CN115894155A - Extraction method of D-limonene - Google Patents
Extraction method of D-limonene Download PDFInfo
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- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 title claims abstract description 86
- 238000000605 extraction Methods 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000012074 organic phase Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000003960 organic solvent Substances 0.000 claims description 30
- 241000207199 Citrus Species 0.000 claims description 23
- 235000020971 citrus fruits Nutrition 0.000 claims description 22
- 238000000638 solvent extraction Methods 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 14
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 12
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 7
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 5
- 229940090181 propyl acetate Drugs 0.000 claims description 5
- 235000002639 sodium chloride Nutrition 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 235000011132 calcium sulphate Nutrition 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000004042 decolorization Methods 0.000 claims description 3
- 238000005191 phase separation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 238000002137 ultrasound extraction Methods 0.000 abstract description 14
- 238000005185 salting out Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
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- 238000012216 screening Methods 0.000 abstract 1
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 32
- 235000001510 limonene Nutrition 0.000 description 16
- 229940087305 limonene Drugs 0.000 description 16
- 239000000341 volatile oil Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 10
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
According to the method, the extraction efficiency can be improved, the content of D-limonene can be greatly improved, and the subsequent purification operation is reduced by screening a specific salting-out reagent through an ultrasonic-assisted salting-out method; the ultrasonic extraction can be carried out at normal temperature without heating, and the time required by the ultrasonic extraction step is shorter, thereby being more beneficial to industrial production.
Description
Technical Field
The invention relates to the field of extraction methods of D-limonene.
Background
Limonene, also known as limonene, belongs to a monoterpene compound, and is a chemical basic raw material which is widely applied in the aspects of medicine, washing, sterilization, disinsection and the like.
Currently, limonene is produced primarily by physical and/or chemical extraction from natural plants, such as citrus, that have relatively high limonene content. The usual extraction methods include, for example, cold pressing, steam distillation, organic solvent extraction, etc.
1. Cold pressing method
The cold pressing method is also called squeezing method, which is characterized in that the pressing force of mechanical equipment is utilized to destroy the oil cell cells on the surface of citrus peel under the condition of low temperature, citrus essential oil is released, a water-flushing method is adopted to collect mixed liquid, and the mixed liquid is precipitated, filtered and centrifugally separated to obtain crude essential oil. Because the method is operated at room temperature, the natural quality of the citrus essential oil is kept, the fragrance of the citrus essential oil is similar to the smell of citrus peel, but the citrus essential oil product prepared by the cold pressing method has low purity, higher requirement on equipment and low extraction rate, generally less than 60 percent, and the oil yield is low.
Masayoshi (Biotechnology and Biochemistry,2004,68 (8): 1690) et al produced cold pressed essential oils from peel of mature ponkan citrus by cold pressing, and analyzed the main components of the cold pressed essential oils, and showed a predominance of monoterpenes (89.6% (w/w)) with the highest d-limonene content (80.3%).
2. Steam distillation process
The steam distillation method is a method of separating a target substance by utilizing a difference in boiling point between the target substance and water. The d-limonene obtained by the method has high purity, but due to the fact that the temperature in the azeotropic process is high and the time is long, loss and oxidative deterioration of the d-limonene can be caused, and the fragrance is greatly changed. Dingjie (Hunan agricultural science, 2017,56 (17): 3326) and the like optimize the optimal steam distillation process conditions of the citrus peel volatile oil through an orthogonal test, analyze the d-limonene content of five citrus peel essential oils which are produced, wherein the content of Hanzhongzhi is 87.29 percent, the content of Hunan mandarin orange is 95.80 percent,(Hubei)95.44 percent of Yichang orange, 75.66 percent of Sichuan sweet orange and 90.18 percent of Yunnan tangerine. Gamarra (Brazilian Journal of Chemical Engineering,2006,23 (01): 147) and the like, using lime as a material, distilled for 10 hours at 110 ℃ by steam distillation (1.0 bar/25 ℃) to obtain lime volatile oil, which, by gas chromatographic analysis, has a d-limonene content of 49.66ml/Kg, and it was found that the aldehyde content in the oil during the 10 hours of distillation was more than 3% due to the oxidation reaction.
3. Organic solvent extraction process
The organic solvent leaching method is a selective separation method of substances and mainly utilizes the principle of substance similarity and intermiscibility. The method has low temperature in the extraction process, is not easy to cause the d-limonene to be heated and decomposed, but has the problem of organic reagent residue. The volatile components of the fresh pulp and the fresh peel of mandarin oranges are studied by using petroleum ether as an organic solvent, such as young phoenix (analytical laboratory, 2007,26 (1): 85), and the d-limonene is 86.39% in the mandarin orange peel extract and 4.31% in the mandarin orange pulp extract through analysis.
4. Ultrasonic assisted extraction method
The ultrasonic auxiliary extraction method is a novel technology which utilizes physical effects generated by ultrasonic radiation, such as cavitation and disturbance effects, crushing and stirring, mechanical vibration and the like, to ensure that substances are in maximum contact with solvent substances and promote target compounds to be dissolved in the solvent so as to achieve the purpose of separation. The d-limonene extracted by the method has the advantages of good quality, high extraction rate, short time and high repeatability, but further research is needed for large-scale application in production.
Sun hao (Flavour and Fragrance Journal,2014,29 (5): 305) and the like take shaddock peel as a material, n-hexane is ultrasonically assisted to extract shaddock peel volatile matters, sensory analysis evaluates that the shaddock volatile extract has similar odor characteristics with natural shaddock, and GC-MS analysis obtains that the d-limonene content in the shaddock volatile extract is 464436 +/-15467 mu g/ml. Hujunwu (food industry, 2012 (1): 42) and the like take fresh ponkan peel as an experimental material, an extraction solvent is n-hexane, and the relative content of d-limonene in the ponkan essential oil is 77.2% by GC-MS analysis by adopting an ultrasonic-microwave synergistic extraction method.
5. Supercritical CO2 extraction process
The supercritical CO2 extraction method is to extract target components by utilizing the special dissolving property of CO2 under the supercritical condition, and is particularly suitable for extracting heat-sensitive substances. The method has the advantages of low extraction temperature, short extraction time, high d-limonene yield, greenness and safety, but the equipment is expensive and has high requirements on operators and technology required by the equipment.
Valle (Journal of Supercritical Fluids,2019,144, 108) et al investigated the effect of pressure drop in a 3.6 meter high extraction vessel on citrus peel oil CO2 extraction and suggested that pressure drop in extraction may negatively impact Supercritical CO2 extraction of citrus peel essential oil in an industrial scale extraction vessel. Mirra et al, which uses dried navel orange peel as an experimental material, studied the influence of pressure and temperature on the percentage of d-limonene in orange peel essential oil, obtained the optimal conditions of d-limonene supercritical CO2 extraction as 12.5mpa and 308K, at which time d-limonene accounts for more than 99.5% of volatile oil.
6. Molecular distillation method
The molecular distillation method realizes separation by utilizing the difference of molecular motion mean free path between substances in a certain space, belongs to a physical technology of liquid-liquid separation, ensures that d-limonene separated from citrus essential oil is not polluted, avoids polymerization, oxidation and isomerization reaction of the d-limonene at high temperature, and furthest ensures the natural quality. The influence of the vacuum degree, distillation temperature, feeding speed and film scraping rotation speed of molecular distillation on the yield and purity of limonene is researched by using orange peel oil as a material in the Wang Wen Yuan (food research and development, 2010,3 (10): 59) and the like, and under the optimal process condition, the yield of d-limonene is 86.54 percent, and the purity is as high as 99 percent. Experiments show that after the pomelo peel essential oil is subjected to molecular distillation, the d-limonene is obviously enriched in light fractions, the absolute content is enriched from 66.33g/L to 324.27g/L, the concentration ratio reaches 4.9, and the enrichment effect is obvious.
7. Microwave assisted water extraction process
The microwave-assisted water extraction technology is an extraction method newly developed in recent years. The microwave assisted water extraction technology mainly utilizes the heat effect of microwaves to heat a limonene-containing solid substance and water to boil in a short time, so that limonene is separated from the solid and enters a water phase. For example, CN200510032262 provides a method for extracting orange oil and pectin by using microwave-assisted water extraction technology, and the extraction rate of the method reaches about 95%. However, the method has high water consumption and complicated process steps.
The prior art discloses a large number of methods for extracting D-limonene, but the methods have the defects of low extraction rate, low purity or complex extraction process, and are not suitable for industrial production. Therefore, the method for extracting the D-limonene has very important significance in simplicity, high efficiency and contribution to industrialization.
Disclosure of Invention
In the prior art, an ultrasonic-assisted method or a steam-salting-out method is reported to be used for extracting D-limonene, but the purity of the obtained D-limonene crude product is low, and the D-limonene crude product needs to be further purified by a molecular distillation method and the like. According to the method, the extraction efficiency can be improved, the content of D-limonene can be greatly improved, the subsequent purification operation is reduced, and the industrial production is facilitated.
The invention aims to provide a simple and efficient method for extracting D-limonene, which is beneficial to industrialization.
In one embodiment, the present invention provides a method for extracting D-limonene from citrus peel by ultrasonic assisted solvent extraction in combination with salting out techniques, said method comprising the steps of:
(1) Adding citrus peel into an extraction kettle, adding water, an organic solvent and an inorganic salt additive, heating and stirring until uniform mixing;
(2) Performing ultrasonic-assisted solvent extraction at 10-70 deg.C;
(3) Adding activated carbon for decolorization, performing solid-liquid separation on the decolorized product to obtain filtrate and filter residue,
(4) Phase separation is carried out on the filtrate to obtain a first organic phase and a first water phase;
(5) Extracting the first water phase with organic solvent for 2-3 times, collecting corresponding organic phase to obtain second organic phase, and collecting the remaining water phase as second water phase;
(6) And combining the first organic phase and the second organic phase, and distilling to remove the organic solvent to obtain the D-limonene.
In one embodiment, before the citrus peel of step (1) is added to the extraction kettle, the method further comprises the steps of washing and pulverizing the peel, preferably, the peel is pulverized to a particle size of 5-50 mesh.
In one embodiment, the inorganic salt additive of step (1) is selected from: one or more of ammonium chloride, sodium chloride, potassium chloride, ammonium sulfate and calcium sulfate; preferably, the inorganic salt additive is ammonium sulfate; preferably, the mass ratio of the peel to the inorganic salt is 100: (1-10).
In one embodiment, the organic solvent of step (1) is selected from one or more of tetrahydrofuran, petroleum ether, butanone, ethyl acetate, methyl acetate, propyl acetate, butyl acetate; preferably petroleum ether, ethyl acetate; the mass ratio of the organic solvent to the fruit peel is 1-8, preferably 3-5.
In one embodiment, the mass ratio of water to pericarp in step (1) is 5-15, preferably 6-9.
In one embodiment, the frequency of the ultrasonic wave in the ultrasonic-assisted solvent extraction of the step (2) is 20KHz-60KHz and the like, and the duration is 5 to 60 minutes; preferably, the ultrasonic waves have a frequency of 40KHz to 50KHz, etc., and a duration of 5 to 15 minutes.
In one embodiment, the ultrasonic-assisted solvent extraction is performed at 20 ℃ to 40 ℃; preferably, the ultrasound-assisted solvent extraction is performed at room temperature.
In one embodiment, the method further comprises returning the residue of step (3) to the extraction vessel for repeated secondary extraction.
In one embodiment, the solid separation means of step (3) is filtration or centrifugation.
In one embodiment, the organic solvent of step (5) is selected from ethers, ketones, esters and/or combinations thereof; preferably, the organic solvent of step (5) is selected from one or more of tetrahydrofuran, petroleum ether, butanone, ethyl acetate, methyl acetate, propyl acetate, butyl acetate.
In one embodiment, the method further comprises returning the organic solvent in step (6) to the extraction tank for reuse.
In one embodiment, the method further comprises returning the first aqueous phase from step (4) to the extraction tank for reuse.
The method disclosed by the invention can be used for quickly and efficiently separating the limonene from the citrus peel by using an ultrasonic mixed solvent extraction technology, is high in extraction rate, simple and economic in process and suitable for large-scale industrial and industrial application.
According to the method, the extraction efficiency can be improved, the content of D-limonene can be greatly improved, the subsequent purification operation is reduced, and the industrial production is facilitated.
Inorganic salt is added in the ultrasonic extraction step, so that the osmotic pressure of the cells in the peels of the citrus fruits is changed, the cells are easier to dehydrate, the D-limonene substances in the peels are favorably extracted, and the extraction efficiency is improved. Meanwhile, partial impurities can be subjected to salting-out sedimentation, so that the purity of the product is improved.
In order to improve the extraction efficiency, the prior art generally needs to perform extraction at a higher temperature for a long time in the extraction step of the pericarp. However, when the extraction temperature is high, problems of loss of d-limonene and oxidative deterioration are caused; when the extraction time is too long, a large amount of other impurities can be extracted, great difficulty is brought to subsequent separation and extraction, and the purity of the product is reduced.
The ultrasonic extraction of the invention can be carried out at normal temperature, does not need heating, can reduce energy consumption and further reduce production cost. The invention needs shorter time in the ultrasonic extraction step and can save the production time. Meanwhile, the purity of the finally obtained product is high due to the fact that the temperature is reduced and long-time extraction is not needed.
Detailed Description
The Citrus plants of the present invention include plants of 6 genera in total of the family Rutaceae (Rutaceae), i.e., kumquat (Fortunella), kumquat (eremocitus), poncirus (Poncirus), kumquat (clemenia), kumquat (microctrus) and Citrus (Citrus). Specifically, the citrus plants of the invention can be navel oranges, mandarins and the like produced in Gannan of Jiangxi, hexagon and Guangyuan provinces of China, and mandarins, oranges and the like produced in Zhejiang provinces of China. Furthermore, although the invention will be described with respect to the extraction of limonene from citrus peel, it will be appreciated that the method of the invention is equally applicable to all limonene-containing plant tissues or parts, such as pulp and the like.
The amount of water added is 5 to 15 times the mass of the peel, preferably 6 to 9 times the mass. If the amount of water is more than 15 times by mass, the amount of water used increases, and the amount of waste water increases. In addition, excessive water amount may cause a decrease in the proportion of organic solvent, which in turn reduces the solubility of limonene, resulting in a decrease in extraction efficiency. If the amount of water is less than 5 times of the mass, the solid content of the system is increased, the fluidity of the system is poor, the ultrasonic oscillation effect is reduced in the ultrasonic-assisted extraction process, and the extraction effect is reduced.
The amount of organic solvent added is 1 to 8 times the volume of the pericarp, preferably 3 to 5 times the volume. If the amount of the organic solvent is more than 8 times by volume, although the solubility of the product is increased, the extraction efficiency is high, and the extraction speed is high, the energy consumption is high when the solvent is recovered by distillation. The organic solvent with weight more than 10 times brings unnecessary energy consumption loss, and simultaneously, reduces the productivity of equipment and is not easy to be applied in actual production. If the amount of the organic solvent is less than 1 time by volume, the solubility of the mixed solvent to limonene decreases, and the extraction efficiency decreases.
Herein, the organic solvent includes, but is not limited to: ethers such as petroleum ether, tetrahydrofuran; ketones, such as butanone; esters, such as ethyl acetate, methyl acetate, propyl acetate, butyl acetate, and/or combinations thereof. For environmental, economic, etc. reasons and considering the yield, in one embodiment, the organic solvent of the present invention is preferably petroleum ether, ethyl acetate, methyl acetate, propyl acetate, and/or butyl acetate.
Subsequently, the mixture of pericarp, water and organic solvent is subjected to ultrasound assisted solvent extraction at 20 ℃ to 40 ℃, preferably at room temperature.
At present, the ultrasonic technology is mainly applied to cleaning, a large number of ultrasonic cleaning equipment with different models are generated in various cleaning processes, and the application range of the equipment is continuously expanded along with the continuous increase of the power of an ultrasonic generator.
The prior art discloses that ultrasonic waves are applied to extraction of D-limonene, vibration frequency of the ultrasonic waves is very high, peel particles vibrate rapidly due to the high-frequency vibration, and the limonene and other components are rapidly separated from attached matrixes of peels in the high-frequency vibration process and enter a mixed solvent, so that the effect of rapid extraction is achieved. The penetrability of the ultrasonic effect is very strong, and limonene in the peel particles can be efficiently released, so that high extraction efficiency is realized. However, the inventor finds that ultrasonic-assisted extraction can extract other impurities in the pericarp while improving the extraction efficiency, so that the purity of the final product is reduced, and more difficulties are brought to subsequent separation and purification. Therefore, the inventor adds inorganic salt in the extraction step, improves the extraction efficiency, and simultaneously causes partial impurities to have salting-out sedimentation, thereby improving the purity of the product.
Moreover, conventional ultrasonic assisted solvent extraction for limonene extraction requires longer extraction times at higher temperatures. In the method of the present invention, the extraction becomes easier due to the vibration effect of the ultrasonic waves and the wall-breaking effect of the inorganic salts. Therefore, the extraction can be carried out at a lower temperature and in a shorter time, so that the energy consumption is low, the extraction speed is high, the operation is convenient, and the extraction cost is greatly reduced.
The ultrasonic-assisted mixed solvent extraction can be carried out at 20 ℃ to 40 ℃. In one embodiment, the ultrasound-assisted solvent extraction may be performed at room temperature. The ultrasonic extraction of the present invention can be carried out by a commercially available ultrasonic generator. The pulse frequency of the ultrasonic wave is 20KHz, 25KHz, 28KHz, 33KHz, 40KHz, 60KHz, etc., and the duration is 5 to 15 minutes. Those skilled in the art can select suitable ultrasonic extraction conditions according to the size of the extract to be extracted.
The inorganic salt additive is selected from: one or more of ammonium chloride, sodium chloride, potassium chloride, ammonium sulfate and calcium sulfate; preferably, the inorganic salt additive is ammonium sulfate; preferably, the mass ratio of the peel to the inorganic salt is 100: (1-10).
After ultrasonic-assisted solvent extraction, activated carbon was added for decolorization, stirred for about 30 minutes and cooled to 15 to 25 ℃. In one embodiment, activated carbon is added in an amount of 0.2 to 2%, preferably 0.5 to 1%, more preferably 0.8 to 1.2%, and most preferably 1% of the initial peel weight.
And carrying out solid-liquid separation on the decolored crude product to obtain filtrate and filter residue. The solid-liquid separation mode comprises filtration and centrifugation. In one embodiment, the filtered residue can be returned to the initial reflux extraction kettle again for the next cycle, which can maximize the limonene extraction rate. The filtrate obtained after filtration can be subjected to phase separation by standing in a phase separator to obtain a first organic phase and a first aqueous phase.
Extracting the first water phase with organic solvent for 2-3 times, taking corresponding organic phase to obtain a second organic phase, and taking the rest water phase as a second water phase;
the first organic phase and the second organic phase are combined. And removing the organic solvent from the combined organic phase to obtain the D-limonene. The organic solvent can be recycled for use in the extraction step described previously.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
taking 100 g of fresh fruit peel of Jiangxi Gannan navel orange, cleaning, crushing to 30 meshes, adding the fruit peel into a round-bottomed flask, adding 600 g of water and 400 g of ethyl acetate into the round-bottomed flask, then adding 3g of ammonium sulfate, and uniformly stirring at room temperature. Then, the ultrasonic equipment is started, and ultrasonic-assisted solvent extraction is carried out for 10 minutes. After ultrasonic extraction, 2g of activated carbon was added and stirred for 20 minutes. After the solution was cooled to 10 ℃, the reaction mixture was filtered with suction to obtain a filtrate and a solid residue. The filtrate is separated into a first organic phase and a water phase after standing. The aqueous phase was extracted again 2 times with ethyl acetate to give a second organic phase. The first and second organic phases were combined and the organic phase was desolventized by distillation to give 3.3 g of a pale yellow oil. The content of D-limonene was 95.8% by HPLC.
Examples 2 to 5: ammonium chloride, sodium chloride, potassium chloride and calcium sulfate were used instead of ammonium sulfate in example 1, and the amount of the inorganic salt added was 3g, but the other conditions were the same as in example 1.
Comparative example 1: the conditions were the same as in example 1 except that no inorganic salt additive was added.
The extraction results were as follows:
it can be seen from examples 1-5 and comparative example 1 that the addition of the inorganic salt additive in the ultrasonic-assisted organic solvent extraction stage increases the extractant of D-limonene and provides product purity. Most preferred among the additives is ammonium sulfate.
Example 6:
taking 100 g of fresh fruit peel of Jiangxi Jiangnan navel orange, cleaning, crushing to 25 meshes, adding into a round bottom flask, adding 600 g of water and 500 g of petroleum ether, then adding 2g of ammonium sulfate, and uniformly stirring at room temperature. Then the ultrasonic equipment is started to carry out ultrasonic-assisted solvent extraction for 8 minutes. After ultrasonic extraction, 2g of activated carbon was added and stirred for 20 minutes. After the solution was cooled to 10 ℃, the reaction mixture was filtered with suction to obtain a filtrate and a solid residue. The filtrate is separated into a first organic phase and a water phase after standing. The aqueous phase was extracted again 2 times with ethyl acetate to give a second organic phase. The first and second organic phases were combined and the organic phase was desolventized by distillation to give 3.2 g of a pale yellow oil. The content of D-limonene was 94.3% by HPLC.
Example 7:
taking 100 g of fresh fruit peel of Jiangxi south navel orange, cleaning, crushing to 30 meshes, adding into a round bottom flask, adding 700 g of water and 600 g of methyl acetate, then adding 5g of ammonium sulfate, and uniformly stirring at room temperature. Then, the ultrasonic equipment is started to perform ultrasonic-assisted solvent extraction for 10 minutes. After ultrasonic extraction, 2g of activated carbon was added and stirred for 20 minutes. After the solution was cooled to 10 ℃, the reaction mixture was filtered with suction to obtain a filtrate and a solid residue. The filtrate is separated into a first organic phase and a water phase after standing. The aqueous phase was extracted again 2 times with ethyl acetate to give a second organic phase. The first and second organic phases were combined and the organic phase was desolventized by distillation to give 3.4 g of a pale yellow oil. The content of D-limonene was 94.6% by HPLC.
Example 8:
taking 100 g of fresh fruit peel of Jiangxi south navel orange, cleaning, crushing to 30 meshes, adding into a round bottom flask, adding 500 g of water and 700 g of methyl acetate, then adding 4g of ammonium sulfate, and uniformly stirring at room temperature. Then the ultrasonic equipment is started to carry out ultrasonic-assisted solvent extraction for 15 minutes. After ultrasonic extraction, 2g of activated carbon was added and stirred for 20 minutes. After the solution was cooled to 10 ℃, the reaction mixture was filtered with suction to obtain a filtrate and a solid residue. The filtrate was allowed to stand and then separated into a first organic phase and an aqueous phase. The aqueous phase was extracted again 2 times with ethyl acetate to give a second organic phase. The first and second organic phases were combined and the organic phase was desolventized by distillation to give 3.3 g of a pale yellow oil. The content of D-limonene was 92.6% by HPLC.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for extracting D-limonene is characterized by comprising the following steps: (1) Adding citrus peel into an extraction kettle, adding water, an organic solvent and an inorganic salt additive, heating and stirring until uniform mixing;
(2) Performing ultrasonic-assisted solvent extraction at 10-70 deg.C;
(3) Adding activated carbon for decolorization, performing solid-liquid separation on a decolorized product to obtain filtrate and filter residue,
(4) Phase separation is carried out on the filtrate to obtain a first organic phase and a first water phase;
(5) Extracting the first water phase with organic solvent for 2-3 times, collecting corresponding organic phase to obtain second organic phase, and collecting the remaining water phase as second water phase;
(6) Combining the first organic phase and the second organic phase, and distilling to remove the organic solvent to obtain D-limonene;
wherein the inorganic salt additive of step (1) is selected from: one or more of ammonium chloride, sodium chloride, potassium chloride, ammonium sulfate and calcium sulfate.
2. The extraction process of claim 1, wherein the inorganic salt additive is ammonium sulfate; the mass ratio of the peel to the inorganic salt is 100: (1-10).
3. The extraction method according to claim 1, wherein the organic solvent in step (1) is one or more selected from tetrahydrofuran, petroleum ether, butanone, ethyl acetate, methyl acetate, propyl acetate, and butyl acetate; preferably petroleum ether, ethyl acetate;
the mass ratio of the organic solvent to the pericarp in the step (1) is 1-8, preferably 3-5;
the mass ratio of water to peel in step (1) is 5-15, preferably 6-9.
4. The extraction method according to claim 1, wherein the frequency of the ultrasonic wave in the ultrasonic-assisted solvent extraction of the step (2) is 20KHz-60KHz, etc., and the duration is 5 to 60 minutes; preferably, the ultrasonic waves have a frequency of 40KHz to 50KHz, etc., and a duration of 5 to 15 minutes.
5. The extraction process according to claim 1, characterized in that the ultrasound-assisted solvent extraction is carried out at 20 to 40 ℃; preferably, the ultrasound-assisted solvent extraction is performed at room temperature.
6. The method of claim 1, wherein the solid separation in step (3) is filtration or centrifugation.
7. The extraction method as claimed in claim 1, further comprising returning the residue of step (3) to the extraction vessel for repeated secondary extraction.
8. The extraction process of claim 1, further comprising returning the organic solvent of step (6) to the extraction tank for reuse.
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