WO2018050695A1 - Procédé électrochimique pur la fabrication de méthyléthylcétone - Google Patents

Procédé électrochimique pur la fabrication de méthyléthylcétone Download PDF

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WO2018050695A1
WO2018050695A1 PCT/EP2017/073021 EP2017073021W WO2018050695A1 WO 2018050695 A1 WO2018050695 A1 WO 2018050695A1 EP 2017073021 W EP2017073021 W EP 2017073021W WO 2018050695 A1 WO2018050695 A1 WO 2018050695A1
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Prior art keywords
mek
acetoin
process according
solution
aqueous medium
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PCT/EP2017/073021
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English (en)
Inventor
José Ramón OCHOA GÓMEZ
Francisca RÍO PÉREZ
Cristina DIÑEIRO GARCÍA
Tomás RONCAL MARTÍNEZ
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Biosyncaucho, S.L.
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Priority to CN201780055234.8A priority Critical patent/CN109790630B/zh
Priority to EP17764416.8A priority patent/EP3512982B1/fr
Priority to US16/329,428 priority patent/US20190194814A1/en
Priority to ES17764416T priority patent/ES2813570T3/es
Publication of WO2018050695A1 publication Critical patent/WO2018050695A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells

Definitions

  • the present invention is related to an electrochemical method for
  • methyl ethyl ketone also known as 2-butanone and MEK
  • acetoin also known as 3-hydroxybutanone
  • MEK is an important chemical widely used industrially as a solvent in the vinyl resins and synthetic rubber industries.
  • MEK is industrially produced by dehydrogenation of 2-butanol over cooper and zinc oxide catalysts at 400- 500 °C and pressures lower than 0.4 MPa, such as disclosed in US4075128.
  • Other chemical methods described in the prior art are the Wacker liquid phase oxidation of butenes at about 85 °C and 0.69 MPa as disclosed in US5506363; and the dehydration of 2,3-butanediol using acidic catalysts as reported in Zhao et al. "Catalytic dehydration of 2,3-butanediol over P/HZSM- 5: effect of catalyst, reaction temperature and reactant configuration on rearrangement products", RSC Adv., 2016, Vol. 14, pp. 16988-16995.
  • US3247085 discloses an electrochemical process for making MEK by electro- oxidation of 1 -butene.
  • Baizer et al. "Electrochemical conversion of 2,3-butanediol to 2-butanone in undivided flow cells: a paired synthesis"
  • J. Appl. Electrochem, 1987, Vol. 14, pp.197-208 discloses a procedure for converting 2,3-butanediol in ca. 10% aqueous solution to MEK by passing it through a porous anode at which it is selectively oxidized to acetoin by electrogenerated NaBrO and then pumping to a porous cathode at which it is reduced to MEK.
  • Baizer et al. states that an increase in the current density above 20 A/m 2 caused more H 2 evolution and resulted in poor current efficiency as well as high cell voltage due to the gas trapped inside the cell, concluding that the paired reaction should be run at a low current density (10 or 20 A/m 2 ) to obtain relatively high current efficiencies.
  • WO2016097122 discloses a process for manufacturing 2,3-butanediol by electroreduction of 3-hydroxybutanone in an aqueous media by using porous Pt or Ni cathodes.
  • MEK is obtained by electroreduction of 3-hydroxybutanone using a Sigracet® GDL-24BC cathode in a 64.0% selectivity for a 75.7% conversion of 3-hydroxybutanone.
  • productivity i.e. the kg of MEK produced per hour and per m 2 of electrode (cathode) area (kg-MEK h/m 2 )
  • productivity i.e. the kg of MEK produced per hour and per m 2 of electrode (cathode) area (kg-MEK h/m 2 )
  • P MEK the lower the capital investment
  • the invention relates to a process for the preparation of methyl ethyl ketone (MEK) by electroreduction of acetoin in aqueous media using a high hydrogen overvoltage cathode made of lead, the process comprising the steps of:
  • electrochemical reactor by applying a voltage between an anode and the cathode using a direct current power supply at a current density from 500 to 5000 A/m 2 , particularly of 2500, 2000, 1500, or 1000 A/m 2 .
  • hydrogenation catalyst means a catalyst which is capable of catalysing the reduction by hydrogen of a group susceptible of being reduced in a bulk catholyte, wherein hydrogen was previously electrogenerated in the cathode by electroreduction of water.
  • hydrogenation catalyst electrolysis is used for generating hydrogen not for electroreducing directly the group susceptible of being reduced.
  • hydrogenation catalysts are supported noble metals (such as supported Pt, Pd, Ru Ir and Rh), Raney Ni, and supported Ni.
  • Acetoin has an asymmetric carbon and consequently it is a chiral molecule. Any one of the stereoisomers as well as their mixtures can be used as a raw material in the process of the present invention. Accordingly, throughout the present invention the term acetoin encompasses its enantiomers as well as mixtures thereof in any proportions, e.g. a racemic mixture or an
  • Acetoin can be obtained by fermentation of an aqueous solution of glucose, sacarose or molasses as disclosed in ES2352633, wherein the
  • microorganism carrying out the bioconversion is a mutant strain of
  • Lactococcus lactis lactis By means of such a process the manufacturing cost of acetoin is low enough for making the electrosynthesis of MEK from acetoin economically feasible.
  • cell As used herein, the terms "cell”, “electrochemical cell” and “electrochemical reactor” are interchangeable.
  • aqueous medium means 100 wt% water, or a mixture of water with a fully or partially water-miscible solvent in which the amount of water is from 50 to 99 wt%, particularly from 70 and 99 wt%, and more particularly from 85 and 99 wt%.
  • Suitable fully or partially water-miscible solvents are those which are not electroactive under the electrolysis conditions of the present invention. Examples of said solvents, but not limited to, are alcohols such as methanol, ethanol, propanol and isopropanol; ethers such as tetrahydrofuran and dioxane; and nitriles such as acetonitrile.
  • the present invention relates to a process for the preparation of MEK by electroreduction of acetoin in aqueous media using a high hydrogen overvoltage cathode made of lead. Particularly, the reaction is carried out in the absence of a hydrogenation catalyst.
  • the cathode material is lead as a flat sheet or deposited in a porous support such as a carbon felt, carbon foam, or a similar material.
  • the electrochemical reactor used in the process of the present invention can be any one of those known by a person skilled in the art such as a tank-type electrochemical reactor or a flow-through filter press-type electrochemical reactor.
  • the electrochemical reactor is a flow-through filter press-type electrochemical reactor.
  • the electrochemical reactor can be divided or undivided, with this last configuration being the most preferred because leads to both a lower power consumption and a lower capital investment. If a divided
  • anode and cathode are separated by a material preventing mixing of the anolyte (the acetoin-free solution being fed through the anodic compartment, e.g. an aqueous solution of sulfuric acid) and the catholyte (the acetoin-containing solution being fed through the cathode compartment) while allows the flow of ions transporting electricity in solution.
  • a cation exchange membrane is the most preferred separating material for divided electrochemical reactors. Examples of cation exchange membranes include, but are not limited to, any one of those marketed under the trademark of Nafion® such as, e.g., Nafion® N-324 and Nafion® N-424.
  • anodic materials anodic materials (anode) carbon steel, and platinum supported on titanium (Pt/Ti) and iridium-based DSA® (dimensionally stable anodes) are used in the method of the present invention. They can be used in non-porous flat form and as perforated materials such as nets, metal meshes, lamellae, shaped webs and grids.
  • the electroreduction of acetoin to MEK according to the present invention is performed in the presence of a supporting electrolyte added to adjust the conductivity of the electrolysis solution and/or to control the selectivity of the reaction.
  • the amount of the supporting electrolyte is generally adjusted to a level from 0.1 to 20 wt%, particularly from about 1 to about 15 wt%, and more particularly from about 5 to about 10 wt%, based on the total mass of the solution.
  • Examples of supporting electrolytes in undivided cells and for catholyte when divided cells are used include, but are not limited to, ammonium and alkaline and alkaline earth metals salts of inorganic acids such as sulfuric, phosphoric and nitric acids, and ammonium quaternary salts, such as, e.g., tetraethyl ammonium bromide, chloride and sulfate, and tetrabutyl ammonium bromide, chloride and sulfate.
  • additional supporting electrolytes for catholyte are ammonium and alkaline and alkaline-earth metals salts of hydrochloric acid, hydrobromic acid and hydrofluoric acid; and supporting electrolytes for anolyte include, but are not limited to, inorganic acids, such as sulfuric and phosphoric acids, as well as ammonium and alkaline and alkaline earth metals salts of said inorganic acids.
  • the process of the invention is carried out in a divided cell and the supporting electrolyte forming a solution with acetoin is selected from the group consisting of ammonium and alkaline and alkaline earth metal salts of an inorganic acid, ammonium quaternary salts, and mixtures thereof, and the supporting electrolyte for anolyte is a non-oxidizable inorganic acid.
  • pH of electrolyte in undivided cells or pH of catholyte in divided cells can be from 2.5 to 7.
  • the pH of the solution formed by mixing acetoin with the aqueous medium and the supporting electrolyte soluble in such a medium is from 2.5 and 7, particularly from 3 to 7, and more particularly from 4 to 7.
  • pH adjustment can be done by adding a suitable acid such as phosphoric or sulfuric acid, or base such as sodium or potassium hydroxide. If pH is lower than 2.5 current efficiency decreases due hydrogen evolution by
  • Acetoin concentration in the solution, formed by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in such a medium, to be electrolyzed is at least 10 g/L, particularly at least 25 g/L, more particularly at least 50 g/L and the most particularly at least 100 g/L, based on the total volume of solution to be electrolyzed.
  • the amount of electricity circulated for electroreducing acetoin to MEK is from 50% to 125% of the theoretical one for obtaining a 100% conversion of acetoin assuming a current efficiency of 100% (2 faradays per mol of acetoin), more particularly from 55% and 100%, and most particularly from 60% and 75%.
  • the temperature for electroreduction of acetoin to MEK is from 10 °C to 70 °C.
  • the electrolysis temperature is room temperature.
  • MEK is continuously removed from the aqueous medium during electrolysis by vacuum evaporation.
  • the MEK-containing aqueous medium exiting from the electrochemical reactor is heated to a temperature from 40 °C to 50 °C and sent to a vacuum evaporator where MEK is evaporated and condensed.
  • the MEK-depleted aqueous medium is cooled down in a heat exchanger to the electrolysis temperature and sent back to the electrochemical reactor where the remaining acetoin is electroreduced to MEK.
  • the acetoin concentration decreases below a level from 40 to 50% of the initial one, the initial concentration is restored by adding fresh acetoin.
  • MEK is continuously removed from the aqueous medium during electrolysis by liquid-liquid extraction using a water- insoluble inert solvent such as toluene, xylenes, tert-butyl methyl ether, and methyl isobutyl ketone.
  • a water- insoluble inert solvent such as toluene, xylenes, tert-butyl methyl ether, and methyl isobutyl ketone.
  • suitable solvents are easily recognizable by those skilled in the art.
  • the process of the invention is carried out: i) in one electrochemical reactor, or
  • a solution (60 mL) of acetoin (100 g/L) and KH 2 PO 4 (5 wt%) in water was recirculated at a flow-rate of 2 L/min by means of a magnetic pump through the cathode compartment of a divided filter press cell consisting of a Ti- supported iridium oxide-based DSA flat sheet as an anode (20 cm 2 ), a
  • Nafion® N-324 cation exchange membrane for separating anode and cathode compartments, and a lead flat sheet as a cathode (20 cm 2 ). Inter-electrode gap was 1 .7 cm.
  • An aqueous 5 wt% sulfuric acid solution was recirculated through the anode compartment by means of another magnetic pump.
  • An electrical current was circulated (3 A, 1500 A/m 2 ) by applying a voltage between anode and cathode using a DC Power Supply. Electrolysis was kept at room temperature (20-25 °C) for 73.01 min (100% of the theoretical charge for full conversion of acetoin assuming a current efficiency of 100%).
  • acetoin conversion was 71 % (71 % current efficiency) and MEK yield was 53.1 % (53.1 % current efficiency) resulting in a selectivity to MEK, the ratio between yield and conversion, of 74.9%.
  • MEK productivity was 1 .07 kg MEK/h/m 2 .
  • Example 2 As in example 1 , but using as catholyte a solution (60 mL) of acetoin (100 g/L), KH 2 PO 4 (5 wt%) and tetraethyl ammonium bromide (1 wt%) in water. Initial catholyte pH was 4.31 and final one 4.23 (mean pH 4.27). After electrolysis completion, the catholyte solution (64 mL) contained an acetoin concentration of 25.1 g/L and a MEK concentration of 46.7 g/L, as shown by HPLC.
  • acetoin conversion was 73.2% (73.2% current efficiency) and MEK yield was 60.8% (60.8% current efficiency) resulting in a selectivity to MEK of 83.1 %.
  • MEK productivity was 1 .23 kg MEK h/m 2 .
  • Example 5 As in example 1 , but using as catholyte a solution (60 mL) of acetoin (100 g/L), KH 2 PO 4 (5 wt%) in water adjusted to pH 3.07 con H 2 SO 4 . Final pH was 2.64 (mean pH 2.86). After electrolysis completion, the catholyte solution (63 mL) contained an acetoin concentration of 20.6 g/L and a MEK concentration of 39.5 g/L, as shown by HPLC. Therefore, acetoin conversion was 78.4% (78.4% current efficiency) and MEK yield was 50.6% (50.6% current efficiency) resulting in a selectivity to MEK of 64.5%. MEK productivity was 1 .02 kg MEK/h/m 2 .
  • acetoin conversion was 88.2% (88.2% current efficiency) and MEK yield was 64.7% (64.7% current efficiency) resulting in a selectivity to MEK of 73.4%.
  • MEK productivity was 0.87 kg MEK/h/m 2 .
  • Examples 8, 9 (comparative), 10 (comparative), and 1 1 -24 These examples illustrate the influence of cathode material (examples 8, 9 (comparative), 10 (comparative), and 1 1 -15), acetoin concentration (examples 8, 16 and 17; and 19 and 21 ), electric charge (examples 18-20) and temperature (examples 21 -24).
  • Experiments were performed as in example 1 (1500 A/m 2 and a divided cell) using as catholyte a solution (60 mL) of acetoin (in the concentration specified in Table 1 ) and KH 2 PO 4 (in the concentration specified in Table 1 ) in water adjusted to pH 5.5 with KOH, by circulating an electric charge also specified in Table 1 . pH was 5.5 and kept constant throughout the electrolysis. Results are given in Table 1 , wherein the meaning of symbols is as follows:
  • Electrolyte (Catholyte for divided cells)
  • Sigracet GDL-24BC/SS A gas diffusion layer (SGL Group, The Carbon Company) supported by gluing on 20 cm 2 of a stainless steel sheet
  • Pb-X/GDL-24BC/SS Pb electrodeposited on Sigracet GDL-24BC/SS in an amount of X g/cm 2 of geometric area.
  • A KH 2 P0 4 (5 wt%) adjusted to pH 5.5 with KOH;
  • B KH 2 P0 4 (10 wt%) adjusted to pH 5.5 with KOH.
  • Electrolysis was kept at room temperature (20-25°C) for 1 .90 h corresponding to 102.8% of the theoretical charge for full conversion of 3- hydroxybutanone assuming a current efficiency of 100%.
  • Initial solution pH was 3.8 and final pH 3.7.
  • the electrolyzed solution (57.8 mL) contained a 3-hydroxybutanone concentration of 25.5 g/L and a methyl ethyl ketone concentration of 41 .7 g/L, as shown by HPLC. Therefore, 3-hydroxybutanone conversion was 75.7% (73.6% current yield), MEK yield was 48.5% (a MEK selectivity of 64%) and MEK productivity was 0.65 kg MEK/h/m 2 .
  • Example 25 As in Example 25 (comparative), but using a lead flat sheet instead of Sigracet® GDL-24BC as a cathode. 3-hydroxybutanone conversion was 82.3% (80.1 % current yield), MEK yield was 62.1 % (a MEK selectivity of 75.4%) and MEK productivity was 0.83 kg MEK h/m 2 , 27.7% higher than that obtained in Comparative Example 1 .
  • Examples 27-31 Similarly as in Example 26, these examples show the good performance of the present process using an undivided cell.
  • example 9 comparative; Table 1 ) except that the catholyte comprised 40 mL of acetoin (100 g/L), KH 2 PO 4 (5 wt%) in water adjusted to pH 5.5 with KOH, and 20 mL of xylenes for extracting continuously MEK from the aqueous phase.
  • the concentration of acetoin in the catholyte aqueous phase 42 mL was 7.95 g/L and the concentration of MEK was 18.75 g/L
  • the acetoin concentration in the catholyte organic phase (15 mL) was 0 g/L and the MEK concentration was 67.7 g/L, as shown by HPLC.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un procédé de préparation de méthyléthylcétone par électroréduction de l'acétoïne dans un milieu aqueux à l'aide d'une cathode à haute surtension d'hydrogène constituée de plomb, le procédé comprenant les étapes de : a) la formation d'une solution par mélange d'acétoïne avec un milieu aqueux et d'un électrolyte de support soluble dans un tel milieu, et b) l'électrolyse de ladite solution de façon continue ou discontinue dans un réacteur électrochimique par application d'une tension entre une anode et la cathode à l'aide d'une alimentation en courant continu à une densité de courant de 500 à 5000 A/m2.
PCT/EP2017/073021 2016-09-14 2017-09-13 Procédé électrochimique pur la fabrication de méthyléthylcétone WO2018050695A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780055234.8A CN109790630B (zh) 2016-09-14 2017-09-13 用于制造甲基乙基酮的电化学方法
EP17764416.8A EP3512982B1 (fr) 2016-09-14 2017-09-13 Procédé électrochimique de fabrication de méthyl éthyl cétone
US16/329,428 US20190194814A1 (en) 2016-09-14 2017-09-13 Electrochemical method for manufacturing methyl ethyl ketone
ES17764416T ES2813570T3 (es) 2016-09-14 2017-09-13 Método electroquímico para la fabricación de metil etil cetona

Applications Claiming Priority (2)

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EP16382424 2016-09-14
EP16382424.6 2016-09-14

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WO (1) WO2018050695A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3247085A (en) 1963-06-14 1966-04-19 Exxon Research Engineering Co Electrochemical process for making methyl-ethyl ketone
US4075128A (en) 1976-11-26 1978-02-21 Atlantic Richfield Company Preparation of methyl ethyl ketone
US5506363A (en) 1990-03-05 1996-04-09 Catalytica, Inc. Catalytic system for olefin oxidation to carbonyl products
ES2352633A1 (es) 2009-08-04 2011-02-22 Fundacion Leia Centro De Desarrollo Tecnologico Cepa mutante de lactococcus lactis lactis y método para la producción industrial de acetoína.
US20150008139A1 (en) * 2012-03-06 2015-01-08 Board Of Trustees Of Michigan State University Electrocatalytic Hydrogenation and Hydrodeoxygenation of Oxygenated and Unsaturated Organic Compounds
WO2016097122A1 (fr) 2014-12-18 2016-06-23 Fundacion Tecnalia Research & Innovation Procédé de production de 2,3-butanediol

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DE19620861A1 (de) * 1996-05-23 1997-11-27 Basf Ag Verfahren zur elektrochemischen Reduktion organischer Verbindungen
WO2014079844A1 (fr) * 2012-11-20 2014-05-30 Carbios Procédé permettant de recycler des produits plastiques
CN104313635A (zh) * 2014-10-31 2015-01-28 北京工业大学 α-羰基酮类化合物的电化学催化合成方法

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Publication number Priority date Publication date Assignee Title
US3247085A (en) 1963-06-14 1966-04-19 Exxon Research Engineering Co Electrochemical process for making methyl-ethyl ketone
US4075128A (en) 1976-11-26 1978-02-21 Atlantic Richfield Company Preparation of methyl ethyl ketone
US5506363A (en) 1990-03-05 1996-04-09 Catalytica, Inc. Catalytic system for olefin oxidation to carbonyl products
ES2352633A1 (es) 2009-08-04 2011-02-22 Fundacion Leia Centro De Desarrollo Tecnologico Cepa mutante de lactococcus lactis lactis y método para la producción industrial de acetoína.
US20150008139A1 (en) * 2012-03-06 2015-01-08 Board Of Trustees Of Michigan State University Electrocatalytic Hydrogenation and Hydrodeoxygenation of Oxygenated and Unsaturated Organic Compounds
WO2016097122A1 (fr) 2014-12-18 2016-06-23 Fundacion Tecnalia Research & Innovation Procédé de production de 2,3-butanediol

Non-Patent Citations (5)

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Title
BAIZER ET AL.: "Electrochemical conversion of 2,3-butanediol to 2-butanone in undivided flow cells: a paired synthesis", J. APPL. ELECTROCHEM, vol. 14, 1987, pages 197 - 208, XP055188544, DOI: doi:10.1007/BF00618738
FRANK D. POPP ET AL: "Electrolytic Reduction of Organic Compounds.", CHEMICAL REVIEWS, vol. 62, no. 1, 1 February 1962 (1962-02-01), US, pages 19 - 40, XP055325295, ISSN: 0009-2665, DOI: 10.1021/cr60215a002 *
M. M. BAIZER ET AL: "Electrochemical conversion of 2,3-butanediol to 2-butanone in undivided flow cells: a paired synthesis", JOURNAL OF APPLIED ELECTROCHEMISTRY, vol. 14, no. 2, 1 March 1984 (1984-03-01), pages 197 - 208, XP055188544, ISSN: 0021-891X, DOI: 10.1007/BF00618738 *
POPP FD; SCHULTZ HP: "Electrolytic reduction of organic compounds'' Electrolytic Reduction of Organic Compounds", CHEM REV, vol. 62, 1962, pages 19 - 40, XP055325295, DOI: doi:10.1021/cr60215a002
ZHAO ET AL.: "Catalytic dehydration of 2,3-butanediol over P/HZSM-5: effect of catalyst, reaction temperature and reactant configuration on rearrangement products", RSC ADV., vol. 14, 2016, pages 16988 - 16995

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CN109790630B (zh) 2021-05-25
EP3512982A1 (fr) 2019-07-24
CN109790630A (zh) 2019-05-21
US20190194814A1 (en) 2019-06-27
EP3512982B1 (fr) 2020-06-17
ES2813570T3 (es) 2021-03-24

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