CN109790630B - Electrochemical process for the manufacture of methyl ethyl ketone - Google Patents
Electrochemical process for the manufacture of methyl ethyl ketone Download PDFInfo
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- CN109790630B CN109790630B CN201780055234.8A CN201780055234A CN109790630B CN 109790630 B CN109790630 B CN 109790630B CN 201780055234 A CN201780055234 A CN 201780055234A CN 109790630 B CN109790630 B CN 109790630B
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- acetoin
- mek
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- aqueous medium
- supporting electrolyte
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 title claims abstract description 310
- 238000000034 method Methods 0.000 title claims description 57
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 claims abstract description 159
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000012736 aqueous medium Substances 0.000 claims abstract description 28
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- -1 alkali metal salts Chemical class 0.000 claims description 11
- 150000007522 mineralic acids Chemical class 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 239000010962 carbon steel Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 239000002609 medium Substances 0.000 abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 11
- 239000007836 KH2PO4 Substances 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 8
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 4
- 229910000457 iridium oxide Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000194035 Lactococcus lactis Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000014897 Streptococcus lactis Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010963 scalable process Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
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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
The invention provides a method for producing methyl ethyl ketone by means of the electroreduction of acetoin in an aqueous medium using a high-hydrogen overvoltage cathode made of lead, comprising the following steps: a) forming a solution by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in such a medium, and b) using a direct current power supply at 500 to 5000A/m2Applying a voltage between the anode and said cathode, continuously or discontinuously electrolyzing said solution in the electrochemical reactor.
Description
The present application claims the benefit of european patent application EP16382424.6 filed on 9, 14/2016.
Technical Field
The present invention relates to an electrochemical process for the manufacture of methyl ethyl ketone (also known as 2-butanone and MEK) by electro-reduction of acetoin (also known as 3-hydroxy butanone) in a solution formed by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in such medium, using a high hydrogen overvoltage cathode in divided and non-divided electrolysis cells.
Background
MEK is an important chemical widely used industrially as a solvent in the vinyl and synthetic rubber industries. MEK is currently produced commercially by dehydrogenation of 2-butanol over copper and zinc oxide catalysts at 400-. Other chemical processes described in the prior art are the Wacker liquid phase oxidation of butenes at about 85 ℃ and 0.69MPa as disclosed in US 5506363; and the use of an acidic catalyst to dehydrate 2,3-butanediol as reported in "Catalytic dehydration of 2,3-butanediol over P/HZSM-5: effect of catalyst, reaction temperature and reaction configuration on registration products", RSC adv.,2016, Vol.14, pp.16988-1699, by Zhao et al.
In addition to starting from 2,3-butanediol, which can be obtained by fermentation of sugars, these processes involve a severe environmental burden and use non-renewable fossil resources as raw materials. However, the last method operates at high temperatures and therefore consumes a lot of energy. Therefore, there is a need for a new pollution-free process for the manufacture of MEK starting from renewable raw materials and capable of operating at low temperatures and pressures.
US3247085 discloses an electrochemical process for the preparation of MEK by the electro-oxidation of 1-butene.
Baizer et al, "Electrochemical conversion of 2,3-butanediol to 2-butanol in undivided flow cells," a Pair Synthesis ", J.Appl.Electrochem,1987, Vol.14, pp.197-208 disclose a process for converting 2,3-butanediol in an approximately 10% aqueous solution to MEK by: 2,3-butanediol in an approximately 10% aqueous solution was passed through a porous anode where it was selectively oxidized to acetoin by electrogenerated NaBrO and then pumped to a porous cathode where it was reduced to MEK. Acetoin formed in the solution by oxidation of 2,3-butanediol with the electrolytically generated NaBrO is electro-reduced to MEK at the cathode. However, this method is due to its 20A/m2Very low current density (well below at least 500A/m)2To about 5000A/m2Useful industrial density) without industrial solidsThe utility model is good in use property. Thus, the Baizer et al method results in very poor productivity, requiring a large capital investment. Another strong current drawback of this method from an environmental point of view is the use of Hg based cathodes and the presence of NaBrO in the electrolytic solution. Furthermore, Baizer et al noted that the current density increased above 20A/m2Will result in more H2Resulting in low current efficiency and high cell voltage due to trapped gas inside the cell, it was concluded that the pairing reaction should be at low current density (10 or 20A/m)2) To obtain a relatively high current efficiency.
WO2016097122 discloses a process for the preparation of 2,3-butanediol by electroreduction of 3-hydroxybutanone in an aqueous medium using a porous Pt or Ni cathode. In comparative example 1, MEK was prepared by using
GDL-24BC was obtained by cathodic electro-reduction of 3-hydroxybutanone with a selectivity of 64.0% and a conversion of 75.7% for 3-hydroxybutanone. However, productivity, i.e. hourly per m, which is a key parameter directly related to industrial productivity2Kilogram MEK (kg-MEK/h/m) generated in the electrode (cathode) area of (1)2)(PMEKThe higher the capital investment, the lower) for practical use.
Thus, there remains a need for an industrially scalable process that allows MEK to be obtained at an increased productivity.
Disclosure of Invention
The inventors have discovered a new method of preparing MEK that overcomes and/or minimizes some of the disadvantages of the methods disclosed in the prior art. In particular, an economical and industrially scalable process for the production of MEK with a higher productivity than that obtained by the processes of the prior art is provided. Since it can be seen from the examples that MEK is obtained in aqueous solution at a significantly high productivity by electro-reduction of acetoin at room temperature and ambient pressure at the current densities required for industrial feasibility by the new process.
The invention therefore relates to a process for preparing Methyl Ethyl Ketone (MEK) by electro-reduction of acetoin in an aqueous medium using a high hydrogen overvoltage cathode made of lead, comprising the steps of:
a) forming a solution by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in such a medium, and
b) by using a DC power supply at 500 to 5000A/m2In particular 2500, 2000, 1500 or 1000A/m2Applying a voltage between the anode and said cathode, continuously or discontinuously electrolyzing said solution in the electrochemical reactor.
Detailed Description
As used herein, "hydrogenation catalyst" refers to a catalyst capable of catalyzing the reduction of groups that are readily reduced in the bulk catholyte by hydrogen, which is previously electrogenerated in the cathode by the electroreduction of water. Thus, in the presence of a hydrogenation catalyst, electrolysis is used to generate hydrogen, rather than direct electro-reduction of groups that are readily reduced. Examples of hydrogenation catalysts are supported noble metals (e.g., supported Pt, Pd, Ru, Ir and Rh), raney Ni and supported Ni.
Acetoin has an asymmetric carbon and is therefore a chiral molecule. Any one of the stereoisomers and mixtures thereof may be used as starting material for the process of the present invention. Thus, throughout the present invention, the term acetoin includes its enantiomers as well as mixtures thereof in any proportion, for example racemic mixtures or enantiomerically enriched mixtures of its enantiomers.
Acetoin may be obtained by fermentation of an aqueous solution of glucose, syrup or molasses, wherein the microorganism undergoing the bioconversion is a mutant strain of Lactococcus lactis (Lactococcus lactis), as disclosed in ES 2352633. By this method, acetoin is manufactured at a cost low enough to make electrosynthesis of MEK from acetoin economically viable.
As used herein, the terms "electrolyzer", "electrochemical electrolyzer" and "electrochemical reactor" are interchangeable.
As used herein, "aqueous medium" refers to 100% by weight of water, or a mixture of water and a completely or partially water-miscible solvent in which the amount of water is from 50% to 99% by weight, particularly from 70% to 99% by weight, more particularly from 85% to 99% by weight. Suitable fully or partially water miscible solvents are those which are not electroactive under the electrolysis conditions of the present invention. Examples of the solvent include, but are not limited to, alcohols such as methanol, ethanol, propanol, and isopropanol; ethers such as tetrahydrofuran and dioxane; and nitriles such as acetonitrile.
As described above, the present invention relates to a process for the preparation of MEK by the electro-reduction of acetoin in an aqueous medium using a high hydrogen overvoltage cathode made from lead. In particular, the reaction is carried out in the absence of a hydrogenation catalyst.
In one embodiment, the cathode material is lead in the form of flat sheets, or lead deposited in a porous support such as carbon felt, carbon foam, or similar material.
The electrochemical reactor used in the process of the invention may be any known to the person skilled in the art, such as a pot electrochemical reactor or a flow-through filter-press type electrochemical reactor. In one embodiment of the method of the invention, the electrochemical reactor is a flow-through filter-press type electrochemical reactor. The electrochemical reactor may be divided or undivided, with the last configuration being most preferred because it can reduce power consumption and reduce capital investment. If a divided electrochemical reactor is used, the anode and cathode are separated by a material that prevents mixing of the anolyte (the acetoin-free solution supplied through the anode compartment, e.g. aqueous sulfuric acid) and catholyte (the acetoin-containing solution supplied through the cathode compartment), while allowing ion flow to transport current in solution. Cation exchange membranes are the most preferred separation material for divided electrochemical reactors. Examples of cation exchange membranes include, but are not limited to, those prepared by
Any of those sold under trade marks, e.g.
N-324 and
N-424。
in one embodiment of the process of the invention, as anode material (anode), carbon steel, platinum supported on titanium (Pt/Ti) and iridium-based are used in the process of the invention
(dimensionally stable anode). They can be used in non-porous flat form and as perforated materials such as meshes, metal screens, sheets (lamellas), formed meshes (shaped webs) and grids.
The electro-reduction of acetoin to MEK according to the present invention is carried out in the presence of a supporting electrolyte added to adjust the conductivity of the electrolytic solution and/or to control the selectivity of the reaction. In one embodiment of the process of the present invention, the amount of supporting electrolyte is generally adjusted to a level of from 0.1 to 20% by weight, in particular from about 1 to about 15% by weight, more in particular from about 5 to about 10% by weight, based on the total mass of the solution. Examples of supporting electrolytes in non-divided cells and for use in catholyte solutions when using divided cells include, but are not limited to, ammonium salts of inorganic acids (e.g., sulfuric, phosphoric and nitric acids) as well as alkali and alkaline earth metal salts, and quaternary ammonium salts, such as tetraethylammonium bromide, tetraethylammonium chloride and sulfate and tetrabutylammonium bromide, tetrabutylammonium chloride and sulfate.
If the process of the invention is carried out in a divided electrolytic cell, further supporting electrolytes for the catholyte are ammonium salts of hydrochloric, hydrobromic and hydrofluoric acids and also alkali and alkaline earth metal salts; supporting electrolytes for the anolyte include, but are not limited to, inorganic acids (e.g., sulfuric acid and phosphoric acid), and ammonium salts and alkali metal and alkaline earth metal salts of such inorganic acids. Thus, in a particular embodiment, the process of the invention is carried out in a divided electrolytic cell and the supporting electrolyte forming the solution with acetoin is selected from the group consisting of ammonium salts and alkali and alkaline earth metal salts of inorganic acids, quaternary ammonium salts and mixtures thereof and the supporting electrolyte for the anolyte is a non-oxidizable inorganic acid.
The pH of the electrolyte in the non-divided cell or the pH of the catholyte in the divided cell may be from 2.5 to 7. Thus, in one embodiment of the process of the invention, the pH of the solution formed by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in such a medium is from 2.5 to 7, in particular from 3 to 7, more in particular from 4 to 7. The pH adjustment can be carried out by adding a suitable acid (e.g. phosphoric acid or sulfuric acid) or base (e.g. sodium hydroxide or potassium hydroxide). If the pH is less than 2.5, the current efficiency decreases due to hydrogen evolution by electroreduction of protons. If the pH is above 7, the selectivity of the reaction is negatively affected by the aldol condensation of acetoin and MEK.
The concentration of acetoin in the solution to be electrolysed formed by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in such a medium is at least 10g/L, in particular at least 25g/L, more in particular at least 50g/L, most in particular at least 100g/L, based on the total volume of the solution to be electrolysed.
In one embodiment of the process of the invention, the amount of power recycled for the electro-reduction of acetoin to MEK is 50% to 125%, more particularly 55% to 100%, most particularly 60% to 75% of the theoretical amount for obtaining 100% conversion of acetoin, assuming a current efficiency of 100% (2 faradays per mole of acetoin).
In one embodiment of the method of the present invention, the temperature at which acetoin is electro-reduced to MEK is from about 10 ℃ to 70 ℃. Particularly, the electrolysis temperature is room temperature.
In one embodiment, after electrolysis is complete, MEK is isolated by vacuum evaporation and the aqueous phase is loaded with fresh acetoin to restore its initial concentration and electrolysis is resumed.
In one embodiment, MEK is continuously removed from the aqueous medium during electrolysis by vacuum evaporation. Thus, the MEK-containing aqueous medium discharged from the electrochemical reactor was heated to a temperature of 40 ℃ to 50 ℃ and sent to a vacuum evaporator where the MEK was evaporated and condensed. The aqueous medium depleted of MEk is cooled in a heat exchanger to the electrolysis temperature and returned to the electrochemical reactor where the remaining acetoin is electro-reduced to MEk. When the acetoin concentration is reduced to a level of 40% to 50% below the initial concentration, the initial concentration is restored by adding fresh acetoin.
In another embodiment, MEK is continuously removed from the aqueous medium during electrolysis by liquid-liquid extraction using water-insoluble inert solvents such as toluene, xylene, t-butyl methyl ether and methyl isobutyl ketone. Other suitable solvents will be readily recognized by those skilled in the art.
In another embodiment, the process of the invention is carried out in the following reactor:
i) an electrochemical reactor; or
ii) at least two electrochemical reactors connected in series in such a way that a solution produced by one electrochemical reactor is fed to a subsequent electrochemical reactor, the solution comprising a mixture of unreacted acetoin, MEK, an aqueous medium and a supporting electrolyte soluble in such a medium.
If more than two electrochemical reactors connected in series are used, the current density and the circulating charge decrease from the first electrochemical reactor to the last electrochemical reactor. For example, if two electrochemical reactors connected in series are used, the current density used in the first electrochemical reactor is higher than the current density used in the second electrochemical reactor; and the proportion of the circulating charge in the first electrochemical reactor is higher than the proportion of the circulating charge in the second electrochemical reactor with respect to the total charge circulating through the two electrochemical reactors. In this way, electrical energy is more efficiently used to electroreduce acetoin to MEK.
Throughout the description and claims the word "comprise" and variations of the word are not intended to exclude other technical features, additives, ingredients or steps. Furthermore, the word "comprising" encompasses the case where "consists of. The following examples are provided for illustration and are not intended to limit the invention. Moreover, the present invention encompasses all possible combinations of the specific and preferred embodiments described herein.
Examples
Example 1
Mixing acetoin (100g/L) and KH2PO4(5% by weight) of an aqueous solution (60mL) was recirculated by means of a magnetic pump at a flow rate of 2L/min through a DSA plate (20 cm) based on iridium oxide supported by Ti as anode2) Cathode chamber of composed divided filter-pressing electrolytic tank, and method for separating anode and cathode chamber
N-324 cation exchange membrane and lead plate (20 cm) as cathode2). The gap between the electrodes was 1.7 cm. A 5 wt% aqueous solution of sulfuric acid was recirculated through the anode compartment by means of another magnetic pump. Applying a voltage between the anode and the cathode by using a DC power supply to induce a current (3A, 1500A/m)2) And (6) circulating. The electrolysis was maintained at room temperature (20-25 deg.C) for 73.01 minutes (100% of the theoretical charge for complete conversion of acetoin, assuming 100% current efficiency). The initial catholyte pH was 4.32 and the final pH was 3.75 (average pH 4.04). After the electrolysis was complete, the catholyte solution (64mL) contained acetoin at a concentration of 27.2g/L and MEK at a concentration of 40.8g/L as indicated by HPLC. Thus, acetoin conversion was 71% (71% current efficiency) and MEK yield was 53.1% (53.1% current efficiency), resulting in a selectivity to MEK (ratio of yield to conversion) of 74.9%. MEK productivity was 1.07kg MEK/h/m2。
Example 2
Same as example 1, but using acetoin (100g/L), KH2PO4An aqueous solution (60mL) of (5 wt%) and tetraethylammonium bromide (1 wt%) was used as the catholyte. The initial catholyte had a pH of 4.31 and a final pH of 4.23 (average pH of 4.27). After the electrolysis was complete, the catholyte solution (64mL) contained acetoin at a concentration of 25.1g/L and MEK at a concentration of 46.7g/L as indicated by HPLC. Thus, the acetoin conversion was 73.2% (73.2% electricity)Flow efficiency), MEK yield of 60.8% (60.8% current efficiency), resulting in a selectivity to MEK of 83.1%. MEK productivity was 1.23kg MEK/h/m2。
Example 3
Same as example 1, but using acetoin (100g/L), KH2PO4(5 wt%) and tetrabutylammonium bromide (0.5 wt%) in water (60mL) as the catholyte. The initial catholyte pH was 4.32 and the final pH was 6.68 (average pH 5.50). After the electrolysis was complete, the catholyte solution (63mL) contained acetoin at a concentration of 11.7g/L and MEK at a concentration of 38.7g/L as indicated by HPLC. Thus, the acetoin conversion was 87.8% (87.8% current efficiency) and the MEK yield was 49.7% (49.7% current efficiency), resulting in a selectivity to MEK of 56.6%. MEK productivity was 1.00kg MEK/h/m2。
Example 4
Same as example 1, but using acetoin (100g/L), KH2PO4(5 wt.%) aqueous solution (60mL) (adjusted to pH 7.0 with KOH) was used as catholyte. The final pH was 6.97 (average pH 6.99). After the electrolysis was complete, the catholyte solution (63mL) contained acetoin at a concentration of 21.8g/L and MEK at a concentration of 42.4g/L as indicated by HPLC. Thus, acetoin conversion was 77.1% (77.1% current efficiency) and MEK yield was 54.3% (54.3% current efficiency), resulting in a selectivity to MEK of 70.4%. MEK productivity was 1.10kg MEK/h/m2。
Example 5
Same as example 1, but using acetoin (100g/L), KH2PO4(5% by weight) of an aqueous solution (60mL) (with concentrated H)2SO4Adjusted to pH 3.07) as catholyte. The final pH was 2.64 (average pH 2.86). After the electrolysis was complete, the catholyte solution (63mL) contained acetoin at a concentration of 20.6g/L and MEK at a concentration of 39.5g/L as indicated by HPLC. Thus, the 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 1.02kg MEK/h/m2。
Example 6
Same as example 1, but using acetoin (100g/L), KH2PO4(5% by weight) of an aqueous solution (60mL) (adjusted to pH5.5 with KOH) as catholyte, at a current density of 1000A/m2(2A, electrolysis time 109.6 minutes, corresponding to 100% charge relative to theoretical). The final pH was 5.53. After the electrolysis was complete, the catholyte solution (61mL) contained acetoin at a concentration of 11.6g/L and MEK at a concentration of 52.2g/L as indicated by HPLC. Thus, the acetoin conversion was 88.2% (88.2% current efficiency) and the MEK yield was 64.7% (64.7% current efficiency), resulting in a MEK selectivity of 73.4%. The MEK production rate was 0.87kg MEK/h/m2。
Example 7 (comparative example)
As in example 6, but using cadmium as the cathode. The final pH was 5.51. After the electrolysis was complete, the catholyte solution (63mL) contained acetoin at a concentration of 7.5g/L and MEK at a concentration of 45.6g/L as indicated by HPLC. Thus, the acetoin conversion was 92.1% (92.1% current efficiency) and MEK yield was 58.4% (58.4% current efficiency), resulting in a selectivity to MEK of 63.5%. The MEK production rate was 0.79kg MEK/h/m2。
Examples 8, 9 (comparative examples), 10 (comparative examples)) and 11 to 24
These examples illustrate the effect of cathode materials (examples 8, 9 (comparative), 10 (comparative) and 11-15), acetoin concentration (examples 8, 16 and 17; and 19 and 21), charge (examples 18-20) and temperature (examples 21-24). Acetoin (concentration specified in table 1) and KH were used2PO4An experiment was performed in the same manner as in example 1, using an aqueous solution (60mL) (adjusted to pH5.5 with KOH) of (the concentration specified in table 1) as a catholyte, and circulating the charges also specified in table 1. The pH was 5.5 and remained constant throughout the electrolysis. The results are given in table 1, where the symbols have the following meanings:
-E: electrolyte (catholyte for divided cell)
-Q: charge, the percentage of theoretical charge that the acetate has completely converted, assuming a current efficiency of 100%,
-C: the conversion rate of the acetoin is improved,
-SMEK: the degree of selectivity to the MEK is,
-ηMEK: the efficiency of the current in the MEK is high,
- [ acetoin]i: the initial concentration of acetoin is determined,
-[MEK]f: the final MEK concentration after the end of the electrolysis,
sigracet GDL-24 BC/SS: by passing at 20cm2A gas diffusion layer (SGL Group, The Carbon Company),
Pb-X/GDL-24 BC/SS: pb electrodeposited on Sigracet GDL-24BC/SS in an amount of X μ g/cm2Geometric area.
-P: MEK productivity
- Δ P: increase in productivity (%) relative to comparative example 1%
Example 25 (comparative example, from WO2016097122)
Mixing 3-hydroxy butanone (101.1g/L) and KH2PO4(2.5% by weight) and Na2SO4(4% by weight) of an aqueous solution (60mL) (adjusted to pH 3.8 with phosphoric acid) was recirculated by means of a magnetic pump through a non-divided filter-press cell consisting of an iridium oxide based DSA anode (20 cm)2) And 20cm2(geometric area)
GDL-24BC cathodes (spaced 0.8cm apart from each other by PP separators). Applying a voltage between the anode and the cathode by using a DC power supply to induce a current (2A, 1000A/m)2) And (6) circulating. The electrolysis was maintained at room temperature (20-25 ℃) for 1.90h, corresponding to 102.8% of the theoretical charge for complete conversion of 3-hydroxybutanone, assuming a current efficiency of 100%. The initial solution had a pH of 3.8 and the final pH was 3.7.After the end of the electrolysis, the electrolytic solution (57.8mL) contained 3-hydroxybutanone at a concentration of 25.5g/L and methyl ethyl ketone at a concentration of 41.7g/L, as indicated by HPLC. Thus, the 3-hydroxybutanone conversion was 75.7% (73.6% current efficiency), the MEK yield was 48.5% (MEK selectivity 64%), and the MEK yield was 0.65kg MEK/h/m2。
Example 26
Same as example 25 (comparative example), but using a lead flat plate instead of
GDL-24BC acts as the cathode. The 3-hydroxybutanone conversion was 82.3% (80.1% current efficiency), the MEK yield was 62.1% (MEK selectivity 75.4%), and the MEK yield was 0.83kg MEK/h/m2And 27.7% higher than the MEK production rate obtained in comparative example 1.
Examples 27 to 31
These examples, like example 26, show the superior performance of the process of the invention using a non-divided cell. Mixing acetoin (200g/L) and KH2PO4(10% by weight) of an aqueous solution (60mL) (adjusted to pH5.5 with KOH) was recirculated by means of a magnetic pump at a flow rate of 2L/min through the chamber of a non-divided filter-press electrolyser consisting of a Ti-supported iridium oxide-based DSA screen (20 cm) as anode2Geometric area) and a lead plate (20 cm) as a cathode2) And (4) forming. The gap between the electrodes was 0.8 cm. The current was cycled by applying a voltage between the anode and cathode using a DC power supply (current density, J (A/m) given in Table 22)). The charge Q, expressed as% of the theoretical charge, is given in table 2 and the temperature is 22 ℃. The results are given in table 2.
Table 2 results in a non-divided cell. The meanings of coincidences are the same as in table 1.
Example 32
The same as example 28 (Table 2) but using carbon steel (C: 0.40-0.50%; Mn: 0.50-0.80%; Si: 0.15-0.40%) anodes instead of Ti supported iridium oxide based DSA screens. Acetoin conversion was 68% (100% current efficiency) and MEK yield was 50.2% (50.2% current efficiency), resulting in a selectivity to MEK of 73.8%.
Example 33 (comparative example)
The same as in example 9 (comparative example; Table 1) except that the catholyte comprised 40mL of acetoin (100g/L), KH2PO4(5 wt.%) of an aqueous solution (adjusted to ph5.5 with KOH), and 20mL of xylene for continuous extraction of MEK from the aqueous phase. After the end of the electrolysis, the concentration of acetoin in the aqueous phase of the catholyte (42mL) was 7.95g/L and the concentration of MEK was 18.75g/L, while the concentration of acetoin in the organic phase of the catholyte (15mL) was 0g/L and the concentration of MEK was 67.7g/L, as indicated by HPLC. Thus, acetoin conversion was 91.7% (91.7% current efficiency) and MEK yield was 55% (55% current efficiency), resulting in a 60% selectivity for MEK. Thus, the conversion was equal to that obtained in the absence of extraction solvent, but the selectivity to MEK was 8.3% higher. The MEK production rate was 0.79kg MEK/h/m2And a MEK production rate 8.8% higher than that of example 10. This comparative example demonstrates the positive effect of continuously removing MEK by liquid-liquid extraction as electrolysis proceeds.
Industrial applicability
The above examples demonstrate the industrial applicability of the process of the invention and its advantages. It can be operated at room temperature and ambient pressure at current densities commonly used in industrial electrochemical processes for the manufacture of organic matter (in relation to the process productivity, the higher the current density, the higher the productivity, provided that the current efficiency remains constant, or the percentage of its decrease is lower than the percentage increase in current density). In addition, it works in both divided and non-divided cells, with MEK selectivity as high as 85.5% in non-divided cells (see example 30, table 2) or 86.7% in divided cells (see example 26, table 1), and MEK productivity is suitable for industrial production.
References cited in this application
1.US4075128
2.US5506363
Zhao et al, "Catalytic reduction of 2, 3-branched over P/HZSM-5: effect of catalyst, reaction temperature and reaction configuration on registration products", RSC adv, 2016, Vol.14, pp.16988-1699.
4.WO2016097122
5.US3247085
Baizer et al, "Electrochemical conversion of 2, 3-butyl to 2-butyl in undivided flow cells: a Pair synthesis", J.appl.Electrochem,1987, Vol.14, pp.197-208
7.ES2352633
8.Popp FD and Schultz HP"Electrolytic reduction of organic compounds"Electrolytic Reduction of Organic Compounds.Chem Rev,1962,Vol.62,pp:19-40
Claims (20)
1. A method for preparing Methyl Ethyl Ketone (MEK) by electro-reducing acetoin in an aqueous medium using a cathode made of lead, the method comprising the steps of:
a) forming a solution by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in said aqueous medium, and
b) by using a DC power supply at 500 to 5000A/m2Applying a voltage between the anode and said cathode, continuously or discontinuously electrolyzing said solution in the electrochemical reactor.
2. The process of claim 1, wherein the process is carried out in the absence of a hydrogenation catalyst.
3. The method of claim 1, wherein the cathode made of lead is lead in a flat plate shape, or lead deposited in a porous carrier.
4. The method of claim 1, wherein the anode is selected from the group consisting of: carbon steel, platinum on titanium and iridium-based dimensionally stable anodes in a non-porous flat form and as a perforated material.
5. The method of claim 1, wherein the aqueous medium comprises 100% by weight of water or a mixture of water and a completely or partially water-miscible, non-electroactive solvent, the amount of water in the mixture being from 50% to 99% by weight.
6. The method of claim 1, wherein the electrochemical reactor is a non-divided reactor.
7. The method of claim 6, wherein the supporting electrolyte that forms a solution with acetoin is selected from the group consisting of: ammonium salts of inorganic acids, alkali metal salts of inorganic acids, alkaline earth metal salts of inorganic acids, quaternary ammonium salts, and mixtures thereof.
8. The method of claim 7, wherein the amount of supporting electrolyte forming a solution with acetoin is 0.1 wt% to 20 wt% based on the total mass of the solution.
9. The method of claim 1, wherein a solution formed by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in the aqueous medium has a pH of 2.5 to 7.
10. The method of claim 1, wherein the amount of power recycled for the electro-reduction of acetoin to MEK is 50% to 125% of the theoretical amount used to obtain 100% conversion of acetoin assuming 100% current efficiency.
11. The method of claim 1, wherein the electroreduction is performed at a temperature of 10 ℃ to 70 ℃.
12. The method of claim 1, wherein the MEK is continuously removed from the aqueous medium by vacuum evaporation.
13. The method of claim 1, wherein the MEK is continuously removed from the aqueous medium by liquid-liquid extraction using a water-insoluble inert solvent.
14. The process of claim 1, which is carried out in the following reactor:
i) an electrochemical reactor; or
ii) at least two electrochemical reactors connected in series in such a way that a solution produced by one electrochemical reactor is fed to a subsequent electrochemical reactor, the solution comprising a mixture of unreacted acetoin, MEK, an aqueous medium and a supporting electrolyte soluble in said aqueous medium.
15. The method of claim 2, wherein the cathode made of lead is lead in a flat plate shape, or lead deposited in a porous carrier.
16. The method of claim 15, wherein the aqueous medium comprises 100% by weight of water or a mixture of water and a completely or partially water-miscible, non-electroactive solvent, the amount of water in the mixture being from 50% to 99% by weight.
17. The method of claim 16, wherein the electrochemical reactor is a non-divided reactor.
18. The method of claim 17, wherein the supporting electrolyte that forms a solution with acetoin is selected from the group consisting of: ammonium salts of inorganic acids, alkali metal salts of inorganic acids, alkaline earth metal salts of inorganic acids, quaternary ammonium salts, and mixtures thereof.
19. The method of claim 18, wherein the amount of supporting electrolyte forming a solution with acetoin is 0.1 wt% to 20 wt% based on the total mass of the solution.
20. The method of claim 19, wherein a solution formed by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in the aqueous medium has a pH of 2.5 to 7.
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|---|---|---|---|
| EP16382424.6 | 2016-09-14 | ||
| 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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| CN109790630A CN109790630A (en) | 2019-05-21 |
| CN109790630B true CN109790630B (en) | 2021-05-25 |
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| US (1) | US20190194814A1 (en) |
| EP (1) | EP3512982B1 (en) |
| CN (1) | CN109790630B (en) |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919349A (en) * | 1996-05-23 | 1999-07-06 | Basf Aktiengesellschaft | Electrochemical reduction of organic compounds |
| CN104313635A (en) * | 2014-10-31 | 2015-01-28 | 北京工业大学 | Electrochemical catalytic synthesis method of alpha-carbonyl ketone compounds |
| WO2016097122A1 (en) * | 2014-12-18 | 2016-06-23 | Fundacion Tecnalia Research & Innovation | Method for manufacturing 2,3-butanediol |
Family Cites Families (6)
| 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 |
| WO1991013852A1 (en) | 1990-03-05 | 1991-09-19 | Catalytica, Inc. | Process for the production of methyl ethyl ketone |
| ES2352633B8 (en) | 2009-08-04 | 2012-02-20 | Fundacion Leia Centro De Desarrollo Tecnologico | MUTANT strain of LACTOCOCCUS LACTIS LACTIS AND METHOD FOR INDUSTRIAL PRODUCTION OF ACETOINE. |
| US11566332B2 (en) * | 2012-03-06 | 2023-01-31 | Board Of Trustees Of Michigan State University | Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds |
| CA2890828C (en) * | 2012-11-20 | 2021-01-12 | Carbios | Method for recycling plastic products |
-
2017
- 2017-09-13 EP EP17764416.8A patent/EP3512982B1/en active Active
- 2017-09-13 WO PCT/EP2017/073021 patent/WO2018050695A1/en unknown
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- 2017-09-13 CN CN201780055234.8A patent/CN109790630B/en active Active
- 2017-09-13 US US16/329,428 patent/US20190194814A1/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919349A (en) * | 1996-05-23 | 1999-07-06 | Basf Aktiengesellschaft | Electrochemical reduction of organic compounds |
| CN104313635A (en) * | 2014-10-31 | 2015-01-28 | 北京工业大学 | Electrochemical catalytic synthesis method of alpha-carbonyl ketone compounds |
| WO2016097122A1 (en) * | 2014-12-18 | 2016-06-23 | Fundacion Tecnalia Research & Innovation | Method for manufacturing 2,3-butanediol |
Non-Patent Citations (1)
| Title |
|---|
| Electrochemical conversion of 2,3-butanediol to 2-butanone in undivided flow cells: a paired synthesis;M. M. BAIZER et. al.;《JOURNAL OF APPLIED ELECTROCHEMISTRY》;19841231;第14卷;第197-208页 * |
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| EP3512982B1 (en) | 2020-06-17 |
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| US20190194814A1 (en) | 2019-06-27 |
| CN109790630A (en) | 2019-05-21 |
| WO2018050695A1 (en) | 2018-03-22 |
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