CN111807962A - Method for directly producing propyl gallate by using tannic acid - Google Patents
Method for directly producing propyl gallate by using tannic acid Download PDFInfo
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- CN111807962A CN111807962A CN202010554780.XA CN202010554780A CN111807962A CN 111807962 A CN111807962 A CN 111807962A CN 202010554780 A CN202010554780 A CN 202010554780A CN 111807962 A CN111807962 A CN 111807962A
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- propyl gallate
- tannic acid
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- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 235000010388 propyl gallate Nutrition 0.000 title claims abstract description 78
- 239000000473 propyl gallate Substances 0.000 title claims abstract description 78
- 229940075579 propyl gallate Drugs 0.000 title claims abstract description 78
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000001263 FEMA 3042 Substances 0.000 title claims abstract description 55
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 title claims abstract description 55
- 235000015523 tannic acid Nutrition 0.000 title claims abstract description 55
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 title claims abstract description 55
- 229940033123 tannic acid Drugs 0.000 title claims abstract description 55
- 229920002258 tannic acid Polymers 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 54
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000010992 reflux Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008213 purified water Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 239000012043 crude product Substances 0.000 claims description 37
- 239000000047 product Substances 0.000 claims description 24
- 238000007670 refining Methods 0.000 claims description 22
- 239000012452 mother liquor Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000000413 hydrolysate Substances 0.000 claims description 12
- 230000020477 pH reduction Effects 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
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- 238000001291 vacuum drying Methods 0.000 claims description 6
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- 239000000203 mixture Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 abstract description 26
- 235000004515 gallic acid Nutrition 0.000 abstract description 13
- 229940074391 gallic acid Drugs 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000003963 antioxidant agent Substances 0.000 abstract description 4
- 230000003078 antioxidant effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 abstract description 2
- 235000006408 oxalic acid Nutrition 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 6
- 229920001864 tannin Polymers 0.000 description 6
- 235000018553 tannin Nutrition 0.000 description 6
- 239000001648 tannin Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 238000007254 oxidation reaction Methods 0.000 description 5
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- 239000000243 solution Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002210 biocatalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000011831 acidic ionic liquid Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- -1 gallate compound Chemical class 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000015067 sauces Nutrition 0.000 description 2
- BVCOHOSEBKQIQD-UHFFFAOYSA-N 2-tert-butyl-6-methoxyphenol Chemical compound COC1=CC=CC(C(C)(C)C)=C1O BVCOHOSEBKQIQD-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 235000017399 Caesalpinia tinctoria Nutrition 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 235000019542 Cured Meats Nutrition 0.000 description 1
- 102000009123 Fibrin Human genes 0.000 description 1
- 108010073385 Fibrin Proteins 0.000 description 1
- BWGVNKXGVNDBDI-UHFFFAOYSA-N Fibrin monomer Chemical compound CNC(=O)CNC(=O)CN BWGVNKXGVNDBDI-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000388430 Tara Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000916 dilatatory effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 229950003499 fibrin Drugs 0.000 description 1
- 230000020764 fibrinolysis Effects 0.000 description 1
- 235000013332 fish product Nutrition 0.000 description 1
- 235000019261 food antioxidant Nutrition 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000008172 hydrogenated vegetable oil Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 235000008446 instant noodles Nutrition 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- 235000012424 soybean oil Nutrition 0.000 description 1
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- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
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- 108010038851 tannase Proteins 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of antioxidant preparation, and particularly relates to a method for directly producing propyl gallate by using tannic acid, which comprises the steps of firstly mixing tannic acid, purified water and concentrated sulfuric acid according to a certain proportion, heating, refluxing, reacting, and evaporating water under reduced pressure; then adding a certain proportion of n-propanol and cyclohexane to react and synthesize propyl gallate. Compared with the traditional process, the scheme of the invention avoids using a large amount of chemical raw materials such as active carbon, oxalic acid, EDTA disodium and the like in the production process of the gallic acid and a large amount of waste water and waste residue which are difficult to treat and are generated in the production process, thereby saving resources; and the process route is shortened, the production cost is reduced, the product yield is improved, and the method is an energy-saving, consumption-reducing and emission-reducing technology.
Description
Technical Field
The invention belongs to the technical field of antioxidant preparation, and particularly relates to a method for directly producing propyl gallate by using tannic acid.
Background
Propyl Gallate (PG) is white to light brown crystal powder or micro-emulsion white needle crystal, is chemically 3, 4, 5-trihydroxy Propyl benzoate, has good oxidation resistance, stronger oxidation resistance than tert-Butyl Hydroxy Anisole (BHA) and 2, 6-di-tert-butyl-p-cresol (BHT), good heat resistance, is mainly used for the oxidation resistance of grease or oil-based food and the preservation of fruits and vegetables, and can be used as an oxidation resistance stabilizer or an anti-aging agent of biodiesel and certain materials. The gallate compound also has significant pharmacological activity and biological activity, can effectively eliminate free radicals, and can be used for resisting oxidation and resisting microorganisms. Therefore, the compound has wide application in the fields of medicines, cosmetics, feeds and the like.
Propyl gallate is one of synthetic food antioxidants from Food and Agricultural Organization (FAO)/World Health Organization (WHO), and has antibacterial, bacteriostatic and antiseptic effects. PG also has obvious effects in treating cardiovascular and cerebrovascular diseases, resisting platelet aggregation, enhancing fibrin and thrombolysis, dilating blood vessels, enhancing coronary blood flow and the like. Propyl gallate is used as fat-soluble antioxidant, is suitable for use in vegetable oil, and has remarkable effect in stabilizing soybean oil, cotton seed oil, palm oil and hydrogenated vegetable oil. The maximum usage amount of the fish meat sauce is 0.1g/kg when the fish meat sauce is used in grease, fried food, dried fish products, biscuits, instant noodles and cured meat products according to the regulations of China.
The traditional preparation method of propyl gallate usually uses concentrated sulfuric acid or p-toluenesulfonic acid as a catalyst, gallic acid and n-propanol as raw materials to perform esterification reaction, uses cyclohexane as an entrainer to separate water, and prepares high-purity propyl gallate through crystallization and purification. The conventional method for preparing propyl gallate has the following disadvantages: (1) the production process from the preparation of gallic acid to propyl gallate is complicated, the cost is high, the wastewater amount is large, and the treatment is difficult: (2) the traditional concentrated sulfuric acid is used as a catalyst, the yield is low, the reactant gallic acid is easily oxidized, a plurality of byproducts are generated, equipment is seriously corroded, and the waste liquid can cause great pollution to the environment if the waste liquid is directly discharged without being treated. (3) The p-toluenesulfonic acid is used as a catalyst and a water-carrying agent is added, so that although the yield is improved, the catalyst is large in dosage, difficult to recover and environment-friendly.
Due to the defects of the traditional propyl gallate preparation method, people begin to improve and innovate the traditional propyl gallate preparation process, and a plurality of novel propyl gallate preparation processes are researched. These novel preparation processes are mainly divided into two categories: one is the improvement of catalyst and process for producing propyl gallate. For example, in the method for synthesizing propyl gallate by using acidic ionic liquid catalysis disclosed in application No. CN201210036200.3, acidic ionic liquid of bisulfate anion is used as a catalyst to catalyze the reaction of gallic acid and n-propanol to generate propyl gallate. The method disclosed in this patent has a low ionic liquid usage and a high yield, but the recovery cycle cost is high. For example, the document "Synthesis of propyl gallate by catalysis of Strong acid cation exchange resin" (development of Fine petrochemical, 2003) discloses the synthesis of propyl gallate from gallic acid and n-propanol using D001-CC type of Strong acid cation exchange resin as a catalyst. Research on synthesis of propyl gallate as antioxidant by TiSiW12O40/TiO2 catalysis (food science and technology, 2004) discloses TiSiW12O40/TiO2As a catalyst, gallic acid and n-propanol are directly esterified to synthesize propyl gallate. The novel catalysts disclosed in these two documents are expensive to produce. For example, the document "research on synthesis of propyl gallate by organic phase biocatalytic ester conversion" (china university of science and technology, 2012) discloses a biocatalytic process for synthesizing propyl gallate by one-step ester conversion in an organic solvent by using imprinted tannase as a catalyst and tannic acid and n-propanol as substrates. The biocatalytic process disclosed in this document is environmentally friendly, but the reaction time is long and the yield is low.
The other is the improvement of the raw material and the process for producing the propyl gallate. As disclosed in the document "technical research on preparation of propyl gallate from tannic acid" (proceedings of south forestry science and technology university, 2010): tannic acid and n-propanol are used as initial raw materials, concentrated sulfuric acid is selected as a catalyst in the synthesis process, the mass ratio of the tannic acid to the n-propanol to the concentrated sulfuric acid is 1:2:0.2, the reaction time is 10 hours, the reaction condition is better, and the yield is 52.32%. The product meets the quality standard of propyl gallate through infrared spectroscopy, high performance liquid chromatography and melting point detection. According to the technical scheme provided by the document, the yield of propyl gallate is low; for example, patent application No. CN200610086070.9 discloses a method for directly synthesizing propyl gallate from tala powder, which comprises soaking tala powder in n-propanol, filtering to remove impurities, decolorizing with activated carbon and diatomaceous earth, filtering, adding acidic catalyst, performing ester exchange reaction at 80-110 deg.c for 5-12 hr, filtering at room temperature to remove impurities, concentrating the liquid phase to dryness, dissolving with 5-10 times of water, and recrystallizing to obtain the product; the invention changes the traditional process that the tara powder is firstly synthesized into the gallic acid and then synthesized into the propyl ester, and eliminates a large amount of acid and alkali used for synthesizing the gallic acid and further produced wastewater which is difficult to treat; simple process and environment protection. The technical proposal disclosed by the patent has low yield of the gallopropyl ester, and the organic acid-quinic acid is generated in the reaction product, thereby increasing the difficulty of wastewater treatment. Also, for example, patent No. CN201610502259.5 discloses a method for preparing propyl gallate, comprising breaking gallnut, taking out core, pulverizing, baking, steaming, fermenting, collecting fermentation liquid, placing the fermentation liquid in a ventilated place, acidifying with concentrated sulfuric acid, adding n-propanol, stirring, mixing, and heating to obtain propyl gallate; the propyl gallate ester prepared by the method has high yield which reaches more than 97 percent; the preparation process is simple, green and pollution-free in the preparation process, and environment is protected. The technical scheme provided by the patent is that tannic acid in gallnut is extracted by roasting, cooking and fermentation treatment, and then is acidified and hydrolyzed to prepare propyl gallate; the production process is complex and is not suitable for industrial production.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for directly producing propyl gallate by using tannic acid, and particularly realizes the method by the following technical scheme.
A method for directly producing propyl gallate from tannic acid comprises mixing tannic acid, purified water and concentrated sulfuric acid at a certain ratio, heating and refluxing for reaction, and evaporating water under reduced pressure; then adding a certain proportion of n-propanol and cyclohexane to react and synthesize propyl gallate.
Preferably, the method for directly producing propyl gallate by using tannic acid specifically comprises the following steps:
(1) firstly, mixing tannic acid, purified water and concentrated sulfuric acid, feeding the mixture into a reaction kettle, heating and refluxing the mixture for reaction, and then, evaporating water under reduced pressure to prepare a tannic acid acidification hydrolysate;
(2) adding n-propanol and cyclohexane into the reaction kettle, heating and refluxing, and reacting with the tannic acid acidification hydrolysate to synthesize propyl gallate to obtain a crude product; separating water generated in the reaction in the reflux reaction process, and decompressing and recovering cyclohexane and excessive n-propanol for recycling;
(3) adding refined activated carbon slag and refined and purified mother liquor into the reaction kettle to treat the crude product, heating to dissolve the crude product, preserving heat, and performing hot filter pressing;
(4) cooling, crystallizing and centrifugally separating the filtrate obtained by hot pressing filtration to obtain a crude product; refining and decolorizing the crude product, filter pressing, cooling and crystallizing, centrifugally separating to obtain a refined product, and then carrying out vacuum drying and packaging to obtain the finished product of propyl gallate.
Preferably, in the step (1), the mass ratio of the tannic acid to the purified water to the concentrated sulfuric acid is 1: 3-4: 0.1-0.3.
Preferably, in the step (1), the conditions of the heating reflux reaction are as follows: the temperature is 120 ℃ and 130 ℃, and the time is 5-8 h.
Preferably, in the step (2), the mass ratio of the n-propanol, the cyclohexane and the tannic acid is: 2-6:1-3: 1.
preferably, in the step (2), the conditions of the heating reflux reaction are as follows: the temperature is 100 ℃ and 130 ℃, and the time is 5-10 h.
Preferably, in the step (3), the addition amount of the refined activated carbon residue is 3-5 times of the mass of the crude product; wherein, the refined and purified mother liquor is the filtrate generated in the refining and purifying process, and the refined activated carbon residue is the activated carbon residue generated in the refining and purifying process. .
Preferably, in the step (3), the crude product is dissolved by heating to 80-95 ℃, and the temperature is kept for 0.5-1 hour for hot press filtration.
It should be noted that, step (4) is performed according to a conventional production process.
The invention has the following effective effects:
the invention utilizes tannic acid sulfuric acid method to hydrolyze and distill water and directly carry out esterification reaction, while the traditional process is to carry out esterification reaction after the tannic acid is made into gallic acid; the advantages are that: 1) adding sulfuric acid for the first time to participate in two-step catalytic reaction; 2) the production process is shortened, and gallic acid production wastewater which is difficult to treat is not generated. Therefore, the preparation method provided by the invention has the advantages of short production process, less investment and low cost.
The invention utilizes the tannic acid sulfuric acid method to hydrolyze and evaporate water and directly carry out esterification reaction, and compared with the technical research of preparing propyl gallate from tannic acid by directly catalyzing esterification reaction of tannic acid, n-propyl alcohol and concentrated sulfuric acid in the literature, the yield is obviously improved
The esterification reaction product of the refined activated carbon residue adopted by the invention is as follows: 1) the refined activated carbon residue is not in a state of adsorption saturation, and can be continuously adsorbed and saturated by being put into the esterified aqueous solution to remove part of crude product impurities; 2) the refined activated carbon residue contains a small amount of propyl gallate products, and the propyl gallate products are washed and recovered after being put into use, so that the washing is less than that of newly added carbon, and the effective ingredients are less wasted; 3) the cake layer formed by the refined activated carbon residue is beneficial to removing solid impurities in the crude product.
Compared with the traditional process, the scheme of the invention avoids using a large amount of chemical raw materials such as active carbon, oxalic acid, EDTA disodium and the like in the production process of the gallic acid and a large amount of waste water and waste residue which are difficult to treat and are generated in the production process, thereby saving resources; and the process route is shortened, the production cost is reduced, the product yield is improved, and the method is an energy-saving, consumption-reducing and emission-reducing technology.
Detailed Description
The technical solution of the present invention is further limited by the following specific embodiments, but the scope of the claims is not limited to the description.
Example 1
A method for directly producing propyl gallate by using tannic acid specifically comprises the following steps:
(1) firstly, mixing tannic acid, purified water and concentrated sulfuric acid according to a ratio of 1: 4: feeding the materials into a reaction kettle according to the mass ratio of 0.2, heating to 130 ℃, performing reflux reaction for 5 hours, and performing reduced pressure water distillation to obtain a tannin acidification hydrolysate;
(2) adding n-propanol and cyclohexane into the reaction kettle, heating to 115 ℃, refluxing for 10 hours, and reacting with the tannin acidification hydrolysate to synthesize propyl gallate to obtain a crude product; separating water generated in the reaction in the reflux reaction process, and decompressing and recovering cyclohexane and excessive n-propanol in the water for recycling; wherein the mass ratio of the n-propanol, the cyclohexane and the tannic acid is as follows: 5:3: 1;
(3) adding refined activated carbon slag and refined and purified mother liquor into the reaction kettle to treat the crude product, heating to 80-90 ℃, dissolving, preserving heat for 1 hour, and then carrying out hot press filtration;
(4) refining and purifying: cooling, crystallizing and centrifugally separating the filtrate obtained by hot pressing filtration to obtain a crude product; refining and decolorizing the crude product, filter pressing, cooling and crystallizing, centrifugally separating to obtain a refined product, and then carrying out vacuum drying and packaging to obtain the finished product of propyl gallate.
In the step (3), the addition amount of the refined activated carbon residue corresponds to all the activated carbon residues refined and decolored by the crude propyl gallate product of the batch, and the addition amount of the refined purification mother liquor is 4 times of the mass of the crude product; wherein, the refined and purified mother liquor is the filtrate generated in the refining and purifying process, and the refined activated carbon residue is the activated carbon residue generated in the refining and purifying process.
Example 2
A method for directly producing propyl gallate by using tannic acid specifically comprises the following steps:
(1) firstly, mixing tannic acid, purified water and concentrated sulfuric acid according to a ratio of 1: 3: feeding the materials into a reaction kettle according to the mass ratio of 0.3, heating to 135 ℃, performing reflux reaction for 5 hours, and performing reduced pressure water distillation to obtain a tannin acidification hydrolysate;
(2) adding n-propanol and cyclohexane into the reaction kettle, heating to 120 ℃, refluxing for 8 hours, and reacting with the tannic acid acidification hydrolysate to synthesize propyl gallate to obtain a crude product; separating water generated in the reaction in the reflux reaction process, and decompressing and recovering cyclohexane and excessive n-propanol in the water for recycling; wherein the mass ratio of the n-propanol, the cyclohexane and the tannic acid is 4: 2: 1;
(3) adding refined activated carbon slag and refined and purified mother liquor into the reaction kettle to treat the crude product, heating to 90 ℃, dissolving, preserving heat for 0.5 hour, and then carrying out hot press filtration;
(4) refining and purifying: cooling, crystallizing and centrifugally separating the filtrate obtained by hot pressing filtration to obtain a crude product; refining and decolorizing the crude product, filter pressing, cooling and crystallizing, centrifugally separating to obtain a refined product, and then carrying out vacuum drying and packaging to obtain the finished product of propyl gallate.
In the step (3), the addition amount of the refined activated carbon residue corresponds to all the activated carbon residues refined and decolored by the crude propyl gallate product of the batch, and the addition amount of the refined purification mother liquor is 3 times of the mass of the crude product; wherein the refined and purified mother liquor is a filtrate generated in the process of refining and purifying the gallic acid, and the refined activated carbon residue is activated carbon residue generated in the process of refining and purifying the propyl gallate.
Example 3
A method for directly producing propyl gallate by using tannic acid specifically comprises the following steps:
(1) firstly, mixing tannic acid, purified water and concentrated sulfuric acid according to a ratio of 1: 4: feeding the materials into a reaction kettle according to the mass ratio of 0.3, heating to 130 ℃, performing reflux reaction for 4 hours, and performing reduced pressure water distillation to obtain a tannin acidification hydrolysate;
(2) adding n-propanol and cyclohexane into the reaction kettle, heating to 120 ℃, refluxing for 5 hours, and reacting with the tannin acidification hydrolysate to synthesize propyl gallate to obtain a crude product; separating water generated in the reaction in the reflux reaction process, and decompressing and recovering cyclohexane and excessive n-propanol in the water for recycling; wherein the mass ratio of n-propanol, cyclohexane and tannic acid is 4: 3: 1;
(3) adding refined activated carbon slag and refined and purified mother liquor into the reaction kettle to treat the crude product, heating to 95 ℃, dissolving, preserving heat for 0.5 hour, and then carrying out hot press filtration;
(4) refining and purifying: cooling, crystallizing and centrifugally separating the filtrate obtained by hot pressing filtration to obtain a crude product; refining and decolorizing the crude product, filter pressing, cooling and crystallizing, centrifugally separating to obtain a refined product, and then carrying out vacuum drying and packaging to obtain the finished product of propyl gallate.
In the step (3), the addition amount of the refined activated carbon residue corresponds to all the activated carbon residues refined and decolored by the crude propyl gallate product of the batch, and the addition amount of the refined purification mother liquor is 5 times of the mass of the crude product; wherein the refined and purified mother liquor is a filtrate generated in the process of refining and purifying the propyl gallate, and the refined activated carbon residue is activated carbon residue generated in the process of refining and purifying the propyl gallate.
Example 4
A method for directly producing propyl gallate by using tannic acid specifically comprises the following steps:
(1) firstly, mixing tannic acid, purified water and concentrated sulfuric acid according to a ratio of 1: 4: feeding the materials into a reaction kettle according to the mass ratio of 0.1, heating to 120 ℃, performing reflux reaction for 5 hours, and performing reduced pressure water distillation to obtain a tannin acidification hydrolysate;
(2) adding n-propanol and cyclohexane into the reaction kettle, heating to 120 ℃, refluxing for 8 hours, and reacting with the tannic acid acidification hydrolysate to synthesize propyl gallate to obtain a crude product; separating water generated in the reaction in the reflux reaction process, and decompressing and recovering cyclohexane and excessive n-propanol in the water for recycling; wherein the mass ratio of the n-propanol, the cyclohexane and the tannic acid is 3: 2: 1;
(3) adding refined activated carbon slag and refined and purified mother liquor into the reaction kettle to treat the crude product, heating to 80 ℃, dissolving, preserving heat for 1 hour, and then carrying out hot press filtration;
(4) refining and purifying: cooling, crystallizing and centrifugally separating the filtrate obtained by hot pressing filtration to obtain a crude product; refining and decolorizing the crude product, filter pressing, cooling and crystallizing, centrifugally separating to obtain a refined product, and then carrying out vacuum drying and packaging to obtain the finished product of propyl gallate.
In the step (3), the addition amount of the refined activated carbon residue corresponds to all the activated carbon residues refined and decolored by the crude propyl gallate product of the batch, and the addition amount of the refined purification mother liquor is 4 times of the mass of the crude product; wherein the refined and purified mother liquor is a filtrate generated in the process of refining and purifying the propyl gallate, and the refined activated carbon residue is activated carbon residue generated in the process of refining and purifying the propyl gallate.
Comparative example 1
Comparative example 1 is a method as disclosed in the document "research on process for preparing propyl gallate with tannic acid" (proceedings of southern forestry science and technology university, 2010): adding tannic acid, n-propanol and concentrated sulfuric acid (mass ratio of 1:2:0.2) into a reaction kettle, heating to 95-100 ℃, and carrying out reflux reaction for 10 h. After the reaction is finished, performing reduced pressure finishing under the protection of nitrogen, and recovering the n-propanol. And adding 20ml of distilled water into the residue for hot dissolution, adding 10% sodium bicarbonate solution for neutralization until the pH value is 6-7, adding 1.0g of activated carbon, preserving the temperature at 85 ℃ for 60min, cooling and crystallizing, carrying out suction filtration, dissolving a filter cake (crude product) by using 40ml of hot water, adding 0.7g of activated carbon, preserving the temperature at 85 ℃ for 50min, and cooling and crystallizing. And (5) filtering, and drying the filter cake in vacuum.
Experimental example 1
Propyl gallate was prepared according to the published technical schemes of examples 1-4 and comparative example 1, and the yield (based on the mass of the product divided by the mass of tannic acid) was calculated and the results are shown in table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| Yield of the product | 95％ | 92％ | 94％ | 90％ | 52.37％ |
| Purity of | 99.1％ | 98.6％ | 99.4％ | 98.5％ | 99.5％ |
It should be noted that the above examples and test examples are only for further illustration and understanding of the technical solutions of the present invention, and are not to be construed as further limitations of the technical solutions of the present invention, and the invention which does not highlight essential features and significant advances made by those skilled in the art still belongs to the protection scope of the present invention.
Claims (8)
1. A method for directly producing propyl gallate by using tannic acid is characterized in that tannic acid, purified water and concentrated sulfuric acid are mixed according to a certain proportion, heated for reflux reaction, and water is evaporated under reduced pressure; then adding a certain proportion of n-propanol and cyclohexane to react and synthesize propyl gallate.
2. The method for directly producing propyl gallate with tannic acid according to claim 1, comprising the following steps:
(1) firstly, mixing tannic acid, purified water and concentrated sulfuric acid, feeding the mixture into a reaction kettle, heating and pressurizing the mixture for reaction, and then decompressing and steaming water to prepare a tannic acid acidification hydrolysate;
(2) adding n-propanol and cyclohexane into the reaction kettle, heating and refluxing, and reacting with the tannic acid hydrolysate to synthesize propyl gallate to obtain a crude product; separating water generated in the reaction in the reflux reaction process, and decompressing and recovering cyclohexane and excessive n-propanol in the water for recycling;
(3) adding refined activated carbon residue and refined purification mother liquor into the reaction kettle to treat the crude product, heating to dissolve the crude product, preserving heat, and performing hot filter pressing;
(4) cooling, crystallizing and centrifugally separating the filtrate obtained by hot pressing filtration to obtain a crude product; refining and decolorizing the crude product, filter pressing, cooling and crystallizing, centrifugally separating to obtain a refined product, and then carrying out vacuum drying and packaging to obtain the finished product of propyl gallate.
3. The method for directly producing propyl gallate with tannic acid according to claim 2, wherein in the step (1), the mass ratio of tannic acid, purified water and concentrated sulfuric acid is 1: 3-4: 0.1-0.3.
4. The method for directly producing propyl gallate with tannic acid according to claim 2, wherein in the step (1), the heating reflux reaction conditions are as follows: the temperature is 120 ℃ and 130 ℃, and the time is 2-5 h.
5. The method for directly producing propyl gallate with tannic acid according to claim 2, wherein in the step (2), the mass ratio of the n-propanol, the cyclohexane and the tannic acid is as follows: 2-5:1-3: 1.
6. the method for directly producing propyl gallate with tannic acid according to claim 2, wherein in the step (2), the heating reflux reaction conditions are as follows: the temperature is 100 ℃ and 130 ℃, and the time is 5-10 h.
7. The method for directly producing propyl gallate with tannic acid as claimed in claim 2, wherein in the step (3), the addition amount of the refined activated carbon residue is 3-5 times of the mass of the crude product; wherein, the refined and purified mother liquor is the filtrate generated in the refining and purifying process, and the refined activated carbon residue is the activated carbon residue generated in the refining and purifying process.
8. The method for directly producing propyl gallate from tannic acid as claimed in claim 2, wherein in the step (3), the crude product is dissolved by heating to 80-95 ℃, and the heat pressure filtration is carried out for 0.5-1 hour under heat preservation.
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| WO2001030299A2 (en) * | 1999-10-27 | 2001-05-03 | Kemin Industries, Inc. | Method of synthesizing alkyl gallates |
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| WO2001030299A2 (en) * | 1999-10-27 | 2001-05-03 | Kemin Industries, Inc. | Method of synthesizing alkyl gallates |
| CN102557946A (en) * | 2012-02-17 | 2012-07-11 | 扬州大学 | Method for catalyzing to synthesize propyl gallate by acidic ionic liquid |
| CN102964252A (en) * | 2012-11-27 | 2013-03-13 | 湖南先伟实业有限公司 | Technology for preparing propyl gallate by utilizing mixed catalyst |
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