CN106146284A - A kind of method that tannin biomass prepare gallic acid and pyrogallic acid - Google Patents
A kind of method that tannin biomass prepare gallic acid and pyrogallic acid Download PDFInfo
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- CN106146284A CN106146284A CN201610613784.4A CN201610613784A CN106146284A CN 106146284 A CN106146284 A CN 106146284A CN 201610613784 A CN201610613784 A CN 201610613784A CN 106146284 A CN106146284 A CN 106146284A
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- acid
- gallic acid
- pyrogallic
- pressure
- pyrogallic acid
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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
Abstract
The invention provides a kind of method that tannin biomass prepare gallic acid and pyrogallic acid, belong to chemical industry manufacture technology field, the present invention utilizes deionized water, dehydrated alcohol, the mixed solution of Methanamide carries out the acid-base catalysis performance that contains in high-temperature liquid state and special solubility property, Galla Chinensis or tower are drawn and is decomposed into gallic acid and pyrogallic acid, through anhydrating and ethanol, react with strongly acidic styrene type cation exchange resin under microwave environment, Galla Chinensis or tower is made to draw hydrolysis thoroughly, process at some processing steps of result, the gallic acid obtained and the purity assay of pyrogallic acid product are high, total recovery is high.Through detection, the purity assay of gallic acid and pyrogallic acid product is high at 90wt% and more than 95wt%.The total recovery of product is more than 75%.
Description
Technical field
The invention belongs to chemical industry manufacture technology field, particularly relate to one tannin biomass and prepare gallic acid and Jiao's property
The method of gallic acid.
Background technology
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, it is common that presented in monohydrate, proportion 1.694, fusing point
235～240 DEG C.Gallic acid applied range, can be used for organic synthesis, coating, dyestuff, medicine, food, chemical industry, daily use chemicals, agriculture
The aspect such as industry, mineral products, is mainly used in medicine, dyestuff, ink manufacture, also serve as food antioxidant, preservative, METAL EXTRACTION agent,
UV absorbent, disinfectant, hemostasis astringent, developing agent etc..At present, generally draw etc. containing tannin raw with Galla Chinensis or tower
Material is that raw material prepares gallic acid, the most again with gallic acid as raw material through acid-base method, fermentation method or enzymatic isolation method hydrolysis
Pyrogallic acid is prepared through vacuum decarboxylation, normal pressure decarboxylation, pressurization decarboxylation or decarboxylate of microorganisms.But its productivity and purity are not
High.
Summary of the invention
For solving above-mentioned technical problem, the invention provides one tannin biomass and prepare gallic acid and Jiao's property no food
The method of son acid, the specific scheme is that
A kind of method that tannin biomass prepare gallic acid and pyrogallic acid, comprises the following steps:
1) in autoclave add through pulverizing containing tannin biomass, deionized water, dehydrated alcohol, Methanamide,
It is wherein 1:1～3:2～4:0.5～1 containing tannin biomass, deionized water, dehydrated alcohol, the ratio of Methanamide；Open stirring
Device, normal temperature and pressure is warming up to boiling, and is passed through the air in carbon dioxide replacement reactor；
2) close the valve of reactor, be continuously heating to 170～190 DEG C, react 30～60min；
3) open the valve of reactor, and with CO 2 gas-shielded, add the Methanamide of solution 1 times amount, then add
Deionized water and dehydrated alcohol, to 110～115 DEG C, are evaporated so that stop when both content is less than 1% by hot solution；
4) by step 3) solution be placed in microwave applicator, and add 1～3% strongly acidic styrene's cation exchange
Resin, is reduced to 0.1～0.3 atmospheric pressure by the pressure of heater, and microwave power is 700～900w, heats 20～50min；
5) gallic acid makes: by step 4) solution that obtains carries out pressurizeing and is concentrated into the 1/5 of original volume, then lower the temperature
To room temperature, filter isolated aqueous phase and solid phase；Solid phase deionized water dissolving, entered activated carbon decolorizing, recrystallization, vacuum do
Dry obtain gallic acid product；
6) pyrogallic acid makes: add oxidant in aqueous phase, after reaction a period of time, is concentrated to give Jiao's property no food
Sub-acid product.
Further, described tannin biomass are Galla Chinensis or tower draws.
Further, described concentrating under reduced pressure parameter is: pressure is 0.1～0.2 atmospheric pressure, and temperature is 100～110
℃。
Further, the making step of described pyrogallic acid is particularly as follows: add 3～the benzenesulfonic acid of 8% in aqueous phase
Ferrum, 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,
Heating 10～30min；Filtering at a temperature of 80～100 DEG C, the filtrate obtained adds the chloroform of 1 times amount the most again, carries out reducing pressure dense
Being reduced to the 1/10 of original volume, the crystal of precipitation cleans through chloroformic solution again, and vacuum drying obtains pyrogallic acid product.
The beneficial effects of the present invention is: the present invention utilizes deionized water, dehydrated alcohol, the mixed solution of Methanamide to carry out
The acid-base catalysis performance contained in high-temperature liquid state and special solubility property so that Galla Chinensis or tower draw and be decomposed into gallic acid and Jiao
Property gallic acid, through anhydrating and ethanol, react with strongly acidic styrene type cation exchange resin under microwave environment, make
Obtaining Galla Chinensis or tower draws hydrolysis thoroughly, process at some processing steps of result, the gallic acid obtained and pyrogallic acid produce
The purity assay of product is high, and total recovery is high.Through detection, the purity assay height of gallic acid and pyrogallic acid product exists
90wt% and more than 95wt%.The total recovery of product is more than 75%.
Detailed description of the invention
Technical scheme is described further below, but claimed scope is not limited to described.
Embodiment one
Present embodiments provide a kind of method that tannin biomass prepare gallic acid and pyrogallic acid, including with
Lower step:
1) in autoclave add through pulverizing containing tannin biomass, deionized water, dehydrated alcohol, Methanamide,
It is wherein 1:1:2:0.5 containing tannin biomass, deionized water, dehydrated alcohol, the ratio of Methanamide；Turn on agitator, room temperature is normal
Pressure is warming up to boiling, and is passed through the air in carbon dioxide replacement reactor；Described tannin biomass are Galla Chinensis or tower draws
2) close the valve of reactor, be continuously heating to 170 DEG C, react 30min；
3) open the valve of reactor, and with CO 2 gas-shielded, add the Methanamide of solution 1 times amount, then add
Deionized water and dehydrated alcohol, to 110 DEG C, are evaporated so that stop when both content is less than 1% by hot solution；
4) by step 3) solution be placed in microwave applicator, and add 1% strongly acidic styrene's cation exchange tree
Fat, is reduced to 0.1 atmospheric pressure by the pressure of heater, and microwave power is 700w, heats 20min；
5) by step 4) solution that obtains carries out pressurization and concentrates (pressure is 0.1 atmospheric pressure, and temperature is 100 DEG C) to originally
The 1/5 of volume, is then cooled to room temperature, filters isolated aqueous phase and solid phase；Solid phase deionized water dissolving, entered activated carbon
Decolouring, recrystallization, vacuum drying obtain gallic acid product；
6) aqueous phase adds the benzenesulfonic acid ferrum of 3%, then is placed in microwave applicator, the pressure of heater is reduced to 0.1
Atmospheric pressure, microwave power is 700w, heats 10min；Filtering at a temperature of 80 DEG C, the filtrate obtained adds the chlorine of 1 times amount the most again
Imitative, carry out concentrating under reduced pressure (pressure is 0.1 atmospheric pressure, and temperature is 100 DEG C) to the 1/10 of original volume, the crystal of precipitation warp again
Crossing chloroformic solution to clean, vacuum drying obtains pyrogallic acid product.
A height of 90.5wt% and 95.6wt% of purity assay of gallic acid therein and pyrogallic acid product.Product
Total recovery be 75.5%.
Embodiment two
Present embodiments provide a kind of method that tannin biomass prepare gallic acid and pyrogallic acid, including with
Lower step:
1) in autoclave add through pulverizing containing tannin biomass, deionized water, dehydrated alcohol, Methanamide,
It is wherein 1:3:4:1 containing tannin biomass, deionized water, dehydrated alcohol, the ratio of Methanamide；Turn on agitator, normal temperature and pressure
It is warming up to boiling, and is passed through the air in carbon dioxide replacement reactor；Described tannin biomass are Galla Chinensis or tower draws
2) close the valve of reactor, be continuously heating to 190 DEG C, react 60min；
3) open the valve of reactor, and with CO 2 gas-shielded, add the Methanamide of solution 1 times amount, then add
Deionized water and dehydrated alcohol, to 115 DEG C, are evaporated so that stop when both content is less than 1% by hot solution；
4) by step 3) solution be placed in microwave applicator, and add 3% strongly acidic styrene's cation exchange tree
Fat, is reduced to 0.3 atmospheric pressure by the pressure of heater, and microwave power is 900w, heats 50min；
5) by step 4) solution that obtains carries out pressurization and concentrates (pressure is 0.2 atmospheric pressure, and temperature is 110 DEG C) to originally
The 1/5 of volume, is then cooled to room temperature, filters isolated aqueous phase and solid phase；Solid phase deionized water dissolving, entered activated carbon
Decolouring, recrystallization, vacuum drying obtain gallic acid product；
6) addition 3～the benzenesulfonic acid ferrum of 8% in aqueous phase, then it is placed in microwave applicator, the pressure of heater is reduced to 0.3
Individual atmospheric pressure, microwave power is 900w, heats 30min；Filtering at a temperature of 100 DEG C, the filtrate obtained adds 1 times amount the most again
Chloroform, to the 1/10 of original volume, the crystal of precipitation is again to carry out concentrating under reduced pressure (pressure is 0.2 atmospheric pressure, and temperature is 110 DEG C)
Cleaning through chloroformic solution, vacuum drying obtains pyrogallic acid product.
A height of 91.3wt% and 96.4wt% of purity assay of gallic acid therein and pyrogallic acid product.Product
Total recovery be 76.8%.
Embodiment three
Present embodiments provide a kind of method that tannin biomass prepare gallic acid and pyrogallic acid, including with
Lower step:
1) in autoclave add through pulverizing containing tannin biomass, deionized water, dehydrated alcohol, Methanamide,
It is wherein 1:2:3:0.8 containing tannin biomass, deionized water, dehydrated alcohol, the ratio of Methanamide；Turn on agitator, room temperature is normal
Pressure is warming up to boiling, and is passed through the air in carbon dioxide replacement reactor；Described tannin biomass are Galla Chinensis or tower draws
2) close the valve of reactor, be continuously heating to 180 DEG C, react 45min；
3) open the valve of reactor, and with CO 2 gas-shielded, add the Methanamide of solution 1 times amount, then add
Deionized water and dehydrated alcohol, to 113 DEG C, are evaporated so that stop when both content is less than 1% by hot solution；
4) by step 3) solution be placed in microwave applicator, and add 2% strongly acidic styrene's cation exchange tree
Fat, is reduced to 0.2 atmospheric pressure by the pressure of heater, and microwave power is 800w, heats 40min；
5) by step 4) solution that obtains carries out pressurization and concentrates (pressure is 0.15 atmospheric pressure, and temperature is 105 DEG C) to the most former
Come the 1/5 of volume, be then cooled to room temperature, filter isolated aqueous phase and solid phase；Solid phase deionized water dissolving, entered activity
Carbon decoloring, recrystallization, vacuum drying obtain gallic acid product；
6) aqueous phase adds the benzenesulfonic acid ferrum of 5%, then is placed in microwave applicator, the pressure of heater is reduced to 0.2
Atmospheric pressure, microwave power is 800w, heats 20min；Filtering at a temperature of 90 DEG C, the filtrate obtained adds the chlorine of 1 times amount the most again
Imitative, to the 1/10 of original volume, the crystal of precipitation is again to carry out concentrating under reduced pressure (pressure is 0.15 atmospheric pressure, and temperature is 105 DEG C)
Cleaning through chloroformic solution, vacuum drying obtains pyrogallic acid product.
The a height of 92.3wt% and more than 97.6wt% of purity assay of gallic acid therein and pyrogallic acid product.
The total recovery of product is 78%.
Claims (4)
1. the method preparing gallic acid and pyrogallic acid by tannin biomass, it is characterised in that: include following step
Rapid:
1) in autoclave add through pulverizing containing tannin biomass, deionized water, dehydrated alcohol, Methanamide, wherein
It is 1:1～3:2～4:0.5～1 containing tannin biomass, deionized water, dehydrated alcohol, the ratio of Methanamide；Turn on agitator, often
Normal temperature and pressure is warming up to boiling, and is passed through the air in carbon dioxide replacement reactor；
2) close the valve of reactor, be continuously heating to 170～190 DEG C, react 30～60min；
3) open the valve of reactor, and with CO 2 gas-shielded, add the Methanamide of solution 1 times amount, then add thermosol
Deionized water and dehydrated alcohol, to 110～115 DEG C, are evaporated so that stop when both content is less than 1% by liquid；
4) by step 3) solution be placed in microwave applicator, and add 1～3% strongly acidic styrene's cation exchange tree
Fat, is reduced to 0.1～0.3 atmospheric pressure by the pressure of heater, and microwave power is 700～900w, heats 20～50min；
5) gallic acid makes: by step 4) solution that obtains carries out pressurizeing and is concentrated into the 1/5 of original volume, be often then cooled to
Temperature, filters isolated aqueous phase and solid phase；Solid phase deionized water dissolving, entered activated carbon decolorizing, recrystallization, was vacuum dried
To gallic acid product；
6) pyrogallic acid makes: adds oxidant in aqueous phase, after reaction a period of time, is concentrated to give pyrogallic acid
Product.
2. the method preparing gallic acid and pyrogallic acid by tannin biomass as claimed in claim 1, its feature exists
It is Galla Chinensis or tower draws in: described tannin biomass.
3. the method preparing gallic acid and pyrogallic acid by tannin biomass as claimed in claim 1, its feature exists
In: described concentrating under reduced pressure parameter is: pressure is 0.1～0.2 atmospheric pressure, and temperature is 100～110 DEG C.
4. the method preparing gallic acid and pyrogallic acid by tannin biomass as claimed in claim 1, its feature exists
In the making step of: described pyrogallic acid particularly as follows: aqueous phase adds 3～the benzenesulfonic acid ferrum of 8%, then it is placed in microwave and adds
Hot device, is reduced to 0.1～0.3 atmospheric pressure by the pressure of heater, and microwave power is 700～900w, heats 10～30min；
Filtering at a temperature of 80～100 DEG C, the filtrate obtained adds the chloroform of 1 times amount, carries out being evaporated to original volume the most again
1/10, the crystal of precipitation cleans through chloroformic solution again, and vacuum drying obtains pyrogallic acid product.
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| CN201610613784.4A CN106146284B (en) | 2016-07-30 | 2016-07-30 | A method of gallic acid and pyrogallic acid are prepared with tannin biomass |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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2016
- 2016-07-30 CN CN201610613784.4A patent/CN106146284B/en active Active
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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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