CN106242949B - A kind of method that the decarboxylation of high pressure water phase prepares pyrogallic acid - Google Patents
A kind of method that the decarboxylation of high pressure water phase prepares pyrogallic acid Download PDFInfo
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- CN106242949B CN106242949B CN201610613740.1A CN201610613740A CN106242949B CN 106242949 B CN106242949 B CN 106242949B CN 201610613740 A CN201610613740 A CN 201610613740A CN 106242949 B CN106242949 B CN 106242949B
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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
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
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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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
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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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
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Abstract
The present invention relates to pyrogallic acid preparation technical fields, especially a kind of method that the decarboxylation of high pressure water phase prepares pyrogallic acid, it is extracted by ultrasound, catalyzing hydrolysis, microwave radiation preheating, air-discharging and catalysis, in conjunction with increasing temperature and pressure, so that decarboxylic reaction occurs in high pressure water phase for gallic acid, and in the effect of microwave, hydrochloric acid, tartaric acid, so that decarboxylation energy consumption is lower；After the high pressure water phase decarboxylation stage, pyridine is added and carries out high-temperature catalytic decarboxylation, so that the decarboxylation of gallic acid is complete, reduces energy consumption, improve the purity of pyrogallic acid, improve the yield of pyrogallic acid.
Description
Technical field
The present invention relates to pyrogallic acid preparation technical field, especially a kind of high pressure water phase decarboxylation prepares coke and does not eat
The method of sub- acid.
Background technique
Gallic acid also known as gallic acid, the entitled Gallic Acid of chemistry, are important Organic Ingredients,
In the industries such as chemical industry, medicine, food and electronics, the effective component as antioxidant, water stabilizer or drug, purposes is very
Extensively, demand cumulative year after year.And pyrogallic acid, it is the product by being obtained after gallic acid decarboxylation, also known as burnt times
Phenol, pyrogallol, the entitled Pyrogallic acid of chemistry, are widely used in chemical analysis, photographic process, fuel, coating, food
The industries such as product, pharmacy, electronic material, pesticide, are also important industrial chemicals.In the prior art, at for gallic acid decarboxylation
The method that reason prepares pyrogallic acid mainly has: vacuum decarboxylation, normal pressure decarboxylation, pressurization decarboxylation, decarboxylate of microorganisms.
In addition to the method described above, decarboxylation processing is carried out for gallic acid, somebody combines not to be had containing tanning matter
The preparation process of gallate-based will contain after tanning matter mixes with deionized water, and in a high pressure reaction kettle by it, heat air-discharging,
It is further continued for being heated to 160-250 DEG C, so that it is reacted, and after separation of solid and liquid, solid phase is used to prepare gallic acid, by water
It is mutually extracted using organic solvent, prepares pyrogallic acid.The method is not added during producing pyrogallic acid
Catalyst, but by heating shows weak so that being ionized into so that water evaporation is at gas, and after increasing the pressure in reaction kettle
Acid or weakly alkaline ingredient reaches the gallic acid in biomass containing tannin and obtains hydrolysis generation, and occurs at high temperature
Decarboxylic reaction achievees the purpose that prepare pyrogallic acid.Although it is being handled as it can be seen that the method is without adding catalyst
In the process, need to reach temperature at least 160 DEG C, so that the energy consumption of preparation process is higher.
Based on this, this researcher is by long-term working practice and exploration, so that decarboxylation under the high pressure water phase of gallic acid
Reaction, reduces energy consumption, provides a kind of new approaches for the preparation of pyrogallic acid.
Summary of the invention
In order to solve the above technical problems existing in the prior art, it is burnt to provide a kind of high pressure water phase decarboxylation preparation by the present invention
The method of property gallic acid.
It is achieved particular by following technical scheme:
A kind of method that the decarboxylation of high pressure water phase prepares pyrogallic acid, comprising the following steps:
(1) will contain tannin biomass with water is that 1:4-7 is mixed according to mass ratio, is extracted using ultrasound and handles 20-30min,
Obtain mixed liquor；
(2) mixture of hydrochloric acid and tartaric acid, mixing mass ratio 1:2-7, mixture additional amount are added into mixed liquor
For the 11-19% of mixed liquor quality, stir while adding uniformly；
(3) use frequency for the microwave radiation 20-30min of 300-700W, closed reactor, adjustment temperature is 120-140
DEG C, constant temperature handles 2-4h, and reducing the pressure in reaction kettle is opening reaction kettle after normal pressure, and is added accounts for mixed liquor matter thereto
The pyridine of 0.1-0.7% is measured, constant temperature is handled to bubble-free and generated, when being cooled to 90-100 DEG C, is separated by solid-liquid separation while hot, then by liquid
Crystallisation by cooling, filtering, then add it in chloroformic solution, it stirs evenly, then filtered, and eluted with chloroform, after being filtered dry,
Placing it in vacuum degree is to obtain pyrogallic acid using 40-60 DEG C of drying under 0.02-0.08MPa.
The hydrochloric acid, mass concentration 1-7%.
The chloroformic solution, mass concentration 10-30%.
The ultrasound, frequency 30-60KHz.
Biomass containing tannin in the invention can also be the substances such as tealeaves other than Chinese gall, tower are drawn.
Compared with prior art, technical effect of the invention is embodied in:
It is extracted by ultrasound, catalyzing hydrolysis, microwave radiation preheating, air-discharging and catalysis, in conjunction with increasing temperature and pressure, so that not having
Decarboxylic reaction occurs in high pressure water phase for gallate-based, and in the effect of microwave, hydrochloric acid, tartaric acid, so that decarboxylation energy consumption is lower；
After the high pressure water phase decarboxylation stage, pyridine is added and carries out high-temperature catalytic decarboxylation, so that the decarboxylation of gallic acid is complete,
Energy consumption is reduced, the purity of pyrogallic acid is improved, improves the yield of pyrogallic acid.
The present invention is combined into hydrolyst by hydrochloric acid and tartaric acid, and high pressure occurs under the action of hydrolyst
Water phase decarboxylation processing so that the temperature that high pressure water phase is formed reduces, and then promotes energy consumption lower, so that in 120-140 DEG C of temperature
Under degree, it will be able to realize decarboxylic reaction, and pyridine catalysis is added at a high temperature of combining after subsequent decompression, so that gallic acid is de-
Carboxylic is complete, so that the yield of pyrogallic acid is higher, reduces the production cost of pyrogallic acid, improves coke and does not eat
The quality of sub- acid.
The invention passes through to be separated by solid-liquid separation while hot, then by after liquid crystalization, chloroformic solution is washed, and is done under vacuum environment
It is dry, so that the purity of pyrogallic acid is higher.
The relatively simple high pressure water phase decarboxylation of the present invention prepares pyrogallic acid, and energy consumption is lower, pyrogallic acid
Yield improve 5.4% or so, and the purity for finally obtaining pyrogallic acid can reach 97.86% or more, reduce
The preparation cost of pyrogallic acid.
Specific embodiment
It is limited below with reference to specific embodiment technical solution of the present invention is further, but claimed
Range is not only limited to made description.
Embodiment 1
A kind of method that the decarboxylation of high pressure water phase prepares pyrogallic acid, comprising the following steps:
(1) it is that 1:4 is mixed according to mass ratio with water by Chinese Gall, is extracted using ultrasound and handle 20min, mixed
Liquid；
(2) mixture of hydrochloric acid and tartaric acid, mixing mass ratio 1:2 are added into mixed liquor, mixture additional amount is
The 11% of mixed liquor quality stirs while adding uniformly；
(3) use frequency for the microwave radiation 20min of 300W, closed reactor, adjustment temperature is 120 DEG C, constant temperature processing
2h, reducing the pressure in reaction kettle is opening reaction kettle after normal pressure, and the pyridine for accounting for mixed liquor quality 0.1% is added thereto,
Constant temperature is handled to bubble-free and is generated, and when being cooled to 90 DEG C, is separated by solid-liquid separation while hot, then by liquid crystallisation by cooling, filtering, then is added
Enter into chloroformic solution, stir evenly, then filtered, and eluted with chloroform, after being filtered dry, placing it in vacuum degree is
40 DEG C of dryings are used under 0.02MPa, obtain pyrogallic acid.
The hydrochloric acid, mass concentration 1%.
The chloroformic solution, mass concentration 10%.
The ultrasound, frequency 30KHz.
Embodiment 2
A kind of method that the decarboxylation of high pressure water phase prepares pyrogallic acid, comprising the following steps:
(1) it is that 1:7 is mixed according to mass ratio with water by tower draw powder, is extracted using ultrasound and handle 30min, mixed
Liquid；
(2) mixture of hydrochloric acid and tartaric acid, mixing mass ratio 1:7 are added into mixed liquor, mixture additional amount is
The 19% of mixed liquor quality stirs while adding uniformly；
(3) use frequency for the microwave radiation 30min of 700W, closed reactor, adjustment temperature is 140 DEG C, constant temperature processing
4h, reducing the pressure in reaction kettle is opening reaction kettle after normal pressure, and the pyridine for accounting for mixed liquor quality 0.7% is added thereto,
Constant temperature is handled to bubble-free and is generated, and when being cooled to 100 DEG C, is separated by solid-liquid separation while hot, then by liquid crystallisation by cooling, filtering, then by its
It is added in chloroformic solution, stirs evenly, then filtered, and eluted with chloroform, after being filtered dry, placing it in vacuum degree is
60 DEG C of dryings are used under 0.08MPa, obtain pyrogallic acid.
The hydrochloric acid, mass concentration 7%.
The chloroformic solution, mass concentration 30%.
The ultrasound, frequency 60KHz.
Embodiment 3
A kind of method that the decarboxylation of high pressure water phase prepares pyrogallic acid, comprising the following steps:
(1) it is that 1:6 is mixed according to mass ratio with water by Chinese Gall, is extracted using ultrasound and handle 25min, mixed
Liquid；
(2) mixture of hydrochloric acid and tartaric acid, mixing mass ratio 1:5 are added into mixed liquor, mixture additional amount is
The 17% of mixed liquor quality stirs while adding uniformly；
(3) use frequency for the microwave radiation 25min of 500W, closed reactor, adjustment temperature is 130 DEG C, constant temperature processing
3h, reducing the pressure in reaction kettle is opening reaction kettle after normal pressure, and the pyridine for accounting for mixed liquor quality 0.5% is added thereto,
Constant temperature is handled to bubble-free and is generated, and when being cooled to 95 DEG C, is separated by solid-liquid separation while hot, then by liquid crystallisation by cooling, filtering, then is added
Enter into chloroformic solution, stir evenly, then filtered, and eluted with chloroform, after being filtered dry, placing it in vacuum degree is
50 DEG C of dryings are used under 0.06MPa, obtain pyrogallic acid.
The hydrochloric acid, mass concentration 5%.
The chloroformic solution, mass concentration 20%.
The ultrasound, frequency 50KHz.
Embodiment 4
A kind of method that the decarboxylation of high pressure water phase prepares pyrogallic acid, comprising the following steps:
(1) it is that 1:7 is mixed according to mass ratio with water by Ta La, is extracted using ultrasound and handle 20min, obtain mixed liquor；
(2) mixture of hydrochloric acid and tartaric acid, mixing mass ratio 1:2 are added into mixed liquor, mixture additional amount is
The 11% of mixed liquor quality stirs while adding uniformly；
(3) use frequency for the microwave radiation 20min of 700W, closed reactor, adjustment temperature is 140 DEG C, constant temperature processing
2h, reducing the pressure in reaction kettle is opening reaction kettle after normal pressure, and the pyridine for accounting for mixed liquor quality 0.7% is added thereto,
Constant temperature is handled to bubble-free and is generated, and when being cooled to 90 DEG C, is separated by solid-liquid separation while hot, then by liquid crystallisation by cooling, filtering, then is added
Enter into chloroformic solution, stir evenly, then filtered, and eluted with chloroform, after being filtered dry, placing it in vacuum degree is
40 DEG C of dryings are used under 0.08MPa, obtain pyrogallic acid.
The hydrochloric acid, mass concentration 1%.
The chloroformic solution, mass concentration 30%.
The ultrasound, frequency 30KHz.
Embodiment 5
A kind of method that the decarboxylation of high pressure water phase prepares pyrogallic acid, comprising the following steps:
(1) it is that 1:4 is mixed according to mass ratio with water by Chinese Gall, is extracted using ultrasound and handle 30min, mixed
Liquid；
(2) mixture of hydrochloric acid and tartaric acid, mixing mass ratio 1:2 are added into mixed liquor, mixture additional amount is
The 19% of mixed liquor quality stirs while adding uniformly；
(3) use frequency for the microwave radiation 20min of 700W, closed reactor, adjustment temperature is 120 DEG C, constant temperature processing
4h, reducing the pressure in reaction kettle is opening reaction kettle after normal pressure, and the pyridine for accounting for mixed liquor quality 0.1% is added thereto,
Constant temperature is handled to bubble-free and is generated, and when being cooled to 100 DEG C, is separated by solid-liquid separation while hot, then by liquid crystallisation by cooling, filtering, then by its
It is added in chloroformic solution, stirs evenly, then filtered, and eluted with chloroform, after being filtered dry, placing it in vacuum degree is
60 DEG C of dryings are used under 0.02MPa, obtain pyrogallic acid.
The hydrochloric acid, mass concentration 3%.The chloroformic solution, mass concentration 10%.Described is super
Sound, frequency 40KHz.
Claims (5)
1. a kind of method that the decarboxylation of high pressure water phase prepares pyrogallic acid, which comprises the following steps:
(1) will contain tannin biomass with water is that 1:4-7 is mixed according to mass ratio, is extracted using ultrasound and handles 20-30min, obtained
Mixed liquor；
(2) mixture of hydrochloric acid and tartaric acid is added into mixed liquor, mixing mass ratio 1:2-7, mixture additional amount is mixed
The 11-19% for closing liquid quality is stirred while adding uniformly；
(3) use frequency for the microwave radiation 20-30min of 300-700W, closed reactor, adjustment temperature is 120-140 DEG C, permanent
Temperature processing 2-4h, reducing the pressure in reaction kettle is opening reaction kettle after normal pressure, and is added accounts for mixed liquor quality 0.1- thereto
0.7% pyridine, constant temperature are handled to bubble-free and are generated, when being cooled to 90-100 DEG C, is separated by solid-liquid separation while hot, then liquid cooling is tied
Crystalline substance, filtering, then add it in chloroformic solution, it stirs evenly, then filtered, and eluted with chloroform, after being filtered dry, is set
It is to use 40-60 DEG C of drying under 0.02-0.08MPa in vacuum degree, obtains pyrogallic acid.
2. the method that high pressure water phase decarboxylation as described in claim 1 prepares pyrogallic acid, which is characterized in that the salt
Acid, mass concentration 1-7%.
3. the method that high pressure water phase decarboxylation as described in claim 1 prepares pyrogallic acid, which is characterized in that the chlorine
Imitative solution, mass concentration 10-30%.
4. the method that high pressure water phase decarboxylation as described in claim 1 prepares pyrogallic acid, which is characterized in that described is super
Sound, frequency 30-60KHz.
5. the method that high pressure water phase decarboxylation as described in claim 1 prepares pyrogallic acid, which is characterized in that described contains
Tannin biomass is the mixture of Chinese gall or Ta La or Chinese gall and tower drawing according to any ratio of mass ratio.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1680239A (en) * | 2005-01-26 | 2005-10-12 | 中国林业科学研究院林产化学工业研究所 | Preparation of pyrogallic acid with pyridine as decarboxylation catalyst of 3,4,5-trihydroxybenzoic acid |
| CN101143806A (en) * | 2007-09-30 | 2008-03-19 | 浙江大学 | Method for preparing pyrogallic acid from gallic acid in high temperature liquid state water medium by catalyst-free decarboxylating |
| CN102140121A (en) * | 2010-01-28 | 2011-08-03 | 中国林业科学研究院林产化学工业研究所 | Preparation method of tara industrial tannic acid |
| 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 |
-
2016
- 2016-07-30 CN CN201610613740.1A patent/CN106242949B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1680239A (en) * | 2005-01-26 | 2005-10-12 | 中国林业科学研究院林产化学工业研究所 | Preparation of pyrogallic acid with pyridine as decarboxylation catalyst of 3,4,5-trihydroxybenzoic acid |
| CN101143806A (en) * | 2007-09-30 | 2008-03-19 | 浙江大学 | Method for preparing pyrogallic acid from gallic acid in high temperature liquid state water medium by catalyst-free decarboxylating |
| CN102140121A (en) * | 2010-01-28 | 2011-08-03 | 中国林业科学研究院林产化学工业研究所 | Preparation method of tara industrial tannic acid |
| 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 |
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