CN102285862B - Method for extracting limonene from fruit skin of citrus - Google Patents
Method for extracting limonene from fruit skin of citrus Download PDFInfo
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- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 235000001510 limonene Nutrition 0.000 title claims abstract description 58
- 229940087305 limonene Drugs 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 53
- 241000207199 Citrus Species 0.000 title claims abstract description 21
- 235000020971 citrus fruits Nutrition 0.000 title claims abstract description 21
- 235000013399 edible fruits Nutrition 0.000 title abstract 6
- 238000000605 extraction Methods 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012074 organic phase Substances 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000004821 distillation Methods 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000000638 solvent extraction Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008346 aqueous phase Substances 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 6
- 229940090181 propyl acetate Drugs 0.000 claims description 5
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005304 joining Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000004042 decolorization Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000012230 colorless oil Substances 0.000 description 8
- 238000010025 steaming Methods 0.000 description 8
- 239000000284 extract Substances 0.000 description 6
- 238000002137 ultrasound extraction Methods 0.000 description 6
- 235000005976 Citrus sinensis Nutrition 0.000 description 5
- 240000002319 Citrus sinensis Species 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 230000003292 diminished effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 229940043232 butyl acetate Drugs 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 241001672694 Citrus reticulata Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 235000017317 Fortunella Nutrition 0.000 description 2
- 241001523486 Poncirus Species 0.000 description 2
- 241001093501 Rutaceae Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 241000059098 Clymenia Species 0.000 description 1
- 235000008736 Clymenia polyandra Nutrition 0.000 description 1
- 235000002319 Microcitrus Nutrition 0.000 description 1
- 239000001071 citrus reticulata blanco var. mandarin Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 125000000396 limonene group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229930003658 monoterpene Natural products 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- -1 monoterpenes compound Chemical class 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The invention provides a method for extracting from fruit skin of citrus, which comprises the following steps: adding fruit skin of citrus into a reflux extraction kettle, adding water in an amount which is 5 to 15 times the mass of the fruit skin and an organic solvent in an amount which is 2 to 10 times the mass of fruit skin, heating and stirring till the materials are mixed uniformly; performing ultrasonic wave assisted solvent extraction at 30 to 80 DEG C for 10 to 30 minutes continuously; adding active carbon for decolorization, stirring for about 30 minutes and cooling to 15 to 25 DEG C; filtering and separating decolorized product to obtain filtrate and filter residue, and subjecting the filtrate to phase splitting to obtain an organic phase A' and a water phase B; extracting the water phase B by using the organic solvent in an amount which is 0.2 to 0.5 percent based on the mass of the added fruit skin to obtain an organic phase A' and a water phase B'; and mixing the organic phase A and the organic phase A', performing normal pressure distillation separation at 40 to 100 DEG C to obtain limonene and the solvent, and collecting the limonene. The method has the advantages of high limonene extraction rate, simple process, suitability for industrial production and the like.
Description
Technical field
The invention belongs to compound and extract preparation field, be specifically related to a kind of method of extracting limonene from citrus peel.
Background technology
Limonene has another name called limonene, belongs to monoterpenes compound, and it is a kind of at aspect application a kind of chemical fundamentals raw materials very widely such as medicine, washing, sterilization, desinsections.
At present, limonene preparation method be mainly method by physics and/or chemistry from the relatively high natural phant of limonene content as extracted citrus.Conventional extraction method comprises as squeezing extraction method, water extraction extraction method etc.Although squeezing extraction method is simple, this method is higher and extraction yield is very low, less than 60% conventionally to equipment requirements.Water extraction extraction method extracts by water and the mode of wet distillation distills limonene volatile oil form, although the method extraction yield can reach approximately 85%, but still have the shortcoming of highly energy-consuming, and 20% the limonene volatile oil of still having an appointment cannot be extracted.
Using microwave assisted aqueous extraction abstraction technique be in recent years newly developed go out a kind of extracting method.Using microwave assisted aqueous extraction abstraction technique mainly utilizes the heat effect of microwave, solid and water containing limonene are heated to boil at short notice, make limonene depart from the mode that solid enters water, it is high that this method is extracted temperature, and because limonene solubleness in water is bad, therefore, water consumption is large, and energy consumption is high, also because the strong heat effect of microwave, can not adopt mixed extractant solvent, cause its substep operation, make operating process complicated.For example, CN200510032262 provides a kind of method that adopts using microwave assisted aqueous extraction abstraction technique to extract mandarin oil and pectin, and the method extraction rate reached is to approximately 95%.But the method water loss is higher, and processing step is loaded down with trivial details
Along with limonene is in the continuous expansion of the application of the aspects such as medicine, chemical industry, deinsectization synergy, need to develop a kind of efficient, simple, energy-conservation and economic limonene extracting method.
Summary of the invention
The object of the present invention is to provide a kind of efficient, simple, energy-conservation and economic limonene extracting method.
In one embodiment, the invention provides a kind of method of extracting limonene by ultrasonic wave secondary solvent abstraction technique from citrus peel, said method comprising the steps of:
(1) citrus peel is joined in reflux extraction still, and add the water of 5 to 15 times of quality and the organic solvent of 2 to 10 times of quality in described pericarp quality, heated and stirred is to evenly mixing;
(2) at 30 DEG C to 80 DEG C, carry out the extraction of ultrasonic wave secondary solvent, continue 10 to 30 minutes;
(3) add decolorizing with activated carbon, stir about 30 minutes is also cooled to 15 DEG C to 25 DEG C;
(4) the product filtering separation after decolouring is obtained to filtrate and filter residue, and described filtrate phase-splitting is obtained to organic phase A and aqueous phase B;
(6) aqueous phase B is obtained to organic phase A ' and aqueous phase B in order to the described organic solvent extraction of 0.2 to 0.5 quality of described pericarp quality meter again ';
(7) organic phase A and A ' are merged, at 40 to 100 DEG C, air distillation separates and obtains limonene and described organic solvent, collects described limonene.
In one embodiment, described method further comprises that step 4 filter residue is back to described reflux extraction still repeats reextraction.
In one embodiment, described method further comprises that the organic solvent in step 7 is back to described reflux extraction still to be reused.
In one embodiment, described method further comprises aqueous phase B in step 6 ' be back to the recycling of described reflux extraction still.
In one embodiment, described method further comprises that by the citrus peel precrushing in step 1 be the powder of diameter 1mm.
In one embodiment, in the group forming below described organic solvent choosing freely: ethers, ketone, ester class and/or their combination.
In one embodiment, described organic solvent is tetrahydrofuran (THF), sherwood oil, butanone, ethyl acetate, methyl acetate, propyl acetate, butylacetate or their combination.
In one embodiment, the water joining in reflux extraction still is 6 to 8 times of quality, in the quality of pericarp.
In one embodiment, what join organic solvent in reflux extraction still is 3 to 4 times of quality, in pericarp quality.
In one embodiment, described ultrasonic wave secondary solvent extraction is carried out at 40 DEG C to 60 DEG C.
The present invention is by using ultrasonic wave mixed extractant solvent technology, rapidly and efficiently separate limonene from citrus peel, and this method percentage extraction is high, technique simple economy, be applicable to large-scale industry and industry application.
Brief description of the drawings
Fig. 1: according to the exemplary process flow figure of the method for extracting limonene from citrus peel of one embodiment of the present invention.
Embodiment
In conjunction with illustrative embodiments, the present invention is more fully described hereinafter with reference to accompanying drawing.But the present invention can multi-form embodiment and be should not be construed as and be limited to embodiment described in literary composition.On the contrary, provide these embodiments to make the disclosure thorough and complete, and intactly scope of the present invention is conveyed to those skilled in the art.
Fig. 1 is according to the process flow sheet of the method for extracting limonene from citrus peel of one embodiment of the present invention.
As shown in Figure 1, first citrus peel, water and organic solvent are joined in reflux extraction still, and heated and stirred, until evenly mix.
Before citrus peel is joined to reflux extraction still, as required, can carry out precut/chopping to pericarp.In one embodiment, pericarp being cut/shreds is the fritter of 0.5 to 5mm diameter.In another embodiment, pericarp being cut/shreds is the fritter of 1 to 3mm diameter.In one embodiment, pericarp is cut/shreds the fritter into 1mm diameter.Cutting/chopping can be carried out with the conventional cutting unit in this area.
Citrus of the present invention comprises Rutaceae (Rutaceae) plant of totally 6 genus, and Fortunella (Fortunella), the husky lemon of Australia belong to (Eremocitrus), Poncirus (Poncirus), many stamens tangerine belongs to (Clymenia), Australia tangemon genus (Microcitrus) and Citrus (Citrus).Particularly, citrus of the present invention can be navel orange, the ponkan etc. of the real estates such as Sichuan Province China Fengjie, Guangyuan, ponkan, the oranges and tangerines etc. of the real estates such as Zhejiang Province, China, annex.In addition, although the present invention will be described for extract limonene from citrus peel, it should be understood that method of the present invention can be applicable to all plant tissue or parts containing limonene equally, as pulp etc.
The amount of the water adding is 5 to 15 times of pericarp quality, preferably 6 to 10 times of quality, more preferably 6 to 8 times of quality.If the amount of water is greater than 15 times of quality, can cause, heating energy consumption increases.In addition, the water yield is crossed conference and is caused organic solvent ratio to reduce, and then reduces limonene solubleness, causes extraction efficiency to reduce.If the amount of water is less than 5 times of quality, can cause system solid content to increase, system mobility is bad, and in the auxiliary extraction process of ultrasonic wave, ultra-sonic oscillation effect reduces, and extraction effect reduces.
The amount of the organic solvent adding is 2 to 10 times of volumes of pericarp volume, preferably 3 to 8 times of volumes, more preferably 4 to 6 times of volumes.If the amount of organic solvent is greater than 10 times of volumes, although product solubility increases, extraction efficiency is high, and extraction rate is fast, and in the time of distillating recovering solvent, energy consumption is higher.Higher than the organic solvent of 10 times of weight, will bring unnecessary energy loss, meanwhile, reduce equipment capacity, be not easy to production application.If the amount of organic solvent is less than 2 times of volumes, mixed solvent reduces the solubleness of limonene, and extraction efficiency reduces.
Herein, described organic solvent includes but not limited to: ethers, as sherwood oil, tetrahydrofuran (THF); Ketone, as butanone; Ester class, as ethyl acetate, methyl acetate, propyl acetate, butylacetate, and/or their combination.For the consideration of environmental protection, economic dispatch aspect factor and take into account productive rate, in one embodiment, the preferred sherwood oil of organic solvent of the present invention.In one embodiment, organic solvent ethyl acetate of the present invention, methyl acetate, propyl acetate and/or butylacetate.
Subsequently, at 30 DEG C to 80 DEG C, the mixture of pericarp, water and organic solvent is carried out to the extraction of ultrasonic wave secondary solvent.
At present, ultrasonic technology is mainly used in cleaning aspect, in various cleanings, has produced ultrasonic cleaning device a large amount of, different model, and along with the power of ultrasonic generator continues to increase, the range of application of equipment is also in continuous expansion.But, not yet have up to now about the report in extracting or technology enlightenment by ultrasonic applications.Inventor's discovery, because hyperacoustic vibrational frequency is very high, this high-frequency vibration makes pericarp particle fast vibration.The compositions such as limonene separate with the attaching substratum of pericarp fast in high-frequency vibration process, enter in mixed solvent, reach the effect of Rapid Extraction.The penetrance of ultrasonic wave effect is very strong, the limonene in pericarp particle can be discharged efficiently, therefore realizes high extraction efficiency.
And conventional limonene is extracted and need at high temperature be carried out and need to use a large amount of solvents.In the method for the invention, due to hyperacoustic vibration effect, extraction is become and be more prone to.Therefore extraction can be carried out under lower temperature and lower solvent strength, and solvent load is economized, and energy consumption is low, and rate of extraction is fast, the easy to operate extraction cost that reduced greatly.
In one embodiment, the auxiliary mixed extractant solvent of ultrasonic wave can carry out at 40 DEG C to 60 DEG C.In one embodiment, the extraction of ultrasonic wave secondary solvent can be carried out at 40 DEG C to 50 DEG C.Ultrasonic extraction of the present invention can be undertaken by commercially available ultrasonic generator, as WS-VI type ultrasonoscope.Hyperacoustic condition is: voltage 220V, electric current 4A, pulse-repetition 20KHz, 25KHz, 28KHz, 33KHz, 40KHz, 60KHz etc., the time length is 10 to 30 minutes.Those skilled in the art can select suitable ultrasonic extraction condition according to the size of extract etc.In one embodiment, hyperacoustic processing condition preferably: 40 DEG C of temperature, the water of 6 times of quality, the sherwood oil of 4 times of quality, frequency 25KHz, the time length is 10 to 20 minutes, now can obtain 70% extraction efficiency.In another embodiment, hyperacoustic processing condition preferably: 40 DEG C of temperature, the water of 6 times of quality, the sherwood oil of 4 times of quality, frequency 60KHz, the time length is 10 to 15 minutes, now also can obtain 70% extraction efficiency.In theory, frequency is higher, and extraction efficiency is better, and speed is faster.But through facts have proved, too high frequency easily causes equipment to break down, common frequency (comprises 40KHz) and can realize good extraction effect more than 40KHz.If frequency is lower than 40KHz, corresponding extraction time will be multiplied, and to a certain extent, extraction efficiency reduces.
After the extraction of ultrasonic wave secondary solvent, add activated carbon to decolour, stir about 30 minutes is also cooled to 15 DEG C to 25 DEG C.In one embodiment, the add-on of activated carbon is 0.2 to 2% of initial pericarp weight, is preferably 0.5 to 1%, more preferably 0.8 to 1.2%, most preferably be 1%.
The crude product of decolouring is filtered, obtain filtrate and filter residue.
Herein, filtration can adopt the filter method of this area routine, includes but not limited to: decompress filter, centrifuging, bag type filtering, filter press etc.In one embodiment, the filter residue filtering out can be turned back in initial reflux extraction still again, enter next circulation, can at utmost improve like this extraction yield of limonene.The filtrate obtaining after filtration can, by leave standstill phase-splitting in phase splitter, obtain organic phase A and aqueous phase B.
As required, in order at utmost to improve the extraction yield of limonene, alternatively by aqueous phase B again with adding the aforementioned organic solvent with 0.2 to 0.5 times of weight of pericarp weighing scale simply to extract.Aqueous phase B obtains organic phase A ' and aqueous phase B after again extracting '.Organic phase A and organic phase A ' are merged, enter next step.To aqueous phase B ' carry out aftertreatment.
In one embodiment, can be by aqueous phase B ' be back in reflux extraction still.Conventionally, aqueous phase B ' recycle after 3 to 5 times, enter wastewater treatment, recycle.Like this, can invent saving utilization, the minimizing three waste discharge that can realize water resources, reduce costs, and, can further guarantee that a small amount of limonene of dissolving in water can further be extracted, improve recycled in its entirety rate.
The organic phase of merging is carried out to air distillation at 40 DEG C to 100 DEG C.The inventor further finds, this step adopts air distillation can reduce solvent loss, and solvent recovering rate can reach approximately 95%.In one embodiment, distillation can be carried out at 50 DEG C to 80 DEG C.In another embodiment, distillation can be carried out at 60 DEG C to 70 DEG C.
In one embodiment, also can omit the step that aqueous phase B is extracted again, can directly carry out above-mentioned distillation processing to organic phase A.
After distillation, can obtain the organic solvent and the oily matter that separate.Through qualification, oily matter is limonene, and content is up to 85% to 98%.The organic solvent that separation obtains turns back in reflux extraction still again, for next reaction cycle, at utmost improves limonene productive rate and saves organic solvent to realize.
In sum, the auxiliary mixed extractant solvent of ultrasonic wave of the present invention mainly adopts HF oscillation effect, and extraction temperature is low, can have good effect of extracting at 30 to 80 DEG C.Owing to adopting mixed solvent, increase greatly the solubleness of limonene in mixed solvent, effect of extracting is good, and solvent load is economized, both energy-conservation, environmental protection again.
Embodiment
Embodiment 1:
Get 100 grams of fresh Peel of Navel Oranges that originate from Sichuan Navel orange, add wherein 200 grams of 500 grams, water and ethyl acetate, heat simultaneously and stir.In the time that temperature is heated to 30 DEG C of left and right, open ultrasonic device, carry out the extraction of ultrasonic wave secondary solvent, continue 10 minutes.After ultrasonic extraction, add 2 grams of activated carbon, stir about 30 minutes.In the time that solution is cooled to 15 DEG C, mother liquor is carried out to filtration under diminished pressure, obtain filtrate and solid residue.Filtrate is layered as organic phase and water after leaving standstill.Water, again with 20 grams of ethyl acetate extractions, is obtained to extra organic phase.The organic phase of twice is merged, to organic phase air distillation, obtain ethyl acetate and the yellowish steaming excess to colorless oil.
After measured, the yellowish steaming excess to colorless oil is limonene, approximately 3.2 grams.
Solid residue is placed in to 2000ml water, adopts the water vapour distillation of spending the night for a long time, obtain 0.1 gram of limonene less than, this illustrates that the limonene in pericarp is almost all extracted, more than extraction rate reached to 95%.
Embodiment 2:
Get 100 grams of fresh ponkan skins that originate from Sichuan Guangyuan ponkan, add wherein 1000 grams of 1500 grams, water and sherwood oils, heat simultaneously and stir.In the time that temperature is heated to 80 DEG C of left and right, open ultrasonic device, carry out the extraction of ultrasonic wave secondary solvent, continue 20 minutes.After ultrasonic extraction, add 2 grams of activated carbon, stir about 30 minutes.In the time that solution is cooled to 20 DEG C, mother liquor is carried out to filtration under diminished pressure, obtain filtrate and solid residue.Filtrate is layered as organic phase and water after leaving standstill.Water is used to 20 grams of petroleum ether extractions again, obtain extra organic phase.The organic phase of twice is merged, to organic phase air distillation, obtain sherwood oil and the yellowish steaming excess to colorless oil.
After measured, the yellowish steaming excess to colorless oil is limonene, approximately 3.6 grams.
Solid residue is placed in to 2000ml water, adopts the water vapour distillation of spending the night for a long time, obtain 0.1 gram of limonene less than, this illustrates that the limonene in pericarp is almost all extracted, more than extraction rate reached to 95%.
Embodiment 3:
Get 100 grams of orange peels that originate from the orange in Australia, add wherein 600 grams of 1000 grams, water and butanone, heat simultaneously and stir.In the time that temperature is heated to 50 DEG C of left and right, open ultrasonic device, carry out the extraction of ultrasonic wave secondary solvent, continue 25 minutes.After ultrasonic extraction, add 3 grams of activated carbon, stir about 30 minutes.In the time that solution is cooled to 25 DEG C, mother liquor is carried out to filtration under diminished pressure, obtain filtrate and solid residue.Filtrate is layered as organic phase and water after leaving standstill.Water, again with 50 grams of butanone extractions, is obtained to extra organic phase.The organic phase of twice is merged, to organic phase air distillation, obtain sherwood oil and the yellowish steaming excess to colorless oil.
After measured, the yellowish steaming excess to colorless oil is limonene, approximately 3.5 grams.
Solid residue is placed in to 2000ml water, adopts the water vapour distillation of spending the night for a long time, obtain 0.1 gram of limonene less than, this illustrates that the limonene in pericarp is almost all extracted, more than extraction rate reached to 95%.
Embodiment 4:
Get 100 grams of orange peels that originate from the orange in Australia, the size that precrushing is 1mm, adds 600 grams of 1000 grams, water and propyl acetates wherein, heats simultaneously and stirs.In the time that temperature is heated to 40 DEG C of left and right, open ultrasonic device, carry out the extraction of ultrasonic wave secondary solvent, continue 30 minutes.After ultrasonic extraction, add 2 grams of activated carbon, stir about 30 minutes.In the time that solution is cooled to 20 DEG C, mother liquor is carried out to filtration under diminished pressure, obtain filtrate and solid residue.Filtrate is layered as organic phase and water after leaving standstill.Water, again with 40 grams of propyl acetate extractions, is obtained to extra organic phase.The organic phase of twice is merged, to organic phase air distillation, obtain sherwood oil and the yellowish steaming excess to colorless oil.
After measured, the yellowish steaming excess to colorless oil is limonene, approximately 3.8 grams.
Solid residue is placed in to 2000ml water, adopts the water vapour distillation of spending the night for a long time, obtain 0.1 gram of limonene less than, this illustrates that the limonene in pericarp is almost all extracted, more than extraction rate reached to 95%.
Comparative example 1
Get 100 grams of fresh Peel of Navel Oranges that originate from Sichuan Navel orange, add squeezing machine, be adjusted to suitable pressure, squeeze; Increase gradually pressure, repeat to squeeze 3 times; By the liquid stratification obtaining after squeezing, obtain oily compound.After measured, oily compound is limonene, approximately 2.1 grams of content.
Comparative example 2
Get 100 grams of fresh ponkan skins that originate from Sichuan Guangyuan ponkan, add squeezing machine, be adjusted to suitable pressure, squeeze; Increase gradually pressure, repeat to squeeze 5 times; By the liquid stratification obtaining after squeezing, obtain oily compound.After measured, oily compound is limonene, approximately 1.9 grams of content.
Comparative example 3
Get 100 grams of orange peels that originate from the orange in Australia, add squeezing machine, be adjusted to suitable pressure, squeeze; Increase gradually pressure, repeat to squeeze 5 times; By the liquid stratification obtaining after squeezing, obtain oily compound.After measured, oily compound is limonene, approximately 2.2 grams of content.
Comparative example 4
Get 100 grams of orange peels that originate from the orange in Australia, add squeezing machine, be adjusted to suitable pressure, squeeze; Increase gradually pressure, repeat to squeeze 10 times; By the liquid stratification obtaining after squeezing, obtain oily compound.After measured, oily compound is limonene, approximately 2.26 grams of content.
Can comparative example from above embodiment, the method that the auxiliary mixed extractant solvent of ultrasonic wave of the present invention extracts limonene has very high limonene productive rate.Method technique of the present invention is simple, energy consumption is low, high, the whole reaction process of the citric acid rate of recovery is integrated, and is applicable to industrialization and industrialization and produces.
Wen Zhongyi discloses illustrative embodiments, although used concrete term, they are only not for purposes of limitation with common using and explain with descriptive sense.Therefore, it will be appreciated by those skilled in the art that and can carry out the change in various forms and details, and do not depart from the scope of the present invention providing in following claim.
Claims (8)
1. a method of extracting limonene, said method comprising the steps of:
(1) citrus peel is joined in reflux extraction still, and add the water of 5 to 15 times of quality and the organic solvent of 2 to 10 times of quality in described pericarp quality, heated and stirred is to evenly mixing;
(2) at 30 DEG C to 80 DEG C, carry out the extraction of ultrasonic wave secondary solvent, continue 10 to 30 minutes;
(3) add activated carbon decolorizing, stir about 30 minutes is also cooled to 15 DEG C to 25 DEG C;
(4) the product filtering separation after decolouring is obtained to filtrate and filter residue, and described filtrate phase-splitting is obtained to organic phase A and aqueous phase B;
(5) aqueous phase B is obtained to organic phase A ' and aqueous phase B in order to the described organic solvent extraction of 0.2 to 0.5 quality of described pericarp quality meter again '; With
(6) organic phase A and A ' are merged, at 40 to 100 DEG C, air distillation separates and obtains limonene and described organic solvent, collects described limonene;
Wherein, in step (1), described organic solvent comprises: ethyl acetate, sherwood oil, butanone or propyl acetate;
In step (2), described hyperacoustic condition is: voltage 220V, electric current 4A, pulse-repetition 40KHz or 60KHz.
2. method according to claim 1, is characterized in that, described method further comprises that step (4) filter residue is back to described reflux extraction still repeats reextraction.
3. method according to claim 1, is characterized in that, described method further comprises that the organic solvent in step (6) is back to described reflux extraction still to be reused.
4. method according to claim 1, is characterized in that, described method further comprises aqueous phase B in step (5) ' be back to described reflux extraction still recycling.
5. method according to claim 1, is characterized in that, described method further comprises that by the citrus peel precrushing in step (1) be the powder of diameter 1mm.
6. method according to claim 1, is characterized in that, the water joining in described reflux extraction still is 6 to 8 times of quality, in the quality of pericarp.
7. method according to claim 1, is characterized in that, the organic solvent joining in described reflux extraction still is 3 to 4 times of quality, in pericarp quality.
8. method according to claim 1, described ultrasonic wave secondary solvent extraction is carried out at 40 DEG C to 60 DEG C.
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| WO2017182552A1 (en) * | 2016-04-20 | 2017-10-26 | Gcr - Global Commodity Resources Ug (Haftungsbeschränkt) | Method for obtaining etheric oils and/or constituents of etheric oils from moist extraction material |
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| CN105237323B (en) * | 2015-10-20 | 2016-11-30 | 永州山香香料有限公司 | A kind of method extracting limonene from Fructus Litseae |
| CN111606775A (en) * | 2020-05-28 | 2020-09-01 | 广西壮族自治区林业科学研究院 | Method for extracting limonene from rosin |
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| CN1749379A (en) * | 2005-10-18 | 2006-03-22 | 中南大学 | Method for extracting orange oil and pectin from organic skin |
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| CN1749379A (en) * | 2005-10-18 | 2006-03-22 | 中南大学 | Method for extracting orange oil and pectin from organic skin |
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| WO2017182552A1 (en) * | 2016-04-20 | 2017-10-26 | Gcr - Global Commodity Resources Ug (Haftungsbeschränkt) | Method for obtaining etheric oils and/or constituents of etheric oils from moist extraction material |
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Denomination of invention: Extraction of limonene from citrus peel Effective date of registration: 20210521 Granted publication date: 20140716 Pledgee: Science and Technology Branch of Leshan Commercial Bank Co.,Ltd. Pledgor: Emei Mountain in Sichuan Pharmaceutical Co.,Ltd. Registration number: Y2021510000072 |