CN106349074B - The method of microwave-assisted ultrasonic extraction fructus lycii Content of Chlorogenic Acid - Google Patents

The method of microwave-assisted ultrasonic extraction fructus lycii Content of Chlorogenic Acid Download PDF

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CN106349074B
CN106349074B CN201610762474.9A CN201610762474A CN106349074B CN 106349074 B CN106349074 B CN 106349074B CN 201610762474 A CN201610762474 A CN 201610762474A CN 106349074 B CN106349074 B CN 106349074B
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extraction
fructus lycii
chlorogenic acid
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CN106349074A (en
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潘泰安
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Ningxia Wolfberry Wolfberry Industry Ltd By Share Ltd
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/48Separation; Purification; Stabilisation; Use of additives
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/48Separation; Purification; Stabilisation; Use of additives
    • C07C67/56Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/732Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids

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Abstract

A kind of process of microwave-assisted ultrasonic extraction fructus lycii Content of Chlorogenic Acid, include the following steps: 1) pretreatment of raw material: raw material is the leftover bits and pieces in skin slag and dried fruit of lycium barbarum production after medlar fresh fruit juicing, it is dried to moisture≤12%, removal of impurities, Lowtemperaturepulverizer crushes, and fineness degree reaches >=40 mesh.2) extract: smashed fructus lycii raw material carries out the extraction of fructus lycii chlorogenic acid in microwave-assisted ultrasonic extraction tank, Extraction solvent is pure water, solid-liquid ratio 1:5-1:30 (m/v), pH 4-5, microwave frequency 800-1500MHz, ultrasonic frequency 30-50kHz, microwave extraction time 5-30min, ultrasonic wave extraction time 60-90min, is extracted 1 time by 30-50 DEG C of temperature.3) post-process: extracting solution passes through filtering and concentrating, and cryogenic vacuum drying bu sublimation smashes, and packs to get fructus lycii chlorogenic acid finished product.Present invention process is at low cost, high production efficiency, stable product quality, high financial profit.

Description

The method of microwave-assisted ultrasonic extraction fructus lycii Content of Chlorogenic Acid
Technical field
The present invention relates to a kind of extraction process of fructus lycii Content of Chlorogenic Acid, in particular to a kind of microwave-assisted ultrasonic extraction fructus lycii The method of Content of Chlorogenic Acid belongs to bioactive substance extractive technique field.
Background technique
Lycium barbarum is China's tradition rare medicinal herbs, has various pharmacology such as strengthen immunity, anti-oxidant, antitumor Effect.Zhang Ziping (Ningxia University professor) etc. shows Ningxia in " research of flavonoids from Lycium barbarum HPLC finger-print " Fructus lycii chlorogenic acid peak area is higher.The academic paper was published on " Chinese herbal medicine " 2008 the 1st phase of volume 39.Mountain is forever triumphant (researcher) 7.1g extract Content of Chlorogenic Acid can be mentioned by, which being determined in 1000g fructus lycii in " Study on extraction of fructus lycii Content of Chlorogenic Acid ", contains Amount is 32%.Enterprise can generate a large amount of fructus lycii defect ware (offal) when producing fructus lycii processing, can using defect ware fructus lycii Polysaccharides is extracted, the also extractable chlorogenic acid of the residue after extracting polysaccharides.
Chlorogenic acid (Chlorogenic acid, hereinafter referred to as CA) is by caffeic acid (Caffeic acid) and chinic acid The depside that (Quinic acid, 1-Hydroxyhexahydro gallic acid) condensation dehydration generates, is plant during aerobic respiration A kind of phenylpropanoids generated through shikimic acid pathway, molecular formula C16H18O9, molecular weight 345.30.Chlorogenic acid is anti- Bacterium, hemostasis, anti-inflammatory, cholagogue, the important source material for increasing white blood cell, antiviral drugs have effect as adrenin;Green original Acid has sensitization to people, after inhaling the plant dust that people contains chlorogenic acid, asthma, dermatitis etc. can occur, but can be through small after anthropophagy The effect of intestinal secretion object, becomes no allergenic substance;Chlorogenic acid has decompression and antitumor action: the Polyphenols in veterinary antibiotics Such as chlorogenic acid, caffeic acid can inhibit the mutagen of carcinogenic substance aflatoxin B and benzo [a] pyrene by inhibiting activating enzymes Property;Chlorogenic acid can also achieve the effect that anti-cancer, anticancer by the carcinogenic utilization rate of reduction and its transport in liver;It is green Ortho acid has kidney tonifying, diuresis, enhancing immunity of organism effect.Chlorogenic acid acts on than vitamin E, vitamin DDPH radicals scavenging C and caffeic acid are eager to excel, and DDPH free radical, hydroxyl radical free radical and ultra-oxygen anion free radical can be effectively removed.By hydrogen peroxide In the haemolysis Inhibition test of the mouse erythrocyte of induction, the inhibiting effect of more several organic Polyphenol Acids, with the suppression of chlorogenic acid It is most strong to make use.Effective removing of the chlorogenic acid to free radical, can maintain the normal structure and function of body cell, prevent and delay The generation of the pathologic, physiologics phenomenon such as tumour, mutation, aging.
Chlorogenic acid is the ester formed by caffeic acid and chinic acid, there is ester bond, unsaturated double-bond and polynary in molecular structure 3 unstable parts of phenol.During from plant extract, is migrated often through hydrolysis and intramolecular ester group and isomerization occurs. Due to the special construction of chlorogenic acid, determine that it can use ethyl alcohol, acetone, methanol isopolarity solvent and is extracted from plants out Come, but due to the unstability of chlorogenic acid itself, when extraction is unable to high temperature, Qiang Guang and long-time heating.Mountain is forever triumphant " in fructus lycii The Study on extraction of chlorogenic acid " (food carries out the technique for extracting fructus lycii Content of Chlorogenic Acid with mechanical, 2012-9-18) comprehensive Analysis and research, using ethyl alcohol as solvent, by test, are determined volume fraction of ethanol, solid-liquid ratio, mentioned using ultrasonic extraction Time, extraction time and pH value are taken, obtains chlorogenic acid optimum extraction parameter: volume fraction of ethanol 74%, solid-liquid ratio 1: 35 (m: V), extraction time 70min, extraction time be 3 times, pH value 4.2.Extracting solution is through macroporous resin purification, 1 000g fructus lycii In can mention 7.1g extract, extract Content of Chlorogenic Acid is 32%.Patent application 200910216294.0 discloses " a kind of The method of extracting chlorogenic acid from Chinese wolfberry ", which is characterized in that the method includes the following steps: 1) fructus lycii pre-treatment step Fructus lycii is set baking oven first and is dried, and is put into hothouse and is stood for 24 hours after taking-up, crushes and flow back in the common reflux unit of postposition Degreasing, filters out solvent, and residue air-dries spare.2) polysaccharides step is extracted using ethyl alcohol as solvent, using ultrasonic wave auxiliary law, is mentioned It takes liquid to pass through concentration, alcohol precipitation, drying, obtains polysaccharides coarse powder;Its process conditions are as follows: volume fraction of ethanol 60%, feed liquid Than for 1:30, extraction time 60min, extraction time is 3 times.3) residual after extracting fructus lycii chlorogenic acid step extraction polysaccharides Slag, using ethyl alcohol as solvent, ultrasonic wave auxiliary law extracts fructus lycii Content of Chlorogenic Acid, and macroreticular resin separate to institute's chlorogenic acid extracting pure To change, reversed-phase high performance liquid chromatography analyzes fructus lycii Content of Chlorogenic Acid: its process conditions are as follows: volume fraction of ethanol is 55%~ 85%, solid-liquid ratio is 1:25~1:40, and the pH value of solution is 3!5, extraction time is 30~110min, and extraction time is 2~4 It is secondary.Patent application 201410528464.X discloses " a method of separating chlorogenic acid is extracted in Chinese wolfberry fruit dregs from mentioning after oil ", It is characterized in that, it includes following operating procedure: (1) taking the Chinese wolfberry fruit dregs after mentioning oil, carried out using ethyl alcohol as entrainer overcritical Carbon dioxide abstraction, extract are spare;(2) by macroporous absorbent resin on supercritical carbon dioxide extracting extract, it is preferable to use (in addition macroreticular resin D140, HPD100, HPD300 AB-8, DM130, DM130 and ADS-17 can also be with for D101 type macroreticular resin It is applicable in), water, 10~15% (v/v) ethanol elutions are successively used, collects each alcohol elution respectively, is concentrated, it is dry to get green Ortho acid.
Summary of the invention
For fructus lycii chlorogenic acid in the prior art, complex process, material content are low during the extraction process, extract lytic activity Be not easy to retain, extract the technical problems such as yield is low, the present invention provide it is a kind of utilize microwave-assisted ultrasound assisted extraction technique, shorten and extract Time does not use chemical solvent, the fructus lycii chlorogenic acid novel technology for extracting for avoiding high temperature that chlorogenic acid is caused to decompose.What the technique was extracted Fructus lycii chlorogenic acid has high, at low cost, stable product quality the significant advantage of yield.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that.
A kind of process of microwave-assisted ultrasonic extraction fructus lycii Content of Chlorogenic Acid, includes the following steps:
1) pretreatment of raw material: raw material is the leftover bits and pieces in skin slag and dried fruit of lycium barbarum production after medlar fresh fruit juicing, drying To moisture≤12%, removal of impurities, Lowtemperaturepulverizer is crushed, and fineness degree reaches >=40 mesh.
2) extract: smashed fructus lycii raw material carries out the extraction of fructus lycii chlorogenic acid in microwave-assisted ultrasonic extraction tank, Extraction solvent is pure water, solid-liquid ratio 1:5-1:30 (m/v), pH 4-5, microwave frequency 800-1500 MHz, ultrasonic frequency 30-50kHz, microwave extraction time 5-30min, ultrasonic wave extraction time 60-90min, are extracted 1 time by 30-50 DEG C of temperature.
3) post-process: extracting solution passes through filtering and concentrating, and cryogenic vacuum drying bu sublimation smashes, and packs green to get fructus lycii Ortho acid finished product.
It further, at least 80% is the leftover bits and pieces in dried fruit of lycium barbarum production in the raw material, it is broken including fructus lycii Grain, adhesion fruit, fallen fruits, oily fruit etc..
Further, the removal of impurities includes: to remove raw material after drying through electrostatic hair place to go machine, metal detector It is miscellaneous.
Further, smashed raw material can first impregnate 1-2h, soaking temperature control before extraction in pure water At 30-50 DEG C.
Further, the filtering and concentrating includes: to carry out coarse filtration through plate and frame filter, is then filtered through molecular film dense Contracting;Further, the molecular film is preferably the PS ultrafiltration membrane of transit dose 200-500 molecular equivalency.
The fructus lycii chlorogenic acid finished product of above-mentioned process production is produced according to labeling after enterprise's production standard test qualification, qualification Product items physical and chemical index is as follows.
1, organoleptic indicator: product sensory index should meet the requirement of table 1.
1 organoleptic indicator of table
Project Index
Color Canescence
Flavour and smell With the due flavour of fructus lycii chlorogenic acid and smell, free from extraneous odour
Character It is powdered
Impurity The exogenous impurity being visible by naked eyes
2, microbiological indicator: product microbiological indicator should meet the requirement of table 2.
2 microbiological indicator of table
3, product marking ingredient: chlorogenic acid >=30%.
Extraction process production fructus lycii chlorogenic acid product of the present invention meets company standard, and stable product quality has decompression, resists It the effects of tumour, kidney tonifying, enhancing immunity of organisms, anti-aging, anti-muscle skeleton aging, antibacterial, antiviral, antibacterial anti-inflammatory, can It is widely applied in food, health care product, medicine and other fields.
The utility model has the advantages that
1, the present invention is applied to the extraction of fructus lycii chlorogenic acid, extraction efficiency using microwave-assisted ultrasonic wave extraction for the first time Height, the extraction yield of fructus lycii chlorogenic acid is up to 85% or more;
2, Extraction solvent is pure water, solvent-free pollution, economical environment-protective;
3, Extracting temperature is low, is effectively retained the physiological activator of fructus lycii Content of Chlorogenic Acid.
4, process costs are low, high production efficiency, stable product quality, high financial profit, have been formed and produced 1000 kilograms per year Fructus lycii chlorogenic acid industrialization production line.
Detailed description of the invention
Fig. 1: fructus lycii chlorogenic acid extraction process flow chart in specific embodiment;
Fig. 2: influence of the solid-liquid ratio to chlorogenic acid yield;
Fig. 3: influence of the extraction time to chlorogenic acid yield;
Fig. 4: the pH influence to chlorogenic acid yield.
Specific embodiment
Below by specific embodiment, it is further discussed below the present invention.Unless stated otherwise, it is not described in embodiment Technological means can be realized with mode known in those skilled in the art.In addition, embodiment be interpreted as it is illustrative , the range being not intended to limit the present invention, the spirit and scope of the invention are limited only by the claims that follow.For art technology For personnel, under the premise of without departing substantially from spirit and scope of the present invention, to material component, dosage, the ruler in these embodiments Very little, shape progress various modifications, replacement, improvement also belong to protection scope of the present invention, and specific defined by the present invention Parameter should have admissible error range.
Embodiment 1
A kind of process of microwave-assisted ultrasonic extraction fructus lycii Content of Chlorogenic Acid, includes the following steps:
1) pretreatment of raw material: raw material is the leftover bits and pieces in skin slag and dried fruit of lycium barbarum production after medlar fresh fruit juicing, drying To moisture≤12%, removal of impurities, Lowtemperaturepulverizer is crushed, and fineness degree reaches >=40 mesh.
2) extract: smashed fructus lycii raw material carries out the extraction of fructus lycii chlorogenic acid in microwave-assisted ultrasonic extraction tank, Extraction solvent is pure water, solid-liquid ratio 1:5-1:30 (m/v), pH 4-5, microwave frequency 800-1500 MHz, ultrasonic frequency 30-50kHz, microwave extraction time 5-30min, ultrasonic wave extraction time 60-90min, 30-50 DEG C of temperature.
3) post-process: extracting solution is through carrying out coarse filtration through plate and frame filter, then through molecular film filtering and concentrating, cryogenic vacuum Drying bu sublimation smashes, and aseptic packaging is to get fructus lycii chlorogenic acid finished product.
It further, at least 80% is the leftover bits and pieces in dried fruit of lycium barbarum production in the raw material, it is broken including fructus lycii Grain, adhesion fruit, fallen fruits, oily fruit etc..
Further, smashed raw material can first impregnate 1-2h, soaking temperature control before extraction in pure water At 30-50 DEG C.
The yield of fructus lycii chlorogenic acid is extracted in present embodiment up to 85%.Active ingredient chlorogenic acid content reaches in detection finished product 30%.
Embodiment 2
(Fig. 1 process flow chart is referred to) in one provided by the invention preferable embodiment, it is a kind of microwave-assisted super Sound extracts the process of fructus lycii Content of Chlorogenic Acid, includes the following steps:
1) pretreatment of raw material: raw material be medlar fresh fruit juicing after skin slag and dried fruit of lycium barbarum production in leftover bits and pieces (at least It accounting for 80%), is dried to moisture≤12%, clean through electrostatic hair place to go machine, metal detector, Lowtemperaturepulverizer crushes, Fineness degree reaches >=40 mesh.
2) extract: smashed fructus lycii raw material first impregnates 1h in pure water, and soaking temperature is controlled at 30-50 DEG C;Then The extraction of fructus lycii chlorogenic acid is carried out in microwave-assisted ultrasonic extraction tank, Extraction solvent is pure water, preferred process conditions: Microwave Extraction power be 900 MHz, ultrasonic wave extraction power be 40 kHz, solid-liquid ratio 1:15 (m/v), 45 DEG C of Extracting temperature, pH Value 4-5, microwave extraction time 20min, ultrasonic wave extraction time 90min, extraction time 1 time.
3) post-process: extracting solution is through carrying out coarse filtration through plate and frame filter, then through transit dose 200-500 molecular equivalency The concentration of PS ultrafiltration membrance filter, cryogenic vacuum drying bu sublimation smash, and aseptic packaging is to get fructus lycii chlorogenic acid finished product.
Chlorogenic acid extracting yield is 86.3% under present embodiment process conditions.Active ingredient chlorogenic acid contains in detection finished product Amount is 30.2%.
Embodiment 3
The optimization of chlorogenic acid extracting factor is analyzed.
(1) influence of the solid-liquid ratio to chlorogenic acid yield
As shown in Figure 2, solid-liquid ratio has large effect to chlorogenic acid yield.When solid-liquid ratio is less than 1:20 (m/v), green original Sour yield is constantly in the trend of rising, and when solid-liquid ratio is greater than 1:20 (m/v), yield highest becomes in slowly decline later Gesture.When illustrating that aqueous solvent additive amount increases, effective component is conducive to dissolve out in a solvent, improves yield.When solid-liquid ratio reaches When 1:20 (m/v), the solvability of possible chlorogenic acid has reached maximum, therefore selects solid-liquid ratio for 1:15 (m/v), dense in this way Contracting, drying are both economical.
(2) influence of the extraction time to chlorogenic acid yield
From the figure 3, it may be seen that chlorogenic acid, when extracting 40-100min, yield is in slow growth trend, but increasing degree is not Greatly, therefore, it is considered that extraction time is smaller on the influence of chlorogenic acid yield.The factors such as comprehensive extraction efficiency, economic cost consider, select Extraction time is that 90 min are preferable.
(3) influence of the pH to chlorogenic acid yield
As shown in Figure 4, the variation of pH value is affected to the extraction of chlorogenic acid, this is with chlorogenic acid sheet as a kind of organic acid It is related.Ionization, hydrolysis may occur for the advantageous extraction in chlorogenic acid of acid condition, alkaline condition next part chlorogenic acid, can The yield of chlorogenic acid can be caused to decline.When the pH value of solution is about 4~5, chlorogenic acid yield is relatively high.
(4) PS, PAN, PVDF ultrafiltration effect compare
For PS, PAN, PVDF (Vingon) film that molecular cut off is 10000 to 100 kg feed liquid ultrafiltration lh, measurement is super With soluble solids content after ultrafiltration before filter, experiments have shown that the decaying of PS film is slower, stain resistance is strong, and pvdf membrane decaying is very fast, It is preferable to use PS films in technique.

Claims (4)

1. a kind of process of microwave-assisted ultrasonic extraction fructus lycii Content of Chlorogenic Acid, which comprises the steps of:
1) pretreatment of raw material: raw material is the leftover bits and pieces in skin slag and dried fruit of lycium barbarum production after medlar fresh fruit juicing, wherein at least 80% is the leftover bits and pieces in dried fruit of lycium barbarum production, is dried to moisture≤12%, is removed through electrostatic hair removing machine, metal detector Miscellaneous, Lowtemperaturepulverizer crushes, and fineness degree reaches >=40 mesh;
2) extract: smashed fructus lycii raw material first impregnates 1-2h in pure water, and soaking temperature controls at 30-50 DEG C, then exists The extraction of fructus lycii chlorogenic acid is carried out in microwave-assisted ultrasonic extraction tank, Extraction solvent is pure water, process conditions: feed liquid weight Volume ratio 1:15, pH 4-5, microwave frequency 800-1500 MHz, ultrasonic frequency 30-50kHz, microwave extraction time 5- 30min, ultrasonic wave extraction time 60-90min, are extracted 1 time by 30-50 DEG C of temperature;
3) post-process: extracting solution passes through filtering and concentrating, and cryogenic vacuum drying bu sublimation smashes, and packs to get fructus lycii chlorogenic acid Finished product;The filtering and concentrating includes: to carry out coarse filtration through plate and frame filter, then through molecular film filtering and concentrating.
2. a kind of process of microwave-assisted ultrasonic extraction fructus lycii Content of Chlorogenic Acid as described in claim 1, which is characterized in that Leftover bits and pieces in the dried fruit of lycium barbarum production includes the broken kernel of fructus lycii, adhesion fruit, fallen fruits, oily fruit.
3. a kind of process of microwave-assisted ultrasonic extraction fructus lycii Content of Chlorogenic Acid as described in claim 1, which is characterized in that The process conditions of extraction are as follows: Microwave Extraction frequency is 900 MHz, and ultrasonic wave extraction frequency is 40 kHz, feed liquid w/v 1:15,45 DEG C of Extracting temperature, pH value 4-5, microwave extraction time 20min, ultrasonic wave extraction time 90min, extraction time 1 time.
4. a kind of process of microwave-assisted ultrasonic extraction fructus lycii Content of Chlorogenic Acid as described in claim 1, which is characterized in that The molecular film is the PS ultrafiltration membrane of transit dose 200-500 molecular equivalency.
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CN108586241B (en) * 2018-01-17 2021-03-05 浙江树人学院 Method for extracting and separating chlorogenic acid of sweet potato leaves by ultrasonic-microwave-aqueous two-phase cooperation
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