CN113150869A - Method for continuously extracting essential oil, pectin and hesperidin from orange peel - Google Patents
Method for continuously extracting essential oil, pectin and hesperidin from orange peel Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
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Abstract
The invention discloses a method for continuously extracting essential oil, pectin and hesperidin from orange peel, which belongs to the technical field of food processing, and adopts an industrially mature superfine grinding technology to crush the cell walls of the orange peel, so that the essential oil, the pectin, the hesperidin and other substances are fully exposed from the original cell structure, therefore, the continuous operation and the sequential extraction of three main functional components, namely the essential oil, the pectin and the hesperidin in the orange peel can be realized by utilizing the obvious solubility difference of the three substances in different media under mild conditions, and the extraction rate of each product can reach or exceed the optimal value reported in the current literature and patent publications; the method provided by the invention has the advantages that the extraction yield of the oil component in the orange peel is more than 40% (for the total content), the extraction yield of the pectin in the orange peel is more than 20% (for dry matters), the extraction yield of the hesperidin in the orange peel is 1-2% (for dry matters), and the purity is not lower than 97%.
Description
Technical Field
The invention relates to a method for continuously extracting essential oil, pectin and hesperidin from orange peel, belonging to the technical field of food processing.
Background
Oranges are bulk agricultural products, so that orange peel resources are very abundant. The orange peel essential oil is one of the most expensive varieties in the current essence and spice markets, mainly exists in an oil coating layer of orange peel, is generally 0.5-2.0% of the fresh weight of the peel, and mainly contains limonene. The pectin in orange peel is mainly present in the middle layer of orange peel cell wall, and is a heteropolysaccharide, and its main chain structure is D-galacturonic acid connected by alpha-1, 4 glycosidic bond, and contains more than ten hair branch chains composed of neutral sugar. The content of pectin in the orange peel is 20-30% (w/w, dry weight). Hesperidin (flavanone glycoside) in orange peel is an important flavonoid in orange peel, has vitamin P-like potency, and is typically present in the orange peel at about 1% (w/w, on a dry orange peel basis).
At present, the most common methods for extracting essential oil, pectin and hesperidin from orange peel are steam distillation, acid-heat extraction and alkali-dissolution and acid-precipitation respectively. The steam distillation method is characterized by utilizing the principle that essential oil and water are immiscible, crushing orange peel, mixing the crushed orange peel with water, adding hot water for distillation, gradually taking away the essential oil by steam in the distillation process, and finally, carrying out phase separation and collection on the essential oil in a collection container. The acid heat extraction of pectin is carried out in a water phase environment with pH of 1-2By H+Acid hydrolysis of cell wall fibers of orange peel exposes pectin in the middle layer of the cell wall, and then>The pectin is dissolved in hot water at an elevated temperature of 80 ℃. The extraction of hesperidin is generally carried out under the strong alkaline condition (pH is 12-13), pectin molecule degradation is catalyzed by using alkalinity, and the hesperidin is exposed and becomes Na+The hesperidin is in a salt form, so that the hesperidin can be dissolved in a methanol solution, the pH of the system is adjusted to be neutral, the hesperidin is changed into a carboxylic acid form again, and the hesperidin is crystallized and precipitated in a solvent at low temperature.
At present, the main problem of extracting the orange peel essential oil, the pectin and the hesperidin is that the three extraction methods are independent from each other, cannot be effectively connected in series and are generally respectively and independently extracted. If continuous extraction operation is to be realized, the problems of large energy consumption and pollution exist. For example, steam distillation consumes a lot of energy, acid heat extraction of pectin produces a lot of acidic waste water, and adjusting the pH value in the extraction of hesperidin requires adding a lot of acid and alkali. Therefore, the process widely adopted at present has the problems of high cost and great pollution.
Disclosure of Invention
The technical problem is as follows:
the invention aims to solve the technical problem of providing a method which is low in cost, green and environment-friendly and can realize continuous extraction of essential oil, pectin and hesperidin in orange peel, compared with the existing technical method for respectively extracting three products, the method can obviously save cost, shorten process flow and reduce pollution, and the extraction rates of the essential oil, the pectin and the hesperidin all reach or exceed the superior values reported in the existing literature and patent publications.
The technical scheme is as follows:
in order to solve the technical problems, the invention provides a method for continuously extracting essential oil, pectin and hesperidin from orange peel, which comprises the following steps:
(1) crushing orange peel;
(2) extracting essential oil: mixing ethanol as extractant with pulverized pericarpium Citri Tangerinae raw materials, filtering to obtain ethanol extractive solution, concentrating the ethanol extractive solution, and extracting to obtain dark brown essential oil;
(3) extracting pectin: mixing the solid remaining after filtering in the step (2) with water to obtain a reaction solution, reacting the reaction solution at 60-90 ℃, continuing to react at 18-25 ℃, filtering after the reaction is finished, and collecting filtrate, namely pectin extracting solution; concentrating the pectin extract, adding ethanol to precipitate pectin, filtering, collecting precipitate, and drying to obtain pectin product;
(4) extraction of hesperidin: adding a glycerol-ethanol mixed solvent into the residual solid after the pectin extracting solution is collected in the step (3) for reaction, filtering after the reaction is finished, and collecting filtrate; adsorbing the filtrate with nonpolar macroporous adsorbent resin, desorbing with ethanol to obtain ethanol solution, and concentrating to remove ethanol to obtain hesperidin extract.
In one embodiment of the present invention, in step (1), the orange peel is pulverized into particles having a particle size of less than 100 microns.
In one embodiment of the invention, the dried orange peel is crushed by a superfine pulverizer and then the raw material is collected.
In one embodiment of the invention, in the step (2), ethanol is used as an extracting agent, the extracting agent is mixed with the crushed orange peel raw material according to a material-liquid ratio of 1: 5-1: 10, the mixture reacts for 30-60 min at a temperature of 18-25 ℃ and a rotating speed of 100-300 rpm, the feed liquid is filtered to collect an ethanol extracting solution, and the ethanol extracting solution is concentrated to prepare the dark brown orange peel essential oil.
In one embodiment of the present invention, in the step (2), the concentration method of the ethanol extract solution prepared is: and (5) distilling under reduced pressure.
In one embodiment of the invention, in the step (3), mixing the filtered residual solid and water according to a material-to-liquid ratio of (1:20) - (1:40) to obtain a reaction solution, reacting the reaction solution at 60-90 ℃ and 100-300 rpm for 10-60 min to inactivate endogenous pectinase, reacting at 18-25 ℃ and 100-300 rpm for 1-2 h, filtering, and collecting a pectin extracting solution; concentrating the pectin extract, adding ethanol to precipitate pectin, and filtering to obtain pectin product.
In one embodiment of the invention, in the step (3), the reaction solution is reacted for 30min at a pH of 5-6, a temperature of 80 ℃ and a rotation speed of 100-300, so that the endogenous pectinase is inactivated, reacted for 2h at a temperature of 20 ℃ and a rotation speed of 100-300 rpm, and the filtrate is filtered and collected, so that the pectin extracting solution is obtained.
In one embodiment of the invention, the water is pure water.
In one embodiment of the invention, in the step (4), a glycerol-ethanol mixed solvent is added into the solid remained after the pectin extracting solution is collected in the step (3), the mixture is reacted for 1 to 3 hours at the temperature of 18 to 25 ℃ and the rotating speed of 100 to 300rpm, and then the mixture is filtered, and the filtrate is collected; adding nonpolar macroporous adsorption resin into the filtrate, adsorbing for 1-3 h at 18-25 ℃, collecting the resin, desorbing the resin for 1-3 h by adopting ethanol, filtering and collecting the filtrate, namely the hesperidin extract.
In one embodiment of the present invention, in the step (4), a glycerol-ethanol mixed solvent is added to the solid remaining after the pectin extraction solution is collected in the step (3), and after the reaction is performed for 1 hour at a rotation speed of 200rpm at 20 ℃, the filtrate is collected after filtration.
In one embodiment of the invention, nonpolar macroporous adsorption resin is added into the prepared filtrate, the filtrate is adsorbed at 25 ℃ for 1 hour, then the resin is filtered and recovered, and then the resin is added into ethanol for desorption for 1 hour, and the obtained ethanol solution is the hesperidin extract.
In one embodiment of the invention, the nonpolar macroporous adsorbent resin is D101, AB-8 or HD-100.
In one embodiment of the present invention, the glycerol-ethanol mixed solvent is prepared by mixing glycerol and ethanol at a volume ratio of (7:3) to (3: 7).
In one embodiment of the invention, the ethanol is anhydrous ethanol.
The application of the method of the invention in preparing products containing orange peel essential oil, or products containing orange peel pectin, or products containing hesperidin is provided.
Advantageous effects
(1) The invention adopts the industrially mature superfine grinding technology to break the cell wall of the orange peel, thereby realizing the full exposure of essential oil, pectin, hesperidin and other substances from the original cell structure, and therefore, the invention can realize continuous operation and sequential extraction of three main functional components in the orange peel essential oil, pectin and hesperidin, namely essential oil, pectin and hesperidin, by utilizing the obvious solubility difference of the three substances in different media under mild conditions, and the extraction rate of each product can reach or exceed the superior value reported in the current literature and patent publications.
(2) By adopting the method provided by the invention, in the process of extracting the essential oil, relatively safe ethanol is adopted, the extraction is completed in a short time at normal temperature, and compared with the traditional steam distillation method, the extraction time is shortened to be within 1 hour by more than 10 hours required by steam distillation, so that the extraction time is obviously shortened, and the steam energy consumption is saved. Meanwhile, the natural pigments such as carotenoid and the like in the orange peel can be simultaneously extracted by taking absolute ethyl alcohol as an extracting agent, the problem of decolorization of subsequent pectin products is solved, and the extraction yield of the oil component in the orange peel by adopting the method provided by the invention is more than 40% (to the total content).
(3) By adopting the method provided by the invention, pectin molecules are fully exposed due to the destructive effect of the ultrafine grinding on cell walls in the pectin extraction process, so that the pectin is extracted by heating for a short time under the natural pH of a system. Compared with the traditional acid-heating orange peel pectin extraction method, the method does not add an acid reagent, does not heat for a long time, reduces pollution and energy consumption, and has the extraction rate of pectin in orange peel higher than 20% (to dry matter).
(4) By adopting the method provided by the invention, because the hesperidin is insoluble in absolute ethyl alcohol or water, the hesperidin is not lost in the process of extracting the essential oil and the pectin, and particularly after the essential oil and the pectin are extracted, the dissolving effect of the hesperidin is easier to dissolve due to the obviously reduced mass transfer resistance. The technology realizes normal-temperature extraction by selecting a high-safety good solvent of hesperidin. Compared with the method for extracting hesperidin by destroying cell walls of orange peels with strong alkali in the prior art, the method provided by the invention has the advantages that pollution is obviously reduced, the extraction rate of the hesperidin in the orange peels is 1-2% (on dry matters), and the purity is not lower than 97%.
Drawings
FIG. 1: the technical flow chart of the invention.
FIG. 2: the invention relates to an HPLC chart of extracted hesperidin.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The detection methods referred to in the following examples are as follows:
the method for measuring the extraction rate of the essential oil comprises the following steps:
the mass of the essential oil obtained after the ethanol is completely removed by concentration is m1(ii) a Total content m of oil component in orange peel0The determination is carried out by a Soxhlet extraction method. Extract rate (%) of essential oil (m)1/m0×100。
The detection method of the main components in the essential oil comprises the following steps:
the essential components in the essential oil were detected by gas chromatography, with the operating parameters as described in ISO 3528: 2012.
The pectin extraction rate determination method comprises the following steps:
the content of galacturonic acid in the pectin extract is determined by carbazole colorimetry. The calculation formula of the pectin extraction rate is as follows: pectin extraction rate (%). galacturonic acid mass/raw material mass in the extract × 100.
The purity detection method of pectin comprises the following steps:
the purity of the pectin is measured according to the national standard GB25533-2010 food safety national standard food additive pectin, and the specific detection method is based on the A.4 total galacturonic acid and the amidation degree in the national standard according to the content of the total galacturonic acid; the acid insoluble ash content was measured using the ignition method described in GB 25533-2010.
The pectin molecular weight detection method comprises the following steps:
the molecular weight of the pectin is determined by adopting a high performance liquid chromatography, and the specific conditions are as follows: shodex KS-802 column and KS-804 column were combined with 0.1N NaNO3As a mobile phase, the flow rate was 1.0mL/min at room temperature.
The method for measuring the extraction rate of hesperidin comprises the following steps:
and (3) measuring the extraction rate of the hesperidin by a colorimetric method. The colorimetric method comprises adding 45 microliters of 5% sodium nitrite into 300 microliters of a sample, standing for 6min after shaking, adding 45 microliters of 10% aluminum nitrate, shaking, standing for 6min, adding 600 microliters of 4% sodium hydroxide, standing for 20min after shaking, carrying out color comparison at 340nm, and taking hesperidin standard solutions of 40, 80, 120, 160 and 200 micrograms/ml as standard curves. The calculation formula of the hesperidin extraction rate is as follows: the extraction rate (%) of hesperidin is equal to the mass of hesperidin in the extract/mass of raw material x 100.
The method for detecting the purity of the hesperidin comprises the following steps:
according to the determination of hesperidin in fingered citron in the department of Chinese pharmacopoeia (2015 edition), the purity of hesperidin is detected by an HPLC method. The concrete conditions are as follows: a chromatographic column JADE-PAK ODS was prepared by using methanol, water and glacial acetic acid (33:63:2) as mobile phases, and detecting at 284nm at room temperature at a flow rate of 1.0 mL/min.
Example 1: process for continuously extracting essential oil, pectin and hesperidin from orange peel
The specific process flow is shown in figure 1, and the specific steps are as follows:
(1) crushing orange peel into particles with the particle size range of 80-100 microns;
(2) mixing absolute ethyl alcohol serving as an extracting agent with the crushed orange peel raw material prepared in the step (1) according to a material-liquid ratio of 1:5, stirring for 50 minutes at 18-25 ℃, filtering to obtain an ethanol extracting solution, and concentrating by adopting a reduced pressure distillation technology to remove ethanol to obtain dark brown orange peel essential oil;
the extraction rate of the essential oil was measured to be 42% (to the total content); the essential oil contains 150 volatile components, wherein the content of limonene accounts for 75%, and other main essential oil components also comprise linalool (accounting for 5%), beta-myrcene (accounting for 3%), 1, 3-dihydroxy-acetone (accounting for 1.5%), methyl acetate (accounting for 1.2%) and the like.
(3) Continuously mixing the solid residue obtained after filtration in the step (2) with pure water at a material-liquid ratio of 1:30 to obtain a reaction solution, stirring the reaction solution for 30 minutes at 70 ℃ under the condition of pH 5.5, then continuously stirring for 2 hours at 25 ℃, and filtering to collect filtrate, namely pectin extracting solution;
concentrating the pectin extractive solution by 3 times under reduced pressure, adding anhydrous ethanol until ethanol ratio is 60% (by volume), to obtain pectin precipitate, filtering, drying the precipitate, and pulverizing to obtain pectin product. Through detection, the extraction rate of the pectin is 25%, the content of galacturonic acid in the pectin is 82%, the molecular weight is 198kDa, and the insoluble ash content is less than 0.5%.
(4) Adding a glycerol-absolute ethyl alcohol mixed solvent into the residual solid after the pectin extracting solution is collected in the step (3) to obtain a mixed solvent for reaction, wherein the glycerol-absolute ethyl alcohol mixed solvent is prepared by mixing glycerol and absolute ethyl alcohol according to a volume ratio of 7: 3; stirring the obtained mixed solution for 1 hour at 18-25 ℃, filtering and collecting filtrate, adding D101 nonpolar macroporous adsorption resin, adsorbing for 1 hour at 25 ℃, filtering and recovering the resin, adding the resin into absolute ethyl alcohol, and desorbing for 1 hour to obtain an absolute ethyl alcohol solution, namely the hesperidin extract;
concentrating anhydrous ethanol, and completely removing to obtain hesperidin product, wherein the hesperidin extraction rate is 1.5% and the purity is 97% according to the analysis method (shown in figure 2).
Example 2: process for continuously extracting essential oil, pectin and hesperidin from orange peel
The method comprises the following specific steps:
(1) crushing orange peel into particles with the particle size range of 200-300 microns;
(2) mixing absolute ethyl alcohol serving as an extracting agent with the crushed orange peel raw material prepared in the step (1) according to a material-liquid ratio of 1:5, stirring for 50 minutes at 18-25 ℃, filtering to obtain an ethanol extracting solution, and concentrating by adopting a reduced pressure distillation technology to remove ethanol to obtain dark brown orange peel essential oil;
the extraction rate of the essential oil is measured to be 30% (to the total content); the essential oil contains 126 volatile components, wherein the content of limonene accounts for 78%, and other main essential oil components also comprise linalool (accounting for 3%), beta-myrcene (accounting for 2%), 1, 3-dihydroxy-acetone (accounting for 1%), methyl acetate (accounting for 1%) and the like.
(3) Continuously mixing the solid residue obtained after filtration in the step (2) with pure water at a material-liquid ratio of 1:30 to obtain a reaction solution, stirring the reaction solution for 30 minutes at 70 ℃ under the condition of pH 5.2, then continuously stirring for 2 hours at 25 ℃, and filtering to collect filtrate, namely pectin extracting solution;
concentrating the pectin extractive solution by 3 times under reduced pressure, adding anhydrous ethanol until ethanol ratio is 60% (by volume), to obtain pectin precipitate, filtering, drying the precipitate, and pulverizing to obtain pectin product. Empirically, the extraction rate of pectin was 8%, the galacturonic acid content in pectin was 79%, the molecular weight was 223kDa, and the insoluble ash was < 0.5%. (ii) a
(4) Adding a glycerol-absolute ethyl alcohol mixed solvent into the residual solid after the pectin extracting solution is collected in the step (3) to obtain a mixed solution, wherein the glycerol-absolute ethyl alcohol mixed solvent is obtained by mixing glycerol and absolute ethyl alcohol according to a volume ratio of 7: 3; stirring the obtained mixed solution for 1 hour at 18-25 ℃, filtering and collecting filtrate, adding D101 nonpolar macroporous adsorption resin, adsorbing for 1 hour at 18-25 ℃, filtering and recovering the resin, adding the resin into absolute ethyl alcohol, and desorbing for 1 hour to obtain an absolute ethyl alcohol solution, namely the hesperidin extract;
concentrating anhydrous ethanol, and completely removing to obtain hesperidin product with hesperidin extraction rate of 0.4% and purity of 98%.
Example 3: process for continuously extracting essential oil, pectin and hesperidin from orange peel
The method comprises the following specific steps:
(1) crushing orange peel into particles with the particle size range of 20-80 microns;
(2) mixing absolute ethyl alcohol serving as an extracting agent with the crushed orange peel raw material prepared in the step (1) according to a material-liquid ratio of 1:5, stirring for 50 minutes at 18-25 ℃, filtering to obtain an ethanol extracting solution, and concentrating by adopting a reduced pressure distillation technology to remove ethanol to obtain dark brown orange peel essential oil;
the extraction rate of the essential oil is measured to be 50% (to the total content); the essential oil contains 153 volatile components, wherein the content of limonene is 74%, and other main essential oil components also comprise linalool (6%), beta-myrcene (4%), 1, 3-dihydroxy-acetone (2%), methyl acetate (2%) and the like.
(3) Continuously mixing the solid residue obtained after filtration in the step (2) with pure water at a material-liquid ratio of 1:30 to obtain a reaction solution, directly stirring and extracting the reaction solution at 18-25 ℃ for 2 hours under the condition of pH 5.8, and filtering to obtain a filtrate to obtain a pectin extracting solution;
concentrating the pectin extract by 3 times by adopting a reduced pressure distillation technology, then adding absolute ethyl alcohol until the proportion of the ethyl alcohol is 60 percent (by volume ratio), and almost no obvious precipitation exists, which shows that the pectin is degraded into low-molecular soluble fragments by endogenous enzyme, the molecular weight is less than 5000Da, and the pectin cannot be used as normal pectin;
(4) adding a glycerol-absolute ethyl alcohol mixed solvent into the residual solid after the pectin extracting solution is collected in the step (3) to obtain a mixed solution, wherein the glycerol-absolute ethyl alcohol mixed solvent is obtained by mixing glycerol and absolute ethyl alcohol according to a volume ratio of 7: 3; stirring the obtained mixed solution for 1 hour at 18-25 ℃, filtering to obtain a liquid part, adding D101 nonpolar macroporous adsorption resin, adsorbing for 1 hour at 18-25 ℃, filtering to recover the resin, adding the resin into absolute ethyl alcohol, and desorbing for 1 hour to obtain an absolute ethyl alcohol solution, namely the hesperidin extract;
concentrating anhydrous ethanol, and completely removing to obtain hesperidin product with hesperidin extraction rate of 1.2% and purity of 97%.
Example 4: process for continuously extracting essential oil, pectin and hesperidin from orange peel
The method comprises the following specific steps:
(1) crushing orange peel into particles with the particle size range of 50-100 micrometers;
(2) mixing absolute ethyl alcohol serving as an extracting agent with the crushed orange peel raw material prepared in the step (1) according to a material-liquid ratio of 1:10, stirring for 60 minutes at 18-25 ℃, filtering to obtain an ethanol extracting solution, and concentrating by adopting a reduced pressure distillation technology to remove ethanol to obtain dark brown orange peel essential oil;
the extraction rate of the essential oil is measured to be 50% (to the total content); the essential oil contains 148 volatile components, wherein the content of limonene accounts for 81%, and other main essential oil components also comprise linalool (accounting for 4%), beta-myrcene (accounting for 3%), 1, 3-dihydroxy-acetone (accounting for 1%), methyl acetate (accounting for 1%) and the like.
(3) Continuously mixing the solid residue obtained after filtration in the step (2) with pure water at a material-liquid ratio of 1:40 to obtain a reaction solution, stirring the reaction solution for 10 minutes at 90 ℃ under the condition of pH 5.5, then continuously stirring for 1.5 hours at 18-25 ℃, and filtering to obtain a filtrate, namely a pectin extracting solution; concentrating the pectin extractive solution by 3 times under reduced pressure, adding anhydrous ethanol until ethanol ratio is 60% (by volume), to obtain pectin precipitate, filtering, drying the precipitate, and pulverizing to obtain pectin product.
The pectin extraction rate was found to be 22%, the galacturonic acid content in pectin was 84%, the molecular weight was 200kDa, and the insoluble ash was < 0.5%.
(4) Adding a glycerol-absolute ethyl alcohol mixed solvent into the residual solid after the pectin extracting solution is collected in the step (3) to obtain a mixed solution, wherein the glycerol-absolute ethyl alcohol mixed solvent is formed by mixing glycerol and absolute ethyl alcohol according to a volume ratio of 9: 1; after the obtained mixed solution is stirred for 1 hour at the temperature of 18-25 ℃, the hesperidin product cannot be obtained because the viscosity of the system is too high and the filtration and separation cannot be smoothly carried out.
Example 5: process for continuously extracting essential oil, pectin and hesperidin from orange peel
The specific implementation manner is the same as that of example 1, except that the resin is selected to be HD-100 nonpolar macroporous resin;
the extraction rate of the prepared dark brown orange peel essential oil is 48 percent (relative to the total content); the essential oil contains 158 volatile components, wherein the content of limonene accounts for 72%, and other main essential oil components also comprise linalool (accounting for 5%), beta-myrcene (accounting for 5%), 1, 3-dihydroxy-acetone (accounting for 3%), methyl acetate (accounting for 2%) and the like.
The extraction rate of the prepared pectin product is 25%, the content of galacturonic acid in the pectin is 82%, the molecular weight is 188kDa, and the insoluble ash content is less than 0.5%.
The extraction rate of hesperidin is 1.4%, and the purity is 98%.
Example 6: process for continuously extracting essential oil, pectin and hesperidin from orange peel
The specific implementation mode is the same as that of the embodiment 1, except that the resin is selected to be AB-8 nonpolar macroporous resin;
the extraction rate of the prepared dark brown orange peel essential oil is 54 percent (relative to the total content); the essential oil contains 143 volatile components, wherein the content of the limonene accounts for 76%, and other main essential oil components also comprise linalool (accounting for 8%), beta-myrcene (accounting for 3%), 1, 3-dihydroxy-acetone (accounting for 3%), methyl acetate (accounting for 2%) and the like.
The extraction rate of the prepared pectin product is 21%, the content of galacturonic acid in the pectin is 76%, the molecular weight is 204kDa, and the insoluble ash content is less than 0.5%.
The extraction rate of hesperidin is 1.3%, and the purity is 98%.
Comparative example 1
The specific implementation manner is the same as that of example 1, except that the resin is adjusted to 701 anion exchange resin;
the extraction rate of the prepared dark brown orange peel essential oil is 50 percent (relative to the total content); the essential oil contains 148 volatile components, wherein the content of limonene accounts for 81%, and other main essential oil components also comprise linalool (accounting for 4%), beta-myrcene (accounting for 3%), 1, 3-dihydroxy-acetone (accounting for 1%), methyl acetate (accounting for 1%) and the like.
The extraction rate of the prepared pectin product is 23%, the content of galacturonic acid in the pectin is 78%, the molecular weight is 205kDa, and the insoluble ash content is less than 0.5%.
The extraction rate of hesperidin is 1.4%, but the obtained hesperidin has lower purity which is only 23%.
Comparative example 2
The specific embodiment is the same as example 1, except that the resin was a 732 cation exchange resin;
the extraction rate of the prepared dark brown orange peel essential oil is 48 percent (relative to the total content); the essential oil contains 156 volatile components, wherein the content of limonene accounts for 78%, and other main essential oil components also comprise linalool (accounting for 5%), beta-myrcene (accounting for 4%), 1, 3-dihydroxy-acetone (accounting for 3%), methyl acetate (accounting for 1%) and the like.
The extraction rate of the prepared pectin product is 24%, the content of galacturonic acid in the pectin is 80%, the molecular weight is 195kDa, and the insoluble ash content is less than 0.5%.
The extraction rate of hesperidin is 1.4%, but the obtained hesperidin has lower purity, which is only 18%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for continuously extracting essential oil, pectin and hesperidin from orange peel is characterized by comprising the following steps:
(1) crushing orange peel;
(2) extracting essential oil: mixing ethanol as extractant with pulverized pericarpium Citri Tangerinae raw materials, filtering to obtain ethanol extractive solution, concentrating the ethanol extractive solution, and extracting to obtain dark brown essential oil;
(3) extracting pectin: mixing the solid remaining after filtering in the step (2) with water to obtain a reaction solution, reacting the reaction solution at 60-90 ℃, continuing to react at 18-25 ℃, filtering after the reaction is finished, and collecting filtrate, namely pectin extracting solution; concentrating the pectin extract, adding ethanol to precipitate pectin, filtering, collecting precipitate, and drying to obtain pectin product;
(4) extraction of hesperidin: adding a glycerol-ethanol mixed solvent into the residual solid after the pectin extracting solution is collected in the step (3) for reaction, filtering after the reaction is finished, and collecting filtrate; adsorbing the filtrate with nonpolar macroporous adsorbent resin, desorbing with ethanol to obtain ethanol solution, and concentrating to remove ethanol to obtain hesperidin extract.
2. The method of claim 1, wherein in step (1), the orange peel is pulverized to a particle size of less than 100 microns.
3. The method according to claim 1 or 2, wherein in the step (2), ethanol is used as an extracting agent, the extracting agent is mixed with the crushed orange peel raw material according to a material-liquid ratio of 1: 5-1: 10, the mixture is reacted for 30-60 min at a temperature of 18-25 ℃ and a rotating speed of 100-300 rpm, the material liquid is filtered to obtain an ethanol extracting solution, and the ethanol extracting solution is concentrated to obtain the dark brown orange peel essential oil.
4. The method according to any one of claims 1 to 3, wherein the ethanol extract prepared in the step (2) is concentrated by a method comprising: and (5) distilling under reduced pressure.
5. The method according to any one of claims 1 to 4, wherein in the step (3), the solid remaining after extraction of the essential oil is mixed with water according to a material-to-liquid ratio of (1:20) to (1:40) to obtain a reaction solution, the reaction solution is reacted at 60-90 ℃ and 100-300 rpm for 10-60 min to inactivate endogenous pectinase, then reacted at 18-25 ℃ and 100-300 rpm for 1-2 h, filtered, and the pectin extract is collected; concentrating the pectin extract, adding ethanol to precipitate pectin, and filtering to obtain pectin product.
6. The method according to any one of claims 1 to 5, wherein in the step (4), a glycerol-ethanol mixed solvent is added into the solid remained after the pectin extracting solution is collected in the step (3), the mixture is reacted for 1 to 3 hours at the temperature of 18 to 25 ℃ and the rotating speed of 100 to 300rpm, and then the filtrate is collected; adding nonpolar macroporous adsorption resin into the filtrate, adsorbing for 1-3 h at 18-25 ℃, collecting the resin, desorbing the resin for 1-3 h by adopting ethanol, filtering and collecting the filtrate, namely the hesperidin extract.
7. The method of claim 6, wherein the prepared filtrate is added with nonpolar macroporous adsorption resin, the adsorption is carried out for 1 hour at 25 ℃, then the resin is filtered and recovered, and then the resin is added into ethanol for desorption for 1 hour, and the obtained ethanol solution is the hesperidin extract.
8. The method of any one of claims 1 to 7, wherein the non-polar macroporous adsorbent resin is D101, AB-8 or HPD-100.
9. The method according to any one of claims 1 to 8, wherein the glycerol-ethanol mixed solvent is prepared by mixing glycerol and ethanol in a volume ratio of (7:3) to (3: 7).
10. Use of the method of any one of claims 1 to 9 in the preparation of a product containing essential oil of citrus peel, or in the preparation of a product containing pectin of citrus peel, or in the preparation of a product containing hesperidin.
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