Natural borneol refining method
Through the coordinated extraction method of anhydrous ethanol under microwave and ultrasound, combined with multiple repeated extraction and calcium oxide precipitation separation, the problems of expensive equipment and complex process in the existing technology were solved, and efficient and low-cost natural head purification was achieved, and the product purity reached more than 94%.
Patent Information
- Application Number
- CN202411638069.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-16
- Publication Date
- 2025-03-25
AI Technical Summary
The existing natural adenoplasty purification methods require expensive equipment and solvents, and the process is complex, time-consuming and has safety risks.
Anhydrous ethanol was used for the coordinated extraction of microwave and ultrasound, and the high-purity natural dragon brain was obtained by repeated extraction and calcium oxide precipitation separation.
There is no need for complex machinery and equipment and expensive solvents, which reduces energy consumption and production costs, improves purification efficiency and product purity, and the content of dextrone canal is greater than or equal to 94%, and the content of camphor is less than or equal to 5%.
Smart Images
Figure CN119684089A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of borneol preparation, in particular to a method for refining natural borneol. Background Art
[0002] Natural borneol, also known as dextrorotatory borneol, borneol, plum blossom borneol, plum blossom borneol, and plum slices, is one of the precious Chinese medicinal materials. In the field of medicine, borneol has the effects of awakening the mind, clearing away heat and relieving pain, and antiseptic and muscle regeneration. It can be used to treat stroke coma, fever coma, red and swollen eyes, and other symptoms. In the field of spices, borneol's unique aromatic smell makes it widely used in perfumes, flavors, cosmetics and other products. The main source of natural borneol includes the borneol tree. The resin of the borneol tree contains natural borneol, and high-purity borneol crystals can be obtained after extraction and purification.
[0003] At present, the main methods for purifying natural borneol are solvent extraction, distillation and adsorption. The solvent extraction method utilizes the difference in solubility of natural borneol in different solvents to dissolve it from the borneol raw material, and then removes impurities through filtration and other operations. The distillation method uses the difference in boiling points between natural borneol and impurities to separate natural borneol through distillation operations. The adsorption method utilizes the difference in adsorption capacity of the adsorbent for natural borneol and impurities, adsorbs natural borneol and then desorbs it to obtain a high-purity product.
[0004] However, currently used purification methods often require the use of expensive equipment and reagents. For example, organic solvents such as ether and petroleum ether commonly used in solvent extraction are not only relatively expensive, but also dangerous to use. The distillation equipment used in the distillation method is expensive and has high maintenance costs. It also requires more energy for distillation. The adsorbent used in the adsorption method takes too long in the adsorption-desorption process and requires more adsorbent for complete adsorption. Therefore, a solution is urgently needed to improve the above problems. Summary of the invention
[0005] The object of the present invention is to provide a method for refining natural borneol, which can obtain alcohol-soluble and water-soluble substances by pre-extraction with anhydrous ethanol, and then remove the water-soluble substances, without complex mechanical equipment and expensive solvents, to obtain a natural borneol purified material with a natural right-handed borneol content greater than or equal to 94% and a camphor content less than or equal to 5%.
[0006] The invention provides a natural borneol refining method, comprising: extracting a borneol raw material in anhydrous ethanol at 300-600W microwave power, 300-400W ultrasonic power and 60-80°C for 20-30min, and then centrifuging to obtain an extract; repeating the process 5-8 times, combining the extracts, and evaporating to obtain a crude extract; dissolving the crude extract in 50-70vol.% aqueous ethanol to obtain a crude extract solution, adding calcium oxide into the crude extract solution, stirring for reaction, standing for precipitation, and separating a supernatant; evaporating the supernatant to obtain a refined extract, and repeating the process 2-3 times to obtain a refined extract solution; evaporating the refined extract solution, and then washing with hot water at 80-90°C for 2-5 times to obtain purified natural borneol.
[0007] Optionally, the content of d-borneol in the borneol raw material is less than or equal to 80%, and the content of camphor is greater than or equal to 8%.
[0008] Optionally, the content of d-borneol in the purified natural borneol is greater than or equal to 94%, and the content of camphor is less than or equal to 5%.
[0009] Optionally, the water content of the borneol raw material is less than or equal to 1%.
[0010] Optionally, the volume fraction of ethanol in the 50-70 vol.% aqueous ethanol is 50-70%.
[0011] Optionally, when the borneol raw material is extracted in anhydrous ethanol at 60-80°C for 20-30 min at 300-600 W microwave power, 300-400 W ultrasonic power, and 60-80°C: the microwave power and the ultrasonic power are gradually increased, and the temperature change of the anhydrous ethanol is less than or equal to 5°C.
[0012] Optionally, when the borneol raw material is extracted in anhydrous ethanol at 60-80° C. at 300-600 W microwave power, 300-400 W ultrasonic power for 20-30 min, the volume ratio of the borneol raw material to the anhydrous ethanol is 1:(5-10).
[0013] Optionally, when the borneol raw material is extracted in anhydrous ethanol at 300-600 W microwave power, 300-400 W ultrasonic power and 60-80° C. for 20-30 min: the borneol raw material is extracted in a sealed container.
[0014] Optionally, when the borneol raw material is extracted in anhydrous ethanol at 60-80° C. with a microwave power of 300-600 W, an ultrasonic power of 300-400 W, for 20-30 min: the borneol raw material is mixed with anhydrous ethanol and heated to 60-80° C. at a microwave power of 300-600 W for 10-15 min, and ultrasonic extraction is performed at a power of 300-400 W for 10-15 min.
[0015] Optionally, when the crude extract is obtained by evaporating the combined extracts for 5-8 times: the microwave power and / or the ultrasonic power are increased successively.
[0016] Optionally, when the crude extract is obtained by combining the extracts and evaporating to dryness for 5-8 times, the microwave power gradient between two adjacent extractions is 20-30W.
[0017] Optionally, when the crude extract is obtained by combining the extracts and evaporating to dryness for 5-8 times, the ultrasonic power gradient between two adjacent extractions is 10-15W.
[0018] Optionally, when the crude extract is obtained by repeatedly combining the extracts and evaporating to dryness for 5-8 times: after combining the extracts, evaporate to dryness at 60-70° C. and recover anhydrous ethanol.
[0019] Optionally, when the crude extract is obtained by combining the extracts and evaporating to dryness for 5-8 times, the extracts are combined and evaporated to dryness, and then the extracts are rinsed with anhydrous ethanol for 3-5 times in a cycle and then dried to obtain the crude extract.
[0020] Optionally, when the crude extract is dissolved in 50 vol.% aqueous ethanol to prepare a crude extract solution, the volume ratio of the crude extract to the 50 vol.% aqueous ethanol is 1:(5-8).
[0021] Optionally, when the crude extract is dissolved in 50 vol.% aqueous ethanol to prepare a crude extract solution: after the crude extract is dissolved in 50 vol.% aqueous ethanol, the crude extract is centrifuged at a speed of 300-500 rpm for 2-3 minutes, and then the crude extract solution is filtered under reduced pressure.
[0022] Optionally, when the crude extract is dissolved in 50 vol. % aqueous ethanol to prepare the crude extract solution: the crude extract is dissolved in 50 vol. % aqueous ethanol at 40-50° C. to prepare the crude extract solution.
[0023] Optionally, when calcium oxide is added to the crude extraction solution and stirred for reaction, the mass ratio of the calcium oxide to the crude extraction solution is 1:(1-1.5).
[0024] Optionally, when calcium oxide is added into the crude extraction solution and stirred for reaction: calcium oxide is added into the crude extraction solution and stirred for reaction at a rotation speed of 100-200 rpm.
[0025] Optionally, when calcium oxide is added to the crude extraction solution and stirred for reaction: calcium oxide powder with an average particle size of 0.1-1 mm is added to the crude extraction solution and stirred for reaction.
[0026] Optionally, when calcium oxide is added to the crude extraction solution and stirred for reaction: calcium oxide is added to the crude extraction solution and stirred for reaction at a constant temperature of 40-50°C.
[0027] Optionally, when separating the supernatant after standing and settling: separating the supernatant after standing at 20-30°C.
[0028] Optionally, when separating the supernatant after standing and settling: separating the supernatant after standing and settling for 2-3 hours.
[0029] Optionally, when separating the supernatant after standing and settling: standing and settling, filtering out the precipitate, and then centrifuging at a speed of 500-1000 rpm to separate the supernatant.
[0030] Optionally, when separating the supernatant after standing and settling: standing and settling, filtering out the precipitate, and centrifuging for 5-10 minutes to separate the supernatant.
[0031] Optionally, after evaporating the supernatant to obtain a refined extract, the process is repeated 2-3 times to obtain a refined extract: the volume fraction of ethanol in the aqueous ethanol in each of the 2-3 repetitions is independent of each other.
[0032] Optionally, after evaporating the supernatant to obtain a refined extract, the process is repeated 2-3 times to obtain a refined extract: evaporating the supernatant at 50-60° C. and recovering anhydrous ethanol.
[0033] Optionally, when the supernatant is evaporated to dryness to obtain a refined extract and the process is repeated 2-3 times to obtain a refined extract: the volume fraction of ethanol in the aqueous ethanol used increases successively when the process is repeated 2-3 times. BRIEF DESCRIPTION OF THE DRAWINGS
[0034] Figure 1 The present invention provides a flowchart of a method for refining natural borneol. DETAILED DESCRIPTION
[0035] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein should be the common meanings understood by people with general skills in the field to which the present invention belongs.
[0036] See also Figure 1 The present invention provides a method for refining natural borneol, comprising the following steps:
[0037] S1. Extract the borneol raw material in anhydrous ethanol at 300-600W microwave power, 300-400W ultrasonic power and 60-80°C for 20-30min and then centrifuge to obtain an extract;
[0038] S2, repeating step S1 5-8 times, combining the extracts and evaporating to dryness to obtain a crude extract;
[0039] S3, dissolving the crude extract in 50-70 vol.% aqueous ethanol to prepare a crude extract solution, adding calcium oxide to the crude extract solution, stirring the reaction, standing to precipitate, and separating the supernatant;
[0040] S4, after evaporating the supernatant to obtain a refined extract, repeat step S3 2-3 times to obtain a refined extract;
[0041] S5. After evaporating the extract, rinse it with hot water at 80-90° C. for 2-5 times to obtain purified natural borneol.
[0042] In fact, in step S1, by performing anhydrous ethanol extraction in a microwave and ultrasonic environment, the microwave and ultrasonic effects can be used to promote the separation of d-borneol and impurities in the borneol raw material, and promote the dissolution of d-borneol in anhydrous ethanol. At the same time, anhydrous ethanol is beneficial to the dissolution of alcohol-soluble substances (d-borneol and camphor) in the borneol raw material, thereby achieving the initial separation of d-borneol and other impurity molecules.
[0043] Specifically, when anhydrous ethanol is extracted at a microwave power of 300-600W, not only can the heating characteristics of microwaves be used to quickly heat the anhydrous ethanol, but also the temperature uniformity of the anhydrous ethanol during extraction can be improved, which is beneficial to uniformly heat the borneol raw material and promote the diffusion of d-borneol in the borneol raw material into the anhydrous ethanol. In addition, the microwave perturbation effect can also destroy the binding force between d-borneol and impurity molecules in the borneol raw material, further promote the dissolution of d-borneol, and improve the selectivity of d-borneol.
[0044] Specifically, when anhydrous ethanol extraction is performed at an ultrasonic power of 300-400W, the strong cavitation effect and mechanical vibration generated by ultrasound in anhydrous ethanol are firstly utilized to generate a local high temperature and high pressure environment around the borneol raw material, thereby destroying the internal microstructure of the borneol raw material and promoting the dissolution of right-handed borneol and other alcohol-soluble substances. In addition, the mechanical vibration in the anhydrous ethanol can promote the full contact between the anhydrous ethanol and the borneol raw material, thereby effectively improving the dissolution efficiency.
[0045] Specifically, the anhydrous ethanol is heated to 60-80° C. by microwave heating, so that a high-pressure environment can be formed in the extraction space, which is beneficial to the high-pressure extraction of the borneol raw material. At the same time, the fluidity of the anhydrous ethanol can be improved, the viscosity of the anhydrous ethanol can be reduced, and the rapid dissolution and rapid diffusion of the right-handed borneol in the anhydrous ethanol can be facilitated. In addition, as a common solvent, anhydrous ethanol is inexpensive and easy to obtain, and is easy to quickly heat, volatilize and recover, without causing residues. At the same time, the recyclability is improved, and the purification cost is further reduced.
[0046] In fact, in step S1, when the borneol raw material is extracted in anhydrous ethanol at 60-80° C., the synergistic effect of microwaves and ultrasound can be used to promote the rapid dissolution and diffusion of d-borneol from the borneol raw material into the anhydrous ethanol, which greatly shortens the extraction time and improves the extraction efficiency. The microwave perturbation effect and the ultrasonic cavitation effect can reduce the extraction of impurity molecules, thereby improving the purity of d-borneol in anhydrous ethanol. In addition, the operation of step S1 is simple, does not require the use of complex equipment and expensive solvents, and consumes less energy.
[0047] In some embodiments, when performing step S1, the content of d-borneol in the borneol raw material is less than or equal to 80%, and the content of camphor is greater than or equal to 8%. In fact, the borneol raw material can be a semi-finished product in the borneol preparation process, or camphor branches and leaves can be directly used as raw materials. Specifically, the water content in the borneol raw material is less than or equal to 1%.
[0048] In some embodiments, when performing step S1 in anhydrous ethanol extraction, the microwave power and the ultrasonic power are gradually increased, and the temperature change of anhydrous ethanol is less than or equal to 5°C. In fact, by gradually increasing the microwave power, the molecular motion in the extraction system is gradually promoted, and after controlling the temperature change of anhydrous ethanol, the molecular motion can be promoted and the right-handed borneol can be dissolved during the constant temperature extraction process. In the process of gradually increasing the ultrasonic power, the cavitation effect will be gradually enhanced, and the alcohol-soluble substances in the borneol raw material will be gradually released, and it is conducive to the precise regulation of the ultrasonic power in the extraction process. As the extraction deepens, stronger microwaves and ultrasound can be applied to meet different needs, thereby comprehensively improving the extraction efficiency and extraction quality.
[0049] In some embodiments, when performing step S1, the volume ratio of the borneol raw material to the anhydrous ethanol used is 1: (5-10). In fact, mixing the borneol raw material and anhydrous ethanol at this volume ratio is beneficial to the dissolution of alcohol-soluble substances such as d-borneol in the borneol raw material during the extraction process, and at the same time, a uniform high-temperature and high-pressure microenvironment can be formed on the surface of the borneol raw material under the action of ultrasound, thereby promoting the dissolution of d-borneol in the borneol raw material.
[0050] In some embodiments, when performing step S1, the borneol raw material is extracted in a closed container. In fact, when the anhydrous ethanol is heated by microwaves in a closed space, the anhydrous ethanol evaporates and a high-pressure environment can be formed in the closed container, thereby increasing the boiling point of the anhydrous ethanol and facilitating the alcohol extraction of the borneol raw material under high pressure. Specifically, the closed container used can be a metal container or a glass container commonly used in industrial production or laboratories.
[0051] In some embodiments, when performing step S1, after mixing the borneol raw material with anhydrous ethanol, the borneol raw material is heated to 60-80°C at a microwave power of 300-600W and then kept warm for 10-15min, and an ultrasonic power of 300-400W is added and extracted for 10-15min. In fact, during the 60-80°C insulation process, the microwave power of 300-600W is still added, and the anhydrous ethanol is kept warm by a cooling device. In fact, by pre-heating the anhydrous ethanol with microwaves, it is beneficial to quickly increase the temperature of the anhydrous ethanol, and when the temperature of the anhydrous ethanol is maintained during the insulation process and microwaves are applied, the temperature of the borneol raw material can be increased, and the dissolution of the right-handed borneol in the borneol raw material is promoted. In fact, when the ultrasonic power is added for extraction, microwave radiation of 300-600W power is applied simultaneously.
[0052] In some embodiments, when performing step S2, the microwave power is increased sequentially, for example, when the microwave power is 300-400 W during the first extraction, the microwave power can be maintained at 400-600 W during the second extraction. In fact, by increasing the microwave power sequentially during repeated extractions, it is beneficial to perform microwave-assisted extraction of borneol raw materials at different levels, thereby improving the extraction degree of dextrorotatory borneol in the borneol raw material.
[0053] In some embodiments, when executing step S2, the ultrasonic power is increased successively, for example, when the ultrasonic power is 300-320 W during the first extraction, the ultrasonic power during the second extraction can be maintained at 320-340 W. In fact, by gradually increasing the ultrasonic power during repeated extractions, the extraction efficiency of d-borneol can be gradually improved, while avoiding excessive damage to the structure of the borneol raw material by directly performing high-intensity ultrasonic extraction. In addition, energy can be saved, which is conducive to reducing the refining cost of natural borneol.
[0054] In some embodiments, when the microwave power is increased successively during multiple extractions in step S2, the gradient of the microwave power of two adjacent times is 20-30 W. For example, when the microwave power during the first extraction is 320 W, the microwave power during the second extraction is 350 W, and the microwave power during the third extraction is 370 W. In fact, by increasing the microwave power in a gradient, the microwave can act progressively on the borneol raw material, and the extraction purity of the right-handed borneol can be further improved.
[0055] In some embodiments, when performing multiple extractions in step S2 and the ultrasonic power increases successively, the gradient of the ultrasonic power during two adjacent extractions is 10-15 W. For example, when the ultrasonic power during the first ultrasonic extraction is 300 W, the ultrasonic power during the second ultrasonic extraction may be 315 W, and the ultrasonic power during the third extraction may be 330 W. In fact, by utilizing the gradually increasing ultrasonic effect, the impurities in the borneol raw material that are closely bound to the d-borneol can be effectively broken down, and the dissolution of the d-borneol can be promoted.
[0056] In some embodiments, after the extracts are combined in step S2, the anhydrous ethanol is evaporated to dryness at 40-50° C. and recovered, which is conducive to the recycling of the anhydrous ethanol and the removal of volatile impurities in the extract, thereby obtaining a relatively pure crude extract. In fact, the evaporation to dryness can be carried out in a vacuum environment or a low pressure environment, which is conducive to the boiling of the extract and thus improves the removal rate of the evaporated anhydrous ethanol on the impurity molecules, which can increase the content of d-borneol in the crude extract.
[0057] Specifically, after performing step S2 and merging the extract and evaporating the solvent, the solid obtained after evaporating the solvent can be rinsed with absolute ethanol. In fact, the impurities soluble in absolute ethanol in the solid can be removed when rinsing with absolute ethanol, although a small amount of d-borneol is removed synchronously, d-borneol can be removed from the total amount. Specifically, when using absolute ethanol to rinse the solid obtained after evaporating the solvent, it is controlled to be 3-4s for each rinse, and vacuum drying is performed after each rinse, and the number of rinses is controlled to be 3-5 times.
[0058] In some embodiments, when performing step S3 to dissolve the crude extract in 50-70 vol.% aqueous ethanol to prepare the crude extract solution, the volume ratio of the crude extract to the aqueous ethanol is 1:(5-8). In fact, by dissolving the crude extract in aqueous ethanol, alcohol-soluble substances and water-soluble substances can be simultaneously dissolved, and some impurities that cannot be removed by washing can also be separated. In fact, for example, in 50 vol.% aqueous ethanol, the volume fraction of ethanol to deionized water is 1:1.
[0059] Specifically, the crude extract is dissolved in aqueous ethanol, centrifuged at a speed of 300-500 rpm for 2-3 minutes, and then filtered under reduced pressure to obtain a crude extract solution. In fact, by pre-dissolving the crude extract and centrifuging it, it is beneficial to precipitate and remove the tiny impurities and insolubles in the aqueous ethanol, and it can also promote the uniform dispersion of alcohol-soluble substances and water-soluble substances in the aqueous ethanol.
[0060] In some embodiments, when executing step S3, the crude extract is dissolved in 50-70 vol.% aqueous ethanol at 40-50°C to prepare a crude extract solution. In fact, the aqueous ethanol can be fully preheated in a 40-50°C water bath environment, and then the crude extract is added to the aqueous ethanol for stirring and dissolving. In fact, after the crude extract is dissolved in the aqueous ethanol, it can be stirred at a speed of 100-150 rpm in a 40-50°C water bath environment and kept warm for 1-2 hours. In fact, in
[0061] In some embodiments, when calcium oxide is added to the crude solution and stirred for reaction in step S3, the mass ratio of the added calcium oxide to the crude solution is 1: (1-1.5). In fact, after calcium oxide is added to the crude solution, calcium oxide reacts with water to form calcium hydroxide, which can adsorb and remove water-soluble substances dissolved in the aqueous phase, thereby improving the purity of alcohol-soluble substances (d-borneol) in the crude solution. Specifically, adjusting the mass ratio of calcium oxide to the crude solution can cause the water in the crude solution to be completely removed by calcium oxide, thereby improving the extraction purity of d-borneol.
[0062] In some embodiments, when executing step S3, after calcium oxide is added to the crude extraction solution, the stirring reaction can be carried out at a rotation speed of 100-200 rpm to promote the full mixing and reaction of calcium oxide and water, and at the same time, it can promote the adsorption of water-soluble substances and impurities precipitated therein by calcium hydroxide, thereby improving the purity of the purified d-borneol.
[0063] In some embodiments, when executing step S3, calcium oxide powder with an average particle size of 0.1-1 mm can be added to the crude extraction solution for stirring reaction. This is conducive to promoting the full reaction of calcium oxide and water, while avoiding the formation of a coating structure after the surface calcium oxide reacts to cover the unreacted calcium oxide inside, which is conducive to the adsorption of water-soluble substances in the crude extraction solution.
[0064] Specifically, when performing step S3 to carry out stirring reaction, the crude extraction solution can be controlled to carry out stirring reaction at a constant temperature of 40-50° C. In fact, it is beneficial for calcium oxide to react with water to release a large amount of heat, so by controlling the constant temperature to react, it is beneficial to avoid excessive temperature causing a large amount of ethanol evaporation, which is beneficial to maintain the solubility of d-borneol in the crude extraction solution. In addition, the solubility of calcium hydroxide in the crude extraction solution can also be reduced, thereby improving the adsorption and removal of water-soluble substances by calcium hydroxide.
[0065] In some embodiments, after performing step S3 to stir the reaction, the supernatant is separated after standing at 20-30° C. for 2-3 hours, so that the anhydrous ethanol after impurities removal and the dextrorotatory borneol dissolved therein can be obtained. In fact, the crude extract solution after the reaction can be allowed to stand and precipitate at room temperature, which is conducive to precipitating the calcium hydroxide dispersed therein and stratifying with the ethanol.
[0066] In some embodiments, after performing step S3 to allow the solution to settle and filter out the precipitate, the supernatant can be centrifuged at a speed of 500-1000 rpm for 5-10 min to separate the supernatant. In fact, free calcium hydroxide can be removed by centrifugation, while the purity of the supernatant can be further improved.
[0067] Specifically, when step S4 is performed, after the supernatant is evaporated to obtain a refined extract, the main components in the refined extract are d-borneol and a small amount of camphor impurities, and after step S3 is repeated 2-3 times, the camphor impurities in the refined extract can be further removed to improve the purity of d-borneol. In fact, when step S4 is performed, when the refined extract is redissolved, the ethanol volume fraction of the aqueous ethanol used each time is independent of each other, and the supernatant can be evaporated at 50-60° C. and anhydrous ethanol can be recovered. Specifically, when step S4 is performed, the volume fraction of the aqueous ethanol used increases successively.
[0068] In fact, after executing step S4, using hot water to rinse the solids after evaporating the extract is beneficial to further remove the camphor impurities therein and obtain purified natural borneol, and the content of dextrorotatory borneol in natural borneol is greater than or equal to 94%, and the camphor content is less than or equal to 5%.
[0069] Preparation Example 1
[0070] This preparation example 1 provides a preparation method for a borneol raw material, comprising the following steps: collecting 10 kg of dark green old leaves and twigs from borneol camphor trees in August, rinsing them with deionized water, and drying them in a 50°C hot air drying oven to a moisture content of 10%, crushing and sieving them, adding 100 kg of deionized water, and keeping them warm at 60°C in a vacuum environment for 10 hours, distilling them at 65°C, collecting the distillate, and evaporating them to obtain a borneol raw material with a purity of about 72%, a camphor content of about 12%, and a moisture content of less than 1%.
[0071] Example 1
[0072] This Example 1 provides a method for refining natural borneol based on Preparation Example 1, comprising the following steps:
[0073] S1. Mix the borneol raw material and anhydrous ethanol in a volume ratio of 1:8 and put them into an extraction tank. Apply 400W microwave and 350W ultrasound outside the extraction tank simultaneously, control the constant temperature in the extraction tank to 65°C for post-treatment for 25 minutes, and then centrifuge at a speed of 200rpm to obtain an extract and a separation residue;
[0074] S2, mixing the separated residue with anhydrous ethanol in a volume ratio of 1:8 and putting it into an extraction tank, and treating it outside the extraction tank in the same manner as step S1, and repeating it 7 times, and then combining all the obtained extracts, evaporating to dryness in a vacuum environment at 45° C. and recovering the anhydrous ethanol to obtain a crude extract;
[0075] S3, dissolving the crude extract and mixing it with 60% aqueous ethanol in a volume ratio of 1:7 into an extraction tank, stirring and mixing at 50°C to dissolve, centrifuging at a speed of 500rpm for 2min and filtering under reduced pressure to obtain a crude extract solution; mixing calcium oxide powder with an average particle size of 1mm with the crude extract solution in a mass ratio of 1:1, stirring and reacting under mechanical stirring at 150rpm, and controlling the inside of the extraction tank to react at a constant temperature of 45°C; cooling to room temperature of 25°C after the reaction is completed, and letting it stand for 2h to remove the precipitate, and centrifuging at a speed of 800rpm for 10min to separate the supernatant;
[0076] S4, evaporating the supernatant to dryness in a vacuum environment at 45°C and recovering anhydrous ethanol to obtain a refined extract, and mixing the refined extract with 60% aqueous ethanol by volume at a volume ratio of 1:7 and putting it into an extraction tank, and repeating the process in step S3 three times to obtain a refined extract solution;
[0077] S5. After the refined extract was evaporated to dryness in a vacuum environment at 45° C. and anhydrous ethanol was recovered, the purified natural borneol was obtained after being rinsed three times with deionized water at 85° C. The detection showed that the content of dextrorotatory borneol in the purified natural borneol was about 95.4%, and the content of camphor was about 4.2%.
[0078] Example 2
[0079] This embodiment 2 provides a method for refining natural borneol based on preparation example 1, comprising the following steps:
[0080] S1. Mix the borneol raw material and anhydrous ethanol in a volume ratio of 1:7 and put them into an extraction tank. Apply a microwave treatment of 400 W power outside the extraction tank in advance to raise the temperature in the extraction tank to 65°C, and then keep the temperature for 12 minutes. Then, simultaneously apply an ultrasonic treatment of 350 W power and extract for 13 minutes, and then centrifuge at a speed of 200 rpm to obtain an extract and a separation residue;
[0081] S2, mixing the separated residue and anhydrous ethanol in a volume ratio of 1:7 and putting them into an extraction tank, and treating them outside the extraction tank in the same manner as step S1, and repeating the process 7 times, combining all the obtained extracts, evaporating to dryness in a vacuum environment at 45° C., and recovering the anhydrous ethanol to obtain a crude extract;
[0082] S3, dissolving the crude extract and mixing it with 60% aqueous ethanol in a volume ratio of 1:7 into an extraction tank, stirring and mixing at 50°C to dissolve, centrifuging at a speed of 500rpm for 2min and filtering under reduced pressure to obtain a crude extract solution; mixing calcium oxide powder with an average particle size of 1mm with the crude extract solution in a mass ratio of 1:1, stirring and reacting under mechanical stirring at 150rpm, and controlling the inside of the extraction tank to react at a constant temperature of 45°C; cooling to room temperature of 25°C after the reaction is completed, and letting it stand for 2h to remove the precipitate, and centrifuging at a speed of 800rpm for 10min to separate the supernatant;
[0083] S4, evaporating the supernatant to dryness in a vacuum environment at 45°C and recovering anhydrous ethanol to obtain a refined extract, and mixing the refined extract with 60% aqueous ethanol by volume at a volume ratio of 1:7 and putting it into an extraction tank, and repeating the process in step S3 three times to obtain a refined extract solution;
[0084] S5. After the refined extract was evaporated to dryness in a vacuum environment at 45° C. and anhydrous ethanol was recovered, the purified natural borneol was obtained after being rinsed three times with deionized water at 85° C. The detection showed that the content of dextrorotatory borneol in the purified natural borneol was about 96.1%, and the content of camphor was about 2.8%.
[0085] Example 3
[0086] This Example 3 provides a method for refining natural borneol based on Preparation Example 1, comprising the following steps:
[0087] S1. Mix the borneol raw material and anhydrous ethanol in a volume ratio of 1:7 and put them into an extraction tank. Apply microwave treatment with a power of 350 W to the outside of the extraction tank in advance to raise the temperature in the extraction tank to 65° C., and then keep the temperature for 12 minutes. Then, simultaneously apply ultrasonic treatment with a power of 320 W and extract for 13 minutes, and then centrifuge at a speed of 200 rpm to obtain an extract and a separation residue;
[0088] S2, mixing the separated residue with anhydrous ethanol in a volume ratio of 1:7 and putting it into an extraction tank, performing the same treatment as step S1 outside the extraction tank and repeating it for 7 times, combining all the obtained extracts, evaporating to dryness in a vacuum environment at 45°C and recovering the anhydrous ethanol to obtain a crude extract; when repeating for the first time, the microwave power is 370W and the ultrasonic power is 330W, when repeating for the second time, the microwave power is 390W and the ultrasonic power is 340W, when repeating for the third time, the microwave power is 410W and the ultrasonic power is 350W, when repeating for the fourth time, the microwave power is 430W and the ultrasonic power is 360W, when repeating for the fifth time, the microwave power is 450W and the ultrasonic power is 370W, when repeating for the sixth time, the microwave power is 470W and the ultrasonic power is 380W, and when repeating for the seventh time, the microwave power is 490W and the ultrasonic power is 390W;
[0089] S3, dissolving the crude extract and mixing it with 60% aqueous ethanol in a volume ratio of 1:7 into an extraction tank, stirring and mixing at 50°C to dissolve, centrifuging at a speed of 500rpm for 2min and filtering under reduced pressure to obtain a crude extract solution; mixing calcium oxide powder with an average particle size of 1mm with the crude extract solution in a mass ratio of 1:1, stirring and reacting under mechanical stirring at 150rpm, and controlling the inside of the extraction tank to react at a constant temperature of 45°C; cooling to room temperature of 25°C after the reaction is completed, and letting it stand for 2h to remove the precipitate, and centrifuging at a speed of 800rpm for 10min to separate the supernatant;
[0090] S4, evaporating the supernatant to dryness in a vacuum environment at 45°C and recovering anhydrous ethanol to obtain a refined extract, and mixing the refined extract with 60% aqueous ethanol by volume at a volume ratio of 1:7 and putting it into an extraction tank, and repeating the process in step S3 three times to obtain a refined extract solution;
[0091] S5. After the refined extract was evaporated to dryness in a vacuum environment at 45° C. and anhydrous ethanol was recovered, the purified natural borneol was obtained after being rinsed three times with deionized water at 85° C. The detection showed that the content of dextrorotatory borneol in the purified natural borneol was about 96.9%, and the content of camphor was about 2.4%.
[0092] Although the embodiments of the present invention are described in detail above, it is obvious to those skilled in the art that various modifications and variations can be made to these embodiments. However, it should be understood that such modifications and variations are within the scope and spirit of the present invention as described in the claims. Moreover, the present invention described herein may have other embodiments and may be implemented or realized in a variety of ways.
Claims
1. A method for refining natural borneol, characterized in that, include: The borneol raw material is extracted in anhydrous ethanol at 300-600W microwave power, 300-400W ultrasonic power and 60-80°C for 20-30min, and then centrifuged to obtain an extract; the extraction solution is combined and evaporated to dryness after being repeated 5-8 times to obtain a crude extract; the crude extract is dissolved in 50-70vol.% aqueous ethanol to obtain a crude extract solution, calcium oxide is added to the crude extract solution, stirred for reaction, and then allowed to stand for precipitation, and then the supernatant is separated; the supernatant is evaporated to obtain a refined extract, and the extraction solution is repeated 2-3 times to obtain a refined extract solution; after the refined extract solution is evaporated to dryness, it is rinsed with hot water at 80-90°C for 2-5 times to obtain purified natural borneol.
2. The refining method according to claim 1, characterized in that The content of d-borneol in the borneol raw material is less than or equal to 80%, and the content of camphor is greater than or equal to 8%; and / or, the content of d-borneol in the purified natural borneol is greater than or equal to 94%, and the content of camphor is less than or equal to 5%; and / or, the water content of the borneol raw material is less than or equal to 1%; and / or, the volume fraction of ethanol in the 50-70 vol.% hydrous ethanol is 50-70%.
3. The purification method according to claim 1, characterized in that: When the borneol raw material is extracted in anhydrous ethanol at 60-80° C. with a microwave power of 300-600 W, an ultrasonic power of 300-400 W, and a temperature of 60-80° C. for 20-30 min: the microwave power and the ultrasonic power are gradually increased, and the temperature change of the anhydrous ethanol is less than or equal to 5° C.; and / or, the volume ratio of the borneol raw material to the anhydrous ethanol is 1:(5-10); and / or, the borneol raw material is extracted in a closed container; and / or, the borneol raw material is mixed with anhydrous ethanol and heated to 60-80° C. at a microwave power of 300-600 W for 10-15 min, and ultrasonic extraction is performed at a power of 300-400 W for 10-15 min.
4. The refining method according to claim 1, characterized in that: When the crude extract is obtained by repeatedly combining the extracts and evaporating to dryness for 5-8 times: the microwave power and / or the ultrasonic power are increased in sequence; and / or, the microwave power gradient of two adjacent extractions is 20-30W; and / or, the ultrasonic power gradient of two adjacent extractions is 10-15W; and / or, after combining the extracts, evaporating to dryness at 60-70°C and recovering anhydrous ethanol; and / or, after combining the extracts and evaporating to dryness, the extracts are rinsed with anhydrous ethanol for 3-5 times in a cycle and then dried to obtain the crude extract.
5. The purification method according to claim 1, characterized in that: When the crude extract is dissolved in 50-70 vol.% aqueous ethanol to prepare a crude extract solution: the volume ratio of the crude extract to the 50-70 vol.% aqueous ethanol is 1:(5-8); and / or, after the crude extract is dissolved in 50-70 vol.% aqueous ethanol, the crude extract is centrifuged at a speed of 300-500 rpm for 2-3 minutes and then filtered under reduced pressure to obtain a crude extract solution; and / or, the crude extract is dissolved in 50-70 vol.% aqueous ethanol at 40-50°C to obtain a crude extract solution.
6. The purification method according to claim 1, characterized in that: When calcium oxide is added to the crude extraction solution and stirred for reaction: the mass ratio of the calcium oxide to the crude extraction solution is 1:(1-1.5); and / or, the calcium oxide is added to the crude extraction solution and stirred for reaction at a rotation speed of 100-200 rpm; and / or, calcium oxide powder with an average particle size of 0.1-1 mm is added to the crude extraction solution and stirred for reaction; and / or, calcium oxide is added to the crude extraction solution and stirred for reaction at a constant temperature of 40-50°C.
7. The purification method according to claim 1, characterized in that: When separating the supernatant after standing and settling: separating the supernatant after standing at 20-30°C; and / or separating the supernatant after standing and settling for 2-3h; and / or separating the supernatant after standing and filtering out the precipitate, and centrifuging at a speed of 500-1000rpm to obtain the supernatant; and / or separating the supernatant after standing and filtering out the precipitate, and centrifuging for 5-10min to obtain the supernatant.
8. The purification method according to claim 1, characterized in that: When the supernatant is evaporated to dryness to obtain a refined extract and then the process is repeated 2-3 times to obtain a refined extract: the volume fraction of ethanol in the aqueous ethanol used each time is independent of each other when repeated 2-3 times; and / or, the supernatant is evaporated to dryness at 50-60° C. and anhydrous ethanol is recovered; and / or, the volume fraction of ethanol in the aqueous ethanol used is increased successively when repeated 2-3 times.