EP4165236B1 - Method for the electrochemical preparation of alkanedicarboxylic acids by ring-opening oxidation using a doped ni(o)oh foam electrode - Google Patents
Method for the electrochemical preparation of alkanedicarboxylic acids by ring-opening oxidation using a doped ni(o)oh foam electrode Download PDFInfo
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- EP4165236B1 EP4165236B1 EP21727488.5A EP21727488A EP4165236B1 EP 4165236 B1 EP4165236 B1 EP 4165236B1 EP 21727488 A EP21727488 A EP 21727488A EP 4165236 B1 EP4165236 B1 EP 4165236B1
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- 238000000034 method Methods 0.000 title claims description 46
- 239000006260 foam Substances 0.000 title claims description 28
- 150000007513 acids Chemical class 0.000 title claims description 15
- 239000002253 acid Substances 0.000 title claims description 10
- 230000003647 oxidation Effects 0.000 title claims description 7
- 238000007254 oxidation reaction Methods 0.000 title claims description 7
- 238000007142 ring opening reaction Methods 0.000 title claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 229910018583 Ni(O) Inorganic materials 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- -1 aliphatic monocarboxylic acid Chemical class 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000006184 cosolvent Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- 239000000376 reactant Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007858 starting material Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 238000010923 batch production Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 241001136792 Alle Species 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- BRRVXFOKWJKTGG-UHFFFAOYSA-N 3,3,5-trimethylcyclohexanol Chemical compound CC1CC(O)CC(C)(C)C1 BRRVXFOKWJKTGG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- DDTJYYQKMINBMN-UHFFFAOYSA-N acetic acid;cyclooctanol Chemical compound CC(O)=O.OC1CCCCCCC1 DDTJYYQKMINBMN-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005100 correlation spectroscopy Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 1
- 238000005570 heteronuclear single quantum coherence Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007248 oxidative elimination reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000003385 ring cleavage reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940030010 trimethoxybenzene Drugs 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/047—Ceramics
-
- 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
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- 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
- C25B9/13—Single electrolytic cells with circulation of an electrolyte
- C25B9/15—Flow-through cells
Definitions
- the invention relates to a process for the electrochemical production of alkylenedicarboxylic acids by ring-opening oxidation using a doped Ni(O)OH foam electrode in an aqueous alkaline solution.
- BV Lyalin and VA Petrosyan disclose the production of unsubstituted adipic acid and the oxidation of carbohydrates.
- EP 2907898 A1 ( US 2015/0225861 A1 ) discloses the use of nickel foam at reaction temperatures of 80 ° C for the oxidative ring cleavage of 3,3,5-trimethylcyclohexanol in one embodiment variant. The reaction was carried out in a highly diluted solution with low yields.
- Schmitt et al. (Beilstein J. Org. Chem., 2015, 11, 473-480 ) reveal the cleavage of lignin into various oxo-substituted aromatics using different electrodes. The oxidation to the corresponding acids was not successful.
- Another advantage is the high yield of the process according to the invention.
- the present invention thus opens up for the first time the possibility of developing a technically relevant continuous process for obtaining alkanedicarboxylic acids without the use of aggressive chemicals and still in high yields.
- R 1 , R 2 , R 3 can be the same or different, hydrogen or alkyl radical with 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, linear or branched, where at least one of the radicals R 1 , R 2 , R 3 is an alkyl radical.
- radicals R 1 , R 2 , R 3 are particularly preferably hydrogen and R 2 is an alkyl radical with 1 to 4 carbon atoms.
- the process according to the invention is preferably carried out according to scheme (IV).
- A is a hydrocarbon with 4 to 9 carbons, all ring carbons of A in the cyclic starting material of scheme (IV) carrying at least one hydrogen substituent, A has at least 2 ring carbon atoms, more preferably 3 to 9 ring carbon atoms.
- the process according to the invention is preferably carried out according to at least one of the schemes (II), (III) or (IV).
- Isomers are known to those skilled in the art; reference is made in particular to the definitions by Prof. Kazmaier of Saarland University, e.g. E.g. http://www.uni-saarland.de/fak8/kazmaier/PDF_files/vorlesungen/Stereochemie%20Strassb%20V orlage.pdf.
- the doping content information relates to the elementary state of the doping based on the mass of the metal of the electrode.
- the Ni(O)OH foam electrode preferably has 3 to 9% by weight of phosphorus and more preferably 4 to 9% by weight; phosphorus is considered an element and is based on the metal mass of the electrode.
- the content determination of the phosphorus doping is preferably carried out in accordance with DIN EN ISO 5427, Appendix D.1.
- the Ni(O)OH foam electrode preferably has a thickness of several millimeters, more preferably more than 3 mm, more preferably more than 5 mm and particularly preferably equal to or thicker than 6 mm.
- the Ni(O)OH foam electrode preferably contains at least 90% by weight of metal, more preferably at least 95, 98, 99% by weight, more preferably at least 99.9, particularly preferably at least 99.99% by weight. Nickel, based on the total metal content.
- Ni(O)OH foam electrode can contain other metals besides nickel.
- Preferred other metals are Co, Fe and Cu.
- Content of other metals in the Ni(O)OH foam electrode is preferably equal to or less than 10% by weight, more preferably 5% by weight, more preferably 2% by weight, particularly preferably less than or equal to 1% by weight based on the total metal content.
- the Ni(O)OH foam electrode preferably contains a maximum of 5% by weight, preferably 2% by weight, more preferably 1% by weight and particularly preferably 0.5% by weight and particularly preferably a maximum of 0.1% by weight.
- % iron or iron compounds where the content information relates to the element in relation to the total metal content.
- the Ni(O)OH foam electrode preferably contains a maximum of 1% by weight, preferably 0.1% by weight and more preferably a maximum of 0.01% by weight of V, Wo and Mo; These metals are subject to corrosion in an alkaline-aqueous medium, which can have an unfavorable effect on the process according to the invention.
- any metal that is inert to the reaction medium can be used as a cathode material.
- cosolvents can be alcohols or DMSO. Up to 30% by volume of a cosolvent is preferably present, more preferably 1 to 20% by volume, based on the sum of the solvents, more preferably the solvent consists of water.
- alkaline additives are suitable as alkaline additives.
- Alkaline metal hydroxides such as LiOH, NaOH, KOH, and soluble alkaline earth metal hydroxides are preferred in the process according to the invention.
- Sodium hydroxide is particularly preferably used according to the invention.
- the concentration of the alkaline additive is preferably 0.5 to 2 mol/l based on the aqueous alkaline solution, more preferably 0.8 to 1.5 mol/l and particularly preferably 1 mol/l with a possible deviation of up to 10% , preferably a deviation of up to 5% of the molarity.
- the concentration of the starting materials according to scheme (I) is preferably 0.06 to 0.5 mol/l, more preferably 0.08 to 0.3 and particularly preferably 0.09 to 0.11 mol/l.
- the total current that leads to the reaction according to the invention according to schemes (II) and (III) is 8 F.
- 8 to 10 F are used, more preferably 8.5 to 9 F.
- 6 F are required for implementation according to scheme (IV).
- 6 to 8 F are used, more preferably 6.5 to 7 F.
- the method according to the invention is preferably carried out with a current density of 2 to 10 mA/cm 2 , more preferably 2.5 to 7.5 mA/cm 2 and particularly preferably 3.3 to 6 mA/cm 2 .
- the area specification refers to the geometric area without taking the inner surface of the foam into account.
- This current density information refers to the largest area on one of the sides and is therefore independent of the flow direction in the case of the flow cell.
- the process according to the invention can be carried out discontinuously, for example in a batch electrolysis cell or continuously in an electrolysis cell through which flow occurs, preferably in an electrolysis cell through which flow is continuous.
- the process according to the invention is preferably carried out at temperatures of 20 - 70°C, preferably 30 - 60°C, more preferably 35 - 50°C.
- the method according to the invention is carried out using a doped Ni(O)OH foam electrode, the doping being selected from phosphorus, arsenic, selenium and sulfur, the concentration of alkali being 0.8 to 1.5 mol/l and the concentration of starting material according to scheme (I) is 0.08 to 0.3 mol/l.
- the method according to the invention is carried out using a Ni(O)OH foam electrode doped with phosphorus, the concentration of alkali being 0.8 to 1.5 mol/l and the current density being 2 to 10 mA/cm 2 .
- the method according to the invention is carried out using a Ni(O)OH foam electrode doped with phosphorus according to scheme (IV).
- A is a hydrocarbon with 4 to 9 carbons, all ring carbons of A in the cyclic starting material of scheme (IV) carrying at least one hydrogen substituent, preferably A has at least 2 ring carbon atoms, more preferably 3 to 9 ring carbon atoms.
- the method according to the invention is more preferably carried out using a phosphorus-doped Ni(O)OH foam electrode in a flow cell, the concentration of alkali being 0.8 to 1.5 mol/l and the concentration of starting material according to scheme (I). is 0.08 to 0.3 mol/l.
- the method according to the invention is particularly preferably carried out using a phosphorus-doped Ni(O)OH foam electrode in a flow cell, the concentration of alkali being 0.8 to 1.5 mol/l, whereby the Concentration of starting material according to scheme (I) is 0.08 to 0.3 mol/l and the flow rate of the reaction medium in the anode space is at least 5 cm/min, preferably at least 8 cm/min, more preferably at least 10 cm/min .
- Figure 1 shows the schematic structure with a reaction cell with continuous flow
- Figure 2 shows the temperature dependence of the yield of the reaction according to Table 1, entry 1, for the doped anode in the batch test.
- All anodes used had dimensions of length 60 mm, width 20 and thickness 6 mm. In the batch process, however, only half of the surface (length 30 mm) was immersed to carry out the process according to the invention.
- the cathodes have the same surface area as the anodes, but are made of sheet metal. The thickness does not play a significant role, especially in the flow process only one surface is exposed to the reaction medium.
- the nickel foam electrodes had a density of 0.35 to 0.44 g/cm 3 . This corresponds to a porosity of 95 to 96%.
- the phosphorus-doped electrodes were purchased from Aqua Titan, Dortmund.
- Ni(O)OH layer of the anodes was carried out in 280 ml of a solution of 0.1 mol/l NiSO 4 * 6H 2 O, 0.1 mol/l NaOAc * 3H 2 O, 0.005 mol/l NaOH in carried out with distilled water.
- the electrodes were completely immersed and coated with a pole change (10 s) at 150 coulombs and 10 mA/cm 2 at room temperature. After the reaction was complete, the electrodes were rinsed and then dried.
- the reaction cell was filled (25 ml) with water and sodium hydroxide dissolved therein (1 mol/l) and the substance to be oxidized (educt according to scheme (I)). The concentration of starting material was 0.1 mol/l. The stirred solution was then tempered. The electrooxidation was carried out under galvanostatic conditions.
- the doped Ni(O)OH foam electrode prepared above was used as the anode in the experiments according to the invention; in the experiments not according to the invention, electrodes of basically the same construction and not doped with phosphorus were used and stainless steel sheet electrodes were used as cathodes.
- the solution was discharged quantitatively (with rinsing using demineralised water and dichloromethane (20 ml each)) and extracted with dichloromethane (volume ratio: water to organic solvent approximately 2 to 1).
- the remaining aqueous phase was adjusted to pH 1 with 50% sulfuric acid and extracted four times with diethyl ether (volume ratio: water to organic solvent approximately 2 to 1).
- the organic phases were dried separately over sodium sulfate and the solvent was then removed on a rotary evaporator.
- the doped Ni(O)OH foam electrode produced above was installed in a multilayer Teflon block in such a way that it was completely flowed through; the entry area was 6 mm * 20 mm, i.e. the flow direction was in the longitudinal axis of the electrode.
- the cathode was separated by a slot plate at a distance of less than a millimeter.
- the chamber was flowed through from bottom to top in an upright position.
- a Ritmo ® 05 from Fink Chem+Tec GmbH & Co. KG was used as the pump.
- reaction solutions were carried out as in the batch process.
- the workup was carried out as in the batch process.
- DC6 octanedioic acid
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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)
- Ceramic Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Description
Die Erfindung bezieht sich auf ein Verfahren zur elektrochemischen Herstellung von Alkylendicarbonsäuren durch ringöffnende Oxidation mittels einer dotierten Ni(O)OH Schaumelektrode in wässriger alkalischer Lösung.The invention relates to a process for the electrochemical production of alkylenedicarboxylic acids by ring-opening oxidation using a doped Ni(O)OH foam electrode in an aqueous alkaline solution.
Dieselben Autoren offenbaren in "
Weiterer Stand der Technik findet sich in
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur elektrochemischen Herstellung von Alkandicarbonsäuren durch ringöffnende Oxidation mittels einer mit Elementen der 5. und/oder 6. Hauptgruppe dotierten Ni(O)OH Schaumelektrode in wässriger alkalischer Lösung,
- wobei die Ni(O)OH Schaumelektrode 2 bis 10 Gew.-% Phosphor aufweist, hierbei wird Phosphor als Element betrachtet und auf die Metallmasse der Elektrode bezogen,
- gemäß Schema (I)
- wobei eine Einfach- oder Doppelbindung darstellt, entsprechend ist R vorhanden oder nicht,
- wobei R Wasserstoff oder ein Acylrest ist, wobei der Acylrest der Rest einer aliphatischen Monocarbonsäure mit 2 bis 8 Kohlenstoffatomen ist und wobei A ein Kohlenwasserstoff mit 4 bis 30 Kohlenstoffen ist, wobei alle Ringkohlenstoffe von A im cyclischen Edukt des Schemas (I) mindestens einen Wasserstoffsubstituenten tragen.
- where the Ni(O)OH foam electrode has 2 to 10% by weight of phosphorus, here phosphorus is considered an element and is based on the metal mass of the electrode,
- according to scheme (I)
- where represents a single or double bond, correspondingly R is present or not,
- where R is hydrogen or an acyl radical, where the acyl radical is the radical of an aliphatic monocarboxylic acid with 2 to 8 carbon atoms and where A is a hydrocarbon with 4 to 30 carbons, all ring carbons of A in the cyclic starting material of scheme (I) having at least one hydrogen substituent carry.
Das erfindungsgemäße Verfahren wird nachfolgend beispielhaft beschrieben, ohne dass die Erfindung auf diese beispielhaften Ausführungsformen beschränkt sein soll. Sind nachfolgend Bereiche, allgemeine Formeln oder Verbindungsklassen angegeben, so sollen diese nicht nur die entsprechenden Bereiche oder Gruppen von Verbindungen umfassen, die explizit erwähnt sind, sondern auch alle Teilbereiche und Teilgruppen von Verbindungen, die durch Herausnahmen von einzelnen Werten (Bereichen) oder Verbindungen erhalten werden können. Werden im Rahmen der vorliegenden Beschreibung Dokumente zitiert, so soll deren Inhalt vollständig zum Offenbarungsgehalt der vorliegenden Erfindung gehören. Werden nachfolgend %-Angaben gemacht, so handelt es sich, wenn nicht anders angegeben, um Angaben in Gewichts-%. Bei Zusammensetzungen beziehen sich die %-Angaben, wenn nicht anders angegeben auf die Gesamtzusammensetzung. Werden nachfolgend Mittelwerte angegeben, so handelt es sich, wenn nicht anders angegeben, um Massenmittel (Gewichtsmittel). Werden nachfolgend Messwerte angegeben, so wurden diese Messwerte, wenn nicht anders angegeben, bei einem Druck von 101325 Pa und einer Temperatur von 25 °C ermittelt.The method according to the invention is described below by way of example, without the invention being limited to these exemplary embodiments. If ranges, general formulas or compound classes are given below, these should include not only the corresponding ranges or groups of compounds that are explicitly mentioned, but also all sub-ranges and sub-groups of compounds that are obtained by removing individual values (ranges) or compounds can be. If documents are quoted in the context of the present description, their content should belong entirely to the disclosure content of the present invention. If percentage information is given below, unless otherwise stated, it is information in percent by weight. For compositions, the percentages refer to the total composition unless otherwise stated. If average values are given below, they are mass averages (weight averages), unless otherwise stated. If measured values are given below, these measured values were determined at a pressure of 101325 Pa and a temperature of 25 °C, unless otherwise stated.
Vorteil dieses Verfahrens gegenüber chemischen Oxidationsverfahren ist die Vermeidung des Einsatzes von chemischen Oxidationsmitteln wie z.B. Sal petersäure.The advantage of this process over chemical oxidation processes is that it avoids the use of chemical oxidizing agents such as nitric acid.
Ein weiterer Vorteil ist die hohe Ausbeute des erfindungsgemäßen Verfahrens.Another advantage is the high yield of the process according to the invention.
Die Ausführung in einer Durchflusszelle ist technisch einfacher und robuster als alle Ausführungen des Standes der Technik. Alle mechanisch aufwendigen Prozesse, wie z.B. Rührprozesse, können entfallen.The design in a flow cell is technically simpler and more robust than all prior art designs. All mechanically complex processes, such as stirring processes, can be omitted.
Damit eröffnet die vorliegende Erfindung erstmals die Möglichkeit der Entwicklung eines technisch relevanten kontinuierlichen Prozesses zur Gewinnung von Alkandicarbonsäuren ohne die Verwendung von aggressiven Chemikalien und trotzdem in hohen Ausbeuten.The present invention thus opens up for the first time the possibility of developing a technically relevant continuous process for obtaining alkanedicarboxylic acids without the use of aggressive chemicals and still in high yields.
Bevorzugt werden im erfindungsgemäßen Verfahren Alkandicarbonsäuren (DC) gemäß Schema (I) hergestellt
- wobei eine Einfach- oder Doppelbindung darstellt, entsprechend ist R vorhanden oder nicht,
- wobei R Wasserstoff oder ein Acylrest ist, wobei der Acylrest der Rest einer aliphatischen Monocarbonsäure mit 2 bis 5 Kohlenstoffatomen, besonders bevorzugt ein Acetyl ist, und
- wobei A ein Kohlenwasserstoff mit 4 bis 30 Kohlenstoffen ist, wobei alle Ringkohlenstoffe von A im cyclischen Edukt des Schemas (I) mindestens einen Wasserstoffsubstituenten tragen, A weist mindestens 2 Ringkohlenstoffatome auf, mehr bevorzugt 3 bis 9 Ringkohlenstoffatome.
- where represents a single or double bond, correspondingly R is present or not,
- where R is hydrogen or an acyl radical, the acyl radical being the radical of an aliphatic monocarboxylic acid with 2 to 5 carbon atoms, particularly preferably an acetyl, and
- where A is a hydrocarbon with 4 to 30 carbons, all ring carbons of A in the cyclic starting material of scheme (I) carrying at least one hydrogen substituent, A has at least 2 ring carbon atoms, more preferably 3 to 9 ring carbon atoms.
Für den Fall dass gleich einer Einfachbindung und R gleich Wasserstoff ist (Cycloalkanole), wird das erfindungsgemäße Verfahren bevorzugt nach Schema (II) durchgeführt.
R1, R2, R3 können gleich oder verschieden sein, Wasserstoff oder Alkylrest mit 1 bis 8 Kohlenstoffatomen bevorzugt 1 bis 5 Kohlenstoffatomen, linear oder verzweigt, wobei mindestens einer der Reste R1, R2, R3 ein Alkylrest ist.R 1 , R 2 , R 3 can be the same or different, hydrogen or alkyl radical with 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, linear or branched, where at least one of the radicals R 1 , R 2 , R 3 is an alkyl radical.
Mehr bevorzugt ist nur einer der Reste R1, R2, R3 ein Alkylrest mit 1 bis 4 Kohlenstoffatomen. Besonders bevorzugt sind die Reste R1 und R3 Wasserstoff und R2 ein Alkylrest mit 1 bis 4 Kohlenstoffatomen.More preferably, only one of the radicals R 1 , R 2 , R 3 is an alkyl radical with 1 to 4 carbon atoms. The radicals R 1 and R 3 are particularly preferably hydrogen and R 2 is an alkyl radical with 1 to 4 carbon atoms.
Für den Fall dass gleich einer Einfachbindung und R gleich ein Acylrest ist (Acylcycloalkanole), wird das erfindungsgemäße Verfahren bevorzugt nach Schema (III) durchgeführt.
- wobei der Acylrest ein Acetyl ist, und
- A ein Kohlenwasserstoff mit 4 bis 9 Kohlenstoffen ist, wobei alle Ringkohlenstoffe von A im cyclischen Edukt des Schemas (III) mindestens einen Wasserstoffsubstituenten tragen, A weist mindestens 3 Ringkohlenstoffatome auf (Acylhexanole), mehr bevorzugt 3 bis 9 Ringkohlenstoffatome.
- where the acyl radical is acetyl, and
- A is a hydrocarbon with 4 to 9 carbons, all ring carbons of A in the cyclic starting material of scheme (III) carrying at least one hydrogen substituent, A has at least 3 ring carbon atoms (acylhexanols), more preferably 3 to 9 ring carbon atoms.
Für den Fall dass gleich einer Doppelbindung und R nicht vorhanden ist (Cycloalkanone), wird das erfindungsgemäße Verfahren bevorzugt nach Schema (IV) durchgeführt.
Bevorzugt wird das erfindungsgemäße Verfahren nach mindestens einem der Schemas (II), (III) oder (IV) durchgeführt.The process according to the invention is preferably carried out according to at least one of the schemes (II), (III) or (IV).
Wo immer Moleküle beziehungsweise Molekülfragmente ein oder mehrere Stereozentren aufweisen oder aufgrund von Symmetrien in Isomere unterschieden werden können oder aufgrund anderer Effekte z.B. eingeschränkter Rotation in Isomere unterschieden werden können, sind alle möglichen Isomere von der vorliegenden Erfindung mit eingeschlossen.Wherever molecules or molecular fragments have one or more stereocenters or are differentiated into isomers based on symmetries can be or can be differentiated into isomers due to other effects, for example limited rotation, all possible isomers are included in the present invention.
Isomere sind dem Fachmann bekannt, in besonderer Weise wird auf die Definitionen von Prof. Kazmaier der Universität des Saarlandes verwiesen, z. B. http://www.uni-saarland.de/fak8/kazmaier/PDF_files/vorlesungen/Stereochemie%20Strassb%20V orlage.pdf verwiesen.Isomers are known to those skilled in the art; reference is made in particular to the definitions by Prof. Kazmaier of Saarland University, e.g. E.g. http://www.uni-saarland.de/fak8/kazmaier/PDF_files/vorlesungen/Stereochemie%20Strassb%20V orlage.pdf.
Die Gehaltsangaben der Dotierung beziehen sich auf den Elementarzustand der Dotierung bezogen auf die Masse des Metalls der Elektrode.The doping content information relates to the elementary state of the doping based on the mass of the metal of the electrode.
Bevorzugt weist die Ni(O)OH Schaumelektrode 3 bis 9 Gew.-% Phosphor und mehr bevorzugt 4 bis 9 Gew.-% auf, hierbei wird Phosphor als Element betrachtet und auf die Metallmasse der Elektrode bezogen.The Ni(O)OH foam electrode preferably has 3 to 9% by weight of phosphorus and more preferably 4 to 9% by weight; phosphorus is considered an element and is based on the metal mass of the electrode.
Die Gehaltsbestimmung der Phosphordotierung wird bevorzugt gemäß DIN EN ISO 5427, Anhang D.1 durchgeführt.The content determination of the phosphorus doping is preferably carried out in accordance with DIN EN ISO 5427, Appendix D.1.
Bevorzugt weist die Ni(O)OH Schaumelektrode eine Dicke von mehreren Millimetern auf, mehr bevorzugt von mehr als 3 mm, weiter mehr bevorzugt mehr als 5 mm und insbesondere bevorzugt gleich oder dicker als 6 mm.The Ni(O)OH foam electrode preferably has a thickness of several millimeters, more preferably more than 3 mm, more preferably more than 5 mm and particularly preferably equal to or thicker than 6 mm.
Die Ni(O)OH Schaumelektrode enthält als Metall bevorzugt mindestens zu 90 Gew.-%, mehr bevorzugt mindestens 95, 98, 99 Gew.-%, weiter mehr bevorzugt mindestens 99,9, insbesondere bevorzugt mindestens 99,99 Gew.-% Nickel, bezogen auf den Gesamtmetallgehalt.The Ni(O)OH foam electrode preferably contains at least 90% by weight of metal, more preferably at least 95, 98, 99% by weight, more preferably at least 99.9, particularly preferably at least 99.99% by weight. Nickel, based on the total metal content.
Die Ni(O)OH Schaumelektrode kann außer Nickel weitere Metalle enthalten. Bevorzugte weitere Metalle sind Co, Fe und Cu.The Ni(O)OH foam electrode can contain other metals besides nickel. Preferred other metals are Co, Fe and Cu.
Gehalt anderer Metalle in der Ni(O)OH Schaumelektrode ist bevorzugt gleich oder kleiner als 10 Gew.-%, mehr bevorzugt 5 Gew.-%, weiter mehr bevorzugt 2 Gew.-%, insbesondere bevorzugt kleiner oder gleich 1 Gew.-% bezogen auf den Gesamtmetallgehalt.Content of other metals in the Ni(O)OH foam electrode is preferably equal to or less than 10% by weight, more preferably 5% by weight, more preferably 2% by weight, particularly preferably less than or equal to 1% by weight based on the total metal content.
Bevorzugt enthält die Ni(O)OH Schaumelektrode maximal 5 Gew.-%, bevorzugt 2 Gew.-%, mehr bevorzugt 1 Gew.-% und besonders bevorzugt 0,5 Gew.-% und insbesondere bevorzugt maximal 0,1 Gew.-% Eisen oder Eisenverbindungen, wobei die Gehaltsangaben auf das Element in Bezug auf den Gesamtmetallgehalt bezogen sind.The Ni(O)OH foam electrode preferably contains a maximum of 5% by weight, preferably 2% by weight, more preferably 1% by weight and particularly preferably 0.5% by weight and particularly preferably a maximum of 0.1% by weight. % iron or iron compounds, where the content information relates to the element in relation to the total metal content.
Bevorzugt enthält die Ni(O)OH Schaumelektrode maximal je 1 Gew.-%, bevorzugt je 0,1 Gew.-% und mehr bevorzugt maximal je 0,01 Gew.-% an V, Wo und Mo; diese Metalle unterliegen in alkalisch-wässrigen Medium einer Korrosion, dies kann sich ungünstig auf das erfindungsgemäße Verfahren auswirken.The Ni(O)OH foam electrode preferably contains a maximum of 1% by weight, preferably 0.1% by weight and more preferably a maximum of 0.01% by weight of V, Wo and Mo; These metals are subject to corrosion in an alkaline-aqueous medium, which can have an unfavorable effect on the process according to the invention.
Als Kathodenmaterial kommt prinzipiell jedes gegenüber dem Reaktionsmedium inerte Metall in Frage. Bevorzugt wird erfindungsgemäß Edelstahl, Platin oder Nickel oder eine Mischung eingesetzt.In principle, any metal that is inert to the reaction medium can be used as a cathode material. According to the invention, preference is given to using stainless steel, platinum or nickel or a mixture.
Das erfindungsgemäße Verfahren wird in wässriger alkalischer Lösung durchgeführt. Bevorzugte Cosolventien können Alkohole oder DMSO sein. Bevorzugt sind bis zu 30 Vol.-% eines Cosolvenzes anwesend, mehr bevorzugt 1 bis 20 Vol.-%, bezogen auf die Summe der Lösungsmittel, mehr bevorzugt besteht das Lösungsmittel aus Wasser.The process according to the invention is carried out in an aqueous alkaline solution. Preferred cosolvents can be alcohols or DMSO. Up to 30% by volume of a cosolvent is preferably present, more preferably 1 to 20% by volume, based on the sum of the solvents, more preferably the solvent consists of water.
Als alkalische Zusätze eignen sich im Prinzip alle bekannten anorganischen Basen. Bevorzugt werden im erfindungsgemäßen Verfahren Alkalimetallhydroxide, wie LiOH, NaOH, KOH, und lösliche Erdalkalimetallhydroxide. Besonders bevorzugt wird erfindungsgemäß Natriumhydroxid eingesetzt. Bevorzugt liegen keine weiteren Anionen von Basen vor.In principle, all known inorganic bases are suitable as alkaline additives. Alkaline metal hydroxides, such as LiOH, NaOH, KOH, and soluble alkaline earth metal hydroxides are preferred in the process according to the invention. Sodium hydroxide is particularly preferably used according to the invention. Preferably there are no further anions of bases present.
Die Konzentration des alkalischen Zusatzes beträgt bevorzugt 0,5 bis 2 mol/l bezogen auf die wässrige alkalische Lösung, mehr bevorzugt 0,8 bis 1,5 mol/l und insbesondere bevorzugt 1 mol/l mit einer möglichen Abweichung von bis zu 10%, bevorzugt einer Abweichung von bis zu 5% der Molarität.The concentration of the alkaline additive is preferably 0.5 to 2 mol/l based on the aqueous alkaline solution, more preferably 0.8 to 1.5 mol/l and particularly preferably 1 mol/l with a possible deviation of up to 10% , preferably a deviation of up to 5% of the molarity.
Bevorzugt beträgt im erfindungsgemäßen Verfahren die Konzentration der Edukte gemäß Schema (I) 0,06 bis 0,5 mol/l, mehr bevorzugt 0,08 bis 0,3 und insbesondere bevorzugt 0,09 bis 0,11 mol/l.In the process according to the invention, the concentration of the starting materials according to scheme (I) is preferably 0.06 to 0.5 mol/l, more preferably 0.08 to 0.3 and particularly preferably 0.09 to 0.11 mol/l.
Der Gesamtstrom, der zur erfindungsgemäßen Umsetzung nach Schema (II) und (III) führt, beträgt gemäß der Theorie 8 F. Bevorzugt werden 8 bis 10 F eingesetzt, mehr bevorzugt 8,5 bis 9 F.According to theory, the total current that leads to the reaction according to the invention according to schemes (II) and (III) is 8 F. Preferably 8 to 10 F are used, more preferably 8.5 to 9 F.
Die Einheit F steht für Faraday, welche definiert ist als Produkt aus Avogadrokonstante und Elementarladung eines Elektrons: F = NA * e.The unit F stands for Faraday, which is defined as the product of Avogadro's constant and the elementary charge of an electron: F = N A * e.
Zur Umsetzung gemäß Schema (IV) werden theoretisch 6 F benötigt. Bevorzugt werden 6 bis 8 F eingesetzt, mehr bevorzugt 6,5 bis 7 F.Theoretically, 6 F are required for implementation according to scheme (IV). Preferably 6 to 8 F are used, more preferably 6.5 to 7 F.
Bevorzugt wird das erfindungsgemäße Verfahren mit einer Stromdichte von 2 bis 10 mA/cm2, mehr bevorzugt 2,5 bis 7,5 mA/cm2und insbesondere bevorzugt 3,3 bis 6 mA/cm2 ausgeführt. Die Flächenangabe bezieht sich auf die geometrische Fläche ohne Berücksichtigung der inneren Oberfläche des Schaumes. Diese Angaben zur Stromdichte beziehen sich auf die größte Fläche einer der Seiten und sind damit im Fall der Durchflusszelle unabhängig von der Fließrichtung.The method according to the invention is preferably carried out with a current density of 2 to 10 mA/cm 2 , more preferably 2.5 to 7.5 mA/cm 2 and particularly preferably 3.3 to 6 mA/cm 2 . The area specification refers to the geometric area without taking the inner surface of the foam into account. This current density information refers to the largest area on one of the sides and is therefore independent of the flow direction in the case of the flow cell.
Das erfindungsgemäße Verfahren kann diskontinuierlich zum Beispiel in einer Batch-Elektrolysezelle oder kontinuierlich in einer durchströmbaren Elektrolysezelle erfolgen, bevorzugt in einer kontinuierlich durchströmten Elektrolysezelle.The process according to the invention can be carried out discontinuously, for example in a batch electrolysis cell or continuously in an electrolysis cell through which flow occurs, preferably in an electrolysis cell through which flow is continuous.
Das erfindungsgemäße Verfahren wird bevorzugt bei Temperaturen von 20 - 70°C, bevorzugt von 30 - 60°C, mehr bevorzugt von 35 - 50°C durchgeführt.The process according to the invention is preferably carried out at temperatures of 20 - 70°C, preferably 30 - 60°C, more preferably 35 - 50°C.
Weiter bevorzugt wird das erfindungsgemäße Verfahren unter Verwendung einer dotierten Ni(O)OH-Schaumelektrode durchgeführt, wobei die Dotierung ausgewählt ist aus Phosphor, Arsen, Selen und Schwefel, wobei die Konzentration an Alkali 0,8 bis 1,5 mol/l beträgt und die Konzentration an Edukt gemäß Schema (I) 0,08 bis 0,3 mol/l beträgt.More preferably, the method according to the invention is carried out using a doped Ni(O)OH foam electrode, the doping being selected from phosphorus, arsenic, selenium and sulfur, the concentration of alkali being 0.8 to 1.5 mol/l and the concentration of starting material according to scheme (I) is 0.08 to 0.3 mol/l.
Weiter bevorzugt wird das erfindungsgemäße Verfahren unter Verwendung einer mit Phosphor dotierten Ni(O)OH-Schaumelektrode durchgeführt, wobei die Konzentration an Alkali 0,8 bis 1,5 mol/l beträgt und die Stromdichte von 2 bis 10 mA/cm2 beträgt.More preferably, the method according to the invention is carried out using a Ni(O)OH foam electrode doped with phosphorus, the concentration of alkali being 0.8 to 1.5 mol/l and the current density being 2 to 10 mA/cm 2 .
Weiter mehr bevorzugt wird das erfindungsgemäße Verfahren unter Verwendung einer mit Phosphor dotierten Ni(O)OH-Schaumelektrode nach Schema (II) durchgeführt
- wobei R1, R2, R3 gleich oder verschieden sind, Wasserstoff oder Alkylrest mit 1 bis 8 Kohlenstoffatomen bevorzugt 1 bis 5 Kohlenstoffatomen, linear oder verzweigt, wobei mindestens einer der Reste R1, R2, R3 ein Alkylrest ist,
- wobei mehr bevorzugt nur einer der Reste R1, R2, R3 ein Alkylrest mit 1 bis 4 Kohlenstoffatomen ist und besonders bevorzugt sind die Reste R1 und R3 Wasserstoff und R2 ein Alkylrest mit 1 bis 4 Kohlenstoffatomen.
- where R 1 , R 2 , R 3 are the same or different, hydrogen or alkyl radical with 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, linear or branched, where at least one of the radicals R 1 , R 2 , R 3 is an alkyl radical,
- where more preferably only one of the radicals R 1 , R 2 , R 3 is an alkyl radical with 1 to 4 carbon atoms and particularly preferably the radicals R 1 and R 3 are hydrogen and R 2 is an alkyl radical with 1 to 4 carbon atoms.
Weiter mehr bevorzugt wird das erfindungsgemäße Verfahren unter Verwendung einer mit Phosphor dotierten Ni(O)OH-Schaumelektrode nach Schema (IV) durchgeführt
Das erfindungsgemäße Verfahren wird mehr bevorzugt unter Verwendung einer mit Phosphor dotierten Ni(O)OH-Schaumelektrode in einer Durchflusszelle durchgeführt, wobei die Konzentration an Alkali 0,8 bis 1,5 mol/l beträgt und die Konzentration an Edukt gemäß Schema (I) 0,08 bis 0,3 mol/l beträgt.The method according to the invention is more preferably carried out using a phosphorus-doped Ni(O)OH foam electrode in a flow cell, the concentration of alkali being 0.8 to 1.5 mol/l and the concentration of starting material according to scheme (I). is 0.08 to 0.3 mol/l.
Das erfindungsgemäße Verfahren wird besonders bevorzugt unter Verwendung einer mit Phosphor dotierten Ni(O)OH-Schaumelektrode in einer Durchflusszelle durchgeführt, wobei die Konzentration an Alkali 0,8 bis 1,5 mol/l beträgt, wobei die Konzentration an Edukt gemäß Schema (I) 0,08 bis 0,3 mol/l beträgt und wobei die die Strömungsgeschwindigkeit des Reaktionsmediums im Anodenraum mindestens 5 cm/min beträgt, bevorzugt mindestens als 8 cm/min, mehr bevorzugt mindestens 10 cm/min.The method according to the invention is particularly preferably carried out using a phosphorus-doped Ni(O)OH foam electrode in a flow cell, the concentration of alkali being 0.8 to 1.5 mol/l, whereby the Concentration of starting material according to scheme (I) is 0.08 to 0.3 mol/l and the flow rate of the reaction medium in the anode space is at least 5 cm/min, preferably at least 8 cm/min, more preferably at least 10 cm/min .
Alle verwendeten Anoden hatten die Abmessungen Länge 60 mm, Breite 20 und Dicke 6 mm. Im Batchverfahren wurde jedoch zur Durchführung des erfindungsgemäßen Verfahrens nur die Hälfte der Fläche (Länge 30mm) eingetaucht. Die Kathoden haben die gleichen Flächenausdehnungen wie die Anoden, jedoch als Blech ausgearbeitet. Die Dicke spielt keine wesentliche Rolle, insbesondere im Durchflussverfahren ist lediglich eine Oberfläche dem Reaktionsmedium ausgesetzt.All anodes used had dimensions of
Die Nickelschaumelektroden hatten eine Dichte von 0,35 bis 0,44 g/cm3. Das entspricht einer Porosität von 95 bis 96%.The nickel foam electrodes had a density of 0.35 to 0.44 g/cm 3 . This corresponds to a porosity of 95 to 96%.
Die Phosphor-dotierten Elektroden wurden von der Firma Aqua Titan, Dortmund bezogen.The phosphorus-doped electrodes were purchased from Aqua Titan, Dortmund.
Die Ausbildung der Ni(O)OH-Schicht der Anoden wurde in 280 ml einer Lösung aus 0,1 mol/l NiSO4 * 6H2O, 0,1 mol/l NaOAc * 3H2O, 0,005 mol/l NaOH in destilliertem Wasser durchgeführt. Die Elektroden wurden vollständig eingetaucht und unter Polwechsel (10 s) bei 150 Coulomb und 10 mA/cm2 bei Raumtemperatur beschichtet. Die Elektroden wurden nach beendeter Reaktion abgespült und anschließend getrocknet.The formation of the Ni(O)OH layer of the anodes was carried out in 280 ml of a solution of 0.1 mol/l NiSO 4 * 6H 2 O, 0.1 mol/l NaOAc * 3H 2 O, 0.005 mol/l NaOH in carried out with distilled water. The electrodes were completely immersed and coated with a pole change (10 s) at 150 coulombs and 10 mA/cm 2 at room temperature. After the reaction was complete, the electrodes were rinsed and then dried.
Zur Elektrooxidation wurde die Reaktionszelle mit Wasser sowie darin gelöstem Natriumhydroxid (1 mol/l) und der zu oxidierenden Substanz (Edukt nach Schema (I)) befüllt (25ml). Die Konzentration an Edukt betrug 0,1 mol/l. Anschließend wurde die gerührte Lösung temperiert. Die Elektrooxidation wurde unter galvanostatischen Bedingungen durchgeführt. Als Anode wurde in den erfindungsgemäßen Versuchen die oben hergestellte dotierte Ni(O)OH Schaumelektrode verwendet, in den nicht erfindungsgemäßen Versuchen wurden prinzipiell baugleiche nicht mit Phosphor dotierte Elektroden verwendet und als Kathoden dienten Edelstahlblechelektroden.For electrooxidation, the reaction cell was filled (25 ml) with water and sodium hydroxide dissolved therein (1 mol/l) and the substance to be oxidized (educt according to scheme (I)). The concentration of starting material was 0.1 mol/l. The stirred solution was then tempered. The electrooxidation was carried out under galvanostatic conditions. The doped Ni(O)OH foam electrode prepared above was used as the anode in the experiments according to the invention; in the experiments not according to the invention, electrodes of basically the same construction and not doped with phosphorus were used and stainless steel sheet electrodes were used as cathodes.
Nach Beendigung der Reaktion wurde die Lösung quantitativ (mit Nachspülen mittels VE-Wasser und Dichlormethan (jeweils 20 ml)) ausgetragen und mit Dichlormethan (Volumenverhältnis: Wasser zu org. Lösemittel etwa 2 zu 1) extrahiert. Die verbliebene wässrige Phase wurde mit 50%-iger Schwefelsäure auf pH 1 eingestellt und viermal mit Diethylether (Volumenverhältnis: Wasser zu org. Lösemittel etwa 2 zu 1) extrahiert. Die organischen Phasen wurden beide (Dichlormethan/Diethylther) getrennt voneinander über Natriumsulfat getrocknet und anschließend das Lösungsmittel am Rotationsverdampfer entfernt.After the reaction had ended, the solution was discharged quantitatively (with rinsing using demineralised water and dichloromethane (20 ml each)) and extracted with dichloromethane (volume ratio: water to organic solvent approximately 2 to 1). The remaining aqueous phase was adjusted to pH 1 with 50% sulfuric acid and extracted four times with diethyl ether (volume ratio: water to organic solvent approximately 2 to 1). The organic phases (dichloromethane/diethyl ether) were dried separately over sodium sulfate and the solvent was then removed on a rotary evaporator.
In einem mehrschichtigen Teflonblock wurde die oben hergestellte dotierte Ni(O)OH Schaumelektrode so eingebaut, dass sie vollständig durchflossen wurde, die Eintrittsfläche war 6 mm * 20 mm groß, die Fließrichtung also in Längsachse der Elektrode. Die Kathode war durch eine Schlitzplatte getrennt im Abstand von weniger als einem Millimeter angebracht. Die Kammer wurde aufrechtstehend von unten nach oben durchströmt. Als Pumpe wurde eine Ritmo® 05 der Fink Chem+Tec GmbH & Co. KG verwendet.The doped Ni(O)OH foam electrode produced above was installed in a multilayer Teflon block in such a way that it was completely flowed through; the entry area was 6 mm * 20 mm, i.e. the flow direction was in the longitudinal axis of the electrode. The cathode was separated by a slot plate at a distance of less than a millimeter. The chamber was flowed through from bottom to top in an upright position. A Ritmo ® 05 from Fink Chem+Tec GmbH & Co. KG was used as the pump.
Die Reaktionslösungen waren wie im Batch-Verfahren ausgeführt.The reaction solutions were carried out as in the batch process.
Die Aufarbeitung wurde wie im Batch-Verfahren durchgeführt.The workup was carried out as in the batch process.
1H- und 13C-NMR-Spektren wurden an einem Multikernresonanzspektrometer des Typs AC 300 und AC II 400 der Firma Bruker Analytische Messtechnik, Karlsruhe vorgenommen. Als Lösungsmittel diente CDCl3. Die chemischen Verschiebungen sind dabei in ppm angegeben und beziehen sich auf das Protonensignal des deuterierten Lösungsmittels. Die Zuordnung der Signale erfolgte dann unter zur Hilfenahme von H-COSY, H,C-HSQC sowie H,C-HMBC-Experimenten, wobei die letztendliche Auswertung der Spektren mit dem Programm MestReNova (Version: 7.01-8414) durchgeführt wurde. 1 H and 13 C NMR spectra were recorded on an AC 300 and AC II 400 multinuclear resonance spectrometer from Bruker Analytische Messtechnik, Karlsruhe performed. CDCl 3 served as the solvent. The chemical shifts are given in ppm and refer to the proton signal of the deuterated solvent. The signals were then assigned with the help of H-COSY, H,C-HSQC and H,C-HMBC experiments, with the final evaluation of the spectra being carried out using the MestReNova program (version: 7.01-8414).
Die in den Tabellen angegebenen Ausbeuten wurden mittels Integration der Signale im 13C-NMR (inverse gated) gegen den Standard Trimethoxybenzol bestimmt. Die Ausbeuten sind molar bezogene Angaben.
Claims (14)
- Method for the electrochemical preparation of alkanedicarboxylic acids by ring-opening oxidation in aqueous alkaline solution, characterized in that the oxidation is carried out at a Ni(O)OH foam electrode doped with elements of main group 5 and/or 6, wherein the Ni(O)OH foam electrode comprises 2 to 10% by weight phosphorus, phosphorus here being considered as an element, and based on the metal mass of the electrode, according to scheme (I)where R is hydrogen or an acyl radical, wherein the acyl radical is the radical of an aliphatic monocarboxylic acid having 2 to 8 carbon atoms and where A is a hydrocarbon having 4 to 30 carbon atoms, in which all ring carbons of A in the cyclic reactant of scheme (I) bear at least one hydrogen substituent.
- Method according to Claim 1, characterized in that the Ni(O)OH foam electrode comprises 3 to 9% by weight and preferably 4 to 9% by weight, phosphorus here being considered as an element and based on the metal mass of the electrode.
- Method according to Claims 1 to 2, characterized in that the Ni(O)OH foam electrode is two or more millimetres thick, preferably more than 3 mm, more preferably more than 5 mm and especially preferably equal to or thicker than 6 mm.
- Method according to at least one of Claims 1 to 3, characterized in that the Ni(O)OH foam electrode comprises nickel as metal to an extent of at least 80% by weight, preferably at least 90, 95, 98, 99% by weight, more preferably at least 99.9, especially preferably at least 99.99% by weight.
- Method according to at least one of Claims 1 to 4, characterized in that the aqueous solution signifies that up to 30% by volume of a cosolvent may be present in the solution.
- Method according to at least one of Claims 1 to 5, characterized in that the alkaline additive to the aqueous solution is lithium hydroxide, sodium hydroxide or potassium hydroxide, preferably no further anions of the bases are present.
- Method according to at least one of Claims 1 to 6, characterized in that the concentration of the alkaline additive is 0.5 to 2 mol/l, based on the aqueous alkaline solution, preferably 0.8 to 1.5 mol/l and particularly preferably 1 mol/l with a possible deviation of up to 10%, preferably a deviation of up to 5% in the molarity.
- Method according to at least one of Claims 1 to 8, characterized in that the method according to
where R1, R2, R3 are the same or different, hydrogen or alkyl radical having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, linear or branched, wherein at least one of the radicals R1, R2, R3 is an alkyl radical, wherein more preferably only one of the radicals R1, R2, R3 is an alkyl radical having 1 to 4 carbon atoms and particularly preferably the radicals R1 and R3 are hydrogen and R2 is an alkyl radical having 1 to 4 carbon atoms. - Method according to Claim 9, wherein the total amount of electrons applied is 8 to 10 F, more preferably 8.5 to 9 F, where F is the Faraday unit.
- Method according to at least one of Claims 1 to 9, characterized in that the method is carried out at a current density of 2 to 10 mA/cm2, more preferably 2.5 to 7.5 mA/cm2 and especially preferably 3.3 to 6 mA/cm2, the area referring to the geometric area without consideration of the inner surface area of the foam.
- Method according to at least one of the preceding claims, characterized in that the electrolysis is carried out in a batch electrolytic cell or in a continuous flow electrolytic cell, preferably in a continuous flow electrolytic cell.
- Method according to at least one of the preceding claims, characterized in that the cathode material used is stainless steel, platinum or nickel or a mixture.
- Method according to at least one of the preceding claims, characterized in that the electrolysis is carried out at temperatures of 20 - 70°C, preferably 30 - 60°C, more preferably 35 - 50°C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP20179245.4A EP3922758A1 (en) | 2020-06-10 | 2020-06-10 | Method for the electrochemical preparation of alkanedicarboxylic acids by ring-opening oxidation using a doped ni(o)oh foam electrode |
PCT/EP2021/064057 WO2021249775A1 (en) | 2020-06-10 | 2021-05-26 | Method for electrochemically producing alkane dicarboxylic acids by means of a ring-opening oxidation using a doped ni(o)oh foam electrode |
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EP4165236A1 EP4165236A1 (en) | 2023-04-19 |
EP4165236B1 true EP4165236B1 (en) | 2023-12-27 |
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EP20179245.4A Withdrawn EP3922758A1 (en) | 2020-06-10 | 2020-06-10 | Method for the electrochemical preparation of alkanedicarboxylic acids by ring-opening oxidation using a doped ni(o)oh foam electrode |
EP21727488.5A Active EP4165236B1 (en) | 2020-06-10 | 2021-05-26 | Method for the electrochemical preparation of alkanedicarboxylic acids by ring-opening oxidation using a doped ni(o)oh foam electrode |
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EP (2) | EP3922758A1 (en) |
JP (1) | JP2023529827A (en) |
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DE19536056A1 (en) | 1995-09-28 | 1997-04-03 | Huels Chemische Werke Ag | Liquid solutions of dicarboxylic acids |
DE10207924A1 (en) | 2002-02-23 | 2003-09-04 | Clariant Gmbh | Highly concentrated aqueous solutions of betaines or amine oxides |
DE102010002809A1 (en) | 2010-03-12 | 2011-11-17 | Evonik Degussa Gmbh | Process for the preparation of linear alpha, omega-dicarboxylic acid diesters |
DE102013203866A1 (en) | 2013-03-07 | 2014-09-11 | Evonik Industries Ag | Electrochemical coupling of a phenol with a naphthol |
DE102013203865A1 (en) | 2013-03-07 | 2014-09-11 | Evonik Industries Ag | Electrochemical coupling of two phenols, which differ in their oxidation potential |
DE102014202502A1 (en) | 2014-02-12 | 2015-08-13 | Evonik Degussa Gmbh | Process for the electrochemical preparation of 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid |
EP3498759A1 (en) | 2017-12-13 | 2019-06-19 | Evonik Degussa GmbH | Method for the preparation of polymers from monomers comprising laurolactam |
CN109837555B (en) * | 2019-04-11 | 2019-12-31 | 浙江工业大学 | Method for preparing 2, 5-furandicarboxylic acid by electrocatalytic oxidation of nickel-vanadium phosphide catalyst |
EP3741790A1 (en) | 2019-05-20 | 2020-11-25 | Evonik Operations GmbH | Polyamides with cyclic terpenoid substructures |
WO2021063630A1 (en) | 2019-10-01 | 2021-04-08 | Evonik Operations Gmbh | Method for producing thermoplastic compositions for mechanically and/or thermally stressed components |
CN111229267B (en) * | 2020-01-16 | 2021-04-20 | 湖南大学 | Supported phosphorus-doped metal oxyhydroxide nanosheet material and preparation method and application thereof |
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- 2021-05-26 CN CN202180041010.8A patent/CN115917047A/en active Pending
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WO2021249775A1 (en) | 2021-12-16 |
EP3922758A1 (en) | 2021-12-15 |
ES2975117T3 (en) | 2024-07-03 |
EP4165236A1 (en) | 2023-04-19 |
CN115917047A (en) | 2023-04-04 |
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