EP3512982B1 - Electrochemical method for manufacturing methyl ethyl ketone - Google Patents
Electrochemical method for manufacturing methyl ethyl ketone Download PDFInfo
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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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- Prior art keywords
- mek
- acetoin
- process according
- solution
- aqueous medium
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 title claims description 315
- 238000004519 manufacturing process Methods 0.000 title description 7
- 238000002848 electrochemical method Methods 0.000 title description 2
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 claims description 155
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 claims description 73
- 238000000034 method Methods 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000005868 electrolysis reaction Methods 0.000 claims description 25
- 239000012736 aqueous medium Substances 0.000 claims description 20
- 239000003115 supporting electrolyte Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- -1 nets Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000002609 medium Substances 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910000975 Carbon steel 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
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000003839 salts Chemical group 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 2
- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007836 KH2PO4 Substances 0.000 description 12
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 12
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 12
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000007423 decrease Effects 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000010963 scalable process Methods 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 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
- 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
- 150000003738 xylenes Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical class NCC(O)C(O)=O BMYNFMYTOJXKLE-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000194041 Lactococcus lactis subsp. lactis 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000014969 Streptococcus diacetilactis Nutrition 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
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 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
- 239000012074 organic phase Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 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
- 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
- 239000011701 zinc Substances 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
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.
Description
- 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.
- MEK is an important chemical widely used industrially as a solvent in the vinyl resins and synthetic rubber industries. Currently, 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 inUS5506363 ; 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. - These methods involve a serious environmental burden and use non-renewable fossil resources as raw materials, with the exception of that starting from 2,3-butanediol which can be obtained by fermentation of sugars. Nevertheless, this last method operates at a high temperature so that it is intensive in energy consumption. Therefore, there is a need for non-polluting new methods for manufacturing MEK starting from renewable raw materials and able to work at low temperatures and pressures.
-
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. The acetoin formed in solution by oxidation of 2,3-butanediol with the electrogenerated NaBrO is electroreduced to MEK in the cathode. However, this process has no industrial applicability due to its very low current density of 20 A/m2, far below the useful industrial ones ranging from at least 500 A/m2 to about 5000 A/m2. Therefore, the process of Baizer et al. results in very poor productivities requiring a huge capital investment. Another strong current drawback of this process from an environmental standpoint is that Hg-based cathodes are used as well as the presence of NaBrO within the electrolyzed solution. Additionally, Baizer et al. states that an increase in the current density above 20 A/m2 caused more H2 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/m2) 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. In the example comparative 1, 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. However, productivity, i.e. the kg of MEK produced per hour and per m2 of electrode (cathode) area (kg-MEK/h/m2), a key parameter directly related to the industrial productivity (the higher PMEK 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. - Thus, there continues to be a need of an industrially scalable process which allows obtaining MEK with an increased productivity.
- Inventors have found a new process for the preparation of MEK that overcomes and/or minimizes some of the drawbacks of the processes disclosed in the prior art. Particularly, an economical and industrially scalable process for the production of MEK with higher productivities than the ones obtained by the processes of the prior art is provided. As it can be seen from the examples, by means of the new process, MEK is obtained in an aqueous solution by electroreduction of acetoin at room temperature and ambient pressure, at the current densities required for industrial feasibility, and with a significantly high productivity.
- Thus, 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:
- a) forming a solution by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in such a medium, and
- b) electrolyzing said solution continuously or discontinuously in an 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/m2, particularly of 2500, 2000, 1500, or 1000 A/m2.
- As used herein "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. Examples of 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 - As used herein, the terms "cell", "electrochemical cell" and "electrochemical reactor" are interchangeable.
- As used herein, "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.
- As mentioned above 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.
- In a particular embodiment, 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. In a particular embodiment of the process of the invention, 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. 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.
- In a particular embodiment of the process of the invention, as 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. In a particular embodiment of the process of the invention, 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.
- If the process of the present invention is carried out in a divided cell, 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. Accordingly, in a particular embodiment, 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.
- 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.
- In a particular embodiment of the process of the invention, 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%.
- In a particular embodiment of the process of the invention, the temperature for electroreduction of acetoin to MEK is from 10 °C to 70 °C. Particularly the electrolysis temperature is room temperature.
- In a particular embodiment, after electrolysis completion 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.
- In a particular embodiment, MEK is continuously removed from the aqueous medium during electrolysis by vacuum evaporation. Thus, 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. When the acetoin concentration decreases below a level from 40 to 50% of the initial one, the initial concentration is restored by adding fresh acetoin.
- In another particular embodiment, 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. Other suitable solvents are easily recognizable by those skilled in the art.
- In another particular embodiment, the process of the invention is carried out:
- i) in one electrochemical reactor, or
- ii) in at least two electrochemical reactors connected in series in such a way that the solution, comprising a mixture of unreacted acetoin, MEK, an aqueous medium, and a supporting electrolyte soluble in such a medium, resulting from one electrochemical reactor feeds the subsequent one.
- If two or more electrochemical reactors connected in series are used 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.
- Throughout the description and claims the word "comprise" and variations of the word, are not intended to exclude other technical features, additives, components, or steps. Furthermore, the word "comprise" encompasses the case of "consisting of". The following examples are provided by way of illustration, and they are not intended to be limiting of the present invention. Furthermore, the present invention covers all possible combinations of particular and preferred embodiments described herein.
- A solution (60 mL) of acetoin (100 g/L) and KH2PO4 (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 cm2), a Nafion® N-324 cation exchange membrane for separating anode and cathode compartments, and a lead flat sheet as a cathode (20 cm2). 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/m2) 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. Therefore, 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/m2.
- As in example 1, but using as catholyte a solution (60 mL) of acetoin (100 g/L), KH2PO4 (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. Therefore, 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/m2.
- As in example 1, but using as catholyte a solution (60 mL) of acetoin (100 g/L), KH2PO4 (5 wt%) and tetrabutyl ammonium bromide (0.5 wt%) in water. Initial catholyte pH was 4.32 and final one 6.68 (mean pH 5.50). After electrolysis completion, the catholyte solution (63 mL) contained an acetoin concentration of 11.7 g/L and a MEK concentration of 38.7 g/L, as shown by HPLC. Therefore, acetoin conversion was 87.8% (87.8% current efficiency) and MEK yield was 49.7% (49.7% current efficiency) resulting in a selectivity to MEK of 56.6%. MEK productivity was 1.00 kg MEK/h/m2.
- As in example 1, but using as catholyte a solution (60 mL) of acetoin (100 g/L), KH2PO4 (5 wt%) in water adjusted to pH 7.0 with KOH. Final pH was 6.97 (mean pH 6.99). After electrolysis completion, the catholyte solution (63 mL) contained an acetoin concentration of 21.8 g/L and a MEK concentration of 42.4 g/L, as shown by HPLC. Therefore, 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 1.10 kg MEK/h/m2.
- As in example 1, but using as catholyte a solution (60 mL) of acetoin (100 g/L), KH2PO4 (5 wt%) in water adjusted to pH 3.07 con H2SO4. 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/m2.
- As in example 1, but using as catholyte a solution (60 mL) of acetoin (100 g/L), KH2PO4 (5 wt%) in water adjusted to pH 5.5 with KOH, and a current density of 1000 A/m2 (2 A, electrolysis time of 109.6 min corresponding to an electric charge of 100% relative to the theoretical one). Final pH was 5.53. After electrolysis completion, the catholyte solution (61 mL) contained an acetoin concentration of 11.6 g/L and a MEK concentration of 52.2 g/L, as shown by HPLC. Therefore, 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/m2.
- As in example 6, but using cadmium as a cathode. Final pH was 5.51. After electrolysis completion, the catholyte solution (63 mL) contained an acetoin concentration of 7.5 g/L and a MEK concentration of 45.6 g/L, as shown by HPLC. Therefore, 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%. MEK productivity was 0.79 kg MEK/h/m2.
- These examples illustrate the influence of cathode material (examples 8, 9 (comparative), 10 (comparative), and 11-15), 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/m2 and a divided cell) using as catholyte a solution (60 mL) of acetoin (in the concentration specified in Table 1) and KH2PO4 (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:
- E: Electrolyte (Catholyte for divided cells)
- Q: electric charge, % of the theoretical charge for full conversion of acetoin assuming a current efficiency of 100%,
- C: Acetoin conversion,
- SMEK. Selectivity to MEK,
- ηMEK: MEK current efficiency,
- [Acetoin]i: initial acetoin concentration,
- [MEK]f: final MEK concentration after electrolysis completion,
- Sigracet GDL-24BC/SS: A gas diffusion layer (SGL Group, The Carbon Company) supported by gluing on 20 cm2 of a stainless steel sheet, Pb-X/GDL-24BC/SS: Pb electrodeposited on Sigracet GDL-24BC/SS in an amount of X µg/cm2 of geometric area.
- P: MEK productivity
- ΔP: Productivity increase (%) vs Comparative Example 1 (%)
- A solution (60 mL) of 3-hydroxybutanone (101.1 g/L), KH2PO4 (2.5 wt%) and Na2SO4 (4 wt%) in water adjusted to pH 3.8 with phosphoric acid, was recirculated by means of a magnetic pump through an undivided filter press cell consisting of a Iridium oxide-based DSA anode (20 cm2) and a 20 cm2 (geometric area) Sigracet® GDL-24BC cathode separated 0.8 cm each other by means of a PP separator. An electrical current was circulated (2 A, 1000 A/m2) by applying a voltage between anode and cathode using a DC Power Supply. 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. After electrolysis completion, 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/m2.
- 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/m2, 27.7% higher than that obtained in Comparative Example 1.
- Similarly as in Example 26, these examples show the good performance of the present process using an undivided cell. A solution (60 mL) of acetoin (200 g/L) and KH2PO4 (10 wt%) in water, adjusted to pH 5.5 with KOH, was recirculated at a flow-rate of 2 L/min by means of a magnetic pump through the compartment of an undivided filter press cell consisting of a Ti-supported iridium oxide-based DSA mesh as an anode (20 cm2 geometric area) and a lead flat sheet as a cathode (20 cm2). Inter-electrode gap was 0.8 cm. An electrical current was circulated (at the current density, J (A/m2), given in Table 2) by applying a voltage between anode and cathode using a DC Power Supply. Electrical charge, Q, as % of the theoretical one was as given in Table 2, and temperature was 22 °C. Results are given in Table 2.
Table 2. Results in an undivided cell. Meaning of symbols as in Table 1 Ex. J (A/m2) Q (%) [MEK]final (g/L) C (%) SMEK (%) ηMEK (%) P (kg-MEK/h/m2) ΔP (%) 27 1500 75 85.2 72.5 71.8 69.4 1.40 115.4 28 1000 68 91.2 63.9 85.5 80.4 1.08 66.4 29 1000 75 98.2 74.1 79.5 78.6 1.06 62,6 30 1000 50 65.7 47.5 84.6 80.4 1.08 66.4 31 750 75 97.2 73.5 80.8 79.2 0.80 22.9 - As in example 28 (Table 2), but using a carbon steel (C: 0.40-0.50%; Mn: 0.50-0.80%; Si: 0.15-0.40%) anode instead a Ti-supported iridium oxide-based DSA mesh. 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%.
- As example 9 (comparative; Table 1) except that the catholyte comprised 40 mL of acetoin (100 g/L), KH2PO4 (5 wt%) in water adjusted to pH 5.5 with KOH, and 20 mL of xylenes for extracting continuously MEK from the aqueous phase. After electrolysis completion, 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, while 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. Therefore, acetoin conversion was 91.7% (91.7% current efficiency) and MEK yield was 55% (55% current efficiency) resulting in a selectivity to MEK of 60%. Thus, conversion was equal to that obtained in the absence of an extraction solvent, but selectivity to MEK was 8.3% higher. MEK productivity was 0.79 kg MEK/h/m2, 8.8% higher than that in example 10. This comparative example shows the positive effect of removing continuously MEK by liquid-liquid extraction as electrolysis proceeds.
- The above examples demonstrated the industrial applicability of the method of the present invention and its advantages. It can be operated at room temperature and ambient pressure under current densities (related to the process productivity, the higher the current density the higher the productivity, provided that the current efficiency keeps constant, or it decreases in a percentage lower than the increase in current density percentage) typically used in industrial electrochemical processes for manufacturing organics. Additionally, it works both in divided and undivided cells, with selectivities to MEK as high as 85.5% (see example 30, Table 2) in undivided cells or 86.7% (see example 26, Table 1) in divided cells, and with MEK productivities suitable for industrial production.
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- 1.
US4075128 - 2.
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US3247085 - 6. 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
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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
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US20150008139
Ex. | Cathode | J (A/m2) | [Acetoin]i (g/L) | E | Q (%) | T (°C) | [MEK]f g/L | C (%) | SMEK (%) | ηMEK (%) | P (kg MEK/h/m2) | ΔP (%) |
8 | Pb | 1500 | 100 | A | 100 | 20 | 43.4 | 74.3 | 77.2 | 57.4 | 1.16 | 78.2 |
9 | Cd | 1500 | 100 | A | 100 | 20 | 39.6 | 91.8 | 55.4 | 50.8 | 1.02 | 57.7 |
10 | Zn | 1500 | 100 | A | 100 | 20 | 34.2 | 88.1 | 49.7 | 43.8 | 0.88 | 36.0 |
11 | Pb-200/GDL-24BC/SS | 1500 | 100 | A | 100 | 20 | 37.6 | 80.2 | 62.0 | 49.7 | 1.00 | 54.3 |
12 | Pb-500/GDL-24BC/SS | 1500 | 100 | A | 100 | 20 | 40.5 | 83.1 | 64.5 | 53.6 | 1.08 | 66.4 |
13 | Pb-1000/GDL-24BC/SS | 1500 | 100 | A | 100 | 20 | 41.4 | 81.9 | 66.8 | 54.7 | 1.10 | 69.8 |
14 | Pb-5000/GDL-24BC/SS | 1500 | 100 | A | 100 | 20 | 39 | 85.0 | 62.6 | 53.2 | 1.07 | 65.1 |
15 | Pb-20000/GDL-24BC/SS | 1500 | 100 | A | 100 | 20 | 44.4 | 98.3 | 59.8 | 58.7 | 1.18 | 82.2 |
16 | Pb | 1500 | 200 | A | 100 | 20 | 85.5 | 90.2 | 67.5 | 60.9 | 1.23 | 89.0 |
17 | Pb | 1500 | 300 | A | 100 | 20 | 116.1 | 86.3 | 64.8 | 55.9 | 1.13 | 73.5 |
18 | Pb | 1500 | 100 | B | 50 | 20 | 26.1 | 39.6 | 81.9 | 64.9 | 1.31 | 101.4 |
19 | Pb | 1500 | 100 | B | 75 | 20 | 37.7 | 67.4 | 56,9 | 51.1 | 1.03 | 58.6 |
20 | Pb | 1500 | 100 | B | 100 | 20 | 41.5 | 72.0 | 76.2 | 54.9 | 1.11 | 70.4 |
21 | Pb | 1500 | 200 | B | 75 | 12 | 85.8 | 75.2 | 78.9 | 79.1 | 1.60 | 145.5 |
22 | Pb | 1500 | 200 | B | 75 | 20 | 83.5 | 66.7 | 86.7 | 77.0 | 1.55 | 139.0 |
23 | Pb | 1500 | 200 | B | 75 | 35 | 75.1 | 73.2 | 64.7 | 63.1 | 1.27 | 95.9 |
24 | Pb | 1500 | 200 | B | 75 | 45 | 68.5 | 72.6 | 64.3 | 62.3 | 1.26 | 93.4 |
A: KH2PO4 (5 wt%) adjusted to pH 5.5 with KOH; B: KH2PO4 (10 wt%) adjusted to pH 5.5 with KOH. |
Claims (15)
- A process for the preparation of methyl ethyl ketone (MEK) by electroreduction of acetoin in aqueous media using a cathode made of lead, the process comprising the steps of:a) forming a solution by mixing acetoin with an aqueous medium and a supporting electrolyte soluble in such a medium, andb) electrolyzing said solution continuously or discontinuously in an 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/m2.
- The process according to claim 1, wherein the reaction is carried out in the absence of a hydrogenation catalyst which is a catalyst which is capable of catalysing the reduction by hydrogen of a group susceptible of being reduced in a bulk catholyte.
- The process according to claim 2, wherein the hydrogenation catalyst is selected from the group consisting of a supported-metal noble metal, Raney Ni, and supported Ni.
- The process according to any one of claims 1 to 3, wherein the cathode material is lead as a flat sheet or deposited in a porous support such as a carbon felt, and carbon foam.
- The process according to any one of claims 1 to 4, wherein the anode is selected from carbon steel, platinum supported on titanium, and iridium-based dimensionally stable anodes in non-porous flat form and as perforated materials such as nets, metal meshes, lamellae, shaped webs and grids.
- The process according to any one of claims 1 to 5, wherein the aqueous medium comprises 100 wt% water or a mixture of water with a fully or partially water-miscible non-electroactive solvent in which the amount of water is from 50 to 99 wt%, particularly from 70 to 99 wt%, more particularly from 85 to 99 wt%.
- The process according to any one of claims 1 to 6, wherein the electrochemical reactor is an undivided reactor.
- The process according to any one of claims 1 to 7, wherein the supporting electrolyte forming a solution with acetoin is selected from the group comprising ammonium and alkaline and alkaline earth metal salts of inorganic acids, and ammonium quaternary salts, and mixtures thereof, and the supporting electrolytes for anolyte in divided cells are non-oxidizable inorganic acids.
- The process according to claim 8, wherein the amount of the supporting electrolyte forming a solution with acetoin is from 0.1 to 20 wt%, particularly from 1 to 15 wt%, and more particularly from 5 to 10 wt%, based on the total mass of the solution.
- The process according to any one of claims 1 to 9, wherein 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 and 7, particularly from 3 to 7, and more particularly from 4 to 7.
- The process according to any one of claims 1 to 10, wherein the amount of electricity circulated for electroreducing acetoin to MEK is from 50% and 125% of the theoretical one for obtaining a 100% conversion of acetoin assuming a current efficiency of 100%, more particularly from 55% to 100%, and most particularly from 60% to 75%.
- The process according to any one of claims 1 to 11, wherein the electrolysis temperature is from 10 °C to 70 °C, particularly room temperature.
- The process according to any one of claims 1 to 12, wherein the MEK is continuously removed from the aqueous medium by vacuum evaporation.
- The process according to any one of claims 1 to 12, wherein the obtained MEK is continuously removed from the aqueous medium by liquid-liquid extraction using a water-insoluble inert solvent.
- The process according to any one of claims 1 to 14, which is carried out:i) in one electrochemical reactor; orii) in at least two electrochemical reactors connected in series in such a way that the solution, comprising a mixture of unreacted acetoin, MEK, an aqueous medium, and a supporting electrolyte soluble in such a medium, resulting from one electrochemical reactor feeds the subsequent one.
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PCT/EP2017/073021 WO2018050695A1 (en) | 2016-09-14 | 2017-09-13 | Electrochemical method for manufacturing methyl ethyl ketone |
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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 |
EP0519010A4 (en) | 1990-03-05 | 1993-03-10 | Catalytica Inc. | Catalytic system for olefin oxidation to carbonyl products |
DE19620861A1 (en) * | 1996-05-23 | 1997-11-27 | Basf Ag | Process for the electrochemical reduction of organic compounds |
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 |
EP2922906B1 (en) * | 2012-11-20 | 2018-10-31 | Carbios | Method for recycling plastic products |
CN104313635A (en) * | 2014-10-31 | 2015-01-28 | 北京工业大学 | Electrochemical catalytic synthesis method of alpha-carbonyl ketone compounds |
US20170369406A1 (en) | 2014-12-18 | 2017-12-28 | Fundacion Tecnalia Research & Innovation | Method for manufacturing 2,3-butanediol |
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