CN106146284B - A method of gallic acid and pyrogallic acid are prepared with tannin biomass - Google Patents
A method of gallic acid and pyrogallic acid are prepared with tannin biomass Download PDFInfo
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- CN106146284B CN106146284B CN201610613784.4A CN201610613784A CN106146284B CN 106146284 B CN106146284 B CN 106146284B CN 201610613784 A CN201610613784 A CN 201610613784A CN 106146284 B CN106146284 B CN 106146284B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
- C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
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Abstract
The present invention provides a kind of methods for preparing gallic acid and pyrogallic acid with tannin biomass, belong to chemical industry manufacture technology field, the present invention utilizes deionized water, dehydrated alcohol, the mixed solution of formamide carries out the acid-base catalysis performance contained in high-temperature liquid state and special solubility property, so that Chinese gall or tower drawing are decomposed into gallic acid and pyrogallic acid, through past water and ethyl alcohol, it is reacted under microwave environment with strongly acidic styrene type cation exchange resin, so that Chinese gall or tower draw hydrolysis thorough, in some processing step processing of result, the purity assay of obtained gallic acid and pyrogallic acid product is high, total recovery is high.After testing, gallic acid and the purity assay height of pyrogallic acid product are in 90wt% and 95wt% or more.The total recovery of product is 75% or more.
Description
Technical field
The invention belongs to chemical industry manufacture technology field more particularly to a kind of gallic acid and coke are prepared with tannin biomass
The method of gallic acid.
Background technique
Gallic acid (GallicAcid, GA), chemical name Gallic Acid, also known as gallic acid, gallic acid do not have
Gallate-based is white or faint yellow acicular crystal or powder, is existed usually in the form of monohydrate, specific gravity 1.694, fusing point
235~240 DEG C.Gallic acid has a wide range of application, and can be used for organic synthesis, coating, dyestuff, medicine, food, chemical industry, daily use chemicals, agriculture
Industry, mineral products etc., be mainly used for drug, dyestuff, ink manufacture, also serve as food antioxidant, preservative, METAL EXTRACTION agent,
Ultraviolet absorbing agent, disinfectant, hemostasis astringent, developer etc..Currently, usually raw containing tannin with Chinese gall or tower drawing etc.
Substance prepares gallic acid by acid-base method, fermentation method or enzymatic isolation method hydrolysis for raw material, then again using gallic acid as raw material
Pyrogallic acid is prepared through vacuum decarboxylation, normal pressure decarboxylation, pressurization decarboxylation or decarboxylate of microorganisms.But its yield and purity are not
It is high.
Summary of the invention
In order to solve the above technical problems, preparing gallic acid and coke no food with tannin biomass the present invention provides a kind of
The method of sub- acid, the specific scheme is that
A method of gallic acid and pyrogallic acid are prepared with tannin biomass, comprising the following steps:
1) biomass containing tannin, the deionized water, dehydrated alcohol, formamide by crushing are added in a high pressure reaction kettle,
Wherein biomass containing tannin, deionized water, dehydrated alcohol, formamide ratio be 1:1~3:2~4:0.5~1；Open stirring
Device, the air that normal temperature and pressure is warming up to boiling, and is passed through in carbon dioxide replacement reaction kettle；
2) valve for closing reaction kettle, is continuously heating to 170~190 DEG C, reacts 30~60min；
3) open the valve of reaction kettle, and with CO 2 gas-shielded, 1 times of the solution formamide measured be added, then plus
Hot solution evaporates deionized water and dehydrated alcohol to 110~115 DEG C, so that the content of the two stops when being lower than 1%；
4) solution of step 3) is placed in microwave applicator, and the exchange of 1~3% strongly acidic styrene's cation is added
The pressure of heater is reduced to 0.1~0.3 atmospheric pressure by resin, and microwave power is 700~900w, heats 20~50min；
5) gallic acid makes: the solution that step 4) obtains being carried out pressurization and is concentrated into the 1/5 of original volume, is then cooled down
To room temperature, it is separated by filtration to obtain water phase and solid phase；Solid phase deionized water dissolving, it is dry into excessively active carbon decoloring, recrystallization, vacuum
It is dry to obtain gallic acid product；
6) pyrogallic acid makes: oxidant being added in water phase, after reacting a period of time, is concentrated to get coke and does not eat
Sub- acid product.
Further, the tannin biomass is that Chinese gall or tower are drawn.
Further, the reduced pressure parameter are as follows: pressure is 0.1~0.2 atmospheric pressure, and temperature is 100~110
℃。
Further, the making step of the pyrogallic acid specifically: 3~8% benzene sulfonic acid is added in water phase
Iron, then it is placed in microwave applicator, the pressure of heater is reduced to 0.1~0.3 atmospheric pressure, microwave power is 700~900w,
Heat 10~30min；Then it filters at a temperature of 80~100 DEG C again, the chloroform of 1 times of amount is added in obtained filtrate, depressurize dense
It is reduced to the 1/10 of original volume, the crystal of precipitation is cleaned using chloroformic solution, and vacuum drying obtains pyrogallic acid product.
The beneficial effects of the present invention are: the present invention is carried out using the mixed solution of deionized water, dehydrated alcohol, formamide
The acid-base catalysis performance contained in high-temperature liquid state and special solubility property, so that Chinese gall or tower drawing are decomposed into gallic acid and coke
Property gallic acid reacts under microwave environment with strongly acidic styrene type cation exchange resin through past water and ethyl alcohol, makes
It obtains Chinese gall or tower draws hydrolysis thoroughly, in some processing steps processing of result, obtained gallic acid and pyrogallic acid production
The purity assay of product is high, and total recovery is high.After testing, gallic acid and the purity assay height of pyrogallic acid product exist
90wt% and 95wt% or more.The total recovery of product is 75% or more.
Specific embodiment
Be described further below technical solution of the present invention, but claimed range be not limited to it is described.
Embodiment one
Present embodiments provide a kind of method for preparing gallic acid and pyrogallic acid with tannin biomass, including with
Lower step:
1) biomass containing tannin, the deionized water, dehydrated alcohol, formamide by crushing are added in a high pressure reaction kettle,
Wherein biomass containing tannin, deionized water, dehydrated alcohol, formamide ratio be 1:1:2:0.5；Turn on agitator, room temperature are normal
Press the air for being warming up to boiling, and being passed through in carbon dioxide replacement reaction kettle；The tannin biomass is that Chinese gall or tower are drawn
2) valve for closing reaction kettle, is continuously heating to 170 DEG C, reacts 30min；
3) open the valve of reaction kettle, and with CO 2 gas-shielded, 1 times of the solution formamide measured be added, then plus
Hot solution evaporates deionized water and dehydrated alcohol to 110 DEG C, so that the content of the two stops when being lower than 1%；
4) solution of step 3) is placed in microwave applicator, and 1% strongly acidic styrene's cation exchange tree is added
The pressure of heater is reduced to 0.1 atmospheric pressure by rouge, and microwave power 700w heats 20min；
5) solution for obtaining step 4) carries out pressurization concentration (pressure is 0.1 atmospheric pressure, and temperature is 100 DEG C) to original
The 1/5 of volume, is then cooled to room temperature, is separated by filtration to obtain water phase and solid phase；Solid phase deionized water dissolving, into active carbon excessively
Decoloration, recrystallization, vacuum drying obtain gallic acid product；
6) 3% benzene sulfonic acid iron is added in water phase, then is placed in microwave applicator, the pressure of heater is reduced to 0.1
Atmospheric pressure, microwave power 700w heat 10min；Then it filters at a temperature of 80 DEG C again, the chlorine of 1 times of amount is added in obtained filtrate
It is imitative, (pressure is 0.1 atmospheric pressure, and temperature is 100 DEG C) is concentrated under reduced pressure to the 1/10 of original volume, the crystal of precipitation passes through again
Chloroformic solution cleaning is crossed, vacuum drying obtains pyrogallic acid product.
The purity assay of gallic acid therein and pyrogallic acid product a height of 90.5wt% and 95.6wt%.Product
Total recovery be 75.5%.
Embodiment two
Present embodiments provide a kind of method for preparing gallic acid and pyrogallic acid with tannin biomass, including with
Lower step:
1) biomass containing tannin, the deionized water, dehydrated alcohol, formamide by crushing are added in a high pressure reaction kettle,
Wherein biomass containing tannin, deionized water, dehydrated alcohol, formamide ratio be 1:3:4:1；Turn on agitator, normal temperature and pressure
The air for being warming up to boiling, and being passed through in carbon dioxide replacement reaction kettle；The tannin biomass is that Chinese gall or tower are drawn
2) valve for closing reaction kettle, is continuously heating to 190 DEG C, reacts 60min；
3) open the valve of reaction kettle, and with CO 2 gas-shielded, 1 times of the solution formamide measured be added, then plus
Hot solution evaporates deionized water and dehydrated alcohol to 115 DEG C, so that the content of the two stops when being lower than 1%；
4) solution of step 3) is placed in microwave applicator, and 3% strongly acidic styrene's cation exchange tree is added
The pressure of heater is reduced to 0.3 atmospheric pressure by rouge, and microwave power 900w heats 50min；
5) solution for obtaining step 4) carries out pressurization concentration (pressure is 0.2 atmospheric pressure, and temperature is 110 DEG C) to original
The 1/5 of volume, is then cooled to room temperature, is separated by filtration to obtain water phase and solid phase；Solid phase deionized water dissolving, into active carbon excessively
Decoloration, recrystallization, vacuum drying obtain gallic acid product；
6) 3~8% benzene sulfonic acid iron is added in water phase, then is placed in microwave applicator, the pressure of heater is reduced to 0.3
A atmospheric pressure, microwave power 900w heat 30min；Then it filters at a temperature of 100 DEG C again, 1 times of amount is added in obtained filtrate
(pressure is 0.2 atmospheric pressure, and temperature is 110 DEG C) is concentrated under reduced pressure to the 1/10 of original volume in chloroform, and the crystal of precipitation is again
It is cleaned by chloroformic solution, vacuum drying obtains pyrogallic acid product.
The purity assay of gallic acid therein and pyrogallic acid product a height of 91.3wt% and 96.4wt%.Product
Total recovery be 76.8%.
Embodiment three
Present embodiments provide a kind of method for preparing gallic acid and pyrogallic acid with tannin biomass, including with
Lower step:
1) biomass containing tannin, the deionized water, dehydrated alcohol, formamide by crushing are added in a high pressure reaction kettle,
Wherein biomass containing tannin, deionized water, dehydrated alcohol, formamide ratio be 1:2:3:0.8；Turn on agitator, room temperature are normal
Press the air for being warming up to boiling, and being passed through in carbon dioxide replacement reaction kettle；The tannin biomass is that Chinese gall or tower are drawn
2) valve for closing reaction kettle, is continuously heating to 180 DEG C, reacts 45min；
3) open the valve of reaction kettle, and with CO 2 gas-shielded, 1 times of the solution formamide measured be added, then plus
Hot solution evaporates deionized water and dehydrated alcohol to 113 DEG C, so that the content of the two stops when being lower than 1%；
4) solution of step 3) is placed in microwave applicator, and 2% strongly acidic styrene's cation exchange tree is added
The pressure of heater is reduced to 0.2 atmospheric pressure by rouge, and microwave power 800w heats 40min；
5) solution for obtaining step 4) carries out pressurization concentration (pressure is 0.15 atmospheric pressure, and temperature is 105 DEG C) to original
Come the 1/5 of volume, be then cooled to room temperature, is separated by filtration to obtain water phase and solid phase；Solid phase deionized water dissolving, into excessively active
Carbon decoloring, recrystallization, vacuum drying obtain gallic acid product；
6) 5% benzene sulfonic acid iron is added in water phase, then is placed in microwave applicator, the pressure of heater is reduced to 0.2
Atmospheric pressure, microwave power 800w heat 20min；Then it filters at a temperature of 90 DEG C again, the chlorine of 1 times of amount is added in obtained filtrate
It is imitative, (pressure is 0.15 atmospheric pressure, and temperature is 105 DEG C) is concentrated under reduced pressure to the 1/10 of original volume, the crystal of precipitation is again
It is cleaned by chloroformic solution, vacuum drying obtains pyrogallic acid product.
The a height of 92.3wt% and 97.6wt% or more of the purity assay of gallic acid therein and pyrogallic acid product.
The total recovery of product is 78%.
Claims (1)
1. a kind of method for preparing gallic acid and pyrogallic acid with tannin biomass, it is characterised in that: including following step
It is rapid:
1) biomass containing tannin, the deionized water, dehydrated alcohol, formamide by crushing are added in a high pressure reaction kettle, wherein
Biomass containing tannin, deionized water, dehydrated alcohol, formamide ratio be 1:1~3:2~4:0.5~1；Turn on agitator, often
Normal temperature and pressure is warming up to boiling, and the air being passed through in carbon dioxide replacement reaction kettle；
2) valve for closing reaction kettle, is continuously heating to 170~190 DEG C, reacts 30~60min；
3) valve of reaction kettle is opened, and with CO 2 gas-shielded, 1 times of the solution formamide measured is added, then heats molten
Liquid evaporates deionized water and dehydrated alcohol to 110~115 DEG C, so that the content of the two stops when being lower than 1%；
4) solution of step 3) is placed in microwave applicator, and 1~3% strongly acidic styrene's cation exchange tree is added
The pressure of heater is reduced to 0.1~0.3 atmospheric pressure by rouge, and microwave power is 700~900w, heats 20~50min；
5) gallic acid makes: the solution that step 4) obtains is subjected to pressurization and is concentrated into the 1/5 of original volume, pressurization concentration parameter
Are as follows: pressure is 0.1~0.2 atmospheric pressure, and temperature is 100~110 DEG C, is then cooled to room temperature, be separated by filtration to obtain water phase and
Solid phase；Solid phase deionized water dissolving obtains gallic acid product into excessively active carbon decoloring, recrystallization, vacuum drying；
6) pyrogallic acid makes: oxidant being added in water phase, after reacting a period of time, is concentrated to get pyrogallic acid
Product；The tannin biomass is that Chinese gall or tower are drawn；The making step of the pyrogallic acid specifically: in water phase
3~8% benzene sulfonic acid iron is added, then is placed in microwave applicator, the pressure of heater is reduced to 0.1~0.3 atmospheric pressure, it is micro-
Wave power is 700~900w, heats 10~30min；Then it filters at a temperature of 80~100 DEG C again, 1 times of amount is added in obtained filtrate
Chloroform, carry out being concentrated under reduced pressure into the 1/10 of original volume, the crystal of precipitation is cleaned using chloroformic solution, and vacuum drying obtains
Pyrogallic acid product.
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| CN110790638A (en) * | 2019-11-20 | 2020-02-14 | 湖南棓雅生物科技有限公司 | Process technology for directly producing pyrogallic acid by using Chinese gall leaching liquor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161628A (en) * | 2007-11-15 | 2008-04-16 | 浙江大学 | Method for preparing gallic acid and pyrogallic acid synchronously by non-catalyzed hydrolysis of tannin-containing biomass in high-temperature liquid water medium |
| 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 |
| CN105198734A (en) * | 2015-10-20 | 2015-12-30 | 湖南中医药大学 | Method of preparing gallic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161628A (en) * | 2007-11-15 | 2008-04-16 | 浙江大学 | Method for preparing gallic acid and pyrogallic acid synchronously by non-catalyzed hydrolysis of tannin-containing biomass in high-temperature liquid water medium |
| 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 |
| CN105198734A (en) * | 2015-10-20 | 2015-12-30 | 湖南中医药大学 | Method of preparing gallic acid |
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