CN105523919A - Method for microwave-ultrasonic-assistant hydrolysis extraction of Caesalpinia spiosa pod gallic acid - Google Patents
Method for microwave-ultrasonic-assistant hydrolysis extraction of Caesalpinia spiosa pod gallic acid Download PDFInfo
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- CN105523919A CN105523919A CN201510639331.4A CN201510639331A CN105523919A CN 105523919 A CN105523919 A CN 105523919A CN 201510639331 A CN201510639331 A CN 201510639331A CN 105523919 A CN105523919 A CN 105523919A
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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Abstract
The invention relates to a method for microwave-ultrasonic-assistant hydrolysis extraction of Caesalpinia spiosa pod gallic acid. The method comprises adding deionized water into Caesalpinia spiosa pod powder as a raw material, carrying out reflux condensation, carrying out filtration to obtain a filtrate, adding an ion exchange resin catalyst and an antioxidation reagent into the filtrate and carrying out microwave-ultrasonic-assistant heating extraction to obtain gallic acid, wherein in heating, under the action of ionic liquid catalysis, tannic acid is decomposed to form gallic acid so that a gallic acid yield is effectively improved. The ion exchange resin is convenient for recovery, can be recycled, is economic and environmentally friendly, is suitable for large scale production and has high economic and practical value.
Description
Art:
The invention belongs to high-technology field, particularly a kind of microwave ultrasound assisting hydrolyzing extraction column draws the method for fruit pod gallic acid.
Background technology:
Tower draws (Caesalpiniaspiosa) also known as Caesalpinia spinosaKuntze, blue bush, belong to Caesalpiniaceae Spruce beetle, mainly be distributed in the countries such as the Peru of South America northwestward, Ecuador, Colombia, for shrub or dungarunga, general 3 ~ 5m, in moistening, fertile and that illumination is sufficient place, 8 ~ 10m can be grown to; There are 10 mutation; Well developed root system, main root is obvious; Androgyny, self-pollination; Fruit pod is flats, reddish-brown time ripe, and generally long 8 ~ 15cm, wide 1.5 ~ 2.1cm, inside have 2 ~ 10, seed; Thousand grain weigth 306.8g; Seedling tree 3a can be yielded positive results, the best fruiting period 10a, the every strain of rich bearing tree can be born pods 100 ~ 400kg.Tower draws the physical geography condition of normal growth to be that height above sea level 400 ~ 3000m, average temperature of the whole year 8 ~ 27 DEG C, adaptability is very strong.
Gallic acid (Gallicacid), has another name called gallate, gallic acid, and chemical name is Gallic Acid (3,4,5-Trihydroxybenzoicacid), molecular formula C7H6O5, molecular weight 170.12.Be white or faint yellow needle-like or prismatic crystallization or powder under normal temperature, normally exist with the form of monohydrate, fusing point: 235-240 DEG C (decomposition), 1g is fused to 87ml cold water, 3ml boiling water, 6ml ethanol, 100m ether, 10ml glycerine and 5ml acetone.Be dissolved in benzene, chloroform and sherwood oil hardly.The preparation method that gallic acid is conventional has acid-hydrolysis method, alkali hydrolysis method etc., also has a small amount of Enzymatic Extraction.The vitriol oil is commonly used in acid hydrolysis, and its strong oxidizing property easily causes benzene ring structure destroy and affect yield.Gallic acid is easily oxidized in alkaline environment, has stronger reductibility.Gallic acid is a kind of important organic raw material, is a kind of important organic raw material, is used as the active principle of antioxidant or medicine in the industries such as chemical industry, medicine, food, dyestuff, light industry and electronics, and purposes is very extensive, and demand increases year by year.Can be used as antioxidant in the food industry, gallic acid is can synthesizing ester, and the alkyl of gallic acid is the food antioxidant of excellent property.In medical, it is active that gallic acid has the various biological such as anti-inflammatory, anti-mutation, anti-oxidant, Green Tea Extract, and gallic acid has antitumor action simultaneously.Gallic acid can also be used to manufacture many medicines.Gallic acid can obtain pyrogallol through adding thermal decarboxylation, and it is widely used in the fields such as light industry, dyestuff, pharmacy.Chemical industry aspect, gallic acid can be used for manufacture tens kinds of chemical reagent.
Gallic acid is the hydrolysate of tannin, and tannin is the ester that gallic acid and polyvalent alcohol generate.At present, often to draw etc. containing tannin biomass as raw material with Turkey-galls or tower, be hydrolyzed under the katalysis of acid, alkali, enzyme.Method for hydrolysis is divided into chemical method and biological process, chemical method acid hydrolysis or basic hydrolysis, biological process fermentable hydrolysis or enzymic hydrolysis.Hydrolysis reaction equation is as follows:
Tower draws the method extracting gallic acid in fruit pod with microwave ultrasound assisting hydrolyzing, relative to traditional operational path, avoid in the leaching process of gallic acid, Weibull is converted into the waste of gallic acid rear catalyst, be convenient to recycle and reuse, save production cost, and improve the productive rate of gallic acid.
Chinese patent CN1104627 " doubly the method for gallic acid is prepared in the basic hydrolysis of flower raw material " and CN1057255 " utilizes tower to draw powder to produce gallic acid " and, with first using acid neutralization again with basic hydrolysis, adds complicated operation degree.Direct enzymolysis is often produced because solvent diffusion speed is slow, and reaction conditions problem is limited, as solubilizing agent enzymolysis in CN1083532 " technique of preparation of gallic acid by using enzyme " has stricter requirement to temperature, PH, dissolved oxygen amount, more difficult control.Yang Shunkai etc. " enzymatic Synthesis of Gallic Acid from Tannic Acid " also take the method for enzymolysis in solution, and solvent diffusion is comparatively slow, and enzymolysis speed is restricted.
Summary of the invention:
(1) a kind of microwave ultrasound assisting hydrolyzing extraction column is the object of the present invention is to provide to draw the method for fruit pod gallic acid.
(2) in order to achieve the above object, the technical solution used in the present invention comprises:
A () draws fruit pod powder for raw material with tower, add deionized water, condensing reflux 2h, filters to get filtrate, and filtrate adds ion-exchange resin catalyst, anti-oxidant reagent, in the auxiliary lower heating of microwave ultrasound, extracts gallic acid.
B () draws the method for fruit pod gallic acid according to a kind of microwave ultrasound assisting hydrolyzing extraction column described in (a), it is characterized in that: liquid ratio is 25:3.
C () draws the method for fruit pod gallic acid according to a kind of microwave ultrasound assisting hydrolyzing extraction column described in (a), it is characterized in that: catalyzer is ion exchange resin, Ion exchange resins type is strong basicity (201*7, D201, D290), strongly-acid (7320, CAT600, CAT601, NKC-9), weakly alkaline (D311, D301), slightly acidic (110, D113).Through optimizing the ratio obtained be: it is best that every 50ml stoste adds 6g over dry heavy ion exchange resin effect.
D () draws the method for fruit pod gallic acid according to a kind of microwave ultrasound assisting hydrolyzing extraction column described in (a), it is characterized in that: antioxidant is chosen as TBHQ, its concentration is 10mg/ml.
E () draws the method for fruit pod gallic acid according to a kind of microwave ultrasound assisting hydrolyzing extraction column described in (a), it is characterized in that: microwave ultrasound boosting power 385W, heat-up time is 15min.
(3) advantage of the present invention is: utilize ion-exchange resin catalyzed effect, can be effectively gallic acid by the Weibull catalytic decomposition in extracting solution, and for the effect that the productive rate of gallic acid increases significantly.Ion exchange resin has to be convenient to reclaim, can reuse, and economic environmental protection, is suitable for large-scale production, has higher economical and practical value.After obtaining gallic acid extracting solution again, do not need repetition adjusted to ph, directly can purify to extracting solution, dry, the step such as crystallization, obtain the gallic acid powder that concentration is higher.
Embodiment:
(1) below the invention process is described in further detail:
(2) draw fruit pod powder for raw material with tower, add deionized water, liquid ratio is 25:3, and condensing reflux 2h, filters to get filtrate, and filtrate adds the anti-oxidant reagent TBHQ of 10mg/ml, ion-exchange resin catalyst.Catalyzer is ion exchange resin, and Ion exchange resins type is strong basicity (201*7, D201, D290), strongly-acid (7320, CAT600, CAT601, NKC-9), weakly alkaline (D311, D301), slightly acidic (110, D113).Be: it is best that every 50ml stoste adds 6g over dry heavy ion exchange resin effect that, in the auxiliary lower heating of power 385W microwave ultrasound, heat-up time is 15min, extracts gallic acid through optimizing the ratio obtained.
In the present invention, product adopts high performance liquid chromatography (Waters717plusautosampler) to carry out analysis gallic acid content, concrete analysis condition is as follows: HiQsil-C18 (4.6mm × 250mm, 5 μm), moving phase is water-acetonitrile-formic acid (93:7:0.025, v/v/v), flow velocity 1mLmin-1, column temperature 25 DEG C, ultraviolet detection wavelength 274nm.Adopt quantified by external standard method.
Yield is defined as follows:
Yield=(gallic acid quality product × purity/containing the quality of tannin biomass) × 100%
(3) below, the present invention will be further detailed by embodiment, but it is not limited to any one or similar example of these embodiments.
Embodiment
(1) tower draws fruit pod powder to be raw material 100g, and add deionized water 1L, condensing reflux 2h, filters to get filtrate.Get 50ml filtrate and add 0.25g anti-oxidant reagent TBHQ, 6g strong basicity 201*7 ion-exchange resin catalyst (over dry weight), in the auxiliary lower heating of power 385W microwave ultrasound, heat-up time is 15min, extracts gallic acid.Solid-liquid separation after hydrolysate crystallisation by cooling, solid phase is with hot water dissolving, gallic acid product 2.06g is obtained after activated carbon decolorizing, recrystallization, vacuum-drying, product is 98.3% (wt%) through HPLC purity assay, yield is 41.9%, and product yield is 1.3 times that do not add acidic ion exchange resin catalyst.
(2) tower draws fruit pod powder to be raw material 100g, and add deionized water 1L, condensing reflux 2h, filters to get filtrate.Get 50ml filtrate and add 0.25g anti-oxidant reagent TBHQ, 6g strongly-acid 7320 ion-exchange resin catalyst (over dry weight), in the auxiliary lower heating of power 385W microwave ultrasound, heat-up time is 15min, extracts gallic acid.Solid-liquid separation after hydrolysate crystallisation by cooling, solid phase is with hot water dissolving, gallic acid product 2.24g is obtained after activated carbon decolorizing, recrystallization, vacuum-drying, product is 97.1% (wt%) through HPLC purity assay, yield is 43.5%, and product yield is 1.45 times that do not add acidic ion exchange resin catalyst.
Claims (5)
1. a microwave ultrasound assisting hydrolyzing extraction column draws the method for fruit pod gallic acid, it is characterized in that: draw fruit pod powder for raw material with tower, add deionized water, condensing reflux, filter to get filtrate, filtrate adds ion-exchange resin catalyst, anti-oxidant reagent, auxiliary lower heating extract gallic acid, in heat-processed, under the katalysis of ionic liquid, Weibull can be decomposed into gallic acid, thus reaches the object improving gallic acid productive rate.
2. draw the method for fruit pod gallic acid according to a kind of microwave ultrasound assisting hydrolyzing extraction column according to claim 1, it is characterized in that: liquid ratio is 25:3.
3. the method for fruit pod gallic acid is drawn according to a kind of microwave ultrasound assisting hydrolyzing extraction column according to claim 1, it is characterized in that: catalyzer is ion exchange resin, Ion exchange resins type is strong basicity (201*7, D201, D290), strongly-acid (7320, CAT600, CAT601, NKC-9), weakly alkaline (D311, D301), slightly acidic (110, D113).
4. draw the method for fruit pod gallic acid according to a kind of microwave ultrasound assisting hydrolyzing extraction column according to claim 1, it is characterized in that: antioxidant is chosen as TBHQ, its concentration is 10mg/ml.
5. draw the method for fruit pod gallic acid according to a kind of microwave ultrasound assisting hydrolyzing extraction column according to claim 1, it is characterized in that: microwave ultrasound boosting power 385W, heat-up time is 15min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112957269A (en) * | 2021-02-09 | 2021-06-15 | 常州大学 | Plant hair dye and dyeing method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112957269A (en) * | 2021-02-09 | 2021-06-15 | 常州大学 | Plant hair dye and dyeing method thereof |
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