CN102382093A - Process for producing quercitin - Google Patents
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- CN102382093A CN102382093A CN2011104081339A CN201110408133A CN102382093A CN 102382093 A CN102382093 A CN 102382093A CN 2011104081339 A CN2011104081339 A CN 2011104081339A CN 201110408133 A CN201110408133 A CN 201110408133A CN 102382093 A CN102382093 A CN 102382093A
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Abstract
The invention belongs to the field of plant extraction, particularly relates to a process for producing quercitin by taking rutin as a raw material and aims to provide a novel and easily-controlled process for producing quercitin to overcome technical defects in the production of the quercitin in the prior art. The process for producing quercitin comprises the following steps of feeding; hydrolyzing; filtering; washing; and refining, wherein emphasizing the control over the acidity of a fed mixture of acid and water, the feeding amount of the rutin, the hydrolyzing time, the washing temperature and reagent and using amount in the refining process, and obtaining the refined product of quercitin with high purity. The process for producing quercitin is simple, easy to control and high in conversion rate, and the cost can be greatly reduced; the product is high in purity; relevant impurities and bacteria are up to the standard; the process for producing quercitin is environment-friendly and does not emit any other harmful substances; and compared with the conventional process, the process for producing quercitin is pollution-free and is a novel process for producing quercitin.
Description
Technical Field
The invention belongs to the field of plant extraction, and particularly relates to a production process for obtaining quercetin by taking rutin as a raw material.
Background
Quercetin is dihydrate, yellow or yellow-green needle crystal, and has no odor, slightly bitter and astringent taste, and dark color when exposed to air. Molecular formula C15H10O7·2H2O, the structural formula is as follows.
The research shows that: the medical effect of the quercetin is obvious, such as the quercetin has a protective effect on ischemia-reperfusion arrhythmia; lowering blood pressure, enhancing capillary resistance, reducing capillary lipid, reducing blood lipid, dilating coronary artery, and increasing coronary blood flow; the quercetin can complex or capture free radicals to prevent lipid peroxidation of organisms; has strong pharmacological action in the aspects of resisting bacteria and viruses, resisting inflammation and preventing and treating diabetic complications; also has good effects of eliminating phlegm, relieving cough and relieving asthma. Quercetin has wide application and large market demand.
At present, aiming at the process for preparing quercetin, few reports are reported, the inventor tries to prepare isoquercetin and quercetin by hydrolyzing rutin with an enzyme method, the output is large, but the process is complex to operate, and related impurities are not easy to control: the purity of the product produced by the method can be generally more than 90 percent, but can not reach 95 percent of the medical and food grade requirements, and if the purity is to be ensured to reach 95 percent from 90 percent, the refining process is complex for separating impurities; the enzymolysis process needs a large amount of water for fermentation, and the fermented water is difficult to treat and has serious pollution; the cost is high due to impurity removal and pollution discharge treatment. Therefore, the production quality of the quercetin is unstable due to the lagged related production technology of the quercetin, and certain technical defects exist. The inventors sought a novel method for producing quercetin.
Disclosure of Invention
The invention aims to solve the technical defects existing in the prior production of the quercetin and provide a brand-new and easily controlled production process of the quercetin.
The production process of the quercetin provided by the invention is characterized in that: the production process comprises the following steps: feeding → hydrolysis → filtration → washing → refining.
Wherein, the parameters to be controlled in the above steps are as follows:
A. feeding: mixing inorganic strong acid with water to obtain an acid-water mixture, heating to boil, and adding rutin;
wherein, the feeding amount of rutin is as follows: adding 7-15L of acid water mixture into 1kg of rutin; h in acid-water mixtures+A concentration of 0.4 to 1mol/L (more preferably 0.5 to 1mol/L, still more preferably 0.7 to 1 mol/L); the inorganic strong acid can be hydrochloric acid or sulfuric acid. The liquid may be controlled to remain stirred for sufficient hydrolysis.
2. Hydrolysis: boiling for at least 1 hour; preferably, the boiling is kept for 2 to 3 hours, and the full hydrolysis can be realized.
3. And (3) filtering: and filtering the hydrolyzed solution, and reserving the filtrate for later use.
4. Washing: washing the filter cake obtained after filtering with water at 60-70 deg.C (preferably 70 deg.C), stopping washing until the pH value of the eluate is neutral, and drying to obtain crude quercetin filter cake; the temperature is controlled to remove water-soluble impurities.
5. Refining: adding the crude quercetin filter cake into 5-15 times of refined methanol, uniformly stirring, standing and filtering; washing the filter cake with 2-10 times of refined methanol, washing with 5-10 times of pure water until the filter cake is colorless and odorless, and drying to obtain a quercetin refined product.
The purity of the quercetin refined product obtained by the method can reach more than 95 percent, and the quercetin refined product is completely suitable for food and medicine raw materials.
During refining, 5-15 times of fine methanol is adopted for stirring a crude quercetin filter cake, and 2-10 times of fine methanol is adopted for washing the filter cake, so that the functions of: 1. the consumption of the methanol is saved, namely the cost is saved; 2. alcohol-soluble impurities can be removed. And finally washed with pure water to remove residual methanol.
The by-products obtained by the production process can be further utilized. Mainly utilizes the filtrate obtained by filtering in the step 3: neutralizing and decoloring the hot filtrate by using dry lime and activated carbon until the pH value of the filtrate is 7-8, standing, and filtering to obtain filtrate and filter residue; concentrating the filtrate until the specific gravity is 1.2-1.3. The concentrated filtrate obtained in the method can be used as syrup, and can also be used for preparing rhamnose; the filter residue obtained by filtering can be used for building construction.
The production process has the beneficial effects that:
1. the production process is green and environment-friendly, has no emission of any other harmful substances, and has no pollution compared with the prior process.
2. The production process is simple, easy to control, high in conversion rate and capable of greatly reducing cost.
3. The product obtained by the production process has high purity, and related impurities and bacteria reach the standard.
Detailed Description
The following description of specific embodiments of the invention illustrates, but does not limit, the invention.
The inventor tries to use rutin as raw material to produce quercetin by enzymolysis.
The process for producing the quercetin comprises the following steps: feeding → hydrolysis → filtration → washing → refining. Wherein:
1. feeding: mixing inorganic strong acid with water to obtain an acid-water mixture, heating to boil, and adding rutin;
wherein, the ratio of rutin is as follows: rutin 1kg, acid water mixture 7-15L (preferably rutin 1kg, acid water mixture 8-13L); h in acid-water mixtures+A concentration of 0.4 to 1mol/L (more preferably 0.5 to 1 mol/L); the inorganic strong acid can be hydrochloric acid or sulfuric acid. The liquid may be controlled to remain stirred for sufficient hydrolysis.
2. Hydrolysis: keeping boiling for 2-3 hours.
3. And (3) filtering: and filtering the hydrolyzed solution, and reserving the filtrate for later use.
4. Washing: washing the filter cake obtained after filtering with water at 60-70 deg.C (preferably 70 deg.C), stopping washing until the pH value of the eluate is neutral, and drying to obtain crude quercetin; the temperature is controlled between 60 ℃ and 70 ℃, and the temperature is preferably 70 ℃, so that water-soluble impurities in the water-soluble impurities can be filtered out more easily.
5. Refining: putting the crude quercetin into 5-15 times of refined methanol, uniformly stirring, standing and filtering; washing the filter cake with 2-10 times of refined methanol, washing with 5-10 times of pure water until colorless and odorless, and drying to obtain a quercetin refined product
The following is the experiment for screening and inspecting each parameter in the production process of the invention.
Test example 1 screening of charging conditions
In order to examine the influence of feeding conditions on the production process. The following 7 groups of quercetin were prepared separately by performing experiments using the orthogonal test method. The production was carried out under the feeding conditions shown in tables 1-1 and 1-2. Wherein:
hydrolysis: keeping boiling for 2-3 hours.
And (3) filtering: and filtering the hydrolyzed solution, and reserving the filtrate for later use.
Washing: washing the filter cake obtained after filtering with water at 60-70 deg.C until the pH value of the eluate is neutral, and drying to obtain crude quercetin filter cake.
Refining: putting the crude quercetin filter cake into 10 times of refined methanol, uniformly stirring, standing and filtering; washing the filter cake with 2 times of refined methanol, washing with 5-10 times of pure water until colorless and odorless, and drying to obtain a quercetin refined product.
TABLE 1-1 sulfuric acid feed conditions
| Rutin (kg) | Volume of acid water mixture (L) | Acid water mixture H+Concentration of | Purity of Quercetin | Yield of quercetin |
| 400 | 4880 | 0.616mol/L | 97.80％ | 48.3％ |
| 400 | 4270 | 0.616mol/L | 97.73％ | 48％ |
| 400 | 5660 | 0.398mol/L | 83.69％ | 53％ |
| 400 | 5680 | 0.528mol/L | 96.94％ | 48.5％ |
| 400 | 6480 | 0.463mol/L | 93.89％ | 51％ |
| 400 | 4080 | 0.736mol/L | 96.34％ | 48％ |
| 400 | 3280 | 0.916mol/L | 98.34％ | 47％ |
TABLE 1-2 hydrochloric acid charging conditions
| Rutin (kg) | Volume of acid water mixture (L) | Acid water mixture H+Concentration of | Purity of Quercetin | Yield of quercetin |
| 400 | 4960 | 0.624mol/L | 97.59％ | 48％ |
| 400 | 4340 | 0.624mol/L | 92.56％ | 48％ |
| 400 | 5120 | 0.382mol/L | 82.89％ | 53.5％ |
| 400 | 5760 | 0.540mol/L | 97.17％ | 48％ |
| 400 | 6560 | 0.474mol/L | 92.32％ | 50.4％ |
| 400 | 4160 | 0.744mol/L | 96.35％ | 48％ |
| 400 | 3360 | 0.918mol/L | 98.14％ | 47.3％ |
Tables 1-1 and 1-2 show that:
1. sulfuric acid and hydrochloric acid as H+The concentration of 0.4-1mol/L is prepared into acid water mixture, and the aim of preparing the quercetin can be achieved; when H is present+Concentration of 0.5-When the concentration is 1mol/L, the purity of the quercetin is more than 95 percent; when H is present+When the concentration is 0.6-1mol/L, the purity of the quercetin can reach 97%, even more than 98%.
2. The material amount of rutin is as follows: the obtained mixture of rutin and acid water 7-15L can be used for preparing quercetin, and quercetin with purity of at least 80% can be obtained. When 8-13L of acid water mixture is added into per 1kg of rutin, the purity of the quercetin can reach 95%, even more than 98%.
3. The comprehensive consideration of the cost and the product purity, the preferable rutin feeding amount during the production is as follows: adding 8-13L of acid water mixture into 1kg of rutin; h in acid-water mixtures+The concentration is 0.5-1 mol/L.
Test example 2 screening of hydrolysis conditions
In order to examine the influence of the hydrolysis conditions on the production process. The following 5 groups of quercetin were prepared separately by performing experiments using the orthogonal test method. The production was carried out according to the hydrolysis conditions of Table 2. Wherein:
feeding: adding rutin into boiling water, wherein the rutin feeding amount is as follows: adding 12L of acid-water mixture per 1kg rutin, and adding H in acid-water mixture+The concentration was 0.616 mol/L.
And (3) filtering: and filtering the hydrolyzed solution, and reserving the filtrate for later use.
Washing: washing the filter cake obtained after filtering with water at the temperature of 60-70 ℃, stopping washing until the pH value of the eluate is neutral, and drying to obtain a crude quercetin filter cake.
Refining: putting the crude quercetin filter cake into 5 times of refined methanol, stirring uniformly, standing, and filtering; washing the filter cake with 2 times of refined methanol, washing with 5-10 times of pure water until colorless and odorless, and drying to obtain a quercetin refined product.
TABLE 2 hydrolysis conditions
| Maintaining the boiling time (h) | Temperature of | Purity of Quercetin | Yield of quercetin |
| 1 | 100-110 | 94.45％ | 50％ |
| 2 | 100-110 | 97.43％ | 48％ |
| 3 | 100-105 | 96.95％ | 48％ |
| 4 | 100-120 | 97.03％ | 48％ |
| 5 | 100-110 | 97.47％ | 48％ |
And (3) displaying in a table:
1. boiling for 1 hour to obtain the purity of more than 90 percent.
2. The boiling time is the optimum value within 2-3 hours, and less than 2 hours, the hydrolysis is not sufficient, and the purity is less than 95%. The time is more than 3 hours, the purity of the product is not obviously increased, and energy is wasted.
Test example 3 screening of washing conditions
To investigate the effect of washing conditions on the production process. The following 5 groups of quercetin were prepared separately by performing experiments using the orthogonal test method. The production was carried out according to the washing conditions of Table 3: and washing the filter cake obtained after filtering with water at different temperatures until the pH value of the eluate is neutral, and stopping washing, wherein the filter cake is a crude quercetin product. Wherein:
feeding: adding rutin into boiling water, wherein the rutin feeding amount is as follows: adding 12L of acid-water mixture per 1kg rutin, and adding H in acid-water mixture+The concentration was 0.616 mol/L.
Hydrolysis: keeping boiling for 2-3 hours
And (3) filtering: and filtering the hydrolyzed solution, and reserving the filtrate for later use.
Refining: putting the crude quercetin filter cake into 5 times of refined methanol, stirring uniformly, standing, and filtering; washing the filter cake with 2 times of refined methanol, washing with 5-10 times of pure water until colorless and odorless, and drying to obtain a quercetin refined product.
TABLE 3 washing conditions
| Temperature of washing Water (. degree.C.) | Dry oakPurity of the skin extract | Sulfate residue in the product |
| 40 | 94.97％ | 850PPM |
| 50 | 95.08％ | 550PPM |
| 60 | 96.26％ | 450PPM |
| 70 | 97.54％ | 500PPM |
| 80 | 97.62％ | 300PPM |
It can be seen from the table that the washing water temperature below 60 deg.C can not remove water-soluble impurities and sulfate residues well, but the water temperature above 70 deg.C has no obvious effect of improving the quality, but increases the production cost. The optimal value is 60-70 degrees.
Test example 4 screening of purification conditions
In order to examine the influence of refining conditions on the production process. The following 7 groups of quercetin were prepared separately by performing experiments using the orthogonal test method. The production was carried out according to the refining conditions of Table 4: putting the crude quercetin filter cake into refined methanol with different times, stirring uniformly, standing, and filtering; washing the filter cake with refined methanol of different times, washing with pure water of 5-10 times until colorless and odorless, and drying to obtain a quercetin refined product. Wherein,
feeding: adding rutin into boiling water, wherein the rutin feeding amount is as follows: adding 12L of acid-water mixture per 1kg rutin, and adding H in acid-water mixture+The concentration was 0.616 mol/L.
Hydrolysis: keeping boiling for 2-3 hours.
And (3) filtering: and filtering the hydrolyzed solution, and reserving the filtrate for later use.
Washing: washing the filter cake obtained after filtering with water at 60-70 deg.C until the pH value of the eluate is neutral, and drying to obtain crude quercetin filter cake.
TABLE 4 refining conditions
The above data show that: the dissolving times of methanol are controlled to be 5-15 times (weight), and the washing times are controlled to be 2-10 times (weight), so that the purposes of effectively controlling product impurities and improving the product purity to be more than 95% can be achieved, and the use amount of methanol is increased and the cost is increased by more than the times; methanol is used for dissolution or washing, and even if the total multiple reaches the use amount, the effect is not ideal.
In conclusion, the production process is simple and feasible, the field process flow is convenient to modify, the feasibility is strong, the application prospect is wide, and a new production process is provided for preparing the quercetin.
Claims (8)
1. The production process of the quercetin is characterized by comprising the following steps: the steps are as follows
A. Feeding: mixing inorganic strong acid with water to obtain an acid-water mixture, heating to boil, and adding rutin;
wherein, the feeding amount of rutin is as follows: adding 7-15L of acid water mixture into 1kg of rutin; h in acid-water mixtures+The concentration is 0.4-1 mol/L;
B. hydrolysis: boiling for at least 1 hour;
C. and (3) filtering: filtering the hydrolyzed solution to obtain filtrate for later use;
D. washing: washing the filter cake obtained after filtering with water at 60-70 deg.C until the pH value of the eluate is neutral, and drying to obtain crude quercetin filter cake;
E. refining: adding the crude quercetin filter cake into 5-15 times of refined methanol, uniformly stirring, standing and filtering; washing the filter cake with 2-10 times of refined methanol, washing with 5-10 times of pure water until the filter cake is colorless and odorless, and drying to obtain a quercetin refined product.
2. The process for producing quercetin according to claim 1, wherein: the inorganic strong acid in the step A is hydrochloric acid and sulfuric acid.
3. The process for producing quercetin according to claim 1, wherein: and B, maintaining boiling for 2-3 hours in hydrolysis.
4. The process for producing quercetin according to claim 1, wherein: and D, washing a filter cake obtained after filtering in the step D by using water at the temperature of 70 ℃.
5. The process for the production of quercetin according to any one of claims 1-4, wherein: h in the acid-water mixture in the step A+The concentration is 0.5-1 mol/L.
6. The process of producing quercetin according to claim 5, wherein: h in the acid-water mixture in the step A+The concentration is 0.7-1 mol/L.
7. The process for the production of quercetin according to any one of claims 1-4, wherein: the material amount of rutin in the step A is as follows: adding acid water mixture 8-13L per 1kg rutin.
8. The process for the production of quercetin according to any one of claims 1-4, wherein: the material amount of rutin in the step A is as follows: adding 8-13L of acid water mixture into 1kg of rutin; h in acid-water mixtures+The concentration is 0.5-1 mol/L.
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Cited By (2)
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| CN103570663A (en) * | 2013-11-25 | 2014-02-12 | 广东众生药业股份有限公司 | Preparation method of high-purity quercetin |
| CN105671101A (en) * | 2016-03-17 | 2016-06-15 | 李军 | Method for producing quercetin with microorganisms |
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Cited By (3)
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| CN103570663A (en) * | 2013-11-25 | 2014-02-12 | 广东众生药业股份有限公司 | Preparation method of high-purity quercetin |
| CN103570663B (en) * | 2013-11-25 | 2015-08-26 | 广东众生药业股份有限公司 | A kind of preparation method of high-purity quercetin |
| CN105671101A (en) * | 2016-03-17 | 2016-06-15 | 李军 | Method for producing quercetin with microorganisms |
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Application publication date: 20120321 |