WO2019123055A1 - Valorisation de gaz de synthèse par hydroformylation de formaldéhyde à l'aide de complexes organométalliques hétérogénéisés de métaux du groupe viii - Google Patents

Valorisation de gaz de synthèse par hydroformylation de formaldéhyde à l'aide de complexes organométalliques hétérogénéisés de métaux du groupe viii Download PDF

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Publication number
WO2019123055A1
WO2019123055A1 PCT/IB2018/059420 IB2018059420W WO2019123055A1 WO 2019123055 A1 WO2019123055 A1 WO 2019123055A1 IB 2018059420 W IB2018059420 W IB 2018059420W WO 2019123055 A1 WO2019123055 A1 WO 2019123055A1
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group viii
viii metal
glycolaldehyde
catalyst
metal salt
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Makarand DIWAKAR
Rakesh Kesavan NAMBOOTHIRI
Raj Deshpande
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SABIC Global Technologies BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid
    • 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
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • 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
    • Y02P20/10—Process efficiency

Definitions

  • the present invention provides a process and catalyst for the production of glycolaldehyde from mixtures of H 2 , CO, and formaldehyde.
  • Glycolaldehyde is an important chemical due to the presence of two reactive groups on the molecule. Glycolaldehyde has various applications in the food industry, for example, as a cross-linking agent for proteinaceous materials such as sausage casings. Another use is as a browning promoter during the cooking of foods. Glycolaldehyde promotes the Maillard reaction that occurs between protein amines and reducing sugar ketones or aldehydes during the carmelization process. As an intermediate in organic synthesis, glycolaldehyde is used for the preparation of serine.
  • Glycolaldehyde is particularly useful as an intermediate in the production of chemicals having a variety of applications. Glycolaldehyde can be used to produce ethylene glycol by a catalytic hydrogenation process. Ethylene glycol is a valuable commercial chemical with a wide variety of uses, e.g., as a coolant and antifreeze, monomer for polyester production, solvent, and an intermediate for production of commercial chemicals.
  • Glycolaldehyde can be converted to glycolic acid (an important alpha-hydroxy acid) and glycolic acid esters.
  • Glycolic acid is used in the textile industry as a dyeing and tanning agent, in food processing as a flavoring agent and preservative, and in the pharmaceutical industry as a skin care agent.
  • Glycolic acid is often included in emulsion polymers, solvents, and inks and paints to improve flow properties and impart gloss.
  • Glycolic acid is also useful as a synthetic organic intermediate in a range of reactions including redox reactions, esterifications, and long-chain polymerizations.
  • Glycolic acid is used as a monomer in the preparation of polyglycolic acid and other biocompatible copolymers such as poly(lactic-co-glycolic acid), PLGA.
  • glycolaldehyde involves dihydroxymaleic acid as a starting material. However, this method is ill-suited to large-scale production and is impractical for industrial usage. Accordingly, several alternative methods and processes for production of glycolaldehyde are found in the prior art. Glycolaldehyde may be produced from the pyrolysis of ligno-cellulosic materials, however, the yields form these cellulosic feedstocks is small. Another production method involves the vapor-phase conversion of ethylene glycol to glycolaldehyde. This method suffers from low conversion, low yields, and high byproduct concentrations.
  • the primary method for the preparation of glycolaldehyde involves hydroformylation of formaldehyde.
  • Current methods employ organometallic complexes of rhodium as catalysts under homogeneous reaction conditions. In these processes, separation of the glycolaldehyde product from the catalyst is difficult, as the catalyst, starting material, and product are present in the same phase.
  • Distillation or extraction techniques are typically employed in order to separate the catalyst from the reaction mixture. These techniques are challenging as the catalyst can decompose during distillation, or may leach out during the extraction process. Both distillation and extraction may result in the loss of valuable transition metal catalysts.
  • the solution is premised on the use of heterogenized organometallic complexes of Group VIII metal, particularly rhodium as catalysts for the hydroformylation of formaldehyde to synthesize glycolaldehyde.
  • the heterogenized catalyst complexes may be separated from reaction mixtures by simple filtration and or settling techniques.
  • the presently disclosed heterogenized catalyst complexes may be recovered in higher amounts, with lower risk of catalyst loss or decomposition.
  • the high-recovery heterogenized catalyst complexes of the present invention improve process economics by allowing higher proportions of catalyst to be recycled.
  • a process for the production of glycolaldehyde is described.
  • the process can include heating a mixture of H 2 , CO, CH 2 0, and a heterogenized catalyst in the presence of an organic solvent and catalytically reacting the mixture under conditions favorable to the formation of glycolaldehyde.
  • the heterogenized catalyst comprises a heterogeneous metal-ligand complex comprising a Group VIII metal and a non-Group VIII metal salt.
  • the heterogeneous metal-ligand complex may be deposited on a support material that may be an organic, inorganic or polymeric material.
  • a process for the conversion of a mixture of H 2 , CO, and CH 2 0 into a product stream comprising glycolaldehyde includes a step of preparing a first pre-catalyst material comprising a non-Group VIII metal salt on a support material by mixing a support material and a non-Group VIII metal salt in a liquid followed by removal of the liquid to achieve deposition of said salt on said support material.
  • the first pre-catalyst material is mixed with a Group VIII metal compound in a liquid.
  • the liquid may be selected from the group consisting of alcohols, water, ethers, aromatic hydrocarbons, aliphatic hydrocarbons, N-monosubstituted or N,N-disubstituted formamides, acetamides, propionamides, butyramides, higher amides, aromatic amides.
  • a higher amide is an amide in which a Cs or larger group is attached to the amide nitrogen atom through a carbon atom.
  • the liquid is dimethylacetamide.
  • N,N-dihexylbutyramide is not employed.
  • the liquid may then be removed to give a heterogenized metal-ligand catalyst complex including a non-Group VIII metal salt.
  • Liquid removal may be accomplished by techniques known to those of skill in the art, including but not limited to evaporation, distillation, decanting, filtration, rotary evaporation, and the like.
  • the process further includes the step of contacting a mixture of the heterogenized metal- ligand catalyst complex, H 2 , CO, and CH 2 0 in the presence of an organic solvent under conditions to effect the production of glycolaldehyde.
  • the conversion of formaldehyde may be greater than 10%, preferably greater than 15%, more preferably greater than 20%.
  • a method for preparing a catalyst complex for conversion of H 2 , CO, and CH 2 0 into glycolaldehyde comprises the steps of preparing a solution of a non-Group VIII metal salt and a support material in a first solvent, and removing the first solvent to provide the support material loaded with the non-Group VIII metal salt, preparing a solution of the support material loaded with the non-Group VIII metal salt and an organo-rhodium composition in a second solvent, and removing the second solvent to provide the support material loaded with a non-Group VIII metal salt and organo-rhodium compound as a catalyst complex.
  • the non-Group VIII metal salt and organo-rhodium compound chemically react to provide the catalyst complex, which may be insoluble in the second solvent.
  • the organo-rhodium compound comprises a phosphine ligand, preferably a phosphine-sulfonate ligand, more preferably a triphenylphosphine trisulfonate ligand.
  • the first and second solvents are essentially free of N,N-dihexylbutyramide.
  • ligand as used herein, is intended to have its commonly accepted meaning as would be understood by persons having ordinary skill in the art, that is a molecule, atom, ion, or group of atoms that is bound or capable of binding to a central atom as a complex or coordination compound.
  • hydroformylation also is understood to have its commonly accepted meaning of a catalytic process in which hydrogen and carbon monoxide are reacted with formaldehyde resulting in the net addition of CO and H 2 to the formaldehyde.
  • formaldehyde is intended to include monomeric formaldehyde and any formaldehyde source that is readily converted to formaldehyde under the conditions of the hydroformylation reaction.
  • formaldehyde would include formaldehyde in its monomeric form as well as its various acetals, hemiacetals, and low molecular weight oligomers such as, for example, paraformaldehyde and trioxane.
  • glycolaldehyde is intended to include 2-hydroxy-acetaldehyde and any derivatives thereof such as, for example, acetals, ethers, hemiacetals, oligomers, and hydrogenated products, that may be produced from glycolaldehyde under hydroformylation reaction conditions.
  • the terms“about” or“approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
  • wt.% refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or total moles of a material, that includes the component.
  • 10 grams of component in 100 grams of the material is 10 wt.% of component.
  • the term“substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.
  • the methods of the present invention can“comprise,”“consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc. disclosed throughout the specification.
  • a basic and novel characteristic of the methods of the present invention are their abilities to efficiently produce glycolaldehyde from mixtures of H 2 , CO, and CH 2 0.
  • the catalysts that are currently employed in the production of glycolaldehyde suffer from potential decomposition and/or loss during reaction work-up and catalyst recovery.
  • the processes disclosed herein address this problem by providing heterogenized catalyst complexes that are amenable to less wasteful catalyst recovery techniques.
  • the heterogenized catalyst complexes of the present invention may be recovered by simple filtration or settling/decanting processes. These techniques are associated with higher catalyst recovery.
  • the increase in catalyst recovery is associated with improved process economics because a higher proportion of catalyst may be recovered and re-used.
  • the presently disclosed catalysts are based on heterogenized organometallic complexes of Group VIII metal and a non-Group VIII metal as catalysts for the hydroformylation of formaldehyde to synthesize glycolaldehyde.
  • the first pre-catalyst material non-Group VIII metal salt reacts with the Group VIII metal compound to form a complex that is insoluble in the liquid, in some aspects.
  • the Group VIII metal is rhodium.
  • the heterogeneous metal-ligand complex further comprises a phosphine ligand coordinated to the Group VIII metal, the non-Group VIII metal, or both the Group VIII metal and the non-Group VIII metal.
  • the ligand comprises a sulfonate group.
  • the sulfonate ligand may partially or fully react with the non-Group VIII metal to provide a catalyst complex in which the at least a portion of the sulfonate ligand is complex or bound to the Group VIII metal, the non-Group VIII metal, or both.
  • the ligand is a triphenylphosphine trisulfonate salt.
  • the catalyst does not include a phosphine- amine ligand.
  • the non-Group VIII metal salt may be the salt of an alkaline metal, an alkaline earth metal, or at least one transition metal of Columns 4-7 and 9-12 of the Periodic Table.
  • the non-Group VIII metal is an alkaline earth metal, preferably barium.
  • the heterogenized organometallic complex support material is an organic, inorganic, or polymeric material.
  • a preferred support material is carbon.
  • conditions to effect the production of glycolaldehyde comprise a reaction or reactor temperature ranging from 50 °C to 150 °C, preferably from 75 °C to 125 °C, more preferably from 80 °C to 120 °C.
  • the CH2O may be sourced or provided by monomeric formaldehyde, paraformaldehyde, trioxane, or other source that contains or is capable of generating a formaldehyde monomer.
  • Formaldehyde sources include but are not limited to paraformaldehyde, methylal, formalin solutions, polyoxymethylenes, and trioxane.
  • the CH2O is provided as a formalin solution.
  • the production of glycolaldehyde may be performed at a reactor pressure ranging from 500 to 2100 psig, preferably from 650 to 1100 psig, more preferably from 800 to 900 psig.
  • Fb and CO may be provided to the reactor in a Fb:CO ratio ranging from 0.5:1 to 2:1, preferably from 0.75:1 to 1.5:1, more preferably from 0.8:1 to 1.2:1.
  • the Fb and CO are provided in the form of syngas.
  • the glycolaldehyde production reaction duration may range from 1 to 10 hours, preferably from 2 to 5 hours, more preferably from 2.5 to 3.5 hours.
  • the glycolaldehyde production reaction may be performed in a liquid phase, in some embodiments. When performed in a liquid phase one or more solvents may be employed. In a particular aspect, a liquid phase glycolaldehyde production reaction is performed in a N,N- dimethylacetamide solvent.
  • TPPTS-Ba-loaded carbon A 250 ml round bottom flask was charged with 1.01 g triphenylphosphinetrisulfonate sodium salt and 50 ml of distilled water. The mixture was stirred until a clear solution was obtained. 5 g of 15% Ba(N0 3 ) 2 -loaded carbon prepared above was added to the solution and stirred for 15 hours. The mixture was filtered through a Buchner funnel under vacuum. The filtered solid was dried under vacuum to obtain the TPPTS-Ba loaded carbon.
  • Rh-TPPTS-Ba-loaded carbon A 250 ml round bottom flask was charged with 0.0535 g (RhCODCl) 2 and 50 ml of dimethylacetamide. The mixture was stirred until a clear solution was obtained. 5 g TPPTS-Ba loaded carbon was added to the solution and stirred for 6 hours. The mixture was filtered through a Buchner funnel under vacuum. The filtered solid was dried under vacuum to obtain the catalyst complex Rh- TPPTS-Ba loaded carbon, (Rh-TPPTS/C).
  • a 60 ml PARR reactor was charged with 1.0 g Rh-TPPTS/C catalyst, 19.5 ml (17.93 g) dimethylacetamide solvent, and 0.5 ml (0.456 g) of formalin solution (37% aqueous formaldehyde, catalyst: substrate ratio of 1:200). 780 psig of 1:1 CO:H 2 gas was added to the reactor and the reactor was heated to 100 °C. Heating was stopped after 3 hours and the reactor was allowed to cool overnight. The reactor was allowed to vent gases during the overnight cooling period. The formaldehyde conversion for this reaction was 17.79%, with a glycolaldehyde selectivity of 72.45%. The catalyst was recovered by filtration, washed with reaction solvent, then washed with acetone.
  • Embodiment 1 is a process for the production of glycolaldehyde.
  • the process includes heating a mixture of H 2 , CO, CH 2 0, and a heterogenized catalyst in the presence of an organic solvent, and catalytically reacting the mixture under conditions favorable to the formation of glycolaldehyde.
  • the heterogenized catalyst of embodiment 1 comprises a heterogeneous metal-ligand complex comprising a Group VIII metal and a non-Group VIII metal salt deposited on a support material.
  • Embodiment 2 is the process of embodiment 1, wherein the non-Group VIII metal salt is a salt of alkaline earth metal.
  • Embodiment 3 is the process of embodiment 1 or 2, wherein the H 2 and CO are provided in a H 2 :CO ratio ranging from 0.5:1 to 2:1.
  • Embodiment 4 is the process of any of embodiments 1 to 3, wherein the support material is an organic, inorganic, or polymeric material.
  • Embodiment 5 is the process of any of embodiments 1 to 4, wherein the CH 2 0 is provided by monomeric formaldehyde, paraformaldehyde, trioxane, or other source that contains or is capable of generating a formaldehyde monomer.
  • Embodiment 6 is a process for the conversion of a mixture of H 2 , CO, and CH 2 0 into a product stream comprising glycolaldehyde.
  • the process includes: a) preparing a first pre-catalyst material comprising a non-Group VIII metal salt on a support material by mixing a support material and a non-Group VIII metal salt in a liquid followed by removal of the liquid to achieve deposition of said salt on said support material, b) preparing a mixture of the first pre-catalyst material and a Group VIII metal compound in a liquid, and removing the liquid to give a heterogenized metal-ligand catalyst complex including a non-Group VIII metal salt, and c) contacting a mixture of the catalyst complex, H 2 , CO, and CH 2 0 in the presence of an organic solvent under conditions to effect the production of glycolaldehyde with greater than 15% formaldehyde conversion.
  • Embodiment 7 is the process of embodiment 6, wherein the first pre-catalyst material non-Group VIII metal salt reacts with the Group VIII metal compound to form a complex that is insoluble in the liquid.
  • Embodiment 8 is the process of embodiment 6 or 7, wherein the conditions to effect the production of glycolaldehyde comprise a reactor pressure ranging from 500 to 2100 psig.
  • Embodiment 9 is the process of any of embodiments 6 to 8, wherein the conditions to effect the production of glycolaldehyde comprise a reaction temperature ranging from 50 °C to 150 °C.
  • Embodiment 10 is the process of any of embodiments 6 to 9, wherein the conditions to effect the production of glycolaldehyde comprise a reaction duration ranging from 1 to 10 hours.
  • Embodiment 11 is the process of any of embodiments 6 to 10, wherein the H 2 and CO are provided in a H 2 :CO ratio ranging from 0.5:1 to 2:1.
  • Embodiment 12 is a method of preparing a catalyst complex for conversion of H 3 ⁇ 4 CO, and CH 2 0 into glycolaldehyde.
  • the method includes: a) preparing a solution of a non- Group VIII metal salt and a support material in a first solvent, and removing the first solvent to provide the support material loaded with the non-Group VIII metal salt, and b) preparing a solution of the support material loaded with the non-Group VIII metal salt and an organo- rhodium composition in a second solvent, and removing the second solvent to provide the support material loaded with a non-Group VIII metal salt and organo -rhodium compound as a catalyst complex.
  • the first and second solvents of embodiment 1 are essentially free of N,N- dihexylbutyramide.
  • Embodiment 13 is the method of embodiment 12, wherein the first pre catalyst material non-Group VIII metal salt reacts with the Group VIII metal compound to form a complex that is insoluble in the second solvent.
  • Embodiment 14 is the method of embodiment 12 or 13, wherein the non-Group VIII metal salt is a salt of an alkaline earth metal.
  • Embodiment 15 is the method of any of embodiments 12 to 14, wherein the organo- rhodium compound comprises a phosphine ligand.
  • Embodiment is the method of any of embodiments 12 to 15, wherein the support material is an organic, inorganic, or polymeric material.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un processus et un catalyseur pour la production de glycolaldéhyde à partir de mélanges de formaldéhyde, de monoxyde de carbone et d'hydrogène. Le processus de l'invention utilise un complexe de catalyseur hétérogénéisé pour la production de glycolaldéhyde avec des niveaux élevés de conversion de formaldéhyde. Les complexes de catalyseur hétérogénéisés peuvent être récupérés dans des quantités relativement élevées par comparaison avec d'autres catalyseurs de production de glycolaldéhyde.
PCT/IB2018/059420 2017-12-21 2018-11-28 Valorisation de gaz de synthèse par hydroformylation de formaldéhyde à l'aide de complexes organométalliques hétérogénéisés de métaux du groupe viii Ceased WO2019123055A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112337508A (zh) * 2020-11-03 2021-02-09 中国科学院福建物质结构研究所 一种乙醇醛合成用铑基催化剂及其制备方法
CN114751813A (zh) * 2022-05-05 2022-07-15 天津大学 一种甲醛氢甲酰化制备乙醇醛的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0046680A1 (fr) * 1980-08-26 1982-03-03 The Halcon Sd Group, Inc. Hydrogénation catalytique d'aldéhyde glycolique pour la préparation d'éthylène glycol
US20080081931A1 (en) * 2006-09-29 2008-04-03 Eastman Chemical Company Process for the preparation of glycolaldehyde
WO2012108973A1 (fr) * 2011-02-11 2012-08-16 Dow Global Technologies Llc Catalyseur hétérogène et son utilisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0046680A1 (fr) * 1980-08-26 1982-03-03 The Halcon Sd Group, Inc. Hydrogénation catalytique d'aldéhyde glycolique pour la préparation d'éthylène glycol
US20080081931A1 (en) * 2006-09-29 2008-04-03 Eastman Chemical Company Process for the preparation of glycolaldehyde
WO2012108973A1 (fr) * 2011-02-11 2012-08-16 Dow Global Technologies Llc Catalyseur hétérogène et son utilisation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112337508A (zh) * 2020-11-03 2021-02-09 中国科学院福建物质结构研究所 一种乙醇醛合成用铑基催化剂及其制备方法
CN114751813A (zh) * 2022-05-05 2022-07-15 天津大学 一种甲醛氢甲酰化制备乙醇醛的方法
CN114751813B (zh) * 2022-05-05 2023-12-15 天津大学 一种甲醛氢甲酰化制备乙醇醛的方法

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