CN114907191A - Hemp impurity removal method - Google Patents

Hemp impurity removal method Download PDF

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Publication number
CN114907191A
CN114907191A CN202110167670.2A CN202110167670A CN114907191A CN 114907191 A CN114907191 A CN 114907191A CN 202110167670 A CN202110167670 A CN 202110167670A CN 114907191 A CN114907191 A CN 114907191A
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hemp
extract
organic solvent
impurity removal
extraction
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叶彬
田汉玉
罗飞
柴岩岩
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Zhejiang Shuangzi Intelligent Equipment Co ltd
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Zhejiang Shuangzi Intelligent Equipment Co ltd
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Priority to PCT/CN2021/131077 priority patent/WO2022166301A1/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/72Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68Purification; separation; Use of additives, e.g. for stabilisation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/86Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/23Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing six-membered aromatic rings and other rings, with unsaturation outside the aromatic rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The application relates to the field of hemp impurity removal, and particularly discloses a hemp impurity removal method. A hemp impurity removal method comprises the following steps: s1: pretreatment: drying and crushing cannabis sativa flowers and leaves to obtain raw material powder; extracting the raw material powder by using an ethanol solution to obtain a hemp extract; s2: concentrating the hemp extract, winterizing, filtering to obtain filtrate, and concentrating the filtrate into extract; s3: performing decarboxylation treatment on the extract; s4: adding an organic solvent into the decarboxylated extract for extraction, and filtering to obtain an extract liquid; s5: concentrating the extractive solution to remove organic solvent to obtain hemp extract; the organic solvent is at least one of alkane or halogenated hydrocarbon. The preparation method can be used for removing impurities from the cannabis sativa in cannabidiol extraction, and has the advantages of proper cost and good impurity removal effect.

Description

Hemp impurity removal method
Technical Field
The application relates to the field of hemp impurity removal, in particular to a hemp impurity removal method.
Background
In recent years, with the continuous research and exploration of cannabis, cannabis plants are found to contain a unique class of substances, namely cannabinol compounds. Cannabinoids are the main active ingredients of cannabis plant, and mainly comprise Tetrahydrocannabinol (THC), Cannabinol (CBN), Cannabidiol (CBD), Cannabigerol (CBG), cannabicycloterpene phenol (CBC), etc., wherein the content of tetrahydrocannabinol, cannabinol and cannabidiol is more than 90% of cannabinols phenolic compounds.
Wherein, the cannabidiol has no neurotoxicity and significant medicinal value; related pharmacological research shows that the tetrahydrocannabinol can block the influence of the tetrahydrocannabinol on the human nervous system, has pharmacological activities of resisting spasm, rheumatic arthritis, anxiety and the like, and has great industrial development value.
In recent years, the market demand for cannabidiol has been increasing, and a large number of enterprises have started to focus on the field of industrial cannabis. The process for extracting cannabidiol from cannabis mainly comprises two parts of impurity removal and refining, the effect of the impurity removal can directly influence the effect of subsequent refining, and the effective impurity removal mode can reduce the pressure and cost consumption of refining.
In the related art, the impurity removal process is most commonly performed by chromatographic column chromatography impurity removal and membrane filtration impurity removal. The purpose of removing impurities by using a column chromatography method only needs to pass through two or even more chromatographic columns, so that the loss of effective components is increased, the consumption of solvents is increased, the use of fillers is increased, the operation cost of the whole process is finally increased, and the efficiency is low. The membrane equipment for membrane filtration and impurity removal is high in price and high in operation and maintenance cost, and is difficult to widely use. Generally, the impurity removal method cannot give consideration to both the cost and the impurity removal effect.
Disclosure of Invention
In order to consider the cost of impurity removal and the impurity removal effect, the application provides a hemp impurity removal method.
In a first aspect, the present application provides the following technical solutions: a hemp impurity removal method comprises the following steps:
s1: pretreatment: drying and crushing cannabis sativa flowers and leaves to obtain raw material powder; extracting the raw material powder by using an ethanol solution to obtain a hemp extract;
s2: concentrating the hemp extract, winterizing, filtering to obtain filtrate, and concentrating the filtrate into extract;
s3: decarboxylating the extract;
s4: adding an organic solvent into the decarboxylated extract for extraction, and filtering to obtain an extract liquid;
s5: concentrating the extractive solution to remove organic solvent to obtain hemp extract;
the organic solvent is at least one of alkane or halogenated hydrocarbon.
By adopting the technical scheme, the hemp is processed into the hemp extract by pretreatment, so that the subsequent impurity removal treatment is facilitated. Winterization is a crystallization separation method, and glyceride and other substances with higher freezing points are crystallized and separated out by cooling, so that waxy substances, solid fat and other impurities in a hemp extracting solution are separated out. After concentration, the extract contains special substances and partial impurities contained in hemp plants such as CBD, CBG, CBC, CBN, THC and the like; decarboxylation removes carbon dioxide from carboxyl group, converts cannabidiolic acid, tetrahydrocannabinolic acid, cannabinolic acid, cannabigerolic acid and cannabichromenic acid into cannabidiol, tetrahydrocannabinol, cannabinol, cannabigerol and cannabigeroterpene phenol, and improves the yield of final products; meanwhile, part of organic matters are carbonized to generate impurities. And dissolving and taking out the CBD in the extract by using an organic solvent, and removing most impurities to finish impurity removal. Through the steps, the original chromatographic column chromatography and membrane filtration method can be replaced by the organic solvent extraction separation, the effects of simple operation and cost input reduction are achieved, the quality of the final product is improved, and the problems of environmental pollution and the like caused by waste fillers are solved.
Further, the organic solvent is at least one of chloroform, n-hexane, n-heptane and n-octane.
By adopting the technical scheme, in an organic solvent, the trichloromethane, the normal hexane, the normal heptane and the normal octane have the advantages of stronger practicability, stability at an operation temperature, difficult volatilization, moderate boiling point, low recovery energy consumption and convenient complete removal; has proper cost and no toxicity. These organic solvents can be used in combination, but the recovery treatment is difficult.
Further, in the step S4, the temperature of the organic solvent extraction is 50 to 90 ℃.
By adopting the technical scheme, the extraction is carried out within the temperature range, and on the basis of reasonably controlling the energy consumption, the experiment shows that the extraction speed is higher, and the extraction effect is better.
Further, in the step S4, the ratio of the mass of the extract to the volume of the organic solvent is 1:5-1: 15.
By adopting the technical scheme, experiments show that the extraction is more complete, the extraction effect is better, and the efficiency is higher.
Further, in the step S4, the organic solvent is added in 2 to 4 portions.
By adopting the technical scheme, experiments show that the extraction is more complete, the extraction effect is better, and the efficiency is higher.
Further, the extraction time of the organic solvent is 5-30min each time.
By adopting the technical scheme, experiments show that the extraction is more complete and the extraction effect is better.
Further, in the step S4, the extraction is continued while stirring.
By adopting the technical scheme, experiments show that the extraction is more complete, the extraction effect is better, and the efficiency is higher.
Further, in the step S2, the hemp extract is concentrated to a cannabidiol content of 1 to 5% and then winterization is performed.
By adopting the technical scheme, experiments show that the subsequent winterization impurity removal effect is improved, and finally the extraction effect is further improved.
In summary, the present application has the following beneficial effects:
1. pretreatment, concentration, winterization, extractum, decarboxylation and organic solvent extraction are preferably adopted in the application, and finally concentration is carried out to complete impurity removal of hemp, so that the effects of simple operation and cost investment reduction are achieved, the quality of a final product is improved, and the problems of environmental pollution and the like caused by waste fillers are avoided.
2. At least one of trichloromethane, normal hexane, normal heptane and normal octane is preferably adopted as the organic solvent in the application, so that the practicability is high, the recovery energy consumption is low, and the cost is moderate.
3. In the application, the extraction temperature and time and the organic solvent dosage are preferably adopted, so that the extraction speed is higher, and the extraction effect is better.
Drawings
FIG. 1 is a liquid chromatogram of an extract obtained in example 22 after step S3;
FIG. 2 is a liquid chromatogram of the cannabis extract obtained in example 22 after step S5.
Detailed Description
The present application is described in further detail below with reference to the attached drawings.
Examples
Example 1: a hemp impurity removal method comprises the following steps:
s1: pretreatment: harvesting hemp flowers and leaves, putting into a dryer, drying at 140 ℃ until the water content is 5%; then the mixture is sent to a grinder to be ground into 60 meshes or more to obtain raw material powder;
weighing 60kg of raw material powder, adding the raw material powder into a countercurrent extraction device at a feeding speed of 15kg/h, continuously feeding 480kg of 95V/V ethanol aqueous solution into the countercurrent extraction device at a feeding speed of 120L/h, and extracting at the extraction temperature of 25 +/-5 ℃ for 60min to obtain a hemp extract;
s2: transferring the hemp extract to vacuum low-temperature concentration equipment, concentrating at 50 deg.C until the CBD content is 8%, adding 95V/V ethanol water solution to adjust the volume content of ethanol to 60%, and stirring at 60r/min for 5 min;
and then winterization treatment is carried out: standing the hemp extract added with the ethanol water solution at the temperature of-50 ℃ for 24h, and then transferring to plate and frame type filter pressing equipment for filtering to remove impurities to obtain a filtrate;
putting the filtrate into a decompression concentration device, and concentrating under the pressure of-0.09 MPa to obtain an extract;
s3: heating the extract to 140 deg.C until no bubble is generated, and stopping heating;
s4: adding an organic solvent into the decarboxylated extract, extracting at 25 ℃ for 40min, transferring to a stirrer after extraction is finished, adding a filter aid accounting for 50% of the mass of the extract, and stirring for 10min at 20r/min to obtain an extract;
the organic solvent is dichloromethane, and the volume ratio of the extract to the organic solvent is 1: 1; the filter aid is activated carbon and diatomite with the mass part ratio of 1: 1;
s5: transferring the extractive solution to vacuum concentration equipment, and concentrating under-0.08 MPa to remove organic solvent to obtain Cannabis sativa extract.
Example 2: a hemp impurity removal method, which is different from the method in example 1 in that:
in S1, drying at 150 deg.C until the water content is 1%; the extraction temperature of the ethanol water solution is 35 deg.C, and the extraction time is 50 min.
S2, concentrating until the CBD content is 10%, adding 95V/V ethanol water solution to adjust the ethanol volume content to 90%; winterization temperature is-30 deg.C, processing time is 28h, and pressure is-0.08 MPa during concentration.
In S3, the heating temperature was 120 ℃.
In S4, the organic solvent is n-nonane, the extraction temperature is 95 ℃, the extraction time is 30min, and the ratio of the mass of the extract to the volume of the organic solvent is 1: 10. the usage amount of the filter aid is 20 percent of the mass of the extract, and the filter aid is diatomite.
Example 3: a hemp impurity removal method, which is different from the method in example 1 in that:
s1, drying at 120 ℃ until the water content is 3%; the extraction temperature of the ethanol water solution is 15 deg.C, and the extraction time is 75 min.
S2, concentrating until the CBD content is 5%, adding 95V/V ethanol water solution to adjust the ethanol volume content to 85%; the winterization temperature is-60 ℃, and the treatment time is 22 h.
In S3, the heating temperature was 150 ℃.
In S4, the organic solvent consists of trichloromethane and n-nonane in a mass portion ratio of 1:1, the extraction temperature is 45 ℃, the extraction time is 40min, and the ratio of the mass of the extract to the volume of the organic solvent is 1: 20. the usage amount of the filter aid is 10 percent of the mass of the extract, and the filter aid is activated carbon.
In S5, the pressure is-0.09 MPa.
Example 4: a process for removing impurities from hemp, which is different from the process of example 1 in that the organic solvent is chloroform.
Example 5: a hemp impurity removal method is different from the method in example 1 in that the organic solvent is n-heptane.
Example 6: a hemp impurity removal method is different from that in example 1 in that an organic solvent consists of trichloromethane, n-hexane and n-heptane in a mass ratio of 1:1: 1.
Example 7: a process for removing impurities from hemp, which differs from example 5 in that the extraction temperature is 50 ℃.
Example 8: a process for removing impurities from hemp, which differs from example 5 in that the extraction temperature is 70 ℃.
Example 9: a process for removing impurities from hemp, which differs from example 5 in that the extraction temperature is 90 ℃.
Example 10: the difference between the hemp impurity removal method and the embodiment 8 is that the ratio of the mass of the extract to the volume of the organic solvent is 1: 5.
example 11: the difference between the hemp impurity removal method and the embodiment 8 is that the ratio of the mass of the extract to the volume of the organic solvent is 1: 10.
example 12: the difference between the hemp impurity removal method and the embodiment 8 is that the ratio of the mass of the extract to the volume of the organic solvent is 1: 15.
example 13: a process for removing impurities from hemp, which is different from that of example 12, is that the extraction times is 2 times, the organic solvent is divided into two parts on average, one part is added each time, and the extraction time is 40min each time.
Example 14: a hemp impurity removing method is different from the method in example 12 in that the extraction times are 3 times, the organic solvent is averagely divided into two parts, one part is added each time, and the extraction time is 40min each time.
Example 15: a process for removing impurities from hemp, which is different from example 12, includes extracting for 4 times, dividing organic solvent into two parts, adding one part each time, and extracting for 40min each time.
Example 16: a process for removing impurities from hemp, which is different from example 14, is carried out in 5min per extraction.
Example 17: a process for removing impurities from hemp, which is different from example 14, is carried out in 10min per extraction.
Example 18: a process for removing impurities from hemp, which is different from that in example 14, is carried out in 30min per extraction.
Example 19: a process for removing impurities from hemp, which is different from example 17, includes stirring at 60 r/min.
Example 20: a process for removing impurities from hemp, which is different from example 17, includes stirring at 30 r/min.
Example 21: a process for removing impurities from hemp, which is different from the process of example 19, is that in S2, the hemp is concentrated to a CBD content of 1%.
Example 22: a process for removing impurities from hemp, which differs from example 19 in that, in S2, it is concentrated to a CBD content of 5%.
In the above embodiment, activated carbon was purchased from Jiangsu Eggenis environmental science and technology Co., Ltd, and diatomaceous earth was purchased from Hao Mega chemical Co., Ltd, Guangzhou city.
Comparative example
Comparative example 1: cannabidiol-rich cannabis sativa extract and a preparation method thereof, wherein the publication number is CN105535111A, and the disclosed embodiment 3: the ripe cannabis sativa leaves are spread in a common oven, the temperature is set at 80 ℃, and the dry heat treatment time is 3 hours. Then grinding the leaves by a grinder, taking 1.5 kg of dried cannabis sativa leaves, placing the leaves in a material tank of a subcritical extraction device, injecting subcritical n-butane containing 40% ethanol in a solvent tank into the material tank, and extracting for 45 minutes at 45 ℃ under the extraction pressure of 0.6 MPa. Then, the mixture was desolventized under reduced pressure, and the extract was taken out and extracted 3 times. Adding ethanol solution containing extract into a certain amount of ethanol to make solid-liquid ratio reach 1:7, and winterizing in a refrigerator at-10 deg.C for 45 min. Then, the mixture was centrifuged at-10 ℃ for 20 minutes in a centrifuge. The rotation speed was 4500 rpm. Adding activated carbon into the supernatant for decolorization, and then placing the supernatant on a shaking table at the rotating speed of 150 rpm for 25 minutes. Then, the mixture was filtered to obtain a filtrate. Placing the filtrate in a rotary evaporation bottle, and performing rotary evaporation treatment at 50 deg.C and 50 rpm in water bath to obtain hemp extract.
Comparative example 2: a process for extracting dihydrocannabinol (CBD) from industrial cannabis sativa, publication No. CN103739585A, disclosed in example 1: step 1, flower leaves in full bloom stage are adopted as raw materials, the flower leaves are dried in the sun or baked in advance, the water content is 10-15%, and the ash soil content is below 3%. The raw materials are put into a baking device, the temperature is controlled between 130 ℃ and 160 ℃ (160 ℃ is selected in the comparative example), and the time is controlled between 15 minutes and 35 minutes (20 minutes is selected in the comparative example).
And step 2, grinding the dried flowers and leaves to 5-10 meshes.
And 3, putting the ground flower leaves into a soaking device for soaking, wherein a soaking solvent adopts petroleum ether, n-hexane or No. 6 solvent oil. In order to improve the soaking effect, the soaking can be repeatedly carried out for a plurality of times, the soaking temperature is not higher than 50 ℃ (50 ℃ is selected in the comparative example), and the soaking time is not lower than 1 hour each time (1 hour is selected in the comparative example). Filtering the soaked mixed solution by a filter screen in the equipment, and pumping the mixed solution to a concentrator for separation and concentration.
And 4, concentrating and separating the mixture in a separator, and controlling the temperature to be between 90 and 120 ℃ (100 ℃ is adopted in the comparative example). Evaporating and concentrating the solvent to obtain solid and semisolid paste, which is the CBD-rich extract.
Comparative example 3: the difference from the embodiment 1 is that the hemp extract obtained from S1 is concentrated until the CBD content is 8%, 95V/V ethanol water solution is added to adjust the ethanol volume content to be 60%, after stirring for 5min under the condition of 60r/min, winterization is carried out, then decarboxylation of S3 is carried out, and then the mixture is put into a reduced pressure concentration device to be concentrated into extract under the pressure of-0.09 MPa.
Comparative example 4: the difference from the example 1 is that the hemp extract obtained in the step S1 is concentrated until the CBD content is 8%, 95V/V ethanol water solution is added to adjust the ethanol volume content to be 60%, the mixture is stirred for 5min under the condition of 60r/min, and then put into a decompression concentration device to be concentrated into extract under the pressure of-0.09 MPa, and then decarboxylation treatment in the step S3 is carried out.
Characterization test:
1. CBD content and attrition Rate test
Test subjects: examples 1-22 and comparative examples 1-4, for a total of 26 test groups.
The test method comprises the following steps: examples 1-22 and comparative examples 1-4 were tested from the same batch of raw meal. After the step S3 is completed in the embodiments 1-22, the extract is sampled and CBD content detection is carried out, the CBD content in 80g is converted and recorded as the CBD content of the extract before extraction, after the step S5 is completed, the extract is sampled and CBD content detection is carried out, the CBD content in 80g is converted and recorded as the CBD content of the extract after extraction; and (4) calculating the CBD loss rate (original CBD content-CBD content of the extract after extraction)/original CBD content. Comparative examples 1-4 CBD content testing was performed on the hemp extract or extract obtained at the end.
The original CBD content was determined from the cannabis extract of example 1 by CBD content test, and was 40.2%.
The CBD content was measured by HPLC at a wavelength of 210nm, and the CBD standard was purchased from Changshengsheng Biotech limited.
And (3) test results: the CBD content and wear rate test results are reported in table 1.
TABLE 1 CBD content and attrition Rate test results record
Figure BDA0002937973740000071
And (3) data analysis: as shown in Table 1, the examples all showed a very good CBD content and a low loss rate as compared to the comparative examples.
CBD content of the pre-extraction extracts of comparative examples and comparative examples 3-4. The processing step parameters before extraction and the processing step sequence have influence on the content of the CBD before extraction, and the steps before extraction adopted in the embodiment can effectively improve the content of the CBD of the extract before extraction, so that the final content of the CBD is improved, and the hemp impurity removal effect is improved.
Compared with the example 1, the compositions of the organic solvents are limited in examples 4-6, the extraction temperature is further limited on the basis of the example 5 in examples 7-9, and the use amount of the organic solvents is further limited on the basis of the example 8 in examples 10-12, so that the CBD content is further increased and the loss rate is reduced. Examples 13-15 increased the number of extractions on the basis of example 12, greatly improved the CBD content of the extract after extraction on the basis of example 12, which indicated that the parameters of extraction have a great influence on the extraction effect and efficiency, and the preferred parameters of the examples can bring better extraction effect for extraction.
Examples 16 to 18 were each time the extraction time was limited based on example 14, and it can be seen that example 16 is less effective, but the effect was good each time 10min was reached, and the extraction effect could be ensured based on the energy saving.
Examples 19 to 20 in example 17 in addition to the stirring, can further improve the extraction effect, can be widely used.
In addition, compared with column chromatography and membrane filtration for removing impurities, the method can greatly reduce the use of solvents and resource consumption.
2. Test of impurity removal Effect
Test subjects: example 22, total of 1 set of test samples.
The test method comprises the following steps: performing CBD component detection on the extract obtained in step S3 and the hemp extract obtained in step S5 by using a high performance liquid chromatograph.
And (3) test results: the impurity removal effect test is shown in fig. 1 and fig. 2.
And (3) data analysis: as can be seen from fig. 1 and 2, after the step S3, the impurity removal effect is good, and after the step S5, the impurity removal effect is improved, and the CBD loss is small.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (8)

1. A hemp impurity removal method is characterized by comprising the following steps:
s1: pretreatment: drying and crushing cannabis sativa flowers and leaves to obtain raw material powder; extracting the raw material powder by using an ethanol solution to obtain a hemp extract;
s2: concentrating the hemp extract, winterizing, filtering to obtain filtrate, and concentrating the filtrate into extract;
s3: performing decarboxylation treatment on the extract;
s4: adding an organic solvent into the decarboxylated extract for extraction, and filtering to obtain an extract liquid;
s5: concentrating the extractive solution to remove organic solvent to obtain hemp extract;
the organic solvent is at least one of alkane or halogenated hydrocarbon.
2. A hemp impurity removal method according to claim 1, wherein the organic solvent is at least one of chloroform, n-hexane, n-heptane and n-octane.
3. A method for removing impurities from hemp according to claim 1 or 2, wherein the temperature of the organic solvent extraction in the step S4 is 50-90 ℃.
4. A hemp impurity removal method according to claim 1 or 2, wherein in the step S4, the volume ratio of the mass of the extract to the organic solvent is 1:5-1: 15.
5. A hemp impurity removal method according to claim 1, wherein in the step S4, the organic solvent is added in 2-4 times.
6. A method for removing impurities from hemp according to claim 5, wherein the time for extracting the organic solvent is 5-30 min.
7. A hemp impurity removal method according to claim 1, wherein the extraction is performed in step S4 by continuous stirring.
8. The method for removing impurities from hemp according to claim 1, wherein in the step S2, the hemp extract is concentrated to have 1-5% of cannabidiol content and then winterization is performed.
CN202110167670.2A 2021-02-07 2021-02-07 Hemp impurity removal method Pending CN114907191A (en)

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