CN112358512A - Method for preparing hesperidin from citrus - Google Patents
Method for preparing hesperidin from citrus Download PDFInfo
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Abstract
The invention discloses a method for preparing hesperidin from citrus, which comprises the following steps: (1) pretreatment of orange peel and residues: cleaning, drying and crushing citrus peel residues; (2) ultrasonic extraction: adding the citrus peel residue powder into an ultrasonic extraction device, extracting with NaOH-ethanol, and filtering to obtain citrus hesperidin extract; (3) low-temperature concentration: concentrating the hesperidin extract in a low-temperature concentration device to obtain hesperidin concentrate, and recovering ethanol; (4) separation and purification: adding HCl solution into the concentrated solution of hesperidin to adjust pH, separating out crude hesperidin, cleaning, and recrystallizing with ethanol; (5) preparing a finished product: the method adopts ultrasonic-assisted organic solvent extraction, improves extraction rate of hesperidin, shortens extraction time, reduces extraction solvent consumption, and reduces heat energy consumption by low-temperature concentration.
Description
Technical Field
The invention belongs to the field of natural product extraction, and particularly relates to a method for preparing hesperidin from citrus.
Background
Citrus (Citrus reticulata Blanco), plants of Rutaceae, and citrus peel residues have high medicinal value. Hesperidin is one of main components in citrus flavonoids, is called as hesperetin-7-O-neohesperidin, has high biological activity and good antioxidation, and has an inhibiting effect on mutagenicity of heterocyclic amine substances, 1-methyl-1, 2, 3, 4-tetrahydro-beta-carboline-3-carboxylic acid and N-methyl-N-nitro-N-nitrosoguanidine; can inhibit carcinogenesis of ammonium nitrite, aflatoxin and other carcinogenic substances, and has certain effect in preventing tumor such as breast cancer and lung cancer; can be used for preventing and treating gastric ulcer; has inhibitory effect on Staphylococcus aureus and Salmonella; antagonism against certain poisons; in addition, it also has antiinflammatory, blood lipid reducing, cholesterol reducing, spasmolytic, and analgesic effects.
Hesperidin is widely used in food industry and pharmaceutical industry, and in food industry, hesperidin can be used as natural pigment, flavor modifier and bittering agent for producing food and beverage, and also can be used as raw material for synthesizing novel sweetener dihydronaringin chalcone; in the pharmaceutical industry, can be used for producing medicaments for treating cardiovascular and cerebrovascular diseases and diminishing inflammation.
China is a large citrus planting country, annual yield of citrus is high, a large amount of citrus peel is generated along with increase of the yield of citrus, many citrus peel are discarded at present without further processing and utilization, and the discarded citrus peel causes environmental pollution and is extremely resource waste.
At present, common extraction methods of hesperidin from citrus are a soaking method and an alcohol solvent reflux method, but the extraction methods have the defects of large solvent consumption, large toxic and side effects, low extraction rate, long time and the like, and are not beneficial to industrialization. The difference of the extraction method not only can directly influence the extraction rate, the purity and the production cost of the hesperidin, but also can play an important role in the functions and the quality of downstream products. Therefore, establishing a safe, green and efficient hesperidin extraction method becomes a research hotspot for development and utilization of hesperidin.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method for preparing the hesperidin from the citrus aurantiamarus is high in extraction rate, small in extraction solvent consumption and high in automation degree, and solves the problems that the loss of effective components is large, the extraction rate is low, the consumption of an organic solvent is large, the toxic and side effects of the organic solvent are large, the large-scale industrial production of the hesperidin from the citrus aurantiamarus is difficult, and the like.
In order to solve the technical problems, the technical scheme of the invention is as follows: a process for preparing hesperidin from citrus, comprising the steps of:
1) pretreatment of orange peel and residues: cleaning fresh raw materials of citrus peel residues with clear water, drying with hot air at the temperature of 40-70 DEG C
Drying for 5-24 h to ensure that the water content of the citrus peel residues is lower than 10%; crushing the dried orange peel residues by a high-speed crusher, sieving by a 40-mesh sieve to obtain orange peel residue powder, and directly crushing and sieving if dried orange peel residues are selected;
2) ultrasonic countercurrent extraction: weighing the citrus peel residue powder obtained in the step 1), adding the citrus peel residue powder and 50-80% of ethanol aqueous solution into a continuous ultrasonic extraction device according to the mass-volume ratio of 1: 8-1: 15kg/L, adding NaOH solution, adjusting the PH of an extracting solution to be 11-12, then carrying out continuous ultrasonic extraction, and filtering with a filter screen to obtain a citrus hesperidin extracting solution;
3) low-temperature concentration: performing rotary evaporation on the hesperidin extract obtained in the step 2), and recovering ethanol for the step 2) to obtain a hesperidin concentrate, wherein the water bath temperature of the rotary evaporation is 40-70 DEG
The rotating speed is 20-100 rpm, the vacuum degree is-0.07 to-0.09 MPa, and the citrus hesperidin concentrate is subjected to rotary evaporation until the volume of the citrus hesperidin concentrate is 1/3-1/10 of the volume of the extract;
4) separation and purification: adding an HCl solution into the hesperidin concentrate obtained in the step 3), enabling the pH of the concentrate to be 3-4, standing for 8-24 hours, performing suction filtration to obtain a white solid precipitate, washing with clear water to obtain crude hesperidin, and recrystallizing the crude hesperidin with 80-100% ethanol to obtain hesperidin crystals;
5) preparing a finished product: and (4) putting the citrus hesperidin crystals obtained in the step (4) into a vacuum freeze dryer for freeze drying at the temperature of-60 to-50 ℃, pre-freezing for 6 to 10 hours, vacuumizing for less than 20pa, and drying to ensure that the water content of the sample is less than 1% to obtain the high-purity citrus hesperidin.
Preferably, when the continuous countercurrent ultrasonic extraction is carried out in the step 2), the addition amount of the citrus peel slag powder is 100-500 g/min, the flow rate of the ethanol water solution is 1000-5000 ml/min, the ultrasonic power is 200-800 w, and the extraction temperature is 30-70 ℃.
Preferably, the ultrasonic extraction mode in the step 2) is continuous extraction for 2 times, and each time lasts for 10-15 min.
Preferably, one end of the continuous ultrasonic extraction device in the step 2) is connected with the citrus peel slag powder storage tank and the extracting solution collection tank, the other end of the continuous ultrasonic extraction device is connected with the residue collection tank and the ethanol water solution storage tank, and the citrus peel slag powder and the ethanol water solution as raw materials respectively enter the ultrasonic extraction device from opposite directions to realize continuous extraction.
Preferably, the ethanol recovered in step 3) is recycled for use in step 2).
Preferably, the temperature of the water bath subjected to rotary evaporation in the step 3) is 50-70 DEG
The rotating speed is 40-100 rpm, the vacuum degree is-0.08 to-0.09 MPa, and the citrus hesperidin concentrate is subjected to rotary evaporation until the volume of the citrus hesperidin concentrate is 1/5-1/8 of the volume of the extract.
Preferably, in the step 4), the crude hesperidin is recrystallized by 95% ethanol, the crystallization solution is subjected to low-temperature rotary concentration at 30-60 ℃, the concentrated crystallization solution is subjected to standing recrystallization at 4-10 ℃, and is filtered and washed with clear water for 2-3 times to obtain hesperidin crystals.
Preferably, in the step 5), pre-freezing is carried out in a vacuum freeze dryer at the temperature of-56 ℃ for 8-10 h, the vacuumizing is less than 15pa, and drying is carried out to ensure that the water content of the sample is less than 0.8%.
After the technical scheme is adopted, the invention has the effects that: a method for preparing citrus hesperidin adopts an extraction mode of ultrasonic-assisted organic solvent extraction, ultrasonic cavitation can accelerate citrus hesperidin in plants to enter a solvent, the extraction rate of the citrus hesperidin is increased, the use amount of the extraction solvent is reduced, the method is more environment-friendly, in addition, a low-temperature energy-saving concentration technology is adopted, a heating medium can be recycled for multiple times, the heat energy consumption is reduced, the solvent recovery rate is improved, and meanwhile, the discharge pollution is reduced.
The application of the invention also adopts a method for recrystallizing the hesperidin of the citrus by using ethanol with the concentration of more than 80 percent to further separate and purify the flavonoid of the citrus and optimize the parameters of the separation process.
In addition, the ethanol recovered in the step 3) can be further recycled in the step 2), so that the ethanol is fully utilized, and the production cost is reduced.
Detailed Description
The present invention is described in further detail below with reference to specific examples.
Example 1
A process for preparing hesperidin from citrus, comprising the steps of:
1) pretreatment of orange peel and residues: cleaning fresh raw materials of citrus peel residues with clear water, drying with hot air at 55 deg.C for 10h to make the water content of the citrus peel residues 8%; crushing the dried orange peel residues by a high-speed crusher, sieving by a 40-mesh sieve to obtain orange peel residue powder, and directly crushing and sieving if dried orange peel residues are selected;
2) extraction: weighing 2kg of the citrus peel residue powder obtained in the step 1), putting the citrus peel residue powder into a container, adding 20L of 70% ethanol water solution, wherein the mass-volume ratio of the citrus peel residue powder to the 70% ethanol water solution is 1:10kg/L, then continuously adding NaOH solution into the container, adjusting the pH of an extracting solution to be 11, extracting for 4 hours at the temperature of 50 ℃, and filtering by using a filter screen to obtain an orange hesperidin extracting solution;
3) low-temperature concentration: performing rotary evaporation on the citrus hesperidin extract obtained in the step 2), and recovering ethanol for the step 2) to obtain a citrus hesperidin concentrate, wherein the water bath temperature of the rotary evaporation is 55 ℃, the rotary speed is 80rpm, the vacuum degree is-0.08 MPa, and the rotary evaporation is performed until the volume of the citrus hesperidin concentrate is 1/4 of the volume of the extract;
4) separation and purification: adding an HCl solution into the hesperidin concentrate obtained in the step 3), enabling the pH of the concentrate to be 3, standing for 24 hours, performing suction filtration to obtain a white solid precipitate, washing with clear water to obtain crude hesperidin, recrystallizing the crude hesperidin with 95% ethanol, performing low-temperature rotary concentration on the crystallized solution at 50 ℃, standing the concentrated crystallized solution at 8 ℃ for recrystallization, filtering, and washing with clear water for 2-3 times to obtain hesperidin crystals;
5) preparing a finished product: and (4) putting the citrus hesperidin crystals obtained in the step (4) into a vacuum freeze dryer for freeze drying at the temperature of-56 ℃, pre-freezing for 6 hours, vacuumizing for 10pa, and drying to enable the water content of the sample to be 0.8% to obtain 61.2g of high-purity citrus hesperidin.
In this example 1, only the method of organic solvent extraction is adopted, the method of continuous ultrasonic extraction is not adopted, the hesperidin standard is used as a standard sample, and a spectrophotometer is used to measure the absorbance at 287nm absorption wavelength to detect the hesperidin content in the hesperidin product, so that the hesperidin purity detected finally is 95.6%.
Example 2
A process for preparing hesperidin from citrus, comprising the steps of:
1) pretreatment of orange peel and residues: cleaning fresh raw materials of citrus peel residues with clear water, drying with hot air at 55 deg.C for 10h to make the water content of the citrus peel residues 8%, pulverizing the dried citrus peel residues with a high-speed pulverizer, sieving with 40 mesh sieve to obtain citrus peel residue powder, and directly pulverizing and sieving if dried citrus peel residues are selected;
2) ultrasonic countercurrent extraction: one end of the continuous ultrasonic extraction device is connected with the citrus peel slag powder storage tank and the extracting solution collection tank, the other end of the continuous ultrasonic extraction device is connected with the residue collection tank and the ethanol water solution storage tank, and the citrus peel slag powder and the ethanol water solution as raw materials respectively enter the ultrasonic extraction device from opposite directions to realize continuous extraction.
Weighing 2kg of the citrus peel slag powder obtained in the step 1) in a citrus peel slag powder storage tank, and adding the citrus peel slag powder into a continuous ultrasonic extraction device at a speed of 100 g/min. Preparing 20L of 70% ethanol solution, storing in an ethanol water solution storage tank, adding NaOH solution, adjusting the pH of the extracting solution to be 11, flowing into a continuous ultrasonic extraction device at a flow rate of 1000ml/min, then carrying out continuous ultrasonic extraction with an ultrasonic power of 300w and an extraction temperature of 50 ℃, filtering by a filter screen, and carrying out continuous ultrasonic extraction for 2 times, 10min each time, thus obtaining the hesperidin extract;
3) low-temperature concentration: performing rotary evaporation on the citrus hesperidin extract obtained in the step 2), and recovering ethanol for the step 2) to obtain a citrus hesperidin concentrate, wherein the water bath temperature of the rotary evaporation is 55 ℃, the rotary speed is 80rpm, the vacuum degree is-0.08 MPa, and the rotary evaporation is performed until the volume of the citrus hesperidin concentrate is 1/4 of the volume of the extract;
4) separation and purification: adding an HCl solution into the hesperidin concentrate obtained in the step 3), enabling the pH of the concentrate to be 3, standing for 24 hours, performing suction filtration to obtain a white solid precipitate, washing with clear water to obtain crude hesperidin, recrystallizing the crude hesperidin with 95% ethanol, performing low-temperature rotary concentration on the crystallized solution at 50 ℃, standing the concentrated crystallized solution at 8 ℃ for recrystallization, filtering, and washing with clear water for 2-3 times to obtain hesperidin crystals;
5) preparing a finished product: and (4) putting the citrus hesperidin crystals obtained in the step (4) into a vacuum freeze dryer for freeze drying at the temperature of minus 50 ℃, pre-freezing for 6 hours, vacuumizing for 10pa, and drying to enable the water content of the sample to be 0.8% to obtain 78.9g of high-purity citrus hesperidin.
Taking a hesperidin standard sample as a standard sample, and measuring absorbance at 287nm absorption wavelength by using a spectrophotometer to detect the hesperidin content in the citrus hesperidin product, wherein the purity of the citrus hesperidin is finally detected to be 96.2%.
Example 3
A process for preparing hesperidin from citrus, comprising the steps of:
1) pretreatment of orange peel and residues: cleaning fresh raw materials of citrus peel residues with clear water, drying with hot air at 70 deg.C for 5h to make the water content of the citrus peel residues 5%, pulverizing the dried citrus peel residues with a high-speed pulverizer, sieving with 40 mesh sieve to obtain citrus peel residue powder, and directly pulverizing and sieving if dried citrus peel residues are selected;
2) ultrasonic countercurrent extraction: one end of the continuous ultrasonic extraction device is connected with the citrus peel slag powder storage tank and the extracting solution collection tank, the other end of the continuous ultrasonic extraction device is connected with the residue collection tank and the ethanol water solution storage tank, and the citrus peel slag powder and the ethanol water solution as raw materials respectively enter the ultrasonic extraction device from opposite directions to realize continuous extraction.
Weighing the citrus peel slag powder in the step 1), adding the citrus peel slag powder and 80% ethanol aqueous solution into a continuous ultrasonic extraction device according to the mass-volume ratio of 1:8kg/L, wherein the adding speed of the citrus peel slag powder is 500g/min, the flow of the ethanol aqueous solution is 4000ml/min, adding NaOH solution, adjusting the pH of an extracting solution to be 12, then carrying out continuous ultrasonic extraction, wherein the ultrasonic power is 200w, the extraction temperature is 70 ℃, filtering with a filter screen, and continuously extracting for 2 times, each time for 15min to obtain a citrus hesperidin extracting solution;
3) low-temperature concentration: performing rotary evaporation on the citrus hesperidin extract obtained in the step 2), and recovering ethanol for the step 2) to obtain a citrus hesperidin concentrate, wherein the water bath temperature of the rotary evaporation is 60 ℃, the rotary speed is 60rpm, the vacuum degree is-0.09 MPa, and the rotary evaporation is performed until the volume of the citrus hesperidin concentrate is 1/3 which is about the volume of the extract;
4) separation and purification: adding an HCl solution into the hesperidin concentrate obtained in the step 3), enabling the pH value of the concentrate to be 4, standing for 10 hours, performing suction filtration to obtain a white solid precipitate, washing with clear water to obtain crude hesperidin, recrystallizing the crude hesperidin with 100% ethanol, performing low-temperature rotary concentration on the crystallization dissolving solution at 40 ℃, standing the concentrated crystallization dissolving solution at 10 ℃ for recrystallization, filtering, and washing with clear water for 2-3 times to obtain hesperidin crystals;
5) preparing a finished product: and (4) putting the citrus hesperidin crystals obtained in the step (4) into a vacuum freeze dryer for freeze drying at the temperature of-60 ℃, pre-freezing for 8 hours, vacuumizing for 18pa, and drying to enable the water content of the sample to be 0.6% so as to obtain 79.2g of high-purity citrus hesperidin.
Taking a hesperidin standard sample as a standard sample, and measuring absorbance at 287nm absorption wavelength by using a spectrophotometer to detect the hesperidin content in the citrus hesperidin product, wherein the purity of the citrus hesperidin is finally detected to be 95.8%.
Example 4
A process for preparing hesperidin from citrus, comprising the steps of:
1) pretreatment of orange peel and residues: cleaning fresh raw materials of citrus peel residues with clear water, drying with hot air at 40 deg.C for 24h to make the water content of the citrus peel residues 6%, pulverizing the dried citrus peel residues with a high-speed pulverizer, sieving with 40 mesh sieve to obtain citrus peel residue powder, and directly pulverizing and sieving if dried citrus peel residues are selected;
2) ultrasonic countercurrent extraction: one end of the continuous ultrasonic extraction device is connected with the citrus peel slag powder storage tank and the extracting solution collection tank, the other end of the continuous ultrasonic extraction device is connected with the residue collection tank and the ethanol water solution storage tank, and the citrus peel slag powder and the ethanol water solution as raw materials respectively enter the ultrasonic extraction device from opposite directions to realize continuous extraction.
Weighing the citrus peel slag powder in the step 1), adding the citrus peel slag powder and a 50% ethanol aqueous solution into a continuous ultrasonic extraction device according to the mass-volume ratio of 1:8kg/L, wherein the adding speed of the citrus peel slag powder is 500g/min, the flow of the ethanol aqueous solution is 4000ml/min, adding a NaOH solution, adjusting the pH of an extracting solution to be 11, then carrying out continuous ultrasonic extraction, wherein the ultrasonic power is 500w, the extraction temperature is 30 ℃, filtering with a filter screen, and continuously extracting for 2 times, each time for 10min to obtain a citrus hesperidin extracting solution;
3) low-temperature concentration: performing rotary evaporation on the citrus hesperidin extract obtained in the step 2), and recovering ethanol for the step 2) to obtain a citrus hesperidin concentrate, wherein the water bath temperature of the rotary evaporation is 70 ℃, the rotary speed is 20rpm, the vacuum degree is-0.09 MPa, and the rotary evaporation is performed until the volume of the citrus hesperidin concentrate is 1/10 of the volume of the extract;
4) separation and purification: adding an HCl solution into the hesperidin concentrate obtained in the step 3), enabling the pH value of the concentrate to be 4, standing for 8 hours, performing suction filtration to obtain a white solid precipitate, washing with clear water to obtain crude hesperidin, recrystallizing the crude hesperidin with 100% ethanol, performing low-temperature rotary concentration on a crystallization dissolving solution at 60 ℃, standing and recrystallizing the concentrated crystallization dissolving solution at 4 ℃, filtering, and washing with clear water for 2-3 times to obtain a hesperidin crystal;
5) preparing a finished product: and (4) putting the citrus hesperidin crystals obtained in the step (4) into a vacuum freeze dryer for freeze drying at the temperature of-56 ℃, pre-freezing for 6 hours, vacuumizing for 15pa, and drying to enable the water content of the sample to be 0.8% to obtain 68.3g of high-purity citrus hesperidin.
Taking a hesperidin standard sample as a standard sample, and measuring absorbance at 287nm absorption wavelength by using a spectrophotometer to detect the hesperidin content in the citrus hesperidin product, wherein the purity of the citrus hesperidin is finally detected to be 94.9%.
Example 5
A process for preparing hesperidin from citrus, comprising the steps of:
1) pretreatment of orange peel and residues: cleaning fresh raw materials of citrus peel residues with clear water, drying with hot air at 60 deg.C for 24h to make the water content of the citrus peel residues 5%, pulverizing the dried citrus peel residues with a high-speed pulverizer, sieving with 40 mesh sieve to obtain citrus peel residue powder, and directly pulverizing and sieving if dried citrus peel residues are selected;
2) ultrasonic countercurrent extraction: one end of the continuous ultrasonic extraction device is connected with the citrus peel slag powder storage tank and the extracting solution collection tank, the other end of the continuous ultrasonic extraction device is connected with the residue collection tank and the ethanol water solution storage tank, and the citrus peel slag powder and the ethanol water solution as raw materials respectively enter the ultrasonic extraction device from opposite directions to realize continuous extraction.
Weighing the citrus peel slag powder in the step 1), adding the citrus peel slag powder and a 60% ethanol aqueous solution into a continuous ultrasonic extraction device according to a mass-volume ratio of 1:8kg/L, wherein the adding speed of the citrus peel slag powder is 200g/min, the flow of the ethanol aqueous solution is 3000ml/min, adding a NaOH solution, adjusting the pH of an extracting solution to be 12, then carrying out continuous ultrasonic extraction, wherein the ultrasonic power is 200w, the extraction temperature is 50 ℃, filtering with a filter screen, and continuously extracting for 2 times, each time for 15min to obtain a citrus hesperidin extracting solution;
3) low-temperature concentration: performing rotary evaporation on the citrus hesperidin extract obtained in the step 2), and recovering ethanol for the step 2) to obtain a citrus hesperidin concentrate, wherein the water bath temperature of the rotary evaporation is 40 ℃, the rotary speed is 100rpm, the vacuum degree is-0.07 MPa, and the rotary evaporation is performed until the volume of the citrus hesperidin concentrate is 1/3 of the volume of the extract;
4) separation and purification: adding an HCl solution into the hesperidin concentrate obtained in the step 3), enabling the pH value of the concentrate to be 3, standing for 20 hours, performing suction filtration to obtain a white solid precipitate, washing with clear water to obtain crude hesperidin, recrystallizing the crude hesperidin with 95% ethanol, performing low-temperature rotary concentration on the crystallized solution at 30 ℃, standing the concentrated crystallized solution at 8 ℃ for recrystallization, filtering, and washing with clear water for 2-3 times to obtain hesperidin crystals;
5) preparing a finished product: and (4) putting the citrus hesperidin crystals obtained in the step (4) into a vacuum freeze dryer for freeze drying at the temperature of-56 ℃, pre-freezing for 10 hours, vacuumizing for 10pa, and drying to enable the water content of the sample to be 0.5% to obtain 72.6g of high-purity citrus hesperidin.
Taking a hesperidin standard sample as a standard sample, and measuring absorbance at 287nm absorption wavelength by using a spectrophotometer to detect the hesperidin content in the citrus hesperidin product, wherein the purity of the citrus hesperidin is finally detected to be 95.9%.
Example 6
A process for preparing hesperidin from citrus, comprising the steps of:
1) pretreatment of orange peel and residues: cleaning fresh raw materials of citrus peel residues with clear water, drying with hot air at 70 deg.C for 15h to make the water content of the citrus peel residues 8%, pulverizing the dried citrus peel residues with a high-speed pulverizer, sieving with 40 mesh sieve to obtain citrus peel residue powder, and directly pulverizing and sieving if dried citrus peel residues are selected;
2) ultrasonic countercurrent extraction: one end of the continuous ultrasonic extraction device is connected with the citrus peel slag powder storage tank and the extracting solution collection tank, the other end of the continuous ultrasonic extraction device is connected with the residue collection tank and the ethanol water solution storage tank, and the citrus peel slag powder and the ethanol water solution as raw materials respectively enter the ultrasonic extraction device from opposite directions to realize continuous extraction.
Weighing the citrus peel slag powder in the step 1), adding the citrus peel slag powder and 80% ethanol water solution into a continuous ultrasonic extraction device according to the mass-volume ratio of 1:10kg/L, wherein the adding speed of the citrus peel slag powder is 500g/min, the flow of the ethanol water solution is 5000ml/min, adding NaOH solution, adjusting the PH of an extracting solution to be 11, then carrying out continuous ultrasonic extraction, wherein the ultrasonic power is 800w, the extraction temperature is 70 ℃, filtering with a filter screen, and continuously extracting for 2 times, each time for 12min to obtain a citrus hesperidin extracting solution;
3) low-temperature concentration: performing rotary evaporation on the citrus hesperidin extract obtained in the step 2), and recovering ethanol for the step 2) to obtain a citrus hesperidin concentrate, wherein the water bath temperature of the rotary evaporation is 40 ℃, the rotary speed is 80rpm, the vacuum degree is-0.07 MPa, and the rotary evaporation is performed until the volume of the citrus hesperidin concentrate is 1/4 of the volume of the extract;
4) separation and purification: adding an HCl solution into the hesperidin concentrate obtained in the step 3), enabling the pH of the concentrate to be 3, standing for 24 hours, performing suction filtration to obtain a white solid precipitate, washing with clear water to obtain crude hesperidin, recrystallizing the crude hesperidin with 80% ethanol, performing rotary concentration on the crystallized solution at a low temperature of 50 ℃, standing the concentrated crystallized solution at a temperature of 6 ℃ for recrystallization, filtering, and washing with clear water for 2-3 times to obtain hesperidin crystals;
5) preparing a finished product: and (4) putting the citrus hesperidin crystals obtained in the step (4) into a vacuum freeze dryer for freeze drying at the temperature of-60 ℃, pre-freezing for 10 hours, vacuumizing for 10pa, and drying to enable the water content of the sample to be 0.5% to obtain 77.5g of high-purity citrus hesperidin.
Taking a hesperidin standard sample as a standard sample, and measuring absorbance at 287nm absorption wavelength by using a spectrophotometer to detect the hesperidin content in the citrus hesperidin product, wherein the purity of the citrus hesperidin is finally detected to be 94.3%.
From the above examples 1 to 6, it can be seen that the application of the present invention adopts an extraction manner of ultrasonic-assisted organic solvent extraction, ultrasonic cavitation accelerates the entry of hesperidin from citrus into a solvent, and improves the extraction rate of hesperidin, and the ethanol recovered in step 3) can be repeatedly used in step 2), so that the usage amount of the extracted organic solvent is greatly reduced, and the application of the present invention also adopts an ethanol recrystallization method for hesperidin to further separate and purify citrus flavonoids, optimizes separation process parameters, and is simple and convenient to operate.
The above-mentioned embodiments are merely descriptions of the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various modifications and alterations made to the technical solution of the present invention without departing from the spirit of the present invention are intended to fall within the scope of the present invention defined by the claims.
Claims (8)
1. A method for preparing citrus hesperidin is characterized in that: the method comprises the following steps:
1) pretreatment of orange peel and residues: cleaning fresh orange peel residue raw materials with clear water, drying with hot air at 40-70 ℃ for 5-24 h to ensure that the water content of the orange peel residue is lower than 10%, crushing the dried orange peel residue with a high-speed crusher, sieving with a 40-mesh sieve to obtain orange peel residue powder, and directly crushing and sieving the orange peel residue powder if dried orange peel residue is selected;
2) ultrasonic countercurrent extraction: weighing the citrus peel residue powder obtained in the step 1), adding the citrus peel residue powder and 50-80% of ethanol aqueous solution into a continuous ultrasonic extraction device according to the mass-volume ratio of 1: 8-1: 15kg/L, adding NaOH solution, adjusting the PH of an extracting solution to be 11-12, then carrying out continuous ultrasonic extraction, and filtering with a filter screen to obtain a citrus hesperidin extracting solution;
3) low-temperature concentration: performing rotary evaporation on the citrus hesperidin extract obtained in the step 2), and recovering ethanol for the step 2) to obtain a citrus hesperidin concentrate, wherein the temperature of a water bath for rotary evaporation is 40-70, the rotation speed at the temperature of 20-100 rpm is controlled at the vacuum degree of-0.07-0.09 MPa, and the volume of the citrus hesperidin concentrate is 1/3-1/10 of the volume of the extract;
4) separation and purification: adding an HCl solution into the hesperidin concentrate obtained in the step 3), enabling the pH of the concentrate to be 3-4, standing for 8-24 hours, performing suction filtration to obtain a white solid precipitate, washing with clear water to obtain crude hesperidin, and recrystallizing the crude hesperidin with 80-100% ethanol to obtain hesperidin crystals;
5) preparing a finished product: and (4) putting the citrus hesperidin crystals obtained in the step (4) into a vacuum freeze dryer for freeze drying at the temperature of-60 to-50 ℃, pre-freezing for 6 to 10 hours, vacuumizing for less than 20pa, and drying to ensure that the water content of the sample is less than 1% to obtain the high-purity citrus hesperidin.
2. A process of preparing hesperidin from citrus as claimed in claim 1, wherein: when the continuous countercurrent ultrasonic extraction is carried out in the step 2), the addition amount of the citrus peel slag powder is 100-500 g/min, the flow of the ethanol water solution is 1000-5000 ml/min, the ultrasonic power is 200-800 w, the extraction temperature is 30-70 ℃, and the extraction time is 20-30 min.
3. A process of preparing hesperidin from citrus as claimed in claim 1, wherein: the ultrasonic extraction mode in the step 2) is continuous extraction for 2 times, and each time lasts for 10-15 min.
4. A process of preparing hesperidin from citrus as claimed in claim 1, wherein: one end of the continuous ultrasonic extraction device in the step 2) is connected with the citrus peel slag powder storage tank and the extracting solution collection tank, the other end of the continuous ultrasonic extraction device is connected with the residue collection tank and the ethanol water solution storage tank, and the citrus peel slag powder and the ethanol water solution as raw materials respectively enter the ultrasonic extraction device from opposite directions to realize continuous extraction.
5. A process of preparing hesperidin from citrus as claimed in claim 1, wherein: the ethanol recovered in the step 3) is recycled in the step 2).
6. A process of preparing hesperidin from citrus as claimed in claim 1, wherein: the temperature of the water bath for rotary evaporation in the step 3) is 50-70, the rotary speed at the temperature of 40-100 rpm is controlled, the vacuum degree is-0.08 to-0.09 MPa, and the rotary evaporation is carried out until the volume of the hesperidin concentrate is 1/5-1/8 of the volume of the extract.
7. A process of preparing hesperidin from citrus as claimed in claim 1, wherein: and (3) recrystallizing the crude hesperidin from 95% ethanol in the step 4), rotationally concentrating the crystallization dissolved solution at a low temperature of 30-60 ℃, standing the concentrated crystallization dissolved solution at a temperature of 4-10 ℃ for recrystallization, filtering, and washing with clear water for 2-3 times to obtain the hesperidin crystals.
8. A process of preparing hesperidin from citrus as claimed in claim 1, wherein: in the step 5), pre-freezing for 8-10 h at-56 ℃ in a vacuum freeze dryer, vacuumizing to less than 15pa, and drying to ensure that the water content of the sample is less than 0.8%.
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