EP4222137A1 - Purification d'acide ferulique - Google Patents
Purification d'acide feruliqueInfo
- Publication number
- EP4222137A1 EP4222137A1 EP21782762.5A EP21782762A EP4222137A1 EP 4222137 A1 EP4222137 A1 EP 4222137A1 EP 21782762 A EP21782762 A EP 21782762A EP 4222137 A1 EP4222137 A1 EP 4222137A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ferulic acid
- liquid medium
- precipitate
- medium
- complexing agent
- 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.)
- Pending
Links
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 title claims abstract description 214
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 title claims abstract description 208
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 title claims abstract description 207
- 229940114124 ferulic acid Drugs 0.000 title claims abstract description 207
- 235000001785 ferulic acid Nutrition 0.000 title claims abstract description 207
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 238000000746 purification Methods 0.000 title description 15
- 239000007788 liquid Substances 0.000 claims abstract description 140
- 238000000034 method Methods 0.000 claims abstract description 83
- 239000002244 precipitate Substances 0.000 claims abstract description 73
- 239000008139 complexing agent Substances 0.000 claims abstract description 53
- 239000002904 solvent Substances 0.000 claims abstract description 52
- 239000012535 impurity Substances 0.000 claims abstract description 46
- 150000003254 radicals Chemical class 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 6
- 239000002516 radical scavenger Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 60
- 230000008569 process Effects 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 25
- 150000001768 cations Chemical class 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- -1 diphosphate ions Chemical class 0.000 claims description 8
- 239000002537 cosmetic Substances 0.000 claims description 7
- 235000013305 food Nutrition 0.000 claims description 7
- 239000012963 UV stabilizer Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000001177 diphosphate Substances 0.000 claims description 3
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 239000002609 medium Substances 0.000 description 179
- 239000007787 solid Substances 0.000 description 34
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 23
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 23
- 235000012141 vanillin Nutrition 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000001914 filtration Methods 0.000 description 16
- 229920005610 lignin Polymers 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 239000013638 trimer Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000539 dimer Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 229940114123 ferulate Drugs 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 238000000855 fermentation Methods 0.000 description 6
- 230000004151 fermentation Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- GLEVLJDDWXEYCO-UHFFFAOYSA-N Trolox Chemical compound O1C(C)(C(O)=O)CCC2=C1C(C)=C(C)C(O)=C2C GLEVLJDDWXEYCO-UHFFFAOYSA-N 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 235000007319 Avena orientalis Nutrition 0.000 description 2
- 244000075850 Avena orientalis Species 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000011138 biotechnological process Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- BOLQJTPHPSDZHR-UHFFFAOYSA-N dihydroferulic acid Chemical compound COC1=CC(CCC(O)=O)=CC=C1O BOLQJTPHPSDZHR-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229930005346 hydroxycinnamic acid Natural products 0.000 description 1
- DEDGUGJNLNLJSR-UHFFFAOYSA-N hydroxycinnamic acid group Chemical class OC(C(=O)O)=CC1=CC=CC=C1 DEDGUGJNLNLJSR-UHFFFAOYSA-N 0.000 description 1
- 235000010359 hydroxycinnamic acids Nutrition 0.000 description 1
- 238000011090 industrial biotechnology method and process Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000004161 plant tissue culture Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3481—Organic compounds containing oxygen
- A23L3/3508—Organic compounds containing oxygen containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/805—Corresponding aspects not provided for by any of codes A61K2800/81 - A61K2800/95
Definitions
- the present invention relates to a method for purifying a liquid medium comprising ferulic acid, a solvent and at least one impurity.
- the invention also relates to a composition comprising purified ferulic acid having a purity greater than or equal to 90%. Furthermore, the invention relates to a process for the production of natural vanillin using ferulic acid purified according to the process of the invention.
- the present invention also relates to a method for separating ferulic acid oligomers and to their use as a scavenger of free radicals or radical species, in particular as a polymerization inhibitor, antioxidant or UV stabilizer.
- the invention finds applications in particular in the field of food, cosmetics and flavorings.
- Ferulic acid or 3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid is an antioxidant naturally present in plants and in particular cereals such as rice, corn, wheat or oats. It can also be present in solid or liquid co-products from the agri-food industry, in particular from the oilseed, cereal, sugar or alcohol sectors.
- Ferulic acid can be prepared by chemical synthesis, or by a biotechnological route involving microbial fermentation or plant tissue culture. It can also be obtained by a route qualified as natural and/or biosourced in which a plant material is treated in order to extract ferulic acid from said plant material. By example, it can be extracted from by-products of the agro-food industry or from grains, for example according to the method described in WO2014/187784.
- Ferulic acid is used in various fields ranging from cosmetics to food, in particular in the preparation of a widely consumed flavoring substance, vanillin.
- Vanillin can be produced by chemical synthesis, however natural flavors are preferred over synthetic flavors by consumers. In order to satisfy current demand, particular interest has been shown in the preparation of non-synthetic vanillin. Thus, we have seen the growth of methods for preparing natural vanillin using natural and/or biosourced materials, these methods being able to be qualified as natural according to the legislation in force.
- natural vanilla can be obtained by a biotechnological process comprising in particular the culture of a microorganism capable of allowing the biotransformation of a fermentation substrate into vanillin.
- a biotechnological process is for example described in application EP0885968 in which a microorganism converts ferulic acid into vanillin.
- the natural vanillin thus obtained generally undergoes extraction and/or purification steps.
- vanillin can be purified according to the methods described in applications WO20 14/114590, EP2791098 or WO2018/146210.
- Bio-based ferulic acid especially that available commercially, may have an unsatisfactory degree of purity. Impurities in ferulic acid supplied by suppliers are generally unidentified and may affect the efficiency of industrial processes in which ferulic acid is used. Therefore, in order to obtain better production yields, of natural vanillin in particular, it is desirable to have a starting product of high purity.
- the document WO2004/110975 describes the treatment of the cooking juice with lime from the corn grain leading to an effluent called nejayote containing ferulic acid, the treatment comprising filtration, acidification, adsorption of the ferulic acid on a matrix then washing the matrix and eluting with an organic solvent.
- the recovered ferulic acid then undergoes an additional recrystallization step.
- the document CN104628553 describes the purification of an alkaline solution of ferulic acid in which the solution undergoes successive passages in membrane separation systems which can cause losses of ferulic acid and a reduction in the yield of ferulic acid.
- the permeate then obtained is acidified in order to precipitate the ferulic acid which is recovered by centrifugation or filtration.
- the ferulic acid obtained undergoes an additional step of purification on activated charcoal and purification by recrystallization.
- Document EP3612511 describes the extraction and purification of ferulic acid from agricultural biomass. Purification of extracted ferulic acid can be achieved by extraction methods using an organic solvent.
- the aim of the present invention is to provide a simple and effective solution making it possible to have ferulic acid of sufficient purity for use in fermentation directly or indirectly.
- the impurities present in the solid or liquid compositions of ferulic acid contribute to the fouling of the industrial installation with which the composition is in contact.
- these impurities can lead to difficulties in using ferulic acid in processes on an industrial scale.
- impurities which are in solid form can lead to deposits, partial or complete clogging or fouling which make it difficult to carry out the process and lead to losses in yield, productivity or quality of the final product.
- impurities can react with reactants, intermediates, or end products of ferulic acid conversion to the product of interest. As a result, the presence of impurities leads to losses and a drop in production yield, of vanillin for example.
- the object of the invention is to provide a process for purifying ferulic acid, in particular biobased ferulic acid, with a high yield of ferulic acid, in particular greater than 90%.
- the purified ferulic acid obtained according to the invention can be natural and biobased, contained in a liquid medium or in solid form.
- a first aspect of the invention proposes a process for purifying a liquid medium C comprising ferulic acid, a solvent and at least one impurity, the process comprising:
- Step (b) also makes it possible to obtain a first PI precipitate.
- - ferulic acid is a biosourced ferulic acid
- the liquid medium Cl comprises purified ferulic acid having a purity greater than 90%, preferably greater than 95%,
- step (al) in which the liquid medium Cl obtained following step (a) is heated to a temperature between 40 and 70°C, preferably at 50°C,
- the pH of the liquid medium obtained in step (a) and/or (al) is between 6 and 9, preferably between 6 and 7,
- the first complexing agent is a divalent or trivalent cation chosen from the group consisting of transition metals, metals or alkaline-earth metals or a mixture thereof,
- the first complexing agent is chosen from aluminum or zinc
- the method comprises a step (c) of adding a second complexing agent to the liquid medium (Fl) so as to obtain a second precipitate and a liquid medium (C2),
- the second precipitate P2 is distinct from the first precipitate PI
- the second complexing agent is chosen from phosphate, dihydrogen phosphate or diphosphate ions,
- the method comprises a step (d) of separating the second precipitate P2 from the liquid medium (C2) so as to obtain a liquid medium (F2) comprising the purified ferulic acid,
- the solvent is water and the liquid medium is an aqueous liquid medium
- the method comprises a step for recovering ferulic acid in solid form in which the liquid medium F1 or the liquid medium F2 is brought to a pH of between 1 and 4, and the solid ferulic acid is separated from the liquid medium.
- the method according to the invention comprises few steps, thus limiting the losses of ferulic acid.
- the present invention also relates to a process for purifying the impurities present in the solid or liquid compositions of ferulic acid. Indeed, these impurities can be recovered in different applications in the food and cosmetics industry, stabilizers for fuels, unsaturated monomers or polymers. These compounds can in particular be used as scavengers of free radicals or radical species, in particular, in particular as polymerization inhibitors, antioxidants or UV stabilizers.
- the present invention relates to a process for extracting ferulic acid oligomers present in the precipitate PL
- the present invention relates to the use of a PI precipitate or ferulic acid oligomers present in the PI precipitate, or obtained by the extraction process of the present invention in the field of industrial food or cosmetics, stabilizers for fuels, unsaturated monomers or polymers, in particular as polymerization inhibitors, antioxidants or UV stabilizers.
- FIG 1 is a diagram showing a step diagram illustrating one embodiment of the method.
- FIG 2 illustrates an example of implementation of the method according to one embodiment.
- FIG 3 illustrates the free radical scavenger properties of ferulic acid oligomers compared to a control Trolox.
- the subject of the present invention is a method for purifying a liquid medium C comprising ferulic acid, a solvent and at least one impurity, the method comprising at least one step (a) of bringing the liquid medium C into contact with a first complexing agent.
- Ferulic acid of natural origin corresponds to the following formula:
- Ferulic acid when biobased, can be referred to as a “natural product”. According to regulations in Europe and the United States, this means that the product is obtained by physical, enzymatic or microbiological processes and from plant or animal materials.
- bio-based ferulic acid we mean ferulic acid entirely or significantly of vegetable or marine origin.
- bio-based ferulic acid can be derived from agricultural by-products, plants, seeds, forestry materials or algae.
- bio-based ferulic acid is of vegetable origin. Thus, biobased ferulic acid is not the result of chemical synthesis.
- the process of the present invention consists in purifying a liquid medium C comprising crude ferulic acid, the medium containing at least one unidentified impurity and a solvent.
- the method of the present invention consists in purifying a liquid medium C comprising crude ferulic acid, the medium containing at least one unidentified and/or known impurity and a solvent.
- the medium C to be purified is also referred to as “starting medium or composition C” or “initial medium C”.
- the initial liquid medium C can be prepared by mixing crude commercial ferulic acid in solid form with a solvent.
- the process then comprises a preliminary stage of preparation of the liquid medium C in which the starting ferulic acid in solid form is brought into contact with a solvent, preferably the solvent consists of water.
- the crude ferulic acid in solid form to be purified or in the liquid medium C has a purity of less than or equal to 87%, preferably less than or equal to 85%, more preferably less than or equal to 83%.
- the initial crude ferulic acid has a purity greater than or equal to 60%, preferably greater than or equal to 70%, more preferably greater than or equal to 80%.
- the solvent of medium C consists of water.
- the ferulic acid in solid form to be purified is biosourced.
- bio-based ferulic acid is ferulic acid obtained by processing all or part of corn grains, or grains of rice or oats.
- biobased ferulic acid can be produced according to the process described in document WO2004/187784.
- the initial crude ferulic acid is a natural ferulic acid.
- a starting medium C in the form of a suspension comprising a liquid phase and a solid phase insoluble in said solvent.
- the crude ferulic acid may be in dissolved form in the liquid phase of medium C and/or may be contained in the solid phase of the liquid medium.
- the impurities can be in dissolved form in the liquid phase of the medium C and/or can be in the solid phase of the liquid medium C.
- the liquid medium C can also be a liquid composition resulting from a ferulic acid extraction process in which at least one plant material has been treated, such as that described in application WO2004/187784, that described in application WO 2001/06789, or according to document W004110975A1.
- the total impurities/ferulic acid weight ratio in the initial liquid medium C is generally between 0.05 and 0.5, preferably 0.20 and 0.25.
- the method according to the invention aims in particular to eliminate all or part of these impurities in order to improve the purity of the initial ferulic acid. In some cases, these impurities can be recovered in various applications.
- the liquid medium C comprising the ferulic acid to be purified is brought into contact with a first complexing agent.
- complexing agent is meant a substance capable of generating a precipitate which is insoluble in the solvent of the liquid medium, in particular insoluble in water.
- the first complexing agent is a cation, in solution in a solvent, preferably in water or in a solvent mixture.
- the first complexing agent is advantageously in the form of a monovalent, divalent, trivalent, tetravalent or pentavalent cation salt solution, in particular a divalent or trivalent cation salt.
- the cation salt in particular divalent or trivalent, can be a sulphate, chloride, nitrate, carbonate, phosphate, hydroxide, acetate salt or a mixture thereof.
- the cation in particular divalent or trivalent, can be chosen from the group consisting of transition metals, metals, alkaline earths or rare earths, it being understood that the cation, when it is brought into contact with the medium C starting point, is capable of forming a precipitate which is insoluble in the solvent of medium C, in particular in water.
- the first complexing agent is a cation of a transition metal selected from the group consisting of iron, nickel, copper, titanium, zirconium or a mixture thereof, preferably selected from iron or copper.
- the first complexing agent is a metal cation chosen from the group consisting of aluminum and zinc.
- the first complexing agent is a cation of an alkaline earth chosen from the group consisting of calcium and magnesium.
- the first complexing agent is chosen from the group consisting of rare earths such as yttrium or lanthanides, or metal oxides such as Al2O3, TiCL, SiCL and/or ZnO.
- the quantity of the first complexing agent added to the liquid medium C may be greater than or equal to 1%, preferably greater than or equal to 5% by weight relative to the total weight of crude ferulic acid in starting solid form.
- the quantity of the first complexing agent is lower or equal to 12%, preferably less than or equal to 10% by weight relative to the total weight of crude ferulic acid in starting solid form.
- the medium obtained after the addition of the first complexing agent to the liquid medium C is called “liquid medium Cl”.
- the medium Cl comprises a solvent or a mixture of solvent, ferulic acid, the first precipitate PI and at least one impurity.
- step (a) of bringing the liquid medium C into contact with a first complexing agent makes it possible to obtain a first precipitate PI and a liquid medium Cl, the liquid medium Cl comprising the first precipitate PI.
- the solvent for the liquid medium C1 may comprise the solvent for the starting medium C and optionally the solvent for the first complexing agent.
- the solvent comprises or consists of water.
- the ferulic acid of the Cl medium can be in dissolved form in the solvent of the Cl medium and/or can be in the solid phase of the liquid CL medium
- Known or unidentified impurities may be in dissolved form in the solvent of medium C1 and/or may be in the precipitate of liquid medium C.
- the inventors are of the opinion that the first precipitate PI consists partially or totally of a complex formed between at least one cation (first complexing agent) and at least one impurity.
- the complex formed is a complex comprising a divalent or trivalent cation.
- the at least one impurity is a lignocellulose material chosen from the group consisting of lignin, cellulose, lignocellulose and hemicellulose.
- the at least one impurity is an oligomer of hydroxycinnamic acids, such as a dimer, trimer or tetramers of ferulic acid or a mixture thereof.
- the first complex is formed selectively between the first complexing agent and at least one impurity, relative to the ferulic acid present in the starting liquid medium C.
- lignocellulosic material a material containing cellulose, hemicellulose or lignin.
- Lignin is a macromolecular compound and a major structural component of the plant cell wall.
- the ferulic acid dimer can be a dihydroferulic acid of the following structure:
- the ferulic acid trimer may be a dehydrotriferulic acid of the following structure:
- the ferulic acid tetramer may be a dehydrotetraferulic acid of the following structure:
- the liquid medium C comprises ferulic acid, a solvent and at least one impurity chosen from the group consisting of lignin and lignocellulose.
- the ferulic acid has a purity greater than or equal to 80%.
- the liquid medium C comprises ferulic acid, a solvent and at least one impurity chosen from the group consisting of dimers, trimers or tetramers of ferulic acid.
- the ferulic acid has a purity greater than or equal to 80%. Furthermore, the inventors have demonstrated that the impurities present in the liquid medium C can comprise coumaric acid.
- the liquid medium C as defined above may also comprise coumaric acid.
- the liquid medium C1 comprises ferulic acid, a solvent or a mixture of solvent and coumaric acid.
- the liquid medium C can comprise at least 0.5% coumaric acid, for example at least 0.9% coumaric acid, in particular less than 2% coumaric acid by weight relative to the weight total crude ferulic acid in initial solid form.
- the starting liquid medium C comprises at least 5% lignin, for example more than 12% lignin, in particular less than 16% lignin by weight relative to total crude ferulic acid in solid form.
- the starting liquid medium C comprises at least 5% of dimers, trimers and/or tetramers of ferulic acid, for example more than 12%, in particular less than 16% of dimers, trimers and/or tetramers of ferulic acid, by weight relative to the total weight of crude ferulic acid in initial solid form.
- the liquid medium Cl obtained in step (a) is heated to a temperature of between 40° C. and 70° C., preferably at a temperature of between 50° C. C and 60°C.
- suitable heating means such as a heat transfer fluid.
- the pH of the liquid medium Cl is adjusted and is between 6 and 9, preferably between 6.5 and 7.5.
- the pH can be adjusted with a base, preferably a strong base.
- the base is chosen from water-soluble mineral bases.
- the base is chosen from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, and mixtures thereof.
- the base is chosen from NaOH, KOH, CaO, Ca(OH)2 and Na2CCh.
- adjusting the pH makes it possible to obtain ferulic acid in the form of ferulate and thus to solubilize the ferulic acid in the liquid medium, in particular in an aqueous liquid medium.
- the first precipitate PI formed in step (a) is then separated from the liquid medium Cl, in a step (b), to lead to a liquid medium Fl on the one hand and to the first precipitate PI on the other hand.
- step (b) of solid/liquid separation is carried out hot, the liquid medium Cl being heated between 40° C. and 70° C. and having a pH of between 6 and 9.
- the liquid medium F1 comprises purified ferulic acid, one or more solvents and at least one impurity in reduced quantity, said impurity being chosen from the group consisting of dimers, trimers and/or tetramers of ferulic acid, coumaric acid and lignin.
- the liquid medium F1 is a homogeneous liquid medium, and the solvent preferably comprises water or consists of water.
- purified ferulic acid is meant ferulic acid which is solid or in a liquid medium, said acid being freed at least partially of at least one impurity.
- Purified ferulic acid is therefore a ferulic acid comprising a reduced quantity of impurities, by weight or by mole, compared to the starting crude ferulic acid.
- the purified ferulic acid is characterized by a higher purity compared to the purity of the starting ferulic acid.
- the dry mass of at least the impurity is reduced by at least half compared to the dry mass of the same impurity in the medium C.
- the purity of the ferulic acid, in particular biobased, in the liquid medium F1 is greater than or equal to 87%, preferably greater than or equal to 90%, more preferably greater than or equal to 95%.
- the liquid medium F1 also contains, in a residual manner, the first complexing agent in the form of a cation.
- the method relates to a method for purifying a liquid medium comprising ferulic acid having a degree of purity greater than or equal to 80%, the method comprising:
- the method further comprises a step (c) in which a second complexing agent is added to the liquid medium F1.
- step (c) is subsequent to step (b) isolation of the precipitate.
- the second complexing agent may be an anion chosen from the group consisting of phosphate PO4 3 -, dihydrogen phosphate EL PC )', diphosphate P2O7 4 ions; oxalates (COO)2 2- , VCU 3 ' vanadates or their mixture.
- the second complexing agent is in solution, preferably in aqueous solution.
- the second complexing agent/first residual complexing agent molar ratio is between 1 and 3, preferably between 1.1 and 1.8.
- a second precipitate P2 is formed.
- the second precipitate P2 is distinct from the first precipitate PL.
- a liquid medium C2 is obtained comprising the second precipitate P2, a solvent, purified ferulic acid and at least one impurity chosen from dimers, trimers and/or tetramers of ferulic acid, coumaric acid and lignin.
- the solvent of the liquid medium C2 may comprise the solvent of the starting medium C and optionally the solvent of the first complexing agent and/or the solvent of the second complexing agent.
- the medium C2 solvent comprises or consists of water.
- the method may comprise a step (d) of separating the second precipitate P2 from the liquid medium C2 in order to obtain on the one hand the second precipitate P2 and on the other share a liquid medium F2.
- the liquid medium F2 comprises a solvent or a solvent mixture, purified ferulic acid and at least one residual impurity, for example the dimers, trimers and/or tetramers of ferulic acid, coumaric acid and lignin.
- the solvent of the liquid medium F2 can comprise the solvent of the starting medium C, the solvent of the first complexing agent and/or the solvent of the second complexing agent.
- the solvent of the medium F2 comprises or consists of water.
- the inventors have found that the addition of the second complexing agent makes it possible, after separation of the second precipitate, to obtain a liquid medium F2 which can be used directly in a process for the preparation of vanillin by fermentation of ferulic acid.
- the residual content of the first complexing agent in the liquid medium F2 is greater than or equal to 1 ppm, preferably greater than or equal to 20 ppm, more preferably greater than or equal to 40 ppm relative to the weight of the medium F2.
- the residual content of first complexing agent in composition F2 is less than 70 ppm relative to the weight of medium F2.
- the separation of the first precipitate PI from the medium C1 or of the second precipitate P2 from the liquid medium C2 can be carried out by any suitable solid/liquid separation technique, including but not limited to filtration, centrifugation, decantation, etc.
- the separation of the aforementioned first PI or of the second precipitate P2 from the liquid medium in which it is contained is carried out by filtration, for example by filtration on a membrane such as ultrafiltration or microfiltration, or by filtration on a frit, or by industrial techniques such as filtration with filter cloths, filter presses or filter cartridges.
- the medium C1 is filtered and the filtrate obtained corresponding to the medium F1 comprises ferulic acid having a purity greater than or equal to 90%, in particular greater than or equal to 93%.
- Filtration of medium C2 leads to a filtrate corresponding to medium F2 comprising ferulic acid having a purity greater than or equal to 90%, in particular greater than or equal to 93%.
- the liquid medium C and/or Cl and/or C2 and/or F1 and/or F2 of the method according to the invention is an aqueous liquid medium consisting of water.
- the process according to the invention makes it possible to operate in an aqueous medium and does not include the use of organic solvent.
- the ferulic acid in the dissolved salified form, that is to say in the form of ferulate.
- the method according to the invention further comprises a step of adjusting the pH of the liquid medium to precipitate the ferulic acid.
- the pH adjustment can be carried out by adding an acid such as a strong acid or a Lewis acid.
- the acid is selected from the group consisting of HCl, H2SO4, H3PO4 or para-toluene sulphonic acid.
- the invention relates to a process for purifying a liquid medium C comprising ferulic acid, a solvent and at least one impurity, the process comprising:
- the method according to the invention does not require a prior stage of filtration of the initial liquid medium C, thus making it possible to minimize the losses due to too many stages.
- the method according to the invention can be operated without the use of organic solvent and therefore in a more environmentally friendly manner. It is thus possible to operate the purification process under mild conditions in order to lead to a composition of natural ferulic acid.
- the yield of purified ferulic acid, in medium F1 or in medium F2 or in solid form is greater than or equal to 85%, preferably greater than or equal to 90, more preferably greater than or equal to 95%.
- step (b) an Fl medium is isolated on the one hand and a PI precipitate on the other hand.
- the present invention relates to a process for extracting ferulic acid oligomers present in the PI precipitate.
- the PI precipitate generally comprises at least one oligomer of ferulic acid, generally in salified form.
- the process for extracting the oligomers of ferulic acid present in the precipitate PI comprises a step (A) in an acid is mixed with the precipitate PL
- the acid allows the protonation of the oligomers of ferulic acid present in the precipitate PL preferably the acid used is phosphoric acid H3PO4.
- the acid is generally used with a concentration by weight between 5% and 25%, preferably between 7% and 15%, for example 8%, 9%, 10%, 11%, 12%, 13% or 14%.
- Step (A) is generally carried out at a temperature between 15°C and 25°C.
- Stage (A) is generally carried out with stirring.
- Step (B) is carried out in the presence of a solvent, preferably a solvent in which the ferulic acid oligomers are soluble.
- a solvent preferably a solvent in which the ferulic acid oligomers are soluble.
- the solvent is an aprotic solvent.
- the solvent is generally of medium polarity.
- the solvent can be ethyl acetate.
- the organic phase comprising the ferulic acid oligomer(s) is separated and recovered.
- acid can be added to repeat the liquid-liquid extraction.
- the acid may be phosphoric acid.
- the organic phase thus recovered is distilled so as to evaporate the solvent.
- composition (O) comprising at least one oligomer of ferulic acid is obtained.
- the process for extracting ferulic acid oligomers may comprise at least one step (i) of washing the precipitate PI, prior to step (A) described above.
- Step (i) is carried out in the presence of a base, preferably a strong base, in particular the base can be NaOH, KOH.
- the added base is in solution, the concentration of the base is generally between 10% and 50% by weight, preferably between 20% and 40% by weight, the concentration can be 30% by weight.
- step (i) is generally greater than or equal to 7, preferably greater than or equal to 8, very preferably greater than or equal to 8.2.
- the pH of step (i) is generally less than or equal to 10, preferably less than or equal to 9, very preferably greater than or equal to 8.5.
- Step (i) is preferably carried out with stirring.
- step (i) would allow the separation of the ferulic acid oligomers from the ferulic acid present in the PI precipitate generally in the form of a ferulate, for example zinc ferulate or d 'aluminum.
- step (i) a liquid medium is separated from a solid phase by filtration in a step (ii). This solid phase can be subjected to a new step (i).
- the present invention also relates to a composition (O) comprising at least one oligomer of ferulic acid.
- the composition (O) is of biosourced origin.
- the present invention also relates to a purified ferulic acid composition obtainable by the process according to the invention.
- the ferulic acid of the composition is in the salified form, that is to say in the form of ferulate ion.
- the purified ferulic acid composition according to the invention may comprise purified ferulic acid, a liquid phase and at least one impurity chosen from dimers, trimers and/or tetramers of ferulic acid, coumaric acid and/or lignin.
- the purified ferulic acid composition may be F1 liquid medium or F2 liquid medium.
- the ferulic acid composition according to the invention is an aqueous liquid composition comprising between 1% and 15% of purified ferulic acid, preferably between 5% and 10% by weight relative to the weight of the composition.
- the residual content of lignin or dimers or trimers and/or tetramers of ferulic acid in the composition is between 1500 and 9000 ppm, preferably between 2500 and 8000 ppm, relative to the weight of the composition.
- the residual content of first complexing agent is between 10 ppm and 650 ppm, preferably between 70 ppm and 200 ppm, relative to the weight of the composition.
- composition of purified ferulic acid according to the invention can be in solid form, for example it can correspond to the solid purified ferulic acid obtained after the stage of acidification of the medium F1 or of the medium F2.
- the aqueous composition of purified ferulic acid comprises ferulic acid having a purity greater than or equal to 90%, preferably greater than or equal to 95%.
- the composition according to the invention has few or no water-insoluble particles.
- the purified ferulic acid composition or the purified ferulic acid can be used, directly or indirectly, in a bioconversion fermenter in order to be converted by a microorganism into natural vanillin.
- the composition consisting of the liquid medium F2 can be used directly in a fermenter in order to to be transformed into vanillin by a microorganism, for example according to the method described in EP0885968.
- the ferulic acid composition obtained is a natural ferulic acid.
- the present invention also relates to a process for the preparation of ferulic acid in which the ferulic acid is purified according to the purification process as defined above.
- the present invention also relates to the use of a composition of ferulic acid or purified ferulic acid obtained by the method described above, for the preparation of vanillin, in particular natural vanillin.
- the invention also relates to a process for the production of natural vanillin comprising - the purification of a medium comprising ferulic acid according to the process as described previously - the transformation of the purified ferulic acid obtained into natural vanillin by a process of fermentation.
- the present invention also relates to a composition of ferulic acid oligomers obtainable by the extraction process of the present invention, the composition may be composition O.
- the present invention also relates to the use of a PI precipitate or of a composition of ferulic acid oligomers present in the PI precipitate, or obtained by the extraction process of the present invention in the field of industry.
- food or cosmetics in particular as antioxidant or UV stabilizer.
- a composition O in the field of the food or cosmetics industry, in particular as a scavenger of free radicals or of radical species, in particular as a polymerization inhibitor, antioxidant or UV stabilizer.
- the starting liquid medium C is prepared by mixing commercial biosourced crude ferulic acid with seven times its weight of water.
- the starting crude ferulic acid has a purity of 82% and contains identified and unidentified impurities.
- the mixture obtained is in the form of a suspension comprising the aqueous liquid medium C and solid particles in suspension in the liquid medium C (not shown).
- a step (a) the starting liquid medium C is brought into contact with an aqueous solution comprising the first complexing agent.
- an aqueous liquid medium Cl is obtained and a first aforementioned PI is formed.
- the resulting medium Cl is a suspension comprising in particular an aqueous liquid phase and the aforementioned first PL.
- the aqueous medium Cl is heated to 50° C. then the pH of the medium Cl is brought to 6.8.
- the hot liquid medium Cl is filtered with a filtration device in order to separate and/or isolate the first precipitate PL
- the first precipitate PI is washed with water heated to 50°C at alkaline pH.
- the filtration leads to a liquid F1 medium comprising water, purified ferulic acid and at least one impurity in reduced quantity.
- the first precipitate PI is retained by the filtration device.
- the purity of the ferulate contained in the liquid medium C1 thus obtained is greater than the purity of the ferulic acid of the starting medium C.
- the medium C1 is acidified to pH 2-3.
- the medium liquid C1 is separated from the solid ferulic acid obtained by filtration (not shown).
- steps (a), (a1) and (b) of the embodiment according to Figure 1 are performed. Following filtration step (b), an aqueous liquid medium F1 is obtained. Then, in a step (c), the liquid medium F1 is brought into contact with an aqueous solution of the second complexing agent. A second precipitate P2 then forms. The resulting composition is the medium C2 comprising the second precipitate P2, an aqueous solvent and at least one residual impurity. The medium C2 is filtered in a step (d) to lead to the second precipitate P2 on the one hand, and to a filtrate F2 on the other hand. The filtrate is recovered and corresponds to medium F2, F2 being a liquid medium devoid of precipitate or particles.
- composition F2 can be used directly in a microbiological process for the preparation of vanillin.
- Example 1 Purification of commercial biobased ferulic acid
- Medium C comprising ferulic acid was prepared by mixing commercial ferulic acid in solid form (55 g) and water (409 g). Medium C obtained is stirred at room temperature for 30 min. 29 mL of an aqueous solution of zinc sulphate (100 g/L) is added to medium C then the medium is brought to a temperature of 50° C. and the pH is adjusted to 6.8. The CI medium obtained is filtered on filter cloth and the filtrate F1 is recovered. A liquid F1 medium comprising purified ferulic acid is thus obtained. A PI precipitate is isolated.
- Example 1 The results of Example 1 are shown in Table 1 below:
- Example 2 does not include a step for adding a first complexing agent or a second complexing agent.
- Medium C comprising ferulic acid was prepared by mixing commercial ferulic acid in solid form (50 g) and water (413 g). Medium C obtained is stirred at room temperature for 30 min. The medium is brought to a temperature of 50° C. and the pH is adjusted to 6.8. The medium C1 obtained is filtered through a filtration cloth and the liquid medium F1 is recovered. A liquid F1 medium comprising purified ferulic acid is thus obtained.
- Example 3 The precipitate PI of example 1 is recovered
- the PI precipitate is dispersed in water and the pH is adjusted to 8.2 with 30% sodium hydroxide, then filtered and dried. This new precipitate is then brought into contact with phosphoric acid at 10% by weight. An extraction with ethyl acetate is then carried out.
- composition (O) comprising at least one oligomer of ferulic acid is obtained.
- the results show that the precipitate PI and the composition (O) of ferulic acid oligomer exhibit interesting free radical species scavenging properties.
- the precipitate PI and the composition (O) have interesting antioxidant properties.
- a spectrophotometric tank In a spectrophotometric tank are placed 3 mL of a DPPET solution at 6 ⁇ 10 ⁇ 5 mol/L and 77 ⁇ L of solution of compound whose antioxidant activity is desired to be measured (Trolox, precipitate PI and composition O at different concentrations).
- the absorbance at 515 nm is measured regularly over a period of 5 hours.
- a dose-effect curve can then be plotted and the effective concentration EC50 is then determined. This measurement indicates the antioxidant concentration necessary to reduce 50% of the initial DPPH°. The lower the EC50, the more effective the antioxidant.
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FR2010088A FR3114813B1 (fr) | 2020-10-02 | 2020-10-02 | Purification d’acide ferulique |
EP21183653 | 2021-07-05 | ||
PCT/EP2021/076973 WO2022069651A1 (fr) | 2020-10-02 | 2021-09-30 | Purification d'acide ferulique |
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CA2238215A1 (en) | 1997-06-19 | 1998-12-19 | Markus Wetli | Process for the production of vanillin |
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AU2003241211A1 (en) | 2003-06-19 | 2005-01-04 | Biokab, S.A. De C.V. | Method for the recovery of ferulic acid |
FR2984314B1 (fr) | 2011-12-15 | 2014-01-17 | Rhodia Operations | Procede de purification de la vanilline par extraction liquide-liquide |
CN108084005B (zh) | 2013-01-24 | 2023-04-18 | 罗地亚经营管理公司 | 用于纯化天然香草醛的方法 |
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AU2016324974B2 (en) * | 2015-09-15 | 2021-02-25 | Fyteko | Bioactive composition for improving stress tolerance of plants |
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US11155513B2 (en) | 2017-04-20 | 2021-10-26 | Spero Renewables, Llc | Extraction of natural ferulate and coumarate from biomass |
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