CN108752400B - Preparation method of naringin dihydrochalcone - Google Patents
Preparation method of naringin dihydrochalcone Download PDFInfo
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- CN108752400B CN108752400B CN201810706176.7A CN201810706176A CN108752400B CN 108752400 B CN108752400 B CN 108752400B CN 201810706176 A CN201810706176 A CN 201810706176A CN 108752400 B CN108752400 B CN 108752400B
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Abstract
The invention discloses a preparation method of naringin dihydrochalcone, which comprises the following steps: drying and micronizing citrus peel and/or fructus Aurantii Immaturus; performing subcritical water extraction on the citrus peel powder; purifying and eluting the naringin extract; concentrating under reduced pressure, and freeze drying naringin eluate; carrying out hydrogenation reaction on naringin; adjusting the pH value of the hydrogenated solution, standing, filtering, and freeze-drying to obtain naringin dihydrochalcone. The preparation method has the advantages of simple process, convenient operation, low cost, environmental protection, high yield, high purity and the like, can improve the comprehensive utilization value of the citrus and the immature bitter orange, has good application prospect and economic benefit, does not need to use an organic solvent in the preparation process, does not bring secondary pollution to the environment, is an environment-friendly preparation method with promising prospect, is suitable for large-scale preparation, and is convenient for industrial utilization.
Description
Technical Field
The invention belongs to the technical field of biological separation and chemical synthesis, relates to an extraction and synthesis process of an effective component of citrus, and particularly relates to a preparation method of naringin dihydrochalcone.
Background
Naringin Dihydrochalcone (Naringin Dihydrochalcone) is a widely-focused sweetness agent, has the sweetness about 1000 times that of cane sugar, is fresh and cool in taste, has lasting aftertaste, and has an excellent effect of shielding bitter taste. Naringin dihydrochalcone is particularly suitable for use as an additive to dairy products, fats and oils, frozen foods, processed vegetables, jellies, jams, soft drinks, chewing gums, toothpastes and buccal tablets. Naringin dihydrochalcone, as a substitute for sugar, can also reduce the intake of sugar by the human body, which is undoubtedly a good news for the prevention of obesity and the patients who are not suitable for sugar. However, naringin dihydrochalcone cannot be directly obtained from the nature, and needs to be prepared by taking naringin as a raw material.
Naringin is naturally present in citrus peel (such as pericarp of mandarin orange, tangerine, orange, pomelo, etc.), contains neohesperidosyl, and is an important citrus flavanone. However, naringin is present in citrus peel at a low level. Therefore, how to effectively extract naringin from citrus peels is very important for the industrial preparation of naringin dihydrochalcone.
In the prior art, there are some reports on the extraction and preparation of naringin in citrus peel, such as: patent document No. CN 107955051A, "a process for extracting and separating naringin," patent document No. CN 104817602 a, "a method for extracting naringin and a method for using the same," and patent document No. CN 102617673B "a method for separating and purifying naringin and neohesperidin from white peel layer of grapefruit. However, the extraction process uses a large amount of organic solvents such as methanol, chloroform, petroleum ether, n-butanol and n-hexane, strong acid and strong base reagents, the extraction cost is high, and the use of the organic solvents can generate a large amount of wastewater, so that the treatment difficulty and the treatment cost are increased, the environmental pollution is large, the process flow is long, the operation is complex, the time consumption is long, the extraction cost is high, the solvent residue is high, and the like. In addition, since citrus peel and immature bitter orange contain pigments and lipid compounds, the existing extraction method can dissolve the impurity components together with naringin, which has great influence on the purification of naringin and is not beneficial to obtaining naringin dihydrochalcone with high yield and purity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the preparation method of the naringin dihydrochalcone, which has the advantages of simple process, convenient operation, low cost, environmental protection, high yield and high purity.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of naringin dihydrochalcone comprises the following steps:
s1, drying and superfine grinding the citrus peel and/or the immature bitter orange to obtain citrus peel powder;
s2, taking the deoxidized distilled water as an extraction solvent, performing first subcritical water extraction on the citrus peel powder obtained in the step S1, performing filter pressing, and discarding filtrate to obtain filter residue;
s3, mixing the filter residue obtained in the step S2 with activated carbon, performing second subcritical water extraction by using deoxidized distilled water as an extraction solvent, centrifuging, and removing the filter residue to obtain a naringin extracting solution;
s4, purifying the naringin extracting solution obtained in the step S3 by using resin, and eluting the naringin adsorbed on the resin to obtain a naringin eluent;
s5, carrying out reduced pressure concentration and freeze drying on the naringin eluent obtained in the step S4 to obtain naringin;
s6, dissolving the naringin obtained in the step S5 in alkali liquor, adding a catalyst, introducing hydrogen to carry out hydrogenation reaction, and filtering to obtain a hydrogenation solution;
s7, adjusting the pH value of the hydrogenated solution obtained in the step S6, standing, filtering, and freeze-drying to obtain the naringin dihydrochalcone.
In the above preparation method, a further improvement is that in step S2, the weight ratio of the deoxygenated distilled water to the citrus peel powder is 1: 4 to 1: 12.
In the above preparation method, further modified, in step S2, the first subcritical water extraction is performed under a nitrogen atmosphere; the pressure intensity of the first subcritical water extraction is 3 MPa-12 MPa; the temperature of the first subcritical water extraction is 80-250 ℃; the time of the first subcritical water extraction is 15-70 min.
In the above preparation method, the preparation method is further improved, in the step S3, the mass ratio of the activated carbon to the filter residue is 0.5-8%; the weight ratio of the deoxygenated distilled water to the filter residue is 1: 4-1: 12.
In the preparation method, further modified, in step S3, the second subcritical water extraction is performed under a nitrogen atmosphere; the pressure intensity of the second subcritical water extraction is 2 MPa-12 MPa; the temperature of the second subcritical water extraction is 80-225 ℃; the time of the second subcritical water extraction is 15-70 min; the centrifugation is carried out at the rotating speed of 5000-10000 rpm; the centrifugation time is 10 min-20 min.
In the above preparation method, further improvement is that in step S1, the citrus peel is at least one of citrus peel, tangerine peel, pomelo peel and orange peel; the particle size of the citrus peel powder is 10-50 mu m.
In a further improvement of the above preparation method, in step S4, the resin is at least one of D101 macroporous adsorption resin, D4020 macroporous adsorption resin, AB-8 macroporous adsorption resin, D130 macroporous adsorption resin, HPD450 macroporous adsorption resin, and D140 macroporous adsorption resin; the eluent adopted in the elution process is an ethanol solution; the volume concentration of the ethanol solution is 65-95%; the volume of the eluent is 5 to 15 times of the volume of the resin.
In a further improvement of the above preparation method, in step S5, the concentration under reduced pressure is performed at a temperature of 40 ℃ to 80 ℃.
In a further improvement of the above preparation method, in step S6, the alkali solution is a sodium hydroxide solution and/or a potassium hydroxide solution; the pH value of the alkali liquor is 9-14; the catalyst is palladium carbon; in the hydrogenation reaction process, the pressure of the reaction system is maintained to be 0.5-5 MPa by introducing hydrogen; the time of the hydrogenation reaction is 30 min-240 min.
In the above preparation method, further improvement is provided, in step S7, the hydrogenated solution is adjusted by concentrated acid; the concentrated acid is concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid; adjusting the pH value of the hydrogenation solution to 7-9; the standing time is 6-48 h.
In the present invention, deoxygenated distilled water is obtained by injecting high-purity nitrogen gas into distilled water to remove residual oxygen.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a preparation method of naringin dihydrochalcone, which is characterized in that citrus peel and/or immature bitter orange are used as raw materials, naringin is obtained by extraction through a subcritical water extraction technology, and naringin is subjected to hydrogenation reaction and ring opening to obtain the naringin dihydrochalcone. In the invention, subcritical water with proper polarity is obtained by utilizing a subcritical water extraction technology, and the subcritical water in a subcritical state is taken as an extraction solvent, so that the phase behavior of an extraction system can be changed, the solvation effect is accelerated, the multiphase reaction under the traditional solvent condition is changed into a single-phase reaction, the diffusion coefficient is increased, the mass transfer and heat transfer resistance is reduced, the extraction balance can be achieved in a shorter time, the treatment time is shortened, and the distribution of an extraction product can be controlled, so that naringin can be effectively extracted, the yield of the obtained naringin is high, the purity of the obtained naringin is high, and the selective extraction of the naringin can be realized, specifically: performing subcritical water extraction on the citrus peel powder, extracting lipid substances and fat-soluble pigments from the citrus peel powder and dissolving the lipid substances and the fat-soluble pigments in a subcritical water solution, centrifuging and discarding a supernatant to remove the lipid compounds and the fat-soluble pigments, mixing the obtained filter residue with active carbon, continuing performing subcritical water extraction, extracting naringin from the filter residue and dissolving the naringin in the subcritical water solution, adsorbing the water-soluble pigments in the filter residue by the active carbon, discarding the filter residue, and effectively removing the lipid substances and the pigments. The subcritical water is only used as the extraction solvent in the extraction process, the method is an environment-friendly solvent, no organic solvent is introduced, no large amount of organic wastewater is generated, no solvent residue is generated in the product, no secondary pollution is caused, and the problem of possible microbial pollution in the raw materials can be completely solved due to the high temperature and high pressure used in the subcritical water extraction process, so that the method is safe and reliable. In the invention, the extraction process of naringin is protected by high-purity nitrogen, and the naringin is extracted by using the deoxidized distilled water, so that the oxidative decomposition of effective substances caused by high temperature is avoided. Compared with an organic solvent, the method takes subcritical water as an extraction solvent, is environment-friendly, has rich resources, has the advantages of higher extraction efficiency, lower cost, greenness, cleanness and the like, and can overcome the defects of low naringin extraction rate, low raw material utilization rate, use of an organic solvent and the like in the conventional method. Compared with the conventional extraction method (such as an extraction method using an organic solvent as an extractant), the method for extracting naringin by using the subcritical water extraction technology has the advantages of simplicity, easiness, short extraction time, high extraction efficiency, green and clean extraction solvent, environmental friendliness and the like, and is a green extraction technology. On the basis, the invention takes the high-purity naringin extracted by utilizing the subcritical water extraction technology as a raw material, and the naringin dihydrochalcone with high yield and high purity is prepared by ring opening through hydrogenation reaction. In the invention, the extraction of naringin and the synthesis of naringin dihydrochalcone are coupled, so that the utilization rate of effective substances in raw materials is improved, and the production efficiency is improved. The preparation method has the advantages of simple process, convenient operation, low cost, environmental protection, high yield, high purity and the like, can improve the comprehensive utilization value of the citrus and the immature bitter orange, has good application prospect and economic benefit, does not need to use an organic solvent in the preparation process, does not bring secondary pollution to the environment, is an environment-friendly preparation method with promising prospect, is suitable for large-scale preparation, and is convenient for industrial utilization.
(2) In the preparation method, the subcritical water extraction condition has an important influence on the yield and the purity of the naringin, so that the subcritical water extraction condition is optimized, and the preparation method specifically comprises the following steps: the pressure of the first subcritical water extraction is 3MPa to 12MPa, and the temperature is 80 ℃ to 250 ℃; the pressure of the second subcritical water extraction is 2MPa to 12MPa, and the temperature is 80 ℃ to 225 ℃. In the invention, the polarity, surface tension and viscosity of water are changed by optimizing the pressure and temperature in the first subcritical water extraction process, so that subcritical water which is easier to dissolve fat-soluble pigments and lipid compounds is obtained, more fat-soluble pigments and lipid compounds are dissolved in the subcritical water, and the removal rate of the fat-soluble pigments and lipid compounds is further improved. On the basis, the polarity, the surface tension and the viscosity of water are changed by optimizing the pressure and the temperature in the second subcritical water extraction process, so that subcritical water which is easier to dissolve naringin is obtained, more naringin is dissolved in the subcritical water, and because the activated carbon is added in the subcritical water extraction process, the added activated carbon can adsorb water-soluble pigment, so that the removal rate of the pigment is further improved, and the yield and the purity of the naringin are further improved. In addition, in the invention, by removing impurity substances in the process of extracting naringin, the purification process can be simplified, the operation difficulty is further reduced, and the extraction efficiency is improved. Therefore, in the preparation method, the yield and the purity of naringin can be further improved by optimizing the subcritical water extraction condition, the yield and the purity of naringin dihydrochalcone can be further improved, naringin dihydrochalcone with higher yield and higher purity can be obtained, and the preparation method has the advantages of simpler process, more convenient operation, lower cost, higher resource utilization rate and higher preparation efficiency.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a process flow diagram for the preparation of naringin dihydrochalcone in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the following examples, unless otherwise specified, materials and instruments used were commercially available, processes used were conventional, equipment used were conventional, and the data obtained were average values of three or more tests.
Example 1:
a preparation method of naringin dihydrochalcone is shown in figure 1, and comprises the following steps:
(1) drying pericarpium Citri Junoris, and micronizing to obtain pericarpium Citri Tangerinae powder with particle size of 20 μm.
(2) Pack into the subcritical extraction cauldron with the oranges and tangerines skin powder that obtains in step (1), let in high-purity nitrogen gas, simultaneously be 1: 12 according to the weight ratio of deoxidization distilled water and oranges and tangerines skin powder, add deoxidization distilled water in the subcritical extraction cauldron (in this embodiment, deoxidization distilled water is obtained through going into distilled water with getting rid of remaining oxygen with high-purity nitrogen gas), be 6MPa at pressure, the temperature is carried out subcritical water extraction 60min for the first time under 250 ℃, the cooling, the filter-pressing, discard the gained filtrating of filter-pressing, obtain the filter residue, this filter residue continues to be used for subcritical water extraction.
(3) Uniformly mixing the filter residue obtained in the step (2) with the active carbon according to the mass ratio of the active carbon to the filter residue of 5%, putting the obtained mixture into a subcritical extraction kettle, adding deoxygenated distilled water into the subcritical extraction kettle according to the weight ratio of the deoxygenated distilled water to the filter residue of 1: 8, introducing high-purity nitrogen gas, performing secondary subcritical water extraction for 50min at the pressure of 4.5MPa and the temperature of 150 ℃, cooling, centrifuging the obtained mixed residue liquid for 15min at the rotating speed of 8000rpm, discarding the centrifuged filter residue, and collecting supernatant to obtain the naringin extracting solution.
(4) Purifying the naringin extracting solution obtained in the step (3) by adopting D130 macroporous adsorption resin, and then eluting the D130 macroporous adsorption resin adsorbed with naringin by taking an ethanol solution with the volume concentration of 90% as an eluent, wherein the volume of the eluent is 7 times that of the D130 macroporous adsorption resin, so as to obtain naringin eluent.
(5) And (4) carrying out reduced pressure concentration on the naringin eluent obtained in the step (4) at 50 ℃, and carrying out freeze drying to obtain the purified naringin, wherein the yield of the naringin is 8.3%, and the purity of the naringin is 82%.
(6) At normal temperature, dissolving the naringin obtained in the step (5) in a potassium hydroxide solution with the pH value of 11, adding palladium-carbon as a catalyst, introducing hydrogen, keeping the pressure at 0.8MPa, carrying out hydrogenation reaction for 160min under the condition of stirring, filtering to remove the palladium-carbon, and obtaining a filtrate which is a hydrogenation solution.
(7) And (3) adjusting the pH value of the filtrate (hydrogenated solution) obtained by filtering in the step (6) to 7 by using concentrated sulfuric acid, standing for 24h, filtering, and freeze-drying the precipitate obtained by filtering to obtain the naringin dihydrochalcone.
The subcritical water extraction conditions, the yield and purity of naringin and the yield and purity of naringin dihydrochalcone in the embodiment 1 are shown as a sequence number 1 in the table 1. In addition, in the embodiment of the invention, the influence of different subcritical extraction conditions on the yield and purity of naringin and naringin dihydrochalcone is also considered, and the preparation method is basically the same as that of the embodiment 1, except for the difference shown in the table 1.
TABLE 1 Effect of different preparation conditions on the extraction of naringin and the preparation of naringin dihydrochalcone
As can be seen from the table 1, the method can improve the yield and the purity of the naringin and the naringin dihydrochalcone, wherein the yield of the naringin is up to 8.5 percent, and the purity is up to 97 percent; the yield of the naringin dihydrochalcone reaches 94 percent, and the purity reaches 95 percent, which shows that the method is favorable for improving the yield and the purity of the naringin and the naringin dihydrochalcone.
Example 2
The influence of different macroporous resins on the extraction effect of naringin is examined:
taking 2.0g of each of D101 macroporous adsorption resin, D4020 macroporous adsorption resin, AB-8 macroporous adsorption resin, D130 macroporous adsorption resin, HPD450 macroporous adsorption resin and D140 macroporous adsorption resin, adding to 30mL of the supernatant obtained in the step (3) of example 1, standing at room temperature for sufficient adsorption to reach saturation, filtering for 24h, and determining the naringin content in the sample solution before and after adsorption and the naringin content in the eluent after elution with an ethanol solution with a volume concentration of 90%, wherein the results are shown in Table 2. Table 2 shows the comparison of the adsorption capacity and the desorption capacity of different macroporous resins.
The adsorption rate and desorption rate of the macroporous resin to the limonin are calculated according to the following formula.
Adsorption rate (%) - (C)0－C1)/C0×100
Desorption rate (%) ═ C2/(C0－C1)×100
In the formula: c0The concentration of a target component solution in an initial sample is mg/mL;
C1the concentration of the target component in the filtrate after the resin adsorption is saturated is mg/mL.
C2The concentration of the target component in the desorption solution is mg/mL.
TABLE 2 comparison of adsorption and desorption capacities of different macroporous resins
| Macroporous resin | Adsorption Capacity (mg/g) | Resolution (%) |
| D101 | 62.8 | 78.7 |
| D130 | 95.2 | 96.2 |
| D140 | 86.3 | 68.4 |
| HPD450 | 71.7 | 95.8 |
| D4020 | 89.6 | 43.5 |
| AB-8 | 93.4 | 86.0 |
As can be seen from table 2, the results of screening 6 macroporous resins by static adsorption and desorption experiments show that: the D130 macroporous adsorption resin shows the best adsorption performance and desorption effect, the adsorption capacity of the resin on the naringin is 95.2%, the resolution rate is 96.2%, and the resin is a resin capable of enriching and purifying the naringin better.
Comparative example 1
A method for preparing naringin dihydrochalcone comprises the following steps:
(1) drying fresh pomelo peel at constant temperature of 50 deg.C, and pulverizing to 2mm to obtain pomelo peel powder; soaking the shaddock peel powder in water for 30min according to the volume ratio of the shaddock peel powder to the water of 1:5, stirring until the shaddock peel powder is colorless, filtering and drying to obtain the shaddock peel powder residue.
(2) Immersing the pomelo peel powder residue obtained in the step (1) in an equal volume of saturated Ca (OH) at 25 DEG C2And performing ultrasonic treatment for 30min under the condition of the frequency of 25KHz to obtain the shaddock peel powder residue mixed solution.
(3) And (3) adjusting the pH value of the shaddock ped powder residue mixed solution obtained in the step (2) to 13 by using a 5mol/L NaOH solution, filtering, adding 1mol/L hydrochloric acid for neutralization until the pH value is 4.5, filtering the obtained precipitate, and drying in vacuum at 70 ℃ to obtain crude naringin.
(4) Dissolving the crude naringin obtained in the step (3) by using an aqueous solution containing NaOH and ethanol (in the aqueous solution, the concentration of NaOH is 1g/mL, the volume concentration of ethanol is 50%), filtering, adding 1mol/L hydrochloric acid to adjust the pH value to 5.0, washing the obtained precipitate by using an ethanol solution with the volume concentration of 50%, washing the precipitate to be nearly neutral by using water, and carrying out vacuum drying at 70 ℃ to obtain the refined naringin, wherein the yield is 5.82%, and the purity is 62.2%.
(5) At normal temperature, dissolving the refined naringin obtained in the step (4) in a potassium hydroxide solution with the pH value of 11, adding palladium carbon as a catalyst, introducing hydrogen to maintain the pressure at 0.8MPa, carrying out hydrogenation reaction for 160min under the stirring condition, filtering to remove the palladium carbon, adjusting the pH value of the filtrate to 7 by using concentrated sulfuric acid, standing for 24h, filtering, taking the precipitate obtained by filtering, and carrying out freeze drying to obtain naringin dihydrochalcone, wherein the yield is 80%, and the purity is 65%.
Comparative example 2
A method for preparing naringin dihydrochalcone comprises the following steps:
(1) 100g of the citrus peel powder prepared in the example 1 is taken and sequentially extracted by 1200mL, 1000mL and 800mL of ethanol solution (the volume concentration is 40%) under reflux for 2h, 1.5h and 1h respectively. Mixing the extractive solutions obtained by 3 times of reflux extraction, concentrating under 0.04MPa to specific gravity of 1.15, adding 3.5 times of water into the concentrated solution, stirring, centrifuging, adsorbing the supernatant with D130 macroporous adsorbent resin, and desorbing with 60 vol% ethanol solution. Adding 2.5% (i.e. the addition amount of the activated carbon is 2.5% of the total mass of the desorption solution) of activated carbon into the desorption solution, refluxing, stirring, decolorizing for 2.5h, cooling, filtering, concentrating the filtrate under reduced pressure until the specific gravity is 1.55, cooling to 35 deg.C, and crystallizing for 14h to obtain crude crystals. The crude crystals were centrifuged, and the precipitated crude crystals were recrystallized 3 times with water. And pouring the recrystallized material into a centrifuge for centrifugation, and leaching the precipitate obtained by centrifugation with water to obtain the naringin precipitate. Drying naringin precipitate in oven at 75 deg.C, pulverizing the refined naringin, and sieving with 80 mesh sieve to obtain naringin product with yield of 2.82% and purity of 82.7%.
(2) At normal temperature, dissolving the naringin finished product obtained in the step (2) in a potassium hydroxide solution with the pH value of 11, adding palladium carbon as a catalyst, introducing hydrogen, introducing the hydrogen under the pressure of 0.8MPa, carrying out hydrogenation reaction for 160min under the stirring condition, filtering to remove the palladium carbon, adjusting the pH value of the filtrate to 7 by using concentrated sulfuric acid, standing for 24h, filtering, taking the precipitate obtained by filtering, and carrying out freeze drying to obtain naringin dihydrochalcone, wherein the yield is 83% and the purity is 76.3%.
In conclusion, the preparation method can improve the yield and the purity of the naringin, wherein the yield of the naringin is up to 8.5 percent, the purity of the naringin is up to 97 percent, and simultaneously can improve the yield and the purity of the naringin dihydrochalcone, wherein the yield of the naringin dihydrochalcone is up to 94 percent, and the purity of the naringin dihydrochalcone is up to 95 percent. In addition, in the preparation method, the flow is simplified, the period is shortened, and the preparation method has the advantages of simple process, convenience in operation, low cost and the like, and simultaneously, as organic solvents such as methanol, petroleum ether, n-butanol and the like are not used, the sewage amount is greatly reduced, the preparation method is economic and environment-friendly, is very suitable for large-scale production, and is easy to realize industrialization. In the comparative example 1, a large amount of strong acid and strong base is used, so that the environmental pollution is serious, and the added harmful substances are not easy to remove completely, can hurt human bodies and are not beneficial to industrial production; the extraction process flow in the comparative example 2 is complex, the required time is long, a large amount of ethanol is required for naringin extraction, the cost is high, the ethanol is discarded and is discharged into sewage directly, so that the environmental pollution is caused, and if the ethanol is discharged after treatment, the enterprise cost is increased, and the industrial mass production is not facilitated. In addition, the naringin obtained in the comparative examples 1 and 2 has not ideal purity, and is easy to generate toxic and side effects on human bodies after being eaten. Therefore, compared with the conventional preparation methods (such as comparative example 1 and comparative example 2), the preparation method disclosed by the invention has the advantages of simple process, convenience in operation, low cost, environmental friendliness, high resource utilization rate, high preparation efficiency, high yield, high purity and the like, can improve the comprehensive utilization value of the citrus, has good application prospect and economic benefit, does not need to use an organic solvent in the preparation process, does not bring secondary pollution to the environment, is an environment-friendly preparation method with a good prospect, is suitable for large-scale preparation, and is convenient for industrial utilization.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (8)
1. A preparation method of naringin dihydrochalcone is characterized by comprising the following steps:
s1, drying and carrying out superfine grinding on the citrus peel to obtain citrus peel powder;
s2, taking the deoxidized distilled water as an extraction solvent, performing first subcritical water extraction on the citrus peel powder obtained in the step S1, performing filter pressing, and discarding filtrate to obtain filter residue; the weight ratio of the deoxygenated distilled water to the citrus peel powder is 1: 4-1: 12; the pressure intensity of the first subcritical water extraction is 3 MPa-12 MPa; the temperature of the first subcritical water extraction is 80-250 ℃;
s3, mixing the filter residue obtained in the step S2 with activated carbon, performing second subcritical water extraction by using deoxidized distilled water as an extraction solvent, centrifuging, and removing the filter residue to obtain a naringin extracting solution; the mass ratio of the active carbon to the filter residue is 0.5-8%; the weight ratio of the deoxygenated distilled water to the filter residue is 1: 4-1: 12; the pressure intensity of the second subcritical water extraction is 2 MPa-12 MPa; the temperature of the second subcritical water extraction is 80-225 ℃;
s4, purifying the naringin extracting solution obtained in the step S3 by using resin, and eluting the naringin adsorbed on the resin to obtain a naringin eluent; the resin is D130 macroporous adsorption resin;
s5, carrying out reduced pressure concentration and freeze drying on the naringin eluent obtained in the step S4 to obtain naringin;
s6, dissolving the naringin obtained in the step S5 in alkali liquor, adding a catalyst, introducing hydrogen to carry out hydrogenation reaction, and filtering to obtain a hydrogenation solution; the hydrogenation reaction time is 30 min-240 min;
s7, adjusting the pH value of the hydrogenated solution obtained in the step S6, standing, filtering, and freeze-drying to obtain the naringin dihydrochalcone.
2. The production method according to claim 1, wherein in step S2, the first subcritical water extraction is performed under a nitrogen atmosphere; the time of the first subcritical water extraction is 15-70 min.
3. The method according to claim 1, wherein in step S3, the second subcritical water extraction is performed under a nitrogen atmosphere; the time of the second subcritical water extraction is 15-70 min; the centrifugation is carried out at the rotating speed of 5000-10000 rpm; the centrifugation time is 10 min-20 min.
4. The preparation method according to any one of claims 1 to 3, wherein in the step S1, the citrus peel is at least one of orange peel, tangerine peel, pomelo peel and orange peel; the particle size of the citrus peel powder is 10-50 mu m.
5. The preparation method according to any one of claims 1 to 3, wherein in the step S4, the eluent used in the elution process is an ethanol solution; the volume concentration of the ethanol solution is 65-95%; the volume of the eluent is 5 to 15 times of the volume of the resin.
6. The production method according to any one of claims 1 to 3, wherein the concentration under reduced pressure in step S5 is performed at a temperature of 40 ℃ to 80 ℃.
7. The method according to any one of claims 1 to 3, wherein in the step S6, the alkali solution is a sodium hydroxide solution and/or a potassium hydroxide solution; the pH value of the alkali liquor is 9-14; the catalyst is palladium carbon; and in the hydrogenation reaction process, the pressure of the reaction system is maintained to be 0.5-5 MPa by introducing hydrogen.
8. The production method according to any one of claims 1 to 3, wherein in the step S7, the hydrogenation solution is adjusted with a concentrated acid; the concentrated acid is concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid; adjusting the pH value of the hydrogenation solution to 7-9; the standing time is 6-48 h.
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| NL2032241A (en) * | 2021-08-23 | 2023-02-27 | Guangdong Lijinyou Agricultural Science & Tech Co Ltd | Method for preparing naringin dihydrochalcone through circulating spray hydrogenation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990013994A2 (en) * | 1990-07-17 | 1990-11-29 | Wm. Wrigley Jr. Company | Controlled release of dihydrochalcones in chewing gum |
| CN105754014A (en) * | 2016-03-03 | 2016-07-13 | 湖南省农产品加工研究所 | Extraction method of pectin and polyphenol in orange peel |
| CN105801636A (en) * | 2016-03-24 | 2016-07-27 | 济南诚汇双达化工有限公司 | Synthetic method for naringin dihydrochalcone |
| CN107602636A (en) * | 2017-08-15 | 2018-01-19 | 涟源康麓生物科技有限公司 | The preparation method of new hesperidin methyl dihydrochalcone |
-
2018
- 2018-06-29 CN CN201810706176.7A patent/CN108752400B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990013994A2 (en) * | 1990-07-17 | 1990-11-29 | Wm. Wrigley Jr. Company | Controlled release of dihydrochalcones in chewing gum |
| CN105754014A (en) * | 2016-03-03 | 2016-07-13 | 湖南省农产品加工研究所 | Extraction method of pectin and polyphenol in orange peel |
| CN105801636A (en) * | 2016-03-24 | 2016-07-27 | 济南诚汇双达化工有限公司 | Synthetic method for naringin dihydrochalcone |
| CN107602636A (en) * | 2017-08-15 | 2018-01-19 | 涟源康麓生物科技有限公司 | The preparation method of new hesperidin methyl dihydrochalcone |
Non-Patent Citations (2)
| Title |
|---|
| 亚临界水提取陈皮中橙皮苷的工艺研究;张锐，等;《中成药》;20131130;第35卷(第11期);第2531-2533页 * |
| 亚临界水萃取陈皮中橙皮苷的工艺研究;齐兵，等;《食品工业科技》;20131231;第34卷(第12期);第225-228页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL2032241A (en) * | 2021-08-23 | 2023-02-27 | Guangdong Lijinyou Agricultural Science & Tech Co Ltd | Method for preparing naringin dihydrochalcone through circulating spray hydrogenation |
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