CN102816062A - Method for preparing gallic acid by hydrochloric acid catalytic hydrolysis of tannin containing biomass in high temperature liquid water - Google Patents
Method for preparing gallic acid by hydrochloric acid catalytic hydrolysis of tannin containing biomass in high temperature liquid water Download PDFInfo
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Abstract
The invention discloses a method for preparing a gallic acid by hydrochloric acid catalytic hydrolysis of tannin containing biomass in high temperature liquid water. The method includes the following steps that (1) deionized water, a hydrochloric acid and tannin containing biomass are sequentially added in a high-pressure reaction kettle, the mass concentration of the hydrochloric acid is 3.5% to 12%, the mass concentration of the tannin containing biomass is 8% to 32%, stirring is performed, the temperature is increased to 105 DEG C to 140 DEG C, and hydrolyzing is performed for 0.5 hour to 6 hours to obtain a hydrolysis product; (2) the hydrolysis product is cooled and crystallized, then a solid-liquid separation is performed, and a solid phase is dissolved by hot water and subjected to active carbon decoloration, recrystallization and vacuum drying to obtain a gallic acid product; and (3) mother liquors are combined, after distillation, the hydrochloric acid and the gallic acid are recycled, and the recycled hydrochloric acid is reused for the hydrolysis reaction. According to the method, the utilized hydrochloric acid catalyst can be recycled, the waste water is not generated, the process is environment-friendly, the product yield and purity are high, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to the polyphenol acids, relate in particular to and contain the method that the hydrolysis of tannin biomass hydrochloric acid catalysis prepares gallic acid in a kind of high temperature liquid water.
Background technology
Gallic acid (Gallic acid, CAS No:149-91-7) has another name called gallate, gallic acid, and chemical name is 3,4,5-trihydroxybenzoic acid (3,4,5-Trihydroxybenzoic acid), molecular formula C
7H
6O
5, molecular weight 170.12.Normal temperature is white or faint yellow needle-like or crystallization of rib shape or powder down, and normally the form with monohydrate exists, fusing point: 235-240 ℃ (decomposition); Can be dissolved in hot water, ethanol, ETHYLE ACETATE, acetone and glycerine; Be dissolved in ether slightly, be insoluble in cold water, be insoluble to benzene and chloroform; Gallic acid is oxidized easily in alkaline environment, has stronger reductibility.Structural formula is following:
Gallic acid is a kind of important organic raw material, is widely used in industries such as chemical industry, medicine, food, dyestuff, light industry and electronics.In foodstuffs industry, can be used as inhibitor; Gallic acid is can synthesizing ester; The alkyl ester of gallic acid can be divided into lower member ester (like methyl esters, ethyl ester, propyl ester etc.) and senior ester (like monooctyl ester, lauryl, octadecanol ester etc.) according to the alkyl carbon atoms number, and these ester compounds all are the food antioxidants of excellent property.Aspect medical, it is active that gallic acid has various biological such as anti-inflammatory, mutation, anti-oxidant, Green Tea Extract; Gallic acid has antitumor action simultaneously, can suppress the transfer of mastocytoma, thereby prolongs lifetime; Liver had provide protection; With the gallic acid is raw material, can synthesize multiple products such as salt, ester class, amides, as 3; 4,5-tri-methoxybenzoate, 3,4; 5-trimethoxy benzoyl hydrazines etc., these all are the important synthetic intermediates of medicines such as synthetic antimicrobial, cardiovascular disease resistant, anticancer, calmness.Gallic acid can also be used to making many medicines, Trimpex TMP for example, the medicine digallic acid antimony of prevention and cure of schistosomiasis, antiseptic bismuth gallate, ulcer medicine front three sulphur quinoline, gallic acid zinc etc.Gallic acid can make pyrogallol through adding thermal decarboxylation, and it is widely used in fields such as light industry, dyestuff, pharmacy.Chemical industry aspect, gallic acid can be used for making tens kinds of chemical reagent, are used to detect antimony, bismuth, calcium, barium, copper, zinc, aluminium and many thuliums.Gallic acid can be used for making pluralities of fuel, fireworks stablizer, blue-black ink and sibilant rale agent, also is UV light absorber, can prepare rust-proofing primer and duraluminum organic coating.
Gallic acid is the hydrolysate of tannin, and tannin is the ester that gallic acid and polyvalent alcohol generate, hydrolysis under the katalysis of acid, alkali, enzyme easily.Method for hydrolysis is divided into chemical method and biological process, and chemical method is with acid hydrolysis or basic hydrolysis, and biological process is with microbial fermentation hydrolysis or enzymic hydrolysis.The hydrolysis reaction equation is following:
Acid hydrolysis is first water from raw material (Turkey-galls, doubly flower, tower draw etc.) lixiviate goes out the tannin aqueous solution that the tannin aqueous solution carries out the homogeneous acid catalyzed reaction with sulfuric acid as catalyzer under heating condition.Acid-hydrolysis method mainly divides single stage method and two step method.Two step method prepares the main technique flow process of gallic acid: raw material → hot water lixiviate → filtering filter residue → tannin aqueous solution is concentrated to about 20% → acid hydrolysis → crystallisation by cooling → centrifugal bullion → dissolving crude product that gets and adds activated carbon decolorizing → filtration postcooling crystallization → centrifugal → drying → gallic acid finished product.The technical process that single stage method prepares gallic acid is exactly the step of having saved the lixiviate tannin than two step method, directly acid hydrolysis.
Alkali hydrolysis method is that the raw material vat liquor is the hydrolysis under alkaline condition of the tannin aqueous solution; Then with generating gallic acid in the acid He after the acidifying, the main technique flow process: raw material → hot water lixiviate → alkaline hydrolysis → add in the acid and acidifying → crystallisation by cooling → centrifugal that bullion → dissolving crude product add carbon decoloring → filtration post crystallization → centrifugal → drying → gallic acid finished product.
Lv Xiuyang, Lv Lili etc. have studied tannin non-catalysis hydrolyzation in high temperature liquid water; Gallic acid and pyrogallol have been generated simultaneously; Both coexist as in the reaction system, and reaction finishes the back separation difficulty, need consume organic solvent and energy with method of extraction.The B.G.Yasnitskii of the FSU, I.E.Korobeinikova, I.E.Kalashnikova and T.A.Bogun under boiling state (100 ℃) generate gallic acid with the hydrochloric acid hydrolysis tannin; Because temperature is lower; Speed of response is slower, and the time is longer, the industrial applications poor effect.
Fermentation method is to utilize mikrobe in containing the tannin aqueous solution, to ferment, and makes carbon source with the glucose in the tannin, supplies the microorganism growth breeding.Mikrobe produces the catalytic hydrolysis effect through inducing the enzyme of generation to tannin.Technical process: raw material is milled to diameter less than 10mm → sift out worm powder → water to be leached into 30% tanning solution → adding black mould bacterial classification → 8～9 days → filtration → washing of fermentation → gallic acid bullion → dissolving-recrystallization → PREPARATION OF INDUSTRIAL GALLIC.
The key of enzyme process is to screen, produce enzyme efficiently.Tannase is the ethanoyl lytic enzyme, belongs to the outer inductive Acyl-hydrolase of spore, and ester bond, contract phenol key and glycosidic link in efficient, single-minded, the directed cracking tannin molecule of ability make it to generate gallic acid.Technical process: enzyme cultivation → fermentation system enzyme → (adding raw material) hydrolysis → filtration → concentrate → coarse crystallization → separation → decolouring → primary crystallization → secondary crystal → drying → pulverizing → finished product gallic acid.
Existing chemical method (acid, the alkali hydrolysis method) reaction times is shorter, as the acid-hydrolysis method reaction times be 2～5h, the alkali hydrolysis method reaction times is merely 1～6h; But the hydrolysis of chemical method tannin is incomplete, and the gallic acid yield is lower, unstable product quality; Can not utilize low-grade Turkey-galls raw material, amount of activated is many during decolouring, and production cost is high; Acid system is serious to equipment corrosion, and the organic liquid waste environmental pollution that hydrolysis produces is serious.Alkali hydrolysis method is little than acid system to equipment corrosion, has reduced the depreciation of equipment greatly, but technological process is more complicated than acid-hydrolysis method.The production of domestic majority gallic acid at present all is to adopt alkali hydrolysis method.The reaction times of fermentation method is the longest, reaches 60～90h, and the formation of enzyme and the hydrolysis of tannin are carried out in same reaction vessel; Process condition is difficult to reach optimum regime; Cause increase (more than 3 days) reaction time, the tannin hydrolysis is incomplete in addition, and residual tannin reaches 15%～20%.The transformation efficiency of enzyme process is the highest, even can reach 100%, and its yield is the most desirable, can reach 90%, and consumption indicators is lower, but shortcoming is that the reaction times is long.
High temperature liquid water typically refers to the compressed liquid water of temperature between 105 ℃～350 ℃.This moment, water was depressed at saturated vapo(u)r, and ionization constant can increase afterwards earlier and reduce, and ionization constant increases the [H3O in the high temperature liquid water with the increase of pressure
+] and [OH
-] near weak acid or weak base, self have the function of acid catalysis and base catalysis; The specific inductivity of water also can change at this moment; Characteristic with ability while dissolved organic matter and inorganics; Simultaneously, physicochemical property such as the specific inductivity of high temperature liquid water, ion-product constant, density, viscosity, spread coefficient, solubleness are adjustable continuously in the scope of broad with temperature, pressure, and promptly the rerum natura of high temperature liquid water has controllability; Therefore as reaction medium, high temperature liquid water has different solvent properties and reactivity worth in different state.In recent years, as a kind of environmental friendliness medium, the applied research of high temperature liquid water in organic synthesis obtained concern, and the organic synthesis in the high temperature liquid water has become one of method of green organic synthesis.
Tannin is the Secondary Metabolism of Plant product, extensively is present in leaf, shell, pulp and the kind skin of plant, and its content is only second to Mierocrystalline cellulose, semicellulose and xylogen.Be divided into Hydrolysable Tannins and condensed tannin by its chemical structure characteristic, and Hydrolysable Tannins is divided into Ellagitannins and Nutgalls tannin according to the difference of its hydrolysis after product.Hydrolysable Tannins all is the meta-bolites of gallic acid in the plant materials.Having formed with Turkey-galls and Ta La in China is the Nutgalls tannin industrial chain of representative, and has opened up its application at emerging field.
Summary of the invention
The purpose of this invention is to provide and contain the method that the hydrolysis of tannin biomass hydrochloric acid catalysis prepares gallic acid in a kind of high temperature liquid water.
The step of method is following:
1) in autoclave, add deionized water, hydrochloric acid and contain the tannin biomass successively, wherein the mass concentration of hydrochloric acid is 3.5%～12%, and the mass concentration that contains the tannin biomass is 8%～32%, opens stirring, is warming up to 105 ℃ ~ 140 ℃ hydrolysis 0.5h ~ 6h;
2) solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets the gallic acid product;
3) merge mother liquor, after distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Because the corrodibility of hydrochloric acid, autoclave used in the step 1) of the present invention needs withstand corrosion, and the equipment that can adopt comprises band teflon-lined autoclave, enamel reaction still etc.
The tannin biomass that contain described in the step 1) of the present invention are that Turkey-galls or tower draw.
Hydrochloric acid mass concentration described in the step 1) of the present invention is preferably 6%～10%.
The mass concentration that contains the tannin biomass described in the step 1) of the present invention is preferably 16%～24%.
Hydrolysis temperature described in the step 1) of the present invention is preferably 110 ℃ ~ 130 ℃.
Distillation described in the step 3) of the present invention comprises normal pressure arrangement and underpressure distillation.
Because the corrodibility and the easy volatile of hydrochloric acid, thereby industriallization is less uses as catalyzer, this just why the Weibull hydrolysis prepare in the research of gallic acid and mostly adopt sulfuric acid, and seldom consider hydrochloric acid.Along with material, equipment and development of technology, the corrosion of hydrochloric acid has not become problem, and the advantage that the easy volatile of hydrochloric acid has become from original shortcoming makes the recycling of hydrochloric acid become possibility just because of hydrochloric acid is volatile.
The present invention has the following advantages:
● gallic acid has certain solubleness (being about 1～2% under the normal temperature) in water, through condensing crystal, and the recyclable utilization of gallic acid, thereby the total recovery of increase product.
● reclaim hydrochloric acid through mother liquor distillation, not only reclaimed catalyzer, and whole process do not produce waste water, industrial green degree is provided greatly.
The used hydrochloric acid catalyst of the present invention can be recycled, the technology environmental protection, and product purity and yield are high, are suitable for suitability for industrialized production.Simultaneously, the invention solves the serious difficult problem of environmental pollution in the current technology.
Description of drawings
Fig. 1 contains the process flow diagram that the hydrolysis of tannin biomass hydrochloric acid catalysis prepares gallic acid in the high temperature liquid water;
Fig. 2 is a technology green property synoptic diagram.
Embodiment
Among the present invention, product adopts HPLC (Agilent 1100 series) to analyze gallic acid content, and the concrete analysis condition is following: Phenomenex-C18 (5 μ m, 250mm * 4.6mm ID), moving phase is 8.5 * 10
-3Mol/L phosphate aqueous solution-acetonitrile (90:10, V/V), flow velocity 0.6mLmin
-1, 25 ℃ of column temperatures, ultraviolet detection wavelength 215nm.The employing external standard method is quantitative.
Turkey-galls and Ta La are provided by Zun Yi mountain forest plant chemical industry Ltd, and tower draws from Peru, and Turkey-galls derives from the Shaanxi of China.Tannin content is in hide powder method detection Turkey-galls: 58.21%, and tannin content was during tower drew: 49.73%.Following examples employing mass concentration is 38% hydrochloric acid, and density is 1.19g/mL.
Yield defines as follows:
Yield=(gallic acid quality product * purity/contain the quality of tannin biomass) * 100%
Embodiment 1
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 104.6mL and Turkey-galls 19.7g, wherein the mass concentration of hydrochloric acid is 12%, and gallic mass concentration is 5%, opens stirring, is warming up to 105 ℃ of hydrolysis 6h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 8.9g, and product is respectively 97.3% (wt%) through the HPLC purity assay, and yield is 43.7%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 2
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 86.8mL and Ta La 39.3g, wherein the mass concentration of hydrochloric acid is 10%, and the mass concentration that tower draws is 10%, opens stirring, is warming up to 110 ℃ of hydrolysis 5h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 15.0g, and product is respectively 98.1% (wt%) through the HPLC purity assay, and yield is 37.6%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 3
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 69.2mL and Turkey-galls 58.6g, wherein the mass concentration of hydrochloric acid is 8%, and gallic mass concentration is 15%, opens stirring, is warming up to 110 ℃ of hydrolysis 4.5h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 27.6g, and product is respectively 96.1% (wt%) through the HPLC purity assay, and yield is 45.2%.Merge mother liquor, after underpressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 4
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 51.7mL and Turkey-galls 77.9g, wherein the mass concentration of hydrochloric acid is 6%, and gallic mass concentration is 20%, opens stirring, is warming up to 110 ℃ of hydrolysis 4h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 35.2g, and product is respectively 97.2% (wt%) through the HPLC purity assay, and yield is 43.9%.Merge mother liquor, after underpressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 5
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 29.4mL and Ta La 95.0g, wherein the mass concentration of hydrochloric acid is 3.5%, and the mass concentration that tower draws is 25%, opens stirring, is warming up to 110 ℃ of hydrolysis 5h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 37.7g, and product is respectively 98.0% (wt%) through the HPLC purity assay, and yield is 38.9%.Merge mother liquor, after underpressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 6
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 182.2mL and Turkey-galls 219.7g, wherein the mass concentration of hydrochloric acid is 12%, and gallic mass concentration is 32%, opens stirring, is warming up to 110 ℃ of hydrolysis 4.5h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 95.9g, and product is respectively 99.2% (wt%) through the HPLC purity assay, and yield is 43.3%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 7
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 80.5mL and Turkey-galls 18.2g, wherein the mass concentration of hydrochloric acid is 10%, and gallic mass concentration is 5%, opens stirring, is warming up to 110 ℃ of hydrolysis 4h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 8.1g, and product is respectively 96.2% (wt%) through the HPLC purity assay, and yield is 42.8%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 8
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 64.1mL and Ta La 36.3g, wherein the mass concentration of hydrochloric acid is 8%, and the mass concentration that tower draws is 10%, opens stirring, is warming up to 120 ℃ of hydrolysis 4h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 13.4g, and product is respectively 97.1% (wt%) through the HPLC purity assay, and yield is 36.0%.Merge mother liquor, after underpressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 9
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 47.9mL and Turkey-galls 54.2g, wherein the mass concentration of hydrochloric acid is 6%, and gallic mass concentration is 15%, opens stirring, is warming up to 120 ℃ of hydrolysis 3.5h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 24.2g, and product is respectively 96.8% (wt%) through the HPLC purity assay, and yield is 43.3%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 10
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 27.3mL and Ta La 70.6g, wherein the mass concentration of hydrochloric acid is 3.5%, and the mass concentration that tower draws is 20%, opens stirring, is warming up to 120 ℃ of hydrolysis 3h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 26.2g, and product is respectively 97.5% (wt%) through the HPLC purity assay, and yield is 36.2%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 11
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 113.6mL and Turkey-galls 128.4g, wherein the mass concentration of hydrochloric acid is 10%, and gallic mass concentration is 25%, opens stirring, is warming up to 120 ℃ of hydrolysis 4h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 55.5g, and product is respectively 96.2% (wt%) through the HPLC purity assay, and yield is 41.6%.Merge mother liquor, after underpressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 12
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 112.3mL and Turkey-galls 180.5g, wherein the mass concentration of hydrochloric acid is 9%, and gallic mass concentration is 32%, opens stirring, is warming up to 120 ℃ of hydrolysis 3.5h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 80.2g, and product is respectively 94.7% (wt%) through the HPLC purity assay, and yield is 42.1%.Merge mother liquor, after underpressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 13
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 70.3mL and Ta La 63.5g, wherein the mass concentration of hydrochloric acid is 8%, and the mass concentration that tower draws is 16%, opens stirring, is warming up to 120 ℃ of hydrolysis 3h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 23.1g, and product is respectively 95.3% (wt%) through the HPLC purity assay, and yield is 34.7%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 14
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 60.9mL and Turkey-galls 70.8g, wherein the mass concentration of hydrochloric acid is 7%, and gallic mass concentration is 18%, opens stirring, is warming up to 120 ℃ of hydrolysis 4h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 30.1g, and product is respectively 97.1% (wt%) through the HPLC purity assay, and yield is 41.3%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 15
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 51.7mL and Ta La 77.9g, wherein the mass concentration of hydrochloric acid is 6%, and the mass concentration that tower draws is 20%, opens stirring, is warming up to 120 ℃ of hydrolysis 3.5h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 28.6g, and product is respectively 96.1% (wt%) through the HPLC purity assay, and yield is 35.3%.Merge mother liquor, after underpressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 16
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 42.6mL and Turkey-galls 84.8g, wherein the mass concentration of hydrochloric acid is 5%, and gallic mass concentration is 22%, opens stirring, is warming up to 120 ℃ of hydrolysis 3h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 37.1g, and product is respectively 95.5% (wt%) through the HPLC purity assay, and yield is 41.8%.Merge mother liquor, after underpressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 17
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 149.3mL and Ta La 135.1g, wherein the mass concentration of hydrochloric acid is 12%, and the mass concentration that tower draws is 24%, opens stirring, is warming up to 130 ℃ of hydrolysis 3h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 49.7g, and product is respectively 97.3% (wt%) through the HPLC purity assay, and yield is 35.8%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 18
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 80.5mL and Ta La 18.2g, wherein the mass concentration of hydrochloric acid is 10%, and the mass concentration that tower draws is 5%, opens stirring, is warming up to 130 ℃ of hydrolysis 2.5h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 7.0g, and product is respectively 96.7% (wt%) through the HPLC purity assay, and yield is 37.2%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 19
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 64.1mL and Ta La 36.3g, wherein the mass concentration of hydrochloric acid is 8%, and the mass concentration that tower draws is 10%, opens stirring, is warming up to 130 ℃ of hydrolysis 2h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 13.4g, and product is respectively 97.8% (wt%) through the HPLC purity assay, and yield is 36.3%.Merge mother liquor, after underpressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 20
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 47.9mL and Turkey-galls 54.2g, wherein the mass concentration of hydrochloric acid is 6%, and gallic mass concentration is 15%, opens stirring, is warming up to 130 ℃ of hydrolysis 3h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 24.6g, and product is respectively 96.8% (wt%) through the HPLC purity assay, and yield is 43.9%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 21
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 27.3mL and Ta La 70.6g, wherein the mass concentration of hydrochloric acid is 3.5%, and the mass concentration that tower draws is 20%, opens stirring, is warming up to 130 ℃ of hydrolysis 2.5h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 27.6g, and product is respectively 94.8% (wt%) through the HPLC purity assay, and yield is 37.1%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 22
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 81.9mL and Turkey-galls 115.9g, wherein the mass concentration of hydrochloric acid is 8%, and gallic mass concentration is 25%, opens stirring, is warming up to 130 ℃ of hydrolysis 2h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 51.8g, and product is respectively 95.0% (wt%) through the HPLC purity assay, and yield is 42.5%.Merge mother liquor, after the normal pressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 23
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 80.5mL and Ta La 18.2g, wherein the mass concentration of hydrochloric acid is 10%, and the mass concentration that tower draws is 5%, opens stirring, is warming up to 140 ℃ of hydrolysis 1h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 7.0g, and product is respectively 97.5% (wt%) through the HPLC purity assay, and yield is 37.5%.Merge mother liquor, after underpressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Embodiment 24
In the 500mL autoclave, add deionized water 250mL, mass concentration successively and be 38% hydrochloric acid 113.6mL and Ta La 42.8g, wherein the mass concentration of hydrochloric acid is 12%, and the mass concentration that tower draws is 10%, opens stirring, is warming up to 140 ℃ of hydrolysis 0.5h.Solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets gallic acid product 16.9g, and product is respectively 96.7% (wt%) through the HPLC purity assay, and yield is 38.2%.Merge mother liquor, after underpressure distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
Claims (6)
1. contain the method that the hydrolysis of tannin biomass hydrochloric acid catalysis prepares gallic acid in the high temperature liquid water, it is characterized in that the step of method is following:
1) in autoclave, add deionized water, hydrochloric acid and contain the tannin biomass successively, wherein the mass concentration of hydrochloric acid is 3.5%～12%, and the mass concentration that contains the tannin biomass is 5%～32%, opens stirring, is warming up to 105 ℃ ~ 140 ℃ hydrolysis 0.5 h ~ 6 h;
2) solid-liquid separation behind the hydrolysate crystallisation by cooling, solid phase is used the hot water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, gets the gallic acid product;
3) merge mother liquor, after distillation, reclaim hydrochloric acid and gallic acid, reclaim hydrochloric acid and be reused for hydrolysis reaction.
2. contain the method that the hydrolysis of tannin biomass hydrochloric acid catalysis prepares gallic acid in a kind of high temperature liquid water according to claim 1, it is characterized in that the tannin biomass that contain described in the step 1) are that Turkey-galls or tower draw.
3. contain the method that the hydrolysis of tannin biomass hydrochloric acid catalysis prepares gallic acid in a kind of high temperature liquid water according to claim 1, it is characterized in that the hydrochloric acid mass concentration described in the step 1) is 6%～10%.
4. contain the method that the hydrolysis of tannin biomass hydrochloric acid catalysis prepares gallic acid in a kind of high temperature liquid water according to claim 1, the mass concentration that it is characterized in that containing in the step 1) tannin biomass is 16%～24%.
5. contain the method that the hydrolysis of tannin biomass hydrochloric acid catalysis prepares gallic acid in a kind of high temperature liquid water according to claim 1, it is characterized in that the hydrolysis temperature described in the step 1) is 110 ℃ ~ 130 ℃.
6. contain the method that the hydrolysis of tannin biomass hydrochloric acid catalysis prepares gallic acid in a kind of high temperature liquid water according to claim 1, it is characterized in that the distillation described in the step 3) comprises normal pressure arrangement and underpressure distillation.
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Cited By (9)
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| CN106146285A (en) * | 2016-07-30 | 2016-11-23 | 遵义市倍缘化工有限责任公司 | A kind of sulphuric acid hydrolysis prepares the method for gallic acid |
| CN106220475A (en) * | 2016-07-30 | 2016-12-14 | 遵义市倍缘化工有限责任公司 | A kind of method preparing pyrogallic acid |
| CN106242966A (en) * | 2016-07-30 | 2016-12-21 | 遵义市倍缘化工有限责任公司 | A kind of method that gallic acid is prepared in hydrochloric acid hydrolysis |
| CN106242950A (en) * | 2016-07-30 | 2016-12-21 | 遵义市倍缘化工有限责任公司 | A kind of method preparing pyrogallic acid |
| CN106631753A (en) * | 2016-11-10 | 2017-05-10 | 遵义林源医药化工有限责任公司 | Method for producing gallic acid by utilizing superfine gallnut extract |
| CN110922327A (en) * | 2019-12-09 | 2020-03-27 | 邱洪 | Gallic acid acidizing device |
| CN111217692A (en) * | 2018-11-26 | 2020-06-02 | 张家界久瑞生物科技有限公司 | Preparation method of high-purity gallic acid |
| CN111454143A (en) * | 2020-05-13 | 2020-07-28 | 遵义市倍缘化工有限责任公司 | Method for preparing gallic acid by hydrolyzing sulfuric acid capable of utilizing by-product |
| CN111548262A (en) * | 2020-05-13 | 2020-08-18 | 遵义市倍缘化工有限责任公司 | Method for preparing gallic acid by hydrochloric acid hydrolysis of byproduct |
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| CN106220475B (en) * | 2016-07-30 | 2018-12-18 | 遵义市倍缘化工有限责任公司 | A method of preparing pyrogallic acid |
| CN106220475A (en) * | 2016-07-30 | 2016-12-14 | 遵义市倍缘化工有限责任公司 | A kind of method preparing pyrogallic acid |
| CN106242966A (en) * | 2016-07-30 | 2016-12-21 | 遵义市倍缘化工有限责任公司 | A kind of method that gallic acid is prepared in hydrochloric acid hydrolysis |
| CN106242950A (en) * | 2016-07-30 | 2016-12-21 | 遵义市倍缘化工有限责任公司 | A kind of method preparing pyrogallic acid |
| CN106242950B (en) * | 2016-07-30 | 2018-12-18 | 遵义市倍缘化工有限责任公司 | A method of preparing pyrogallic acid |
| CN106146285A (en) * | 2016-07-30 | 2016-11-23 | 遵义市倍缘化工有限责任公司 | A kind of sulphuric acid hydrolysis prepares the method for gallic acid |
| CN106242966B (en) * | 2016-07-30 | 2019-01-22 | 遵义市倍缘化工有限责任公司 | A kind of method that hydrochloric acid hydrolysis prepares gallic acid |
| CN106631753A (en) * | 2016-11-10 | 2017-05-10 | 遵义林源医药化工有限责任公司 | Method for producing gallic acid by utilizing superfine gallnut extract |
| CN106631753B (en) * | 2016-11-10 | 2020-01-10 | 遵义林源医药化工有限责任公司 | Method for producing gallic acid by using superfine gallnut powder |
| CN111217692A (en) * | 2018-11-26 | 2020-06-02 | 张家界久瑞生物科技有限公司 | Preparation method of high-purity gallic acid |
| CN110922327A (en) * | 2019-12-09 | 2020-03-27 | 邱洪 | Gallic acid acidizing device |
| CN111454143A (en) * | 2020-05-13 | 2020-07-28 | 遵义市倍缘化工有限责任公司 | Method for preparing gallic acid by hydrolyzing sulfuric acid capable of utilizing by-product |
| CN111548262A (en) * | 2020-05-13 | 2020-08-18 | 遵义市倍缘化工有限责任公司 | Method for preparing gallic acid by hydrochloric acid hydrolysis of byproduct |
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