EP4423184A1 - Procédé de dissociation de (poly)uréthanes - Google Patents

Procédé de dissociation de (poly)uréthanes

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Publication number
EP4423184A1
EP4423184A1 EP22809752.3A EP22809752A EP4423184A1 EP 4423184 A1 EP4423184 A1 EP 4423184A1 EP 22809752 A EP22809752 A EP 22809752A EP 4423184 A1 EP4423184 A1 EP 4423184A1
Authority
EP
European Patent Office
Prior art keywords
chemolysis
product
alcohol
orthosilicate
alcoholysis
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
EP22809752.3A
Other languages
German (de)
English (en)
Inventor
Matthias LEVEN
Norah Heinz
Jens Langanke
Torsten Heinemann
Kai LAEMMERHOLD
Dirk Hinzmann
Tugrul NALBANTOGLU
Nicolas Vogt
Walter Leitner
Elena DIRKSEN
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 EP4423184A1 publication Critical patent/EP4423184A1/fr
Pending legal-status Critical Current

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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
    • C08J11/18—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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • 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
    • C08J11/14—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 steam or water
    • 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
    • C08J11/28—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 compounds containing nitrogen, sulfur or phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a process for cleaving urethanes, in particular polyurethanes, by chemolysis (alcoholysis, hydrolysis or hydroalcoholysis) in the presence of a catalyst.
  • Chemolysis is characterized in that the catalyst used is a salt of an oxygen acid of an element from group five, fourteen or fifteen of the Periodic Table of the Elements or a mixture of two or more such salts, the pKB value of the anion of the salt of the oxygen acid in the range from 0.10 to 6.00, preferably from 0.25 to 5.00, particularly preferably from 0.50 to 4.50, and where, when the chemolysis is carried out as an alcoholysis (Ia), the catalyst does not include any carbonate and Carrying out the chemolysis as hydroalcoholysis, the catalyst does not comprise any carbonate, orthophosphate or metaphosphate.
  • the catalyst used is a salt of an oxygen acid of an element from group five, fourteen or fifteen of the Periodic Table of the Elements or a mixture of two or more such salts, the pKB value of the anion of the salt of the oxygen acid in the range from 0.10 to 6.00, preferably from 0.25 to 5.00, particularly preferably from 0.50 to 4.50, and where, when the
  • the process according to the invention enables valuable raw materials to be recovered from industrially produced urethanes, in particular polyurethanes, after they have served their original intended purpose and thus avoids the loss of such raw materials, such as would result from disposal by incineration or landfill.
  • Urethanes are versatile products. Polyurethanes in particular are used in a wide range of applications in industry and in everyday life. When it comes to polyurethanes, a distinction is usually made between polyurethane foams and so-called “CASE” products, with “CASE” being a collective term for polyurethane coatings (e.g. paints), adhesives, sealants and elastomers.
  • the polyurethane foams are usually divided into rigid foams and flexible foams.
  • the raw materials to be recovered primarily include polyols (ie HOR'-OH in the above example).
  • Various chemical recycling approaches have been developed in the past. The three most important are briefly summarized below: 1. Hydrolysis of urethanes by reaction with water to produce amines and polyols with the formation of carbon dioxide. 2. Glycolysis of urethanes by reaction with alcohols, with the polyols built into the urethane groups being replaced by the alcohol used and being released in this way.
  • the article is part of a series dealing with methods of polyurethane decomposition which are different from the known methods of hydrolysis (see item 1 above), glycolysis (see item 2 above) and aminolysis (not described above) (see the introduction of the article).
  • the reaction products formed were chemically characterized and include products 1 to 3, which can be easily understood as transesterification products of the polyester blocks of the polyurethane elastomer with the alkoxyphosphorus compounds (the "repeating unit" shown in the article does not match the other information in the article about the polyurethane elastomer; it can be assumed that the polyester blocks are considerably longer than shown).
  • N-alkylated urethanes which exist as salts with a positive charge on the urethane nitrogen - product 4.
  • the "exchange reaction” described in the article between ethoxy groups or 1-methyl-2-chloroethoxy groups on the one hand and the urethane groups on the other is based at least predominantly, if not completely, on a cleavage of the ester bonds within the polyester blocks ie essentially no exchange reaction of the polyurethane structure, but of the polyester structure.
  • the products 1 to 3 are formed with a total of 30.6% and the N-alkylated salt (product 4) with 51.6%.
  • EP 0835901 A2 describes a process for producing recycled polyols by glycolysis using a catalyst.
  • Suitable catalysts are Lewis acids (such as zinc chloride, iron chloride, aluminum chloride or mercury chloride), carboxylic acids (such as acetic, formic, propionic, butyric or benzoic acid), inorganic acetates (such as magnesium acetate, lead acetate, calcium acetate, potassium acetate, zinc acetate, sodium acetate or "phosphorus acetate”) and alkali metal salts (such as sodium carbonate, sodium bicarbonate, calcium hydroxide, potassium hydroxide or sodium hydroxide).
  • Lewis acids such as zinc chloride, iron chloride, aluminum chloride or mercury chloride
  • carboxylic acids such as acetic, formic, propionic, butyric or benzoic acid
  • inorganic acetates such as magnesium acetate, lead acetate, calcium acetate, potassium acetate, zinc acetate, sodium acetate or "phosphorus
  • HTC Zn/Sn/Al hydrotalcite
  • one subject of the present invention is a process for cleaving urethanes (particularly polyurethanes) by chemolysis (I), comprising (A) providing a urethane (particularly polyurethane) based on an isocyanate component and an alcohol component, followed by (B ) the chemolysis (I) of the urethane with a chemolysis reagent, the chemolysis (I) with the addition of a catalyst as one of the following reactions (see the explanations in the section “Chemolysis methods (Ia), (Ib) and (Ic)” below ) is carried out: (Ia) alcoholysis of the (poly)urethane, the chemolysis reagent being an alcohol, (Ib) hydrolysis of the (poly)urethane, the chemolysis reagent being water or (Ic) hydroalcoholysis of the (poly)urethane, wherein the chemolysis reagent comprises alcohol and water,
  • polyurethanes generally contain other structures in addition to the basic (poly)urethane structure outlined above, for example structures with urea bonds.
  • the presence of such structures deviating from the pure (poly)urethane basic structure in addition to (poly)urethane structures does not depart from the scope of the present invention.
  • isocyanates includes all isocyanates known in the art in connection with urethane chemistry, in particular phenyl isocyanate (PHI, obtainable by phosgenation of aniline, ANL), tolylene diisocyanate (TDI; obtainable by phosgenation of toluenediamine, TDA), the Di- and polyisocyanates of the diphenylmethane series (MDI; obtainable by phosgenation of the di- and polyamines of the diphenylmethane series, MDA), 1,5-pentane diisocyanate (PDI; obtainable by phosgenation of 1,5-pentanediamine, PDA), 1,6-hexamethylene diisocyanate (HDI; obtainable by phosgenation of 1,6-hexamethylenediamine, HDA), isophorone diisocyanate (IPDI; obtainable by phosgenation of isophoronediamine, IPDA) and
  • PHI phenyl is
  • an isocyanate also includes embodiments in which two or more different isocyanates (e.g. mixtures of MDI and TDI) were used in the production of the (poly)urethane, unless expressly stated otherwise Expressed, for example, by the phrase "exactly one isocyanate".
  • the entirety of all isocyanates used in the production of (poly)urethane is referred to as the isocyanate component (of the (poly)urethane).
  • the isocyanate component includes at least one isocyanate.
  • the entirety of all mono- and polyols used in the production of the (poly)urethane is referred to as the alcohol component (of the (poly)urethane).
  • the alcohol component includes at least one mono- or polyol.
  • mono- or polyols includes all mono- or polyols known in the art in connection with urethane chemistry, such as in particular polyether monools, polyether polyols, polyester polyols, polyether ester polyols and polyether carbonate polyols.
  • polyether monools such as polyether monools, polyether polyols, polyester polyols, polyether ester polyols and polyether carbonate polyols.
  • a monool or “a polyol” also includes embodiments in which two or more different mono- or polyols were used in the production of the urethane.
  • a polyether polyol (or “a polyester polyol” etc.) is mentioned below, this terminology naturally also includes embodiments in which two or more different polyether polyols (or two or more different polyester polyols etc.) are used in the production of the (Poly)urethanes were used.
  • the urethanes formed as a result of the reaction with the alcohol when the chemolysis is carried out as alcoholysis or hydroalcoholysis are referred to as carbamates in order to be able to distinguish them from the urethane used.
  • An amine corresponding to an isocyanate refers to the amine whose phosgenation produces the isocyanate can be obtained.
  • a nitro compound corresponding to an amine denotes that nitro compound by reducing it according to the amine can be obtained.
  • the chemolysis reagents water and alcohol are used superstoichiometrically in the process according to the invention. This means that in the case of hydrolysis, water is used in an amount that is theoretically sufficient to hydrolyze all the urethane bonds of the (poly)urethane with the release of carbon dioxide to form amines and mono- or polyols.
  • alcohol in the case of alcoholysis it is used in an amount that is theoretically sufficient to convert all urethane bonds of the (poly)urethane to form carbamates of the alcohol and mono- or polyols.
  • alcohol and water are each used in such an amount that is theoretically sufficient to hydrolyze all urethane bonds of the (poly)urethane to amines and polyols with the release of carbon dioxide or to form carbamates of the alcohol and mono- or implement polyols.
  • an alcoholysis (Ia) denotes a chemolysis using (at least) one alcohol without (specific) addition of water as a chemolysis reagent. Since alcohols are often not completely anhydrous (unless they are dried and stored in the absence of moisture until they are used), small amounts of water can be present in an alcoholysis within the meaning of the invention for this reason, although water is not used specifically as a chemolysis reagent .
  • water is entered into the chemolysis in an alcoholysis in the sense of the invention in such an amount that the mass of the water present during the alcoholysis is 0% to ⁇ 4.0%, in particular 0% to 3.5%, preferably 0% to 3.4%, particularly preferably 0% to 3.0%, very particularly preferably 0% to 2.0% of the mass of the alcohol used.
  • the water content of an alcohol can be determined by Karl Fischer titration; this is the method relevant for the purposes of the present invention.
  • the Karl Fischer titration has been described many times and is well known to those skilled in the art. Various possible configurations of the basic principle of Karl Fischer titration generally result in results that correspond sufficiently well for the purposes of the present invention.
  • a hydrolysis denotes a chemolysis using only water as the chemolysis reagent. In contrast to alcoholysis, the use of water without unintentionally using other chemolysis reagents is possible without further ado.
  • a hydroalcoholysis denotes a chemolysis using alcohol and water (without further chemolysis reagents), the mass of the water being at least 4.0%, preferably 4.0% to 15%, particularly preferably 4.0 % to 10%, very particularly preferably 5.0% to 10% and extremely particularly preferably 5.0% to 7.0%, of the mass of the alcohol.
  • the comments made above on the alcoholysis apply accordingly. In practice, it will therefore generally be sufficient to consider only the mass of the water that has been added in a targeted manner.
  • a hydroalcoholysis in the sense of the invention includes when initially only the alcohol is added to the urethane in order to bring it into solution as far as possible (which already leads to transurethanization), and only then is water added to the process product thus obtained.
  • salt of an oxyacid of an element of the fifth, fourteenth or fifteenth group of the periodic table of the elements (hereinafter in short: salt of the oxyacid)
  • the oxyacid as such is a stable, isolable compound represents.
  • carbonates can be formally derived from the “carbonic acid 'H 2 CO 3 '”; The fact that this cannot be isolated in free form does not conflict with this and does not depart from the scope of the present invention.
  • the ending “at” is used to identify salts and does not designate esters.
  • alkyl phosphonate denotes a salt with the anion RP(O)O 2 2- , which can be derived from alkyl phosphonic acid, RP(O)(OH) 2 , by its complete deprotonation.
  • salts which can be derived from polybasic acids by their partial deprotonation
  • the number of remaining hydrogens is expressly stated, for example dihydrogen orthosilicate for H 2 SiO 4 2- .
  • the prefix "mono" in the case of a single remaining hydrogen atom can be omitted, for example hydrogen orthosilicate (instead of monohydrogen orthosilicate) for HSiO 4 3- .
  • the pKB values in the present invention are the pKB values in "ideally diluted" aqueous solution, i.e. the pKB values with negligible interaction between cation and anion of the salt of the oxygen acid, in the temperature range of 23 °C understood up to 25 °C.
  • the equation pK S + pK B 14.00, which is known for corresponding acid-base pairs, applies here with sufficient accuracy.
  • the pK B of all hydroxides is set equal to 0.00 for the purposes of the present invention and is therefore not within the range of 0.10 to 6.00 according to the present invention.
  • the pK B value is determined within the scope of the present invention by acid-base titration. This is done by analytically determining the base constant (K B ) of the anion of the oxygen acid and calculating the pK B value therefrom.
  • K B base constant
  • the person skilled in the art is familiar with carrying out such an acid-base titration.
  • Reference is made to the relevant specialist literature such as, in particular, “Gerhart Jander, Karl Friedrich Gonz, Gerhard Schulze, Jürgen Simon (ed.): combined analyses. Theory and practice of titrations with chemical and physical indications, 16th edition, Walter de Gruyter, Berlin 2003, pages 67 to 128”.
  • the method additionally comprises a step (C) working up the chemolysis product to obtain a first product phase containing mono- and/or or polyols (namely the alcohol component and/or other alcohols formed from this in the chemolysis) and a second product phase containing (i), when the chemolysis is carried out as alcoholysis (Ia), carbamates (if appropriate together with small amounts of amines, which, for example, as a result the presence of traces of water in the alcohol), or (ii), when the chemolysis is carried out as hydrolysis (Ib) or hydroalcoholysis (Ic), amines.
  • a step (C) working up the chemolysis product to obtain a first product phase containing mono- and/or or polyols (namely the alcohol component and/or other alcohols formed from this in the chemolysis) and a second product phase containing (i), when the chemolysis is carried out as alcoholysis (Ia), carbamates (if appropriate together with small amounts of
  • step (C) comprises a phase separation of the chemolysis product into the first product phase and into the second product phase.
  • the method comprises carrying out the chemolysis as hydrolysis (Ib), step (C) mixing the chemolysis product with an organic solvent and phase separation into the first product phase and into the second product phase.
  • the method comprises carrying out the chemolysis as alcoholysis (Ia) or hydroalcoholysis (Ic), step (C) involving mixing the chemolysis product with an organic solvent, which is not completely miscible with the alcohol used in step (B), and comprises phase separation into the first product phase and into the second product phase.
  • step (C) involving mixing the chemolysis product with an organic solvent, which is not completely miscible with the alcohol used in step (B), and comprises phase separation into the first product phase and into the second product phase.
  • the method comprises carrying out the chemolysis as alcoholysis (Ia) or hydroalcoholysis (Ic), step (C) comprising: (CI) mixing the chemolysis product with an organic solvent which is miscible with the alcohol used in step (B) to obtain a product mixture, and (C.II) washing the product mixture with an aqueous washing liquid and phase separation into the first product phase and into the second product phase.
  • step (D) obtaining the mono- and/or polyols from the first product phase.
  • step (D) comprises a distillation and/or stripping.
  • step (E) comprises step (E), obtaining the amines from the second product phase.
  • the process comprises carrying out the chemolysis as alcoholysis (Ia), step (E) involving hydrolysis of the carbamates to form amines and removal of alcohol and water by distillation, followed by a purification by distillation of the amines remaining after the separation by distillation.
  • the method comprises carrying out the chemolysis as hydrolysis (Ib) or hydroalcoholysis (Ic), with step (E) a distillative separation of alcohol and water from the second product phase, followed by a purification by distillation of the amines remaining after the separation by distillation.
  • the method comprises carrying out the chemolysis as an alcoholysis (Ia) or hydroalcoholysis (Ic), the alcohol used in the chemolysis is selected from methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl glycol, triethylene glycol, glycerol, 2-methyl-1,3-propanediol or a mixture of two or more of the aforementioned alcohols.
  • the alcohol used in the chemolysis is selected from methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl glycol, triethylene glycol, glycerol, 2-methyl-1,3-propanediol or a mixture of two or more of the aforementioned alcohols.
  • the element of the fifth, fourteenth or fifteenth group of the periodic table of the elements is selected from vanadium, carbon, silicon or phosphorus.
  • the method comprises carrying out the chemolysis as an alcoholysis (Ia), the salt of the oxygen acid being an anion selected from ⁇ orthovanadate (VO 4 3 ⁇ ), ⁇ orthophosphate (PO 4 3– ), ⁇ diphosphate (P 2 O7 4– ), ⁇ triphosphate (P 3 O 9 5– ), ⁇ tetraphosphate (P 4 O 11 6– ), ⁇ metaphosphate ([PO 3 ) – ]n) , ⁇ alkyl phosphonate (RP(O)O 2 2- ; wherein R denotes an alkyl radical having 1 to 18 carbon atoms, preferably 1 to 10
  • the salt of the oxyacid does not include any further anions besides those mentioned above.
  • the anion of the salt of the oxyacid is particularly preferably selected from the group consisting of orthophosphate and orthovanadate.
  • the method comprises carrying out the chemolysis as hydrolysis (Ib), the salt of the oxygen acid being an anion selected from ⁇ orthovanadate (VO 4 3 ⁇ ), ⁇ carbonate (CO3 2– ), ⁇ orthophosphate (PO 4 3– ), ⁇ diphosphate (P 2 O 7 4– ), ⁇ triphosphate (P 3 O 9 5– ), ⁇ tetraphosphate (P 4 O11 6– ), ⁇ metaphosphate ([PO 3 ) ⁇ ]n), ⁇ alkyl phosphonate (RP(O)O 2 2 ⁇ ; where R denotes an alkyl radical having 1 to 18 carbon atoms, preferably 1
  • the salt of the oxyacid does not include any further anions besides those mentioned above.
  • the salt of the oxygen acid (regardless of the chemolysis method selected) comprises an anion selected from ⁇ orthovanadate (VO 4 3– ), ⁇ diphosphate (P 2 O 7 4– ), ⁇ triphosphate (P 3 O9 5– ), ⁇ tetraphosphate (P4O11 6– ), ⁇ alkyl phosphonate (RPO 3 2– ; where R is an alkyl radical with 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms), ⁇ aryl phosphonate (ArPO3 2- ; where Ar denotes an aryl radical, in particular phenyl), ⁇ hydrogen orthosilicate (HSiO 4 3- ), ⁇ metasilicate ([ SiO3 2– ]n), ⁇ hydrogen metasilicate
  • the salt of the oxyacid does not include any further anions besides those mentioned above.
  • the salt of the oxyacid is an alkali metal salt or a quaternary ammonium salt.
  • the alkali metal salt is a sodium or potassium salt.
  • the chemolysis is carried out at a pressure in the range from 200 mbar (abs.) to 50 bar (abs.), preferably 500 mbar (abs.) to 50 bar (abs.), particularly preferably 900 mbar(abs.) to 1.8 bar(abs.), in particular at ambient pressure.
  • the chemolysis at a temperature in the range from 50° C. to 195° C., preferably from 80° C. to 150° C. is particularly advantageous preferably 100°C to 130°C and most preferably 110°C to 120°C.
  • the isocyanate component comprises an isocyanate selected from phenyl isocyanate (PHI; made from aniline, ANL), tolylene diisocyanate (TDI; made from tolylenediamine, TDA), the di- and Polyisocyanates of the diphenylmethane series (MDI; made from the di- and polyamines of the diphenylmethane series, MDA), 1,5-pentane diisocyanate (PDI; made from 1,5-pentanediamine, PDA), 1,6-hexamethylene diisocyanate (HDI; made from 1,6-hexamethylenediamine, HDA), isophorone diisocyanate (IPDI; made from isophoronediamine, IPDA), xylylene diisocyanate (XDI; made from xylylenediamine, XDA) or a mixture of two or more of the a
  • the isocyanate component comprises tolylene diisocyanate or a mixture of tolylene diisocyanate and the di- and polyisocyanates of the diphenylmethane series (and in particular comprises no further isocyanates in addition to the aforementioned isocyanates).
  • the alcohol component comprises a monool or polyol selected from a polyether monool, a polyether polyol, a polyester polyol, a polyether ester polyol, a polyacrylate polyol, a polyether carbonate polyol or a mixture of two or more of the foregoing polyols.
  • the alcohol component preferably contains a polyether polyol.
  • the alcohol component is particularly preferably a polyether polyol (ie contains no other monools or polyols other than polyether polyols; however, a mixture of two or more different polyether polyols is included and does not go beyond the scope of this embodiment).
  • the alcohol component comprises a styrene-acrylonitrile copolymer-filled polyether polyol.
  • the mass of Salt of oxygen acid 0.10% to 20%, preferably 1.0% to 15%, particularly preferably 5.0% to 10% of the mass of the (poly) urethane.
  • the mass ratio of (total) chemolysis reagent to the (poly)urethane is in the range from 0.05 to 90, preferably 1.0 to 80.
  • the chemolysis is carried out in the presence of (at least) one phase transfer catalyst.
  • the phase transfer catalyst comprises a charged organic molecule.
  • the phase transfer catalyst comprises a quaternary ammonium salt, a quaternary phosphonium salt or a mixture of both.
  • the process according to the invention comprises in particular a step of working up (II) the process product of the chemolysis (I) to obtain (at least) one raw material selected from (a) a mono- and/or polyol, (b) a carbamate and/or (c) an amine.
  • This work-up (II) is preferably carried out according to one (step (C)), in which a first product phase containing mono- and/or polyols (namely the alcohol component and/or other alcohols formed from this in the chemolysis) and a second product phase containing (i ), when carrying out the chemolysis as an alcoholysis (Ia), carbamates (possibly together with small amounts of amines, which have arisen, for example, as a result of the presence of traces of water in the alcohol), or (ii), when carrying out the chemolysis as a hydrolysis (Ib) or hydroalcoholysis (Ic), amines.
  • step (C) in which a first product phase containing mono- and/or polyols (namely the alcohol component and/or other alcohols formed from this in the chemolysis) and a second product phase containing (i ), when carrying out the chemolysis as an alcoholysis (Ia), carbamates (possibly together with small amounts
  • the method according to the invention therefore comprises the following steps: (A) providing the urethane (particularly polyurethane) based on an isocyanate component and an alcohol component; (B) carrying out the chemolysis as described above, ie with the addition of a catalyst as one of the following reactions: (Ia) alcoholysis of the (poly)urethane with an alcohol (without deliberate addition of water); (Ib) hydrolysis of the (poly)urethane with water (without adding an alcohol) or (Ic) hydroalcoholysis of the (poly)urethane with an alcohol and water, the catalyst being a salt of an oxyacid of an element of the fifth, fourteenth or fifteenth Group of the Periodic Table of the Elements or a mixture of two or more such salts, wherein the pKB value of the anion of the salt is in the range of 0.10 to 6.00, preferably 0.25 to 5.00, more preferably 0.50 to 4.50, and wherein when the chemolysis is carried out as
  • the carbamates are other urethanes formed by transurethanization reactions, while the amines are those formed by hydrolysis reactions amines corresponding to the isocyanate are formed, as defined above.
  • PREPARING THE (POLY-)URETHANE FOR CHEMICAL RECYCLING the (poly-)urethane to be chemically recycled is prepared in preparation for the chemolysis. In principle, this can be any type of urethane.
  • Polyurethanes ie urethanes derived from polyisocyanates (2 or more isocyanate groups per molecule) and polyols (two or more alcohol groups per molecule) are preferred.
  • this can be any type of polyurethane, ie both polyurethane foams and polyurethane products from the so-called CASE applications described at the outset.
  • Both flexible foams and rigid foams are suitable for the polyurethane foams, with flexible foams (for example from old mattresses, upholstered furniture or car seats) being preferred.
  • Polyurethane foams are usually produced using blowing gases such as pentane or carbon dioxide.
  • blowing gases such as pentane or carbon dioxide.
  • preference is given to polyurethane elastomers, polyurethane adhesives and polyurethane coatings.
  • those urethanes or polyurethanes are preferred which contain an isocyanate selected from phenyl isocyanate (PHI; produced from aniline, ANL), tolylene diisocyanate (TDI; produced from toluenediamine, TDA), the di- and polyisocyanates of the diphenylmethane series (MDI; produced from the di- and polyamines of the diphenylmethane series, MDA), 1,5-pentane diisocyanate (PDI; made from 1,5-pentanediamine, PDA), 1,6-hexamethylene diisocyanate (HDI; made from 1,6-hexamethylenediamine, HDA) , isophorone diisocyanate (IPDI; made from isophorone diamine, IPDA), xylylene diisocyanate (XDI; made from xylylenediamine, XDA) or a mixture of two or more of the aforementioned is
  • PHI phenyl is
  • the isocyanate component comprises tolylene diisocyanate or a mixture of tolylene diisocyanate and the di- and polyisocyanates of the diphenylmethane series and, in particular, comprises no further isocyanates in addition to those mentioned above.
  • the alcohol component preferably comprises a mono- or polyol selected from a polyether monool, a polyether polyol, a polyester polyol, a polyether ester polyol, a polyacrylate polyol, a polyether carbonate polyol, or a mixture of two or more of the foregoing polyols.
  • the alcohol component preferably contains a polyether polyol.
  • the alcohol component is particularly preferably a polyether polyol (ie it does not contain any other mono- or polyols other than polyether polyols; however, a mixture of two or more different polyether polyols is included and does not go beyond the scope of this embodiment).
  • the polyether polyol can also be one filled with a styrene-acrylonitrile (SAN) copolymer. In such cases, it is advantageous to carry out the chemolysis as a hydrolysis (Ib) or hydroalcoholysis (Ic).
  • the challenge in the chemolysis of polyurethanes whose polyol component is based on SAN copolymer-filled polyether polyols is that the SAN copolymer is released as finely divided polymer particles during chemolysis.
  • the SAN polymer present as finely divided polymeric particles in the reaction mixture leads to problems in the subsequent separation, e.g. B. extractive processes.
  • filtration is hardly possible, since the filter quickly becomes blocked and further separation is no longer possible.
  • Step (A) preferably already comprises preparatory steps for the cleavage of the urethane bonds in step (B).
  • preparatory steps are known to those skilled in the art; reference is made, for example, to the literature cited in [1].
  • the polyurethane Before, during or after the mechanical comminution, the polyurethane can be treated with aqueous or alcoholic disinfectants.
  • aqueous or alcoholic disinfectants are preferably hydrogen peroxide, chlorine dioxide, sodium hypochlorite, formaldehyde, sodium N-chloro-(4-methylbenzene)sulfonamide (chloramine T) and/or peracetic acid (aqueous disinfectants) or ethanol, isopropanol and/or 1-propanol (alcoholic disinfectants ).
  • the prepared foam is filled into suitable transport vehicles, such as silo vehicles, for onward transport.
  • suitable transport vehicles such as silo vehicles
  • the prepared foam can also be compressed for onward transport in order to achieve a higher mass-to-volume ratio.
  • the foam is then filled into the reaction device provided for the chemolysis at the location of the chemolysis. It is also conceivable to connect the transport vehicle used directly to the reaction device.
  • CHEMOLYSIS OF THE (POLY)URETHANE The chemolysis of the (poly)urethane, step (B), is preferably carried out with the exclusion of oxygen.
  • the reaction is carried out in an inert gas atmosphere (especially in a nitrogen, argon or helium atmosphere).
  • the chemolysis reagents used (alcohol, water or alcohol and water) are preferably also freed from oxygen by inert gas saturation.
  • the chemolysis can be carried out as alcoholysis (Ia), hydrolysis (Ib) or hydroalcoholysis (Ic).
  • alcoholysis and hydroalcoholysis used here are usually referred to in the literature as glycolysis or hydroglycolysis; see Nos. 2 and 3 above. However, since this is only really correct when using glycol as the alcohol, the more general terms alcoholysis and hydroalcoholysis are used within the scope of the present invention.
  • the alcohol used in the chemolysis is preferably selected from methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl glycol, triethylene glycol, glycerol, 2-methyl-1 ,3-propanediol or a mixture of two or more of the aforementioned alcohols.
  • Diethylene glycol and propylene glycol are particularly preferred.
  • water and alcohol can be premixed; but this is not necessary.
  • a catalyst for the chemolysis a salt of an oxyacid of an element of the fifth, fourteenth or fifteenth group of the periodic table of the elements or a mixture of two or more such salts, the pKB value of the anion of the salt being in the range from 0.10 to 6.00, preferably from 0.25 to 5.00, particularly preferably from 0.50 to 4.50, and where when the chemolysis is carried out as an alcoholysis (Ia) the catalyst does not comprise a carbonate and when the chemolysis is carried out as a hydroalcoholysis (Ic ) the catalyst no carbonate, no orthophosphate and no Includes metaphosphate used.
  • the salt of the oxygen acid preferably comprises an anion selected from ⁇ orthovanadate (VO 4 3 ⁇ ), ⁇ orthophosphate (PO 4 3 ⁇ ), ⁇ diphosphate (P 2 O 7 4 ⁇ ), ⁇ triphosphate (P 3 O 9 5- ) ⁇ tetraphosphate (P 4 O 11 6- ) ⁇ metaphosphate ([PO 3 ) - ]n) ⁇ alkyl phosphonate (RP(O)O 2 2- ) wherein R is an alkyl radical with 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms), ⁇ aryl phosphonate (ArP(O)O 2 2- ; wherein Ar denotes an aryl radical, in particular phenyl), ⁇ hydrogen orthosilicate (HSiO 4 3- ), ⁇ metasi
  • orthovanadate (VO 4 3- ), orthophosphate (PO 4 3- ) and hydrogen orthosilicate (HSiO 4 3- ) are particularly preferred.
  • Orthovanadate (VO 4 3- ) and orthophosphate (PO 4 3- ) are very particularly preferred.
  • the salt of the oxygen acid preferably comprises an anion selected from ⁇ orthovanadate (VO 4 3- ), ⁇ carbonate (CO 3 2- ), ⁇ orthophosphate (PO 4 3- ), ⁇ diphosphate ( P 2 O 7 4– ), ⁇ triphosphate (P 3 O 9 5– ), ⁇ tetraphosphate (P 4 O 11 6- ), ⁇ metaphosphate ([PO 3 ) - ] n ), ⁇ alkylphosphonate (RP(O)O 2 2- , wherein R is an alkyl radical having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, designated), ⁇ aryl phosphonate (ArP(O)O 2 2- ; where Ar denotes an aryl radical, in particular phenyl), ⁇ hydrogen orthosilicate (HSiO 4 3- ), ⁇ metasilicate ([SiO 3 2- ]n ), ⁇ hydrogen metasilicate ([HS
  • orthovanadate (VO 4 3- ), carbonate (CO 3 2- ), orthophosphate (PO 4 3- ) and hydrogen orthosilicate (HSiO 4 3- ) are particularly preferred.
  • the salt of the oxygen acid can be an anion selected from ⁇ orthovanadate (VO 4 3 ⁇ ), ⁇ diphosphate (P 2 O 7 4 ⁇ ), ⁇ triphosphate (P 3 O 9 5– ), ⁇ tetraphosphate (P 4 O 11 6– ), ⁇ alkyl phosphonate (RPO 3 2– ; wherein R is an alkyl radical having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms), ⁇ aryl phosphonate (ArPO 3 2– ; where Ar denotes an aryl radical, in particular phenyl) ⁇ hydrogen orthosilicate (HSiO 4 3– ), ⁇ metasilicate ([SiO 3 2– ]n), ⁇ hydrogen metasilicate ([HSiO 3 – ]n), ⁇ Dihydrogen orthosilicate (H
  • orthovanadate (VO 4 3- ) and hydrogen orthosilicate (HSiO 4 3- ) are particularly preferred. Irrespective of the chemolysis process selected, the following applies: It is preferred to use only one (1) salt of an oxyacid as the catalyst and not a mixture. It is also preferred that no other catalysts not listed above are used. It has proven useful to dose the salt of the oxygen acid in such a way that its mass is 0.10% to 20%, preferably 1.0% to 15%, particularly preferably 5.0% to 10% of the mass of the (poly) to be reacted. urethane is.
  • an alkali metal salt in particular a sodium or potassium salt, or a quaternary ammonium salt as the salt of the oxyacid.
  • Sodium or potassium salts are particularly preferred.
  • a reaction temperature in the range from 50° C. to 195° C., particularly preferably from 80° C. to 150° C., very particularly preferably from 100° C. to 130° C. and extremely particularly preferably from 110° C. to 120° C complied with.
  • the chemolysis can be carried out in an autoclave without pressure compensation, with pressures of up to 50 bar (abs.) being able to set in.
  • the reaction makes no special demands on the pressure; it can also be carried out at ambient pressure or slightly reduced pressure (in particular at a lower pressure limit of 200 mbar (abs.) , preferably 900 mbar (abs.)), which facilitates the separation of carbon dioxide formed.
  • An only slightly increased pressure up to in particular 1.8 bar (abs.) is also possible.
  • the chemolysis is generally within a period of from 1.0 h to 48 h, preferably from 1.5 h to 24 h, more preferably from 2.0 h to 10 h, most preferably from 2.5 h to 6.0 h, and extraordinary very particularly preferably 3.0 h to 5.5 h, ie after a reaction time within this period no or at most only a slight further conversion takes place.
  • a mass ratio of (total used) chemolysis reagent to the (poly)urethane in the range from 0.05 to 90, preferably from 1.0 to 80.
  • this amount is divided between water and alcohol, the mass of the water being at least 4.0%, preferably 4.0% to 15%, particularly preferably 4.0% to 10%, very particularly preferably 5 .0% to 10% and extremely particularly preferably 5.0% to 7.0% of the mass of the alcohol. It is advantageous here not to add the water to be used for the hydroalcoholysis right at the start of the reaction period.
  • the requirement relates that the “mass of the water is at least 4.0%, preferably 4.0% to 15%, particularly preferably 4.0% to 10%, very particularly preferably 5.0% to 10%, and extremely most preferably 5.0% to 7.0%, by mass of the alcohol” to the total amount of water added as part of the chemolysis reagent.
  • the chemolysis as an alcoholysis (Ia)
  • no water is used as the chemolysis reagent. This does not rule out the entry of small amounts of water from other sources, in particular from moisture in the alcohol. It is also possible to dissolve the catalyst in water.
  • water is introduced into the chemolysis at most in such an amount that the mass of the water present during the alcoholysis (regardless of where it comes from) is preferably 0% to ⁇ 4.0%, in particular 0% to 3.5% 0% to 3.4%, particularly preferably 0% to 3.0%, very particularly preferably 0% to 2.0% of the mass of the alcohol used.
  • the alcoholysis initially provides carbamates as products. If the aim is to isolate amines, they must be subjected to hydrolysis in a process step separate from the alcoholysis, which will be explained in more detail below.
  • phase transfer catalysts may be advantageous to add at least one phase transfer catalyst during chemolysis in addition to the catalyst (ie in addition to the chemolysis catalyst) in order to Increase yield and / or shorten the reaction time.
  • a phase transfer catalyst promotes the transport of the actual catalyst (the chemolysis catalyst) into the (hydrophobic) (poly)urethane and thus accelerates the degradation reaction.
  • Suitable phase transfer catalysts are preferably compounds with a charged organic molecule, preferably quaternary ammonium salts ([R 4 N] + X - ) or quaternary phosphonium salts ([R 4 P] + X - ) with organic radicals (R) and a counterion (X - ).
  • Quaternary ammonium salts with organic radicals and a counterion are particularly preferred.
  • the organic radicals (R) are preferably methyl, propyl, butyl, pentyl, hexyl, octyl, hexadecyl or stearyl or benzyl radicals, the four radicals being a quaternary ammonium or phosphonium salt each may be different or the same.
  • the counterion (X - ) is preferably chloride, bromide, sulfate, chlorate or triflate.
  • phase transfer catalysts examples include trimethylbenzylammonium chloride, tetra(1-propyl)ammonium chloride, tetra(1-butyl)ammonium chloride, tetra(1-pentyl)ammonium chloride, tetra(1-hexyl)ammonium chloride, dimethyldistearylammonium chloride, tetraphenylphosphonium chloride, hexa(1-decyl)tributylphosphonium chloride , methyltri(1-octyl)phosphonium chloride and/or methyltri(1-octyl)ammonium chloride ("Aliquat 336"), where tetra(1-butyl)ammonium chloride, tetra(1-pentyl)ammonium chloride, tetra(1-hexyl)ammonium chloride and Methyltri(1-octyl)ammoni
  • chemolysis can be carried out in any reactor known in the art for such a purpose.
  • stirred tanks stirred reactors
  • tubular reactors are particularly suitable as chemolysis reactors.
  • this chemolysis product must be processed (II); this is preferably done according to step (C) of the preferred embodiment mentioned further above.
  • the aim of working up (II) in step (C) is to provide two product phases, one of which (henceforth: first product phase) contains mono- and/or polyols (namely the alcohol component and/or other alcohols formed from this in the chemolysis) and the second (henceforth: second product phase), depending on the type of chemolysis, contains the following: (i) when carrying out the chemolysis as an alcoholysis (Ia): carbamates (possibly together with small amounts of amines which have arisen, for example, as a result of the presence of traces of water in the alcohol), or (ii) when carrying out the chemolysis as a hydrolysis (Ib) or Hydroalcoholysis (Ic): amines.
  • first product phase contains mono- and/or polyols (namely the alcohol component and/or other alcohols formed from this
  • the separation into the two product phases does not necessarily have to be perfect in the sense that all mono- or polyol get into the first product phase and all carbamate or amine get into the second product phase. If, for example, due to the prevailing solubility equilibria, small amounts of the amine get into the first product phase (or small amounts of the mono- or polyol into the second product phase), this of course does not go beyond the scope of this embodiment.
  • the chemolysis product is obtained directly in two phases. This is regularly the case when the chemolysis is carried out as hydrolysis (Ib) or hydroalcoholysis (Ic).
  • the first and the second product phase can be obtained by a simple phase separation.
  • the first product phase can then be fed directly to a further work-up for isolating the mono- or polyols (hereinafter step (D)).
  • the second product phase can be fed directly to further work-up to isolate the amines (hereinafter step (E)).
  • This embodiment is conceivable, for example, when using TDI-based polyurethane foams and carrying out the chemolysis as hydroalcoholysis with diethylene glycol as the alcohol. Due to its water solubility, the TDA formed forms the second product phase (an alcoholic-aqueous phase) together with the likewise water-soluble diethylene glycol and unreacted water, while the recovered polyols form the first product phase (an organic phase). Whether this embodiment is applicable can easily be determined by expert considerations or simple preliminary tests. However, it is also possible that a simple phase separation of the chemolysis product does not lead to a first product phase with a sufficient proportion of monool or polyol and a second product phase with a sufficient proportion of amine or carbamate.
  • the chemolysis product is extracted with an organic solvent and then separated into the first and second product phases.
  • Suitable organic solvents are aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogen-substituted aliphatic hydrocarbons, halogen-substituted alicyclic hydrocarbons, halogen-substituted aromatic hydrocarbons and mixtures of two or more of the above organic solvents.
  • the processing of the chemolysis product comprises mixing it with an organic solvent which is not completely miscible with the alcohol used in the chemolysis, and Phase separation into the first product phase and the second product phase.
  • the requirement that the organic solvent to be used in this extraction is not completely miscible with the alcohol used in the chemolysis means that - under the conditions of temperature and ratio of organic solvent to alcohol from the chemolysis present for the extraction - there is a miscibility gap of such must be that a phase separation is possible.
  • the organic solvent is selected from aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and mixtures of two or more of the aforementioned organic solvents
  • the alcohol to be used in the chemolysis is selected from methanol, ethanol, ethylene glycol, diethylene glycol , propylene glycol, dipropylene glycol, methyl glycol, triethylene glycol, glycerine, 2-methyl-1,3-propanediol and mixtures of two or more of the aforementioned alcohols.
  • simple preliminary tests can be used to determine whether or not there is a suitable miscibility gap.
  • the chemolysis product is also worked up by extraction, but using an organic solvent which is miscible with the alcohol used in the chemolysis is.
  • the work-up comprises the steps: (1) mixing the chemolysis product with an organic solvent which is miscible with the alcohol used in the chemolysis to obtain a product mixture, and (2) Washing of the product mixture with an aqueous washing liquid and phase separation into the first product phase and the second product phase
  • the requirement that the organic solvent to be used in step (1) is miscible with the alcohol used in step (B) means that - under the conditions of temperature and ratio of organic solvent to the chemolytic alcohol present for step (1) - a mixture of the organic solvent and the chemolytic alcohol does not spontaneously separate into two phases.
  • the organic solvent in step (1) is selected from halogen-substituted aliphatic hydrocarbons, halogen-substituted alicyclic hydrocarbons, halogen-substituted aromatic hydrocarbons and mixtures of two or more of the aforementioned organic solvents
  • the alcohol to be used for chemolysis is selected from methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl glycol, triethylene glycol, glycerol, 2-methyl-1,3-propanediol and mixtures of two or more of the aforementioned alcohols.
  • the first product phase contains the mono- and/or polyols and is preferably worked up in as pure a form as possible in order to isolate them (step (D) in the preferred embodiment mentioned further above).
  • Such a work-up is preferably carried out by means of distillation and/or stripping with a stripping gas (such as in particular nitrogen or steam, preferably nitrogen).
  • a distillation is preferably carried out in an evaporator selected from falling film evaporators, thin film evaporators, flash evaporators, rising film evaporators, natural circulation evaporators, forced circulation evaporators or boiler evaporators. It is particularly preferable for the distillation to be followed by stripping with steam.
  • Stripping with steam can be carried out by passing steam through stripping columns known per se.
  • stripping with steam can also be carried out by adding water in liquid form to the first product phase (possibly already pre-purified in a distillation) and then overheating (while maintaining a counter-pressure set by means of a pressure valve that is sufficient to keep the water liquid). ) and expanded after the pressure valve, whereby the water contained in the polyol evaporates and has a stripping effect.
  • the second product phase contains the amines or carbamates and is preferably worked up in as pure a form as possible to isolate the amines (step (E) in the preferred embodiment mentioned further above).
  • the recovery of the amine advantageously first comprises a distillative separation of alcohol and water from the second product phase. This can be done by known distillation techniques.
  • the crude amine that remains is preferably worked up further, in particular by distillation.
  • the recovery of the amine advantageously includes hydrolysis of the carbamates to the amines and a distillative removal of alcohol and water, followed by a distillative purification of the crude amines remaining after the removal by distillation.
  • the hydrolysis and the evaporation of water and alcohol do not necessarily have to occur in this order. It is also quite possible to first evaporate an alcohol fraction (generally together with part of the water), then hydrolyze it and finally separate the remaining water in the crude amine distillation step.
  • Suitable catalysts for a hydrolysis step in the course of working up the second product phase are the catalysts suitable for hydrolysis from the prior art, as well as the catalysts to be used according to the invention in the course of the chemolysis in step (B).
  • the possibility of phase transfer catalysis mentioned above in connection with step (B) can also be used in the same way in a hydrolysis as part of the work-up of the second product phase.
  • This embodiment provides an economical and environmentally friendly outlet for contaminants originating from the polyurethane product.

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Abstract

La présente invention concerne un procédé de dissociation d'uréthanes, en particulier de polyuréthanes, par chimiolyse (alcoolyse, hydrolyse ou hydroalcoolyse) en présence d'un catalyseur. La chimiolyse est caractérisée en ce qu'elle fait intervenir en tant que catalyseur au moins un sel d'un oxyacide d'un élément du cinquième, quatorzième ou quinzième groupe du tableau périodique des éléments ou un mélange de deux ou plus de ces sels, le pKB de l'anion du sel de l'oxyacide valant de 0,10 à 6,00, de préférence de 0,25 à 5,00, de manière particulièrement préférée de 0,50 à 4,50. Lors de la mise en œuvre de la chimiolyse en tant qu'alcoolyse (Ia), le catalyseur ne comprend pas de carbonate et, lors de la mise en œuvre de la chimiolyse en tant qu'hydroalcoolyse, le catalyseur ne comprend pas de carbonate, pas d'orthophosphate et pas de métaphosphate.
EP22809752.3A 2021-10-29 2022-10-26 Procédé de dissociation de (poly)uréthanes Pending EP4423184A1 (fr)

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US4159972A (en) 1977-10-17 1979-07-03 Ford Motor Company Dissolution of polyurethane foams and re-use of the products therefrom
AU704932B2 (en) 1996-10-08 1999-05-06 Jong Han Jeon A method for preparation of recycled polyols and a method for manufacturing polyurethane foams with improved thermal insulation property
WO2020260387A1 (fr) 2019-06-27 2020-12-30 Covestro Deutschland Ag Procédé de récupération de matières premières à partir de produits de polyuréthane
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