CN108503510B - Green natural borneol refining method - Google Patents
Green natural borneol refining method Download PDFInfo
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- CN108503510B CN108503510B CN201810475570.4A CN201810475570A CN108503510B CN 108503510 B CN108503510 B CN 108503510B CN 201810475570 A CN201810475570 A CN 201810475570A CN 108503510 B CN108503510 B CN 108503510B
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
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- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Abstract
The invention provides a refining method of green natural borneol. The method comprises the steps of firstly crushing branches and leaves of borneol cinnamomum camphora, then adopting ethanol-water as a solvent, performing ultrasonic-microwave assisted extraction, concentrating and removing ethanol to obtain a crude extract of natural borneol, then sequentially removing impurities by using a supermolecular solvent to perform recrystallization to purify the crude extract, and quantitatively preparing refined natural borneol by using gas chromatography. The purity of the natural borneol obtained by the invention reaches 98.5 percent, and the natural borneol can be directly used in the biomedical industry and the production of daily chemical toothpaste.
Description
Technical Field
The invention relates to a natural borneol extraction technology, in particular to a green natural borneol refining method.
Background
Natural borneol, also known as natural d-borneol, original name "borneol fragrance", commonly called plum slice, is a crystallized product obtained by steam distillation from branches, leaves and trunk of borneol camphor. Natural borneol has the effects of inducing resuscitation, refreshing mind, clearing heat and relieving pain, and is used for treating fever unconsciousness, convulsion syncope, sore throat, reddish pain and the like. At present, natural borneol is widely applied to medicines, spices, cosmetics, daily chemical product ointments and food industry as rare medicinal materials and high-grade spices. At present, the demand of natural borneol in China is continuously increased, the market is almost occupied by synthetic borneol, the overall level of the natural borneol processing industry in China is not high, the traditional separation and purification method has complicated steps and low yield and purity, and the high-efficiency utilization of natural borneol resources cannot be realized. For example, the method of preparing natural borneol disclosed in patent CN 105837405 a "a method for preparing natural borneol" includes: cutting branches and leaves of borneol camphor trees, distilling the branches and leaves by using a distillation still, removing impurities from collected steam condensate gas by using an oil-water separator, cooling, crystallizing and finally performing centrifugal separation to obtain solid natural borneol. Although the industrial production efficiency is convenient, the extraction efficiency is not high, the process is complicated, and the obtained natural borneol is not pure, so that the application of the natural borneol in the industries of medicines and daily chemicals is limited. Therefore, the invention provides a method for refining green natural borneol.
Disclosure of Invention
The invention provides a method for refining green natural borneol. The method has the advantages of simple operation, less organic solvent, high extraction efficiency and high purity of the obtained natural borneol.
In order to solve the above problems, the present invention provides the following technical solutions: a method for refining green natural borneol is characterized by comprising the following steps:
(1) cleaning and drying the branches and leaves of the borneol camphora, crushing the branches and leaves by using a crusher, and sieving the crushed branches and leaves to obtain powder of the branches and leaves of the borneol camphora;
(2) taking 1.5kg of borneol camphor tree branch and leaf powder and an ethanol-water mixed solvent according to the proportion of 1: 5-10, filtering after microwave-ultrasonic treatment at the ultrasonic power of 400-600W, the microwave power of 200-300W and the temperature of 20-50 ℃ for a period of time, collecting filtrate, continuing microwave-ultrasonic extraction of the residues for 2-3 times, combining the filtrates, and carrying out reduced pressure distillation to obtain crude extracts of natural ice flakes;
(3) weighing 600g of crude natural borneol extract, and mixing the raw materials according to the weight ratio of 1: 1-2, adding a supramolecular solvent, performing vortex for 20s, centrifuging, pouring out supernatant, and mixing the supernatant with the solution according to the ratio of 1: 3-4, adding the solvent, stirring and heating in a water bath until the crude borneol product is complete, keeping the temperature for 1 hour, standing, carrying out suction filtration on the solvent, placing the obtained crystal product in a vacuum drying oven, drying to obtain refined natural borneol, and determining the purity of the borneol by using a gas chromatography.
Further, the sieving in the step (1) is a 60-mesh pharmacopoeia sieve.
Further, the volume percentage of ethanol in the ethanol-water mixed solvent in the step (2) is 15-25%.
Further, the microwave-ultrasonic time in the step (2) is 20-40 min.
Further, the supramolecular solvent in the step (3) is one of tetrahydrofuran-n-octanol-water, tetrahydrofuran-n-hexanol-water and tetrahydrofuran-n-octanoic acid-water supramolecular solvent; the supramolecular solvent contains aggregates with the particle size of 200-600 nm.
Further, the solvent in step (3) is 120#Gasoline; the temperature of the water bath kettle is 40-50 ℃.
Further, the standing time in the step (3) is 10-12 hours, and the standing temperature is 8-15 ℃.
Further, the detection conditions of the gas chromatography in the step (3) are as follows: DB-5 chromatographic column (30m × 250mm × 0.25um), hydrogen Flame Ion Detector (FID), detector temperature of 300 deg.C, and carrier gas of N2，The temperature of a sample inlet is 250 ℃, the sample injection amount is 0.5ul, the temperature is raised by adopting a program, the column temperature is 80 ℃, and the temperature is kept for 2 min and then is raised to 150 ℃ at the speed of 3 ℃/min; the purity of the prepared standing borneol is 98.5-99.2%.
Compared with the traditional preparation method, the green natural borneol refining method provided by the invention adopts a microwave-ultrasonic assisted extraction technology, so that the extraction efficiency of effective components is remarkably improved, and the extraction time is shortened; the method adopts the supermolecule solvent to remove impurities, uses less organic solvent, has high impurity removal efficiency, and is more green and environment-friendly; gasoline is used as a recrystallization solvent, most of polar compounds can be removed, and the purity of the natural borneol is greatly improved. The method is simple to operate, and uses less organic solvent. The purity of the obtained natural borneol is over 98.5 percent by gas phase detection, and the borneol obtained by the invention can be directly used in the production of biological medicines and daily chemical product ointments.
Drawings
FIG. 1 is a gas chromatogram of natural borneol prepared by the invention, and peak 1 is natural borneol.
Detailed Description
The method for refining green natural borneol of the present invention will be further described with reference to the following specific examples to help those skilled in the art to more fully, accurately and deeply understand the inventive concept and technical solution of the present invention.
Example 1
Cleaning and drying the branches and leaves of the borneol camphora, crushing the branches and leaves by a crusher, and screening the crushed branches and leaves through a 60-mesh pharmacopoeia sieve to obtain the branches and leaves powder of the borneol camphora; taking 1.5kg of borneol camphor tree branch and leaf powder and 25% of ethanol-water mixed solvent according to the proportion of 1: 6, performing microwave-ultrasonic treatment at 400W ultrasonic power, 250W microwave power and 35 ℃ for 25min, filtering, collecting filtrate, performing microwave-ultrasonic extraction on the residue for 3 times, combining the filtrates, and performing reduced pressure distillation to obtain a natural ice crude extract; weighing 600g of crude natural borneol extract, and mixing the raw materials according to the weight ratio of 1: 3, adding tetrahydrofuran-n-octanoic acid-water supermolecule solvent, whirling for 20s, centrifuging, pouring out supernatant, and mixing the supernatant with the solution at a solid-to-liquid ratio of 1: 3, adding 120# gasoline into the solid-to-liquid ratio, putting the mixture into a water bath, stirring and heating the mixture until the crude borneol product is complete, keeping the temperature for 1 hour, standing the mixture at 10 ℃ for 2 hours, carrying out suction filtration on the solvent, and putting the obtained crystal product into a vacuum drying oven to be dried to obtain the refined natural borneol.
Example 2
Cleaning and drying the branches and leaves of the borneol camphora, crushing the branches and leaves by a crusher, and screening the crushed branches and leaves through a 60-mesh pharmacopoeia sieve to obtain the branches and leaves powder of the borneol camphora; taking 1.5kg of borneol camphor tree branch and leaf powder and 15% of ethanol-water mixed solvent according to the proportion of 1: 10, performing microwave-ultrasonic treatment at 500W ultrasonic power, 200W microwave power and 30 ℃ for 30min, filtering, collecting filtrate, performing microwave-ultrasonic extraction on the residue for 2 times, combining the filtrates, and performing reduced pressure distillation to obtain a natural ice crude extract; weighing 600g of crude natural borneol extract, and mixing the raw materials according to the weight ratio of 1: 2, adding tetrahydrofuran-n-octanol-water supramolecular solvent, whirling for 20s, centrifuging, pouring out supernatant, and mixing according to the ratio of 1: 4, adding 120# gasoline into the solid-to-liquid ratio, putting the mixture into a water bath, stirring and heating the mixture until the crude borneol product is complete, keeping the temperature for 1 hour, standing the mixture at 10 ℃ for 10 hours, carrying out suction filtration on the solvent, and putting the obtained crystal product into a vacuum drying oven to be dried to obtain the refined natural borneol.
Example 3
Cleaning and drying the branches and leaves of the borneol camphora, crushing the branches and leaves by a crusher, and screening the crushed branches and leaves through a 60-mesh pharmacopoeia sieve to obtain the branches and leaves powder of the borneol camphora; taking 1.5kg of borneol camphor tree branch and leaf powder and 20% of ethanol-water mixed solvent according to the proportion of 1: 8, performing microwave-ultrasonic treatment at 500W ultrasonic power, 250W microwave power and 30 ℃ for 25min, filtering, collecting filtrate, performing microwave-ultrasonic extraction on the residue for 3 times, combining the filtrates, and performing reduced pressure distillation to obtain a natural ice crude extract; weighing 600g of crude natural borneol extract, and mixing the raw materials according to the weight ratio of 1: 3, adding tetrahydrofuran-n-octanol-water supramolecular solvent into the mixture, whirling for 20 seconds, centrifuging, pouring out supernatant, and mixing the supernatant with the mixture according to the ratio of 1: 3, adding 120# gasoline into the solid-to-liquid ratio, putting the mixture into a water bath, stirring and heating the mixture until the crude borneol product is complete, keeping the temperature for 1 hour, standing the mixture at 10 ℃ for 12 hours, carrying out suction filtration on the solvent, and putting the obtained crystal product into a vacuum drying oven to be dried to obtain the refined natural borneol.
The detection method of the natural borneol obtained in the embodiment 1-3 comprises the following steps: DB-5 chromatographic column (30m × 250mm × 0.25um), hydrogen Flame Ion Detector (FID), 300 deg.C, and carrier gas N2，The temperature of a sample inlet is 250 ℃, the sample injection amount is 0.5ul, the temperature is raised by adopting a program, the column temperature is 80 ℃, and the temperature is kept for 2 min and then is raised to 150 ℃ at the speed of 3 ℃/min; the purity of the standing borneol prepared by the invention is 98.5-99.2%. The chromatogram obtained by the method is shown in figure 1, and it can be seen that the purity of natural borneol is high and the impurity content is low.
The extraction rate and purity of natural borneol obtained by the preparation methods of examples 1-3 are shown in table 1.
| Test items | Extraction ratio (%) | Purity (%) |
| Example 1 | 88 | 99.0 |
| Example 2 | 85 | 98.8 |
| Example 3 | 84 | 99.2 |
It is obvious to those skilled in the art that the present invention is not limited to the above embodiments, and it is within the scope of the present invention to adopt various insubstantial modifications of the method concept and technical scheme of the present invention, or to directly apply the concept and technical scheme of the present invention to other occasions without modification.
Claims (5)
1. A method for refining green natural borneol is characterized by comprising the following steps:
(1) cleaning and drying the branches and leaves of the borneol camphora, crushing the branches and leaves by using a crusher, and sieving the crushed branches and leaves to obtain powder of the branches and leaves of the borneol camphora;
(2) taking 1.5kg of borneol camphor tree branch and leaf powder and an ethanol-water mixed solvent according to the proportion of 1: 5-10, filtering after microwave-ultrasonic treatment at the ultrasonic power of 400-600W, the microwave power of 200-300W and the temperature of 20-50 ℃ for a period of time, collecting filtrate, continuing microwave-ultrasonic extraction of the residues for 2-3 times, combining the filtrates, and carrying out reduced pressure distillation to obtain crude extracts of natural ice flakes;
(3) weighing 600g of crude natural borneol extract, and mixing the raw materials according to the weight ratio of 1: 1-2, adding a supramolecular solvent, performing vortex for 20s, centrifuging, pouring out supernatant, and mixing the supernatant with the solution according to the ratio of 1: 3-4 of solid-to-liquid ratio, adding the solvent, stirring and heating in a water bath until crude borneol is completely dissolved, keeping the temperature for 1 hour, standing to carry out suction filtration on the solvent, placing the obtained crystal product in a vacuum drying oven for drying to obtain refined natural borneol, and determining the purity of the borneol by utilizing a gas chromatography, wherein the solvent is 120#Gasoline, the temperature of the water bath kettle is 40-50 ℃, the standing time is 10-12 hours, the standing temperature is 8-15 ℃, and the supramolecular solvent is tetrahydrofuran-n-octanol-water and tetrahydrofuran-n-hexylAlcohol-water, tetrahydrofuran-n-octanoic acid-water supermolecular solvent.
2. The method for refining green natural borneol according to claim 1, characterized in that the sieving in step (1) is a 60 mesh pharmacopoeia sieve.
3. The refining method of green natural borneol as claimed in claim 1, characterized in that the volume percentage of ethanol in the ethanol-water mixed solvent in step (2) is 15-25%.
4. The refining method of green natural borneol according to claim 1, characterized in that the microwave-ultrasonic time in step (2) is 20-40 min.
5. The method for refining green natural borneol according to claim 1, characterized in that the detection conditions of the gas chromatography in step (3) are as follows: DB-5 chromatographic column 30m × 250mm × 0.25um, hydrogen flame ion detector FID, detector temperature 300 deg.C, and carrier gas N2The temperature of a sample inlet is 250 ℃, the sample injection amount is 0.5ul, the temperature is raised by adopting a program, the column temperature is 80 ℃, and the temperature is kept for 2 min and then is raised to 150 ℃ at the speed of 3 ℃/min; the purity of the prepared refined borneol is 98.5-99.2%.
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Address after: 343000 No. 898 beside Lushuihe Avenue, Anfu Industrial Park, Ji'an City, Jiangxi Province Patentee after: Jiangxi Zhangxiang natural borneol Co.,Ltd. Patentee after: Guangdong Kangwang Daily Chemical Co., Ltd Address before: 343200 No. 898 beside Lushuihe Avenue, Anfu county industrial park, Ji'an City, Jiangxi Province Patentee before: JIANGXI ZHANGXIANG NATURAL BORNEOL CO.,LTD. Patentee before: Guangdong Kangwang Daily Chemical Co., Ltd |
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