WO2022187010A1 - Procédé de récupération et/ou de régénération de composants de catalyseur - Google Patents

Procédé de récupération et/ou de régénération de composants de catalyseur Download PDF

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Publication number
WO2022187010A1
WO2022187010A1 PCT/US2022/017147 US2022017147W WO2022187010A1 WO 2022187010 A1 WO2022187010 A1 WO 2022187010A1 US 2022017147 W US2022017147 W US 2022017147W WO 2022187010 A1 WO2022187010 A1 WO 2022187010A1
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compound
metal
composition
polymers
solvent
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PCT/US2022/017147
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English (en)
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Jonathan D. TEDDER
John B. Ruhl
Jeff UHRIG
Steven A. Cohen
Ronald Boyce
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Novomer, Inc.
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Publication of WO2022187010A1 publication Critical patent/WO2022187010A1/fr

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    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
    • C07D305/12—Beta-lactones
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/31—Aluminium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • This disclosure relates to the regeneration and recovery of catalyst components that have been used in the production of propiolactones.
  • Carbonylation is a process that can be used to react carbon monoxide and an epoxide to make a lactone. In some cases, additional steps are taken to react the lactones to make polymers. These lactones or polymers thereof are often used as plastics and disinfectants.
  • a carbonylation catalyst is used to optimize the efficiency of the reaction to produce lactones at competitive prices. After running the reaction for a period of time, the carbonylation catalyst often loses some activity, is spent, or is partially carried out in product streams. The carbonylation catalysts are expensive, and thus, efforts have been undertaken to recover the carbonylation catalyst for at least partial reuse of the carbonylation catalyst in carbonylation reactions.
  • Recovery or reclamation of the catalyst component may occur after a carbonylation reaction.
  • Reclaiming or recovering the catalyst component utilizes a decoupling step, separation steps, or both to remove undesired components or compounds from the product stream or composition so that the metal centered compound containing the polymer containing a residue of the propiolactone, an epoxide, or both from the carbonylation reaction is turned into a Lewis acid that has a useable form.
  • the Lewis acid is in a useable form where the Lewis acid lacks a polymer in contact with the metal center of the Lewis acid and where the Lewis acid contains either a halogen or a polar ligand.
  • the Lewis acid may be subjected to additional steps to form a carbonylation catalyst having a cationic Lewis acid component and an anionic metal carbonyl component.
  • the metal centered compound is converted into a useable Lewis acid form and is used to form the regenerated catalyst, the regenerated catalyst includes at least one component that is recycled, for example, the Lewis acid.
  • a method including decoupling one or more polymers containing the residue of a propiolactone, an epoxide, or both from a metal centered compound in a composition to form a Lewis acid containing one or more polar ligands, a Lewis acid containing one or more acid ion exchange resins, or a Lewis acid containing a halogen.
  • the method further includes removing one or more organic compounds, inorganic compounds, the one or more polymers, or any combination thereof from the composition.
  • the method further includes forming a regenerated carbonylation catalyst by one or more of contacting a metal carbonyl and the Lewis acid containing the one or more polar ligands or contacting a metal carbonyl additive and the Lewis acid containing the halogen with one or more polar ligands.
  • the method may further include contacting the composition and a solvent for dissolving the propiolactone and removing the solvent and the propiolactone from the composition before the decoupling step.
  • the method may further include contacting the composition, an acid compound, and a polar solvent to dissolve the metal centered compound before the decoupling step.
  • the acid compound may cleave the one or more polymers from the metal centered compound.
  • the method may further include removing the polar solvent and an unreacted portion of the acid compound from the composition so that the composition comprises the Lewis acid containing a halogen, after the removing step.
  • the method may further include dissolving the Lewis acid containing the halogen in the one or more polar ligands and contacting the Lewis acid containing the halogen and the one or more polar ligands with a solvent that is miscible in the one or more polar ligands so that the Lewis acid containing the halogen is precipitated out, before the contacting of the Lewis acid containing the halogen and the metal carbonyl additive.
  • the method may further include contacting an acid compound and a first solvent to dissolve the metal centered compound, before the decoupling step.
  • the acid compound may cleave the one or more polymers from the metal centered compound, and the first solvent may be a polar solvent.
  • the method may further include precipitating the Lewis acid containing a halogen using a second solvent that is miscible in the first solvent, after the removing step.
  • the method may further include simultaneously filtering the first solvent and the second solvent so that the composition is a precipitate, before the contacting of the metal carbonyl additive and the Lewis acid containing the halogen with one or more polar ligands.
  • the method may further include contacting a metal carbonyl additive, a polar ligand, and the metal centered compound to form the Lewis acid containing one or more polar ligands, an acid compound, and a metal carbonyl, before the decoupling step.
  • the method may further include capturing the one or more polymers with the acid compound by bonding the one or more polymers to the acid compound so that the acid compound and the one or more polymers are removable from the composition during the removing step, after the decoupling step.
  • the method may further include forming a regenerated carbonylation catalyst by contacting the metal carbonyl and the Lewis acid containing the one or more polar ligands.
  • the method may further include contacting the metal centered compound with an aqueous solvent and an acid ion exchange resin before the decoupling step.
  • the aqueous solvent may dissolve some of the one or more organic compounds, the inorganic compounds, or both.
  • the acid ion exchange resin may exchange with the one or more polymers of the metal centered compound.
  • the method may further include connecting the acid ion exchange resin and the metal centered compound so that the metal centered compound is tethered to the acid ion exchange resin.
  • the method may further include contacting an acid compound containing a halogen with the metal centered compound containing the acid ion exchange resin so that the acid compound removes the metal centered compound from the acid ion exchange resin and the halogen of the acid compound bonds with the metal centered compound to form the Lewis acid containing the halogen, after the removing step.
  • the method may further include contacting a solvent for dissolving the metal centered compound and an anion exchange resin containing a halogen with the metal centered compound, before the decoupling step.
  • the method may further include exchanging the halogen of the anion exchange resin and the one or more polymers of the metal centered compound to form the Lewis acid containing the halogen and an anion exchange resin containing the one or more polymers, during the decoupling step.
  • the method may further include filtering the anion exchange resin containing the one or more polymers from the composition.
  • the method may further include contacting the acid compound, an aprotic solvent, and an aqueous solvent in the composition so that an organic phase, an aqueous phase, and a precipitate are formed, before the decoupling step.
  • the aprotic solvent may dissolve the metal centered compound into the organic phase.
  • the aqueous solvent may dissolve some of the one or more organic compounds, the inorganic compounds, the acid compound, or any combination thereof into the aqueous phase.
  • the precipitate may contain some of the organic compounds.
  • the acid compound may contain a halogen and may cleave the one or more polymers from the metal centered compound.
  • the method may further include removing the aqueous phase so that the organic phase and the precipitate remain, during the removing of the one or more organic compounds, the inorganic compounds, the one or more polymers, or any combination thereof from the composition.
  • the method may further include removing the precipitate containing some of the organic compounds from the composition.
  • the method may further include removing the aprotic solvent so that the Lewis acid containing the halogen is precipitated.
  • the method may further include thermolyzing the composition to form one or more unsaturated acids from the one or more polymers containing the residue of a propiolactone, an epoxide, or both, the one or more organic compounds, or both, before or during the decoupling step.
  • the methods herein provide a way to recover a Lewis acid catalyst component without interference with or from other carbonylation products.
  • the methods herein separate the Lewis acid component of a carbonylation catalyst from interfering polymers to form a regenerated carbonylation catalyst that comprises at least one recycled component.
  • the methods herein remove polymers and other interfering compounds that hinder the Lewis acid’s catalytic activity so that a regenerated catalyst is formed that has catalytic activity with one or more of beta propiolactone, epoxides, succinic anhydrides, or both.
  • FIG. 1 shows methods 1 , 1b, and 2 that reclaim or regenerate the carbonylation catalyst.
  • FIG. 2 shows another method for reclaiming the carbonylation catalyst.
  • FIG. 3 shows another method for reclaiming the carbonylation catalyst.
  • FIG. 4 shows another method for reclaiming the carbonylation catalyst.
  • FIG. 5 shows another method for reclaiming the carbonylation catalyst.
  • FIG. 6A shows a proton NMR analysis of a synthesized tetraphenyl porphyrin aluminum chloride complex.
  • FIG. 6B shows a proton NMR analysis of a recovered tetraphenyl porphyrin aluminum chloride complex.
  • FIG. 7 shows a proton NMR analysis of an analysis of isolated material from the reaction of catalyst residue and 2 Molar HCI to generate the tetraphenyl porphyrin aluminum chloride complex.
  • FIG. 8 shows a proton NMR analysis of isolated material from the reaction of recovered tetraphenyl porphyrin aluminum chloride and Na(Co(CO)4).
  • FIG. 9 shows a reaction Infrared Spectroscopy plot showing the catalytic generation of beta propiolactone using recovered carbonylation catalyst.
  • the top line is beta propiolactone; the middle line is ethylene oxide, and the bottom line is succinic anhydride.
  • a catalyst component as used herein means a metal centered compound, a metal carbonyl, a Lewis acid, a Lewis acid derivative, a metal carbonyl derivative, or any combination thereof.
  • a catalyst as used herein includes at least cationic compound and an anionic compound.
  • An organic compound as used herein includes any compound that is free of a metal atom.
  • An inorganic compound as used herein includes compounds that include at least one metal atom.
  • Composition as used herein includes all components in a stream, reactant stream, product stream, slurry, precipitate, liquid, solid, gas, or any combination thereof that are containable within a single vessel.
  • the present teachings disclose a method for reclaiming and/or regenerating a catalyst component that can be used for catalyzing reactions of beta propiolactone, epoxide, succinic anhydride, or any combination thereof.
  • the method includes steps of at least decoupling a metal centered compound from a polymer containing a residue of a propiolactone, an epoxide, or both and regenerating a carbonylation catalyst.
  • the metal centered compound can be decoupled from the polymer by any method sufficient to chemically remove the metal centered compound from the polymer.
  • the decoupling step forms either a Lewis acid containing a halogen or a Lewis acid containing a polar ligand.
  • the Lewis acid may have a cationic charge.
  • the method may further include contacting the Lewis acid containing a halogen with a polar ligand and a metal carbonyl additive so that a regenerated catalyst is formed that comprises a Lewis acid that is cationic and a metal carbonyl that is anionic.
  • the method may further include contacting the Lewis acid containing a polar ligand with a metal carbonyl additive so that a regenerated catalyst is formed that comprises a Lewis acid that is cationic and a metal carbonyl that is anionic.
  • the carbonylation reaction may include contacting one or more epoxides, lactones, or both with carbon monoxide in the presence of catalyst. This step may occur in a reactor that has one or more inlets, two or more inlets, three or more inlets, or a plurality of inlets.
  • the one or more epoxides, the lactones, the carbon monoxide, and the catalyst may be added in a single inlet, multiple inlets, or each may be added in a separate inlet as separate or combined feed streams.
  • the carbonylation reaction may produce one or more product streams or compositions.
  • the epoxide used in the carbonylation reaction may be any cyclic alkoxide containing at least two carbon atoms and one oxygen atom.
  • the epoxide may have a structure shown by formula (I):
  • R 1 and R 2 are each independently selected from the group consisting of: hydrogen; Ci- Ci5 alkyl groups; halogenated alkyl chains; phenyl groups; optionally substituted aliphatic or aromatic alkyl groups; optionally substituted phenyl; optionally substituted heteroaliphatic alkyl groups; optionally substituted 3 to 6 membered carbocycle; and optionally substituted 3 to 6 membered heterocycle groups, where R 1 and R 2 can optionally be taken together with intervening atoms to form a 3 to 10 membered, substituted or unsubstituted ring optionally containing one or more hetero atoms; or any combination thereof.
  • the lactone formed from the carbonylation reaction may be any cyclic carboxylic ester having at least one carbon atom and two oxygen atoms.
  • the lactone may be an acetolactone, a propiolactone, a butyrolactone, a valerolactone, caprolactone, or a combination thereof. Anywhere in this application where a propiolactone or lactone is used or described, another lactone may be applicable or usable in the process, step, or method.
  • the propiolactone may have a structure corresponding to formula II:
  • R 1 and R 2 are each independently selected from the group consisting of: hydrogen; C1-C15 alkyl groups; halogenated alkyl chains; phenyl groups; optionally substituted aliphatic or aromatic alkyl groups; optionally substituted phenyl; optionally substituted heteroaliphatic alkyl groups; optionally substituted 3 to 6 membered carbocycle; and optionally substituted 3 to 6 membered heterocycle groups, where R 1 and R 2 can optionally be taken together with intervening atoms to form a 3 to 10 membered, substituted or unsubstituted ring optionally containing one or more hetero atoms; or any combination thereof.
  • the product stream or composition may include one or more organic compounds including a propiolactone, a polypropiolactone, succinic anhydride, polyethylene glycol, poly-3- hydroxypropionate, 3-hydroxy propionic acid, 3-hydroxy propionaldehyde, a polyester, a polyethylene, a polyether, unreacted epoxides, any derivative thereof, any other monomer or polymer derived from the reaction of an epoxide and carbon monoxide, or any combination thereof.
  • the product stream or composition may include one or more inorganic compounds that include catalyst components such as metal carbonyls, metal carbonyl derivatives, metal centered compounds, Lewis acids, Lewis acid derivatives, or any combination thereof.
  • a metal carbonyl derivative is a compound that includes one or more metals and one or more carbonyl groups that can be processed to form an anionic metal carbonyl component for use in a carbonylation catalyst.
  • a Lewis acid derivative is a compound that includes one or more metal centered Lewis acids bonded to one or more undesirable compounds at the metal center that can be processed into a cationic Lewis acid for use in a carbonylation catalyst.
  • the product stream or composition may include a catalyst that has not been spent or used up in the process of forming propiolactones.
  • the product stream or composition may include one or more unreacted epoxides or carbon monoxide.
  • the product stream may include a metal centered compound coupled with one or more polymers.
  • the one or more polymers may contain any polymerizable byproduct, reactant or both of a carbonylation reaction.
  • the one or more polymers may contain a residue of a propiolactone, a lactone, an epoxide, an ester, an alkoxide, an oligomer, or any combination thereof.
  • the one or more polymers may be a copolymer.
  • the one or more product streams or compositions may be subjected to one or more separation methods to remove the propiolactones, the organic compounds, the inorganic compounds, or any combination thereof.
  • the one or more product streams or compositions may be subjected to a mechanical separation method such as nanofiltration so that larger products than the propiolactone are removed.
  • Other separation methods may include vacuum distillation, gravity distillation, extraction, filtration, sedimentation, coagulation, centrifugation, or any combination thereof.
  • the one or more product streams or compositions may be subjected to a distillation process to remove any volatile compounds, such as propiolactone.
  • the distillation process may include one or more steps of introducing a solvent that is configured to separate any propiolactone components from the composition so that the propiolactone may be distilled.
  • the solvent may be aprotic.
  • the solvent may be a high boiling solvent that separates the propiolactone from the other components of the composition so that the propiolactone can be distilled off of the composition.
  • the solvent may be chosen based on having a higher boiling point than the boiling point of the propiolactone.
  • the composition containing the organic compounds, the inorganic compounds, the metal centered compound containing the polymer, or any combination thereof may be dissolved the solvent.
  • the solvent can be removed from the composition by any known separation or removal method. Distillation of the product stream may remove substantially all of the propiolactone so that the product stream or composition comprises one or more organic compounds, inorganic compounds, catalyst components, or any combination thereof that are considered byproducts to the propiolactone formation process. More details about distilling propiolactones, such as beta propiolactone, can be found in W02010/118128A1 , which is incorporated herein by reference in its entirety.
  • the one or more product streams or compositions may be subjected to a concentration or precipitation process to separate the one or more solvents used to separate the propiolactone from the composition containing the metal centered compound.
  • the solvent used to separate the propiolactone may be distilled from the composition so that the composition is free of solvent. If the solvent is distilled from the composition, the composition may have a solid or liquid form that is free of solvent. The solvent may be further separated by one or more steps of decantation, distillation, centrifugation, or any combination thereof.
  • the concentration step may be performed at a temperature, time, and pressure sufficient to separate the solvent from the other composition components.
  • the method may include one or more steps of contacting the product stream or the composition and a first solvent that is insoluble in the beta propiolactone to separate the propiolactone from the product stream.
  • the first solvent may be an aprotic solvent having a boiling point that is higher than the boiling point of the propiolactone.
  • the metal centered compound containing the polymer containing a residue of a propiolactone, an epoxide, or both may be soluble in the first solvent.
  • a second solvent may be added that the metal centered compound containing a polymer is insoluble in so that the metal centered compound is precipitated from the first solvent and the second solvent.
  • the second solvent may be a polar solvent.
  • the first solvent and the second solvent may be in any ratio sufficient to precipitate the metal centered compound containing the polymer containing a residue of a propiolactone, an epoxide, or both.
  • the first and second solvents can then be removed from the product stream by any known method of separating solid and liquid compounds.
  • the first and second solvents may be removed by filtering off the first and second solvents from the insoluble components of the product stream.
  • the insoluble components may include one or more of the organic compounds, inorganic compounds, or both discussed herein and the metal centered compound.
  • the precipitation step may be performed at ambient temperatures and pressure. In other examples, the precipitation step may be performed at a temperature of about 25 degrees Celsius or lower, about 20 degrees Celsius or lower, or about 15 degrees Celsius or lower.
  • the precipitation step may be performed at a temperature of about 0 degrees Celsius or more, about 5 degrees Celsius or more, or about 10 degrees Celsius or more. Additional conditions for precipitating the metal centered compound may be found in WO2015/171372A1 , which is incorporated herein in its entirety.
  • the composition may be subject to one or more steps to remove a portion of the organic compounds, inorganic compounds, or both.
  • an aqueous solvent can be contacted with the product stream or composition to dissolve a portion of the organic compounds, the inorganic compounds or both.
  • the aqueous solvent may be a polar solvent. If an aqueous solvent is added, the product stream can be filtered to leave the metal centered compound and a portion of the organic compounds that are insoluble in the aqueous solvent and/or the first solvent and the second solvents described in the precipitation step.
  • the metal centered compound may be decoupled from the polymer containing the residue of a propiolactone, an epoxide, or both by any means sufficient to form a Lewis acid containing a halogen or a Lewis acid containing one or more polar ligands.
  • the composition or product stream may be subjected to a thermolysis step or a contacting step with an acid compound.
  • the decoupling steps functions to remove the polymer from the metal centered compound and to bond or connect a halogen or a polar ligand to the metal centered compound so that the Lewis acid containing a halogen or a polar ligand are formed.
  • Forming the Lewis acid containing a halogen or a polar ligand are precursors to forming the recycled components for the regenerated catalyst.
  • thermolysis step or process may be performed to make one or more unsaturated acids.
  • the thermolysis step functions to denature the polymer, any organic compounds, or both in the product stream to form an unsaturated acid.
  • an unsaturated acid may be one or more of acrylic acid, polyacrylic acid, or any combination thereof.
  • the composition may be contacted with an acid compound and a solvent to form the Lewis acid containing a halogen.
  • any organic compounds contained within the metal centered compound may be decoupled from the metal centered compound, and the acid compound may deliver a halogen to the metal centered compound to form a Lewis acid containing a halogen.
  • the thermolysis step may be performed at any pressure sufficient to denature the polymer, any organic compounds, or both in the product stream to form an unsaturated acid.
  • the thermolysis step may be performed at pressure of about 133 Pa (1 torr) or more, about 3333 Pa (25 torr) or more, or about 6666 Pa (50 torr) or more.
  • the thermolysis step may be performed at a pressure of about 133322 Pa (1000 torr) or less, about 66661 Pa (500 torr) or less, or about 13332 Pa (100 torr) or less.
  • the thermolysis step may be performed at any temperature sufficient to denature the polymer, any organic compounds, or both in the product stream to form an unsaturated acid.
  • the thermolysis step may be performed at a temperature of about 130 degrees Celsius or more, about 160 degrees Celsius or more, or about 190 degrees Celsius or more.
  • the thermolysis step may be performed at a temperature of about 300 degrees Celsius or less, about 250 degrees Celsius or less, or about 220 degrees Celsius or less.
  • the thermolysis step may be performed for any amount of time sufficient to denature the polymer, any organic compounds, or both in the product stream to form an unsaturated acid.
  • the thermolysis step may be performed for about 15 seconds or more, about 15 minutes or more, or about 30 minutes or more.
  • the thermolysis step may be performed for about 24 hours or less, about 12 hours or less, or about 1 hour or less. Additional conditions or steps for the thermolysis process can be found in US10,065,914B1 , which is incorporated herein by reference in its entirety.
  • thermolysis step may be paired with other separation techniques described herein so that the one or more of the organic compounds, the inorganic compounds, the solvents, or both are removed from the composition that includes the metal centered compound, Lewis acid containing the halogen or polar ligand, or both.
  • the composition Before, after, or during the forming of the Lewis acid containing a halogen, the composition may be subjected to any filtering or removing step sufficient to remove any remaining organic compounds, inorganic compounds, or both that may interfere with the formation of the regenerated catalyst.
  • the feed stream or composition may be contacted with an acid compound to decouple the polymer containing the residue of the propiolactone, an epoxide, or both and the metal centered compound.
  • the contacting of the acid compound with the feed stream or composition functions to cleave or decouple the polymer containing the residue of a propiolactone, an epoxide, or both and the metal centered compound.
  • the composition, an acid compound, and a solvent may be contacted so that the solvent dissolves the metal centered compound and the acid compound cleaves or decouples the polymer containing a residue of the propiolactone, an epoxide, or both from the metal centered compound.
  • the components may be stirred by any agitation means known to a skilled artisan, such as utilizing a magnetic stir bar. The components may be stirred for any period of time sufficient to cleave or decouple the polymer containing the residue of a propiolactone, an epoxide, or both and the metal centered compound.
  • the components may be stirred for about 1 minute or more, about 30 minutes or more, or about 45 minutes or more.
  • the components may be stirred for about 180 minutes or less, about 120 minutes or less, or about 60 minutes or less.
  • the contacting step may be performed at ambient conditions including at least ambient temperature and pressure. Some components, such as a portion of the organic compounds, the inorganic compounds, or both, may not be soluble in the solvent, and the composition may be subjected to a step of filtering the insoluble components so that the composition includes the Lewis acid containing the halogen, the solvent, and any unreacted acid compounds remaining. This filtering step may include one or more of gravity filtration, or any combination thereof.
  • the composition may be subjected to a step of removing the acid compound, the solvent, or both so that a solid precipitate of the composition comprising the Lewis acid containing the halogen remains.
  • the removing step may include one or more vacuum filtration, distillation, or any combination thereof.
  • the composition including a Lewis acid containing a halogen may be subjected to one or more steps to regenerate the catalyst.
  • a contacting step is performed that uses an initial solvent to decouple the polymer and the metal centered compound and uses another subsequent solvent to precipitate a Lewis acid containing a halogen.
  • the composition, an initial solvent, and an acid compound may be contacted so that the initial solvent dissolves the metal centered compound and the acid compound cleaves or decouples the polymer containing a residue of the propiolactone, an epoxide, or both.
  • the components may be stirred by any agitation means known to a skilled artisan.
  • the components maybe stirred for any period of time sufficient to cleave or decouple the polymer containing a residue of the propiolactone, an epoxide, or both.
  • the components may be stirred for about 1 minute or more, about 30 minutes or more, or about 45 minutes or more.
  • the components may be stirred for about 180 minutes or less, about 120 minutes or less, or about 60 minutes or less.
  • the contacting step may be performed at ambient conditions including at least ambient temperature and pressure.
  • Some components, such as a portion of the organic compounds, the inorganic compounds, or both, may not be soluble in the initial solvent, and the composition may be subjected to a step of filtering the insoluble components so that the composition includes the Lewis acid containing the halogen, the initial solvent, and any unreacted acid compounds remaining.
  • This filtering step may include one or more of gravity filtration, centrifugation, decantation, or any combination thereof.
  • a subsequent solvent that is miscible in the initial solvent may be contacted with the composition including the Lewis acid containing the halogen, the initial solvent, and any unreacted acid compounds so that the Lewis acid containing the halogen is precipitated from the other components of the composition.
  • the initial solvent and the subsequent solvent may be described as first and second solvents, respectively.
  • the initial solvent may be a polar solvent, and the subsequent solvent may be an aprotic solvent.
  • the initial solvent and the polar solvent may be miscible in each other.
  • the initial solvent and the subsequent solvent may be added to the composition in a ratio sufficient to precipitate the Lewis acid containing the halogen, one or more organic compounds, or both.
  • the precipitated composition including the Lewis acid containing the halogen may be subjected to a filtering step to remove the initial solvent, the subsequent solvent, any remaining organic compounds, and any unreacted acid compound.
  • the filtering step may include one or more of gravity filtration, centrifugation, decantation, or any combination thereof.
  • the composition including a Lewis acid containing a halogen may be subjected to one or more steps to regenerate the catalyst.
  • Another method may be to utilize an extraction technique by contacting an acid compound with a combination of solvents to form a multi-phase composition that can distinctly separate undesirable components from the Lewis acid containing a halogen.
  • the composition may be contacted with an acid compound, aqueous solvent, and an organic solvent to form a slurry with multiple phase layers including an aqueous liquid phase, an organic liquid phase, and a precipitate.
  • the acid compound decouples the polymer and the metal centered compound and bonds the halogen to the metal centered compound to form the Lewis acid containing the halogen.
  • the aqueous solvent may be configured to dissolve one or more of the organic compounds, the polymer containing the residue of the propiolactone, an epoxide, or both, the inorganic compounds, or any combination thereof.
  • the organic solvent may be configured to dissolve the Lewis acid containing a halogen.
  • the precipitate may include any compound that is insoluble in the aqueous solvent or the organic solvent. In some examples, no precipitate is formed.
  • the components may be stirred by any agitation means known to a skilled artisan.
  • the components may be stirred for any period of time sufficient to form a multi-phase composition.
  • the components may be stirred for about 1 minute or more, about 30 minutes or more, or about 45 minutes or more.
  • the components may be stirred for about 180 minutes or less, about 120 minutes or less, or about 60 minutes or less.
  • the contacting step may be performed at ambient conditions including at least ambient temperature and pressure.
  • the components may be contacted for any period of time sufficient to form an organic phase, an aqueous phase, or any combination thereof.
  • the aqueous phase is removed so that the organic phase remains.
  • the aqueous phase may be removed by simple extraction or any other known technique sufficient to remove the aqueous phase from the precipitate, the organic phase, or both. If a precipitate is present, the precipitate may be filtered from the organic phase so that the composition includes the organic solvent and the Lewis acid containing the halogen.
  • the organic solvent may be removed from the Lewis acid containing the halogen by any suitable filtration or removal step, such as vacuum filtration.
  • the Lewis acid containing the halogen may be subjected to steps to regenerate the carbonylation catalyst without interference from other compounds.
  • an acid ion exchange resin or an anion exchange resin may be used to form the Lewis acid containing halogen.
  • the acid ion exchange resin functions to decouple the metal centered compound and the polymer and to physically separate the metal centered compound from the composition.
  • the anion exchange resin functions to exchange the polymer of the metal centered compound with a halogen to form the Lewis acid containing a halogen.
  • the acid ion exchange resin may be used to bond with the metal centered compound and, subsequently, another acid compound may be used to form the Lewis acid containing the halogen.
  • the metal centered compound, a polar solvent, and an acid ion exchange resin may be contacted so that the metal centered compound and the polymer containing the propiolactone are cleaved or decoupled, and the acid ion exchange resin may bond with the metal centered compound.
  • the acid ion exchange resin may be in the form of a bead, gel, or solid support.
  • the polar solvent may be configured to dissolve any components that have aqueous solubility, such as any of the inorganic compounds, the organic compounds, or both.
  • the polar solvent may be an aqueous solvent, such as water.
  • the combination of the metal centered compound and the exchange resin may be insoluble in the solvent.
  • the components dissolved in the aqueous solvent and the aqueous solvent may be removed from the composition so that a precipitate of the compounds that do not have aqueous solubility remain, for example, the acid ion exchange resin tethered to the metal centered compound, any organic compounds not having aqueous solubility, or both.
  • the acid ion exchange resin tethered to the metal centered compound may be separated from any remaining organic compounds so the composition includes acid ion exchange resin tethered to the metal centered compound.
  • One method could include dissolving the organic compounds in a solvent suitable for dissolving the organic compounds, like an aprotic solvent, and filtering the solvent and organic compounds from the composition through gravity filtration.
  • a solvent suitable for dissolving the organic compounds like an aprotic solvent
  • another acid compound could be contacted with the composition to decouple the metal centered compound from the exchange resin and deliver a halogen to the metal centered compound so that a Lewis acid containing a halogen is formed.
  • the acid ion exchange resin may be recovered and used for additional decoupling steps of the metal centered compound and the polymer containing the residue of the propiolactone, an epoxide, or both.
  • the anion exchange resin may directly decouple the metal centered compound and the polymer containing the residue of a propiolactone, an epoxide, or both, and the Lewis acid containing the halogen may be formed without adding an additional acid compound.
  • a polar solvent may dissolve the metal centered compound and other components so that the composition can be simply moved across an anion exchange resin that is a solid support.
  • the anion exchange resin may be a bead.
  • the metal centered compound may be dissolved in the solvent, and then moved over the anion exchange resin so that the anion exchange resin bonds with the polymer containing the residue of the propiolactone, an epoxide, or both, one or more organic compounds, or both.
  • the anion exchange resin may separate the polymer, the one or more organic compounds, or both from the composition so that the composition includes the polar solvent and the Lewis acid containing the halogen. After contacting with metal centered compound with the exchange resin to form the Lewis acid containing a halogen, the anion exchange resin containing the one or more organic compounds, the polymer, or both may be removed from the composition.
  • the composition that is liquid and including the metal centered compound containing a polymer may be inserted into a vessel containing the anion exchange resin, run across the anion exchange resin in the vessel to exchange the polymer and the halogen to form the Lewis acid containing a halogen, and exit the vessel at an outlet so that the liquid composition includes a Lewis acid containing the halogen.
  • the other components that are not captured on the anion exchange resin may be removed by gravity filtration, vacuum filtration, or any combination thereof.
  • the solvent may be separated from the composition including the Lewis acid containing the halogen by filtration, such as vacuum filtration, or any combination thereof.
  • the Lewis acid containing the halogen may be subjected to one or more steps to regenerate the carbonylation catalyst.
  • the contacting conditions may be as follows to sufficiently form either an acid ion exchange resin tethered to the metal centered compound, the Lewis acid containing a halogen, or both:
  • the components may be stirred by any agitation means known to a skilled artisan.
  • the components may be stirred for about 1 minute or more, about 45 minutes or more, or about 2 hours or more.
  • the components may be stirred for about 24 hours or less, about 12 hours or less, or about 4 hours or less.
  • the contacting step may be performed at ambient conditions including ambient temperature and pressure.
  • the contacting conditions may be similar in regards to agitation, time, temperature, pressure, or any combination thereof.
  • the filtering or removing steps taught herein function to remove from the composition any unwanted components that may interfere with the formation of a reclaimed or regenerated catalyst.
  • one or more of solvents, polymers, exchange resins, unreacted acid compounds, inorganic compounds, organic compounds, or any combination thereof may be removed from the composition so that the carbonylation catalyst may be regenerated from the Lewis acid containing a halogen or a polar ligand and have catalytic activity with one or more of succinic anhydride, propiolactone, or an epoxide.
  • the filtering or removing steps may include one or more of vacuum filtration, gravity filtration, centrifugation, decantation, precipitation, phase layer extraction, or any combination thereof.
  • the filtering or removing steps may utilize any method sufficient to separate one or more of solvents, polymers, exchange resins, unreacted acid compounds, inorganic compounds, organic compounds, or any combination thereof and the Lewis acid containing the halogen or a polar ligand, the metal centered compound, or any combination thereof.
  • the filtering or removing steps may remove a single type of compound at a time, such as a precipitate, or may remove a collection of compounds at a time, such as all components dissolved in a solvent.
  • the filtering or removing steps may include forming multiple phases including one or more of one or more organic phases, an aqueous phase, a solid phase (i.e., a precipitate), one or more gaseous or vapor phases, or any combination thereof.
  • the one or more separation or removal steps/methods described herein may be performed at any temperature, pressure, agitation rate, time, or any combination thereof sufficient to separate or remove any undesirable component from the composition including the metal centered compound, the Lewis acid containing the halogen or polar ligand, or any combination thereof.
  • the method may include one or more regeneration steps that function to decouple or cleave either a polymer containing a residue of a propiolactone, an epoxide, or both or a halogen from the metal centered compound and/or Lewis acid.
  • the one or more regeneration steps function to modify a metal centered compound and/or a Lewis acid to a regenerated carbonylation catalyst comprising a Lewis acid and a metal carbonyl.
  • the regeneration step may include contacting the metal centered compound containing a polymer containing a residue of a propiolactone, an epoxide, or both or the Lewis acid containing a halogen with a polar ligand, a metal carbonyl additive, or both.
  • the metal carbonyl additive may contain at least a metal carbonyl that is anionic and a cationic group that is configured to cleave and bond with the polymer of the metal centered compound.
  • the cationic group may be one or more of an alkali metal, Ph 3 Si-, R 3 S1-, any counterion sufficient to ionically bond and/or balance the metal carbonyl, or any combination thereof, where R is independently selected from a phenyl, halophenyl, hydrogen, alkyl, alkylhalo, alkoxy, or any combination thereof.
  • R is independently selected from a phenyl, halophenyl, hydrogen, alkyl, alkylhalo, alkoxy, or any combination thereof.
  • the metal carbonyl additive cleaves or decouples the polymer
  • the polymer may couple with the cationic group, and the polymer and cationic group could be removed via any filtration or removal means described herein.
  • the metal carbonyl cleaves the halogen from the metal centered compound and is contacted with the polar compound
  • the halogen bonds with the cationic group of the metal carbonyl additive and the Lewis acid containing the polar compound is formed. Additional polymers can be removed by any other removal or separation steps described herein.
  • the metal carbonyl additive cleaves or decouples the polymer
  • the Lewis acid may combine with the polar ligand to form a cationic species.
  • the Lewis acid containing the polar ligand then contacts with the metal carbonyl that is anionic of the metal carbonyl additive and forms the regenerated carbonylation catalyst.
  • reaction (I) An example of contacting a polar ligand, a metal carbonyl additive, and the Lewis acid containing a halogen is shown in reaction (I).
  • TPPAI-CI tetraphenyl porphyrin aluminum chloride complex
  • NaCo(CO)4 is the metal additive
  • THF tetrahydrofuran
  • TPPAI(THF) 2 -Co(CO)4 is the regenerated carbonylation catalyst.
  • the steps to regenerate the catalyst may be performed under conditions that are moisture and oxygen free.
  • the regeneration steps may be performed within a dry glove box, on a Schlenk line, or in a reactor under an inert atmosphere.
  • the regeneration steps may be performed under a nitrogen, argon, or any other inert gas.
  • the Lewis acid, the polar ligand, the metal carbonyl, or any combination thereof may be contacted and agitated by stirring for any period of time sufficient to form the regenerated catalyst.
  • the period of time for stirring the components may be about 5 minutes or more, about 30 minutes or more, about 60 minutes or more.
  • the period of time for stirring the components may be about 24 hours or less, about 12 hours or less, or about 6 hours or less.
  • the components in the regeneration step may be completed under ambient temperature and/or pressure. Additional steps to make the regenerated catalyst can be found in US6,852,865B2 and US8,481 ,756B1 , both of which are included herein by reference in their entirety.
  • the acid compound may function to cleave the polymer from the metal centered compound and to deliver a halogen to the metal centered compound.
  • the acid compound may contain a halogen such as fluorine, chlorine, bromine, iodine, or a combination thereof.
  • the acid compound may be any compound capable of delivering a halogen to the metal centered compound to form a Lewis acid containing a halogen.
  • the acid compound may be HF, HCI, HBr, HI, or any combination thereof.
  • the acid compound When mixed or dissolved with an aqueous solvent, such as water, the acid compound may have a molarity of 1 mol/dm 3 or more, 1 .5 mol/dm 3 or more, 1 .8 mol/dm 3 or more, or 2.0 mol/dm 3 or more.
  • the acid compound may have a molarity of 3.5 mol/dm 3 or less, 3.0 mol/dm 3 or less, 2.8 mol/dm 3 or less, or 2.5 mol/dm 3 or less.
  • the acid compound may be an exchange resin, such as an acid ion exchange resin, an anion exchange resin, or both.
  • the acid ion exchange resin, the anion exchange resin, or both may include one or more of a quaternary ammonium compound, a sulfonic group, or any combination thereof.
  • the acid ion exchange resin, the anion exchange resin, or both may be polystyrene based, macro-porous, styrene-divinyl benzene copolymer, or any combination thereof. Any of the exchange resins may be anionic or cationic.
  • the acid compound may be any compound sufficient to cleave or decouple a polymer from a metal centered compound and deliver a halogen compound to the metal centered compound to form a Lewis acid containing a halogen.
  • the acid compound may be a metal carbonyl additive that comprises one or more cationic trisubstituted silyl groups having a structure corresponding to R 3 S1, and one or more anionic metal groups, where R is independently selected from a phenyl, halophenyl, hydrogen, alkyl, alkylhalo, alkoxy, or any combination thereof.
  • the carbonylation catalyst as described herein functions to catalyze a reaction of an epoxide and carbon monoxide to produce one or more propiolactones and other products.
  • the carbonylation catalyst includes at least a metal carbonyl that is anionic and a Lewis acid that is cationic.
  • the metal carbonyl of the carbonylation catalyst functions to provide the anionic component of the carbonylation catalyst.
  • the carbonylation catalyst may include one or more, two more, or a mixture of metal carbonyls.
  • the metal carbonyl may be capable of ring-opening an epoxide and facilitating the insertion of CO into the resulting metal carbon bond.
  • the metal carbonyl may include an anionic metal carbonyl moiety.
  • the metal carbonyl compound may include a neutral metal carbonyl compound.
  • the metal carbonyl may include a metal carbonyl hydride or a hydrido metal carbonyl compound.
  • the metal carbonyl may be a pre-catalyst which reacts in situ with one or more reaction components to provide an active species different from the compound initially provided.
  • the metal carbonyl includes an anionic metal carbonyl species in some examples, the metal carbonyl may have the general formula [Q d M’ e (CO) w ] y+ , where Q is an optional ligand, M’ is a metal atom, d is an integer between 0 and 8 inclusive, e is an integer between 1 and 6 inclusive, w is a number such as to provide the stable anionic metal carbonyl complex, and y is the charge of the anionic metal carbonyl species.
  • the metal carbonyl may include monoanionic carbonyl complexes of metals from groups 5, 7 or 9 of the periodic table or dianionic carbonyl complexes of metals from groups 4 or 8 of the periodic table.
  • the metal carbonyl may contain cobalt, manganese, ruthenium, or rhodium.
  • Exemplary metal carbonyls may include [Co(CO)4] , [Ti(CO)e] 2 , [V(CO) 6 ] , [Rh(CO)4] , [Fe(CO) 4 ] 2 , [RU(CO) 4 ] 2 , [OS(CO) 4 ] 2 , [Cr 2 (CO)i 0 ] 2 -, [Fe 2 (CO) 8 ] 2 -, [Tc(CO) 5 ]-, [Re(CO) 5 ]-, and [Mn(CO) 5 ] .
  • the metal carbonyl may be a mixture of two or more anionic metal carbonyl complexes in the carbonylation catalysts used in the methods.
  • a metal carbonyl additive functions to deliver a metal carbonyl to a Lewis acid that is suitable to combine and form the regenerated carbonylation catalyst.
  • the metal carbonyl additive may function to decouple a halogen or a polymer containing a residue of a propiolactone, an epoxide, or both from a metal centered compound to form the regenerated carbonylation catalyst that includes the Lewis acid and metal carbonyl combination.
  • the metal carbonyl additive includes at least a metal carbonyl as described herein and a cationic compound.
  • the cationic compound may include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, radium, or any combination thereof.
  • the metal carbonyl additive may be a salt.
  • the metal carbonyl additive may be a silicon salt in the form of R 3 S1-, where R is independently selected from a phenyl, halophenyl, hydrogen, alkyl, alkylhalo, alkoxy, or any combination thereof.
  • the Lewis acid functions to provide the cationic component of the carbonylation catalyst.
  • the Lewis acid may be a metal centered compound, a metal complex, or both that is configured to be anionically balanced by one or more metal carbonyls.
  • the Lewis acid component of the carbonylation catalyst may include a dianionic tetradentate ligand.
  • the Lewis acid may include one or more porphyrin derivatives, salen derivatives, dibenzotetramethyltetraaza[14]annulene (tmtaa) derivatives, phthalocyaninate derivatives, derivatives of the Trost ligand, tetraphenylporphyrin derivatives, tetramethyl-tetra-aza-annulene type, and corrole derivatives.
  • the carbonylation catalysts used in the disclosed methods include a cationic Lewis acid including a metal complex
  • the metal complex has the formula [(L c ) v M b ] z+ , where:
  • L is a ligand where, when two or more L are present, each may be the same or different;
  • M is a metal atom where, when two M are present, each may be the same or different; v is an integer from 1 to 4 inclusive; b is an integer from 1 to 2 inclusive; and z is an integer greater than 0 that represents the cationic charge on the metal complex.
  • the Lewis acid or metal centered compound may have a structure of metal complex I or II.
  • the metal complex may be the following configuration:
  • M is a metal atom coordinated to the multidentate ligand; and a is the charge of the metal atom and ranges from 0 to 2.
  • the metal complexes include structures according to metal complex II.
  • the Lewis acid may have the metal complex having the formula of metal complex II:
  • M1 is a first metal atom
  • M2 is a second metal atom; and comprises a multidentate ligand system capable of coordinating both metal atoms.
  • the Lewis acid may include or be one or more of porphyrin derivatives (ligand structure 1), salen derivatives (ligand structure 2), dibenzotetramethyltetraaza[14]annulene (tmtaa) derivatives (ligand structure 3), phthalocyaninate derivatives (ligand structure 4), derivatives of the Trost ligand (ligand structure 5), tetraphenylporphyrin derivatives (ligand structure 6), and corrole derivatives (ligand structure 7).
  • porphyrin derivatives ligand structure 1
  • salen derivatives ligand structure 2
  • dibenzotetramethyltetraaza[14]annulene tmtaa
  • ligand structure 3 phthalocyaninate derivatives
  • derivatives of the Trost ligand ligand structure 5
  • tetraphenylporphyrin derivatives ligand structure 6
  • corrole derivatives ligand structure 7
  • M is a metal; where each ligand structure has an ionic charge of 0 to +4; where R la , R la' , R 2a , R 2a' , R 3a , R 3a' , R d , and R c at each occurrence is independently hydrogen, halogen, -OR 4 , -NR y 2 , -SR, -CN, - N0 2 , -S0 2 R y , -SOR y , -S0 2 NR y 2 ; -CNO, -NRS0 2 R y , -NCO, -N 3 , -SiR 3 ; or an optionally substituted group selected from the group consisting of Ci- 2 o aliphatic; Ci- 20 heteroaliphatic having 1 -4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6 to 10 membered aryl; 5 to 10 membered heteroaryl having 1 -4 heteroatoms independently selected from
  • R 4a is selected from the group consisting of: f) g) where R c is described above and two or more R c groups may be taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more rings; when two R c groups are attached to the same carbon atom, they may be taken together along with the carbon atom to which they are attached to form a moiety selected from the group consisting of: a 3- to 8-membered spirocyclic ring, a carbonyl, an oxime, a hydrazone, an imine; and an optionally substituted alkene;
  • M1 and M2 may each independently be a metal atom selected from the periodic table groups 2-13, inclusive.
  • M, M1 , M2, or a combination thereof may be a transition metal selected from the periodic table groups 4, 6, 11 , 12 and 13.
  • M, M1 , M2, or a combination thereof may be aluminum, chromium, titanium, indium, gallium, zinc, cobalt, copper, or any combination thereof.
  • M1 and M2 may be the same or different metals.
  • M1 and M2 may be the same metal but have different oxidation states.
  • M, M1 , M2, or a combination thereof may have an oxidation state of +2.
  • M1 or M2 may be Zn(ll), Cu(ll), Mn(ll), Co(ll), Ru(ll), Fe(ll), Co(ll), Rh(ll), Ni(ll), Pd(ll) or Mg(ll).
  • M1 is Cu(ll).
  • M, M1 , M2, or a combination thereof may be Zn(ll), Cu(ll), Mn(ll), Co(ll), Ru(ll), Fe(ll), Co(ll), Rh(ll), Ni(ll), Pd(ll) or Mg(ll).
  • M, M1 , M2, or a combination thereof may have an oxidation state of +3.
  • M, M1 , M2, or a combination thereof may be Al(lll), Cr(lll), Fe(lll), Co(lll), Ti(lll) In(lll), Ga(lll) or Mn(lll).
  • M, M1 , M2, or a combination thereof may have an oxidation state of +4.
  • M, M1 , M2, or a combination thereof may be Ti(IV) or Cr(IV).
  • one or more polar ligands may coordinate to M, M1 , M2, or a combination thereof and fill the coordination valence of the metal atom.
  • the Lewis acid may include any number of polar ligands to fill the coordination valence of the metal atom.
  • the Lewis acid may include one or more polar ligands, two or more polar ligands, three or more polar ligands, four or more polar ligands, or a plurality of polar ligands.
  • the polar ligand may be a solvent.
  • the polar ligand may be any compound with at least two free valence electrons.
  • the polar ligand may be aprotic.
  • the compound may be tetrahydrofuran, diethyl ether, acetonitrile, carbon disulfide, pyridine, epoxide, ester, lactone, or a combination thereof.
  • the solvent may function to dissolve or precipitate one or more of the components discussed herein.
  • the solvent may be selected from any solvent discussed herein or a mixtures of solvents.
  • the solvent may be polar, nonpolar, aprotic, protic, aqueous, organic, or any combination thereof.
  • the solvent may be an aprotic solvent that functions to dissolve one or more compounds that lack one or more protic elements.
  • the aprotic solvent may be configured to dissolve the one or more organic compounds, the metal compound containing a polymer, or both.
  • the aprotic solvent may separate one or more lactones from a product stream of a carbonylation reaction.
  • the aprotic solvent may be soluble in one or more other nonpolar or polar solvents.
  • the aprotic solvent may be insoluble with one or more of a carboxylic acid, a lactone, a or any combination thereof.
  • the aprotic solvent may be a high boiling solvent to facilitate filtering or removing of volatile components (e.g., lactones) of the composition.
  • the aprotic solvent may be combined with a second solvent that is miscible in the aprotic solvent to precipitate components that are insoluble in the second solvent.
  • the aprotic solvent may be selected to form an organic phase layer that is distinct from an aqueous phase layer, a precipitate, or both.
  • the solvent may be a polar solvent that functions to dissolve one or more components of the composition that have polar features.
  • the polar solvent may function to dissolve a Lewis acid and to coordinate a metal center of a Lewis acid.
  • the polar solvent may be miscible in one or more other aprotic or protic solvents.
  • the polar solvent may be configured to be miscible in one or more second solvents and be insoluble in a component dissolved in the second solvent so the component dissolved in the second solvent is precipitated.
  • the polar solvent may dissolve one or more of the inorganic components, the organic compounds, the metal centered compound containing a polymer, the Lewis acid, the metal carbonyl, the metal carbonyl additive, or any combination thereof.
  • the polar solvent may be selected to form an aqueous phase layer or an organic phase layer that is distinct from another aqueous phase layer, another organic phase layer, a precipitate, or some combination of different phase layers.
  • the polar solvent may be one or more of water, methanol, ethanol, propanol, tetrahydrofuran, methyltetrahydrofuran, diethyl ether, sulfolane, pyridine, diethyl ether, 1 ,4-dioxane, acetonitrile, ethyl acetate, dimethoxy ethane, acetone, dichloromethane, or any combination thereof.
  • FIG. 1 shows methods 1 , 1b, and 2 that reclaim or regenerate the carbonylation catalyst.
  • Methods 1 and 1b show the reclamation of a tetraphenyl porphyrin aluminum chloride from a starting composition including the metal centered compound containing a polymer and poly- 3-hydroxypropionate, but this method could be applied to a composition that includes one or more other byproducts from a propiolactone product stream, such as any of the organic or inorganic compounds discussed herein.
  • Method 1 includes dissolving the mixture of tetraphenyl porphyrin aluminum complex (i.e., a metal centered compound) containing a polymer containing a residue of propiolactone, an epoxide, or both and poly-3-hydroxypropionate with a solution of methanol and HCI to cleave any polymer from the metal centered compound having an aluminum group and regenerate tetraphenyl porphyrin aluminum chloride catalyst precursor (i.e., the Lewis acid containing a halogen). The solution is filtered to remove the polymer and poly-3-hydroxypropionate, which have limited solubility in methanol.
  • tetraphenyl porphyrin aluminum complex i.e., a metal centered compound
  • a solution of methanol and HCI to cleave any polymer from the metal centered compound having an aluminum group
  • the time of contact between the poly-3-hydroxypropionate, the polymer, and the HCI solution is limited to reduce the amount of degradation of the polymer. Degradation of the polymer can add new impurities to the mixture that would need to be subsequently removed.
  • the filtrate of methanol, unreacted HCI, and tetraphenyl porphyrin aluminum chloride is then concentrated to dryness removing the volatile MeOH and HCI while leaving behind the tetraphenyl porphyrin aluminum chloride.
  • Method 1b includes dissolving the mixture of tetraphenyl porphyrin aluminum complex (i.e., a metal centered compound) containing a polymer containing a residue of propiolactone, an epoxide, or both and poly-3-hydroxypropionate with a solution of ethanol and HCI to cleave any polymer from the aluminum metal center and regenerate tetraphenyl porphyrin aluminum chloride catalyst precursor (i.e., the Lewis acid containing a halogen). The solution is filtered to remove poly- 3-hydroxypropionate and the polymer, which have limited solubility in ethanol.
  • tetraphenyl porphyrin aluminum complex i.e., a metal centered compound
  • a solution of ethanol and HCI to cleave any polymer from the aluminum metal center and regenerate tetraphenyl porphy
  • the filtrate of ethanol, unreacted HCI, and tetraphenyl porphyrin aluminum chloride is contacted with hexane, which is miscible in ethanol, to precipitate the tetraphenyl porphyrin aluminum chloride.
  • hexane which is miscible in ethanol
  • the precipitated cake of the tetraphenyl porphyrin aluminum chloride is recovered.
  • the reclaimed tetraphenyl porphyrin aluminum chloride can be regenerated to the catalyst using any technique described herein.
  • the reclaimed tetraphenyl porphyrin aluminum chloride can be contacted with a metal carbonyl salt and a polar ligand (e.g., tetrahydrofuran) to form the regenerated carbonylation catalyst.
  • a metal carbonyl salt and a polar ligand e.g., tetrahydrofuran
  • Method 2 includes dissolving the tetraphenyl porphyrin aluminum chloride and Ph 3 Si- Co(CO)4 in tetrahydrofuran to cleave the polymer containing the residue of the propiolactone, an epoxide, or both from the tetraphenyl porphyrin aluminum complex. Subsequently, the cobaltate anion is delivered to the tetraphenyl porphyrin aluminum chloride to regenerate the carbonylation catalyst.
  • the Ph 3 SiOR is insoluble in the tetrahydrofuran and Ph 3 SiOR and the poly-3- hydroxypropionate is removed by gravity filtration.
  • FIG. 2 shows another method for reclaiming the carbonylation catalyst.
  • the method includes dissolving a product composition from a propiolactone reaction and Amberlyst-15 (A-15) macro-porous sulfonic acid ion exchange resin in water to cleave the polymer containing a residue of propiolactone, an epoxide, or both from the tetraphenyl porphyrin aluminum complex.
  • A-15 Amberlyst-15
  • A-15 macro-porous sulfonic acid ion exchange resin is tethered to the tetraphenyl porphyrin aluminum complex and insoluble in water, aqueous soluble components, such as hydrolyzed poly- 3-hydroxypropionate, succinic anhydride, and polyethylene glycol, are removed by gravity filtration.
  • the precipitate of A-15 macro-porous sulfonic acid ion exchange resin is tethered to the tetraphenyl porphyrin aluminum complex and poly-3-hydroxypropionate is contacted with chloroform to dissolve the poly-3-hydroxypropionate so that a precipitate of A-15 macro-porous sulfonic acid ion exchange resin that is tethered to the tetraphenyl porphyrin aluminum complex is collected.
  • the collected precipitate is contacted with HCI to remove the tetraphenyl porphyrin aluminum complex from the A-15 macro-porous sulfonic acid ion exchange resin, and a chloride is delivered to form a tetraphenyl porphyrin aluminum chloride.
  • FIG. 3 shows another method for reclaiming the carbonylation catalyst. This method includes dissolving the tetraphenyl porphyrin aluminum complex with methanol and passing the solution over a bed or column of an anion exchange resin.
  • the anion exchange resin captures any poly-3-hydroxypropionate and the polymer from the tetraphenyl porphyrin aluminum complex.
  • the anion exchange resin further delivers a chloride to the tetraphenyl porphyrin aluminum complex.
  • the tetraphenyl porphyrin aluminum chloride can be collected as a precipitate.
  • FIG. 4 shows another method for reclaiming the carbonylation catalyst.
  • the method includes the concurrent addition of water and HCI to a stream of catalyst residue, succinic anhydride, poly-3-hydroxypropionate, polyethylene glycol, and other associated polymers dissolved and/or slurried in diethyl ether or ethyl acetate to achieve phase separation between the organic and aqueous layers.
  • the HCI clips any bound polymer from the aluminum metal center while the tetraphenyl porphyrin aluminum chloride is formed and extracted into the organic phase.
  • the succinic anhydride, polyethylene glycol, and other small acrylate monomers formed from breakdown of the poly-3-hydroxy propionate are extracted into the aqueous phase and removed from the bottom of the separator.
  • the poly-3-hydroxy propionate is collected by filtration since poly-3-hydroxy propionate is expected to be insoluble in both the aqueous and organic solvents.
  • the tetraphenyl porphyrin aluminum chloride is separated from the diethyl ether by vacuum filtration.
  • FIG. 5 shows another method for reclaiming the carbonylation catalyst. This method involves thermolyzing the polymer, the poly-3-hydoxypropionate, or both to make acrylic acid, polyacrylic acid, or both.
  • the remaining composition is mostly comprised of tetraphenyl porphyrin aluminum complex without an associated polymer or with a simple monomer attached.
  • the composition may be subjected to multiple separation steps described herein to remove any other organic or inorganic compounds still remaining in the composition.
  • the composition is then contacted with HCI to generate the tetraphenyl porphyrin aluminum chloride.
  • the methods of FIGS. 2-5 can further be subjected to a regeneration step, as described herein, to reform the carbonylation catalyst.
  • the reclaimed tetraphenyl porphyrin aluminum chloride can be contacted with a metal carbonyl additive and a polar ligand (e.g., tetrahydrofuran) to form the regenerated carbonylation catalyst.
  • a metal carbonyl additive e.g., tetrahydrofuran
  • a polar ligand e.g., tetrahydrofuran
  • a method comprising decoupling one or more polymers containing the residue of a propiolactone, an epoxide, or both from a metal centered compound in a composition to form a Lewis acid containing one or more polar ligands, a Lewis acid containing one or more acid ion exchange resins, or a Lewis acid containing a halogen; and removing one or more organic compounds, inorganic compounds, the one or more polymers, or any combination thereof from the composition.
  • the method further includes forming a regenerated carbonylation catalyst by one or more of the following: contacting a metal carbonyl and the Lewis acid containing the one or more polar ligands; or contacting a metal carbonyl additive and the Lewis acid containing the halogen with one or more polar ligands.
  • the one or more polar ligands include one or more of tetrahydrofuran, methanol, ethanol, ethyl acetate, diethyl ether, or any combination thereof.
  • the one or more organic compounds include one or more of succinic anhydride, polyethylene glycol, poly-3- hydroxypropionate, copolymers of polyethylene glycol, poly-3-hydroxypropionate succinic acid, another monomer, copolymer, or polymer derived from the production of lactones, or any combination thereof.
  • metal carbonyl additive includes one or more of a cobalt salt, Ph 3 Si-Co(CO)4, PR3Si-Co(CO)4, alkali metal- Co(CO)4, or any combination thereof.
  • Lewis acid is one or more of a porphyrin, Salen- type, tetramethyl-tetra-aza-annulene type, or any combination thereof.
  • the metal centered compound includes one or more of a multidentate ligand, a diatomic ligand, an aluminum metal center, a chromium metal center, a polymer, or any combination thereof.
  • the Lewis acid includes one or more of a multidentate ligand, a diatomic multidentate ligand, an aluminum metal center, a chromium metal center, or any combination thereof.
  • halogen may include one or more of fluorine, chlorine, bromine, iodine, or any combination thereof.
  • aprotic solvent includes one or more of ethyl acetate, diethyl ether, toluene, chloroform, dichloromethane, or any combination thereof.
  • aqueous solvent includes one or more of water, methanol, or both.
  • FIGS. 6A to 7 show characterization and comparison of producing a tetraphenyl porphyrin aluminum chloride complex.
  • FIG. 8 depicts the regenerated catalyst that is formed from the reaction of recovered tetraphenyl porphyrin aluminum chloride and NaCo(CO)4.
  • the NMR analysis is conducted on a Bruker Advance II l-HD spectrometer operating at 400.3 MHz and/or a Varian Mercury spectrometer operating at 300.1 MHz. Each of the samples are dissolved in CDCI3 or THF -d8 before testing.
  • FIG. 6A shows a proton NMR analysis of a synthesized tetraphenyl porphyrin aluminum chloride complex, which is a zoomed view of the left box of FIG. 7. These samples are dissolved in CDCI3 and are collected on a Bruker Advance lll-HD spectrometer operating at 400.3 MHz.
  • the synthesized tetraphenyl porphyrin aluminum chloride complex is formed from standard metalation of meso-tetraphenyl porphyrin with Et2AICI.
  • FIG. 6B shows a zoomed in proton NMR analysis of a recovered tetraphenyl porphyrin aluminum chloride complex using a recovery method described herein, such as method 1 of FIG. 1 .
  • FIGS. 6A and 6B show the key peaks of the recovered tetraphenyl porphyrin aluminum chloride match the key peaks of the synthesized tetraphenyl porphyrin aluminum chloride, and therefore, the desired recovered compound has been shown.
  • FIG. 7 shows a proton NMR analysis of an analysis of isolated material from the reaction of catalyst residue and 2 Molar HCI to generate the tetraphenyl porphyrin aluminum chloride complex.
  • the left box shows the recovered tetraphenyl porphyrin aluminum chloride complex
  • the right box shows residual polymer that has been decoupled with the tetraphenyl porphyrin aluminum complex.
  • the left box is highlighted as a zoomed-in snippet in FIG. 6B and the methods to show the compound and subsequent data of FIGS.6B and 7 are the same.
  • FIG. 8 shows a proton NMR analysis of isolated material from the reaction of the recovered tetraphenyl porphyrin aluminum chloride and Na(Co(CO)4 to yield tetraphenyl porphyrin aluminum bis tetrahydrofuran tetracarbonyl cobaltate.
  • Samples of synthesized and recovered tetraphenyl porphyrin aluminum bis tetrahydrofuran tetracarbonyl cobaltate are dissolved in TFIF -d8 in an inert atmosphere (i.e, a glovebox).
  • the recovered tetraphenyl porphyrin aluminum chloride complex is recovered using a method described herein, such as method 1 of FIG. 1 .
  • the data is collected on a Varian Mercury spectrometer operating at 300.1 MFIz.
  • the data shows the peaks of the recovered tetraphenyl porphyrin aluminum bis tetrahydrofuran tetracarbonyl cobaltate matches the synthesized tetraphenyl porphyrin aluminum bis tetrahydrofuran tetracarbonyl cobaltate.
  • FIG. 9 shows a reaction FTIR Spectroscopy plot showing the catalytic generation of beta propiolactone using recovered carbonylation catalyst.
  • a catalyst from the recovered tetraphenyl porphyrin aluminum chloride complex is mixed with TFIF and NaCo(C0 4 ) to form a recycled carbonylation catalyst.
  • the recycled carbonylation catalyst is mixed with ethylene oxide and carbon monoxide in TFIF, and a reaction ensues.
  • the top line is beta propiolactone; the middle line is ethylene oxide, and the bottom line is succinic anhydride.
  • some catalytic activity is shown in synthesizing succinic anhydride, and more catalytic activity is shown in synthesizing beta propiolactone.

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Abstract

Est divulgué ici un procédé consistant à séparer un ou plusieurs polymères contenant le résidu d'une propiolactone, d'un époxyde, ou des deux à partir d'un composé à centre métallique dans une composition pour former un acide de Lewis contenant un ou plusieurs ligands polaires, un acide de Lewis contenant une ou plusieurs résines échangeuses d'ions acides, ou un acide de Lewis contenant un halogène. L'invention concerne en outre l'élimination d'un ou de plusieurs composés organiques, de composés inorganiques, du ou des polymères, ou de toute combinaison de ces derniers à partir de la composition. Le procédé consiste en outre à former un catalyseur de carbonylation régénéré par la mise en contact d'un carbonyle métallique et de l'acide de Lewis contenant le ou les ligands polaires et/ou par la mise en contact d'un additif de carbonyle métallique et de l'acide de Lewis contenant l'halogène avec un ou plusieurs ligands polaires.
PCT/US2022/017147 2021-03-02 2022-02-21 Procédé de récupération et/ou de régénération de composants de catalyseur WO2022187010A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003050154A2 (fr) * 2001-12-06 2003-06-19 Cornell Research Foundation, Inc. Carbonylation catalytique d'heterocycles a trois et quatre chainons
WO2010118128A1 (fr) 2009-04-08 2010-10-14 Novomer, Inc. Procédé de production de bêta-lactone
US8481756B1 (en) 2007-09-04 2013-07-09 Cornell Research Foundation, Inc. Succinic anhydrides from epoxides
WO2014008232A2 (fr) 2012-07-02 2014-01-09 Novomer, Inc. Procédé de production d'acrylate
WO2015171372A1 (fr) 2014-05-05 2015-11-12 Novomer, Inc. Procédés de recyclage de catalyseurs
WO2016130998A1 (fr) * 2015-02-13 2016-08-18 Novomer, Inc. Procédés de carbonylation continue
US10065914B1 (en) 2017-04-24 2018-09-04 Novomer, Inc. Thermolysis of polypropiolactone to produce acrylic acid

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003050154A2 (fr) * 2001-12-06 2003-06-19 Cornell Research Foundation, Inc. Carbonylation catalytique d'heterocycles a trois et quatre chainons
US6852865B2 (en) 2001-12-06 2005-02-08 Cornell Research Foundation, Inc. Catalytic carbonylation of three and four membered heterocycles
US8481756B1 (en) 2007-09-04 2013-07-09 Cornell Research Foundation, Inc. Succinic anhydrides from epoxides
WO2010118128A1 (fr) 2009-04-08 2010-10-14 Novomer, Inc. Procédé de production de bêta-lactone
WO2014008232A2 (fr) 2012-07-02 2014-01-09 Novomer, Inc. Procédé de production d'acrylate
WO2015171372A1 (fr) 2014-05-05 2015-11-12 Novomer, Inc. Procédés de recyclage de catalyseurs
WO2016130998A1 (fr) * 2015-02-13 2016-08-18 Novomer, Inc. Procédés de carbonylation continue
US10065914B1 (en) 2017-04-24 2018-09-04 Novomer, Inc. Thermolysis of polypropiolactone to produce acrylic acid

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