CN104387357A - Quercetin production technology - Google Patents
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- CN104387357A CN104387357A CN201410532829.6A CN201410532829A CN104387357A CN 104387357 A CN104387357 A CN 104387357A CN 201410532829 A CN201410532829 A CN 201410532829A CN 104387357 A CN104387357 A CN 104387357A
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- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 title claims abstract description 166
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 title claims abstract description 83
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 title claims abstract description 83
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 235000005875 quercetin Nutrition 0.000 title claims abstract description 83
- 229960001285 quercetin Drugs 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 238000005516 engineering process Methods 0.000 title abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000005406 washing Methods 0.000 claims abstract description 53
- 238000001914 filtration Methods 0.000 claims abstract description 39
- IKGXIBQEEMLURG-BKUODXTLSA-N rutin Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@@H]1OC[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-BKUODXTLSA-N 0.000 claims abstract description 35
- JMGZEFIQIZZSBH-UHFFFAOYSA-N Bioquercetin Natural products CC1OC(OCC(O)C2OC(OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5)C(O)C2O)C(O)C(O)C1O JMGZEFIQIZZSBH-UHFFFAOYSA-N 0.000 claims abstract description 33
- IVTMALDHFAHOGL-UHFFFAOYSA-N eriodictyol 7-O-rutinoside Natural products OC1C(O)C(O)C(C)OC1OCC1C(O)C(O)C(O)C(OC=2C=C3C(C(C(O)=C(O3)C=3C=C(O)C(O)=CC=3)=O)=C(O)C=2)O1 IVTMALDHFAHOGL-UHFFFAOYSA-N 0.000 claims abstract description 33
- FDRQPMVGJOQVTL-UHFFFAOYSA-N quercetin rutinoside Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 FDRQPMVGJOQVTL-UHFFFAOYSA-N 0.000 claims abstract description 33
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000005493 rutin Nutrition 0.000 claims abstract description 33
- 229960004555 rutoside Drugs 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 230000007062 hydrolysis Effects 0.000 claims abstract description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000007670 refining Methods 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 81
- 239000012065 filter cake Substances 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000009835 boiling Methods 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000009965 odorless effect Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 4
- 241000894006 Bacteria Species 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 230000002860 competitive effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 1
- 208000002249 Diabetes Complications Diseases 0.000 description 1
- 206010012655 Diabetic complications Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- OVSQVDMCBVZWGM-IDRAQACASA-N Hirsutrin Natural products O([C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1)C1=C(c2cc(O)c(O)cc2)Oc2c(c(O)cc(O)c2)C1=O OVSQVDMCBVZWGM-IDRAQACASA-N 0.000 description 1
- FVQOMEDMFUMIMO-UHFFFAOYSA-N Hyperosid Natural products OC1C(O)C(O)C(CO)OC1OC1C(=O)C2=C(O)C=C(O)C=C2OC1C1=CC=C(O)C(O)=C1 FVQOMEDMFUMIMO-UHFFFAOYSA-N 0.000 description 1
- 206010062717 Increased upper airway secretion Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- SHZGCJCMOBCMKK-JFNONXLTSA-N L-rhamnopyranose Chemical compound C[C@@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O SHZGCJCMOBCMKK-JFNONXLTSA-N 0.000 description 1
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 description 1
- 206010058156 Reperfusion arrhythmia Diseases 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 235000019606 astringent taste Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 210000004351 coronary vessel Anatomy 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000000916 dilatatory effect Effects 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 208000028867 ischemia Diseases 0.000 description 1
- OVSQVDMCBVZWGM-QCKGUQPXSA-N isoquercetin Natural products OC[C@@H]1O[C@@H](OC2=C(Oc3cc(O)cc(O)c3C2=O)c4ccc(O)c(O)c4)[C@H](O)[C@@H](O)[C@@H]1O OVSQVDMCBVZWGM-QCKGUQPXSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000003859 lipid peroxidation Effects 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- OVSQVDMCBVZWGM-QSOFNFLRSA-N quercetin 3-O-beta-D-glucopyranoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C(C=2C=C(O)C(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O OVSQVDMCBVZWGM-QSOFNFLRSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention belongs to the field of plant extraction and relates to a quercetin production technology utilizing rutin as a raw material. The quercetin production technology solves the problems of the existing quercetin production technology, is a bran-novel and easily-controllable quercetin production technology and comprises the following steps of material feeding, hydrolysis, filtration, washing and refining. The quercetin production technology realizes preparation of the high-purity quercetin competitive product by main control of fed material acid-water mixture acidity, rutin feeding amount, hydrolysis time , washing temperature, and reagents and use amounts in refining. The quercetin production technology has simple processes, can be controlled easily, has a high conversion rate and greatly reduces a cost. The quercetin production technology has high product purity and satisfies related impurity and bacterium standards. Compared with the prior art, the quercetin production technology is environmentally friendly, does not discharge any other harmful substances and provides a novel production technology of quercetin.
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,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+When the concentration is 0.5-1mol/L, the purity of the quercetin is more than 95 percent; when H is present+The quercetin has purity of 0.6-1mol/LCan reach 97 percent, even more than 98 percent.
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.) | Purity of Quercetin | 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 (6)
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 8-13L of acid water mixture into 1kg of rutin; h in acid-water mixtures+The concentration is 0.5-1 mol/L:
B. hydrolysis: boiling for 2-3 hours;
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 60-80 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 5-20 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 refined quercetin 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 D, washing a filter cake obtained after filtering in the step D with water at the temperature of 80 ℃.
4. The process for producing quercetin according to claim 1, wherein: in the step E, the crude quercetin filter cake is put into 10-20 times of refined methanol, stirred uniformly, stood and filtered; washing the filter cake with 0-10 times of refined methanol, washing with 10 times of pure water until the filter cake is colorless and odorless, and drying to obtain a quercetin refined product.
5. The process for producing quercetin according to claim 1, wherein: in the step E, the crude quercetin filter cake is put into 20 times of refined methanol, stirred uniformly, stood and filtered; washing the filter cake with 10 times of refined methanol, washing with 10 times of pure water until colorless and odorless, and drying to obtain refined quercetin.
6. The process of producing quercetin according to claim 1, characterized by the steps of:
A. feeding: adding rutin into boiling water, wherein the rutin feeding amount is as follows: per 1kg of rutinAcid Water mixture 12L, H in acid-Water mixture+The concentration is 0.616 mol/L;
B. hydrolysis: keeping boiling for 2-3 hours;
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: putting the crude quercetin filter cake into 20 times of refined methanol, stirring uniformly, standing, and filtering; washing the filter cake with 10 times of refined methanol, washing with 10 times of pure water until colorless and odorless, and drying to obtain refined quercetin.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111333602A (en) * | 2020-04-16 | 2020-06-26 | 四川迪菲特药业有限公司 | Recovery and conversion process of waste mother liquor in troxerutin production |
| CN113185485A (en) * | 2021-05-10 | 2021-07-30 | 合肥立方制药股份有限公司 | Semi-synthesis method of dihydroquercetin |
| US11753389B2 (en) | 2021-05-10 | 2023-09-12 | Hefei Lifeon Pharmaceutical Co., Ltd. | Method for preparing dihydroquercetin |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333602A (en) * | 2020-04-16 | 2020-06-26 | 四川迪菲特药业有限公司 | Recovery and conversion process of waste mother liquor in troxerutin production |
| CN111333602B (en) * | 2020-04-16 | 2022-12-16 | 四川协力制药股份有限公司 | Recovery and conversion process of waste mother liquor in troxerutin production |
| CN113185485A (en) * | 2021-05-10 | 2021-07-30 | 合肥立方制药股份有限公司 | Semi-synthesis method of dihydroquercetin |
| CN113185485B (en) * | 2021-05-10 | 2022-03-04 | 合肥立方制药股份有限公司 | Semi-synthesis method of dihydroquercetin |
| US11753389B2 (en) | 2021-05-10 | 2023-09-12 | Hefei Lifeon Pharmaceutical Co., Ltd. | Method for preparing dihydroquercetin |
| US11878963B2 (en) | 2021-05-10 | 2024-01-23 | Hefei Lifeon Pharmaceutical Co., Ltd. | Semi synthetic method for dihydroquercetin |
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