CN114685262A - Method for preparing ferulic acid from soapstock - Google Patents
Method for preparing ferulic acid from soapstock Download PDFInfo
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- CN114685262A CN114685262A CN202011611941.0A CN202011611941A CN114685262A CN 114685262 A CN114685262 A CN 114685262A CN 202011611941 A CN202011611941 A CN 202011611941A CN 114685262 A CN114685262 A CN 114685262A
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- 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 173
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 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 166
- 229940114124 ferulic acid Drugs 0.000 title claims abstract description 166
- 235000001785 ferulic acid Nutrition 0.000 title claims abstract description 166
- 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 166
- 238000000034 method Methods 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000010306 acid treatment Methods 0.000 claims abstract description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 21
- 239000000194 fatty acid Substances 0.000 claims abstract description 21
- 229930195729 fatty acid Natural products 0.000 claims abstract description 21
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000003916 acid precipitation Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 229940114123 ferulate Drugs 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 124
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 111
- 239000012071 phase Substances 0.000 claims description 106
- 230000008859 change Effects 0.000 claims description 85
- 238000007127 saponification reaction Methods 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 239000002253 acid Substances 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 36
- 230000003750 conditioning effect Effects 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 25
- 239000002699 waste material Substances 0.000 claims description 24
- 150000007522 mineralic acids Chemical group 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 18
- 241000209094 Oryza Species 0.000 claims description 13
- 235000007164 Oryza sativa Nutrition 0.000 claims description 13
- 235000009566 rice Nutrition 0.000 claims description 13
- 238000007670 refining Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- -1 alkali metal salts Chemical class 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000003921 oil Substances 0.000 description 35
- 235000019198 oils Nutrition 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 27
- 230000020477 pH reduction Effects 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- 238000001035 drying Methods 0.000 description 15
- 238000001914 filtration Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 108090001060 Lipase Proteins 0.000 description 6
- 239000004367 Lipase Substances 0.000 description 6
- 102000004882 Lipase Human genes 0.000 description 6
- 235000019421 lipase Nutrition 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 241000235015 Yarrowia lipolytica Species 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 4
- 239000003925 fat Substances 0.000 description 4
- 235000019197 fats Nutrition 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009874 alkali refining Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 101150021155 LIP2 gene Proteins 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 235000019774 Rice Bran oil Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000008165 rice bran oil Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-M 9-cis,12-cis-Octadecadienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O OYHQOLUKZRVURQ-HZJYTTRNSA-M 0.000 description 1
- 244000061520 Angelica archangelica Species 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- QVZGAIWUSYVGBJ-UHFFFAOYSA-N Cycloartenyl ferulate Natural products CCC12CCC3(C)C(C(C)CCC=C(C)C)CCC3(C)C1CCC(C1(C)C)C2CCC1OC(=O)C=CC1=CC=C(O)C(OC)=C1 QVZGAIWUSYVGBJ-UHFFFAOYSA-N 0.000 description 1
- 244000228957 Ferula foetida Species 0.000 description 1
- 235000001287 Guettarda speciosa Nutrition 0.000 description 1
- 241001506991 Komagataella phaffii GS115 Species 0.000 description 1
- 241000112528 Ligusticum striatum Species 0.000 description 1
- 244000217433 Melampodium divaricatum Species 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 108700032257 Yarrowia lipolytica LIP2 Proteins 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000000748 cardiovascular system Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- FODTZLFLDFKIQH-UHFFFAOYSA-N cycloartenol trans-ferulate Natural products C1=C(O)C(OC)=CC(C=CC(=O)OC2C(C3CCC4C5(C)CCC(C5(C)CCC54CC53CC2)C(C)CCC=C(C)C)(C)C)=C1 FODTZLFLDFKIQH-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FODTZLFLDFKIQH-FSVGXZBPSA-N gamma-Oryzanol (TN) Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)O[C@@H]2C([C@@H]3CC[C@H]4[C@]5(C)CC[C@@H]([C@@]5(C)CC[C@@]54C[C@@]53CC2)[C@H](C)CCC=C(C)C)(C)C)=C1 FODTZLFLDFKIQH-FSVGXZBPSA-N 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 150000004676 glycans Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920005610 lignin Chemical group 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004161 plant tissue culture Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 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
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 1
- 239000012064 sodium phosphate buffer Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
- 229940114926 stearate Drugs 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002936 tranquilizing effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- 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
-
- 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
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
Abstract
The present invention relates to a process for the preparation of ferulic acid from soapstock, said process comprising the steps of: (1) subjecting a saponified solution obtained by saponifying a soapstock to acid treatment to obtain an oil phase containing fatty acids and a water phase containing ferulate; (2) separating the oil phase and the water phase; (3) ferulic acid is obtained by acid precipitation separation from the water phase. The method can effectively separate the fatty acid and the ferulic acid, and the process of the invention has simple operation, does not modify the existing equipment too much and can quickly realize production in factories.
Description
Technical Field
The present invention relates to a process for the preparation of ferulic acid from soapstock.
Background
Ferulic Acid (Ferulic Acid) has a chemical name of 4-hydroxy-3-methoxycinnamic Acid, and is one of the derivatives of cinnamic Acid (also known as cinnamic Acid, 3-phenyl-2-propenoic Acid). The ferulic acid has relative molecular mass of 194.19, melting point of 174 deg.C, is slightly soluble in cold water, soluble in hot water, soluble in ethanol, methanol and acetone, and insoluble in benzene and petroleum ether, and has good pH stability.
Through years of research, ferulic acid has multiple functions: has tranquilizing effect on central nerve; platelet aggregation and thrombosis resistance; scavenging free radicals in vivo; antibacterial and anti-inflammatory effects; protecting the cardiovascular system; the immunity is improved; has a plurality of effects of protecting organ injury after poisoning, and the like, has good medicinal and edible values, and has wide application in the fields of medicines, foods, cosmetics, pesticides, feed additives, and the like.
Ferulic acid is ubiquitous in the plant world and is widely distributed. In plants, the cross-linking of the plant cell wall polysaccharide and lignin forms a part of the cell wall, and is one of the important effective components of angelica, ligusticum wallichii, ferula asafetida and the like. Wherein ferulic acid is also commonly present in rice, mainly exists in the forms of cycloartenyl ferulate and sterol ferulate, commonly called oryzanol. During the rice oil processing, most oryzanol is retained in the soapstock, and the oryzanol content can reach more than 30% (dry basis), so the soapstock of the rice oil is an ideal raw material for producing ferulic acid.
The current methods for producing ferulic acid are mainly divided into four types: chemical synthesis, enzymatic hydrolysis, plant tissue culture and alkaline hydrolysis of oryzanol. The main literature reports are as follows:
dane et al (responding surface method for optimizing the process for preparing ferulic acid by alkaline hydrolysis of oryzanol, food industry science and technology, 2013, stage 16) report that oryzanol is used as a raw material, and the process for preparing ferulic acid by alkaline hydrolysis of oryzanol is optimized by utilizing the responding surface method. On the basis of a single-factor experiment, hydrolysis time, alkali concentration and substrate concentration are used as influencing factors, a Box-Behnken center combination method is used for carrying out a three-factor three-level experiment, and ferulic acid yield is used as a response value for response surface analysis. The result shows that the optimal process conditions for preparing the ferulic acid by the alkaline hydrolysis of the oryzanol are as follows: the hydrolysis time is 12.5h, the alkali concentration (NaOH mass fraction) is 12%, the substrate concentration is 6.57mg/mL, the theoretical predicted value of the ferulic acid yield is 72.68%, the verified value is 71.33%, and the relative error with the predicted value is only 1.89%.
Chase, et al ("study on hydrolysis of oryzanol by Yarrowia lipolytica lip2 lipase" on production of ferulic acid ", science and technology in food industry, 2014, No. 22) studied the enzymatic reaction system of Yarrowia lipolytica (Yarrowia lipolytica) lipase on hydrolysis of oryzanol on production of ferulic acid. It was found that the yield of ferulic acid produced by hydrolysis of yarrowia lipolytica whole lipase powder (105U/mg) in a system of 50mmol/L Tris-HCl (containing 7.5mmol/L sodium cholate) at pH7.0 and 100mmol/L sodium phosphate buffer (containing 1000U lipase) at pH6.0 was 2.94%. In order to further improve the hydrolysis efficiency of lipase, the main component lip2 lipase gene in yarrowia lipolytica lipase is cloned, the gene is integrated into the genome of Pichia pastoris GS115 and fermented to prepare lip2 lipase powder (70.1U/mg), and a oryzanol hydrolysis experiment is carried out in the enzymolysis system, and the experiment result shows that the yield of ferulic acid is 2.87%.
Noor Hassorieah Mohd Salleh et al ("Optimization of alkali hydrolysis of sodium strand for a bacterial acid extraction", Industrial Crops and Products, 11.2011, Vol.34, No. 3, p.1635-. The optimum process parameters were determined by screening temperature, NaOH concentration and extraction time. After optimization, the content of ferulic acid is increased from 0.518% to 0.817% (8.17 mg/g). The optimal conditions obtained in this study were temperature, NaOH concentration and extraction time 125 deg.C, 3.90M, 2.30 h.
Ma Shuyu, etc. (the "oryzanol hydrolyzes to prepare ferulic acid", the technical information of Heilongjiang, 2010, 14 th) determines the optimal process and purification method for preparing ferulic acid by oryzanol hydrolyzation. The method comprises the following steps: the optimal process for preparing ferulic acid by oryzanol hydrolysis is determined by comparing the influences of different solvents, different reaction times and different alkali concentrations on the oryzanol hydrolysis rate and the ferulic acid yield and by orthogonal experiments, and the optimal purification method of the ferulic acid crude product is determined by comparing the purification results of different purification methods. The results were: the optimal experimental conditions for the reaction are that the reaction time is 9 hours, the alkali concentration is 25 percent, the alcohol-base ratio is 5: 5, the reaction solvent is n-butanol. The purification method comprises the following steps: dissolving in hot ethanol solution, cooling in ice water bath, and recrystallizing (adding sodium sulfite as antioxidant).
CN 101434535A discloses a method for preparing natural ferulic acid, which comprises squeezing or solvent leaching rice bran oil from rice bran, rice bran and rice germ, extracting ferulic acid from byproduct called black foot after oryzanol is prepared from rice bran oil, preparing crude natural ferulic acid product under heating, pressurizing and stirring conditions by using fatty acid salt as dispersant, centrifuging to remove impurities, acid-separating, and refining to obtain pure ferulic acid product. The final yield of ferulic acid was 75%.
CN 109022501A discloses a method for obtaining ferulic acid by using waste, which comprises the steps of mixing vinasse and bran, inoculating and culturing to obtain a vinasse solid fermentation product, and extracting ferulic acid in the vinasse solid fermentation product by a hot water extraction method.
The above documents are all researches on the production process of ferulic acid, mainly focusing on the optimization of the preparation process of ferulic acid, and few documents pay attention to the recovery of ferulic acid from rice oil waste soapstock.
Thus, there remains a need in the art for a more optimized process for the preparation of ferulic acid, including processes for the preparation of ferulic acid from spent soapstock containing ferulic acid and/or salts or esters thereof, produced in the refining of fats and oils.
Disclosure of Invention
The invention relates to a method for preparing and separating ferulic acid in soapstock by an acid method. Specifically, the saponification liquid obtained by saponifying the soapstock is subjected to acid treatment, so that the fatty acid in the saponification liquid is hydrochlorinated into the fatty acid, and the ferulic acid exists in the form of salt in the aqueous phase, thereby realizing the separation of the ferulic acid.
In a first aspect the present invention provides a process for the preparation of ferulic acid from soapstock, the process comprising the steps of:
(1) subjecting a saponified solution obtained by saponifying a soapstock to acid treatment to obtain an oil phase containing fatty acids and a water phase containing ferulate;
(2) separating the oil phase and the water phase;
(3) ferulic acid is obtained by acid precipitation separation from the water phase.
In one or more embodiments, the soapstock is produced from oil refining, such as rice oil refining, or from rice oil subjected to alkali treatment.
In one or more embodiments, the salt is an alkali metal salt, e.g., sodium, potassium.
In one or more embodiments, the acid used for the acid treatment is selected from mineral acids, preferably one or more selected from the group consisting of sulfuric acid, hydrochloric acid, and phosphoric acid.
In one or more embodiments, the acid used in the acid treatment is sulfuric acid, and the concentration of the solution is 30 to 98%, preferably 30 to 50%.
In one or more embodiments, or the acid used in the acid treatment is hydrochloric acid, and the concentration of the solution is 5 to 10%.
In one or more embodiments, the acid used in the acid treatment is phosphoric acid, and the concentration of the solution is 20 to 40%.
In one or more embodiments, the acidification comprises adjusting the pH of the aqueous phase to 2-3 for 3-8 hours.
In one or more embodiments, the temperature of the reaction system is controlled between 50 and 70 ℃ during the acid treatment.
In one or more embodiments, the method comprises: adjusting pH of saponification solution to below 7, such as 5-7 or 5.2-7, stirring thoroughly to react, separating oil phase and water phase, adjusting pH of water phase to 2-3, and separating solid phase containing ferulic acid to obtain ferulic acid; preferably, the saponification solution is adjusted to pH7 or less within 30 minutes and then allowed to react for 2 to 8 hours while stirring.
In one or more embodiments, in the acid treatment, the pH is adjusted stepwise; wherein the step-adjusting the pH comprises a first adjusting stage and a second adjusting stage.
In one or more embodiments, the first adjustment stage comprises adjusting the pH of the saponification liquor from an initial pH to 7. + -. 0.3 at an average pH change rate of 0.1/min or more, preferably 0.1 to 0.3/min.
In one or more embodiments, the second adjustment stage includes adjusting the pH of the reaction system from about 7 to 5.2 to 5.4 at an average pH change rate of 0.05/min or less.
In one or more embodiments, the second conditioning stage has a maximum pH change rate of no more than 0.08/min and a minimum pH change rate of no less than 0.005/min.
In one or more embodiments, the conditioning time of the first conditioning stage is within 60 minutes.
In one or more embodiments, the conditioning time of the second conditioning stage is between 90 and 140 minutes.
In one or more embodiments, after adjusting the pH to 5.2 to 5.4, the reaction is carried out for 2 to 6 hours, and then the oil and water phases are separated.
In one or more embodiments, the pH of the saponification liquor is adjusted in one or more steps from an initial pH to 7. + -. 0.3 in a first adjustment stage, wherein the total adjustment time is within 60 minutes and the average pH change rate throughout the first adjustment stage is 0.1/min or more, preferably 0.1 to 0.3/min.
In one or more embodiments, in the second conditioning stage, the pH of the saponification liquor is adjusted from 7. + -. 0.3 to 5.2-5.4 in one or more portions, wherein the total conditioning time is between 90 and 140 minutes and the average pH change rate over the entire conditioning stage is ≤ 0.05/min, preferably the highest pH change rate is not more than 0.08/min and the lowest pH change rate is not less than 0.005/min.
In one or more embodiments, the second adjustment stage comprises two stages, the A stage adjusting the pH from 7. + -. 0.3 to an intermediate pH, such as 6. + -. 0.3, and the B stage adjusting the pH of the reaction system from this intermediate pH to 5.2-5.4.
In one or more embodiments, the average rate of change of pH value for stage a is in the range of 0.01 to 0.08/min; preferably, the highest pH change rate is no more than 0.08/min and the lowest pH change rate is no less than 0.01/min.
In one or more embodiments, the average rate of change of pH of the B stage is in the range of 0.005 to 0.02 per minute.
In one or more embodiments, the average pH change rate of the B-stage is lower than the average pH change rate of the a-stage.
In one or more embodiments, the rate of change of pH during stage B is no more than 0.02/min at the most and no less than 0.005/min at the least.
In one or more embodiments, the first conditioning stage comprises adjusting the pH of the saponification liquor from an initial pH of 7 ± 0.3 within 30 minutes, and after a reaction time, entering the second conditioning stage, wherein the total time of the first conditioning stage does not exceed 60 minutes, or the saponification liquor is adjusted to a pH of 7 ± 0.3 within 60 minutes and then directly entering the second conditioning stage.
In one or more embodiments, the second adjustment stage comprises a stage a and a stage B, the stage a comprising adjusting the pH of the saponification liquor from 7 ± 0.3 to 6 ± 0.3 within 30 minutes at the first average pH change rate, and entering the stage B after reacting for 20 to 40 minutes, or entering the stage B immediately after adjusting the pH from 7 ± 0.3 to 6 ± 0.3 within 60 minutes at the first average pH change rate, and the stage B comprising adjusting the pH of the reaction system from 6 ± 0.3 to 5.2 to 5.4 at the second average pH change rate; preferably, the average pH change rate of the a-stage is in the range of 0.01-0.08/min, the second average pH change rate is in the range of 0.005-0.02/min, and the first average pH change rate is higher than the second average pH change rate.
In one or more embodiments, the method comprises:
(1) adding the inorganic acid solution into saponification liquid obtained by saponification of soapstock at the temperature of 50-70 ℃, reducing the pH of the saponification liquid to 7 +/-0.3 within 30 minutes, and then stirring for 20-40 minutes;
(2) adding the inorganic acid solution into the mixed solution after the reaction in the step (1), reducing the pH of the mixed solution from 7 +/-0.3 to 6 +/-0.3 within 30 minutes, and then stirring for 20-40 minutes;
(3) adding the inorganic acid solution into the mixed solution after the reaction in the step (2), reducing the pH of the mixed solution from 6 +/-0.3 to 5.2-5.4 within 30 minutes, and then stirring for 2-6 hours, wherein the pH is maintained within the range of 5.2-5.4;
(4) separating an oil phase from a water phase in the mixed solution after the reaction in the step (3) is finished;
(5) adjusting the pH value of the water phase obtained in the step (4) to 2-3, and performing acid precipitation to separate out ferulic acid.
The second aspect of the present invention provides the use of an inorganic acid in the preparation of ferulic acid from waste soapstock produced in the refining of fats and oils; preferably, the inorganic acid is selected from one or more of sulfuric acid, hydrochloric acid and phosphoric acid; preferably, the inorganic acid is sulfuric acid, the concentration of the solution of which is 30 to 98%, preferably 30 to 50%, or the inorganic acid is hydrochloric acid, the concentration of the solution of which is 5 to 10%, or the inorganic acid is phosphoric acid, the concentration of the solution of which is 20 to 40%.
In one or more embodiments, the preparation is carried out using the methods of any of the embodiments of the present invention.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as amounts, amounts and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The main component of soapstock is sodium fatty acid, which is an emulsifier, so the main characteristic of soapstock is that it contains a large amount of water (about 50%), which cannot be separated by conventional means such as centrifugation, pH adjustment, etc. Therefore, based on the above-mentioned characteristics of soapstock, in the conventional production process of ferulic acid, the moisture in the waste soapstock still carries about 2-4% of ferulic acid, thereby causing the reduction of yield of ferulic acid. The main component of the saponified solution of waste soapstock is fatty acid salt, including linoleate, oleate, stearate, palmitate and the like, and is mainly sodium salt, the pKa of which is 4.77, 5.02, 4.75 and 4.95 respectively, and the pKa of ferulic acid is 4.58 (carboxyl group) and 4.42 (phenolic hydroxyl group), so that the difference between the pKa of ferulic acid and the pKa of fatty acid is very small, and the separation cannot be performed by simply adjusting the pH value. The invention relates to a method for preparing and separating ferulic acid in saponification liquid of waste soapstock by an acid method. Further, the present inventors have found that, if the pH of acidification is controlled stepwise, fatty acids in the saponified solution of waste soapstock can be more efficiently hydrochlorinated into fatty acids while ferulic acid remains in the form of a salt in the aqueous phase, thereby more efficiently separating fatty acids from ferulic acid. The process of the invention is simple to operate, does not modify the existing equipment too much, and can realize production in factories quickly.
The acid method refers to treating the saponification liquid of the waste soapstock with acid, especially inorganic acid, to make the fatty acid in the saponification liquid of the waste soapstock hydrochloric acid into fatty acid, while the ferulic acid still exists in the form of salt, then separating the ferulic acid in the form of salt in the water phase, and performing acid precipitation under the acidic condition to separate the ferulic acid.
The acidification herein refers to the precipitation of ferulic acid from a solution to form a solid under acidic conditions, for example at a pH of 2-3. The acid used for the acidification is not particularly limited as long as it can adjust the pH to 2 to 3 without reacting with ferulic acid.
Acids suitable for use in the present invention are preferably inorganic acids, more preferably strong acids, i.e., acids having a pKa of less than 1, including but not limited to sulfuric acid, hydrochloric acid, and phosphoric acid. The concentration of the acid solution used is not particularly limited as long as it can provide a sufficient amount of protons to lower the pH of the reaction system to the range defined in the present invention within the conditions defined in the method of the present invention. For example, the present invention can be practiced using the highest concentration sulfuric acid solution (about 98%), hydrochloric acid solution (about 37%), or phosphoric acid solution (about 85%) known in the art. It is to be understood that, in general, the mass of water in the saponification solution (containing soapstock and water) used in the reaction may be 1.5 to 3 times the mass of soapstock, i.e. the water content may be 60 to 75%; however, when a high-concentration acid solution (e.g., 98% concentrated sulfuric acid) is used, the water content in the saponified solution is preferably 80 wt.% or more, more preferably 90 wt.% or more, in order to sufficiently contact the reactants. In some embodiments, the concentration of the sulfuric acid solution may be 30 to 98 wt%. Preferably, the concentration of the sulfuric acid solution is 30 to 50 wt%. In some embodiments, the concentration of the hydrochloric acid solution used may be 5 to 10 wt%. In some embodiments, the concentration of the phosphoric acid solution used may be 20 to 40 wt%.
In the present invention, soapstock has a meaning well known in the art, and generally refers to a by-product of alkali refining of animal and vegetable fats and oils, which is a product of a deacidification section. Soapstock is usually saponified by treating the soapstock with an alkali to react with the residual fat in the soapstock to produce a fatty acid salt. Saponification conditions for the soapstock are well known in the art. For example, depending on the composition of the soapstock, the saponification reaction may be carried out at a temperature of 110-.
Saponifying the soapstock to obtain saponified liquid, namely the raw material for preparing the ferulic acid. The saponification solution usually contains fatty acid salts and ferulate salts, and the salts may be sodium salts or calcium salts depending on the alkali used for alkali refining and saponification. Soapstock suitable for use in the present invention may be soapstock from the alkali refining of various fats and oils, provided that it contains ferulic acid. In a particular embodiment, the soapstock may be a soapstock from a rice oil caustic refining, and the saponified solution is a saponified solution obtained after saponifying the soapstock from the rice oil caustic refining.
The method for preparing ferulic acid from soapstock (preferably waste soapstock generated by oil refining) comprises the following steps:
(1) subjecting a saponification solution obtained by saponification of a soapstock to acid treatment to obtain an oil phase containing fatty acids and a water phase containing ferulate;
(2) separating the oil phase and the water phase;
(3) ferulic acid is obtained by acid precipitation separation from the water phase.
Usually, the pH of the saponified solution is adjusted to 7 or less, such as 5-7 or 5.2-7, the mixture is stirred sufficiently to react, then the oil phase and the water phase are separated, and the pH of the water phase is adjusted to 2-3 to precipitate ferulic acid, whereby ferulic acid can be prepared. In some embodiments, the saponification liquor is adjusted to a pH of 7 or less within 30 minutes and then allowed to react for 2-8 hours with stirring. In some embodiments, the aqueous phase is acidified for 3-8 hours after adjusting the pH to 2-3. Preferably, the acid treatment is performed using an inorganic acid, preferably using one or more of sulfuric acid, hydrochloric acid and phosphoric acid. Preferably, the concentration of the sulfuric acid solution is 30-50%; preferably, the concentration of the hydrochloric acid solution is 5-10%; preferably, the concentration of the phosphoric acid solution is 20-40%.
Generally, the present invention adjusts the pH of the reaction system by continuously adding an acid solution. During the reaction, the temperature of the reaction system (saponification liquid) is controlled between 50 ℃ and 70 ℃. The acidification can be carried out at room temperature.
The present inventors have found that if the pH of the acidification (i.e., acid treatment) is adjusted stepwise, fatty acids in the soapstock can be more efficiently hydrochlorinated into fatty acids while ferulic acid remains in the form of a salt in the aqueous phase, thereby more efficiently separating fatty acids from ferulic acid. Specifically, the pH stepwise adjustment of the present invention comprises a first adjustment stage (from the pH of the saponification solution to about 7) and a second adjustment stage (from about 7 to the reaction pH). Preferably, in the first adjusting stage, the pH value of the saponification liquid is adjusted from the initial pH value to about 7 at an average pH value change rate of 0.1/min or more, preferably 0.1-0.3/min; preferably, in the second adjusting stage, the pH value of the reaction system is adjusted from about 7 to the reaction pH value at an average pH value change rate of less than or equal to 0.05/min (preferably, the highest pH value change rate is not more than 0.08/min, and the lowest pH value change rate is not less than 0.005/min, namely, the pH change range is 0.005-0.08/min). Preferably, the reaction pH is 5.2-5.4. Preferably, the conditioning time of the first conditioning stage is within 60 minutes. Preferably, the conditioning time of the second conditioning stage is between 90 and 140 minutes. In some embodiments, prior to the first conditioning stage, there is further included the step of adjusting the pH of the saponification liquor of the spent soapstock to 13. In some embodiments, the step of adjusting the pH of the saponified solution of waste soapstock to 13 may be performed by lowering the pH to 13 by adding acid or raising the pH to 13 by adding base.
In some embodiments, in the first adjustment stage, the pH of the saponification liquor is adjusted from the initial pH to 7. + -. 0.3 in one or more portions, wherein the total adjustment time of the entire adjustment stage is controlled to be within 60 minutes and the average pH change rate of the entire first adjustment stage is not less than 0.1/min, preferably 0.1-0.3/min. In some embodiments, in the second conditioning stage, the pH of the saponification liquor is adjusted from 7. + -. 0.3 to 5.2-5.4 in one or more portions, wherein the total conditioning time is between 90 and 140 minutes and the average pH change rate over the entire conditioning stage is ≤ 0.05/min, preferably the highest pH change rate is no more than 0.08/min and the lowest pH change rate is no less than 0.005/min. Herein, the term "one or more times" means that the acid solution can be continuously added during the pH adjustment process to directly adjust the pH of the saponified solution to a predetermined pH value, or a part of the acid solution can be added first to adjust the pH value of the saponified solution to a certain pH value, then the reaction is carried out for a period of time, then the acid solution is continuously added to adjust the pH value to a certain pH value, and then the reaction is carried out for a period of time, and so on until the predetermined pH value is reached.
In some embodiments, the pH of the reaction system may be adjusted to about 7 in a first adjustment stage within a short period of time, e.g., 10-20 minutes, and then reacted at that pH for a period of time before a second adjustment is made, provided that the average rate of change of pH and preferably the total time of adjustment throughout the first adjustment stage prior to the second adjustment meets the requirements described herein; alternatively, the initial pH of the saponification solution may be adjusted to a set pH, e.g., 9, where the pH is reacted for a period of time, then adjusted to the next set pH, e.g., 8, and reacted for a period of time and then adjusted to a target pH, e.g., 7, as long as the average pH change rate over the entire period and preferably the total adjustment time meet the requirements described herein. Likewise, in the second adjustment stage, the pH may be adjusted to a set pH, after the pH has reacted for a period of time, the pH is adjusted to the next set pH, after a period of time, the adjustment is performed, and so on, until the final reaction pH is reached, provided that the average pH change rate and preferably the total adjustment time throughout the second adjustment stage meet the requirements described herein. Herein, the average pH change rate is (initial pH-target pH)/time (minutes). For example, if the initial pH is 13, the target pH is 7, and the total adjustment time is 60 minutes, the average pH change rate is (13-7)/60 ═ 0.1.
Preferably, the end point pH of the first adjustment stage of the pH of the present invention is 7 ± 0.3 and the end point pH of the second adjustment stage (i.e. the reaction pH) is 5.2-5.4.
Preferably, in some embodiments, the second adjustment stage comprises two stages, the a stage being to adjust the pH from the end pH of the first adjustment stage to an intermediate pH, which may be 6 ± 0.3, and the B stage being to adjust the pH of the reaction system from this intermediate pH to the reaction pH, i.e. 5.2 to 5.4. In a preferred embodiment, the average rate of change of pH in stage a is in the range of 0.01 to 0.08/min; preferably, the highest pH change rate is no more than 0.08/min and the lowest pH change rate is no less than 0.01/min. Preferably, the average pH change rate of the B-stage is in the range of 0.005-0.02/min, preferably the average pH change rate of the B-stage is lower than the average pH change rate of the a-stage. More preferably, the rate of change of pH during the B-stage is no more than 0.02/min at the highest and no less than 0.005/min at the lowest. Preferably, the rate of change of the pH value is gradually reduced from a relatively high rate in the initial stage to a lower rate in the final stage of adjustment in different stages of the second stage of adjustment.
In a preferred embodiment, in the first adjustment stage, the pH of the saponification liquor is adjusted from the initial pH of the saponification liquor to 7 ± 0.3; the second adjusting stage comprises two stages, wherein the pH value of the saponification liquid is adjusted from 7 +/-0.3 to 6 +/-0.3 in the stage A at the first average pH value change rate, and the pH value is adjusted from 6 +/-0.3 to 5.2-5.4 in the stage B at the second average pH value change rate; wherein the first average pH value change rate is in the range of 0.01-0.08/min, the second average pH value change rate is in the range of 0.005-0.02/min, and the first average pH value is higher than the second average pH value, and the pH change rate in the A stage is higher than the pH change rate in the B stage.
In some embodiments, the first conditioning stage comprises adjusting the pH of the saponification liquor to 7 ± 0.3 within 30 minutes, reacting for a period of time and then entering the second conditioning stage, wherein the total time of the conditioning stage does not exceed 60 minutes, or adjusting the pH of the saponification liquor to 7 ± 0.3 within a period of time (e.g., within 60 minutes) and then directly entering the second conditioning stage; the second adjusting stage comprises a stage A and a stage B, wherein the stage A comprises the steps of firstly adjusting the pH value of the saponification liquid from 7 +/-0.3 to 6 +/-0.3 within 30 minutes at the first average pH value change rate, reacting for a period of time (such as 20-40 minutes) and then entering the stage B, or immediately entering the stage B after adjusting the pH value from 7 +/-0.3 to 6 +/-0.3 within a period of time (such as 60 minutes) at the first average pH value change rate, and the stage B comprises the steps of adjusting the pH value of the reaction system from 6 +/-0.3 to 5.2-5.4 at the second average pH value change rate; preferably, the average pH change rate of the a-stage is in the range of 0.01-0.08/min, the second average pH change rate is in the range of 0.005-0.02/min, and the first average pH change rate is higher than the second average pH change rate.
After the pH of the saponified solution is adjusted to the reaction pH (5.2-5.4), the reaction is carried out for a period of time, preferably for 2-6 hours, thereby completing the acid treatment of the saponified solution.
The reactants can be brought into full contact by stirring during the adjustment of the pH and the reaction.
In the acid treatment, the same or different acid may be used for each adjustment of pH; when the same acid is used, the concentration of the acid solution may be the same or different, and the pH of the saponified solution may be adjusted to a predetermined pH value, and preferably, the pH of the saponified solution may be adjusted to a predetermined pH value within a time defined in the present invention.
After the acid treatment, the oil phase and the water phase in the saponified solution can be separated by conventional technical means. The water phase contains ferulate. The ferulic acid can be obtained by performing acid precipitation on the water phase, namely adjusting the pH value of the water phase to 2-3, and reacting for 3-8 hours. Similarly, stirring may be performed during the acidification process to allow sufficient precipitation of ferulic acid.
The invention further discovers that under the condition of adjusting the pH value in a staged way, if the concentration of the used acid is further selected, the yield of the ferulic acid can be further improved. In particular, the present invention has found that higher ferulic acid yields can be obtained using sulfuric acid solutions with concentrations of 30-50%. In a preferred embodiment, the acid treatment is carried out by stepwise adjustment of the pH of the saponification solution. Preferably, the pH of the saponified solution is adjusted from an initial pH of 7. + -. 0.3, after a reaction time, the pH of the saponified solution is adjusted from 7. + -. 0.3 to 6. + -. 0.3, after a reaction time, the pH of the saponified solution is adjusted from 6. + -. 0.3 to 5.2-5.4, and then a reaction time is further carried out, thereby completing the acid treatment of the saponified solution. Preferably, each adjustment of the pH is completed within 30 minutes. Preferably, the pH of the saponification solution is adjusted to 7 +/-0.3, and the saponification solution is reacted for 20-40 minutes; preferably, after the pH value of the saponification liquid is adjusted from 7 plus or minus 0.3 to 6 plus or minus 0.3, the saponification liquid is reacted for 20 to 60 minutes; preferably, the pH value of the saponification solution is adjusted from 6 +/-0.3 to 5.2-5.4, and then the saponification solution is reacted for 2-6 hours. In a preferred embodiment, a 30-50% sulfuric acid solution is used for the calculation treatment.
After the ferulic acid is obtained by separation, drying treatment can be carried out on the ferulic acid. The method of drying is conventional in the art.
The present invention will be illustrated below by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. Unless otherwise indicated, the methods, reagents and materials used in the examples are those conventional in the art and are commercially available. The soapstock is purchased from Xingwang grease factory in Cujin, wherein the oryzanol content is 32.1% (dry basis), and the converted ferulic acid content is 12.07%. The saponification method comprises the following steps: adding 200% of water and 120% of flake caustic soda into the soapstock by mass, and reacting for 4 hours at 120 ℃ in a closed reaction kettle to obtain the soap stock.
The calculation method of the ferulic acid yield comprises the following steps:
quality of ferulic acid yield ═ product quality x ferulic acid purity/quality of oryzanol conversion to ferulic acid comparative example 1 (control of acidification pH 7)
Placing saponified solution (containing soapstock and water phase, wherein the mass of the water phase is 2 times of that of the soapstock) after saponification into a beaker, stirring and heating to 60 ℃; adding concentrated sulfuric acid into the beaker, reducing the pH value of the system from 13 to 7 within 30min, and continuing to react for 4 h; stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 5 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating the yield of ferulic acid to be 32.95%.
COMPARATIVE EXAMPLE 2 (pH control for acidification 5.2, sulfuric acid concentrated sulfuric acid)
Placing saponified solution (containing soapstock and water phase, wherein the mass of the water phase is 2 times of that of the soapstock) after saponification into a beaker, stirring and heating to 60 ℃; adding concentrated sulfuric acid into the beaker, reducing the pH value of the system from 13 to 7 within 30min, and continuing to react for 30 min; then slowly adding concentrated sulfuric acid into the beaker, reducing the pH value in the system from 7 to 6 within 30min, stopping adding the acid, and reacting for 30min at the pH value; and continuing to slowly flow concentrated sulfuric acid into the beaker, reducing the pH value in the system from 6 to 5.2 within 30min, stopping adding the acid, and reacting for 4 hours at the pH value. The pH value of the system can rise in the reaction process, and acid is added dropwise in time to maintain the pH value at 5.2. Stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 5 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating the yield of ferulic acid to be 37.89%.
Example 1 (control of acidification pH 5.2, concentration of sulfuric acid solution 30%)
Placing saponified solution (containing soapstock and water phase, wherein the mass of the water phase is 2 times of that of the soapstock) after saponification into a beaker, stirring and heating to 60 ℃; adding 30% sulfuric acid solution into the beaker, reducing the pH value of the system from 13 to 7 within 30min, and continuing to react for 30 min; slowly adding a 30% sulfuric acid solution into the beaker, reducing the pH value of the system from 7 to 6 within 30min, stopping adding the acid, and reacting for 30min at the pH value; slowly adding 30% sulfuric acid solution into the beaker, reducing the pH value of the system from 6 to 5.2 within 30min, stopping adding acid, and reacting for 4h at the pH value. The pH value of the system can rise in the reaction process, and acid is added dropwise in time to maintain the pH value at 5.2. Stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 5 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating the yield of ferulic acid to be 57.72%.
Example 2 (control of acidification pH 5.4, concentration of sulfuric acid solution 30%)
Placing saponified solution (containing nigre and water phase, wherein the mass of the water phase is 2 times of that of the nigre) after saponification into a beaker, stirring and heating to 60 ℃; adding 30% sulfuric acid solution into the beaker, reducing the pH value of the system from 13 to 7 within 30min, and continuing to react for 30 min; slowly adding a sulfuric acid solution with the concentration of 30% into the beaker, reducing the pH value in the system from 7 to 6 within 30min, stopping adding the acid, and reacting for 30min at the pH value; slowly adding 30% sulfuric acid solution into the beaker, reducing the pH value of the system from 6 to 5.4 within 30min, stopping adding acid, and reacting for 4h at the pH value. The pH value of the system can rise in the reaction process, and acid is added dropwise in time to maintain the pH value to be 5.4. Stopping heating and stirring after the reaction is finished, thoroughly separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after acidification for 5 hours to obtain ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating the yield of ferulic acid to be 50.16%.
Example 3 (control of acidification pH 5.2, concentration of sulfuric acid solution 50%)
Placing saponified solution (containing soapstock and water phase, wherein the mass of the water phase is 2 times of that of the soapstock) after saponification into a beaker, stirring and heating to 60 ℃; adding 50% sulfuric acid solution into the beaker, reducing the pH value of the system from 13 to 7 within 30min, and continuing to react for 30 min; slowly adding 50% sulfuric acid solution into the beaker, reducing the pH value of the system from 7 to 6 within 30min, stopping adding acid, and reacting for 30min at the pH value; slowly adding 50% sulfuric acid solution into the beaker, reducing the pH value of the system from 6 to 5.2 within 30min, stopping adding acid, and reacting for 4h at the pH value. The pH value of the system can rise in the reaction process, and acid is added dropwise in time to maintain the pH value at 5.2. Stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 5 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating the yield of ferulic acid to be 48.23%.
Example 4 (control of acidification pH 5.4, concentration of sulfuric acid solution 50%)
Placing saponified solution (containing nigre and water phase, wherein the mass of the water phase is 2 times of that of the nigre) after saponification into a beaker, stirring and heating to 60 ℃; adding 50% sulfuric acid solution into the beaker, reducing the pH value of the system from 13 to 7 within 30min, and continuing to react for 30 min; slowly adding 50% sulfuric acid solution into the beaker, reducing the pH value of the system from 7 to 6 within 30min, stopping adding acid, and reacting for 30min at the pH value; slowly adding 50% sulfuric acid solution into the beaker, reducing the pH value of the system from 6 to 5.4 within 30min, stopping adding acid, and reacting for 4h at the pH value. The pH value of the system can rise in the reaction process, and acid is added dropwise in time to maintain the pH value to be 5.4. Stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 5 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating ferulic acid yield to be 49.82%.
Example 5 (control of System Water content, acidification pH 5.4, sulfuric acid concentration 98%)
Putting saponified liquid (containing waste soapstock and water phase, wherein the mass of the water phase is 2 times of that of the waste soapstock) after saponification into a beaker, then adding pure water with the same mass as that of the saponified liquid, stirring and heating to 60 ℃; adding concentrated sulfuric acid into the beaker, reducing the pH value of the system from 13 to 7 within 30min, and continuing to react for 30 min; then slowly adding concentrated sulfuric acid into the beaker, reducing the pH value in the system from 7 to 6 within 30min, stopping adding the acid, and reacting for 30min at the pH value; and continuing to slowly flow concentrated sulfuric acid into the beaker, reducing the pH value in the system from 6 to 5.4 within 30min, stopping adding the acid, and reacting for 4 hours at the pH value. The pH value of the system can rise in the reaction process, and acid is added dropwise in time to maintain the pH value to be 5.4. Stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 5 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating ferulic acid yield to 42.31%.
Example 6 (control of acidification pH 5.4, concentration of hydrochloric acid solution 8%)
Putting saponified liquid (containing waste soapstock and water phase, wherein the mass of the water phase is 2 times of that of the waste soapstock) after saponification into a beaker, then adding pure water with the same mass as that of the saponified liquid, stirring and heating to 60 ℃; adding 8% hydrochloric acid into the beaker, reducing the pH value of the system from 13 to 6.9 within 30min, and continuing to react for 40 min; slowly adding 8% hydrochloric acid into the beaker, reducing the pH value of the system from 7 to 6.1 within 30min, stopping adding hydrochloric acid, and reacting for 50min at the pH value; slowly adding 8% hydrochloric acid into the beaker, reducing the pH value of the system from 6 to 5.4 within 30min, stopping adding the acid, and reacting for 5h at the pH value. The pH value of the system can rise in the reaction process, and acid is added dropwise in time to maintain the pH value to be 5.4. Stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 6 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, wherein the yield of ferulic acid is 45.29%.
Example 7 (control of acidification pH 5.2, concentration of phosphoric acid solution 35%)
Putting saponified liquid (containing waste soapstock and water phase, wherein the mass of the water phase is 2 times of that of the waste soapstock) after saponification into a beaker, then adding pure water with the same mass as that of the saponified liquid, stirring and heating to 60 ℃; adding 35% phosphoric acid solution into the beaker, reducing the pH value of the system from 13 to 7.1 within 30min, and continuing to react for 25 min; slowly adding 35% phosphoric acid solution into the beaker, reducing the pH value of the system from 7 to 5.9 within 30min, stopping adding phosphoric acid, and reacting for 45min at the pH value; and continuously slowly adding 35% phosphoric acid solution into the beaker, reducing the pH value of the system from 6 to 5.4 within 30min, stopping adding the acid, and reacting for 5h at the pH value. The pH value of the system can rise in the reaction process, and acid is added dropwise in time to maintain the pH value at 5.2. Stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 6 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating ferulic acid yield to 49.22%.
Example 8 (control of acidification pH 5.2, concentration of sulfuric acid solution 30-50%)
Placing saponified solution (containing waste soapstock and water phase, the mass of the water phase is 2 times of that of the waste soapstock) after saponification into a beaker, stirring and heating to 60 ℃; adding 30% sulfuric acid solution into the beaker, reducing the pH value of the system from 13 to 7 within 30min, and continuing to react for 30 min; slowly adding 50% sulfuric acid solution into the beaker, reducing the pH value of the system from 7 to 6 within 30min, stopping adding acid, and reacting for 30min at the pH value; slowly adding 35% sulfuric acid solution into the beaker, reducing the pH value of the system from 6 to 5.2 within 30min, stopping adding acid, and reacting for 4h at the pH value. The pH value of the system can rise in the reaction process, and acid is dripped in time to maintain the pH value at 5.2. Stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 5 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating ferulic acid yield to 48.22%.
Example 9 (control of acidification pH 5.2, concentration of sulfuric acid solution 30%)
Placing saponified solution (containing soapstock and water phase, wherein the mass of the water phase is 2 times of that of the soapstock) after saponification into a beaker, stirring and heating to 60 ℃; adding 30% sulfuric acid solution into the beaker to reduce the pH value of the system from 13 to 7, and controlling the change rate of the pH value to be 0.15/min; then slowly adding a 30% sulfuric acid solution into the beaker to reduce the pH value from 7 to 6, wherein the change rate of the pH value is 0.05/min; and continuously slowly adding a 30% sulfuric acid solution into the beaker to reduce the pH value of the system from 6 to 5.2, wherein the change rate of the pH value is 0.01/min, and reacting for 2 hours at the pH value. Stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 5 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating ferulic acid yield to be 49.88%.
Example 10 (control of acidification pH 5.2, concentration of sulfuric acid solution 30%)
Placing saponified solution (containing waste soapstock and water phase, the mass of the water phase is 2 times of that of the waste soapstock) after saponification into a beaker, stirring and heating to 60 ℃; adding 30% sulfuric acid solution into the beaker to reduce the pH value of the system from 13 to 7, and controlling the change rate of the pH value to be 0.2/min; then slowly adding a 30% sulfuric acid solution into the beaker to reduce the pH value from 7 to 6, wherein the change rate of the pH value is 0.07/min; and continuously slowly adding a 30% sulfuric acid solution into the beaker to reduce the pH value of the system from 6 to 5.2, wherein the change rate of the pH value is 0.008/min, and the reaction is carried out for 2 hours at the pH value. Stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 5 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating the yield of ferulic acid to be 46.20%.
Example 11 (control of acidification pH 5.2, concentration of sulfuric acid solution 40%)
Placing saponified solution (containing waste soapstock and water phase, the mass of the water phase is 2 times of that of the waste soapstock) after saponification into a beaker, stirring and heating to 60 ℃; adding 40% sulfuric acid solution into the beaker to reduce the pH value of the system from 13 to 7, and controlling the change rate of the pH value to be 0.1/min; then slowly adding a 30% sulfuric acid solution into the beaker to reduce the pH value from 7 to 6, wherein the change rate of the pH value is 0.02/min; and continuously slowly adding a 30% sulfuric acid solution into the beaker to reduce the pH value of the system from 6 to 5.2, wherein the change rate of the pH value is 0.01/min, and reacting for 2 hours at the pH value. Stopping heating and stirring after the reaction is finished, completely separating an oil phase from a water phase, adjusting the pH value of the separated water phase to 2-3 to separate out ferulic acid, and filtering after the ferulic acid is separated out for 5 hours to obtain the ferulic acid; drying ferulic acid to obtain ferulic acid product, and calculating the yield of ferulic acid to be 45.72%.
Claims (10)
1. A process for the preparation of ferulic acid from soapstock, characterised in that it comprises the following steps:
(1) subjecting a saponified solution obtained by saponifying a soapstock to acid treatment to obtain an oil phase containing fatty acids and a water phase containing ferulate;
(2) separating the oil phase and the water phase;
(3) ferulic acid is obtained by acid precipitation separation from the water phase.
2. The method of claim 1, wherein the method has one or more of the following features:
the soapstock is produced by oil refining, such as rice oil refining, or rice oil alkali treatment;
the salts are alkali metal salts, such as sodium, potassium;
the acid used for the acid treatment is selected from inorganic acids, preferably one or more selected from sulfuric acid, hydrochloric acid and phosphoric acid; preferably, the acid used in the acid treatment is sulfuric acid, the concentration of the solution of which is 30 to 98%, preferably 30 to 50%, or the acid used in the acid treatment is hydrochloric acid, the concentration of the solution of which is 5 to 10%, or the acid used in the acid treatment is phosphoric acid, the concentration of the solution of which is 20 to 40%;
the acid precipitation comprises adjusting the pH value of the water phase to 2-3, and reacting for 3-8 hours; and/or
During the acid treatment, the temperature of the reaction system is controlled between 50 and 70 ℃.
3. The method of any one of claims 1-2, wherein the method comprises: adjusting pH of saponification solution to below 7, such as 5-7 or 5.2-7, stirring thoroughly to react, separating oil phase and water phase, adjusting pH of water phase to 2-3, and separating solid phase containing ferulic acid to obtain ferulic acid; preferably, the saponification solution is adjusted to pH7 or less within 30 minutes and then allowed to react for 2 to 8 hours while stirring.
4. The method according to any one of claims 1 to 2, wherein in the acid treatment, the pH is stepwise adjusted; the step of adjusting the pH value comprises a first adjusting stage and a second adjusting stage; for example, the first adjustment stage comprises adjusting the pH of the saponified solution from an initial pH to 7. + -. 0.3 at a rate of change in the average pH of 0.1/min or more, preferably 0.1-0.3/min; and/or the second adjusting stage comprises adjusting the pH value of the reaction system from about 7 to 5.2-5.4 at an average pH value change rate of less than or equal to 0.05/min; preferably, in the second conditioning stage, the highest pH change rate is no more than 0.08/min and the lowest pH change rate is no less than 0.005/min;
preferably, the conditioning time of the first conditioning phase is within 60 minutes;
preferably, the conditioning time of the second conditioning phase is between 90 and 140 minutes;
preferably, after the pH is adjusted to 5.2 to 5.4, the reaction is carried out for 2 to 6 hours, and then the oil phase and the aqueous phase are separated.
5. The method of claim 4,
in the first adjusting stage, the pH value of the saponification liquid is adjusted to 7 +/-0.3 from the initial pH value in one or more times, wherein the total adjusting time is within 60 minutes, and the average pH value change rate of the whole first adjusting stage is more than or equal to 0.1/min, preferably 0.1-0.3/min; and/or
In the second adjusting stage, the pH value of the saponification liquid is adjusted from 7 +/-0.3 to 5.2-5.4 in one or more times, wherein the total adjusting time is between 90 and 140 minutes, the average pH value change rate of the whole adjusting stage is less than or equal to 0.05/minute, preferably the highest pH value change rate is not more than 0.08/minute, and the lowest pH value change rate is not less than 0.005/minute.
6. The process according to claim 5, wherein the second adjustment stage comprises two stages, the A stage adjusting the pH from 7. + -. 0.3 to an intermediate pH, such as 6. + -. 0.3, and the B stage adjusting the pH of the reaction system from the intermediate pH to 5.2-5.4;
preferably, the average pH change rate of stage a is in the range of 0.01-0.08/min; preferably, the highest pH change rate is no more than 0.08/min and the lowest pH change rate is no less than 0.01/min;
preferably, the average rate of change of pH in stage B is in the range of 0.005-0.02/min;
preferably, the average pH change rate of the B-stage is lower than the average pH change rate of the a-stage;
more preferably, the rate of change of pH during the B-stage is no more than 0.02/min at the highest and no less than 0.005/min at the lowest.
7. The method of claim 4,
the first adjusting stage comprises adjusting the pH value of the saponification liquid from an initial pH value to 7 +/-0.3 within 30 minutes, and entering a second adjusting stage after reacting for a period of time, wherein the total time of the adjusting stage is not more than 60 minutes, or directly entering the second adjusting stage after adjusting the pH value of the saponification liquid to 7 +/-0.3 within 60 minutes; and/or
The second adjusting stage comprises a stage A and a stage B, wherein the stage A comprises the steps of firstly adjusting the pH value of the saponification liquid from 7 +/-0.3 to 6 +/-0.3 within 30 minutes at a first average pH value changing rate, and entering the stage B after reacting for 20-40 minutes, or immediately entering the stage B after adjusting the pH value from 7 +/-0.3 to 6 +/-0.3 within 60 minutes at the first average pH value changing rate, and the stage B comprises the steps of adjusting the pH value of a reaction system from 6 +/-0.3 to 5.2-5.4 at a second average pH value changing rate; preferably, the average pH change rate of the a-stage is in the range of 0.01-0.08/min, the second average pH change rate is in the range of 0.005-0.02/min, and the first average pH change rate is higher than the second average pH change rate.
8. The method of claim 3, wherein the method comprises:
(1) adding the inorganic acid solution, preferably 30-50% sulfuric acid solution, into saponified solution obtained by saponifying soapstock at 50-70 deg.C, reducing pH of saponified solution to 7 + -0.3 within 30min, and stirring for 20-40 min;
(2) adding the inorganic acid solution into the mixed solution after the reaction in the step (1), reducing the pH of the mixed solution from 7 +/-0.3 to 6 +/-0.3 within 30 minutes, and then stirring for 20-40 minutes;
(3) adding the inorganic acid solution into the mixed solution after the reaction in the step (2), reducing the pH of the mixed solution from 6 +/-0.3 to 5.2-5.4 within 30 minutes, and then stirring for 2-6 hours, wherein the pH is maintained within the range of 5.2-5.4;
(4) separating the oil phase and the water phase in the mixed solution after the reaction in the step (3) is finished;
(5) adjusting the pH value of the water phase obtained in the step (4) to 2-3, and performing acid precipitation to separate out ferulic acid.
9. The application of inorganic acid in preparing ferulic acid from waste soapstock generated by oil refining; preferably, the inorganic acid is selected from one or more of sulfuric acid, hydrochloric acid and phosphoric acid; preferably, the inorganic acid is sulfuric acid, the concentration of the solution of which is 30 to 98%, preferably 30 to 50%, or the inorganic acid is hydrochloric acid, the concentration of the solution of which is 5 to 10%, or the inorganic acid is phosphoric acid, the concentration of the solution of which is 20 to 40%.
10. Use according to claim 9, wherein the preparation is carried out by a method according to any one of claims 1 to 8.
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