EP2870275A1 - Verfahren zur herstellung von vanillin - Google Patents
Verfahren zur herstellung von vanillinInfo
- Publication number
- EP2870275A1 EP2870275A1 EP13734065.9A EP13734065A EP2870275A1 EP 2870275 A1 EP2870275 A1 EP 2870275A1 EP 13734065 A EP13734065 A EP 13734065A EP 2870275 A1 EP2870275 A1 EP 2870275A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lignin
- weight
- aqueous
- solution
- electrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 150
- 239000000956 alloy Substances 0.000 claims abstract description 150
- 229920005610 lignin Polymers 0.000 claims abstract description 145
- 238000000034 method Methods 0.000 claims abstract description 87
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 61
- 239000000725 suspension Substances 0.000 claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 239000002585 base Substances 0.000 claims description 89
- 239000000243 solution Substances 0.000 claims description 83
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 57
- 230000008569 process Effects 0.000 claims description 50
- 239000010949 copper Substances 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- 239000011651 chromium Substances 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 229910052804 chromium Inorganic materials 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 229910052758 niobium Inorganic materials 0.000 claims description 14
- 229920005611 kraft lignin Polymers 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- 239000007772 electrode material Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000007900 aqueous suspension Substances 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229920001732 Lignosulfonate Polymers 0.000 claims description 5
- 239000000123 paper Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 3
- RWYKESRENLAKMN-UHFFFAOYSA-N 1-[4-[1-[4-[2-[4-[5-(1,2-dihydroxypropyl)-3-(hydroxymethyl)-7-methoxy-2,3-dihydro-1-benzofuran-2-yl]-2-methoxyphenoxy]-3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)propoxy]-3-hydroxy-5-methoxyphenyl]-3-hydroxy-2-[4-[4-(4-hydroxy-3,5-dimethoxyphenyl)-1,3,3a,4,6, Chemical compound O1C=2C(OC)=CC(C(O)C(C)O)=CC=2C(CO)C1C(C=C1OC)=CC=C1OC(CO)C(C=1C=C(OC)C(O)=CC=1)OC(C(=C1)OC)=C(O)C=C1C(C(CO)OC=1C(=CC(=CC=1)C1C2COCC2C(O1)C=1C=C(OC)C(O)=C(OC)C=1)OC)OC(C(=C1)OC)=CC=C1C(O)C(CO)OC1=CC=C(C=CCO)C=C1OC RWYKESRENLAKMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000779 depleting effect Effects 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical group [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 claims description 2
- 239000010956 nickel silver Substances 0.000 claims description 2
- 239000010944 silver (metal) Substances 0.000 claims description 2
- 229920001131 Pulp (paper) Polymers 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 210000004027 cell Anatomy 0.000 description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 238000005275 alloying Methods 0.000 description 27
- 239000000470 constituent Substances 0.000 description 22
- 150000001450 anions Chemical class 0.000 description 20
- 239000003792 electrolyte Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 239000003463 adsorbent Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- -1 sodium carbonate Chemical class 0.000 description 11
- DFYRUELUNQRZTB-UHFFFAOYSA-N apocynin Chemical compound COC1=CC(C(C)=O)=CC=C1O DFYRUELUNQRZTB-UHFFFAOYSA-N 0.000 description 10
- 238000006056 electrooxidation reaction Methods 0.000 description 10
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910000856 hastalloy Inorganic materials 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- JMSVCTWVEWCHDZ-UHFFFAOYSA-N syringic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1O JMSVCTWVEWCHDZ-UHFFFAOYSA-N 0.000 description 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910001347 Stellite Inorganic materials 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 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
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910001026 inconel Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XXQGYGJZNMSSFD-UHFFFAOYSA-N 2-[2-(dimethylcarbamoyl)phenoxy]acetic acid Chemical compound CN(C)C(=O)C1=CC=CC=C1OCC(O)=O XXQGYGJZNMSSFD-UHFFFAOYSA-N 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 102100022443 CXADR-like membrane protein Human genes 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910000792 Monel Inorganic materials 0.000 description 2
- 229910000934 Monel 400 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JMFRWRFFLBVWSI-NSCUHMNNSA-N coniferol Chemical compound COC1=CC(\C=C\CO)=CC=C1O JMFRWRFFLBVWSI-NSCUHMNNSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OANFWJQPUHQWDL-UHFFFAOYSA-N copper iron manganese nickel Chemical compound [Mn].[Fe].[Ni].[Cu] OANFWJQPUHQWDL-UHFFFAOYSA-N 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 235000013355 food flavoring agent Nutrition 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- XQYZDYMELSJDRZ-UHFFFAOYSA-N papaverine Chemical compound C1=C(OC)C(OC)=CC=C1CC1=NC=CC2=CC(OC)=C(OC)C=C12 XQYZDYMELSJDRZ-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 125000005496 phosphonium group Chemical group 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- IHSLHAZEJBXKMN-UHFFFAOYSA-L potassium nitrosodisulfonate Chemical compound [K+].[K+].[O-]S(=O)(=O)N([O])S([O-])(=O)=O IHSLHAZEJBXKMN-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 description 2
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 description 2
- LZFOPEXOUVTGJS-ONEGZZNKSA-N trans-sinapyl alcohol Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O LZFOPEXOUVTGJS-ONEGZZNKSA-N 0.000 description 2
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- YKFCISHFRZHKHY-NGQGLHOPSA-N (2s)-2-amino-3-(3,4-dihydroxyphenyl)-2-methylpropanoic acid;trihydrate Chemical compound O.O.O.OC(=O)[C@](N)(C)CC1=CC=C(O)C(O)=C1.OC(=O)[C@](N)(C)CC1=CC=C(O)C(O)=C1 YKFCISHFRZHKHY-NGQGLHOPSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- AHXNYDBSLAVPLY-UHFFFAOYSA-M 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonimidate Chemical compound [O-]S(=O)(=NS(=O)(=O)C(F)(F)F)C(F)(F)F AHXNYDBSLAVPLY-UHFFFAOYSA-M 0.000 description 1
- KCALAFIVPCAXJI-UHFFFAOYSA-N 1,10-phenanthroline-5,6-dione Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CN=C3C2=N1 KCALAFIVPCAXJI-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- CUJPFPXNDSIBPG-UHFFFAOYSA-N 1,3-propanediyl Chemical group [CH2]C[CH2] CUJPFPXNDSIBPG-UHFFFAOYSA-N 0.000 description 1
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- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- HRRVLSKRYVIEPR-UHFFFAOYSA-N 6-hydroxy-5-nitroso-1H-pyrimidine-2,4-dione Chemical compound OC1=NC(O)=C(N=O)C(O)=N1 HRRVLSKRYVIEPR-UHFFFAOYSA-N 0.000 description 1
- 229930008281 A03AD01 - Papaverine Natural products 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
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- 229910001065 Chromium-vanadium steel Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910019589 Cr—Fe Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- 239000004097 EU approved flavor enhancer Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
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- 230000005526 G1 to G0 transition Effects 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
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- 229910001182 Mo alloy Inorganic materials 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
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- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
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- LZFOPEXOUVTGJS-UHFFFAOYSA-N cis-sinapyl alcohol Natural products COC1=CC(C=CCO)=CC(OC)=C1O LZFOPEXOUVTGJS-UHFFFAOYSA-N 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019264 food flavour enhancer Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
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- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- 229930015763 p-coumaryl alcohol Natural products 0.000 description 1
- 229960001789 papaverine Drugs 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- YIBXWXOYFGZLRU-UHFFFAOYSA-N syringic aldehyde Natural products CC12CCC(C3(CCC(=O)C(C)(C)C3CC=3)C)C=3C1(C)CCC2C1COC(C)(C)C(O)C(O)C1 YIBXWXOYFGZLRU-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- DKZBBWMURDFHNE-UHFFFAOYSA-N trans-coniferylaldehyde Natural products COC1=CC(C=CC=O)=CC=C1O DKZBBWMURDFHNE-UHFFFAOYSA-N 0.000 description 1
- PTNLHDGQWUGONS-UHFFFAOYSA-N trans-p-coumaric alcohol Natural products OCC=CC1=CC=C(O)C=C1 PTNLHDGQWUGONS-UHFFFAOYSA-N 0.000 description 1
- PTNLHDGQWUGONS-OWOJBTEDSA-N trans-p-coumaryl alcohol Chemical compound OC\C=C\C1=CC=C(O)C=C1 PTNLHDGQWUGONS-OWOJBTEDSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
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- 239000000602 vitallium Substances 0.000 description 1
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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
- C25B11/04—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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
Definitions
- the invention relates to a process for the production of vanillin, which comprises an electrolysis of an aqueous, alkaline lignin-containing suspension or solution.
- Lignin as well as lignin-containing substances such as alkali lignin, lignin sulfate or lignin sulfonate, fall as waste or by-products of wood processing into pulp.
- the total production of lignocellulosic substances is estimated at about 20 billion tons per year. Lignin thus represents a valuable raw material. Parts of this lignin are still used.
- alkali lignin which can be prepared by alkaline treatment of the black liquor obtained in papermaking, is used in North America as a binder for wood-based and cellulose-based press plates, as a dispersant, for clarifying sugar solutions, for stabilizing asphalt emulsions and for stabilizing foams.
- the vast majority of waste lignin is produced by combustion as an energy source, e.g. used for the pulp process.
- the biopolymer lignin is a group of three-dimensional, occurring in the cell wall of plants macromolecules, which are composed of various phenolic monomer building blocks such as p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol. Due to its composition, it represents the only significant aromatic source of nature. Moreover, the use of this renewable natural product does not compete with its use as food.
- Vanillin 4-hydroxy-3-methoxybenzaldehyde
- Vanillin is a synthetic flavoring agent that is widely used as a food flavor, fragrance in deodorants and perfumes, as well as flavor enhancers for pharmaceuticals and vitamin supplements instead of expensive natural vanilla.
- Vanillin is also an intermediate in the synthesis of various drugs, e.g. L-dopa, methyldopa and papaverine.
- WO 87/03014 describes a process for the electrochemical oxidation of lignin at temperatures of preferably 170 to 190 ° C in aqueous, strongly alkaline solutions. Above all, electrodes made of copper or nickel are used as anodes.
- a complex mixture is obtained which, inter alia, vanillic acid (4-hydroxy-3-methoxybenzoic acid), vanillin, 4-hydroxybenzaldehyde, 4-hydroxyacetophenone and acetovanillon (4-hydroxy-3-methoxyacetophenone) and optionally phenol , Syringic acid (4-hydroxy-3,5-dimethoxybenzoic acid) and syringaldehyde (4-hydroxy-3,5-dimethoxybenzaldehyde).
- 4-hydroxybenzoic acid is the major product.
- the selectivity to vanillin formation is low and reasonably satisfactory only at high temperatures.
- a strong corrosion of the electrode materials takes place. This corrosion is also problematic in terms of contaminating the vanillin with heavy metals.
- the high temperatures are unfavorable from an energetic point of view. However, lowering the temperature leads to a significant loss of selectivity.
- the electrolytic cell used is a circulation cell in which the lignosulfate-containing electrolyte is circulated continuously through a cylindrical electrode arrangement with a central cylindrical nickel network as the cathode and a nickel net surrounding the cathode as an anode. The selectivity problem and corrosion problems are not solved by this.
- WO 2009/138368 describes a process for the electrolytic degradation of lignin, in which an aqueous lignin-containing electrolyte is oxidized on a diamond electrode.
- a low-molecular-weight product is formed which contains vanillin together with other hydroxybenzaldehyde derivatives such as acetovanone or guaiacol in approximately equal proportions.
- the selectivity of lignin oxidation with respect to vanillin is low.
- corrosion of the diamond electrode takes place under the reaction conditions.
- the older European patent application 1 1 177320.6 describes for the production of vanillin, the electrolysis of lignin-containing solutions or suspensions, being used as the anode material silver or silver-containing alloys.
- the object of the present invention is to provide a process which allows the production of vanillin from lignin or lignin-containing substances in good yields and with high selectivity with regard to vanillin formation. Furthermore, the method should be feasible under milder conditions than the methods of the prior art. The task is also to improve the corrosion problem. In particular, the vanillin is to be obtained in a form which does not preclude use as a flavoring agent.
- an aqueous, alkaline lignin-containing suspension or solution is electrolyzed, wherein a base alloy is used as the anode material, which is composed of Co base alloys, Fe base alloys, Cu base alloys and Ni. Base alloys is selected.
- the present invention thus relates to a process for producing vanillin comprising electrolysis of an aqueous alkaline lignin-containing suspension or solution, using as the anode material a base alloy selected from Co-base alloys, Fe-base alloys, Cu-base alloys and Ni-base alloys is.
- the process according to the invention has a number of advantages.
- the electrode materials used lead to a significant increase in selectivity.
- This high selectivity can surprisingly be achieved even at a comparatively low temperature of up to 100 ° C.
- the anode materials used according to the invention prove to be extremely resistant to the corrosive reaction conditions and, unlike the processes of the prior art, no or no appreciable corrosion takes place.
- an aqueous lignin-containing electrolyte containing lignin or a lignin-containing substance which is in the form of an aqueous suspension or solution is subjected to electrolysis under alkaline conditions.
- the oxidation of the lignin contained or the lignin derivative takes place at the anode.
- At the cathode is typically a reduction of the aqueous electrolyte, for example, to form hydrogen.
- one or more anodes of a base alloy are used as the anode material, wherein the base alloy is selected from Co base alloys, Fe base alloys, Cu base alloys and Ni base alloys.
- a base alloy an alloy containing at least 50% by weight, especially at least 55% by weight, especially at least 58% by weight, e.g. 50 to 99 wt .-%, preferably 50 to 95 wt .-%, in particular 55 to 95 wt .-%, particularly preferably 55 to 90 wt .-% and especially 58 to 90 wt .-% of the respective base metal (in the case a Co-base alloy Co, in the case of a Cu-based alloy Cu, in the case of a Ni-base alloy Ni and in the case of an Fe-based alloy Fe) and at least one further alloying constituent, the total amount of all other alloy constituents other than the base metal typically being at least 1 Wt .-%, in particular at least 5 wt .-% and especially at least 10 wt .-% is and, for example in the range of 1 to 50 wt .-%, preferably in the range of 5 to 50 wt .-%, in particular in the range of
- Typical other alloying constituents are, in particular, Cu, Fe, Co, Ni, Mn, Cr, Mo, V, Nb, Ti, Ag, Pb and Zn, but also Si, C, P and S. Accordingly, base alloys which are at least one other of the aforementioned, different from the base metal alloy components.
- Ni base alloys Ni base alloys, Fe base alloys and Co base alloys, in particular Ni base alloys and Co base alloys.
- a first embodiment of the invention relates to a method in which the anode material is a Ni-based alloy.
- Typical nickel-base alloys consist essentially, ie, of at least 95% by weight and in particular at least 98% by weight and especially at least 99% by weight
- the total amount of Al, Si, C and S will preferably not exceed 5 wt%.
- Typical proportions of the further alloying constituents, which may be contained in Ni-base alloys in a quantity significant for the alloy, are given in the following Table 1:
- the Ni base alloys of the first embodiment those containing 5 to 35% by weight, especially 10 to 30% by weight of Cu as a further alloying ingredient are particularly preferred. These alloys are referred to below as Group 1 .1.
- the base alloys of group 1 .1 may contain one or more of the following alloying constituents in an amount of up to 45% by weight, in particular up to 40% by weight: Fe, Co, Mn, Cr, Mo, W, V, Nb, Ti, Si, Al, C and S.
- the further alloying constituent if present, is one in Table 1 given quantity.
- Ni-base alloys of group 1 .1 are alloys of the EN short names NiCu30Fe (Monel 400) and NiCu30AI as well as the nickel-copper alloy of the following composition: 63% by weight Ni, 30% by weight Cu, 2 wt .-% Fe, 1, 5 wt .-% Mn, 0.5 wt .-% Ti (Monel 500K).
- the Ni-base alloys of the first embodiment those which contain 5 to 40% by weight, in particular 15 to 30% by weight of Cr as a further alloying constituent are particularly preferred. These alloys are referred to below as group 1 .2.
- the base alloys of group 1 .2 can contain one or more of the following alloying constituents in an amount of up to 40% by weight, in particular up to 35% by weight: Fe, Co, Mn, Cu, Mo, W, V, Nb, Ti, Si, Al, C and S.
- the further alloying ingredient, if present, is present in an amount shown in Table 1.
- the Ni-base alloys of group 1 .2 particular preference is given to those which contain Mo, Nb and / or Fe as further alloying constituent, in particular in a total amount of from 1 to 30% by weight.
- Examples of group 1 .2 Ni base alloys are alloys of the EN short names NiCr19NbMo (Inconel® alloy 718) and NiCr15Fe (Inconel® alloy 600), NiCr22Mo19Fe5 (Inconel® 625), NiMo17Cr16FeWMn (Hastelloy® C276), a Ni -Cr-Fe alloy with a nickel content of 72 to 76 wt .-%, a Cr content of 18 to 21 wt .-%, a C content of 0.08 to 0.13 wt .-% and a Fe Content of 5 wt% and a Ni-Cr-Co-Mo alloy having a nickel content of 48 to
- Ni-base alloys of the first embodiment those containing 5 to 35% by weight, in particular 10 to 30% by weight of Mo as a further alloying constituent are particularly preferred. These alloys are referred to below as group 1 .3.
- the Group 1 .3 base alloys may contain one or more of the following constituents in an amount of up to
- 40 wt .-% in particular up to 35 wt .-% contain: Fe, Co, Mn, Cu, Cr, W, V, Nb, Ti, Si, Al, C and S.
- the further alloying ingredient if present , in an amount given in Table 1.
- those which are particularly preferred are Cr, Nb and / or Fe as a further alloying ingredient, in particular in an amount of 1 to 30 wt .-%, in total.
- group 1 .3 Ni base alloys are alloys of the EN short names NiMo28 (Hastelloy® B and Hastelloy® B-2) and NiMo29Cr (Hastelloy® B-3).
- Ni-base alloys of the first embodiment those of groups 1 .2 and 1.3 are particularly preferred with regard to high stability and simultaneously high selectivity.
- a second embodiment of the invention relates to a method in which the anode material is a Co-based alloy.
- Typical cobalt base alloys are essentially, i. at least 95% by weight and in particular at least 98% by weight and especially at least 99% by weight of:
- the total amount of Si, C and P will preferably not exceed 5 wt%.
- Typical proportions of the further alloying constituents which may be present in Co-base alloys in a quantity significant for the alloy are given in the following Table 2:
- Si is 0.1 to 3
- the Co base alloys of the second embodiment particularly preferred are those containing 5 to 40% by weight, in particular 7 to 30% by weight, of Cr as a further alloying constituent. These alloys are referred to below as group 2.1.
- the base alloys of group 2.1 may contain one or more of the following alloying constituents in an amount of up to 40% by weight, in particular up to 35% by weight: Fe, Ni, Mn, Cu, Mo, W, V, Nb, Ti, Si, C and P.
- the further alloying ingredient, if present will be present in an amount shown in Table 2.
- the Co base alloys of group 2.1 particular preference is given to those which contain Mo, W and / or Fe as a further alloying constituent, in particular in a total amount of from 1 to 30% by weight.
- Co-base alloys of group 2.1 are alloys of the compositions:
- a third embodiment of the invention relates to a method in which the anode material is an Fe-based alloy.
- Typical iron-based alloys are high-alloy stainless steels.
- d. H. at least 95% by weight and in particular at least 98% by weight and especially at least 99% by weight of:
- the base alloys of group 3.1 may contain one or more of the following alloying ingredients in an amount of up to 40% by weight, in particular up to 35% by weight: Co, Ni, Mn, Cu, Mo, V, Nb, Ti, Si, C, S and P.
- the further alloying ingredient, if present will be present in an amount shown in Table 3.
- Group 3.1 Fe base alloys are chromium steels, e.g. X12Cr13, X6C7 and X20Cr13, chromium-nickel steels, e.g. X2CrNi12, X5CrNi18-10, X8CrNiS18-9, X2CrNi19-1 1, X2CrNi18-9, X10CrNi18-8, X1 CrNi19-9, X2CrNiMo17-12-2,
- a fourth embodiment of the invention relates to a method in which the anode material is a Cu-based alloy.
- Typical copper base alloys generally consist essentially of d. H. at least 95% by weight and in particular at least 98% by weight and especially at least 99% by weight
- Group 3.1 Cu base alloys are nickel silver (alloy of 62 wt.% Cu, 18 wt.% Ni and 20 wt.% Zn) and cupronickel (alloy of 75 wt.% Cu and 25 wt. % Ni).
- any type of electrode known to the person skilled in the art can be used as the anode.
- This may consist entirely of the respective base alloy or be a carrier electrode having a carrier which is coated with the base alloy. Preference is given to electrodes which consist of the respective base alloy.
- the electrodes used as the anode may, for example, be electrodes in the form of expanded metals, nets or sheets.
- any electrode known to the person skilled in the art and suitable for the electrolysis of aqueous systems can be used as the cathode.
- the electrode materials exhibit a low hydrogen overvoltage.
- Preferred electrodes are electrodes which are selected from nickel, Ni base alloys, Co base alloys, Fe base alloys, Cu base alloys, silver, Ag base alloys, ie silver-rich alloys having a silver content of at least 50% by weight. %, RuO x TiO x mixed oxides, platinized titanium, platinum, graphite or carbon.
- the electrode material of the cathode is selected from Ni base alloys, Co base alloys, Fe base alloys, Cu base alloys, more preferably Ni base alloys, Co base alloys and Fe base alloys. alloys and especially among the base alloys of groups 1.1, 1.2, 1 .3, 2.1 and 3.1.
- any type of electrode known to those skilled in the art can be used as the cathode.
- This may consist entirely of the respective electrode material or be a carrier electrode having an electrically conductive carrier which is coated with the electrode material.
- Preference is given to electrodes which consist of the respective electrode material, in particular of one of the abovementioned base alloys, especially of one of the base alloys of groups 1.1, 1.2, 1 .3, 2.1 and 3.1.
- the electrodes used as the cathode may, for example, be electrodes in the form of expanded metals, nets or sheets.
- the arrangement of anode and cathode is not limited and includes, for example, arrangements of planar gratings and / or plates, which may also be arranged in the form of several, alternately poled stacks and cylindrical arrangements of cylindrically shaped networks, gratings or tubes, which also in the form of several , alternately polarized cylinder can be arranged.
- a bipolar arrangement of a plurality of electrodes an arrangement in which a rod-shaped anode is comprised by a cylindrical cathode, or an arrangement in which both the cathode and the anode consist of a wire mesh and these wire nets are superimposed and rolled up cylindrical.
- the anode and cathode are separated by a separator.
- a separator Basically, all separators commonly used in electrolysis cells are suitable as separators.
- the separator is typically a porous sheet placed between the electrodes, e.g. a grid, mesh, woven or nonwoven fabric made of an electrically nonconductive material that is inert under the electrolysis conditions, e.g. a plastic material, in particular a Teflon material or a Teflon-coated plastic material.
- electrolysis it is possible to use any electrolysis cells known to the person skilled in the art, such as divided or undivided flow cell, capillary gap cell or plate stack cell. Particularly preferred is the undivided flow cell, for example a flow cell with circulation, in which the electrolyte is continuously circulated past the electrodes.
- the process can be carried out with good success both batchwise and continuously.
- the process according to the invention can likewise be carried out on an industrial scale.
- Corresponding electrolysis cells are known to the person skilled in the art. All embodiments of this invention relate to both the laboratory and the industrial scale.
- the contents of the electrolytic cell is mixed.
- any mechanical stirrer known to those skilled in the art can be used.
- the use of other mixing methods such as the use of Ultraturrax, ultrasound, jet nozzles or circulation or combinations of these measures is also preferred.
- the electrolysis voltage By applying the electrolysis voltage to the anodes and cathodes, electric current is passed through the electrolyte.
- a current density of 1000 mA / cm 2 in particular 100 mA / cm 2 .
- the current densities at which the process is carried out are generally 1 to 1000 mA cm 2 , preferably 1 to 100 mA / cm 2 .
- the process according to the invention is particularly preferably carried out at current densities between 1 and 50 mA / cm 2 .
- the total duration of the electrolysis naturally depends on the electrolytic cell, the electrodes used and the current density. An optimum duration can be determined by the skilled person by routine tests, e.g. by sampling during electrolysis.
- the polarity can be changed at short intervals.
- the polarity reversal can take place in an interval of 30 seconds to 10 minutes, an interval of 30 seconds to 2 minutes is preferred.
- the anode and cathode are made of the same material.
- the electrolysis is carried out according to the inventive method usually at a temperature in a range of 0 to 100 ° C, preferably 50 to 95 ° C, especially 70 to 90 ° C.
- the electrolysis is generally carried out at a pressure below 2000 kPa, preferably below 1000 kPa, in particular below 150 kPa, e.g. in the range of 50 to 1000 kPa, especially 80 to 150 kPa performed. It is particularly preferred to carry out the process according to the invention at a pressure in the range of atmospheric pressure (101 ⁇ 20 kPa).
- the inventive method is carried out at a temperature in the range of 50 to 95 ° C, in particular 70 to 90 ° C and in the range of atmospheric pressure (101 ⁇ 20 kPa).
- the aqueous, lignin-containing suspension or solution generally contains 0.5 to 30 wt .-%, preferably 1 to 15 wt .-%, in particular 1 to 10 wt .-% lignin based on the total weight of the aqueous, lignin-containing suspension or solution.
- an aqueous, alkaline suspension or solution is electrolyzed to produce the vanillin.
- aqueous and alkaline lignin-containing solutions or suspensions is meant here and below an aqueous solution or suspension which contains lignin or lignin derivatives, for example lignin sulfate, lignin sulfonate, kraft lignin, alkali lignin or organosolv lignin or mixtures thereof, as a liginin constituent and which has an alkaline pH, preferably a pH of at least pH 10, in particular at least pH 12 and especially at least pH 13.
- lignin or lignin derivatives for example lignin sulfate, lignin sulfonate, kraft lignin, alkali lignin or organosolv lignin or mixtures thereof, as a liginin constituent and which has an alkaline pH, preferably a pH of at least pH 10, in particular at least pH 12 and especially at least pH 13.
- the aqueous, alkaline solution or suspension may be an aqueous solution or suspension which is obtained as a by-product in a technical process such as pulp, pulp or cellulose production, e.g.
- the aqueous, alkaline solution or suspension may be an aqueous solution or suspension which is prepared by dissolving a lignin or lignin derivative in aqueous alkali or in water with addition of a base, for example lignin sulfate, lignin sulphonate, kraft lignin, Alkali or organosolv lignin, or a lignin which is used in a technical process such as pulp, cellulose or cellulose Production is obtained, for example lignin from black liquor, from the sulfite process, from the sulfate process, from the Organocell or Organosolv process, from the ASAM process, from the Kraft process or from the Natural-Pulping process.
- a base for example lignin sulfate, lignin sulphonate, kraft lignin, Alkali or organosolv lignin, or a lignin which is used in a technical process such as pulp, cellulose
- lignin-containing wastewater streams are produced. These may, if appropriate after setting an alkaline pH, be used as aqueous, lignin-containing suspension or solution in the process according to the invention.
- the effluent streams of the papermaking sulfite process often contain lignin as lignosulfonic acid. Lignosulfonic acid can be used directly in the process of the invention or first hydrolyzed alkaline.
- lignin-containing wastewater streams occur, for example, in the form of black liquor.
- organocell process which due to its environmental friendliness will gain further importance in the future, lignin is an organosolv lignin. Ligninsulfonklad Organosolv lignin-containing wastewater streams and black liquor are particularly suitable as aqueous, alkaline lignin-containing suspensions or solutions for the process of the invention.
- the aqueous, lignin-containing suspensions or solutions can also be prepared by dissolving or suspending at least one lignin-containing material in aqueous alkali, ie in an aqueous solution of a suitable base or in water with the addition of base.
- the lignin-containing material preferably contains at least 10% by weight, in particular at least 15% by weight and particularly preferably at least 20% by weight of lignin, based on the total weight of the lignin-containing material.
- the lignin-containing material is preferably selected from Kraft lignin, lignin sulfonate, oxidized lignin, Organosolv lignin or other lignin-containing residues from the paper industry or fiber production, in particular kraft lignin, lignin sulfonate and oxidized lignin, which in an electrochemical oxidation of non-oxidized lignin accrues.
- inorganic bases can be used, for example alkali metal hydroxides such as NaOH or KOH, ammonium salts such as ammonium hydroxide and alkali metal carbonates such as sodium carbonate, for example in the form of soda. Preference is given to alkali metal hydroxides, in particular NaOH and KOH.
- concentration of inorganic bases in the aqueous, lignin-containing suspension or solution should not exceed 5 mol / L and in particular 4 mol / L and is typically in the range from 0.01 to 5 mol / L and in particular in the range from 0.1 to 4 minor.
- oxidized lignin is used which originates from a previous electrolysis cycle. It has proved to be advantageous to use oxidized lignin in at least one further electrolysis cycle, preferably in at least two further electrolysis cycles and in particular in at least three further electrolysis cycles.
- An advantage of this repeated use of the oxidized lignin is that repeated vanillin can be obtained. Thus, the yield of vanillin, based on the amount of lignin originally used, significantly increased and therefore increases the efficiency of the overall process.
- the concentration of the oxidation-sensitive vanillin in the electrolyte per oxidation process can be kept so low that the undesirable side reactions such as over oxidation can be effectively suppressed, while the overall yield of vanillin over the entire process (several electrolysis cycles) increases.
- aqueous, alkaline lignin-containing suspension or solution is selected from
- an aqueous suspension or solution which is prepared by depleting vanillin from an aqueous reaction mixture, the reaction mixture being obtained by oxidation, in particular by electrolysis, of an aqueous, alkaline lignin-containing suspension or solution, and
- effluent streams or residues from paper and pulp production in particular black liquor or kraft lignin.
- further preferred embodiments relate to a process according to the invention in which the aqueous, alkaline lignin-containing suspension or solution is selected from wastewater streams from paper and pulp production, in particular black liquor or solutions of kraft lignin.
- the viscosity of the solution or suspension can increase greatly and the solubility of the lignin can be very low.
- the concentration of the alkali metal hydroxide is preferably 0.5 to 5 mol / L, in particular 1, 0 to 3.5 mol / L.
- sodium hydroxide or potassium hydroxide is used.
- the lignin-containing alkali metal hydroxide solution is heated to a temperature of 150 to 250 ° C., in particular 170 to 190 ° C. and stirred vigorously for 1 to 10 h, preferably for 2 to 4 h.
- the pre-hydrolyzed lignin can be separated from the alkali metal hydroxide solution prior to electrochemical oxidation. Alternatively, it is possible to carry out the electrochemical oxidation directly with the lignin-containing alkali metal hydroxide solution.
- the aqueous, alkaline lignin-containing suspension or solution may contain a conductive salt to improve the conductivity.
- a conductive salt to improve the conductivity.
- alkali metal salts such as salts of Li, Na, K or quaternary ammonium salts such as tetra (C 1 -C 6 -alkyl) ammonium or tri (C 1 -C 6 -alkyl) methylammonium salts.
- Possible counterions are sulfate, hydrogensulfate, alkyl sulfates, aryl sulfates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate, hexafluorophosphate, perchlorate, bis-triflates and bis-triflimide.
- suitable conductive salts are ionic liquids ("lonic liquids"). Suitable electrochemically stable ionic liquids are described in "Lonic Liquids in Synthesis", ed. Peter Wasserscheid, Tom Welton, Verlag Wiley-VCH 2003, Chap. 1 to 3.
- a metal-containing or metal-free mediator can be added to the aqueous, alkaline lignin-containing suspension or solution.
- Mediators are understood as meaning redox pairs which allow indirect electrochemical oxidation.
- the mediator is electrochemically transferred to the higher oxidation state, then acts as an oxidant and then regenerates again by electrochemical oxidation. It is therefore an indirect electrochemical oxidation of the organic compound, since the mediator is the oxidizing agent.
- the oxidation of the organic compound with the mediator in the oxidized form can be carried out in the electrolysis cell in which the mediator was converted into the oxidized form, or in one or more separate reactors ("ex-cell method").
- Suitable mediators are compounds which can be present in two oxidation states, act as oxidants in the higher oxidation state and can be regenerated electrochemically.
- salts or complexes of the following dox pairs can be used as mediators: Ce (III / IV), Cr (II / III), Cr (IIIA / I), Ti (II / III), V (II / III), V (III / IV), V (IV / V), Ag (1 / ll), AgOVAgO " , Cu (1 / ll), Sn (II / IV), Co (II / III), Mn (II / III ), Mn (II / IV), Os (IVA / III), Os (III / IV), Br 2 / Br 7 Br 3 , I- / I 2 , I 3VI 2 10 3 + / I0 4 -, Fremy's salt (dipotassium nitroso disulfonate or organic mediators, such as ABTS (2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid), TEMPO, viologens such as violuri
- NADPVNADPH where the stated systems can also be metal complexes with various ligands or also solvent ligands, such as e.g. H2O, NH3, CN, OH, SCN, halogens, O2, acetylacetonate, dipyridyl, phenanthroline or 1, 10-phenanthroline 5,6-dione.
- solvent ligands such as e.g. H2O, NH3, CN, OH, SCN, halogens, O2, acetylacetonate, dipyridyl, phenanthroline or 1, 10-phenanthroline 5,6-dione.
- transition metal-free mediators e.g. Nitrosodisulfonates such as Fremys salt (dipotassium nitrosulfonate) used.
- the mediator is preferred in amounts of 0.1 to
- the method according to the invention is carried out without the addition of mediators.
- the aqueous, alkaline lignin-containing suspension or solution may further contain an inert solvent.
- Suitable solvents are polar-aprotic solvents having high electrochemical stability, such as acetonitrile, propionitrile, adiponitrile, suberonitrile, propylene carbonate, ethylene carbonate, N-methylpyrrolidone, hexamethylphosphoric triamide, dimethyl sulfoxide and dimethylpropyleneurea (DMPU).
- polar-aprotic solvents having high electrochemical stability, such as acetonitrile, propionitrile, adiponitrile, suberonitrile, propylene carbonate, ethylene carbonate, N-methylpyrrolidone, hexamethylphosphoric triamide, dimethyl sulfoxide and dimethylpropyleneurea (DMPU).
- DMPU dimethylpropyleneurea
- the vanillin obtained by the process according to the invention can be obtained from the aqueous, lignin-containing solution by methods known to the person skilled in the art. For example, the vanillin formed in the electrolysis can be removed or depleted by distillation or extraction of the aqueous, lignin-containing suspension or solution.
- Distillation methods which are known to the person skilled in the art are distillation processes, for example vacuum distillation, distillation under a protective gas atmosphere or steam distillation.
- An advantage of vanillin separation via distillative processes is that the vanillin is not contacted with potentially hazardous organic solvents.
- Vanillin can also be removed by extraction from the aqueous, lignin-containing suspension or solution. This is particularly advantageous because the sensitive vanillin is not exposed to any further thermal stress.
- extraction processes known to those skilled in the art are suitable.
- the aqueous, lignin-containing suspension or solution may be used for extraction e.g. be mixed with an organic solvent, so as to separate the vanillin formed (liquid-liquid extraction).
- Suitable organic solvents are water immiscible organic solvents, e.g. Hydrocarbons having 5 to 12 carbon atoms such as hexane or octane, chlorinated hydrocarbons having 1 to 10 carbon atoms such as dichloromethane or chloroform, aliphatic ethers having 2 to 10 carbon atoms such as diethyl ether or diisopropyl ether, cyclic ethers or aliphatic esters such as ethyl ethanoate. Halogen-free organic solvents are preferred.
- supercritical CO2 is suitable for this purpose.
- the lignin formed can also be removed by solid phase extraction from the aqueous, lignin-containing suspension or solution.
- solid phase extraction agents are added to the aqueous, lignin-containing suspension or solution.
- the vanillin (vanillate) adsorbed to the extractant may then be treated with polar organic solvents known to those skilled in the art, e.g. Methanol are eluted from the solid phase.
- polar organic solvents e.g. Methanol are eluted from the solid phase.
- polar organic solvents e.g. Methanol
- a solid phase extraction analogous to the solid phase synthesis is possible.
- the vanillin is covalently bound as vanillate to the solid phase.
- the vanillin is released again by dissolving the covalent bond.
- a concentrated crude product is obtained, which can then be purified and isolated by distillation easier.
- the vanillin produced is obtained by treatment with a basic adsorbent, in particular an anion exchanger, from the aqueous, alkaline, lignin-containing solution or suspension obtained in the electrolysis (hereinafter alkaline electrolysate). won. Since in the alkaline electrolysate the vanillin is present in anionic form as vanillate, it is adsorbed by the basic adsorbent, for example an anion exchanger, and can subsequently be treated by treating the vanillate-laden anion exchanger with acid, preferably a dilute solution of a mineral acid or an organic acid in an organic solvent or in an aqueous-organic solvent mixture are released.
- a basic adsorbent in particular an anion exchanger
- the adsorbent e.g. the anion exchanger into which alkaline electrolyzate obtained in the electrolysis give, after a certain residence time, the adsorbent, e.g. Separate the anion exchanger from the alkaline electrolysate and then release the adsorbed adsorbent vanillin by treating the adsorbent with acid.
- the alkaline electrolysate is first passed through a bed of that of the adsorbent, especially a bed of anion exchanger, for example by one or more, with the adsorbent, e.g. pass an anion exchanger, packed columns and then pass through the bed of the adsorbent a dilute solution of an acid, in particular a mineral acid or an organic acid, thereby eluting the vanillin.
- Suitable adsorbents are basically all substances which have basic groups or are treated with hydroxide ions. These include alkalized activated carbons, basic aluminas, clays, basic adsorber resins, in particular anion exchangers or anion exchanger resins. Anion exchangers or anion exchanger resins generally have functional groups which are selected from tertiary amino groups, quaternary ammonium groups and quaternary phosphonium groups.
- the anion exchangers preferably used for this purpose are generally crosslinked, organic polymer resins which preferably have quaternary ammonium groups or phosphonium groups.
- the anion exchangers which are preferably used are preferably those from the group of crosslinked polystyrene resins in which part of the phenyl rings of the crosslinked polystyrene carry quaternary ammonium groups, for example trialkylammonium groups bonded via alkylene groups, especially trimethylammonium groups bonded via a methylene group.
- Crosslinked polyvinylpyridines in which some of the pyridine groups are present in quaternized form, for example as 1-alkylpyridinium, especially as 1-methylpyridinium, and crosslinked acrylate, the bound via alkylene Trialkylammonium phenomenon, especially on a 1 , 2-ethanediyl or 1, 3-propanediyl bound Tnmethylammonium phenomenon wear.
- this is Charge density, ie the number of ionic groups in accordance with the invention suitable anion exchanger in the range of 0.5 to 6 mmol / g, in particular 1 to 5 mmol / g ion exchange resin or 0.1 to 3 eq / L (molar equivalents per liter, wet).
- Suitable adsorbents are also polymers which have N-C 1 -C 8 -alkylimidazolium groups.
- the N-Ci-Cs-Alkylimidazolium phenomenon are bound directly or via a spacer to the polymer backbone.
- Such polymers can be obtained by polymer-analogous reaction with N-Ci-Cs-alkylimidazole compounds, for example by reacting haloalkyl groups, in particular chlorobenzyl-containing polymers, for example copolymers of styrene and chloromethyl, with N-Ci-Cs alkylimidazoles.
- Hydroxyalkylmethacrylaten or styrene for example by free radical polymerization or by controlled radical polymerization such as RAFT or ATRP.
- Such polymers are known and described, for example, by J. Yuan, M. Antonietti, Polymer 2011, 52, 1469-1482; J. Huang, C. Tao, Q. An, W. Zhang, Y. Wu, X. Li, D. Shen, G. Li, Chem. Comm. 2010, 46, 967; R. Marcilla, J. Alberto Blazquez, J. Rodriguez, J.A. Pomposo, D. Mecerreyes, J. Pol. Be. A:
- Diluted solutions of mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid
- organic solvents and dilute solutions of mineral acids in organic-aqueous solvent mixtures are particularly suitable for the elution of vanillin from the basic adsorbent (for example an anion exchanger).
- Diluted solutions of organic acids such as trifluoromethanesulfonic acid, acetic acid, formic acid or propionic acid, in organic solvents and dilute solutions of organic acids in organic-aqueous solvent mixtures are particularly suitable for the elution of vanillin from the basic adsorbent (for example an anion exchanger).
- Suitable organic solvents are, above all, those which are immiscible with water at 22 ° C. indefinitely or at least dissolve in water in an amount of at least 200 g / l at 22 ° C.
- These include above all dimethyl sulfoxide, acetone, C1-C4 alkanols such as methanol, ethanol, isopropanol, n-propanol, 1-butanol, 2-butanol and tert-butanol, alkanediols such as glycol and 1, 4-butanediol, glycerol, but also cyclic ethers such as dioxane, methyltetrahydrofuran or tetrahydrofuran, nitrogen heterocycles such as pyridine or N-methylpyrrolidine and mixtures. Preference is given to C 1 -C 4 -alkanols and especially to methanol.
- Suitable acids are especially mineral acids such as hydrochloric acid, phosphoric acid, and in particular sulfuric acid and organic acids such as methanesulfonic acid, formic acid, acetic acid and propionic acid.
- the solution of the acid preferably has a concentration of acid in the range from 0.01 to 10 mol kg -1 , in particular from 0.1 to 5 mol kg -1 .
- the eluate obtained during the elution can be subjected to further purification steps, for example crystallization, filtration or chromatography. Furthermore, it is possible to reduce the proportion of volatile constituents of the electrolysate by distillation before separating the vanillin. From the remaining residue, the vanillin can then be extracted with the aid of the abovementioned extractants.
- the separation of vanillin can be continuous or discontinuous. It is particularly advantageous to remove the vanillin continuously or at intervals from the aqueous, lignin-containing suspension or solution during the electrochemical oxidation.
- a partial stream of the electrolysate can be discharged from the electrolysis arrangement and the lignin contained therein can be depleted, for example by continuous (solid phase) extraction or by steam distillation.
- the vanillin is continuously or at intervals isolated from the electrolysate using an anion exchanger. This is achieved, for example, by discharging a substream from the electrolysis assembly during electrolysis and treating it with the ion exchanger, e.g. by passing it through a bed of anion exchanger.
- the so-steeply Vanillin Since the anode materials used in the process according to the invention show no significant corrosion under the reaction conditions, the so-steeply Vanillin has no or no significant heavy metal contamination and can therefore be used in the food industry. Another object of the invention is thus the use of vanillin, which was obtained by the process according to the invention, as a flavoring in the food industry.
- the aqueous, lignin-containing suspension or solution contains oxidized lignin in addition to the vanillin formed.
- the oxidized lignin can be obtained by drying the aqueous, lignin-containing solution.
- a lignin produced in this way can advantageously be used as an additive in the building material industry, for example as a cement or concrete additive.
- the stationary phase used was an HP-5 column from Agilent with a length of 30 m, a diameter of 0.25 mm and a thickness of 1 ⁇ m. This column is heated by means of a temperature program of 50 ° C within 10 min at 10 ° C / min to 290 ° C. This temperature is held for 15 min.
- the carrier gas used was hydrogen at a flow rate of 46.5 mL / min.
- the aqueous phase was extracted three more times with in each case 80 ml of dichloromethane.
- the combined organic phases were washed with 50 mL saturated brine and then dried over Na 2 SO 4 . Removal of the solvent under reduced pressure left an oily, usually golden brown residue, which was analyzed by gas chromatography for its composition.
- Gas chromatographic analysis of the crude organic products revealed typical compositions based on lignin (% by weight), summarized in Table 4.
- the electrolysis was carried out analogously to Example 1 with the following change:
- the electrolyte used was 3 M aqueous sodium hydroxide solution.
- the electrodes used were plates (thickness: 3 mm) of various Ni and Cu base alloys (see Table 5) with dimensions of 3.0 ⁇ 4.0 cm 2 , which were arranged at a distance of 0.5 cm from one another.
- the maximum cell voltage during the electrolysis was 2.9 V.
- Table 5 The results are summarized in Table 5.
- Examples 1 1 to 14 Electrolysis of a lignin solution on electrodes of Co base alloys
- the electrolysis was carried out analogously to Example 1 with the following change:
- the electrolyte used was 3 M aqueous sodium hydroxide solution.
- the electrodes used were plates (thickness: 3 mm) of various Co base alloys (see Table 6) (dimension 3.0 ⁇ 4.0 cm 2 ) with a maximum usable electrode surface area of 9 cm 2 , spaced 0.5 cm apart were arranged to each other.
- the maximum cell voltage during the electrolysis was 2.9 V.
- the electrolysis was carried out analogously to Example 1 with the following change:
- the electrolyte used was 3 M aqueous sodium hydroxide solution.
- the electrodes used were plates (thickness: 1 mm) of Co (dimension 3.0 ⁇ 4.0 cm 2 ) with a maximum usable electrode surface area of 9 cm 2 , which were arranged at a distance of 0.5 cm from each other.
- the maximum cell voltage during the electrolysis was 3.1 V.
- a black layer was formed on the anode.
- the anode was used in a second electrolysis under otherwise identical conditions (Comparative Example C2).
- Example 15 Electrode of Comparative Example 1 without removal of the oxide layer formed.
- Example 16 Electrolysis of a lignin solution on electrodes made of stainless steel
- the electrolysis was carried out analogously to Comparative Example 1 with the following change.
- Stainless steel nets were used as electrodes (binding: fallen body Bdg. 555, mesh: 200, Mw: 0.077, wire diameter: 0.050, material: 1.4404, manufacturer: GKD, item no .: 29370850; 3.0x4.0 cm 2 ).
- Example 5 The procedure was analogous to Example 1 with the following variation: 525-526 mg of kraft lignin were dissolved in 85 g of electrolyte in an undivided cell with stirring.
- the electrolyte used was 3 M aqueous sodium hydroxide solution.
- the cell was provided with an anode and a cathode, which consisted of platinum and had a maximum usable electrode surface of about 12 cm 2 .
- the maximum cell voltage during the reaction was 3.1 V.
- the yield of vanillin was 0.48 wt .-%, based on the applied power-Lginin the yield of acetovanillon 0.06 wt .-%. Comparative Example 5:
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
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Abstract
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EP13734065.9A EP2870275B1 (de) | 2012-07-04 | 2013-07-03 | Verfahren zur herstellung von vanillin |
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EP12174998 | 2012-07-04 | ||
EP13734065.9A EP2870275B1 (de) | 2012-07-04 | 2013-07-03 | Verfahren zur herstellung von vanillin |
PCT/EP2013/064064 WO2014006106A1 (de) | 2012-07-04 | 2013-07-03 | Verfahren zur herstellung von vanillin |
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EP (1) | EP2870275B1 (de) |
JP (1) | JP6215927B2 (de) |
CN (1) | CN104603329B (de) |
BR (1) | BR112014033017A2 (de) |
ES (1) | ES2587780T3 (de) |
MX (1) | MX2015000244A (de) |
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JP6239608B2 (ja) * | 2012-07-04 | 2017-11-29 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | バニリン含有水性塩基性組成物からバニリンを得るための方法 |
CN104476119B (zh) * | 2014-11-05 | 2017-11-10 | 芜湖金龙模具锻造有限责任公司 | 一种抗冲击锤上模锻用锤头的制造方法 |
CN104532284A (zh) * | 2014-12-16 | 2015-04-22 | 广西科技大学 | 一种在离子溶液中的电氧化水热木质纤维素转化方法及其装置 |
CN113073347B (zh) * | 2021-03-25 | 2022-11-25 | 济南大学 | 一种以水为氧源电化学合成丁香醛的方法 |
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GB8527960D0 (en) * | 1985-11-13 | 1985-12-18 | Mini Agriculture & Fisheries | Electro chemical treatment of lignins |
CN1205366A (zh) * | 1997-06-06 | 1999-01-20 | 电化学工业有限公司(国际) | 含木素材料的电化学去木质作用体系及其应用 |
DE19723889A1 (de) * | 1997-06-06 | 1998-12-10 | Consortium Elektrochem Ind | System zur elektrochemischen Delignifizierung ligninhaltiger Materialien sowie Verfahren zu seiner Anwendung |
EP2276877B1 (de) * | 2008-05-14 | 2011-11-09 | Basf Se | Verfahren zur elektrochemischen spaltung von lignin an einer diamantelektrode |
US8506789B2 (en) * | 2009-07-23 | 2013-08-13 | Ceramatec, Inc. | Method of producing coupled radical products |
US8808781B2 (en) * | 2011-08-11 | 2014-08-19 | Basf Se | Method for producing vanillin by electrochemical oxidation of aqueous lignin solutions or suspensions |
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2013
- 2013-07-03 EP EP13734065.9A patent/EP2870275B1/de not_active Not-in-force
- 2013-07-03 MX MX2015000244A patent/MX2015000244A/es unknown
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JP6215927B2 (ja) | 2017-10-18 |
ES2587780T3 (es) | 2016-10-26 |
JP2015531024A (ja) | 2015-10-29 |
EP2870275B1 (de) | 2016-05-25 |
WO2014006106A1 (de) | 2014-01-09 |
CN104603329B (zh) | 2017-06-27 |
MX2015000244A (es) | 2015-08-12 |
BR112014033017A2 (pt) | 2017-06-27 |
CN104603329A (zh) | 2015-05-06 |
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