CN101161628B - Method for preparing gallic acid and pyrogallic acid synchronously by non-catalyzed hydrolysis of tannin-containing biomass in high-temperature liquid water medium - Google Patents
Method for preparing gallic acid and pyrogallic acid synchronously by non-catalyzed hydrolysis of tannin-containing biomass in high-temperature liquid water medium Download PDFInfo
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- CN101161628B CN101161628B CN2007101568642A CN200710156864A CN101161628B CN 101161628 B CN101161628 B CN 101161628B CN 2007101568642 A CN2007101568642 A CN 2007101568642A CN 200710156864 A CN200710156864 A CN 200710156864A CN 101161628 B CN101161628 B CN 101161628B
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- 229940074391 gallic acid Drugs 0.000 title claims abstract description 70
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Abstract
The present invention discloses a method of concurrent preparation of gallic acid and pyrogallol through non-catalytic hydrolysis of biomass containing tannin in high-temperature aqueous medium. The method includes the following procedures that: firstly both powdered biomass containing tannin and deionized water are added into a high-pressure reactor and openly agitated, and the temperature is increased to boiling point, then the exhaust valve is opened; secondly The exhaust valve is kept closed, and the temperature is continuously raised; thirdly, after the reaction liquid is cooled, solid-liquid separation is carried out and the solid phase is decolored, recrystallized, and dried to obtain the intended product of gallic acid; fourthly the liquid phase is extracted with organic solvent to obtain crude pyrogallol, which is recrystallized, decolored and dried to obtain the intended product of pyrogallol. The present invention with simple procedure capable of concurrently preparing gallic acid and pyrogallol has high utility rate of the raw material, high yield of the product, good quality of the product, and green procedure, thereby resolving the puzzle of serious environmental pollution of acid and alkali catalytic equipment in the prior are used to preparation of gallic acid and pyrogallol.
Description
Technical field
The present invention relates to contain in a kind of high-temperature liquid state water medium the method that tannin biomass non-catalysis hydrolyzation prepares gallic acid and pyrogallol simultaneously.
Background technology
Gallic acid (gallic acid, CAS:149-91-7), be doubly acid, gallic acid again, chemical name 3,4, the 5-trihydroxybenzoic acid, it is a kind of important organic raw material, be used as the active principle of antioxidant, water stabilizer or medicine in industries such as chemical industry, medicine, food and electronics, purposes is very extensive, and demand increases year by year.Pyrogallol (pyrogallic acid, CAS:87-66-1), have another name called Pyrogallol, pyrogallol, chemical name 1,2, the 3-trihydroxybenzene is widely used in industries such as chemical analysis, photographic process, fuel, coating, food, pharmacy, electronic material, agricultural chemicals, be a kind of important chemical product, demand constantly increases.
At present, usually draw etc. with Turkey-galls or tower that to contain the tannin biomass be that raw material prepares gallic acid through acid-base method, fermentation method or enzymatic hydrolysis, and then be that raw material prepares pyrogallol through vacuum decarboxylation, normal pressure decarboxylation, pressurization decarboxylation or microorganism decarboxylation with the gallic acid.
With the Chinese tannin is the reaction formula of feedstock production gallic acid and pyrogallol:
With the talas of tannic acid is the reaction formula of feedstock production gallic acid and pyrogallol:
The traditional processing technology of gallic acid is a chemical hydrolysis process, is about to contain biomass Turkey-galls or tower and draws pulverizing, uses the hot water lixiviate, and the filtering residue gets the Weibull feed liquid; Concentrate feed liquid, carry out direct hydrolysis to wherein adding mineral acid or alkali then, hydrolysate is gallic acid and glucose; Reaction mixture obtains the finished product gallic acid through separation, decolouring, refining crystallization, drying.The main drawback of this technology is: the tannin hydrolysis is incomplete, and the gallic acid yield is lower, unstable product quality, and equipment corrosion is serious, the production cost height, activated carbon dosage is many during decolouring, the more important thing is that the organic liquid waste environmental pollution is serious.The natural extract method is the natural gallic acid of leaching from the raw material that contains gallic acid, is usually used in chemical analysis, does not industrially generally adopt.
The fermentation ratio juris is to utilize microorganism to ferment in containing the tannin aqueous solution, makes carbon source with the glucose in the tannin.For the microorganism growth breeding.Microorganism produces the catalytic hydrolysis effect through inducing the biological enzyme of generation to tannin.The subject matter that fermentation method exists is, the formation of biological enzyme and the hydrolysis of tannin are carried out in same reaction vessel, and process condition is difficult to reach optimum regime, causes reaction time very long (more than three days), and the tannin hydrolysis is incomplete, and residual tannin reaches 15～20%.Enzyme process divided two processes, and system enzyme and relieving haperacidity are carried out in two reaction vessels respectively, make the two all reach preferable response behaviour, shorten the reaction times to a certain extent, improved the percent hydrolysis of tannin.Drawbacks limit such as but enzyme is selected difficulty, and hydrolysis is incomplete its in industrial application.
And be in the method for feedstock production pyrogallol with the gallic acid, real industrializedly only be decompression decarboxylation method and normal pressure decarboxylation method, and comparatively general and ripe with decompression decarboxylation method.But mainly there is following shortcoming in decompression decarboxylation method: material is heated inhomogeneous, wastes energy, and reduces the equipment life cycle, usually uses catalyzer in the technological process, and environmental pollution is serious, and AG product ratio is lower in the product, mostly is chemical pure or Industrial products.
(High Temperature Liquid Water HTLW) typically refers to the compressed liquid water of temperature between 180～350 ℃ to high temperature liquid water.Water has following three key properties in this zone:
1) depress at saturated vapo(u)r, the ionization constant of HTLW has a maximum value to be about 10 near 275 ℃
-11(mol/kg)
2, its value is 1000 times of normal temperature and pressure water, and ionization constant increases the [H among the HTLW with the increase of pressure
3O
+] and [OH
-] concentration is near weak acid or weak base, self has the function of acid catalysis and base catalysis, therefore can make some acid-base catalyzed reaction needn't add acid base catalysator, thereby avoid the neutralization of soda acid, the operations such as processing of salt;
2) depress at saturated vapo(u)r, the specific inductivity of 20 ℃ of water is 80.1, and has only 23.5 275 ℃ the time.Although the specific inductivity of HTLW is still bigger, solubilized even ionized salts, enough little of dissolved organic matter, (275 ℃ of saturated vapo(u)rs density of depressing water is 0.76g/cm to add that the density of HTLW is big
3, the specific inductivity of HTLW, density and acetone are close), so HTLW has extraordinary solubility property, has the characteristic of dissolved organic matter and inorganics simultaneously.This can carry out the building-up reactions in many HTLW media in homogeneous phase, thereby eliminates resistance to mass transfer, improves speed of response, and the reaction back only needs simple cooling just can realize oily water separation simultaneously, and water can be recycled;
3) physicochemical property such as the specific inductivity of HTLW, ion-product constant, density, viscosity, spread coefficient, solubleness are adjustable continuously in the scope of broad with temperature, pressure, the rerum natura that is HTLW has controllability (tuning property), therefore as reaction medium, HTLW has different solvent properties and reactivity worth at different states.
The applied research of reacting among the HTLW comprises that offal treatment, macromolecular material recycle, inorganic materials are synthetic, gelatin liquefaction and biomass as resources etc., to going deep into that these three characteristics are familiar with, make the Application Areas among the HTLW constantly obtain enlarging just because of people.The present invention is applied in the characteristic of HTLW in the hydrolysis of biomass, thereby realizing containing the tannin biomass does not have catalysis, quick, green hydrolysis prepares gallic acid and pyrogallol simultaneously.
Summary of the invention
The purpose of this invention is to provide and contain the tannin biomass in a kind of high-temperature liquid state water medium and do not have the method that catalysis, green, effectively hydrolyzing prepare gallic acid and pyrogallol simultaneously.
The step of the inventive method is as follows:
1) add in autoclave through what pulverize and contain tannin biomass and deionized water, the mass ratio of water and biomass is 2: 1～6: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2～5min;
2) close vent valve, continue to be warming up to 160～250 ℃, reaction 20min～6h;
3) reaction product is cooled to solid-liquid separation after the room temperature, the solid phase deionized water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying the gallic acid product;
4) water organic solvent extraction, extraction liquid get the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying.
Containing the tannin biomass in the described step 1) is that Turkey-galls or tower draw.The mass ratio of deionized water and biomass is preferably 3: 1～and 5: 1.Hydrolysis temperature is preferably 180～220 ℃.Organic solvent in the described step 4) is ethyl acetate, methyl acetate or ethyl formate.
The purpose that " is warming up to boiling, opens vent valve 2～5min " in the step 1) of the present invention is to utilize water vapour to take away oxygen in the still, to reduce the generation of side reaction, improves the yield of product.
It is raw material that the present invention adopt that Turkey-galls or tower draw etc. to contain the tannin biomass, utilize high temperature liquid water self acid-base catalysis performance and special solubility property, provide by Turkey-galls or tower and be pulled in the novel method that non-catalysis hydrolyzation in the high-temperature liquid state water medium prepares gallic acid and pyrogallol simultaneously, this method reaction process is simple, the raw material hydrolysis is complete, the product yield height, the production process environmental protection, and products therefrom gallic acid and pyrogallol quality are good, have avoided the serious difficult problem of environmental pollution in the present technology.
Description of drawings
Accompanying drawing is to contain the process flow diagram that tannin biomass non-catalysis hydrolyzation prepares gallic acid and pyrogallol method simultaneously in the high-temperature liquid state water medium.
Embodiment
Among the present invention, product adopts reversed-phased high performace liquid chromatographic (Agilent 1100 series) to analyze, and the concrete analysis condition is as follows:
Chromatographic column adopting Diamonsil C18 (250 * 4.6mm, 5 μ m, enlightening equine skill), column temperature is 25 ℃; Moving phase be 0.008mol/L phosphate aqueous solution-methyl alcohol-second eyeball (80: 10: 10, v/v/v), flow velocity is 0.8mL/min; The detection wavelength is 202nm.
Embodiment 1
Add the Turkey-galls of the sub-water of 267g and 133 through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 2: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 4min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 180 ℃ of hydrolysis 3.0h; Reaction product is cooled to solid-liquid separation after the room temperature, and solid phase deionized water solubleness obtains 50.8g gallic acid product after activated carbon decolorizing, recrystallization, vacuum-drying, and product is 99.5% (wt%) through the HPLC purity assay, and yield is 38.2%.
Embodiment 2
Add 267g deionized water and the Turkey-galls of 133g through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 2: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 180 ℃ of hydrolysis 4.5h; Reaction product extracts with ethyl formate after being cooled to room temperature, extraction liquid gets the pyrogallol crude product after boiling off organic solvent, the crude product deionized water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, get 48.5g pyrogallol product, product is respectively 99.4% (wt%) through the HPLC purity assay, and total recovery is 37.4%.
Embodiment 3
Add 267g deionized water and 133g and draw through the tower of pulverizing in 500mL intermittent type autoclave, it is 2: 1 that deionized water and tower draw the mass ratio of powder, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 5min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 230 ℃ of hydrolysis 1.0h; Reaction product is cooled to solid-liquid separation after the room temperature, and solid phase deionized water solubleness obtains the gallic acid product after activated carbon decolorizing, recrystallization, vacuum-drying; Water ethyl acetate extraction, extraction liquid get the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying; Gallic acid and pyrogallol product are respectively 15.8g and 31.1g, and product is respectively 99.5% (wt%) and 99.4% (wt%) through the HPLC purity assay, and total recovery is 35.3%.
Embodiment 4
Add 267g deionized water and 133g and draw through the tower of pulverizing in 500mL intermittent type autoclave, it is 2: 1 that deionized water and tower draw the mass ratio of powder, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 5min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 250 ℃ of hydrolysis 0.5h; Water extracted with methyl acetate after reaction product was cooled to room temperature, extraction liquid gets the pyrogallol crude product after boiling off organic solvent, the crude product deionized water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, get 48.1g pyrogallol product, product is respectively 99.3% (wt%) through the HPLC purity assay, and yield is 36.2%.
Embodiment 5
Add 300g deionized water and the Turkey-galls of 100g through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 3: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 170 ℃ of hydrolysis 5h; Reaction product is cooled to solid-liquid separation after the room temperature, and solid phase deionized water solubleness obtains the gallic acid product after activated carbon decolorizing, recrystallization, vacuum-drying; Water ethyl acetate extraction, extraction liquid get the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying; Gallic acid and pyrogallol product are respectively 14.3g and 27.3g, and product is respectively 99.7% (wt%) and 99.6% (wt%) through the HPLC purity assay, and total recovery is 41.6%.
Embodiment 6
Add 300g deionized water and the Turkey-galls of 100g through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 3: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 3min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 170 ℃ of hydrolysis 3.5h; Reaction product is cooled to solid-liquid separation after the room temperature, and solid phase deionized water solubleness obtains 42.8g gallic acid product after activated carbon decolorizing, recrystallization, vacuum-drying, and product is respectively 99.7% (wt%) through the HPLC purity assay, and yield is 42.8%.
Embodiment 7
Add 300g deionized water and the Turkey-galls of 100g through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 3: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 5min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 190 ℃ of hydrolysis 3h; Reaction product is cooled to solid-liquid separation after the room temperature, and solid phase deionized water solubleness obtains the gallic acid product after activated carbon decolorizing, recrystallization, vacuum-drying; Water extracts with methyl acetate, and extraction liquid gets the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying; Gallic acid and pyrogallol product are respectively 12.5g and 27.7g, and product is respectively 99.7% (wt%) and 99.6% (wt%) through the HPLC purity assay, and total recovery is 40.2%.
Embodiment 8
Add 300g deionized water and 100g and draw through the tower of pulverizing in 500mL intermittent type autoclave, it is 3: 1 that deionized water and tower draw the mass ratio of powder, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 4min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 240 ℃ of hydrolysis 1h; Reaction product is cooled to water ethyl acetate extraction after the room temperature, extraction liquid gets the pyrogallol crude product after boiling off organic solvent, the crude product deionized water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, get 39.1g pyrogallol product, product is respectively 99.7% through the HPLC purity assay, and total recovery is 39.1%.
Embodiment 9
Add 300g deionized water and the Turkey-galls of 100g through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 3: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 5min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 220 ℃ of hydrolysis 1h; Reaction product is cooled to solid-liquid separation after the room temperature, and solid phase deionized water solubleness obtains the gallic acid product after activated carbon decolorizing, recrystallization, vacuum-drying; Water extracts with ethyl formate, and extraction liquid gets the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying; Gallic acid and pyrogallol product are respectively 20.2g and 19.5g, and product is respectively 99.8% (wt%) and 99.7% (wt%) through the HPLC purity assay, and total recovery is 39.7%.
Embodiment 10
Add 300g deionized water and the Turkey-galls of 100g through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 3: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 3min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 220 ℃ of hydrolysis 2h; Water extracted with ethyl formate after reaction product was cooled to room temperature, extraction liquid gets 40.3 pyrogallol crude products after boiling off organic solvent, the crude product deionized water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, get the pyrogallol product, product is respectively 99.6% (wt%) through the HPLC purity assay, and yield is 40.3%.
Embodiment 11
Add 320g deionized water and 80g and draw through the tower of pulverizing in 500mL intermittent type autoclave, it is 4: 1 that deionized water and tower draw the mass ratio of powder, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 160 ℃ of hydrolysis 6h; Reaction product is cooled to solid-liquid separation after the room temperature, obtains the gallic acid crude product; Crude product is through activated carbon decolorizing, and the deionized water crystallization gets the gallic acid product after the vacuum-drying; Water extracts with methyl acetate, and extraction liquid gets the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying; Gallic acid and pyrogallol product are respectively 19.8g and 12.9g, and product is respectively 99.8% (wt%) and 99.7% (wt%) through the HPLC purity assay, and total recovery is 40.9%.
Embodiment 12
Add 320g deionized water and 80g and draw through the tower of pulverizing in 500mL intermittent type autoclave, it is 4: 1 that deionized water and tower draw the mass ratio of powder, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 4min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 190 ℃ of hydrolysis 3.5h; Water extracted with ethyl formate after reaction product was cooled to room temperature, extraction liquid gets the pyrogallol crude product after boiling off organic solvent, the crude product deionized water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, get 31.8g pyrogallol product, product is respectively 99.7% (wt%) through the HPLC purity assay, and yield is 39.7%.
Embodiment 13
Add 320g deionized water and the Turkey-galls of 80g through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 4: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 5min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 160 ℃ of hydrolysis 4.5h; Reaction product is cooled to solid-liquid separation after the room temperature, obtains the gallic acid crude product; Crude product is through activated carbon decolorizing, and the deionized water crystallization gets 34.6g gallic acid product after the vacuum-drying, and product is respectively 99.8% (wt%) through the HPLC purity assay, and yield is 43.2%.
Embodiment 14
Add 320g deionized water and the Turkey-galls of 80g through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 4: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 3min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 210 ℃ of hydrolysis 1h; Reaction product is cooled to solid-liquid separation after the room temperature, obtains the gallic acid crude product; Crude product is through activated carbon decolorizing, and the deionized water crystallization gets 34.1g gallic acid product after the vacuum-drying, and product is respectively 99.8% (wt%) through the HPLC purity assay, and yield is 42.6%.
Embodiment 15
Add 320g deionized water and 80g and draw through the tower of pulverizing in 500mL intermittent type autoclave, it is 4: 1 that deionized water and tower draw the mass ratio of powder, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 230 ℃ of hydrolysis 1h; Reaction product is cooled to solid-liquid separation after the room temperature, obtains the gallic acid crude product; Crude product is through activated carbon decolorizing, and the deionized water crystallization gets the gallic acid product after the vacuum-drying; Water ethyl acetate extraction, extraction liquid get the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying; Gallic acid and pyrogallol product are respectively 10.3g and 20.6g, and product is respectively 99.7% (wt%) and 99.6% (wt%) through the HPLC purity assay, and total recovery is 38.6%.
Embodiment 16
Add 333g deionized water and the Turkey-galls of 67g through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 5: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 4min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 200 ℃ of hydrolysis 2.5h; Reaction product is cooled to solid-liquid separation after the room temperature, obtains the gallic acid crude product; Crude product is through activated carbon decolorizing, and the deionized water crystallization gets the gallic acid product after the vacuum-drying; Water extracts with methyl acetate, and extraction liquid gets the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying; Gallic acid and pyrogallol product are respectively 6.6g and 20.1g, and product is respectively 99.8% (wt%) and 99.7% (wt%) through the HPLC purity assay, and total recovery is 39.8%.
Embodiment 17
Add 333g deionized water and 67g and draw through the tower of pulverizing in 500mL intermittent type autoclave, it is 5: 1 that deionized water and tower draw the mass ratio of powder, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 5min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 250 ℃ of hydrolysis 20min; Reaction product is cooled to solid-liquid separation after the room temperature, obtains the gallic acid crude product; Crude product is through activated carbon decolorizing, and the deionized water crystallization gets the gallic acid product after the vacuum-drying; Water ethyl acetate extraction, extraction liquid get the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying; Gallic acid and pyrogallol product are respectively 3.5g and 22.8g, and product is respectively 99.7% (wt%) and 99.6% (wt%) through the HPLC purity assay, and total recovery is 39.2%.
Embodiment 18
Add 333g deionized water and 67g and draw through the tower of pulverizing in 500mL intermittent type autoclave, it is 5: 1 that deionized water and tower draw the mass ratio of powder, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 4min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 240 ℃ of hydrolysis 0.5h; Reaction product is cooled to solid-liquid separation after the room temperature, obtains the gallic acid crude product; Crude product is through activated carbon decolorizing, and the deionized water crystallization gets the gallic acid product after the vacuum-drying; Water ethyl acetate extraction, extraction liquid get the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying; Gallic acid and pyrogallol product are respectively 10.6g and 15.8g, and product is respectively 99.6% (wt%) and 99.6% (wt%) through the HPLC purity assay, and total recovery is 39.4%.
Embodiment 19
Add 333g deionized water and the Turkey-galls of 67g through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 5: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 200 ℃ of hydrolysis 1.5h; Reaction product is cooled to solid-liquid separation after the room temperature, obtains the gallic acid crude product; Crude product is through activated carbon decolorizing, and the deionized water crystallization gets 26.9g gallic acid product after the vacuum-drying, and product is respectively 99.8% (wt%) through the HPLC purity assay, and yield is 40.1%.
Embodiment 20
Add 343g deionized water and the Turkey-galls of 57g through pulverizing in 500mL intermittent type autoclave, the mass ratio of deionized water and gallnut extract is 6: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 5min, utilizes water vapour to get rid of air in the still; Close vent valve, continue to be warming up to 160 ℃ of hydrolysis 5h; Reaction product is cooled to solid-liquid separation after the room temperature, obtains the gallic acid crude product; Crude product is through activated carbon decolorizing, and the deionized water crystallization gets the gallic acid product after the vacuum-drying; Water ethyl acetate extraction, extraction liquid get the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying; Gallic acid and pyrogallol product are respectively 16.3g and 5.4g, and product is respectively 99.5% (wt%) and 99.5% (wt%) through the HPLC purity assay, and total recovery is 38.1%.
Embodiment 21
Adding 343g deionized water and the 57g tower through pulverizing in 500mL intermittent type autoclave draws deionized water and tower to draw the mass ratio of powder to be 6: 1, to open stirring, be warming up to boiling under the normal pressure, open vent valve 3min, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 210 ℃ of hydrolysis 2h; Reaction product is cooled to solid-liquid separation after the room temperature, obtains the gallic acid crude product; Crude product is through activated carbon decolorizing, and the deionized water crystallization gets the gallic acid product after the vacuum-drying; Water extracts with methyl acetate, and extraction liquid gets the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying; Gallic acid and pyrogallol product are respectively 3.2g and 17.6g, and product is respectively 99.6% (wt%) and 99.4% (wt%) through the HPLC purity assay, and total recovery is 36.5%.
Embodiment 22
Adding 343g deionized water and the 57g tower through pulverizing in 500mL intermittent type autoclave draws deionized water and tower to draw the mass ratio of powder to be 6: 1, to open stirring, be warming up to boiling under the normal pressure, open vent valve 4min, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 210 ℃ of hydrolysis 2.5h; Reaction product extracts with ethyl formate after being cooled to room temperature, extraction liquid gets the pyrogallol crude product after boiling off organic solvent, the crude product deionized water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying, get 20.1g pyrogallol product, product is respectively 99.3% (wt%) through the HPLC purity assay, and total recovery is 35.3%.
Claims (5)
1. contain the method that tannin biomass non-catalysis hydrolyzation prepares gallic acid and pyrogallol simultaneously in a high-temperature liquid state water medium, it is characterized in that comprising the steps:
1) add in autoclave through what pulverize and contain tannin biomass and deionized water, the mass ratio of water and biomass is 2: 1～6: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2～5min;
2) close vent valve, continue to be warming up to 160～250 ℃, reaction 20min～6h;
3) reaction product is cooled to solid-liquid separation after the room temperature, the solid phase deionized water dissolving, after activated carbon decolorizing, recrystallization, vacuum-drying the gallic acid product;
4) water organic solvent extraction, extraction liquid get the pyrogallol crude product after boiling off organic solvent, and the crude product deionized water dissolving gets the pyrogallol product after activated carbon decolorizing, recrystallization, vacuum-drying;
Described high temperature liquid water is meant the compressed liquid water of temperature between 180～350 ℃.
2. contain the method that tannin biomass non-catalysis hydrolyzation prepares gallic acid and pyrogallol simultaneously in a kind of high-temperature liquid state water medium according to claim 1, it is characterized in that containing in the described step 1) tannin biomass is that Turkey-galls or tower draw.
3. contain the method that tannin biomass non-catalysis hydrolyzation prepares gallic acid and pyrogallol simultaneously in a kind of high-temperature liquid state water medium according to claim 1, the mass ratio that it is characterized in that described step 1) deionized water and biomass is 3: 1～5: 1.
4. contain the method that tannin biomass non-catalysis hydrolyzation prepares gallic acid and pyrogallol simultaneously in a kind of high-temperature liquid state water medium according to claim 1, it is characterized in that described step 2) in hydrolysis temperature be 180～220 ℃.
5. contain the method that tannin biomass non-catalysis hydrolyzation prepares gallic acid and pyrogallol simultaneously in a kind of high-temperature liquid state water medium according to claim 1, it is characterized in that the organic solvent in the described step 4) is ethyl acetate, methyl acetate or ethyl formate.
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| CN102816062A (en) * | 2012-09-10 | 2012-12-12 | 浙江大学 | Method for preparing gallic acid by hydrochloric acid catalytic hydrolysis of tannin containing biomass in high temperature liquid water |
| CN102875367A (en) * | 2012-09-28 | 2013-01-16 | 浙江大学 | Method for preparing gallic acid by means of microwave assisted tannin containing biomass hydrolysis |
| CN102875368A (en) * | 2012-10-30 | 2013-01-16 | 浙江大学 | Method for preparing gallic acid by hydrolyzing tannin-containing biomass with ultrasonic assistance |
| CN106187703B (en) * | 2016-07-30 | 2018-09-28 | 遵义市倍缘化工有限责任公司 | A kind of preparation method of pyrogallic acid |
| CN106146284B (en) * | 2016-07-30 | 2018-12-18 | 遵义市倍缘化工有限责任公司 | A method of gallic acid and pyrogallic acid are prepared with tannin biomass |
| CN106242952B (en) * | 2016-07-31 | 2019-03-26 | 遵义市倍缘化工有限责任公司 | A method of preparing pyrogallic acid from Fructus Corni |
| CN106317134B (en) * | 2016-08-22 | 2018-09-14 | 西北农林科技大学 | A kind of method that hydro-thermal method hydrolysis tannin extract prepares glucose and gallic acid |
| CN106365959B (en) * | 2016-08-28 | 2019-01-22 | 遵义市倍缘化工有限责任公司 | A kind of preparation method of electron level pyrogallic acid |
| CN111517924A (en) * | 2020-04-24 | 2020-08-11 | 遵义市倍缘化工有限责任公司 | Method for producing pyrogallic acid by using tannic acid |
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| CN1453262A (en) * | 2003-05-23 | 2003-11-05 | 六盘水华翔化工工业有限公司 | Production process of pyrogallic acid |
| CN1480446A (en) * | 2002-09-05 | 2004-03-10 | 张家界贸源化工有限公司 | Technique for producing gallic acid by direct acid hydrolysis of gallnut |
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| CN1453262A (en) * | 2003-05-23 | 2003-11-05 | 六盘水华翔化工工业有限公司 | Production process of pyrogallic acid |
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