EP3512982B1 - Elektrochemisches verfahren zur herstellung von methylethylketon - Google Patents

Elektrochemisches verfahren zur herstellung von methylethylketon Download PDF

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EP3512982B1
EP3512982B1 EP17764416.8A EP17764416A EP3512982B1 EP 3512982 B1 EP3512982 B1 EP 3512982B1 EP 17764416 A EP17764416 A EP 17764416A EP 3512982 B1 EP3512982 B1 EP 3512982B1
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mek
acetoin
process according
solution
aqueous medium
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EP3512982A1 (de
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José Ramón OCHOA GÓMEZ
Francisca RÍO PÉREZ
Cristina DIÑEIRO GARCÍA
Tomás RONCAL MARTÍNEZ
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Biosyncaucho SL
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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
    • C25B11/02—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
    • 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 manufacturing methyl ethyl ketone (also known as 2-butanone and MEK) by electroreduction of acetoin (also known as 3-hydroxybutanone) in a solution formed by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in such a medium, using a high hydrogen overvoltage cathode in both divided and undivided cells.
  • 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.
  • 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 ), a key parameter directly related to the industrial productivity (the higher P MEK the lower the capital investment), is low for practical use.
  • US20150008139 discloses processes for the electrocatalytic hydrogenation and/or hydrodeoxygenation of oxygenated and unsaturated organic compounds.
  • 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:
  • 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. Thus, in the presence of a 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 enantiomerically enriched mixture of its enantiomers.
  • 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 electrochemical reactor is used, 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.
  • 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. Accordingly, in a particular embodiment of the process of the invention, 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 electroreduction of protons. If pH is higher than 7 the selectivity of the reaction is negatively affected due to aldol condensations of both acetoin and MEK.
  • a suitable acid such as phosphoric or sulfuric acid
  • base such as sodium or potassium hydroxide
  • 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 separated by vacuum evaporation and the aqueous phase is loaded with fresh acetoin for restoring its initial concentration and the electrolysis is resumed.
  • 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.
  • both current density and circulated electrical charge decrease from the first electrochemical reactor to the last one. For instance, if two electrochemical reactors connected in series are used, the current density used in the first electrochemical reactor is higher than that used in the second electrochemical reactor; and the fraction of the circulated electrical charge in the first electrochemical reactor, relative to the total charge circulated through both electrochemical reactors, is higher than that in the second electrochemical reactor. In this way, electricity is more efficiently employed in electroreducing acetoin to MEK.
  • 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%). Initial catholyte pH was 4.32 and final pH 3.75 (mean pH 4.04). After electrolysis completion, the catholyte solution (64 mL) contained an acetoin concentration of 27.2 g/L and a MEK concentration of 40.8 g/L, as shown by HPLC.
  • 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 .
  • 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 .
  • Example 25 (comparative, from WO 2016097122 )
  • 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.
  • Example 26 show the good performance of the present process using an undivided cell.

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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)

Claims (15)

  1. Ein Verfahren zur Herstellung von Methylethylketon (MEK) durch Elektroreduktion von Acetoin in einem wässrigen Medium unter Verwendung von einer Kathode aus Blei, wobei das Verfahren folgende Schritte umfasst:
    a) das Bilden von einer Lösung, indem Acetoin mit einem wässrigen Medium und einem in einem solchen Medium lösbaren Trägerelektrolyt gemischt wird,
    b) das kontinuierliche oder diskontinuierliche Elektrolysieren der Lösung in einem elektrochemischen Reaktor, indem eine Spannung zwischen einer Anode und der Kathode angewendet wird, durch den Einsatz von einer Gleichspannungsstromversorgung bei einer Stromdichte von 500 bis 5.000 A/m2.
  2. Das Verfahren nach Anspruch 1, wobei die Reaktion ohne einen Hydrierkatalysator durchgeführt wird, der ein Katalysator ist, der fähig ist, die Reduktion von einer in einer Kathodenflüssigkeit reduzierbaren Gruppe durch Wasserstoff zu katalysieren.
  3. Das Verfahren nach Anspruch 2, wobei der Hydrierkatalysator ausgewählt aus der Gruppe ist, die aus einem auf einem Metall geträgerten Edelmetall, Raney-Nickel, und geträgertem Ni besteht.
  4. Das Verfahren nach einem der Ansprüche 1 bis 3, wobei das Material der Kathode Blei ist, das in Form einer flachen Platte ist oder auf einem porösen Träger, wie etwa einem Kohlenstofffilz und Kohlenstoffschaum, abgeschieden ist.
  5. Das Verfahren nach einem der Ansprüche 1 bis 4, wobei die Anode aus Kohlenstoffstahl, auf Titan geträgertem Platin, und auf Iridium basierten formstabilen Anoden in nicht-poröser flacher Form und als perforierten Materialien, wie etwa Netzen, Metallmaschen, Lamellen, geformten Geweben und Gittern ausgewählt ist.
  6. Das Verfahren nach einem der Ansprüche 1 bis 5, wobei das wässrige Medium 100 Gew.-% Wasser oder eine Mischung aus Wasser mit einem vollständig oder teilweise mit Wasser mischbaren nicht-elektroaktiven Lösungsmittel, in welchem die Menge an Wasser von 50 bis 99 Gew.-%, insbesondere von 70 bis 99 Gew.-%, ganz besonders von 85 bis 99 Gew.-% reicht, umfasst.
  7. Das Verfahren nach einem der Ansprüche 1 bis 6, wobei der elektrochemische Reaktor ein ungeteilter Reaktor ist.
  8. Das Verfahren nach einem der Ansprüche 1 bis 7, wobei der Trägerelektrolyt, der eine Lösung mit Acetoin bildet aus der Gruppe umfassend Ammonium und Salze von Alkali- und Erdalkalimetallen von anorganischen Säuren, und quartäre Ammoniumsalze, und Mischungen davon ausgewählt ist, und wobei die Trägerelektrolyte für Anolyte in geteilten Zellen nicht oxidierbare anorganische Säuren sind.
  9. Das Verfahren nach Anspruch 8, wobei die Menge am Trägerelektrolyt, der eine Lösung mit Acetoin bildet von 0,1 bis 20 Gew.-%, insbesondere von 1 bis 15 Gew.-% und ganz besonders von 5 bis 10 Gew.-%, bezogen auf das gesamte Gewicht der Lösung, reicht.
  10. Das Verfahren nach einem der Ansprüche 1 bis 9, wobei der pH-Wert der Lösung, die durch das Mischen von Acetoin mit einem wässrigen Medium und einem in einem solchen Medium lösbaren Trägerelektrolyt entsteht, von 2,5 bis 7, insbesondere von 3 bis 7 und ganz besonders von 4 bis 7 beträgt.
  11. Das Verfahren nach einem der Ansprüche 1 bis 10, wobei die Menge des zur Elektroreduktion des Acetoins auf MEK zu strömenden Stroms von 50% bis 125% der zum Erreichen von einer Konversion von 100% des Acetoins theoretischen Menge, unter Annahme von einer Stromausbeute von 100%, insbesondere von 55% bis 100% und vor allem von 60% bis 75%, beträgt.
  12. Das Verfahren nach einem der Ansprüche 1 bis 11, wobei die Temperatur der Elektrolyse von 10 °C bis 70 °C ist und insbesondere die Raumtemperatur ist.
  13. Das Verfahren nach einem der Ansprüche 1 bis 12, wobei die MEK stets aus dem wässrigen Medium mittels Vakuumverdampfung entfernt wird.
  14. Das Verfahren nach einem der Ansprüche 1 bis 12, wobei die erhaltene MEK stets aus dem wässrigen Medium mittels Flüssig-Flüssig-Extraktion unter Verwendung von einem wasserunlöslichen inerten Lösungsmittel entfernt wird.
  15. Das Verfahren nach einem der Ansprüche 1 bis 14, welches wie folgt durchgeführt wird:
    i) in einem elektrochemischen Reaktor; oder
    ii) in mindestens zwei elektrochemischen Reaktoren, die in Reihe so geschaltet sind, dass die Lösung, die eine Mischung aus Acetoin, das nicht reagiert hat, MEK, einem wässrigem Medium, und einem in einem solchen Medium lösbaren Trägerelektrolyt enthält, welche sich aus dem elektrochemischen Reaktor ergibt, zur Speisung des folgenden dient.
EP17764416.8A 2016-09-14 2017-09-13 Elektrochemisches verfahren zur herstellung von methylethylketon Active EP3512982B1 (de)

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EP16382424 2016-09-14
PCT/EP2017/073021 WO2018050695A1 (en) 2016-09-14 2017-09-13 Electrochemical method for manufacturing methyl ethyl ketone

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CN (1) CN109790630B (de)
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* 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
CA2077552A1 (en) 1990-03-05 1991-09-06 John H. Grate Catalytic system for olefin oxidation to carbonyl products
DE19620861A1 (de) * 1996-05-23 1997-11-27 Basf Ag Verfahren zur elektrochemischen Reduktion organischer Verbindungen
ES2352633B8 (es) 2009-08-04 2012-02-20 Fundacion Leia Centro De Desarrollo Tecnologico Cepa mutante de lactococcus lactis lactis y método para la producción industrial de acetoína.
WO2013134220A1 (en) * 2012-03-06 2013-09-12 Board Of Trustees Of Michigan State University Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds
CN104937015B (zh) * 2012-11-20 2020-03-17 卡比欧斯公司 用于再循环塑料制品的方法
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
JP6702972B2 (ja) 2014-12-18 2020-06-03 ファンダシオン テクナリア リサーチ アンド イノベイション ２，３−ブタンジオールの製造方法

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WO2018050695A1 (en) 2018-03-22
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ES2813570T3 (es) 2021-03-24
CN109790630B (zh) 2021-05-25

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