CN113527120B - Extraction process of levo synephrine - Google Patents
Extraction process of levo synephrine Download PDFInfo
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- CN113527120B CN113527120B CN202110815794.7A CN202110815794A CN113527120B CN 113527120 B CN113527120 B CN 113527120B CN 202110815794 A CN202110815794 A CN 202110815794A CN 113527120 B CN113527120 B CN 113527120B
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- C07—ORGANIC CHEMISTRY
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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Abstract
The invention discloses an extraction process of levo-synephrine, which comprises the following steps: s1, selecting immature bitter orange and cutting immature bitter orange into slices; s2, selecting low-sulfur dioxide or sulfur-dioxide-free polycrystalline yellow rock sugar as a substrate for the sugar solution, mixing the olive flakes with the sugar solution, placing the mixture in a fermentation tank, controlling the temperature to be within 10 ℃ for full reaction, and filtering to separate syrup containing olive flavor and olive residues rich in stable natural substances; s3, grinding the olive pomace into homogenate by using liquid nitrogen ultralow temperature grinding equipment under the working condition of low temperature below zero, and refining the grain size of the pomace by using a screen; s4, uniformly stirring the crushed fruit residue fine powder and ethanol, carrying out reflux extraction, and filtering; s5, selecting cation adsorption resin to adsorb and elute the filtrate; s6, concentrating the resin eluent by using a nanofiltration membrane to obtain the high-purity levo-synephrine. The levo-synephrine product obtained by the invention has good quality, high purity and high yield.
Description
Technical Field
The invention relates to the field of extraction of levo-synephrine, in particular to an extraction process of levo-synephrine.
Background
Fructus Aurantii Immaturus is the dried young fruit of Citrus aurantium and its cultivated variety, such as Citrus sinensis, with bitter, pungent, sour and warm properties, and has effects of invigorating spleen, regulating stomach channel, removing qi, resolving food stagnation, eliminating phlegm and relieving distention. Fructus Aurantii Immaturus mainly contains brass, volatile oil and small amount of alkaloid. The flavonoid has antibacterial, antiviral, antiinflammatory, and vasodilating effects, and also has effects in inhibiting lipid peroxidation, platelet aggregation, and activity of a large amount of enzymes, and improving capillary permeability and fragility. The hesperidin has wide biological activities of resisting oxidation, reducing blood fat, resisting atherosclerosis and the like, and is an important medical raw material; the product is also an industrial raw material such as a flavoring agent, an antioxidant, a pigment, a health product and the like, and has high utilization value; the polymethoxy flavone in the flavone has pharmacological actions of antivirus, antibiosis, anti-tumor, antioxidation, cardiovascular and cerebrovascular disease resistance and the like, and the synthesis of the polymethoxy flavone has great practical value. In addition, the synephrine in the alkaloid is carried in northern three pharmacopoeias and German pharmacopoeias, and the levo-synephrine is an adrenergic alpha-receptor stimulant, has a certain excitation effect on heart-receptors, is a natural stimulant of the 21 st century, has no side effect or positive reaction, is widely used in health-care industries such as medicines, foods, beverages and the like, and the demand and the value of the levo-synephrine (L-synephrine) are multiplied along with the forbidden chemical synthetic medicines.
L-synephrine is the main active component, and has the functions of boosting pressure, resisting shock and promoting metabolism. The synephrine is chiral, mainly exists in the form of L-synephrine (L-synephrine), but is easy to racemize in the extraction and separation process of the synephrine, so that the content of D-synephrine is increased. Research at home and abroad shows that the effective configuration of the levo synephrine (L-synephrine) with the pharmacodynamic action can lead the D-synephrine to generate pharmacodynamic antagonism and even be the reason of the side effect of synephrine drugs. Therefore, the separation and preparation of the product with high proportion content of L-synephrine (L-synephrine) has great significance for researching the pharmacological mechanism of synephrine and developing synephrine chiral drugs. The prior separation and preparation of synephrine have been reported, and the limitation is that resolution and identification of L-synephrine and D-synephrine are not realized.
L-synephrine, which is a natural stimulant with no side effects and belongs to ephedrine, has effects of preventing oxidation of fat, increasing energy consumption and reducing weight, and has effects of constricting blood vessel, increasing blood pressure, dilating trachea and bronchus, regulating intestinal movement, and can be used for antishock, treating bronchial asthma and gastroptosis, etc. Has wide application prospect in the industries of medicines, health products, foods, beverages and the like. Synephrine can be chemically synthesized and extracted from plants, and the chemical synthesis route is that the product obtained by an aminoethyl method and a direct acylation method is a D-racemate, and the chemical synthesis of synephrine is severely restricted because the D-enantiomer possibly has side effects and is difficult to separate. Thus, the extraction and separation from the natural product is the only method for preparing each L-synephrine. L-synephrine (L-synephrine) is present in lime and young fruit bearing and green tangerine peel soluble plants, and the content is only 0.28-2.53%. At present, the commercial L-synephrine (L-synephrine) has low product saturation and more impurities, and cannot be applied to the fields of high added value such as medicines. Thus, the development of a process for preparing high purity L-synephrine (L-synephrine) has been a subject to be solved in the art.
The existing method for separating L-synephrine, such as the patent with publication number CN101402577A 'method for extracting and separating L-synephrine from green tangerine peel' disclosed in 4 months and 8 days 2009, comprises the following steps: reflux extracting L-synephrine from pericarpium Citri Reticulatae viride fine powder with 15-45% ethanol at 80deg.C twice, concentrating the extractive solution under reduced pressure to solid content of 80-85%, loading onto D101 macroporous adsorbent resin column, and eluting with 15% ethanol; concentrating the eluent under reduced pressure, and spray drying to obtain a crude product of the L-synephrine; dissolving the crude L-synephrine with pure acetic acid, adding silica gel with the same mass as the crude L-synephrine, stirring uniformly, removing ethanol, preparing a silica gel adsorption sample, and using dichloromethane according to the volume ratio: methanol: eluting and collecting the L-synephrine component by using an eluent prepared by ammonia water=6-9:2:0.1, concentrating the eluted L-synephrine component by silica gel column under reduced pressure, and spray drying to obtain the L-synephrine product. The main disadvantage of this method is that 80-85% of the solid-containing extract has extremely poor fluidity, the volume of the required eluent is large, the energy consumption is large during the regeneration of silica gel at high temperature, and the reusability is poor. The use of toxic organic solvents such as methylene dichloride and the like has serious pollution and poor production safety. In addition, the reduced pressure concentration and spray drying at high temperature may cause a large amount of heat-sensitive L-synephrine to oxidize and fail, and thus the quality of the obtained product is poor.
As another patent, a method for extracting and separating L-synephrine disclosed in publication No. CN101792394a, 4, 8, 2010, is disclosed as follows: the method takes the commercial immature bitter orange as a raw material, and obtains a finished product through dissolution, suction filtration, ultrafiltration separation, reverse micelle extraction, back extraction, vacuum concentration and freezing, and the method has the following defects: the extraction principle is based on the interaction of positive and negative charges, and the L-synephrine solution contains positively charged small molecules such as amino acid, vitamin and the like, which are also extracted in the actual production process and are difficult to remove. The method uses a vacuum concentration method to remove the solvent, so as to achieve the aim of improving the concentration of the L-synephrine, but the L-synephrine is a thermal compound, and the material is generally heated to more than 65 ℃ during vacuum concentration, and at the moment, the L-synephrine (also called as L-synephrine) starts to be oxidized and failed. Therefore, it is difficult to obtain a high-purity, high-quality product by this method.
Disclosure of Invention
Therefore, the invention aims to provide the extraction process of the levo-synephrine, and the obtained levo-synephrine has the advantages of good quality, high purity, high yield, mild process treatment condition and environmental friendliness.
The adopted technical scheme is as follows:
an extraction process of levo synephrine comprises the following steps:
s1, selecting immature bitter orange and cutting immature bitter orange into slices;
s2, selecting low-sulfur dioxide or sulfur-dioxide-free polycrystalline yellow rock sugar as a substrate for the sugar solution, mixing the olive flakes with the sugar solution, placing the mixture in a fermentation tank, controlling the temperature to be within 10 ℃ for full reaction, and filtering to separate syrup containing olive flavor and olive residues rich in stable natural substances;
s3, grinding the olive pomace into homogenate by using liquid nitrogen ultralow temperature grinding equipment under the working condition of low temperature below zero, and refining the grain size of the pomace by using a screen;
s4, uniformly stirring the crushed fruit residue fine powder and ethanol, carrying out reflux extraction, and filtering;
s5, selecting cation adsorption resin to adsorb and elute the filtrate;
s6, concentrating the resin eluent by using a nanofiltration membrane to obtain the high-purity levo-synephrine.
Further, S7, obtaining the high-purity levo-synephrine by a freeze drying method.
Further, in S1, the selected fructus Aurantii Immaturus is mature, the diameter is 40-60mm, and a slicing machine is used for slicing the fructus Aurantii Immaturus into slices of 3-4 mm.
Further, in S2, the olive flakes and the sugar solution are mixed according to a weight ratio of 1:1.2, placing the mixture in a fermentation tank, controlling the temperature to be 8-10 ℃, reacting for 15 days, and filtering by a 40-mesh sieve after full reaction.
Further, in S3, grinding the olive pomace into homogenate by a liquid nitrogen ultralow temperature grinding device under the working condition of-150 ℃, refining the grain size of the pomace by using a 350-mesh screen, and returning the grains which do not pass through the screen to continue grinding;
further, in S4, the weight-volume ratio of the crushed fruit residue fine powder to ethanol is 1: 9-11, wherein the concentration of ethanol is 60-95%, reflux-extracting for 2-4 times after stirring uniformly, 2-4 hours each time, and combining the filtrate after filtering.
Further, in S5, cation adsorption resin D101 is selected, firstly, a strong acid cation exchange resin column for adsorbing levo synephrine is pretreated, firstly, 10 mass percent sodium chloride solution is used for soaking for 2 hours, the column is filled, distilled water is backwashed until effluent water is clarified, and then, the column is washed by sodium hydroxide solution with the volume of 40g/L which is 2 times that of the column; washing with distilled water until the pH value is neutral, washing with 4 times of hydrochloric acid solution with volume fraction of 5%, and finally washing with distilled water until the pH value is neutral; adsorbing the alcohol extract according to 2-3BV, and adsorbing resin with the adsorption multiple of 6-8BV; after saturation, the resin column is washed with 1-1.5BV ammonia water solution with pH value of 10 as eluent, and the volume ratio of ammonia water to resin is 2:1.
In S5, the pectin waste liquid separated by the overflow is distilled by a tower distiller to recover ethanol, and the obtained filter residue is insoluble colloid.
Further, the nanofiltration membrane is an organic membrane with the molecular weight of 150-500Da, the resin eluent is subjected to 2-level concentration, the operating pressure is 20-35bar, the temperature is 10-20 ℃, and the high-purity L-synephrine with the purity of more than 98% is obtained through 2-level concentration.
Further, the organic membrane material is one or more of polysulfone amide, polysulfone, polyvinyl chloride, polyolefin, fluorine material, acetate fiber, polyetherimide and polyimide.
After the technical scheme is adopted, the process mainly has the following effects:
1. the process method does not use chemical reagent at low temperature, so that the product can keep the characteristics of natural products, and has high purity and high yield. Extracting L-synephrine in fructus Aurantii Immaturus at normal temperature, stabilizing the structure of the target L-synephrine by sugar extraction fermentation, dissolving L-synephrine by alcohol extraction process, purifying by cation resin, concentrating by nanofiltration membrane at normal temperature to obtain L-synephrine with purity of above 98%, and yield of above 80%.
2. In the production process, the used sugar extraction and alcohol extraction equipment, the adsorption resin and the nanofiltration equipment are universal equipment, the operation is convenient and easy to control, the investment is small, and the production is safe.
3. In the production process, common reagents such as ethanol and the like are used, so that the process is low in toxicity, realizes recycling, and is beneficial to improving the product quality and protecting the environment. The process has simple separation and purification steps, reduces the solvent consumption, is efficient and environment-friendly, and is suitable for industrial mass production.
Drawings
Fig. 1 is a route diagram of a process for extracting levo-synephrine.
Detailed Description
The invention provides a method for extracting levo synephrine from immature fruits of immature bitter oranges, which comprises the steps of firstly carrying out dehydration by utilizing sugar extraction, and reserving water-insoluble levo synephrine (L-synephrine) in dehydrated fruit residues. The unstable L-synephrine structure is stabilized by fermenting with sugar and enzyme with activity of fructus Canarii albi. The sugar extraction fermentation can ensure that the L-synephrine can not be converted, effectively improves the extraction rate of active ingredients, has green and harmless fermentation effect, and avoids the use of solvents. And then grinding and crushing by utilizing liquid nitrogen, and obtaining the pectin-free extract by utilizing the characteristic that the L-synephrine is dissolved in ethanol and the pectin is not dissolved in ethanol, thereby greatly improving the extraction rate of the L-synephrine. The filter residue after alcohol extraction of L-synephrine can be used for further extracting pectin to obtain pectin byproduct. Purifying the L-synephrine in the alcohol extract by cation exchange resin. Because the L-synephrine can generate racemization reaction at high temperature, the membrane concentration process is used for completing the concentration of the L-synephrine at low temperature, and the nanofiltration membrane is used for concentrating the resolved L-synephrine, thus obtaining the L-synephrine with high purity concentration.
Referring to FIG. 1, the process takes immature fruits of immature bitter oranges as raw materials, and comprises the following specific steps of pretreatment, sugar extraction, liquid nitrogen grinding, alcohol extraction, resin adsorption, membrane concentration to obtain high-purity and high-yield levo synephrine (L-synephrine):
(1) Pretreatment of immature bitter orange
According to researches and documents, the young fruits of immature bitter oranges have a certain influence on the extraction amount of the final L-synephrine, and the best state is better than the fruits with the diameter of 40 mm. The selected fructus Canarii albi is ripe, the diameter is about 40-60mm, a slicing machine is selected, fructus Canarii albi is cut into slices of 3-4mm, and the slices are reserved for sugar extraction process.
(2) Sugar extraction shallow fermentation process
And selecting low sulfur dioxide or sulfur dioxide-free polycrystalline yellow rock sugar as a substrate, and carrying out a sugar extraction dehydration procedure. The process uses the low sulfur dioxide or sulfur dioxide-free polycrystalline yellow rock sugar as the sugar solution of the substrate, and is an innovative product. The polycrystalline yellow rock sugar with low sulfur dioxide or no sulfur dioxide is selected, so that the dehydration rate of the material can be 35% under the conditions of low temperature and solid state, and more importantly, the separation amount of water-soluble natural substances and non-water-soluble natural substances can be more than 80%. Therefore, the water-insoluble L-synephrine (L-synephrine) is remained in the dehydrated pomace, and the liquid dehydrated liquid contains only aromatic substances and other natural substances such as hesperidin, naringin and the like. Mixing the pretreated olive slices with sugar solution according to the following ratio of 1:1.2, placing the mixture in a fermentation tank, controlling the temperature to be 8-10 ℃ and reacting for 15 days. The sugar liquid after sugar extraction fully provides a carbon source and generates shallow fermentation with active enzymes carried by the Chinese olive. Avoiding severe fermentation reaction, controlling the temperature to be within 10 ℃, and converting unstable natural substances into stable substances by shallow fermentation, so that the target L-synephrine (L-synephrine) structure tends to be stable.
After the sugar extraction and shallow fermentation, filtering by a 40-mesh sieve machine, and separating syrup with the flavor of Chinese olive and Chinese olive pomace rich in stable natural substances.
The syrup is filtered and concentrated by a nano-scale ceramic membrane, so that the syrup can be further prepared into aromatic fruit juice, and 1000 kg of syrup can be prepared into 150 kg of fruit juice with natural lemon and citron mixed aroma, and can be applied to foods, beverages and cosmetics. The residual syrup has a brix of 65 degrees and can be converted into brown sugar or industrial molasses.
(3) Liquid nitrogen grinding process
Grinding dehydrated olive pomace into homogenate by liquid nitrogen ultralow temperature grinding equipment under the working condition of-150 ℃, thereby effectively avoiding the generation of high temperature during grinding, damaging high-heat-sensitivity L-synephrine, refining the grain size of the pomace by utilizing a 350-mesh screen, returning the grains which do not pass through the screen to continue grinding, and being beneficial to the action and reaction of the subsequent alcohol extraction process.
(4) Alcohol extraction process
The crushed fruit residue fine powder and ethanol are mixed according to the weight volume ratio of 1: 9-11, wherein the concentration of ethanol is 60-95%, after stirring uniformly, reflux extraction is carried out for 2-4 times, each time for 2-4 hours, and after filtration, the multiple filtrates are combined and used for the next step of L-synephrine resin adsorption process.
(5) Resin adsorption process
The method comprises the steps of selecting a cation adsorption resin D101 as a levo synephrine (L-synephrine) adsorption resin, firstly, pretreating a strong acid cation exchange resin column for adsorbing the levo synephrine (L-synephrine), firstly, soaking the column for 2 hours by using a sodium chloride solution with the mass fraction of 10%, loading the column, backwashing distilled water until the effluent water is clarified, and then flushing the column by using a sodium hydroxide solution with the volume of 40g/L which is 2 times that of the column. Washing with distilled water until the pH value is neutral, washing with 4 times of hydrochloric acid solution with volume fraction of 5%, and finally washing with distilled water until the pH value is neutral. The alcohol extract is adsorbed according to 2-3BV, and the adsorption multiple of the resin is 6-8BV. After saturation, the resin column is washed with 1-1.5BV ammonia water solution with pH value of 10 as eluent, and the volume ratio of ammonia water to resin is 2:1. And (3) distilling the pectin waste liquid separated by the overflow by using a tower distiller to recycle ethanol, wherein the obtained filter residue is insoluble colloid and can be used as a natural colloid byproduct. The collected analysis liquid is the high-purity L-synephrine (L-synephrine) which is used for preparing the high-concentration L-synephrine.
(6) Membrane concentration process
The concentration process selects organic membrane with molecular weight of 150-500Da, and carries out 2-stage concentration to the resin eluent, the operation pressure is 20-35bar, and the temperature is 10-20 ℃. And 2-stage concentration to obtain high-purity L-synephrine with DS of 30-35%. Finally, the powder is obtained by a freeze drying method.
The organic membrane material mainly comprises polysulfone amide, polysulfone, polyvinyl chloride, polyolefin, fluorine material, acetate fiber, polyether imide, polyimide and the like, and can be one or more materials.
The process is further illustrated by the following examples, which are provided for the purpose of illustration and are not intended to limit the true scope of the invention in any way.
Example 1
The extraction process of the levo-synephrine in the embodiment comprises the following steps:
(1) Pretreatment of immature fruits of immature bitter oranges: 100kg of fructus Aurantii Immaturus is cut into slices of 3-4mm with a diameter of about 40mm (L-synephrine content 1.7%), and a slicer is selected for use.
(2) Sugar extraction fermentation: adding 220-250kg of low sulfur dioxide or sulfur dioxide-free polycrystalline yellow rock sugar as a substrate, placing the pretreated olive slices into a fermentation tank, controlling the temperature to 8-10 ℃ and reacting for 15 days;
(3) Grinding dehydrated olive pomace into 350 mesh homogenate by a liquid nitrogen ultralow temperature grinding device under the working condition of-150 ℃;
(4) Alcohol extraction: the crushed fruit residue fine powder and ethanol are mixed according to the weight volume ratio of 1:11, extracting with 95% ethanol (volume concentration, the same applies below) under stirring for 4 times, each time for 5-7h to obtain ethanol extract;
(5) Resin adsorption process: the alcohol extract is adsorbed according to 2BV, and the adsorption multiple of the resin is 6BV. After adsorption saturation, using ammonia water solution with pH value of 10 as eluent, flushing the resin column with 1BV, wherein the volume ratio of ammonia water to resin is 2:1;
(6) Membrane concentration: concentrating the resin analysis liquid with nanofiltration membrane with molecular weight cut-off of 500 to obtain permeate and retentate, concentrating and recovering the first-stage permeate with 150 nanofiltration membrane at operation pressure of 20-35bar and temperature of 10-20deg.C.
Finally obtaining 1.51kg of L-octalin product with the purity of 98.89wt% and the yield of 88.82%;
example 2
The extraction process of the levo-synephrine in the embodiment comprises the following steps:
(1) Pretreatment of immature fruits of immature bitter oranges: cutting 100kg fructus Aurantii Immaturus with diameter of about 60mm (L-synephrine content 1.32%) into 3-4mm slices;
(2) Sugar extraction fermentation: adding 220-250kg of low sulfur dioxide or sulfur dioxide-free polycrystalline yellow rock sugar as a substrate, placing the pretreated olive slices into a fermentation tank, controlling the temperature to 8-10 ℃ and reacting for 15 days;
(3) Grinding dehydrated olive pomace into 350 mesh homogenate by liquid nitrogen ultralow temperature grinding equipment under the working condition of-150 ℃;
(4) Alcohol extraction: the crushed fruit residue fine powder and ethanol are mixed according to the weight volume ratio of 1:11, extracting with ethanol with stirring for 4 times, each time for 5-7h to obtain ethanol extract;
(5) Resin adsorption process: the alcohol extract is adsorbed according to 2BV, and the adsorption multiple of the resin is 6BV. After adsorption saturation, using ammonia water solution with pH value of 10 as eluent, flushing the resin column with 1BV, wherein the volume ratio of ammonia water to resin is 2:1;
(6) Membrane concentration: concentrating the resin analysis liquid with nanofiltration membrane with molecular weight cut-off of 500 to obtain permeate and retentate, concentrating and recovering the first-stage permeate with nanofiltration membrane with molecular weight of 150, and operating pressure of 20-35bar and temperature of 10-20deg.C.
Finally obtaining 1.11kg of L-octalin product with the purity of 98.02wt% and the yield of 84.09%;
example 3
The extraction process of the levo-synephrine in the embodiment comprises the following steps:
(1) Pretreatment of immature fruits of immature bitter oranges: cutting 100kg fructus Aurantii Immaturus with diameter of about 40mm (L-synephrine content 1.7%) into 3-4mm slices;
(2) Sugar extraction fermentation: adding 220-250kg of low sulfur dioxide or sulfur dioxide-free polycrystalline yellow rock sugar as a substrate, placing the pretreated olive slices into a fermentation tank, controlling the temperature to 8-10 ℃ and reacting for 15 days;
(3) Grinding dehydrated olive pomace into 350 mesh homogenate by liquid nitrogen ultralow temperature grinding equipment under the working condition of-150 ℃;
(4) Alcohol extraction: the crushed fruit residue fine powder and ethanol are mixed according to the weight volume ratio of 1:11, extracting with ethanol with stirring for 4 times, each time for 5-7h to obtain ethanol extract;
(5) Resin adsorption process: the alcohol extract is adsorbed according to 2BV, and the adsorption multiple of the resin is 6BV. After adsorption saturation, using ammonia water solution with pH value of 10 as eluent, flushing the resin column with 1BV, wherein the volume ratio of ammonia water to resin is 2:1;
(6) Membrane concentration: concentrating the resin analysis liquid with nanofiltration membrane with molecular weight cut-off of 150 to obtain permeate and retentate, concentrating and recovering the first-stage permeate with nanofiltration membrane with molecular weight of 150, operating pressure of 20-35bar and temperature of 10-20deg.C.
Finally, 1.37kg of L-octalin product is obtained, the purity is 98.32wt percent, and the yield is 80.59 percent.
Example 4
The extraction process of the levo-synephrine in the embodiment comprises the following steps:
(1) Pretreatment of immature fruits of immature bitter oranges: cutting 100kg fructus Aurantii Immaturus with diameter of about 40mm (L-synephrine content 1.7%) into 3-4mm slices;
(2) Sugar extraction fermentation: adding 220-250kg of low sulfur dioxide or sulfur dioxide-free polycrystalline yellow rock sugar as a substrate, placing the pretreated olive slices into a fermentation tank, controlling the temperature to 8-10 ℃ and reacting for 15 days;
(3) Grinding dehydrated olive pomace into 350 mesh homogenate by liquid nitrogen ultralow temperature grinding equipment under the working condition of-150 ℃;
(4) Alcohol extraction: the crushed fruit residue fine powder and ethanol are mixed according to the weight volume ratio of 1:90, extracting with ethanol with stirring for 4 times, each time for 5-7 hr to obtain ethanol extractive solution;
(5) Resin adsorption process: the alcohol extract is adsorbed according to 3BV, and the adsorption multiple of the resin is 8BV. After adsorption saturation, using ammonia water solution with pH value of 10 as eluent, flushing the resin column with 1.5BV, wherein the volume ratio of ammonia water to resin is 2:1;
(6) Membrane concentration: concentrating the resin analysis liquid with nanofiltration membrane with molecular weight cut-off of 500 to obtain permeate and retentate, concentrating and recovering the first-stage permeate with nanofiltration membrane with molecular weight of 150, and operating pressure of 20-35bar and temperature of 10-20deg.C.
Finally, the L-octalin product of 1.42kg is obtained, the purity is 98.47wt percent, and the yield is 83.53 percent.
For comparison of the extraction effects of the levo-synephrine in the above examples, see table 1:
TABLE 1
Wherein yield (%) = mass of actually obtained L-synephrine product/mass of L-synephrine theory x 100%, yield of levo-synephrine product in example 1 is: 1.51 kg/(100 kg×1.7%) = 88.82%;
the yields of the levosimendan product in example 2 were: 1.11 kg/(100 kg×1.32%) = 84.09%;
the yields of the levosimendan product in example 3 were: 1.37 kg/(100 kg×1.7%) =80.59%;
the yields of the levosimendan product in example 4 were: 1.42 kg/(100 kg×1.7%) =83.53%;
the purity is obtained by detecting the actually obtained L-synephrine product, and the detected value of the content of the obtained L-synephrine is the purity. The content of levo-synephrine can be determined by using the existing reversed-phase high performance liquid chromatography (RP-HPLC).
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the scope of the present invention.
Claims (8)
1. The extraction process of the levo synephrine is characterized by comprising the following steps of:
s1, selecting immature bitter orange and cutting immature bitter orange into slices;
s2, selecting low sulfur dioxide or sulfur dioxide-free polycrystalline yellow rock sugar as a substrate for the sugar solution, and mixing the olive flakes with the sugar solution according to the weight ratio of 1:1.2, placing in a fermentation tank, controlling the temperature to 8-10deg.C, reacting for 15 days, fully reacting, filtering with a 40 mesh sieve, and separating syrup with fructus Canarii albi flavor and fructus Canarii albi residue rich in stable natural substances;
s3, grinding the olive pomace into homogenate by using liquid nitrogen ultralow temperature grinding equipment under the working condition of low temperature below zero, and refining the grain size of the pomace by using a screen;
s4, uniformly stirring the crushed fruit residue fine powder and ethanol, carrying out reflux extraction, and filtering;
s5, selecting cation adsorption resin D101 to adsorb and elute the filtrate;
s6, concentrating the resin eluent by using a nanofiltration membrane, wherein the nanofiltration membrane is an organic membrane with the molecular weight of 150-500Da, concentrating the resin eluent by 2 levels, wherein the operating pressure is 20-35bar, the temperature is 10-20 ℃, and obtaining the high-purity levo-synephrine with the purity of more than 98% through 2 levels of concentration.
2. The process for extracting levo-synephrine according to claim 1, further comprising s7, freeze-drying the high-purity levo-synephrine to obtain a powder.
3. The process for extracting levo-synephrine according to claim 1, wherein in S1, the selected fructus Aurantii Immaturus is mature, the diameter is 40-60mm, and the fructus Aurantii Immaturus is cut into 3-4mm slices by a slicer.
4. The process according to claim 1, wherein in S3, the olive pomace is ground into homogenate by a liquid nitrogen ultra-low temperature grinding device under the working condition of-150 ℃, and the grain size of the pomace is refined by a 350 mesh screen, and the grains which pass through the screen are returned to continue grinding.
5. The process for extracting levo-synephrine according to claim 1, wherein in S4, the weight-to-volume ratio of the crushed fruit residue fine powder to ethanol is 1: 9-11, wherein the concentration of ethanol is 60-95%, reflux-extracting for 2-4 times after stirring uniformly, 2-4 hours each time, and combining the filtrate after filtering.
6. The process for extracting levo-synephrine according to claim 1, wherein in S5, the cation exchange resin column for adsorbing the levo-synephrine is pretreated, soaked for 2 hours with 10% sodium chloride solution by mass, packed, backwashed with distilled water until the effluent water is clarified, and then washed with 40g/L sodium hydroxide solution by 2 times of column volume; washing with distilled water until the pH value is neutral, washing with 4 times of hydrochloric acid solution with volume fraction of 5%, and finally washing with distilled water until the pH value is neutral; adsorbing the alcohol extract according to 2-3BV, and adsorbing resin with the adsorption multiple of 6-8BV; after saturation, the resin column is washed with 1-1.5BV ammonia water solution with pH value of 10 as eluent, and the volume ratio of ammonia water to resin is 2:1.
7. The process according to claim 6, wherein in S5, the pectin waste liquid separated by the overflow is distilled by a tower distiller to recover ethanol, and the obtained residue is insoluble colloid.
8. The process for extracting levo-synephrine according to claim 1, wherein the organic membrane is one or more of polysulfone amide, polysulfone, polyvinyl chloride, polyolefin, fluorine material, acetate fiber, polyetherimide and polyimide.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318538A (en) * | 2001-04-11 | 2001-10-24 | 侯团章 | Method of extracting octaverine from Chinese medicine material immature bitter orange |
| CN101402577A (en) * | 2008-10-23 | 2009-04-08 | 浙江工商大学 | Method for extracting and separating levorotation-synephrine from green tangerine orange peel |
| CN112830881A (en) * | 2020-12-31 | 2021-05-25 | 涟源康麓生物科技有限公司 | Method for separating synephrine from hesperidin waste liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318538A (en) * | 2001-04-11 | 2001-10-24 | 侯团章 | Method of extracting octaverine from Chinese medicine material immature bitter orange |
| CN101402577A (en) * | 2008-10-23 | 2009-04-08 | 浙江工商大学 | Method for extracting and separating levorotation-synephrine from green tangerine orange peel |
| CN112830881A (en) * | 2020-12-31 | 2021-05-25 | 涟源康麓生物科技有限公司 | Method for separating synephrine from hesperidin waste liquid |
Non-Patent Citations (1)
| Title |
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| 沈莲清 等.个青皮中辛弗林两种提取分离方法的比较研究.《食品与生物技术学报》.2008,第27卷(第6期),第14-17页. * |
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