CN103333744A - Apparatus for separating oxygen-containing compounds in concentrated orange essential oil through supercritical chromatography, and method thereof - Google Patents
Apparatus for separating oxygen-containing compounds in concentrated orange essential oil through supercritical chromatography, and method thereof Download PDFInfo
- Publication number
- CN103333744A CN103333744A CN2013102893393A CN201310289339A CN103333744A CN 103333744 A CN103333744 A CN 103333744A CN 2013102893393 A CN2013102893393 A CN 2013102893393A CN 201310289339 A CN201310289339 A CN 201310289339A CN 103333744 A CN103333744 A CN 103333744A
- Authority
- CN
- China
- Prior art keywords
- high pressure
- oxygenatedchemicals
- collector
- valve
- overcritical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000000341 volatile oil Substances 0.000 title claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract 6
- 150000001875 compounds Chemical class 0.000 title abstract 6
- 229910052760 oxygen Inorganic materials 0.000 title abstract 6
- 239000001301 oxygen Substances 0.000 title abstract 6
- 238000004808 supercritical fluid chromatography Methods 0.000 title abstract 4
- 235000007586 terpenes Nutrition 0.000 claims abstract description 61
- -1 terpene compound Chemical class 0.000 claims abstract description 59
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000004164 Wax ester Substances 0.000 claims abstract description 25
- 235000019386 wax ester Nutrition 0.000 claims abstract description 25
- 239000000049 pigment Substances 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 238000000194 supercritical-fluid extraction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000010828 elution Methods 0.000 claims abstract description 4
- 241001672694 Citrus reticulata Species 0.000 claims description 62
- 239000003921 oil Substances 0.000 claims description 61
- 235000019198 oils Nutrition 0.000 claims description 61
- 238000000605 extraction Methods 0.000 claims description 58
- 230000008569 process Effects 0.000 claims description 47
- 238000013375 chromatographic separation Methods 0.000 claims description 36
- 239000012141 concentrate Substances 0.000 claims description 32
- 238000012360 testing method Methods 0.000 claims description 15
- 238000004587 chromatography analysis Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 235000011089 carbon dioxide Nutrition 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000010502 orange oil Substances 0.000 claims description 4
- 244000003027 Bergamotto Species 0.000 claims description 3
- 235000005979 Citrus limon Nutrition 0.000 claims description 3
- 244000131522 Citrus pyriformis Species 0.000 claims description 3
- 235000005976 Citrus sinensis Nutrition 0.000 claims description 2
- 240000002319 Citrus sinensis Species 0.000 claims description 2
- 235000010672 Monarda didyma Nutrition 0.000 claims description 2
- 235000019502 Orange oil Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 4
- 239000000110 cooling liquid Substances 0.000 abstract 1
- 238000001514 detection method Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 15
- 235000013599 spices Nutrition 0.000 description 10
- 235000013305 food Nutrition 0.000 description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 5
- 241000207199 Citrus Species 0.000 description 4
- 235000020971 citrus fruits Nutrition 0.000 description 4
- 235000019499 Citrus oil Nutrition 0.000 description 3
- 239000010500 citrus oil Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 235000001510 limonene Nutrition 0.000 description 3
- 229940087305 limonene Drugs 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 235000019501 Lemon oil Nutrition 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000010501 lemon oil Substances 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000001926 citrus aurantium l. subsp. bergamia wright et arn. oil Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
- 231100000018 phototoxicity Toxicity 0.000 description 1
- 238000004237 preparative chromatography Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Landscapes
- Fats And Perfumes (AREA)
Abstract
The invention relates to orange essential oil, and especially relates to an apparatus for separating oxygen-containing compounds in concentrated orange essential oil through supercritical chromatography, and a method thereof. The apparatus is provided with a carbon dioxide storage tank, a filter, a low temperature cooling liquid circulating pump, a carbon dioxide high-pressure pump, two pressure adjusting valves, a high-pressure extracting kettle, an essential oil storage tank, an essential oil metering pump, a chromatographic column, an online high-pressure ultraviolet spectrophotometer, an online chromatogram detection work station, a collection switching valve, a flow meter, a temperature controller, a terpene compound collector, an oxygen-containing compound collector, a first constant temperature heater, a second constant temperature heater and a constant temperature cooler. The method comprises the following steps: carrying out raw material essential oil metering; carrying out supercritical-extraction wax ester pigment removal; carrying out supercritical-chromatography terpene compound separation; carrying out supercritical-chromatography oxygen-containing compound elution; and opening the material discharging valves at the bottoms of high-pressure extracting kettle, the oxygen-containing compound collector and the terpene compound collector after the above separation processes for collecting wax ester, pigments, the oxygen-containing compounds and terpene compound products.
Description
Technical field
The present invention relates to tangerine oil, especially relate to the device and method that a kind of overcritical chromatographic separation concentrates oxygenatedchemicals in the tangerine oil.
Background technology
Tangerine oil is the big class of one in the natural essence spices, mainly as the spices of products such as food, daily use chemicals, medicine, chemical industry, also is the main raw material of synthetic some spices.Tangerine oil mainly is present in pericarp, flower and the leaf of citrus, but with content in the pericarp the abundantest (1～3wt%).Mainly contain terpene compound (60～94%), oxygenatedchemicals (5～40%), wax ester and pigment (about 2%) four constituents in the tangerine oil, wherein oxygenatedchemicals is mainly compositions such as higher alcohols, aldehydes, ketone, ester class, be the main source of tangerine oil fragrance, it mainly represents composition is phantol; And terpene compound is mainly the unsaturated hydrocarbons constituents, and is very little to the contribution of fragrance, and is heated and the easy oxygenolysis of illumination, influences stability and the fragrance local flavor of product, and it mainly represents composition is limonene; Though wax ester and pigment composition content are seldom, being heated very easily produces the phototoxicity material with illumination, causes that essential oil is rotten and influences its quality product.Therefore, the tangerine oil spice product need remove terpene compound, wax ester and pigment composition.
Traditionally, main employing distillation method removes terpene compound (being mainly limonene) with solvent-extraction process and makes the oxygenatedchemicals (being mainly phantol) in the tangerine oil obtain separating concentrated, but these traditional method ubiquity separation and purification degree are not high, be difficult to remove wax ester and pigment composition, the extraction time is long, product is rotten under the high temperature, problems such as dissolvent residual and contaminate environment.At present, domestic and international research person adopts supercritical CO
2Abstraction technique or other isolation technique that are coupled are separated each constituents in the tangerine oil, and some researchs have also obtained certain progress.([1] wangdan is clear, Wang Hongtao, Wu Dapeng etc., supercritical CO as wangdan green grass or young crops etc.
2Terpenes and oxygenatedchemicals in the extracting and separating tangerine oil, chemical engineering, 2010,38 (5): 9-12) studied the employing supercritical CO
2For solvent directly extracts terpene compound in the cold press tangerine oil, the rate of recovery of gained terpene compound is up to more than 90% in extraction phase.([2] Gironi F such as Gironi, Maschietti M.Supercritical carbon dioxide fractionation of lemon oil by means of a batch process with an external reflux[J] .J.of Supercritical.Fluids, 2005,35 (3): 227-234) utilize supercritical extraction coupled batch distillation process to study the influence of external reflux to the oxygenatedchemicals rate of recovery in the lemon quintessence oil, under bigger reflux ratio condition, the rate of recovery of oxygenatedchemicals can reach 0.81～1; ([3] Sato Masaki such as Sato and Kondo, Goto Motonobu, Hirose Tsutomu.Fractional extraction with supercritical carbon dioxide for the removal of terpenes from citrus oil[J] .Ind.Eng.Chem.Res., 1995,34 (11): 3941 – 3946; [4] Sato Masaki, Goto Motonobu, Hirose Tsutomu.Supercritical fluid extraction on semibatch mode for the removal of terpene in citrus oil[J] .Ind.Eng.Chem.Res., 1996,35 (6): 1906 – 1911; [5] Sato Masaki, Kondo Mitsuru, Goto Motonobu, et al.Fractionation of citrus oil by supercriticalcountercurrent extraction with side-stream withdrawal[J] .J.Supercritical.Fluids, 1998,13 (1-3): 311 – 317; [6] Kondo Mitsuru, Akgun Nalan, Goto Motonobu, et al.Semi-batch operation and countercurrent extraction by supercritical CO2for the fractionation of lemon oil[J] .J.Supercritical.Fluids, 2002,23 (1): 21-27) adopt supercritical CO
2The continuous countercurrent extraction device removes terpene compound to tangerine oil and studies, under lower supercritical pressure (8.8MPa) and thermograde (59.85～39.85 ℃), the product of the terpene compound that is to a certain degree concentrated respectively in extraction tower top, middle part and bottom, oxygenatedchemicals and wax ester enrichment; ([7] Motonobu Goto such as Goto, Gou Gukui, Hongtao Wang, et al.Deterpenation of bergamot oil by pressure swing adsorption in supercritical carbon dioxide[J] .Journal of chemical engineering of Japan, 2002,35 (4): 372-376) utilize supercritical CO
2Extraction coupling transformation adsorption separation process has been studied the separation of Citrus bergamia essential oil, has obtained the oxygenatedchemicals that concentrates in the decompression of desorption tower and desorb operation steps.Though the refining method of above-mentioned citrus essential oil adopts " green " supercritical extraction technique, avoided under the high temperature product rotten, problems such as dissolvent residual and environmental pollution.But the ubiquity separation efficiency is low, terpene compound and wax ester and pigment component separating are incomplete, the content of oxygenatedchemicals problem such as have much room for improvement in the product, also there is the Controlling System complexity in some technological process, from balance to the problems such as overlong time of stablizing the extraction product.Therefore, these methods still can't satisfy the requirement that the oxygenatedchemicals separation concentrates in the tangerine oil at present.
Summary of the invention
The object of the present invention is to provide concentrate the device and method that concentration and the higher overcritical chromatographic separation of the rate of recovery concentrate oxygenatedchemicals in the tangerine oil a kind of the separation.
The present invention adopts commercially available industrial cold press tangerine oil product as raw material, adopts supercritical CO
2Extraction removes terpene compound (being mainly limonene) and wax ester and pigment composition in the tangerine oil respectively in conjunction with the technological process of overcritical chromatographic technique, and is concentrated thereby the oxygenatedchemicals in the tangerine oil (being mainly phantol) obtains separating.
Overcritical chromatographic separation of the present invention concentrates the device of oxygenatedchemicals in the tangerine oil, is provided with carbon dioxide storage tank, strainer, cryogenic liquid recycle pump, CO 2 high pressure pump, first pressure regulator valve, high pressure extraction still, essential oil storage tank, essential oil volume pump, chromatographic column, online high pressure uv-spectrophotometric instrument, on-line chromatograph testing station, second pressure regulator valve, collects switching valve, under meter, temperature regulator, terpene compound collector, oxygenatedchemicals collector, first constent temperature heater, second constent temperature heater and constant temperature water cooler;
The filter entrance is taken in the carbon dioxide storage tank outlet, filter outlet connects the cryogenic liquid pump entry, temperature liquid circulation pump discharge connects the CO 2 high pressure pump intake, first pressure regulator valve and CO 2 high pressure parallel connection of pumps, the CO 2 high pressure pump discharge connects high pressure extraction still entrance and chromatographic column entrance respectively, high pressure extraction still and chromatographic column are located at respectively in first constent temperature heater and second constent temperature heater, the high pressure extraction still outlet connects the chromatographic column entrance, the chromatographic column outlet is connected on line high pressure uv-spectrophotometric instrument and on-line chromatograph testing station, online high pressure uv-spectrophotometric instrument outlet connects the second pressure regulator valve entrance, the outlet of second pressure regulator valve receives collection switching valve entrance, collect the switching valve outlet and connect the entrance of terpene compound collector and the entrance of oxygenatedchemicals collector respectively, the outlet of terpene compound collector and the outlet of oxygenatedchemicals collector all connect the under meter entrance, terpene compound collector and oxygenatedchemicals collector all are located in the constant temperature water cooler, first constent temperature heater, second constent temperature heater and constant temperature water cooler are all established temperature regulator.
Preferably be provided with high pressure valve between described carbon dioxide storage tank outlet and the filter inlet.
Described terpene compound collector bottom and oxygenatedchemicals collector bottom preferably are equipped with high pressure valve.
Preferably be provided with high pressure valve between described CO 2 high pressure pump discharge and the chromatographic column entrance.
Described high pressure extraction still entrance and exit preferably is equipped with high pressure valve, preferably is equipped with tensimeter in the outlet of high pressure extraction still outlet and chromatographic column.
It is the preparative chromatography post of stationary phase that described chromatographic column preferably adopts with silica gel.
The device that described overcritical chromatographic separation concentrates oxygenatedchemicals in the tangerine oil preferably adopts high pressure resistant stainless material to make.
Overcritical chromatographic separation of the present invention concentrates the method for oxygenatedchemicals in the tangerine oil, adopts described overcritical chromatographic separation to concentrate the device of oxygenatedchemicals in the tangerine oil, may further comprise the steps:
1) raw material essential oil metering process: start the essential oil volume pump, the cold press tangerine oil raw material in the essential oil storage tank is squeezed in the high pressure extraction still, close the essential oil volume pump after reaching specified amount;
2) supercritical extraction removes wax ester pigment process: open the set high pressure valve of high pressure extraction still entrance, start the cryogenic liquid recycle pump, open the set high pressure valve of carbon dioxide storage tank outlet, start the CO 2 high pressure pump, carbonic acid gas enters high pressure extraction still through filter by the pressurization of CO 2 high pressure pump; Pressure by the first pressure regulator valve regulating and controlling high pressure extraction still is to specified pressure, by constent temperature heater heating and by the temperature of temperature regulator control high pressure extraction still to specified temperature, the terpene compound in the tangerine oil and oxygenatedchemicals can be dissolved in supercritical CO
2In, and wax ester and pigment composition are owing to be insoluble in supercritical CO
2And residue in the extracting phase of high pressure extraction still;
3) overcritical chromatographic separation terpene compound process: the outlet valve of opening high pressure extraction still, make the extraction phase that has dissolved terpene compound and oxygenatedchemicals enter chromatographic column, the pressure of chromatographic column passes through the pressure regulator valve regulating and controlling to specified pressure, the temperature of chromatographic column is controlled to specified temperature by the constent temperature heater heating and by temperature regulator, observed the chromatographic peak residence time of terpene compound by the on-line chromatograph testing station of online high pressure uv-spectrophotometric instrument and connection thereof, make the decompression of terpene compound product by second pressure regulator valve, the carbonic acid gas that flows out from terpene compound collector and oxygenatedchemicals collector is by the under meter metered flow;
4) overcritical chromatography eluant oxygenatedchemicals process: when the chromatographic peak of observing the oxygenatedchemicals phantol when on-line chromatograph testing station occurs, close inlet valve and the outlet valve of high pressure extraction still immediately, open the high pressure valve between CO 2 high pressure pump discharge and the chromatographic column entrance simultaneously, regulate supercritical CO by pressure regulator valve
2To specified pressure, make supercritical CO
2The oxygenatedchemicals (after cut) of enrichment in the elution chromatography post is regulated and is collected switching valve to the oxygenatedchemicals collector.Collect after cut oxygenatedchemicals product by pressure regulator valve decompression in the oxygenatedchemicals collector, after the chromatographic peak of observing the oxygenatedchemicals phantol when on-line chromatograph testing station disappears, i.e. sepn process finishes;
5) after sepn process finishes, open high pressure extraction still, oxygenatedchemicals collector and terpene compound collector bottom dispensing valve respectively and collect wax ester and pigment, oxygenatedchemicals and terpene compound product.
In step 1), described tangerine oil raw material can be the essential oil of various citrus, comprises at least a in hut mandarin orange essential oil, lemon quintessence oil, natsudaidai essential oil, orange oil, sweet orange oil, red tangerine essential oil, the Bergamot etc.
In step 2) in, the processing condition that described supercritical extraction removes wax ester pigment process can be: extracting pressure 8～16MPa, extraction temperature 308～338K, extraction agent CO
2Flow 5～15L/min.
In step 3), the processing condition of described overcritical chromatographic separation terpene compound process can be: chromatogram pressure 8～16MPa, chromatogram temperature 308～338K, moving phase CO
2Flow 5～15L/min.
In step 4), the processing condition of described overcritical chromatography eluant oxygenatedchemicals process can be: chromatogram pressure 10～25MPa, chromatogram temperature 308～328K, moving phase CO
2Flow 5～10L/min.
By to the product weighing, and adopt gas chromatograph-mass spectrometer (GC-MS) to carry out qualitative and quantitative analysis and calculating.The concentration of the oxygenatedchemicals that can obtain collecting and the rate of recovery.
Compared with the prior art, beneficial effect of the present invention is as follows:
Adopt eco-friendly supercritical co as extraction solvent and chromatogram flow phase, and supercritical extraction and overcritical chromatographic separation technology be combined in the technological process, realize that high-level efficiency removes a plurality of non-effective perfume compositions in the tangerine oil, obtain the tangerine oil oxygenatedchemicals product of high purity and high-recovery, and can realize the semicontinuous operation of sepn process.Whole process can change the separation efficiency of each component in the raw material easily by the pressure and temperature of regulating carbonic acid gas, and operating process is simple, the cycle is short, no solvent residue in each product, and service temperature is moderate, and the process energy consumption is lower.Technique effect of the present invention can be by separating concentration and the rate of recovery checking that concentrates the tangerine oil oxygenatedchemicals product that obtains.In processing condition scope of the present invention, the maximum concentration that separate to concentrate the oxygenatedchemicals product that obtains from the raw material tangerine oil can reach 95.3%, high-recovery can reach 92.9%, and gained oxygenatedchemicals product is better than the raw material tangerine oil through sensory evaluation fragrance.
The present invention is mainly used in the separation field of high additive value composition in the natural plant essential oils, and the separation that especially is applied to oxygenatedchemicals composition in the natural plant essential oils concentrates, and also is fit to the deep processing of citrus essential oil fragrances spices and the raising of added value thereof.
Description of drawings
Fig. 1 is that the structure of the overcritical chromatographic separation concentrating unit embodiment of oxygenatedchemicals in the tangerine oil of the present invention is formed synoptic diagram.
Embodiment
Following examples will the present invention is further illustrated by reference to the accompanying drawings.
Referring to Fig. 1, the overcritical chromatographic separation concentrating unit embodiment of oxygenatedchemicals is provided with carbon dioxide storage tank 1 in the tangerine oil of the present invention, strainer 2, cryogenic liquid recycle pump 3, CO 2 high pressure pump 4, first pressure regulator valve 5, high pressure extraction still 8, essential oil storage tank 6, essential oil volume pump 7, chromatographic column 11, online high pressure uv-spectrophotometric instrument 12, on-line chromatograph testing station 13, second pressure regulator valve 14, collect switching valve 15, under meter 19, temperature regulator TC(3), terpene compound collector 17, oxygenatedchemicals collector 18, first constent temperature heater 9, second constent temperature heater 10 and constant temperature water cooler 16.
Filter 2 entrances are taken in carbon dioxide storage tank 1 outlet, strainer 2 outlets connect cryogenic liquid recycle pump 3 entrances, 3 outlets of temperature coolant recirculation pump connect CO 2 high pressure pump 4 entrances, first pressure regulator valve 5 is in parallel with CO 2 high pressure pump 4,4 outlets of CO 2 high pressure pump connect high pressure extraction still 8 entrances and chromatographic column 11 entrances respectively, high pressure extraction still 8 and chromatographic column 11 are located at respectively in first constent temperature heater 9 and second constent temperature heater 10, high pressure extraction still 8 outlets connect chromatographic column 11 entrances, chromatographic column 11 outlets are connected on line high pressure uv-spectrophotometric instrument 12 and on-line chromatograph testing station 13, online high pressure uv-spectrophotometric instrument 12 outlets connect second pressure regulator valve, 14 entrances, 14 outlets of second pressure regulator valve receive collection switching valve 15 entrances, collect switching valve 15 outlets and connect the entrance of terpene compound collector 17 and the entrance of oxygenatedchemicals collector 18 respectively, 17 outlets of terpene compound collector and 18 outlets of oxygenatedchemicals collector all connect under meter 19 entrances, terpene compound collector 17 and oxygenatedchemicals collector 18 all are located in the constant temperature water cooler 16, first constent temperature heater 9, second constent temperature heater 10 and constant temperature water cooler 16 are all established temperature regulator TC.
Be provided with high pressure valve V1 between described carbon dioxide storage tank 1 outlet and strainer 2 entrances.
Described terpene compound collector 17 bottoms are provided with high pressure valve V6, and oxygenatedchemicals collector 18 bottoms are provided with high pressure valve V7.
Be provided with high pressure valve V3 between described CO 2 high pressure pump 4 outlets and chromatographic column 11 entrances.
Described high pressure extraction still 8 entrances are provided with high pressure valve V2, and outlet is provided with high pressure valve V4.Be equipped with tensimeter P in high pressure extraction still 8 outlets and chromatographic column 11 outlets.
The device that described overcritical chromatographic separation concentrates oxygenatedchemicals in the tangerine oil adopts high pressure resistant stainless material to make.
Overcritical chromatographic separation of the present invention concentrates the method for oxygenatedchemicals in the tangerine oil, adopts described overcritical chromatographic separation to concentrate the device of oxygenatedchemicals in the tangerine oil, may further comprise the steps:
1) raw material essential oil metering process: the outlet of essential oil storage tank 6 connects the entrance of essential oil volume pump 7, and the outlet of essential oil volume pump 7 connects high pressure extraction still 8 tops, by essential oil volume pump 7 the raw material tangerine oil is quantitatively injected in the high pressure extraction still 8.
2) supercritical extraction removes wax ester pigment process: the outlet of carbon dioxide storage tank 1 connects valve V
1, by valve V
1Carbonic acid gas enter strainer 2, after cryogenic liquid recycle pump 3 cooling, enter CO 2 high pressure pump 4, pressure regulator valve 5 and CO 2 high pressure pump 4 adjusting pressure in parallel again.Carbonic acid gas through 4 pressurizations of CO 2 high pressure pump is divided into two paths: first path, and through high pressure valve V
2Feed high pressure extraction still 8, extract terpene compound and oxygenatedchemicals (wax ester and pigment composition residue in the high pressure extraction still 8) in the tangerine oil, again through high pressure valve V
4Feed chromatographic column 11; Second path is through high pressure valve V
3Directly feed chromatographic column 11, be used for the oxygenatedchemicals that subsequent step elution chromatography post 11 concentrates.
3) overcritical chromatographic separation terpene compound process: high pressure extraction still 8 and chromatographic column 11 are located at respectively in constent temperature heater 9 and 10 with heating respectively, the outlet of chromatographic column 11 connects online high pressure uv-spectrophotometric instrument 12, and the separation case in the chromatographic column 11 is by 13 monitorings of on-line chromatograph testing station.The outlet of online high pressure uv-spectrophotometric instrument 12 connects pressure regulator valve 14 successively and collects switching valve 15, and the outlet of collecting switching valve 15 connects the entrance of terpene compound collector 17 and oxygenatedchemicals collector 18 respectively.Front-end volatiles terpene compound by first path distillates through chromatographic column 11 is collected in the terpene compound collector 17 through pressure regulator valve 14 decompressions and collection switching valve 15.
4) overcritical chromatography eluant oxygenatedchemicals process: when the chromatographic peak that monitors the oxygenatedchemicals phantol when on-line chromatograph testing station 13 occurs, close the high pressure valve V in first path immediately
2And V
4, open high pressure valve V simultaneously
3Change second path over to, and switch collection switching valve 15 connection oxygenatedchemicals collectors 18, the oxygenatedchemicals wash-out that concentrates in the chromatographic column 11 is come out, reducing pressure and collect switching valve 15 through pressure regulator valve 14 again is collected in the oxygenatedchemicals collector 18.Terpene compound collector 17 and oxygenatedchemicals collector 18 are located at constant temperature water cooler 16 internal cooling, and have the continuous back of outlet access flow meter 19 to measure carbon dioxide flows on their top.Monitor the chromatographic peak disappearance of oxygenatedchemicals phantol when on-line chromatograph testing station 13 after, can stop sepn process.Open blowing high pressure valve V respectively
5, V
6And V
7Collection obtains wax ester and pigment composition, terpene compound and oxygenatedchemicals product.
To the product weighing, and adopt gas chromatograph-mass spectrometer (GC-MS) to carry out qualitative and quantitative analysis and calculating.By calculating concentration and the rate of recovery that can obtain oxygenatedchemicals.
Below provide supercritical extraction concentrates oxygenatedchemicals in the tangerine oil in conjunction with overcritical chromatographic separation specific embodiment:
Embodiment 1
Tangerine oil (purity 〉=99%) is available from last marine glad spices company limited.Carbonic acid gas (purity 〉=99.5%, food grade) is available from Xiamen City woods moral gas company limited.Supercritical extraction removes the operational condition of wax ester pigment process: pressure 8MPa, temperature 308K, CO
2Flow 5L/min; The operational condition of overcritical chromatographic separation terpene compound process: pressure 8MPa, temperature 308K, CO
2Flow 5L/min; The operational condition of overcritical chromatography eluant oxygenatedchemicals process: pressure 10MPa, temperature 308K, CO
2Flow 5L/min, the rate of recovery that obtains the oxygenatedchemicals product is 67.2%, concentration is 81.8%.
Embodiment 2
Tangerine oil (purity 〉=99%) is available from last marine glad spices company limited.Carbonic acid gas (purity 〉=99.5%, food grade) is available from Xiamen City woods moral gas company limited.Supercritical extraction removes the operational condition of wax ester pigment process: pressure 16MPa, temperature 338K, CO
2Flow 15L/min; The operational condition of overcritical chromatographic separation terpene compound process: pressure 16MPa, temperature 338K, CO
2Flow 15L/min; The operational condition of overcritical chromatography eluant oxygenatedchemicals process: pressure 25MPa, temperature 328K, CO
2Flow 10L/min, the rate of recovery that obtains the oxygenatedchemicals product is 83.8%, concentration is 87.4%.
Embodiment 3
Tangerine oil (purity 〉=99%) is available from last marine glad spices company limited.Carbonic acid gas (purity 〉=99.5%, food grade) is available from Xiamen City woods moral gas company limited.Supercritical extraction removes the operational condition of wax ester pigment process: pressure 12MPa, temperature 318K, CO
2Flow 15L/min; The operational condition of overcritical chromatographic separation terpene compound process: pressure 12MPa, temperature 318K, CO
2Flow 15L/min; The operational condition of overcritical chromatography eluant oxygenatedchemicals process: pressure 25MPa, temperature 328K, CO
2Flow 10L/min, the rate of recovery that obtains the oxygenatedchemicals product is 92.9%, concentration is 95.3%.
Embodiment 4
Tangerine oil (purity 〉=99%) is available from last marine glad spices company limited.Carbonic acid gas (purity 〉=99.5%, food grade) is available from Xiamen City woods moral gas company limited.Supercritical extraction removes the operational condition of wax ester pigment process: pressure 12MPa, temperature 318K, CO
2Flow 10L/min; The operational condition of overcritical chromatographic separation terpene compound process: pressure 12MPa, temperature 318K, CO
2Flow 10L/min; The operational condition of overcritical chromatography eluant oxygenatedchemicals process: pressure 15MPa, temperature 328K, CO
2Flow 10L/min, the rate of recovery that obtains the oxygenatedchemicals product is 78.2%, concentration is 89.6%.
Embodiment 5
Tangerine oil (purity 〉=99%) is available from last marine glad spices company limited.Carbonic acid gas (purity 〉=99.5%, food grade) is available from Xiamen City woods moral gas company limited.Supercritical extraction removes the operational condition of wax ester pigment process: pressure 14MPa, temperature 328K, CO
2Flow 10L/min; The operational condition of overcritical chromatographic separation terpene compound process: pressure 14MPa, temperature 328K, CO
2Flow 10L/min; The operational condition of overcritical chromatography eluant oxygenatedchemicals process: pressure 20MPa, temperature 318K, CO
2Flow 5L/min, the rate of recovery that obtains the oxygenatedchemicals product is 86.1%, concentration is 91.3%.
By each embodiment as seen, compared with the prior art, the invention provides and concentrate the device and method that concentration height, overcritical chromatographic separation that the rate of recovery is high concentrate oxygenatedchemicals in the tangerine oil a kind of the separation.
Claims (10)
1. an overcritical chromatographic separation concentrates the device of oxygenatedchemicals in the tangerine oil, it is characterized in that, be provided with carbon dioxide storage tank, strainer, the cryogenic liquid recycle pump, the CO 2 high pressure pump, first pressure regulator valve, high pressure extraction still, the essential oil storage tank, the essential oil volume pump, chromatographic column, online high pressure uv-spectrophotometric instrument, on-line chromatograph testing station, second pressure regulator valve, collect switching valve, under meter, temperature regulator, the terpene compound collector, the oxygenatedchemicals collector, first constent temperature heater, second constent temperature heater and constant temperature water cooler;
The filter entrance is taken in the carbon dioxide storage tank outlet, filter outlet connects the cryogenic liquid pump entry, temperature liquid circulation pump discharge connects the CO 2 high pressure pump intake, first pressure regulator valve and CO 2 high pressure parallel connection of pumps, the CO 2 high pressure pump discharge connects high pressure extraction still entrance and chromatographic column entrance respectively, high pressure extraction still and chromatographic column are located at respectively in first constent temperature heater and second constent temperature heater, the high pressure extraction still outlet connects the chromatographic column entrance, the chromatographic column outlet is connected on line high pressure uv-spectrophotometric instrument and on-line chromatograph testing station, online high pressure uv-spectrophotometric instrument outlet connects the second pressure regulator valve entrance, the outlet of second pressure regulator valve receives collection switching valve entrance, collect the switching valve outlet and connect the entrance of terpene compound collector and the entrance of oxygenatedchemicals collector respectively, the outlet of terpene compound collector and the outlet of oxygenatedchemicals collector all connect the under meter entrance, terpene compound collector and oxygenatedchemicals collector all are located in the constant temperature water cooler, first constent temperature heater, second constent temperature heater and constant temperature water cooler are all established temperature regulator.
2. a kind of overcritical chromatographic separation as claimed in claim 1 concentrates the device of oxygenatedchemicals in the tangerine oil, it is characterized in that, is provided with high pressure valve between described carbon dioxide storage tank outlet and the filter inlet.
3. a kind of overcritical chromatographic separation as claimed in claim 1 concentrates the device of oxygenatedchemicals in the tangerine oil, it is characterized in that, described terpene compound collector bottom and oxygenatedchemicals collector bottom are equipped with high pressure valve.
4. a kind of overcritical chromatographic separation as claimed in claim 1 concentrates the device of oxygenatedchemicals in the tangerine oil, it is characterized in that, is provided with high pressure valve between described CO 2 high pressure pump discharge and the chromatographic column entrance.
5. a kind of overcritical chromatographic separation as claimed in claim 1 concentrates the device of oxygenatedchemicals in the tangerine oil, it is characterized in that, described high pressure extraction still entrance and exit is equipped with high pressure valve, is equipped with tensimeter in the outlet of high pressure extraction still outlet and chromatographic column.
6. an overcritical chromatographic separation concentrates the method for oxygenatedchemicals in the tangerine oil, it is characterized in that, adopts overcritical chromatographic separation according to claim 1 to concentrate the device of oxygenatedchemicals in the tangerine oil, may further comprise the steps:
1) raw material essential oil metering process: start the essential oil volume pump, the tangerine oil raw material in the essential oil storage tank is squeezed in the high pressure extraction still, close the essential oil volume pump after reaching specified amount;
2) supercritical extraction removes wax ester pigment process: open the set high pressure valve of high pressure extraction still entrance, start the cryogenic liquid recycle pump, open the set high pressure valve of carbon dioxide storage tank outlet, start the CO 2 high pressure pump, carbonic acid gas enters high pressure extraction still through filter by the pressurization of CO 2 high pressure pump; Pressure by the first pressure regulator valve regulating and controlling high pressure extraction still is to specified pressure, by constent temperature heater heating and by the temperature of temperature regulator control high pressure extraction still to specified temperature, the terpene compound in the tangerine oil and oxygenatedchemicals can be dissolved in supercritical CO
2In, and wax ester and pigment composition are owing to be insoluble in supercritical CO
2And residue in the extracting phase of high pressure extraction still;
3) overcritical chromatographic separation terpene compound process: the outlet valve of opening high pressure extraction still, make the extraction phase that has dissolved terpene compound and oxygenatedchemicals enter chromatographic column, the pressure of chromatographic column passes through the pressure regulator valve regulating and controlling to specified pressure, the temperature of chromatographic column is controlled to specified temperature by the constent temperature heater heating and by temperature regulator, observed the chromatographic peak residence time of terpene compound by the on-line chromatograph testing station of online high pressure uv-spectrophotometric instrument and connection thereof, make the decompression of terpene compound product by second pressure regulator valve, the carbonic acid gas that flows out from terpene compound collector and oxygenatedchemicals collector is by the under meter metered flow;
4) overcritical chromatography eluant oxygenatedchemicals process: when the chromatographic peak of observing the oxygenatedchemicals phantol when on-line chromatograph testing station occurs, close inlet valve and the outlet valve of high pressure extraction still immediately, open the high pressure valve between CO 2 high pressure pump discharge and the chromatographic column entrance simultaneously, regulate supercritical CO by pressure regulator valve
2To specified pressure, make supercritical CO
2The oxygenatedchemicals of enrichment in the elution chromatography post is regulated and is collected switching valve to the oxygenatedchemicals collector.Collect after cut oxygenatedchemicals product by pressure regulator valve decompression in the oxygenatedchemicals collector, after the chromatographic peak of observing the oxygenatedchemicals phantol when on-line chromatograph testing station disappears, i.e. sepn process finishes;
5) after sepn process finishes, open high pressure extraction still, oxygenatedchemicals collector and the dispensing valve collection of terpene compound collector bottom respectively and obtain wax ester and pigment, oxygenatedchemicals and terpene compound product.
7. a kind of overcritical chromatographic separation as claimed in claim 6 concentrates the method for oxygenatedchemicals in the tangerine oil, it is characterized in that, in step 1), described tangerine oil raw material is at least a in hut mandarin orange essential oil, lemon quintessence oil, natsudaidai essential oil, orange oil, sweet orange oil, red tangerine essential oil, the Bergamot.
8. a kind of overcritical chromatographic separation as claimed in claim 6 concentrates the method for oxygenatedchemicals in the tangerine oil, it is characterized in that, in step 2) in, the processing condition that described supercritical extraction removes wax ester pigment process are: extracting pressure 8～16MPa, extraction temperature 308～338K, extraction agent CO
2Flow 5～15L/min.
9. a kind of overcritical chromatographic separation as claimed in claim 6 concentrates the method for oxygenatedchemicals in the tangerine oil, it is characterized in that, in step 3), the processing condition of described overcritical chromatographic separation terpene compound process are: chromatogram pressure 8～16MPa, chromatogram temperature 308～338K, moving phase CO
2Flow 5～15L/min.
10. a kind of overcritical chromatographic separation as claimed in claim 6 concentrates the method for oxygenatedchemicals in the tangerine oil, it is characterized in that, in step 4), the processing condition of described overcritical chromatography eluant oxygenatedchemicals process are: chromatogram pressure 10～25MPa, chromatogram temperature 308～328K, moving phase CO
2Flow 5～10L/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310289339.3A CN103333744B (en) | 2013-07-11 | 2013-07-11 | Apparatus for separating oxygen-containing compounds in concentrated orange essential oil through supercritical chromatography, and method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310289339.3A CN103333744B (en) | 2013-07-11 | 2013-07-11 | Apparatus for separating oxygen-containing compounds in concentrated orange essential oil through supercritical chromatography, and method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103333744A true CN103333744A (en) | 2013-10-02 |
| CN103333744B CN103333744B (en) | 2015-01-07 |
Family
ID=49241949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310289339.3A Expired - Fee Related CN103333744B (en) | 2013-07-11 | 2013-07-11 | Apparatus for separating oxygen-containing compounds in concentrated orange essential oil through supercritical chromatography, and method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103333744B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693438A (en) * | 2005-05-12 | 2005-11-09 | 中国科学院广州化学研究所 | Process for extracting and refining lavender oil |
| CN102093321A (en) * | 2010-12-16 | 2011-06-15 | 厦门大学 | Device and method for separating orange oil from honey pomelo essential oil by supercritical fluid chromatography |
| CN102533446A (en) * | 2012-01-10 | 2012-07-04 | 佰香汇生物科技（厦门）有限公司 | New method for removing furocoumarins from citrus essential oil |
-
2013
- 2013-07-11 CN CN201310289339.3A patent/CN103333744B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693438A (en) * | 2005-05-12 | 2005-11-09 | 中国科学院广州化学研究所 | Process for extracting and refining lavender oil |
| CN102093321A (en) * | 2010-12-16 | 2011-06-15 | 厦门大学 | Device and method for separating orange oil from honey pomelo essential oil by supercritical fluid chromatography |
| CN102533446A (en) * | 2012-01-10 | 2012-07-04 | 佰香汇生物科技（厦门）有限公司 | New method for removing furocoumarins from citrus essential oil |
Non-Patent Citations (2)
| Title |
|---|
| MASAKI SATO等: "Fractionation of citrus oil by supercritical countercurrent textractor with side-stream withdrawal", 《JOURNAL OF SUPERCRITICAL FLUIDS》, 31 December 1998 (1998-12-31), pages 311 - 317 * |
| 王丹清等: "超临界CO_2萃取分离桔油中的萜烯和含氧化合物", 《化学工程》, vol. 38, no. 05, 31 December 2010 (2010-12-31), pages 9 - 12 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103333744B (en) | 2015-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rovetto et al. | Supercritical carbon dioxide extraction of cannabinoids from Cannabis sativa L. | |
| US9744200B1 (en) | System for producing a terpene-enhanced cannabinoid concentrate | |
| US9649349B1 (en) | System and method for producing a terpene-enhanced cannibinoid concentrate | |
| CN102093321B (en) | Device and method for separating orange oil from honey pomelo essential oil by supercritical fluid chromatography | |
| Ibanez et al. | Isolation and separation of tocopherols from olive by‐products with supercritical fluids | |
| CN107400563A (en) | For extracting the process units and its production method of fragrant plant composition | |
| CN101928642B (en) | Method for extracting and separating spice and medicinal components from whole plants of Dendranthema indicum | |
| CN103923748B (en) | A kind of volatile oil extracts collects separation equipment | |
| CN103627528A (en) | Method for extracting lavender essential oil | |
| Sato et al. | Fractionation of citrus oil by supercritical countercurrent extractor with side-stream withdrawal | |
| Kondo et al. | Fractional extraction by supercritical carbon dioxide for the deterpenation of bergamot oil | |
| CN101888889A (en) | Method to recover bioactive compounds | |
| CN102553295A (en) | Novel supercritical carbon dioxide extraction technology for continuously carrying out fine extraction on liquid raw materials | |
| CN103952239A (en) | Method for extracting essential oil from fresh bergamot and application of essential oil in cigarettes | |
| Ibáñez et al. | Concentration of sterols and tocopherols from olive oil with supercritical carbon dioxide | |
| CN103333744B (en) | Apparatus for separating oxygen-containing compounds in concentrated orange essential oil through supercritical chromatography, and method thereof | |
| Subra et al. | Supercritical fluid extraction from a brown alga by stagewise pressure increase | |
| CN106433985B (en) | A kind of ginger essential oil and preparation method thereof | |
| Ismail et al. | The flavour of plums (Prunus domestica L.). An examination of the aroma components of plum juice from the cultivar victoria | |
| CN104087423B (en) | Utilize the method for simulation moving-bed extraction fruit of Chinese magnoliavine essential oil | |
| Nautiyal et al. | Supercritical carbon dioxide extraction of Indian orange peel oil and hydro distillation comparison on their compositions | |
| CN101978984B (en) | Method for preparing large-head atractylodes rhizome and sesquiterpene compound | |
| US11554098B2 (en) | Compositions comprising molecularly separated cannabinoids and terpene blends and methods of producing | |
| CN112980587A (en) | Method for extracting kiwi flower essential oil | |
| CN100441669C (en) | Method of extracting fresh pomelo flower fragrant substance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150107 |