CN101864459A - Method for preparing gallic acid - Google Patents
Method for preparing gallic acid Download PDFInfo
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- CN101864459A CN101864459A CN201010165152A CN201010165152A CN101864459A CN 101864459 A CN101864459 A CN 101864459A CN 201010165152 A CN201010165152 A CN 201010165152A CN 201010165152 A CN201010165152 A CN 201010165152A CN 101864459 A CN101864459 A CN 101864459A
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- gallic acid
- acid
- enzyme
- tannin
- hydrolysis
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Abstract
The invention discloses a method for preparing gallic acid. In the method, enzyme preparation and acid preparation processes are performed in two different containers by stages; and NaOH solution is used for adjusting pH value in both the enzyme preparation and acid preparation processes. The invention aims to provide a method for preparing gallic acid, which reduces reaction time and raw and auxiliary material consumption, overcomes the drawbacks of strong smell, effumability and easy environmental pollution of the ammonia water due to the fact that the pH value is adjusted not by ammonia water and reduces environmental pollution. And as microorganism growing and enzyme production processes are still performed in the acid production period, the method is advantageous over a common enzyme method in hydrolysis safety, and product purity and yield and can create great social and economic benefits.
Description
Technical field
The present invention relates to a kind of method for preparing gallic acid, is raw material with the industrial tannic acid, adopts the whole-cell biological catalysis method to prepare gallic acid, belongs to biological technical field.
Background technology
(Gallic Acid GA) has another name called doubly acid, gallic acid to gallic acid, and chemical name is 3,4, the 5-trihydroxybenzoic acid, is white or faint yellow needle crystal or powder, and normally the form from a kind of hydrate exists.Gallic acid has wide application market as a kind of important chemical product; Can be used for fields such as organic synthesis, coating, dyestuff, medicine, food, chemical industry, process hides, daily use chemicals, agricultural, mineral products, be mainly used in fields such as medicine, dyestuff, food, makeup, feed.In addition, certain application market is also being arranged aspect the semi-conductor photosensitive resin.
The traditional processing technology of preparation gallic acid: be to draw with Turkey-galls, tower to be raw material with chemical hydrolysis (CN1706790), be about to Turkey-galls with hot water lixiviate, filtering residue, the Chinese tannin acid solution; Add alkali after concentration is about 20% tanning solution and carry out direct hydrolysis through being concentrated into, the reaction mixture that obtains gallate and glucose again through neutralization separate, decolouring, refining crystallization, dry finished product gallic acid, the main drawback of this technology is that the soda acid consumption is big, wastewater flow rate is many, environmental pollution is serious, energy consumption is big, can't remove and strengthened the pollution load etc. of waste water equipment requirements height, hydrolysising by-product glucose.Compare with traditional chemical hydrolysis, the outstanding feature of enzyme process is a substrate hydrolysis safety, and hydrolysising by-product glucose can be used as carbon source by the biological catalyst metabolism, has not only improved effective utilization rate of resource, and fermented liquid is easy to handle than hydrolysis.Adopt biological fermentation process to prepare gallic acid report is at home and abroad all arranged: as biotechnology journal 2000,16 (5): 614-617 " utilizing immobilization aspergillus niger tannase legal system to be equipped with gallic acid ", but the yield of gallic acid is on the low side, only is 61%.And in general fermentative Production technology, the generation of tannase and the reaction of Hydrolysable Tannins all are to carry out in same reactor (fermentor tank).Because two top condition differences that reaction requires, during the fermentation, always attend to one thing and lose sight of another, mutual restriction, the both can not reach the optimum response state, causes hydrolysis incomplete.N1083532 " technology of preparation of gallic acid by using enzyme " the system enzyme that will ferment separates in different vessels respectively with hydrolysis relieving haperacidity and carries out, and has overcome above defective, has simplified flow process, has improved production environment, has reduced consumption of raw materials, has improved product yield.
But adopting Turkey-galls and Ta La powder is raw material, all adopts ammoniacal liquor to regulate pH value in producing enzyme and acid process, owing to ammoniacal liquor exists shortcomings such as volatile, that flavor is dense, contaminate environment.Do not have microbial growth and produce enzyme process at the product acid phase, used enzyme amount is big, and product enzyme and product acid are produced respectively and needed more than 40 hours, and hydrolysis is safe not enough, and yield is high not enough.
The purpose of this invention is to provide a kind of method for preparing gallic acid that can overcome above-mentioned shortcoming.With the Weibull is raw material, regulates pH value without ammoniacal liquor, selects the reasonable compatibility ratio of various optimum process parameters and substratum, thereby has reduced raw material consumption, has shortened the reaction times, has improved production environment, has improved the yield of product.
Summary of the invention
It is that raw material whole-cell catalytic legal system is equipped with gallic acid that the present invention adopts with the Weibull.Comprise two stages.Fs: utilize microorganism contain tannin and a small amount of outside ferment in the aqueous solution of carbon source, with the glucose that produces after the Weibull hydrolysis as follow-up carbon source, for microorganism growth, breeding, meanwhile microorganism is induced the generation tannase through Weibull in solution; Subordinate phase: the fermented liquid that will produce the fs adds in the tannic acid solution, make the Weibull hydrolysis generate gallic acid, add no carbon source substratum simultaneously, make microorganism growth and produce enzyme process and continued, both guaranteed acid process efficiently, because microbial growth has consumed the glucose that acid process produces, reduce the viscosity of producing acid solution simultaneously, helped the separation of gallic acid.
In fermentation system enzyme process, the proportioning of every fermentation parameter and substratum is very important, must strictly control, and optimal temperature is 23-38 ℃; Initial ph value is 4.0, adds alkali (as the NaoH with 10N) in the reaction process and is adjusted between the 3.0-5.5; Dissolved oxygen amount is controlled between the 3.0-6.00g02/lh.Adopt aspergillus niger N0.316 as the zymogenic bacteria kind.
In the system enzyme substratum, C/N is than being 2-10, and Weibull concentration is 8-15%; Beyond the tannin carbon source add-on be the tannin amount 0.2-0.8 doubly.Additional carbon can be with sucrose or glucose; Add nitrogenous source and can use ammonium sulfate, ammonium chloride or urea etc.The inorganic salt of a spot of sulphur, phosphorus, potassium, sodium, zinc, magnesium and yeast extract paste or vitamin B complexes compounds of group also should be arranged as nutritional additive in the substratum.
The tanning solution made from above-mentioned fermentation condition and substratum proportioning can be used for hydrolysis relieving haperacidity, is that raw material adds dissolving with the Weibull, and the relieving haperacidity optimal temperature is 22-38 ℃; Initial ph value is 4.0, adds 10NnaoH in the reaction process and is adjusted between the 3.0-5.5; Dissolved oxygen amount is controlled between the 3.0-6.00g02/lh.With the tannin is raw material, and tannin concentration is 8-15% (W/V).
Use whole-cell catalytic method of the present invention to produce gallic acid, use Weibull, as raw material, the reaction times is shorter than common fermentation method, the 30h that has shortened altogether, and raw material consumption is low, and product yield height reaches more than 90%, and purity is up to 99%.Additional carbon only is about 0.2 times of tannin consumption, save cost, can make microorganism growth again and produce enzyme process to be continued, also guaranteed acid process efficiently, microbial growth has consumed the glucose that produces in the acid process, reduce the viscosity of acid solution, helped the separation of gallic acid, improved production environment, production technique reaction of the present invention relaxes, no high temperature, high top pressure operation, " three wastes " pollute little, administer easily; The consumption of soda acid and activated carbon all has obvious reduction than chemical hydrolysis and existing fermentation method.Shortened Production Flow Chart, economizing after the hydrolysis decrystallizes and decolour operates each once.
Description of drawings
Fig. 1 prepares the method process flow sheet of gallic acid for the present invention.
Embodiment
Through the bacterial classification seed pre-culture, so open and changing through sterilizing after in the culture medium solution fermentation over to and make enzyme, after measured enzymic activity qualified after, promptly be used for hydrolysis relieving haperacidity.After hydrolysis reaction finishes, add sulfuric acid or hydrochloric acid adjusting PH and remove by filter filter residue, then filtrate is concentrated, obtain coarse crystallization after the cooling.Coarse crystallization is separated, water-soluble again, add activated carbon decolorizing, recrystallization, and then separate reclaims mother liquor, dry again, pulverize, measure, pack the gallic acid product.
System enzyme embodiment 1:
By following composition preparation substratum (g/l)
(NH
4)
2SO
4 2
KH
2PO
4 2
MgSo
47H
2O 1
ZnSo
4 0.6
Yeast extract paste 1
Sucrose 15
Weibull 100
Prepared culture medium is divided in the triangular flask of several 1000ml and sterilizes.For avoiding the tannin high temperature oxidation, it is 4.0 that Weibull adds with 10mol/LNaOH regulator solution initial ph value after sterilization; Then insert black-koji mould NO.316 immediately, be placed on the ZHWY-2102C constant temperature oscillator and react.Design temperature is 23-38 ℃, and the adjusting rotating speed is 120-128r/min, regulates for several times with 10mol/L NaOH, and the pH value of reaction solution is remained on about 3.0-5.5, and successive reaction 30h measures enzymic activity or the residual variation of Weibull and eases up, and promptly is used for relieving haperacidity.
System enzyme embodiment 2:
Prepare substratum (g/L) by following composition:
NH
4cl 2
KH
2PO
4 2
MgSO
47H
2O 1
ZnSO
4 0.6
Yeast extract paste 1
Glucose 15
Weibull 100
Vitamin B complexes 8mg/L
Prepared culture medium is divided in the triangular flask of several 1000ml, the sterilization back adds tannin.Remaining step is carried out according to system enzyme embodiment 1.
Relieving haperacidity embodiment:
Prepare substratum (g/L) by following composition:
(NH
4)
2SO
4 2
KH
2PO
4 2
MgSO
47H
2O 1
ZnSO
4 0.6
Yeast extract paste 1
The prepared culture medium adding is had in the fermentor tank of semi-automatic stream adder-subtractor and external acidometer and dissolved oxygen meter sterilization.
Weibull is added dissolving, and making solution tannin concentration is 8-15% (w/v), initial p H4.0.Add the full cell fermentation enzyme liquid that 15-20% (v/v) newly makes after being cooled to room temperature, design temperature is 22-38 ℃, and the adjusting rotating speed is 100r/min, dissolved oxygen amount 3.0-6.00g O2/L.h.Add adjusting with 10mol/L NaOH stream, the pH value of reaction solution is remained on about 3.0-5.5, successive reaction 40h is till the whole hydrolysis of tannin.Reaction product is regulated PH to 2.6-3.5 with hydrochloric acid, through filtration, concentrate, coarse crystallization, coarse-grain are separated with mother liquor, decolouring, secondary crystal, secondary crystal separate, dry, pulverize, purity is 99%, yield reaches 90.8% finished product.
Claims (5)
1. method for preparing gallic acid, add alkali and make the tannin hydrolysis in drawing of Turkey-galls or tower, concentrate again after filtration,, crystallization, decolouring, drying and make gallic acid, it is characterized in that: be raw material with the Weibull, with microbial fermentation system enzyme and hydrolysis relieving haperacidity, segmentation is carried out at two different containers, and the component of every appropriate processing condition and substratum in definite system enzyme and the acid-making process all adopts NaOH solution to regulate pH value in system enzyme acid-making process.
2. the method for preparing gallic acid according to claim 1 is characterized in that: in the fermentation system enzyme process, optimal temperature is 23-38 ℃; Initial ph value is 4.0, is adjusted to PH3.0-5.5 with the NaOH of 10N; Dissolved oxygen amount is controlled at 3.0-6.0Og O
2Between/the Lh, microorganism is adopted aspergillus niger NO.316.
3. the method for preparing gallic acid according to claim 1 is characterized in that: in the system enzyme substratum, the C/N ratio is 8-15% for 2-10, Weibull concentration; Beyond the tannin carbon source add-on be tannin 0.2-0.8 doubly.
4. the method for preparing gallic acid according to claim 1 is characterized in that: additional carbon can add nitrogenous source and can use ammonium sulfate, ammonification ammonium or urea with sucrose or glucose; Also have the inorganic salt of sulphur, phosphorus, potassium, sodium, zinc, magnesium and yeast extract paste or vitamin B complexes compounds of group in the substratum as nutritional additive.
5. the method for preparing gallic acid according to claim 1 is characterized in that: in the hydrolysis relieving haperacidity, be that raw material adds dissolving with the Weibull, the concentration of solution tannin is 8-15% (w/v), 22-38 ℃ of relieving haperacidity optimal temperature; Initial ph value is 4.0; The NaOH that adds 10N in the reaction process is adjusted between the PH3.0-5.5; Dissolved oxygen amount is controlled at 3.0-6.0Og O
2Between/the Lh.
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| CN201010165152A CN101864459A (en) | 2010-05-07 | 2010-05-07 | Method for preparing gallic acid |
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| CN201010165152A CN101864459A (en) | 2010-05-07 | 2010-05-07 | Method for preparing gallic acid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321681A (en) * | 2011-08-11 | 2012-01-18 | 中南林业科技大学 | A kind of method and device for preparing gallic acid |
| CN102643871A (en) * | 2012-04-17 | 2012-08-22 | 昆明怡普康植物化学有限公司 | Preparation method of high-purity gallic acid |
| CN102988421A (en) * | 2012-11-21 | 2013-03-27 | 江苏大学 | Extract of effective components of antineoplastic gallnut as well as preparation method and application thereof |
| CN103589758A (en) * | 2013-11-12 | 2014-02-19 | 遵义市倍缘化工有限责任公司 | Method for preparing gallic acid by using gallnut tannin as raw material and utilizing fermentation separation coupling technology |
| CN105367414A (en) * | 2014-08-20 | 2016-03-02 | 湘西高源生化科技有限公司 | Galla chinensis zymolite and galla chinensis flower zymolite mixing filtration method |
| CN106349047A (en) * | 2016-08-02 | 2017-01-25 | 遵义市倍缘化工有限责任公司 | Method using organic strong base to prepare gallic acid under normal pressure |
| CN113197809A (en) * | 2021-05-19 | 2021-08-03 | 杭州配方师科技有限公司 | Preparation method of skin care product containing phaeodactylum and tara fermentation compound |
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| SU1146323A1 (en) * | 1983-05-23 | 1985-03-23 | Le Mezhotraslevoj Nii Pishchev | Method of obtaining gallic acid |
| CN1083532A (en) * | 1993-07-08 | 1994-03-09 | 贵州省化工研究院 | The technology of preparation of gallic acid by using enzyme |
| CN1115335A (en) * | 1994-07-16 | 1996-01-24 | 孙东江 | Method for prodn. of gallic acid by fermentation process |
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2010
- 2010-05-07 CN CN201010165152A patent/CN101864459A/en active Pending
Patent Citations (3)
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|---|---|---|---|---|
| SU1146323A1 (en) * | 1983-05-23 | 1985-03-23 | Le Mezhotraslevoj Nii Pishchev | Method of obtaining gallic acid |
| CN1083532A (en) * | 1993-07-08 | 1994-03-09 | 贵州省化工研究院 | The technology of preparation of gallic acid by using enzyme |
| CN1115335A (en) * | 1994-07-16 | 1996-01-24 | 孙东江 | Method for prodn. of gallic acid by fermentation process |
Non-Patent Citations (2)
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321681A (en) * | 2011-08-11 | 2012-01-18 | 中南林业科技大学 | A kind of method and device for preparing gallic acid |
| CN102643871A (en) * | 2012-04-17 | 2012-08-22 | 昆明怡普康植物化学有限公司 | Preparation method of high-purity gallic acid |
| CN102643871B (en) * | 2012-04-17 | 2014-02-26 | 昆明怡普康植物化学有限公司 | Preparation method of high-purity gallic acid |
| CN102988421A (en) * | 2012-11-21 | 2013-03-27 | 江苏大学 | Extract of effective components of antineoplastic gallnut as well as preparation method and application thereof |
| CN102988421B (en) * | 2012-11-21 | 2015-06-10 | 江苏大学 | Extract of effective components of antineoplastic gallnut as well as preparation method and application thereof |
| CN103589758A (en) * | 2013-11-12 | 2014-02-19 | 遵义市倍缘化工有限责任公司 | Method for preparing gallic acid by using gallnut tannin as raw material and utilizing fermentation separation coupling technology |
| CN103589758B (en) * | 2013-11-12 | 2015-07-22 | 遵义市倍缘化工有限责任公司 | Method for preparing gallic acid by using gallnut tannin as raw material and utilizing fermentation separation coupling technology |
| CN105367414A (en) * | 2014-08-20 | 2016-03-02 | 湘西高源生化科技有限公司 | Galla chinensis zymolite and galla chinensis flower zymolite mixing filtration method |
| CN105367414B (en) * | 2014-08-20 | 2017-04-05 | 湘西高源生化科技有限公司 | A kind of hybrid filtering method of gall nut, times flower zymolite |
| CN106349047A (en) * | 2016-08-02 | 2017-01-25 | 遵义市倍缘化工有限责任公司 | Method using organic strong base to prepare gallic acid under normal pressure |
| CN113197809A (en) * | 2021-05-19 | 2021-08-03 | 杭州配方师科技有限公司 | Preparation method of skin care product containing phaeodactylum and tara fermentation compound |
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Application publication date: 20101020 |