CN113501759A - Method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue - Google Patents
Method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue Download PDFInfo
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- CN113501759A CN113501759A CN202110936375.9A CN202110936375A CN113501759A CN 113501759 A CN113501759 A CN 113501759A CN 202110936375 A CN202110936375 A CN 202110936375A CN 113501759 A CN113501759 A CN 113501759A
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- stevia rebaudiana
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention belongs to the technical field of plant extraction, and particularly relates to a method for extracting chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue. A method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana bertoni waste residue mainly takes industrial production stevia rebaudiana bertoni flocculated waste residue as a raw material, after the stevia rebaudiana bertoni waste residue is dispersed by water, the pH value is adjusted to 3.0-4.0, and filtrate and filter residue are filtered and separated; filtering the filtrate with ceramic membrane and organic membrane in sequence to remove impurities, and drying to obtain chlorogenic acid; dissolving the residue with ethanol, filtering, collecting filtrate, concentrating under reduced pressure, recovering ethanol, extracting the extract with ethyl acetate, refining, and drying to obtain isochlorogenic acid. The method fully utilizes the industrial waste residue in the stevia rebaudiana production process, does not influence the stevioside production, simultaneously utilizes the waste residue to extract and separate chlorogenic acid and isochlorogenic acid, does not need to utilize resin to separate and purify in the whole production process, has simple operation, and is suitable for industrial mass production.
Description
Technical Field
The invention belongs to the technical field of plant extraction, and particularly relates to a method for extracting chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue.
Background
Stevia rebaudiana is native to subtropical regions in south America, and leaves of the stevia rebaudiana contain various low-calorie and high-sweetness stevioside; in the last 70 th century, stevia rebaudiana extracts are introduced and cultivated in China, and are widely used as sweeteners in food, beverage and other industries at home and abroad at present. In recent years, research in the field of medicine also finds that the stevia extract has various efficacies of antioxidation, anti-inflammation, blood sugar reduction, blood pressure reduction and the like, and the efficacies are more related to chlorogenic acids contained in the stevia.
Chlorogenic acid is depside produced from caffeic acid and quinic acid, and is a phenylpropanoid compound produced by plants in aerobic respiration process via shikimic acid pathway; the extract has multiple functional activities of resisting bacteria, resisting oxidation, inhibiting cancer, regulating glycolipid metabolism and the like, and the plant raw materials mainly selected for extracting and producing chlorogenic acid substances at present comprise honeysuckle, eucommia leaves or coffee beans and the like, and the raw materials have limited resources and higher production cost.
Modern researches have shown that chlorogenic acid substances in dry leaves of stevia rebaudiana Bertoni are as high as 52.69 mg/g-1The whole plant contains chlorogenic acid, isochlorogenic acid A and isochlorogenic acid C. In the conventional stevia extract production process, only the steviol glycosides in stevia are often obtained, but the chlorogenic acids in stevia are regarded as impurities, and the impurities are physically or chemically changed into precipitated waste residues for removal, which is definitely a waste of resources if the chlorogenic acids in the waste residues are not recovered.
Although partial technical data exist at present, methods for extracting and separating chlorogenic acid and stevioside in stevia rebaudiana are provided, most of the methods greatly change the traditional stevia rebaudiana process, and for enterprises which realize stevioside production, the change production process has high risk and long investment recovery period. On the basis of the traditional process, the extraction and recovery of chlorogenic acid substances in stevia flocculation waste residues have more practical significance, but the prior art method has less utilization of the stevia flocculation waste residues, and although the invention 201210421968.2 relates to a method for obtaining chlorogenic acid in stevia from the stevia flocculation waste residues, the stevia also contains a large amount of isochlorogenic acid which is not recycled due to the limitation of process conditions.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana industrial flocculation waste residue, which has the advantages of simple process flow, easy operation, low production cost and high product yield.
The purpose of the invention is realized by the following technical scheme:
a method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue comprises the following steps:
1) dispersing stevia waste residues with water, adjusting the pH value to 3.0-4.0, and filtering and separating filtrate and filter residues;
2) filtering the filtrate with ceramic membrane and organic membrane, removing impurities, and drying to obtain chlorogenic acid;
3) and continuously dispersing the filter residue with ethanol, filtering, collecting filtrate, concentrating under reduced pressure, recovering ethanol, extracting and refining the extract with ethyl acetate, and drying to obtain the isochlorogenic acid.
Preferably, the stevia rebaudiana residue of step 1) is a precipitate separated after flocculating an extract of stevia rebaudiana obtained by countercurrent extraction of stevia rebaudiana with hot water as a solvent.
Preferably, the flocculation is performed using any one of calcium oxide, calcium hydroxide, or a soluble calcium salt.
Preferably, the pH value is controlled to be 9-11 in the flocculation process.
Preferably, the pH is adjusted in step 1) by using any one of hydrochloric acid, sulfuric acid, and citric acid.
Preferably, the water consumption in the step 1) is 2-4 times of the mass of the stevia rebaudiana waste residue.
Preferably, the molecular weight cut-off of the organic membrane in the step 2) is 200-300, and the filtration pressure is 0.4-0.7 MPa.
Preferably, the ethanol concentration in the step 3) is 50 vt-95 vt%, the dosage is 2-5 times of the mass of the filter residue, the ethanol recovery pressure is 0.01-0.05 MPa, and the recovery temperature is 50-65 ℃.
Preferably, the volume ratio of the extract in the step 3) to the ethyl acetate is 1: 1-1: 3.
The invention has the following beneficial effects:
1. in the flocculation process of the stevia rebaudiana extract, the flocculation and filtration are carried out by utilizing the principle that calcium ions react with chlorogenic acid substances under alkaline conditions to generate insoluble precipitates to obtain flocculation waste residues containing chlorogenic acid calcium precipitates; the working procedure not only removes the chlorogenic acid and other impurities for the normal stevioside production by flocculation, but also provides a waste residue raw material for obtaining the chlorogenic acid and the isochlorogenic acid, thereby achieving multiple purposes.
2. The method utilizes the principle of replacing weak acid by strong acid, and uses acid (hydrochloric acid, sulfuric acid and citric acid) to regulate pH value to 3.0-4.0, so that chlorogenic acid substances in stevia flocculation waste residue can be effectively replaced, and the subsequent separation and purification work is facilitated.
3. The method utilizes the solubility difference of chlorogenic acid and isochlorogenic acid in water, ethanol and other solvents, realizes separation and purification by methods such as filtration, and is simple.
4. The method fully utilizes the industrial waste residue in the stevia rebaudiana production process, does not influence the stevioside production, simultaneously utilizes the waste residue to extract and separate chlorogenic acid and isochlorogenic acid, does not need to utilize resin to separate and purify in the whole production process, has simple operation, and is suitable for industrial mass production.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited to the scope of the examples. These examples are intended to illustrate the invention only and are not intended to limit the scope of the invention. In addition, various modifications may occur to those skilled in the art upon reading the present disclosure, and such equivalent variations are within the scope of the present invention as defined in the appended claims.
Example 1
Pulverizing dried leaves of sweet stevia (100 kg), and extracting with hot water as solvent under countercurrent to obtain sweet stevia extractive solution. Slowly adding calcium oxide into the stevia rebaudiana extractive solution for flocculation, and controlling pH to 10 during flocculation; after the pH value is stable, filtering and separating the flocculated clear liquid and the flocculated waste residues by using a plate-and-frame filter. Stirring the obtained 50kg of stevia flocculation waste residue, uniformly dispersing in 100kg of water, adjusting pH to 3.5 with hydrochloric acid, and separating filtrate and residue with plate and frame filter. Sequentially filtering and clarifying the filtrate rich in chlorogenic acid by a ceramic membrane, and filtering, concentrating and removing impurities by an organic membrane, wherein the molecular weight cut-off of the organic membrane is 250, and the membrane pressure is 0.4 MPa; drying the membrane concentrated solution to obtain 1.3kg of chlorogenic acid. Dispersing and dissolving the filter residue rich in the isochlorogenic acid by using 100kg of 50 vt% (percentage volume concentration) ethanol (the amount of the ethanol is 2 times of the mass of the filter residue containing the isochlorogenic acid), filtering to remove insoluble impurities, concentrating at 50 ℃ and 0.01MPa under reduced pressure and at low temperature to recover the ethanol, extracting and refining the concentrated extract by using 50L of ethyl acetate (the volume ratio of the extract to the ethyl acetate is 1:1), concentrating and recovering an ethyl acetate layer, and performing spray drying on the extract to obtain 3.4kg of isochlorogenic acid. The content of chlorogenic acid obtained by the above process is 55.4% and the content of isochlorogenic acid is 85.7% by HPLC determination.
Example 2
Pulverizing dried leaves of sweet stevia (100 kg), and extracting with hot water as solvent under countercurrent to obtain sweet stevia extractive solution. Slowly adding calcium hydroxide into the stevia extract for flocculation, and controlling the pH value to be 9 in the flocculation process; after the pH value is stable, filtering and separating the flocculated clear liquid and the flocculated waste residues by using a plate-and-frame filter. Stirring the obtained 50kg of stevia flocculation waste residue, uniformly dispersing in 150kg of water, adjusting pH to 3.0 with sulfuric acid, and separating filtrate and residue with plate and frame filter. Sequentially filtering and clarifying the filtrate rich in chlorogenic acid by a ceramic membrane, and filtering, concentrating and removing impurities by an organic membrane, wherein the molecular weight cut-off of the organic membrane is 300, and the membrane pressure is 0.5 MPa; drying the membrane concentrated solution to obtain 1.1kg chlorogenic acid. Dispersing and dissolving the filter residue rich in isochlorogenic acid with 100kg of 75 vt% ethanol (the amount of ethanol is 4 times of the mass of the filter residue), filtering to remove insoluble impurities, concentrating at 55 ℃ under reduced pressure under 0.02MPa to recover ethanol, extracting and refining the concentrated extract with 60L of ethyl acetate (the volume ratio of the extract to the ethyl acetate is 1:2), concentrating and recovering the ethyl acetate layer, and spray-drying the extract to obtain 3.3kg of isochlorogenic acid. The content of chlorogenic acid obtained by the above process is 57.4% and the content of isochlorogenic acid is 86.3% by HPLC determination.
Example 3
Pulverizing 1t dry leaf of sweet stevia, and extracting with hot water as solvent under countercurrent to obtain sweet stevia extractive solution. Slowly adding 50kg of calcium chloride into the stevia extract for flocculation, and controlling the pH value to be 11 by using sodium hydroxide in the flocculation process; after the pH value is stable, filtering and separating the flocculated clear liquid and the flocculated waste residues by using a plate-and-frame filter. Stirring the obtained 0.5t of flocculation waste residue of stevia rebaudiana Bertoni, uniformly dispersing in 2t of water, adjusting pH to 4.0 with citric acid, and separating filtrate and filter residue with plate and frame filter. Sequentially filtering and clarifying the filtrate rich in chlorogenic acid by a ceramic membrane, and filtering, concentrating and removing impurities by an organic membrane, wherein the molecular weight cut-off of the organic membrane is 200, and the membrane pressure is 0.7 MPa; drying the membrane concentrated solution to obtain 12.7kg of chlorogenic acid. Dispersing and dissolving the filter residue rich in isochlorogenic acid with 1t 95 vt% ethanol (the amount of ethanol is 5 times of the mass of the filter residue), filtering to remove insoluble impurities, concentrating at 65 ℃ under 0.05MPa under reduced pressure to recover ethanol, extracting and refining the concentrated extract with 800L ethyl acetate (the volume ratio of the extract to the ethyl acetate is 1:3), concentrating and recovering the ethyl acetate layer, and spray-drying the extract to obtain 35.7kg of isochlorogenic acid. The content of chlorogenic acid obtained by the above process is 56.8% and the content of isochlorogenic acid is 87.1% by HPLC determination.
Claims (9)
1. A method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue is characterized by comprising the following steps:
1) dispersing stevia waste residues with water, adjusting the pH value to 3.0-4.0, and filtering and separating filtrate and filter residues;
2) filtering the filtrate with ceramic membrane and organic membrane, removing impurities, and drying to obtain chlorogenic acid;
3) and continuously dispersing the filter residue with ethanol, filtering, collecting filtrate, concentrating under reduced pressure, recovering ethanol, extracting and refining the extract with ethyl acetate, and drying to obtain the isochlorogenic acid.
2. The method of claim 1, wherein the stevia rebaudiana residue of step 1) is a precipitate separated after flocculating an extract of stevia rebaudiana Bertoni obtained by countercurrent extraction of stevia rebaudiana Bertoni with water as a solvent.
3. The method of claim 2, wherein the flocculation is performed using any one of calcium oxide, calcium hydroxide, or a soluble calcium salt.
4. The method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue as claimed in claim 2 or 3, wherein pH is controlled at 9-11 during the flocculation process.
5. The method of claim 1, wherein step 1) comprises adjusting the pH with any one of hydrochloric acid, sulfuric acid, and citric acid.
6. The method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue as claimed in claim 1, wherein the amount of water used in step 1) is 2-4 times the mass of stevia rebaudiana residue.
7. The method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue as claimed in claim 1, wherein the molecular weight cut-off of the organic membrane in step 2) is 200-300, and the filtration pressure is 0.4-0.7 MPa.
8. The method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue as claimed in claim 1, wherein said ethanol concentration in step 3) is 50 vt% to 95 vt%, the amount of ethanol is 2 to 5 times of the mass of the residue, the ethanol recovery pressure is 0.01 to 0.05MPa, and the recovery temperature is 50 to 65 ℃.
9. The method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue as claimed in claim 1, wherein the volume ratio of the extract in step 3) to ethyl acetate is 1: 1-1: 3.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110936375.9A CN113501759A (en) | 2021-08-16 | 2021-08-16 | Method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue |
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| CN202110936375.9A CN113501759A (en) | 2021-08-16 | 2021-08-16 | Method for obtaining chlorogenic acid and isochlorogenic acid from stevia rebaudiana residue |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031499A (en) * | 2021-12-10 | 2022-02-11 | 桂林莱茵生物科技股份有限公司 | Method for obtaining high-purity isochlorogenic acid from stevia rebaudiana and application |
| CN115385794A (en) * | 2022-09-30 | 2022-11-25 | 上海理工大学 | Method for separating and extracting chlorogenic acid from polyest juice by utilizing tamarind polysaccharide adsorption |
-
2021
- 2021-08-16 CN CN202110936375.9A patent/CN113501759A/en active Pending
Non-Patent Citations (2)
| Title |
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| 赵磊等: "甜叶菊废渣提取物的主要成分分析及其抗氧化作用", 《食品科学》 * |
| 额尔敦巴雅尔等: "甜叶菊水提物和絮凝上清液成分差异研究", 《食品研究与开发》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031499A (en) * | 2021-12-10 | 2022-02-11 | 桂林莱茵生物科技股份有限公司 | Method for obtaining high-purity isochlorogenic acid from stevia rebaudiana and application |
| CN114031499B (en) * | 2021-12-10 | 2024-02-20 | 桂林莱茵生物科技股份有限公司 | Method for obtaining high-purity isochlorogenic acid from stevia rebaudiana and application |
| CN115385794A (en) * | 2022-09-30 | 2022-11-25 | 上海理工大学 | Method for separating and extracting chlorogenic acid from polyest juice by utilizing tamarind polysaccharide adsorption |
| CN115385794B (en) * | 2022-09-30 | 2023-06-02 | 上海理工大学 | Method for separating and extracting chlorogenic acid in multi-juice by utilizing tamarind polysaccharide adsorption |
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