CN1037601C - Preparation of gallic acid by basic hydrolyzation - Google Patents
Preparation of gallic acid by basic hydrolyzation Download PDFInfo
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- CN1037601C CN1037601C CN93114806A CN93114806A CN1037601C CN 1037601 C CN1037601 C CN 1037601C CN 93114806 A CN93114806 A CN 93114806A CN 93114806 A CN93114806 A CN 93114806A CN 1037601 C CN1037601 C CN 1037601C
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- gallic acid
- tannin
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- gall
- chinese gall
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Abstract
The present invention provides a method for preparing gallic acids by gall flowers or gall flower tannic acids as original raw materials. The gallic acids are mainly applied to medicine industry, food industry and electronic industry. The tannin content of the gall flowers as raw materials used by the present invention is more than or equal to 35%, and the moisture content is less than or equal to 14%. The tannin content of the gall flower tannic acids is more than or equal to 62%, and the moisture content is less than or equal to 9 %. The pulverized gall flowers or the gall flower tannic acids are mixed with water, and a high-purity gallic acid crystal is prepared through alkaline hydrolysis, acidification, filter pressing, cooling crystallization, refining, cooling crystallization, separation washing and vacuum drying. Relative to the gall flowers as raw materials, the yield of a gallic acid refined product is from 26.4 to 29.0 % (the theoretical yield is from 77.3 to 84.9 %.). Relative to the gall flower tannic acids, the yield of the gallic acid refined product is from 46.5 to 50.3 % (the theoretical yield is from 76.6 to 82.8 %).
Description
The present invention relates to a kind of preparation field of organic chemicals, specifically a kind of method for preparing gallic acid from doubly flower or Chinese gall Beihua tannin.
Gallic acid has another name called gallate.Chemical name is 3,4, and 5-trihydroxybenzoic acid, molecular weight are 188.4, are white needle-like crystals, as are dissolved in hot water, ethanol, the glycerine, are insoluble to chloroform and benzene.It is mainly used in medicine, food and electronic industry.Generally speaking, if adopt expensive Chinese gallotanninic acid (by tripe doubly or the angle doubly make) make the raw material production gallic acid, uneconomical economically.At present, existing report is implemented with acid-hydrolysis method and fermentation method with doubly spending the preparation gallic acid, in the aforesaid method, acid-hydrolysis method is all more serious to the corrosion of the pollution of environment and equipment, though fermentation method can overcome the shortcoming of acid-hydrolysis method, but the product yield is on the low side, and the production cycle is long.
Home-made is not fully utilized in the objective of the invention is to select for use, and its convenient sources, doubly flower with low cost or Chinese gall Beihua tannin are raw material, provide a kind of and can be beneficial to pollutions that control environment, and can overcome the novel method of shortcoming such as the on the low side and production cycle length of yield again.
Technical scheme of the present invention is to realize like this, doubly flower or the Chinese gall Beihua tannin pulverized are mixed with water, through basic hydrolysis, acidification, press filtration is (when using Chinese gall Beihua tannin, do not need this step), crystallisation by cooling, refining, crystallisation by cooling again, separation, washing, vacuum-drying obtain highly purified gallic acid.
Doubly the tannin chemical structure in flower and the Chinese gall Beihua tannin is consistent with the chemical structure of Chinese gallotanninic acid substantially, also is with galloyl and the compound that β-D-glucose combines with ester bond, can not eaten acid and glucose after its hydrolysis.Chemical principle is as follows:
With flower doubly is that the concrete processing method that the raw material direct hydrolysis prepares gallic acid is: passing through the crushing screening tannin content is 30～40%, the doubly flower of water≤14% mixes by proportioning 1: 1～5 with water, soak in short-term, adding concentration under whipped state is the sodium hydroxide solution of 30～45% (W/W), and be heated to reflux temperature, kept 1～2 hour, after treating hydrolysis fully, adding concentration is the concentrated hydrochloric acid of 30～37% (W/W), the gallic acid that assurance is the sodium salt state all is converted into unbound state, press filtration while hot.Filtrate obtains yellow gallic acid coarse crystal through crystallisation by cooling.Coarse crystal is dissolved in the water of 5～10 times of cleanings, makes with extra care, and its method is the gac of adding 5～20%, and decolouring of 0.1～0.5% iron removing reagent (oxalic acid, disodium ethylene diamine tetraacetate) and absorption impurity, deironing.Stirring heating refluxed 5～30 minutes, filters, and filtrate crystallisation by cooling, separating, washing, vacuum-drying obtains highly purified gallic acid crystal.With respect to a flower raw material doubly, the yield of gallic acid elaboration be 26.4-29.0% (for theoretical yield 77.3～84.9%).
The concrete processing method that with the Chinese gall Beihua tannin is the feedstock production gallic acid is: with tannin content is 55～65%, the Chinese gall Beihua tannin of moisture≤9% mixes with water proportioning 1: 1～3, adding concentration under whipped state is the sodium hydroxide solution of 30～45% (W/W), and be heated to reflux temperature, kept 1～2 hour, after treating hydrolysis fully, adding concentration is the concentrated hydrochloric acid of 30～37% (W/W), assurance is sodium salt state gallic acid and all is converted into unbound state, crystallisation by cooling, pass through above-mentioned same process for purification again, obtain highly purified gallic acid crystal.With respect to a flower tannin doubly, the yield of gallic acid elaboration be 46.5～53.3% (for theoretical yield 76.6～82.8%).
Embodiment one
Times pollen particle 50g adds water 50～250ml, stirs moments later, and adding concentration is the sodium hydroxide solution of 30～45 (W/W), and is heated to reflux temperature, keeps 1～2 hour, and adding concentration is the concentrated hydrochloric acid 40ml of 30～37% (W/W), stirring, press filtration while hot.The filtrate crystallisation by cooling, obtain the wet crystal 3 4g of light yellow gallic acid, wet crystal is dissolved in 5～10 times of water, makes with extra care, and its method is to add gac 2g and trace (0.1～0.5%) iron removing reagent, reflux 20 minutes, heat filtering, filtrate crystallisation by cooling, separating, washing, vacuum-drying obtains white gallic acid crystal 14.5g.The product yield is 29.0%, is 84.9% of theoretical yield.Embodiment two
Times pollen particle 50g adds water 50～250ml, stirs moments later, and adding concentration is the sodium hydroxide solution of 30～45 (W/W), and is heated to reflux temperature, keeps 1～2 hour, and adding concentration is the concentrated hydrochloric acid 38ml of 30～37% (W/W), stirring, press filtration while hot.The filtrate crystallisation by cooling, obtain the wet crystal 4 1g of gallic acid, wet crystal is dissolved in 5～10 times of water, makes with extra care, and its method is to add gac 1g and trace (0.1～0.5%) iron removing reagent, reflux 20 minutes, heat filtering, filtrate crystallisation by cooling, separating, washing, vacuum-drying obtains white gallic acid crystal 13.2g.The product yield is 26.4%, is 77.3% of theoretical yield.Embodiment three
Chinese gall Beihua tannin 31.8g, add water 30～100ml, stir, adding concentration is the sodium hydroxide solution of 30～45 (W/W), and is heated to reflux temperature, kept 1～2 hour, adding concentration is the concentrated hydrochloric acid 43ml of 30～37% (W/W), stirs crystallisation by cooling, filter wet sample 39.5g, wet sample is dissolved in 5～10 times of water, makes with extra care, and its method is to add gac 2g and trace (0.1～0.5%) iron removing reagent, reflux 20 minutes, heat filtering, filtrate crystallisation by cooling, separating, washing, vacuum-drying obtains white gallic acid crystal 16g.The product yield is 50.3%, is 82.8% of theoretical yield.Embodiment four
Chinese gall Beihua tannin 31.8g, add water 30～100ml, stir, adding concentration is the sodium hydroxide solution of 30～45 (W/W), and is heated to reflux temperature, kept 1～2 hour, adding concentration is the concentrated hydrochloric acid 38ml of 30～37% (W/W), stirs crystallisation by cooling, filter wet sample 39.2g, wet sample is dissolved in 5～10 times of water, makes with extra care, and its method is to add gac 2.5g and trace (0.1～0.5%) iron removing reagent, reflux 20 minutes, heat filtering, filtrate crystallisation by cooling, separating, washing, vacuum-drying obtains white gallic acid crystal 15.7g.The product yield is 49.4%, is 81.3% of theoretical yield.Embodiment five
Chinese gall Beihua tannin 50g, add water 50～15ml, stir, adding concentration is the sodium hydroxide solution of 30～45 (W/W), and is heated to reflux temperature, kept 1～2 hour, adding concentration is the concentrated hydrochloric acid 75ml of 30～37% (W/W), stirs crystallisation by cooling, filter wet sample 51.6g, wet sample is dissolved in 5～10 times of water, makes with extra care, and its method is to add gac 5g and trace (0.1～0.5%) iron removing reagent, reflux 20 minutes, heat filtering, filtrate crystallisation by cooling, separating, washing, vacuum-drying obtains white gallic acid crystal 2 6.4g.The product yield is 52.8%, is 78.8% of theoretical yield.
Claims (4)
1. a method of utilizing times flower or Chinese gall Beihua tannin to prepare gallic acid is characterized in that with times flower or Chinese gall Beihua tannin be starting raw material, employed times of flower, its tannin content 〉=35%, moisture≤14%, employed Chinese gall Beihua tannin, its tannin content 〉=62%, moisture≤9%; Doubly flower through crushing screening mixes by proportioning 1: 1～5 with water, and adding concentration under whipped state is the sodium hydroxide solution of 30～45% (w/w), and is heated to reflux temperature, is incubated 1-2 hour, carries out basic hydrolysis; The concentrated hydrochloric acid that adds concentration again and be 30～37% (w/w) carries out acidification; Press filtration while hot; When being raw material, then do not need press filtration with Chinese gall Beihua tannin; Filtrate obtains light yellow gallic acid coarse crystal through crystallisation by cooling: it made with extra care, and crystallisation by cooling again, separation, washing, vacuum-drying are prepared into gallic acid.
2. preparation method according to claim 1, it is characterized in that refining is that the gallic acid coarse crystal is dissolved in 5～6 times the clean water, the gac and 0.1～0.5% iron removing reagent of adding 5～20%, under agitation reflux is 5～30 minutes, heat filtering, filtrate crystallisation by cooling, separating, washing, vacuum-drying makes highly purified gallic acid crystal.
3. preparation method according to claim 1 is characterized in that with the Chinese gall Beihua tannin being that starting raw material mixes by proportioning 1: 1～3 with water.
4. preparation method according to claim 2 is characterized in that said iron removing reagent can be oxalic acid, disodium ethylene diamine tetraacetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93114806A CN1037601C (en) | 1993-11-17 | 1993-11-17 | Preparation of gallic acid by basic hydrolyzation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93114806A CN1037601C (en) | 1993-11-17 | 1993-11-17 | Preparation of gallic acid by basic hydrolyzation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1104627A CN1104627A (en) | 1995-07-05 |
| CN1037601C true CN1037601C (en) | 1998-03-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93114806A Expired - Fee Related CN1037601C (en) | 1993-11-17 | 1993-11-17 | Preparation of gallic acid by basic hydrolyzation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850211A (en) * | 2012-09-19 | 2013-01-02 | 湖南洪江棓雅生物科技有限公司 | Gallic acid and clean and efficient production process thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101779628B (en) * | 2009-12-10 | 2013-04-03 | 张家界奥威科技有限公司 | Method for preparing gallic acid aquiculture sanitizer and product thereof |
| CN102260299A (en) * | 2011-05-24 | 2011-11-30 | 保靖县林力科技开发有限公司 | Preparation method of gall flower tannic acid |
| CN106242951B (en) * | 2016-07-30 | 2018-12-18 | 遵义市倍缘化工有限责任公司 | A method of preparing pyrogallic acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032936A (en) * | 1988-10-08 | 1989-05-17 | 黑龙江省医药工业研究所 | Prepare gallic acid with acer ginnala leaf |
-
1993
- 1993-11-17 CN CN93114806A patent/CN1037601C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032936A (en) * | 1988-10-08 | 1989-05-17 | 黑龙江省医药工业研究所 | Prepare gallic acid with acer ginnala leaf |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850211A (en) * | 2012-09-19 | 2013-01-02 | 湖南洪江棓雅生物科技有限公司 | Gallic acid and clean and efficient production process thereof |
| CN102850211B (en) * | 2012-09-19 | 2014-06-11 | 湖南洪江棓雅生物科技有限公司 | Gallic acid and clean and efficient production process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1104627A (en) | 1995-07-05 |
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