CN102321681A - A kind of method and device for preparing gallic acid - Google Patents

A kind of method and device for preparing gallic acid Download PDF

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CN102321681A
CN102321681A CN201110229669A CN201110229669A CN102321681A CN 102321681 A CN102321681 A CN 102321681A CN 201110229669 A CN201110229669 A CN 201110229669A CN 201110229669 A CN201110229669 A CN 201110229669A CN 102321681 A CN102321681 A CN 102321681A
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jar
tannase
gallic acid
basin
dehvery pump
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CN102321681B (en
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黎继烈
李忠海
王挥
沈珺珺
袁强
朱晓媛
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Central South University of Forestry and Technology
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Abstract

A kind of method and device for preparing gallic acid; This method for preparing gallic acid may further comprise the steps: the preparation of (1) immobilized tannase: the fixation support of tannase is soaked, behind the glutaraldehyde cross-linking, adds the immobilization that tannase is accomplished tannase with deionized water; (2) gallic acid preparation: the raw material that will contain Weibull with flooding, filter after, in gained Weibull vat liquor, add immobilized tannase and carry out enzymic hydrolysis, again through decolouring, filter, concentrated, crystallization, centrifugal, vacuum-drying.The present invention also comprises a kind of device for preparing gallic acid, comprises the immobilization device of tannase and the preparation facilities of gallic acid.The present invention's fixing through to tannase improves the thermostability and the pH accommodation of enzyme; Easy and simple to handle, safe, stable; Production cost is low, is convenient to large-scale production.

Description

A kind of method and device for preparing gallic acid
Technical field
The present invention relates to a kind of method and device for preparing gallic acid, especially relate to method and device that a kind of enzyme process prepares gallic acid.
Background technology
Gallic acid, chemical name are 3,4, and 5-trihydroxybenzoic acid ( English name 3,4,5-trihydroxy benzoic acid) is a kind of important fine chemical product, is widely used in fields such as chemical industry, medicine, food and electronic industry.
At present, in the industry, the raw material of producing gallic acid is that Turkey-galls, times flower or tower draw, and main working method is acid-hydrolysis method or alkali hydrolysis method.There is following problem in these methods: the vitriol oil that uses in (1) acid-hydrolysis method has strong oxidizing property, can destroy the benzene ring structure in the Weibull, and side reaction is many, causes the gallic acid yield to reduce, and bullion face look deepens; (2) alkali hydrolysis method need be used in the hydrochloric acid and caustic soda, makes to contain a large amount of sodium-chlor in the hydrolyzed solution, and follow-up separation process is complicated, and cost improves; (3) the Weibull hydrolysis is incomplete in the hydrolytic process, unstable product quality, and equipment corrosion is serious, the acidic and alkaline waste water serious environment pollution of generation.
In addition, also can adopt the microbe fermentation method preparation gallic acid that combines with enzyme process.CN101643755A discloses a kind of method of producing electronic grade gallic acid on February 10th, 2010, this method prepares tannase enzyme liquid with microbe fermentation method earlier, again enzyme liquid and tower is drawn the mixed gallic acid that gets of powder.Fermentation system enzyme process and hydrolytic process temperature are lower in this method, and the production cycle is long, and hydrolysis is incomplete, and fermented liquid and the hydrolyzed solution individual system that coexists, and have strengthened the difficulty of follow-up filtration, separation and purification.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of cost low, productive rate height, the method for preparing gallic acid that environmental pollution is little.
The further purpose of the present invention is, provides a kind of easy to operate, can improve the device of the preparation gallic acid of stable production process property.
The technical solution adopted for the present invention to solve the technical problems is:
The present invention's the method for preparing gallic acid may further comprise the steps:
(1) preparation of immobilized tannase
A. carrier soaks: subsequent use fixation support is placed carrier pre-treatment jar, add deionized water to fixation support is flooded, fixation support is soaked, add the NaCO that concentration is 1~3mol/L simultaneously 3The pH that solution or NaOH solution are regulated soak solution is 7.8~8.2, soaks after 0.5~3 hour, discharges soaked in water;
B. glutaraldehyde cross-linking: in the described carrier pre-treatment of step a jar, add K 2HPO 4, LUTARALDEHYDE and deionized water, make that the ratio of material is in the pre-treatment jar: fixation support: K 2HPO 4: LUTARALDEHYDE: deionized water=(10~30): (0.4~0.5): (1.0~4.0): (65~88); And adding concentration is the NaCO of 1~3mol/L 3Solution or NaOH solution stir after regulating pH to 7.8~8.2, and stirring velocity is 90~120 r/min (preferred 100r/min), stirs after 1~3 hour, takes out fixation support, cleans up with deionized water;
C. the immobilization of tannase: will place the immobilization jar through the fixation support of step b pre-treatment gained tannase; Volume by tannase liquid: it is the tannase liquid of 5000 U/mL that fixation support quality=1:10~25 add enzyme work; At 25~40 ℃ of temperature (preferred 35 ℃), stir under the condition of pH6.5~7.5 (preferred 6.8~7.1), stirring velocity is 90~120 r/min (preferred 100r/min); Stir 10~50 hours (preferred 24-26 hour); Filter, spend dried up washing, obtain immobilized tannase;
(2) preparation of gallic acid
D. Weibull lixiviate: the gallnut extract after will pulverizing, training pollen or tower draw powder raw material to place raw material lixiviate jar; Add and be equivalent to gallnut extract, training pollen or tower draw powder raw material weight 4-8 deionized water doubly, under 60-90 ℃ of temperature, behind the lixiviate 4-7h;, obtain the Weibull vat liquor;
E. the enzymatic hydrolysis of Weibull: steps d gained Weibull vat liquor is placed hydrolytic decomposition pot, and the Weibull mass concentration is 6~10% (preferred 8%) in the adjustment hydrolyzed solution, adds 0.5~11kg (preferably 3-10 kg) immobilized tannase by the 1000kg hydrolyzed solution simultaneously and is hydrolyzed; Hydrolysis temperature is 30 ℃~70 ℃ (preferred 35 ℃-65 ℃; More preferably 40 ℃-60 ℃), pH is 3.5~6.5 (preferred 4.0-4.5), hydrolysis time 8~60 hours (preferred 10-40 hour); After hydrolysis is accomplished; Hydrolyzed solution filters through hydrolytic decomposition pot bottom sieve plate and discharges, and immobilized tannase is stayed the sieve plate top in the hydrolytic decomposition pot, reuses;
F. gallic acid is purified: with the hydrolyzate decolorizing of step e gained, filter, and evaporation concentration, crystallization, centrifugal, vacuum-drying.
Further, the fixation support of tannase described in the step a is preferred LX-1000HA type resin.
The device of the present invention's preparation gallic acid; Comprise the immobilization device of tannase, the preparation facilities of gallic acid; The immobilization device of said tannase comprises carrier pre-treatment jar, dehvery pump I, basin I, dehvery pump II, basin II, dehvery pump III, immobilization jar, heating and cooling system; The basin I links to each other with the immobilization jar with carrier pre-treatment jar through the dehvery pump I; The basin II is closed the immobilization jar through the dehvery pump II with carrier pre-treatment jar and is linked to each other, and carrier pre-treatment jar is through dehvery pump III and immobilization jar, and said carrier pre-treatment jar, immobilization jar link to each other with the heating and cooling system; The preparation facilities of said gallic acid comprises raw material lixiviate jar, dehvery pump IV, pressure filter I, basin III, dehvery pump V, hydrolytic decomposition pot, bleacher, dehvery pump VI, pressure filter II, basin IV, dehvery pump VII, vaporizer, basin V, dehvery pump VIII, crystallizer, whizzer, drying machine, vacuum system; Said raw material lixiviate jar links to each other with the pressure filter I through the dehvery pump IV; Said pressure filter I links to each other with the basin III, and said basin III links to each other with hydrolytic decomposition pot through the dehvery pump V, and said hydrolytic decomposition pot links to each other with bleacher; Said bleacher links to each other with the pressure filter II through the dehvery pump VI; Said pressure filter II links to each other with the basin IV, and said basin IV links to each other with vaporizer through the dehvery pump VII, and said vaporizer links to each other with the basin V; Said basin V through the dehvery pump VIII with have crystallizer and link to each other; Said crystallizer links to each other with whizzer, and said whizzer links to each other with drying machine, said lixiviate jar, hydrolytic decomposition pot, bleacher, crystallizer and heating and cooling system.
Further, said carrier pre-treatment jar, immobilization jar, lixiviate jar, hydrolytic decomposition pot, bleacher and crystallizer are equipped with pH transmitter and TP.
Further, be provided with pressure transmitter and TP in the said vaporizer.
Further, said carrier pre-treatment jar, immobilization jar, lixiviate jar, hydrolytic decomposition pot, bleacher and crystallizer are all established chuck, and said chuck links to each other with the heating and cooling system.
Further, sieve plate is equipped with in said hydrolytic decomposition pot bottom, and the aperture on the sieve plate is less than immobilized tannase particulate aperture.
The present invention passes through thermostability and the pH accommodation to the fixedly raising enzyme of tannase, has accelerated the conversion rate of Weibull, has shortened the production cycle, has improved the target productive rate; The macromolecule resin material that selection has the well secured performance to tannase further improves the work-ing life of enzyme as fixation support, has reduced production cost; Environmental pollution is few in process of production, adapts to large-scale production.
Description of drawings
Fig. 1 prepares the tannase immobilization device example structure synoptic diagram in the device of gallic acid for the present invention;
Fig. 2 prepares the device example structure synoptic diagram that Weibull enzyme process in the device of gallic acid transforms gallic acid for the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.
Embodiment 1
The method for preparing gallic acid of present embodiment may further comprise the steps:
(1) preparation of immobilized tannase
A. carrier soaks: carrier LX-1000HA resin is placed the carrier pre-treatment jar that has whisking appliance; Adding deionized water (water surface floods resin and gets final product) soaks; Adding concentration is that the pH of the NaOH solution adjusting soak solution of 2mol/L is 8, soaks and discharges soaked in water after 1.5 hours;
B. glutaraldehyde cross-linking: in the described carrier pre-treatment of step a jar, add K 2HPO 4, LUTARALDEHYDE and deionized water, make the massfraction ratio of material in the pre-treatment jar be: carrier LX-1000HA resin: K 2HPO 4: LUTARALDEHYDE: deionized water=10:0.4:1.0:88.6.And stir after adding the NaOH solution adjusting pH to 7.8 that concentration is 2mol/L, stirring velocity is 100r/min, stirs after 1 hour, takes out the LX-1000HA resin carrier, cleans up with deionized water;
C. the immobilization of tannase: will place the immobilization jar that has agitator through the fixation support of step b preliminary treatment gained tannase; Volume by tannase liquid: fixation support quality=1:10 adds tannase liquid (enzyme work is 5000 U/mL); 25 ℃ of temperature; Stir under the condition of pH6.5, mixing speed is 100r/min, stirs 10 hours; Filter; Spend dried up abundant washing, being fixed tannase, enzyme are lived and are 8478U/g;
(2) preparation of gallic acid
D. Weibull lixiviate: the gallnut extract raw material 1000kg after will pulverizing places raw material lixiviate jar, adds 6 times of deionized waters that weigh to raw material of water, behind lixiviate 5h under 80 ℃ of temperature, emits vat liquor and filters, and obtains the Weibull vat liquor;
E. the enzymatic hydrolysis of Weibull: steps d gained Weibull vat liquor is placed hydrolytic decomposition pot; Using the Weibull concentration in the deionized water adjustment hydrolyzed solution is 8%; Add 0.5 kg immobilized tannase (the enzyme 18495U/g that lives gets the immobilized enzyme of the high enzymatic activity among the embodiment 1-6) by the 1000kg hydrolyzed solution and be hydrolyzed, hydrolysis temperature is 35 ℃; PH is 3.5; Hydrolysis time 60 hours, hydrolysis are accomplished posthydrolysis liquid and are filtered discharge through hydrolytic decomposition pot bottom sieve plate, and immobilized tannase is stayed on the sieve plate and reused in the hydrolytic decomposition pot.
F. gallic acid is purified: with step e gained hydrolyzate decolorizing, filter, and evaporation concentration, crystallization, centrifugal, vacuum-drying.
Present embodiment gained Weibull transformation efficiency is 86.3%.
Embodiment 2-6
The operation steps of embodiment 2-6 is identical with the step of embodiment 1, and the glutaraldehyde cross-linking processing condition in the step (1) and the fixing condition of tannase are seen table 1, and the processing condition of the enzymatic hydrolysis of Weibull and the transformation efficiency of Weibull are seen table 2 in the step (2).
Figure 679068DEST_PATH_IMAGE001
Step (2) tannase legal system is equipped with in the technology of gallic acid, and the immobilized tannase of adding is (1) middle embodiment 2 preparations set by step, and other technological parameter is seen shown in the table 2, and is surplus with embodiment 1 .
Figure 734749DEST_PATH_IMAGE002
Embodiment 8
With reference to accompanying drawing; The device of the preparation gallic acid of present embodiment; Comprise the immobilization device of tannase and the preparation facilities of gallic acid; The immobilization device of said tannase comprises carrier pre-treatment jar 1, dehvery pump I 2, basin I 3, dehvery pump II 4, basin II 5, dehvery pump III 6, immobilization jar 7, heating and cooling system (not shown); Basin I 3 links to each other with immobilization jar 7 with carrier pre-treatment jar 1 through dehvery pump I 2; Basin II 5 links to each other with immobilization jar 7 with carrier pre-treatment jar 1 through dehvery pump II 4, and carrier pre-treatment jar 1 passes through dehvery pump III 6 and links to each other with immobilization jar 7, and said carrier pre-treatment jar 1, immobilization jar 7 link to each other with the heating and cooling system; The preparation facilities of said gallic acid comprises raw material lixiviate jar 8, dehvery pump IV 9, pressure filter I 10, basin III 11, dehvery pump V 12, hydrolytic decomposition pot 13, bleacher 14, dehvery pump VI 15, pressure filter II 16, basin IV 17, dehvery pump VII 18, vaporizer 19, basin V 20, dehvery pump VIII 21, crystallizer 22, whizzer 23, drying machine 24, vacuum system (not shown); Said raw material lixiviate jar 8 links to each other with pressure filter I 10 through dehvery pump IV 9; Said pressure filter I 10 links to each other with basin III 11; Said basin III 11 links to each other with hydrolytic decomposition pot 13 through dehvery pump V 12; Said hydrolytic decomposition pot 13 links to each other with bleacher 14, and said bleacher 14 links to each other with pressure filter II 16 through dehvery pump VI 15, and said pressure filter II 16 links to each other with basin IV 17; Said basin IV 17 links to each other with vaporizer 19 through dehvery pump VII 18; Said vaporizer 19 links to each other with basin V 20, and said basin V 20 links to each other with crystallizer 22 through dehvery pump VIII 21, and said crystallizer 22 links to each other with whizzer 23; Said whizzer 23 links to each other with the drying machine that has vacuum system 24, said lixiviate jar 8, hydrolytic decomposition pot 13, bleacher 14, crystallizer 22 and heating and cooling system.
Said carrier pre-treatment jar, immobilization jar, lixiviate jar, hydrolytic decomposition pot, bleacher and crystallizer are equipped with pH transmitter and TP.
Be provided with pressure transmitter and TP in the said vaporizer.
Said carrier pre-treatment jar, immobilization jar, lixiviate jar, hydrolytic decomposition pot, bleacher and crystallizer are all established chuck, and said chuck links to each other with the heating and cooling system.
Sieve plate is equipped with in said hydrolytic decomposition pot bottom, and the aperture on the sieve plate is less than immobilized tannase particulate aperture.

Claims (10)

1. a method for preparing gallic acid is characterized in that, may further comprise the steps:
(1) preparation of immobilized tannase
A. carrier soaks: subsequent use fixation support is placed carrier pre-treatment jar, add deionized water to fixation support is flooded, fixation support is soaked, add the NaCO that concentration is 1~3mol/L simultaneously 3The pH that solution or NaOH solution are regulated soak solution is 7.8~8.2, soaks after 0.5~3 hour, discharges soaked in water;
B. glutaraldehyde cross-linking: in the described carrier pre-treatment of step a jar, add K 2HPO 4, LUTARALDEHYDE and deionized water, make the massfraction ratio of material in the pre-treatment jar be: fixation support: K 2HPO 4: LUTARALDEHYDE: deionized water=(10~30): (0.4~0.5): (1.0~4.0): (65~88); And adding concentration is the NaCO of 1~3mol/L 3Solution or NaOH solution stir after regulating pH to 7.8~8.2, and stirring velocity is 90~120 r/min, stir after 1~3 hour, take out fixation support, clean up with deionized water;
C. the immobilization of tannase: will place the immobilization jar through the fixation support of step b pre-treatment gained tannase, by the volume of tannase liquid: it is the tannase liquid of 5000 U/mL that fixation support quality=1:10~25 add the enzyme work, 25~40 ℃ of temperature; Stir under the condition of pH6.5~7.5; Stirring velocity is 90~120 r/min, stirs 10~50 hours, filters; Spend dried up washing, obtain immobilized tannase;
(2) preparation of gallic acid
D. Weibull lixiviate: the gallnut extract after will pulverizing, training pollen or tower draw powder raw material to place raw material lixiviate jar; Add and be equivalent to gallnut extract, training pollen or tower draw powder raw material weight 4-8 deionized water doubly, under 60-90 ℃ of temperature, behind the lixiviate 4-7h; Filter, obtain the Weibull vat liquor;
E. the enzymatic hydrolysis of Weibull: steps d gained Weibull vat liquor is placed hydrolytic decomposition pot, and the Weibull mass concentration is 6~10% in the adjustment hydrolyzed solution, adds 0.5~11kg immobilized tannase by the 1000kg hydrolyzed solution simultaneously and is hydrolyzed; Hydrolysis temperature is 30 ℃~70 ℃, and pH is 3.5~6.5, hydrolysis time 8~60 hours; After hydrolysis is accomplished; Hydrolyzed solution filters through hydrolytic decomposition pot bottom sieve plate and discharges, and immobilized tannase is stayed the sieve plate top in the hydrolytic decomposition pot, reuses;
F. gallic acid is purified: with the hydrolyzate decolorizing of step e gained, filter, and evaporation concentration, crystallization, centrifugal, vacuum-drying.
2. the method for preparing gallic acid according to claim 1 is characterized in that: the fixation support of tannase described in the step a is a LX-1000HA type resin.
3. the method for preparing gallic acid according to claim 1 and 2 is characterized in that: step b, said stirring velocity is 100r/min.
4. the method for preparing gallic acid according to claim 1 and 2 is characterized in that: step c, 35 ℃ of temperature, stir under the condition of pH6.8~7.1, and stirring velocity is 100r/min, stirs 24-26 hour.
5. the method for preparing gallic acid according to claim 1 and 2; It is characterized in that: step e; The Weibull mass concentration is 8% in the adjustment hydrolyzed solution, adds 3-10 kg immobilized tannase by the 1000kg hydrolyzed solution simultaneously and is hydrolyzed, and hydrolysis temperature is 35 ℃-65 ℃; PH is 4.0-4.5, hydrolysis time 10-40 hour.
6. device for preparing gallic acid; Comprise the immobilization device of tannase and the preparation facilities of gallic acid; It is characterized in that: the immobilization device of said tannase comprises carrier pre-treatment jar, dehvery pump I, basin I, dehvery pump II, basin II, dehvery pump III, immobilization jar, heating and cooling system; The basin I links to each other with the immobilization jar with carrier pre-treatment jar through the dehvery pump I; The basin II is closed the immobilization jar through the dehvery pump II with carrier pre-treatment jar and is linked to each other, and carrier pre-treatment jar is through dehvery pump III and immobilization jar, and said carrier pre-treatment jar, immobilization jar link to each other with the heating and cooling system; The preparation facilities of said gallic acid comprises raw material lixiviate jar, dehvery pump IV, pressure filter I, basin III, dehvery pump V, hydrolytic decomposition pot, bleacher, dehvery pump VI, pressure filter II, basin IV, dehvery pump VII, vaporizer, basin V, dehvery pump VIII, crystallizer, whizzer, drying machine, vacuum system; Said raw material lixiviate jar links to each other with the pressure filter I through the dehvery pump IV; Said pressure filter I links to each other with basin
Figure 358280DEST_PATH_IMAGE001
; Said basin III links to each other with hydrolytic decomposition pot through the dehvery pump V; Said hydrolytic decomposition pot links to each other with bleacher; Said bleacher links to each other with the pressure filter II through the dehvery pump VI; Said pressure filter II links to each other with the basin IV, and said basin IV links to each other with vaporizer through the dehvery pump VII, and said vaporizer links to each other with the basin V; Said basin V through the dehvery pump VIII with have crystallizer and link to each other; Said crystallizer links to each other with whizzer, and said whizzer links to each other with drying machine, said lixiviate jar, hydrolytic decomposition pot, bleacher, crystallizer and heating and cooling system.
7. the device of preparation gallic acid according to claim 6 is characterized in that: said carrier pre-treatment jar, immobilization jar, lixiviate jar, hydrolytic decomposition pot, bleacher and crystallizer are equipped with pH transmitter and TP.
8. according to the device of claim 6 or 7 described preparation gallic acids, it is characterized in that: be provided with pressure transmitter and TP in the said vaporizer.
9. according to the device of claim 6 or 7 described preparation gallic acids, it is characterized in that: said carrier pre-treatment jar, immobilization jar, lixiviate jar, hydrolytic decomposition pot, bleacher and crystallizer are all established chuck, and said chuck links to each other with the heating and cooling system.
10. according to the device of claim 6 or 7 described preparation gallic acids, it is characterized in that: sieve plate is equipped with in said hydrolytic decomposition pot bottom, and the aperture on the sieve plate is less than immobilized tannase particulate aperture.
CN201110229669.4A 2011-08-11 2011-08-11 Method and device for preparing gallic acid Expired - Fee Related CN102321681B (en)

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* Cited by examiner, † Cited by third party
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CN105039298A (en) * 2015-07-02 2015-11-11 曹庸 Preparation method of immobilized tannase
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CN107312768A (en) * 2017-08-14 2017-11-03 山东思科新材料有限公司 A kind of immobilized tannase and its preparation method and application
CN108795749A (en) * 2018-08-23 2018-11-13 五峰赤诚生物科技股份有限公司 A kind of devices and methods therefor of immobilized tannase production gallic acid
CN110129292A (en) * 2019-04-24 2019-08-16 赖鹏 A kind of Rosa roxburghii Tratt SOD extracting method and device
CN111850058A (en) * 2020-06-12 2020-10-30 遵义市倍缘化工有限责任公司 Method for synthesizing propyl gallate through tannic acid biocatalysis
CN112386943A (en) * 2020-09-30 2021-02-23 邱洪 Preparation method of gallic acid
CN112877373A (en) * 2021-01-26 2021-06-01 桂林莱茵生物科技股份有限公司 Preparation method for obtaining gallic acid with content of more than 99%

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Publication number Priority date Publication date Assignee Title
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
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
CN105039298A (en) * 2015-07-02 2015-11-11 曹庸 Preparation method of immobilized tannase
CN105695518A (en) * 2016-04-21 2016-06-22 贵州大学 Method for repeatedly preparing gallic acid by converting tannic acid through immobilized bacteria biological method
CN107312768B (en) * 2017-08-14 2021-01-12 山东森久生物材料有限公司 Immobilized tannase and preparation method and application thereof
CN107312768A (en) * 2017-08-14 2017-11-03 山东思科新材料有限公司 A kind of immobilized tannase and its preparation method and application
CN108795749A (en) * 2018-08-23 2018-11-13 五峰赤诚生物科技股份有限公司 A kind of devices and methods therefor of immobilized tannase production gallic acid
CN110129292A (en) * 2019-04-24 2019-08-16 赖鹏 A kind of Rosa roxburghii Tratt SOD extracting method and device
CN110129292B (en) * 2019-04-24 2023-05-26 赖鹏 Rosa roxburghii SOD extraction method and device
CN111850058A (en) * 2020-06-12 2020-10-30 遵义市倍缘化工有限责任公司 Method for synthesizing propyl gallate through tannic acid biocatalysis
CN112386943A (en) * 2020-09-30 2021-02-23 邱洪 Preparation method of gallic acid
CN112877373A (en) * 2021-01-26 2021-06-01 桂林莱茵生物科技股份有限公司 Preparation method for obtaining gallic acid with content of more than 99%
CN112877373B (en) * 2021-01-26 2023-03-21 桂林莱茵生物科技股份有限公司 Preparation method for obtaining gallic acid with content of more than 99%

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