CN111793099B - Method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter orange - Google Patents
Method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter orange Download PDFInfo
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Abstract
The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges comprises the following steps: (1) heating and leaching; (2) separating hesperidin; (3) separating neohesperidin; (4) separating naringin; (5) and (4) separating synephrine. The four products obtained by the method have higher purity and extraction rate; wherein the content of hesperidin can reach as high as 99.54%, and the extraction rate is 98.29%; the highest content of neohesperidin can reach 99.68%, and the extraction rate is 97.98%; the highest naringin content can reach 97.17%, and the extraction rate is 95.91%; the highest content of synephrine reaches 92.33 percent, and the extraction rate is 97.26 percent; the method realizes the comprehensive utilization of the immature bitter oranges and improves the added value of the immature bitter oranges on the premise of ensuring the extraction rate and the product content; the method has the advantages of simple and easy operation, low cost of the adopted solvent, no toxicity, no harm and low requirement on production equipment, and is suitable for industrial production.
Description
Technical Field
The invention relates to a method for extracting active ingredients from immature bitter oranges, in particular to a method for extracting hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges.
Background
The fructus Aurantii Immaturus is Rutaceae plant Citrus aurantium L and its cultivar or dried young fruit of Citrus sinensis Osbeck, is spherical or hemispherical, hard in texture, fragrant in smell, sour in taste, slightly bitter, mainly produced in Sichuan, Hunan, Hubei, Jiangxi, etc., and has effects of resolving qi, resolving food stagnation, eliminating phlegm, dispersing pathogenic accumulation, etc., and its main active ingredients include flavonoids (hesperidin, neohesperidin, naringin, etc.) and alkaloids (synephrine, N-methyltyramine, etc.).
Hesperidin has a dihydroflavonoxyglycoside structure, has important effects on maintaining osmotic pressure, enhancing toughness of capillary vessels, shortening bleeding time and reducing cholesterol, is mainly used as a medicine for preventing and treating arteriosclerosis and myocardial infarction, and is one of main raw materials of an adult medicine, namely 'Maitong'. Can be used as natural antioxidant in food industry, and can also be used in cosmetic industry.
Neohesperidin has the functions of treating capillary fragility and plasma protein permeability, is called vitamin or vitamin P for maintaining capillary permeability, is hydrogenated to form neohesperidin dihydrochalcone with sweetness about 1000 times that of cane sugar, is one new kind of non-toxic low calorie high sweetness sweetening agent, and may be used as flavor modifier in food. Because the neohesperidin has better heat resistance and acid resistance and is more stable in the sterilization and processing processes of the food, the neohesperidin can be widely applied to thermally processed food.
Naringin is a dihydroflavonoids compound, has the effects of resisting oxidation, resisting tumor, inhibiting bacteria, reducing capillary fragility and the like, can be used as an antioxidant to be applied to food, and can also be used for synthesizing novel dihydrochalcone sweeteners.
Synephrine (Synephrine), also known as parahydroxyfolin, has the effects of contracting blood vessels, raising blood pressure, dilating trachea and bronchus, and is clinically used for improving symptoms of bronchial asthma, hypotension, collapse, shock, orthostatic hypotension and the like in the operation and anesthesia process. Meanwhile, synephrine also has the effects of improving metabolism, increasing calorie consumption, improving energy level, oxidizing fat, losing weight and the like. With the research, the application field of synephrine is gradually widened, and the synephrine also shows great application potential in the industries of functional foods, beverages and other health care products.
CN104230871A discloses a method for separating polymethoxylated flavone, hesperidin and synephrine in immature bitter orange, which specifically comprises the steps of taking immature bitter orange as a raw material, extracting with ethanol, adsorbing with resin, eluting with ethanol and ammonia water respectively, concentrating, drying and the like to obtain synephrine products with the content of more than 28% and the yield of more than 50% and hesperidin products with the content of more than 93% and the yield of more than 70%; the method can only obtain synephrine and hesperidin, the yield is not high, and the obtained synephrine has low purity.
CN105481920A discloses a method for extracting hesperidin, neohesperidin and synephrine, which specifically comprises the steps of taking immature bitter orange and citrus peel as raw materials, carrying out percolation extraction by using an ethanol water solution, carrying out enzymolysis by using pectinase, carrying out alkali extraction and acid adjustment on filter residues, then recrystallizing and drying to obtain an hesperidin sample with the content of 98% and the yield of 8.8%; adsorbing the filtrate by a cation column and a macroporous adsorption resin column, and then carrying out gradient elution, recrystallization and drying by using ethanol to obtain a neohesperidin sample with the content of 98% and the yield of more than 5.3%; adjusting the acid of the filtrate, adsorbing the filtrate by a macroporous adsorption resin column and a cation column, eluting the filtrate by ammonia water, recrystallizing and drying the filtrate to obtain a synephrine product with the content of 98 percent and the yield of more than 2.1 percent; the method can not obtain naringin, needs biological preparation, and has complicated operation and low yield.
CN106220698A discloses a method for separating high-purity hesperidin, neohesperidin, naringin and synephrine from immature bitter orange, which comprises the following steps in sequence: (1) enzymolysis, (2) extraction, (3) membrane separation, (4) synephrine separation, (5) naringin separation, (6) neohesperidin separation, and (7) hesperidin separation; the method needs biological agents and relatively complex nanofiltration membrane equipment, has high cost and ensures that the yield of the synephrine is less than 90 percent.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter orange, which can separate and extract various effective active ingredients in immature bitter orange, has low requirements on production equipment, low cost and high extraction rate.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges comprises the following steps:
(1) heating and leaching: pulverizing fructus Aurantii Immaturus, sieving, extracting with hot water, cooling, filtering with fine filter membrane, and collecting extractive solution and residue respectively;
(2) separating hesperidin: adding a dilute alkali solution into the extraction residue obtained in the step (1), stirring, centrifuging, filtering, adjusting the filtrate to be acidic by hydrochloric acid, standing for crystallization, performing reduced pressure suction filtration, and performing vacuum drying to obtain a hesperidin product;
(3) and (3) separating neohesperidin: passing the extracting solution obtained in the step (1) through macroporous adsorption resin, and collecting effluent liquid for later use; desorbing the macroporous adsorption resin by using an ethanol solution to obtain a desorption solution I; concentrating the desorption solution I under reduced pressure, and spray drying to obtain dry powder I; washing the dry powder I with pure water at room temperature to obtain washing mother liquor and insoluble substances; drying the insoluble substance to obtain neohesperidin product;
(4) and (3) separating naringin: carrying out reduced pressure concentration and vacuum drying on the washing mother liquor obtained in the step (3) to obtain washing mother liquor dry powder; refining with organic solvent and pure water in sequence to obtain naringin product;
(5) and (3) separating synephrine: enabling the effluent liquid obtained in the step (3) to pass through cation exchange resin, and desorbing the cation exchange resin by using ammonia water to obtain desorption liquid II; concentrating the desorption solution II under reduced pressure to obtain synephrine extract; dissolving synephrine extract in water, adding active carbon, stirring for decolorizing, vacuum filtering, adjusting pH to neutral, standing at low temperature for crystallization, vacuum filtering, and vacuum drying to obtain synephrine product.
Preferably, in the step (1), the sieve is a 20-40 mesh sieve.
Preferably, in the step (1), the leaching times are 3-4 times, and the time of single leaching is 1-2 hours.
Preferably, in the step (1), the total mass of the hot water is 30-40 times of the mass of the immature bitter orange, and the temperature of the hot water is 80-95 ℃.
Preferably, in the step (2), the dilute alkali solution is a sodium hydroxide solution with a concentration of 0.5-2 wt%, a potassium hydroxide solution with a concentration of 1-3 wt% or a saturated lime water solution, and the mass of the dilute alkali solution is 15-25 times of that of the raw materials; the temperature of the stirring system is 30-50 ℃; the stirring time is 1-4 h.
Preferably, in the step (2), hydrochloric acid is used for adjusting the pH value to 2-6; more preferably 3 to 5.
Preferably, in the step (3), the macroporous adsorption resin is a D101 resin.
Preferably, in the step (3), the volume concentration of the ethanol solution is 65-75%, and the using amount is 2-3 BV.
Preferably, in the step (3), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 70 to 80 ℃.
Preferably, in the step (3), the mass of the pure water in the washing process is 15-25 times of that of the dry powder I; the inventors have found that this amount of water is such as to dissolve naringin, while leaving the major part of neohesperidin in the insoluble material.
Preferably, in the step (4), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 75-85 ℃.
Preferably, in the step (4), the organic solvent is an ethanol solution or a methanol solution, and the volume concentration is 10-40%, and more preferably 15-30%; the mass of the washing mother liquor is 2-5 times of that of the washing mother liquor dry powder, and more preferably 3-4 times; the mass of the pure water is 2-6 times of that of the washing mother liquor dry powder, and more preferably 2.5-4.5 times.
Preferably, in the step (4), the dry powder of the washing mother liquor is firstly dissolved in an organic solvent at the temperature of 70-85 ℃ during refining, then the temperature is reduced to room temperature, a crude crystal product is obtained, then the crude crystal product is dissolved in pure water at the temperature of 80-90 ℃, the temperature is reduced to room temperature, and crystals are obtained; the solubility of naringin greatly changes with temperature, and the inventor finds that the refining effect is good by adopting the mode through research.
Preferably, in the step (5), the cation exchange resin is 732, D001 or D061 resin, and the ammonia water has a concentration of 1-5 wt% and is used in an amount of 1.5-2.5 BV.
Preferably, in the step (5), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 65 to 75 ℃; the mass of the water is 3-8 times of that of the synephrine extract, and the crystallization temperature is 2-10 ℃.
The principle of the invention is as follows: the neohesperidin, the naringin and the synephrine in the immature bitter orange can be leached out by hot water leaching, and meanwhile, water-soluble impurities are removed, so that the extraction of the hesperidin is facilitated. The hesperidin in the hot water extraction residue is insoluble in hot water and easily soluble in alkaline water, the hesperidin chalcone which is easily soluble in water is generated by ring opening at first under an alkaline condition, the hesperidin chalcone in the filtrate is subjected to ring closing under an acidic condition by adjusting acid to generate hesperidin with poor water solubility, the hesperidin is separated out from an acidic solution, and the filter cake is the hesperidin product after filtering. The macroporous adsorption resin can adsorb neohesperidin, naringin and other substances in the water extract, but does not adsorb synephrine, thereby playing a role in reducing flavonoid components in synephrine products. Because the synephrine in the immature bitter orange has the amphiphilic structure characteristics of phenolic hydroxyl and amino, the synephrine has more impurities in an aqueous extract, and the cation exchange resin has better selective exchange property for the synephrine, so that the impurities can be obviously reduced after the synephrine is exchanged and eluted by the cation exchange resin. The ammonia water has volatility, and can avoid remaining in eluent in the elution process of the ion exchange resin, thereby obtaining a synephrine product with higher content.
The invention has the beneficial effects that:
(1) the four products obtained by the method have higher purity and extraction rate; wherein, in the hesperidin product, the content of hesperidin can reach as high as 99.54%, and the extraction rate is 98.29%; in the neohesperidin product, the content of the neohesperidin can reach as high as 99.68 percent, and the extraction rate is 97.99 percent; in the naringin product, the content of naringin can reach 97.17 percent, and the extraction rate is 95.91 percent; in the synephrine product, the content of the synephrine can reach 92.33 percent, and the extraction rate is 97.26 percent;
(2) the method of the invention is characterized in that under the premise of ensuring the extraction rate and the product purity, the citrus aurantium is subjected to combined extraction of hesperidin, neohesperidin, naringin and synephrine, so that the comprehensive utilization of the citrus aurantium is realized, and the added value of the citrus aurantium is improved;
(3) the method has the advantages of simple and easy operation, low cost of the adopted solvent, no toxicity, no harm and low requirement on production equipment, and is suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
The immature bitter orange raw material adopted in the embodiment of the invention is purchased from Hubei, wherein the mass contents of hesperidin, neohesperidin, naringin and synephrine are 5.63%, 5.36%, 4.24% and 0.31% respectively; the ion exchange resin and the macroporous adsorption resin used in the embodiment of the invention are purchased from Xian lan Xiao science and technology New materials GmbH; in the embodiment of the invention, the water is pure water, and the ethanol, the hydrochloric acid, the sodium hydroxide and the saturated lime water are all food grade; the starting materials or chemicals used in the examples of the present invention are, unless otherwise specified, commercially available in a conventional manner.
In the embodiment of the invention, the contents of hesperidin, neohesperidin, naringin and synephrine in immature bitter orange are measured by adopting a High Performance Liquid Chromatography (HPLC) external standard method, and the specific method is as follows:
(1) the hesperidin detection method comprises the following steps: chromatographic conditions are as follows: a Kromasil (4.6X 150 mm) chromatography column; mobile phase: methanol: acetic acid: water =35:4: 61; flow rate: 1 mL/min; and (3) an elution mode: isocratic elution; detection wavelength: 283 nm.
(2) The neohesperidin detection method comprises the following steps: chromatographic conditions are as follows: a Kromasil (4.6X 250 mm) chromatography column; mobile phase: acetonitrile: water =1:3 (pH =3 adjusted with phosphoric acid); flow rate: 1 mL/min; and (3) an elution mode: isocratic elution; detection wavelength: 283 nm.
(3) The naringin detection method comprises the following steps: chromatographic conditions are as follows: a Kromasil (4.6X 250 mm) chromatography column; mobile phase: acetonitrile: water =1:3 (pH =3 adjusted with phosphoric acid); flow rate: 1 mL/min; and (3) an elution mode: isocratic elution; detection wavelength: 283 nm.
(4) The synephrine detection method comprises the following steps: chromatographic conditions are as follows: a Kromasil (4.6X 250 mm) chromatography column; mobile phase: methanol: potassium dihydrogen phosphate aqueous solution = 50: 50 (wherein 0.6g of monopotassium phosphate, 1.0g of sodium dodecyl sulfate and 1mL of glacial acetic acid are taken to prepare a potassium dihydrogen phosphate solution, and the potassium dihydrogen phosphate solution is diluted to 1000mL by adding a water solution; flow rate: 1 mL/min; and (3) an elution mode: isocratic elution; detection wavelength: 275 nm.
Example 1
(1) Heating and leaching: taking 100kg of immature bitter orange, crushing, sieving with a 20-mesh sieve, adding 3000L of water for 3 times, stirring and extracting for 1h at 85 ℃, cooling, filtering with a fine filter membrane, and respectively collecting an extracting solution and extracting residues;
(2) separating hesperidin: stirring and extracting the extraction residue obtained in the step (1) for 1.5h at 30 ℃ by using 1500L of sodium hydroxide solution with the concentration of 0.5wt%, centrifuging and filtering, regulating the pH value of the filtrate to be 2 by using hydrochloric acid, standing at normal temperature for crystallization, carrying out vacuum drying on the precipitated crystals after vacuum filtration to obtain 5.56kg of hesperidin product with the purity of 99.32wt% and the extraction rate of 98.09%;
(3) and (3) separating neohesperidin: enabling the extracting solution obtained in the step (1) to pass through D101 macroporous adsorption resin, and collecting effluent liquid for later use; desorbing the macroporous adsorption resin by using 2BV ethanol with the volume concentration of 65 percent to obtain desorption liquid I; concentrating the desorption solution I under reduced pressure of-0.08 Mpa at 70 deg.C, and spray drying to obtain 21.5kg of dry powder I; washing the dry powder I with 320L of pure water at room temperature to obtain washing mother liquor and insoluble substances; drying the insoluble substance to obtain neohesperidin product 5.21kg, purity 99.68wt%, and extraction rate 96.89%;
(4) and (3) separating naringin: concentrating the impurity-removed mother liquor obtained in the step (3) under reduced pressure of-0.08 Mpa at 75 ℃, and drying in vacuum to obtain 13.3kg of washing mother liquor dry powder; refining the dry powder with 40L 10% methanol at 80 deg.C, cooling to room temperature, refining the obtained crude crystal product with 36L pure water at 85 deg.C for the second time, and cooling to room temperature to obtain naringin product 4.23kg, purity 96.14wt%, and extraction rate 95.91%;
(5) and (3) separating synephrine: enabling the effluent liquid obtained in the step (3) to pass through a 732 cation exchange resin column, and desorbing the 732 cation exchange resin column by using 1.5BV of 1wt% ammonia water to obtain an analytic liquid II; concentrating the resolving liquid II under reduced pressure of-0.08 Mpa at 65 deg.C to obtain synephrine extract 12 kg; adding 40L of pure water into the synephrine extract, adding activated carbon, stirring and decoloring for 0.5h, filtering, adjusting the pH value to be neutral, standing at 2 ℃ for crystallization, performing reduced pressure filtration, and performing vacuum drying to obtain 0.33kg of synephrine product with the purity of 91.37wt% and the extraction rate of 97.26%.
Example 2
(1) Heating and leaching: pulverizing fructus Aurantii Immaturus 200kg, sieving with 30 mesh sieve, adding 8000L water for 4 times, stirring and extracting at 90 deg.C for 1.5 hr each time, cooling, filtering with fine filter membrane, and collecting extractive solution and residue respectively;
(2) separating hesperidin: extracting the extraction residue obtained in the step (1) with 4000L of potassium hydroxide solution with the concentration of 1.0 wt% at 35 ℃ for 2.5h under stirring, centrifuging and filtering, adjusting the pH value of the filtrate to 4 by using hydrochloric acid, standing at normal temperature for crystallization, performing vacuum filtration on the precipitated crystals, and performing vacuum drying to obtain 11.17kg of hesperidin product with the purity of 99.08wt% and the extraction rate of 98.29%;
(3) and (3) separating neohesperidin: enabling the extracting solution obtained in the step (1) to pass through D101 macroporous adsorption resin, and collecting effluent liquid for later use; desorbing the macroporous adsorption resin by using ethanol with the volume concentration of 2.5BV and the concentration of 70 percent to obtain desorption liquid I; concentrating the desorption solution I under reduced pressure of-0.09 Mpa at 75 ℃, and spray drying to obtain 43kg of dry powder I; washing the dry powder I with 760L pure water at room temperature to obtain washing mother liquor and insoluble substances; drying the insoluble substance to obtain neohesperidin product 10.56kg, with purity of 99.47wt% and extraction rate of 97.99%;
(4) and (3) separating naringin: concentrating the impurity-removed mother liquor obtained in the step (3) under reduced pressure of-0.09 Mpa at 80 ℃, and drying in vacuum to obtain 27.5kg of washing mother liquor dry powder; refining the dry powder with 110L 15% ethanol at 75 deg.C, cooling to room temperature, refining the obtained crude crystal with 93L pure water at 80 deg.C, cooling to room temperature to obtain naringin product 8.42kg, purity 96.37wt%, and extraction rate 95.69%;
(5) and (3) separating synephrine: enabling the effluent liquid obtained in the step (3) to pass through a D001 cation exchange resin column, and desorbing the D001 cation exchange resin column by using 2BV of 3wt% ammonia water to obtain an analytic liquid II; concentrating the resolving liquid II under reduced pressure of-0.09 Mpa at 70 deg.C to obtain synephrine extract 25.5 kg; adding 130L of pure water into the synephrine extract, adding activated carbon, stirring and decoloring for 1.5h, filtering, adjusting the pH value to be neutral, standing at 4 ℃ for crystallization, performing reduced pressure filtration, and performing vacuum drying to obtain 0.64kg of synephrine product with the purity of 92.33wt% and the extraction rate of 95.31%.
Example 3
(1) Heating and leaching: taking 300kg of immature bitter orange, crushing, sieving by a 40-mesh sieve, adding 12000L of water for 4 times, stirring and extracting for 2 hours each time at the temperature of 92 ℃, cooling, filtering by a fine filter membrane, and respectively collecting an extracting solution and extracting residues;
(2) separating hesperidin: stirring and extracting the extraction residue obtained in the step (1) for 4 hours at 45 ℃ by using 7500L of saturated lime water solution, centrifuging and filtering, adjusting the pH value of the filtrate to 6 by using hydrochloric acid, standing at normal temperature for crystallization, carrying out vacuum filtration on the precipitated crystals after decompression filtration, and carrying out vacuum drying to obtain 16.52kg of hesperidin product, wherein the purity is 99.54wt%, and the extraction rate is 97.36%;
(3) and (3) separating neohesperidin: enabling the extracting solution obtained in the step (1) to pass through D101 macroporous adsorption resin, and collecting effluent liquid for later use; desorbing the macroporous adsorption resin by using ethanol with the volume concentration of 3BV being 75 percent to obtain desorption liquid I; concentrating the desorption solution I under reduced pressure of-0.1 Mpa at 80 deg.C, and spray drying to obtain dry powder I64.6 kg; washing the dry powder I with 1300L of pure water at room temperature to obtain washing mother liquor and insoluble substances; drying the insoluble substances to obtain 15.72kg of neohesperidin product with the purity of 99.62wt% and the extraction rate of 97.39%;
(4) and (3) separating naringin: concentrating the impurity-removed mother liquor obtained in the step (3) under reduced pressure of-0.1 Mpa at 85 ℃, and drying in vacuum to obtain 40kg of dry washing mother liquor powder; refining the dry powder with 200L 20% ethanol at 70 deg.C, cooling to room temperature, refining the obtained crude crystal with 170L pure water at 90 deg.C, cooling to room temperature to obtain naringin product 12.47kg, purity 97.17wt%, and extraction rate 95.26%;
(5) and (3) separating synephrine: enabling the effluent liquid obtained in the step (3) to pass through a D061 cation exchange resin column, and desorbing the D061 cation exchange resin column by using 2.5BV of 5wt% ammonia water to obtain an analytic liquid II; concentrating the resolving liquid II under reduced pressure of-0.1 Mpa at 75 deg.C to obtain synephrine extract 38 kg; adding 300L of pure water into the synephrine extract, adding activated carbon, stirring and decoloring for 2.5h, filtering, adjusting the pH value to be neutral, standing at 8 ℃ for crystallization, performing reduced pressure filtration, and performing vacuum drying to obtain 0.97kg of synephrine product with the purity of 92.01wt% and the extraction rate of 95.97%.
The extraction ratios of the extracts of examples 1 to 3 are summarized in Table 1.
TABLE 1 amounts of raw materials and extracts in examples 1-3
The above examples are only intended to illustrate specific preferred embodiments of the present invention and should not be construed as limiting the scope of the claims of the present application. It will be understood by those skilled in the art that various modifications may be made to the above-described embodiments, or equivalents may be substituted for elements thereof, while still remaining within the scope of the claims.
Claims (17)
1. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges is characterized by comprising the following steps of:
(1) heating and leaching: pulverizing fructus Aurantii Immaturus, sieving, extracting with hot water, cooling, filtering with fine filter membrane, and collecting extractive solution and residue respectively;
(2) separating hesperidin: adding a dilute alkali solution into the extraction residue obtained in the step (1), stirring, centrifuging, filtering, adjusting the filtrate to be acidic by hydrochloric acid, standing for crystallization, performing reduced pressure suction filtration, and performing vacuum drying to obtain a hesperidin product;
(3) and (3) separating neohesperidin: passing the extracting solution obtained in the step (1) through macroporous adsorption resin, and collecting effluent liquid for later use; desorbing the macroporous adsorption resin by using an ethanol solution to obtain a desorption solution I; concentrating the desorption solution I under reduced pressure, and spray drying to obtain dry powder I; washing the dry powder I with pure water at room temperature to obtain washing mother liquor and insoluble substances; drying the insoluble substance to obtain neohesperidin product;
(4) and (3) separating naringin: carrying out reduced pressure concentration and vacuum drying on the washing mother liquor obtained in the step (3) to obtain washing mother liquor dry powder; refining with organic solvent and pure water in sequence to obtain naringin product;
(5) and (3) separating synephrine: enabling the effluent liquid obtained in the step (3) to pass through cation exchange resin, and desorbing the cation exchange resin by using ammonia water to obtain desorption liquid II; concentrating the desorption solution II under reduced pressure to obtain synephrine extract; dissolving synephrine extract in water, adding active carbon, stirring for decolorizing, vacuum filtering, adjusting pH to neutral, standing at low temperature for crystallization, vacuum filtering, and vacuum drying to obtain synephrine product;
in the step (3), the macroporous adsorption resin is D101 resin; the volume concentration of the ethanol solution is 65-75%, and the using amount of the ethanol solution is 2-3 BV;
in the step (3), the mass of the pure water in the washing process is 15-25 times of that of the dry powder I;
in the step (4), the organic solvent is an ethanol solution or a methanol solution, the volume concentration is 10-40%, the mass of the organic solvent is 2-5 times of the washing mother liquor dry powder, and the mass of the pure water is 2-6 times of the washing mother liquor dry powder; dissolving dry powder of the washing mother liquor in an organic solvent at 70-85 ℃ during refining, cooling to room temperature, taking a crystallized crude product, dissolving the crystallized crude product in pure water at 80-90 ℃, cooling to room temperature, crystallizing, and filtering to obtain a naringin product;
in the step (5), the cation exchange resin is 732, D001 or D061 resin, the concentration of the ammonia water is 1-5 wt%, and the using amount is 1.5-2.5 BV.
2. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 1, wherein in the step (1), the sieve is a 20-40 mesh sieve; the leaching times are 3-4 times, and the time of single leaching is 1-2 hours; the total mass of the hot water is 30-40 times of the mass of the immature bitter orange, and the temperature of the hot water is 80-95 ℃.
3. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 1 or 2, wherein in the step (2), the dilute alkali solution is a sodium hydroxide solution with the concentration of 0.5-2 wt%, a potassium hydroxide solution with the concentration of 1-3 wt% or a saturated lime water solution, the mass of the dilute alkali solution is 15-25 times of that of the raw materials, the temperature of a stirring system is 30-50 ℃, and the stirring time is 1-4 hours.
4. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 1 or 2, wherein in the step (2), the pH value is adjusted to 2-6 by hydrochloric acid.
5. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 3, wherein in the step (2), the pH value is adjusted to 2-6 by hydrochloric acid.
6. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 1 or 2, wherein in the step (3), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 70 to 80 ℃.
7. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 3, wherein in the step (3), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 70 to 80 ℃.
8. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 4, wherein in the step (3), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 70 to 80 ℃.
9. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 1 or 2, wherein in the step (4), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 75-85 ℃.
10. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 3, wherein in the step (4), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 75-85 ℃.
11. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 4, wherein in the step (4), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 75-85 ℃.
12. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 6, wherein in the step (4), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 75-85 ℃.
13. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 1 or 2, wherein in the step (5), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 65 to 75 ℃; the mass of the water is 3-8 times of that of the synephrine extract, and the crystallization temperature is 2-10 ℃.
14. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 3, wherein in the step (5), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 65 to 75 ℃; the mass of the water is 3-8 times of that of the synephrine extract, and the crystallization temperature is 2-10 ℃.
15. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 4, wherein in the step (5), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 65 to 75 ℃; the mass of the water is 3-8 times of that of the synephrine extract, and the crystallization temperature is 2-10 ℃.
16. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 6, wherein in the step (5), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 65 to 75 ℃; the mass of the water is 3-8 times of that of the synephrine extract, and the crystallization temperature is 2-10 ℃.
17. The method for separating hesperidin, neohesperidin, naringin and synephrine from immature bitter oranges according to claim 9, wherein in the step (5), the vacuum degree of the reduced pressure concentration is-0.08 to-0.1 MPa, and the temperature is 65 to 75 ℃; the mass of the water is 3-8 times of that of the synephrine extract, and the crystallization temperature is 2-10 ℃.
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