • Catalysts can be used to make the pyrolysis process more selective and efficient. More effective and more selective decomposition is obtained if, in one embodiment of the method according to the invention, said pyrolysis material introduced in step (a) contains, in addition to said material, at least one catalyst influencing the decomposition reaction of said material.
  • a suitable catalyst can lower the pyrolysis temperature, reduce the product range to the desired products and, if necessary, minimize coking.
  • Inexpensive catalysts are preferred for an efficient process. These can be, for example, naturally occurring materials such as inorganic salts, refractory oxides, minerals and engineered rocks that can optionally be ion exchanged in a simple ion exchange process as they do not require extensive synthesis. They are readily available and are therefore relatively cheap.
  • synthetic catalysts such as zeolites (e.g. of the ZSM-5, A, X,Y, etc. type) are an example of catalysts which, although effective, are not cheap as they have to be specially manufactured.
  • catalysts can also simplify the dosing and processability of the pyrolysis material in pyrolysis. If a catalyst is used, the amount of filler used can be reduced in this case. In one embodiment, the total amount of filler and catalyst in the Ratio to the amount of said material in a volume ratio of at least 0.1 to 1 to 10 to 1 fed to the pyrolysis material as a mixture.
  • At least one catalyst is selected from the group formed by alkaline inorganic materials, more preferably from the group of naturally occurring materials defined above.
  • These inorganic materials can be refractory oxides.
  • Refractory oxides are metal oxides that are stable at high temperatures from 300°C to 700°C.
  • Such catalyst oxides include the oxides of aluminum, magnesium, zirconium, titanium, chromium, zinc, tin and other metals or combinations of alumina with magnesium oxide and/or calcium oxide.
  • Crystalline inorganic materials include aluminosilicates, silicoaluminophosphates, silicalite, spinels and other natural zeolites and clays. At least one compound from the group consisting of inorganic salts, minerals, metal oxides, mixed oxides, clays and zeolites is therefore particularly suitable as said catalyst.
  • Both homogeneous and heterogeneous catalysts can be used.
  • preferred embodiments of the process according to the invention are those in which the catalyst is a heterogeneous catalyst.
  • the catalyst is preferably introduced into the reactor in the form of solid particles (in particular in the form of a granular mixture).
  • the heterogeneous catalyst used particularly preferably has an average particle size of its solid particles, in particular its loose, solid particles of the granular mixture, an average diameter X o (volume average) of 0.01 mm to 5 cm, preferably 0.1 mm to 5 cm , on.
  • the mean particle size diameter X o is determined by sieving or by means of a particle size analyzer Camsizer from Retsch.
  • the catalyst particles have a smaller or the same particle size as the particles of said material. It is therefore preferred if the mean particle size of the catalyst present in the pyrolysis material corresponds at most to the mean particle size of the said material present therein.
  • the pyrolysis material can contain at least one basic catalyst. If it is a solid, basic catalyst, the number and strength of the basic centers of the catalyst can be determined using Fourier transform infrared spectroscopy and Temperature Programmed Desorption of CO2 (TPD-C02), or using common titrimetric methods.
  • a catalyst If a catalyst is added, it can be admixed with the filler, coated onto the filler, or used as a substitute for the filler.
  • the (e.g. by coking) deactivated catalyst is in the pyrolysis residue and can be fed into a regenerator after the pyrolysis residue has been discharged from the reactor and added to the pyrolysis material of step (b) to be introduced into the pyrolysis reactor after regeneration.
  • Reactors that allow for short contact time, intensive mixing of the components in the feedstream with the catalyst, and continuous recycle of the regenerated catalyst to the pyrolysis zone are most preferred. Since this is the case with a screw reactor, rotary kiln or fluidized bed, these reactors are particularly preferred.
  • the pyrolysis material After being introduced into the reactor, the pyrolysis material is heated to a temperature in the range from 300.degree. C. to 700.degree.
  • a particularly successful improvement in the result of the method according to the invention can be achieved if, within the scope of one embodiment, the pyrolysis material introduced is heated to 300° C. to 700° C. and after this target temperature has been reached, the residence time of the correspondingly temperature-controlled pyrolysis material is increased until the resulting pyrolysis residue is discharged 1 second to 2 hours, preferably between 2 minutes and 60 minutes, and during which time the temperature and the content of oxygen gas in the reactor are the values defined in step (b). If the pyrolysis material contains a catalyst in the process according to the invention, this catalyst is in the pyrolysis residue that is discharged. As part of a further embodiment of the method, the discharged pyrolysis residue is therefore fed to a regeneration step of the catalyst contained therein, as described above.
  • an inert gas preferably selected from nitrogen, argon, CO 2 , NO or a mixture thereof, is particularly suitable as the gas for this gas stream.
  • the reactor filled with said material of said pyrolysis material is filled with inert gas, in particular with nitrogen, argon, CO2, NO or a mixture thereof.
  • the inert gas can also of Oxygen gas mixed with various reactive gases, in particular selected from methane, gaseous H2O, hydrogen gas or mixtures thereof.
  • the pyrolysis material can be freed from oxygen gas before it is introduced in step (a), e.g. by driving out the oxygen gas by means of stripping with a stripping gas, e.g. in one upstream of the reactor storage container.
  • a stripping gas e.g. in one upstream of the reactor storage container.
  • inert gas in particular nitrogen, argon, CO2, NO, mixtures thereof, could be used as a stripping gas from above or below in the storage container (preferably from above) via a frit into the container to the pyrolysis material in order to drive out the oxygen gas.
  • a preferred embodiment of the method provides a continuous process control. For this, at least steps (a) and (b) run simultaneously within the framework of a continuous process control.
  • a further object of the invention is therefore a pyrolysis device for producing pyrolysate from pyrolysis material, containing at least one dosing device for feeding in pyrolysis material, at least one heatable reactor for the pyrolysis, and at least one pyrolysate collector, characterized in that said heatable reactor for the Pyrolysis contains at least one heater that can be used to control the temperature of the reactor to a temperature of 300° C. to 700° C., and contains at least one inlet for pyrolysis material and contains at least one outlet for pyrolysate that is different therefrom; and
  • Metering device and heatable reactor for the pyrolysis are arranged and designed relative to each other in such a way that the metering device is connected via at least one feed line to an inlet for pyrolysis material of said reactor; and the heatable reactor for the pyrolysis and the pyrolysate collector are in fluid communication with one another, so that the preferably gaseous pyrolysate can be discharged from said pyrolysate outlet and the pyrolysate discharged can be introduced into the pyrolysate collector; and at least one pyrolysate collector contains at least one cooling device conditioned to a temperature below 300°C, which is installed in said collector to lower the temperature of the pyrolysate fed out of said reactor to less than 300°C to form a pyrolysis product selected from pyrolysate condensate, pyrolysate resublimate or a mixture thereof, and comprising at least one container for collecting and discharging the product of pyrolysis obtained with cooling; and
  • a heating element e.g. heating coil or heating plates, for example, or a device for heating a gas stream and for introducing the heated gas stream into the reactor can be used to heat the heatable reactor.
  • the pyrolysate collector of the device according to the invention preferably contains a cooling device usable in said collector for lowering the temperature of the pyrolysate fed out of said reactor to less than 50°C (more preferably to less than 30°C) to form pyrolysis product. Cooling units that work according to the heat exchanger principle are particularly suitable for this.
  • the pyrolysis device is used for the recovery of bisphenol-A used in the production of polycarbonate-containing compound, in addition to said simultaneous styrene recovery.
  • the composition contains between 25 and 80% by weight of a total amount of aromatic compounds having at least two hydroxyl groups selected from 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis(4-hydroxyphenyl) -2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfide, 4,4' -Dihydroxydiphenylsulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, or mixtures thereof.
  • aromatic compounds having at least two hydroxyl groups selected from 4,4'-dihydroxydip
  • Process for pyrolysis comprising at least the following steps: (a) introducing pyrolysis material, at least comprising material containing a mixture of polycarbonate-containing compound and polystyrene-containing compound, into a reactor;
  • step (b) decomposition of at least the material of the pyrolysis material introduced in step (a) in the reactor at a temperature of 300° C. to 700° C. to obtain product in the gas phase as pyrolysate and pyrolysis residue not in the gas phase, wherein
  • the amount of oxygen gas in the reactor is at most 2.0% by volume based on the total volume of gases in the reactor
  • CSTR continuous stirred tank reactor
  • CSTR continuous stirred tank reactor
  • fixed bed reactor in particular with continuous bed exchange (shaft reactor) with internal heat exchanger tubes
  • the evacuation of the pyrolysate from the reactor is ensured by a gas stream guided through the reactor or by suction and preferably thereby a residence time of the pyrolysate as a period between the time of introduction of said in the step (a) material introduced into the reactor and the time at which the resulting pyrolysate is discharged is 0.1 seconds to 10 seconds, preferably between 0.5 seconds and 5 seconds, particularly preferably 0.5 seconds to 2 seconds.
  • step (b) the amount of oxygen gas in the reactor is at most 0.5% by volume, preferably 0.1% by volume, based in each case on the total volume of the gases in the reactor amounts to.
  • polycarbonate-containing compound is at least one compound containing at least ten structural units *-O-C-O-*, where * represents a valence of the polymer backbone O marks.
  • polystyrene-containing compound is at least one polymer containing at least ten repeating units of the formula
  • the method according to aspect 16 characterized in that the phosphorus contained in said phosphorus-containing organic compound has a formal oxidation state of +5.
  • R 1 , R 2 , R 3 and R 4 independently of one another, represent optionally halogenated CI to C8-alkyl, optionally substituted by alkyl, preferably CI to C4-alkyl, and/or halogen, preferably chlorine, bromine, C5 to C6- Cycloalkyl optionally substituted by alkyl, preferably C1 to C4-alkyl, and/or halogen, preferably chlorine, bromine, C6 to C20-aryl or optionally substituted by alkyl, preferably C1 to Cd-alkyl, and/or halogen, preferably chlorine, bromine , substituted C7 to C12 aralkyl, n is independently 0 or 1, preferably 1, q is a number from 0 to 30 and
  • X is a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms, or a linear or branched aliphatic radical having 2 to 30 carbon atoms, which may be OH-substituted and contain up to 8 ether bonds.
  • the pyrolysis material according to step (a) contains at least one polycarbonate-containing compound and a limited total amount of phosphorus-containing, organic compound, so that, based on the total weight of the pyrolysis material, a proportion of 0 wt % to at most 0.5% by weight phosphorus, preferably from 0% by weight to at most 0.1% by weight phosphorus, more preferably from 0% by weight to at most 0.05% by weight phosphorus , particularly preferably from 0% by weight to at most 0.01% by weight of phosphorus, is introduced by this total amount of phosphorus-containing organic compound and optionally contains at least one polystyrene-containing compound.
  • said material is introduced into the reactor in the form of solid particles, in particular in the form of a granular mixture.
  • step (a) also contains at least one filler in addition to said material.
  • the filler is at least one metal oxide which is not catalytically active in the pyrolysis of polycarbonate, which is preferably selected from SiCk.
  • step (a) contains, in addition to said material, at least one catalyst influencing the decomposition reaction of said material.
  • the catalyst is at least one compound from the group consisting of inorganic salts, minerals, metal oxides, mixed oxides, clays, zeolites.
  • Pyrolysis device for the production of pyrolysate from pyrolysis material containing at least one metering device for feeding in pyrolysis material, at least one heatable reactor for the pyrolysis, and at least one pyrolysate collector, characterized in that said heatable reactor for the pyrolysis contains at least one heating element which can be used to control the temperature of the reactor to a temperature of 300°C to 700°C, and contains at least one inlet for pyrolysis material and at least one different outlet for pyrolysate; and
  • Metering device and heatable reactor for the pyrolysis are arranged and designed relative to each other in such a way that the metering device is connected via at least one feed line to an inlet for pyrolysis material of said reactor; and the heatable reactor for the pyrolysis and the pyrolysate collector are in fluid communication with one another, so that the preferably gaseous pyrolysate can be discharged from said pyrolysate outlet and the pyrolysate discharged can be introduced into the pyrolysate collector; and at least one pyrolysate collector contains at least one cooling device conditioned to a temperature below 300°C, which is installed in said collector to lower the temperature of the pyrolysate led out of said reactor to less than 300°C with the formation of pyrolysis product selected from pyrolysate condensate, pyrolysate sublimate or a mixture thereof, and comprising at least one container for collecting and discharging the product of pyrolysis obtained with cooling; and at least
  • a pyrolysis device for the recovery of organic compound having at least two hydroxyl groups used in the production of polycarbonate-containing compounds while simultaneously recovering styrene used in the production of polystyrene-containing compound, by simultaneous pyrolysis of said polycarbonate-containing compound and said Polystyrene-containing compound.
  • Use according to aspect 31 characterized in that the pyrolysis device is used for the recovery of bisphenol-A used in the production of polycarbonate-containing compound.
  • composition according to aspect 33 characterized in that it is the
  • Composition is a pyrolysis product.
  • composition according to aspect 34 characterized in that the composition is a pyrolysis product obtained in a process according to any one of aspects 1 to 29.
  • Example 1 (according to the invention):
  • the resulting coke content of the pyrolysis residue was determined by weighing the crucible after pyrolysis.
  • the gas after the 2 condensers was characterized by GC.
  • the components in the pyrolysis product, which occurs as an oil, were determined using GC-FID.
  • An Agilent 7890A with a Supelco SPB 50 column was used for this.
  • the pyrolysis oil was diluted with acetone 1:50 or 1:100.

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Abstract

L'invention concerne un procédé de pyrolyse d'un matériau contenant du polycarbonate afin de récupérer des matières premières. Le procédé comprend au moins les étapes suivantes : (a) L'introduction dans un réacteur d'un matériau pour pyrolyse, comprenant au moins un matériau qui contient un mélange d'un composé contenant du polycarbonate et un composé contenant du polystyrène ; (b) la décomposition, à une température de 300 °C à 700 °C, d'au moins le matériau pour pyrolyse introduit dans le réacteur à l'étape (a) et l'obtention d'un produit en phase gazeuse en tant que pyrolysat et des résidus de pyrolyse en phase non gazeuse, (i) la quantité de gaz oxygène dans le réacteur pendant la décomposition n'étant pas supérieure à 2,0 % en volume par rapport à l'ensemble du volume des gaz présents dans le réacteur, et (ii) le pyrolysat étant retiré du réacteur pendant la décomposition, et (iii) les résidus de pyrolyse étant retirés du réacteur ; (c) le refroidissement du pyrolysat retiré à une température inférieure à 300 °C tout en obtenant un produit de pyrolyse, choisi parmi le condensat de pyrolyse, le sublimé par pyrolyse ou un mélange de ceux-ci ; et (d) éventuellement le traitement du produit de pyrolyse. Lors de la mise en œuvre de ce procédé dans un dispositif correspondant, des matières premières pour la production de matériaux composites contenant du polycarbonate, en particulier du bisphénol-A et du styrène, peuvent être récupérées à partir de ces matériaux composites.
EP21843741.6A 2021-02-17 2021-12-22 Pyrolyse d'un matériau contenant du polycarbonate pour récupérer des matières premières Pending EP4294892A1 (fr)

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PCT/EP2021/087331 WO2022174963A1 (fr) 2021-02-17 2021-12-22 Pyrolyse d'un matériau contenant du polycarbonate pour récupérer des matières premières

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