CN104087423A - Method for extracting fructus schizandrae essential oil by utilizing simulated moving bed - Google Patents
Method for extracting fructus schizandrae essential oil by utilizing simulated moving bed Download PDFInfo
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Abstract
The invention discloses a method for extracting fructus schizandrae essential oil by utilizing a simulated moving bed. The method comprises the following steps pf extracting fructus schizandrae essential oil, separating the simulated moving bed under the following conditions that silicon dioxide is used as a stationary phase, normal hexane/isopropyl alcohol liquor is used as a mobile phase, separating to obtain four active ingredients, which are deoxyschizandrin (Sin-A), schisandrin (Sin-B), schizandrin (Sol-A) and schisandrol (Sol-B), of the fructus schizandrae essential oil. The fructus schizandrae essential oil is prepared by a method comprising the following steps of taking fructus schizandrae dried fruit, soaking the fruit into water, removing pulp and drying to obtain fruit kernels; crushing, carrying out supercritical CO2 fluid extraction to obtain the fructus schizandrae essential oil. The method disclosed by the invention utilizes supercritical fluid to extract fructus schizandrae to obtain the fructus schizandrae essential oil, and then the simulated moving bed is adopted to separate for separating and purifying four active ingredients in the fructus schizandrae essential oil, so that active ingredients in the fructus schizandrae essential oil are effectively extracted, and therefore, the method is beneficial to follow-up research.
Description
Technical field
The present invention relates to a kind of method of utilizing simulation moving-bed extraction shizandra berry essential oil.
Background technology
Schisandra chinensis is medicinal plant, the mountain areas such as NATURAL DISTRIBUTION Xiaoxing ' anling Mountains of Heilongjiang Province, Wanda Mountain, Zhang Guangcai ridge, master ridge.Main product is in the schisandra fruit dry product on the ground such as northeast and Hebei, and commodity custom is called " Schisandra chinensis ".Fresh Schisandra chinensis fruit be the berry of hunting pink, and succulence, taste are sour and micro-puckery, have Chinese prickly ash smell.Fruit drink is the raw material of processing natural health drink; The black red-purple of dry fruit, has crape wrinkle, is traditional Chinese medicinal materials, and central nervous system, respiratory system to human body have excitation, and heart, liver, blood pressure are had to regulating effect, and eyesight, hearing to people are strengthened function; Promote choleresis, improve antibacterial ability.
Shizandra berry essential oil is the activeconstituents in shizandra berry fruit stone, after deliberation, the activeconstituents in shizandra berry essential oil mainly comprises deoxyschizandrin (Sin-A), Wuweizisu B (Sin-B), schisandrin (Sol-A), Wuweizichun B (Sol-B).How extracting shizandra berry essential oil and activeconstituents is separated, is one of focus of current research.
Supercritical CO
2the principle of fluid extraction (SFE) sepn process is: utilize the dissolving power of supercutical fluid and the relation of its density, utilize pressure and temperature to carry out the impact of supercutical fluid dissolving power.Under supercritical state, supercutical fluid is contacted with material to be separated, it is extracted the composition of polarity size, boiling point height and molecular size range selectively successively.Certainly, the extract that corresponding each pressure range obtains can not be single, but can control condition obtain the mixing element of optimum proportion, then make supercutical fluid become common gases by the method for decompression, intensification, being extracted material separates out completely or substantially, thereby reach the object of separating-purifying, so supercritical CO
2fluid extraction process is combined by extraction and fractionation process.Supercritical CO
2the feature of extraction has determined that its range of application is very wide.As in medicine industry, can be used for the extraction of effective component of Chinese herbal medicine, thermo-sensitivity biological medicine refining, and the separation of lipid mixture; In foodstuffs industry, the extraction of hops, the extraction of pigment etc.; In perfume industry, natural and synthetic perfume refining; Separation of mixture etc. in chemical industry.
Simulation moving-bed is a kind of mass transfer apparatus that utilizes absorption principle to carry out liquid separation operation, it is in adverse current operate continuously mode, by the material import and export position of conversion fixed bed absorption equipment, generation is equivalent to sorbent material and moves down continuously, and the effect that material moves up continuously.Throughput and the separation efficiency of this equipment are higher than fixed adsorption bed, can avoid again the channel between moving bed adsorption wearing and tearing, fragment or dust occluding device or pipeline and solid particulate seam.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of method of utilizing simulation moving-bed extraction shizandra berry essential oil isolating active composition.
The present invention is achieved by the following technical solutions:
A method of utilizing simulation moving-bed extraction shizandra berry essential oil, step is as follows: get shizandra berry essential oil, carry out simulation moving-bed separation, condition is: stationary phase used is silicon-dioxide (preparation scale); Moving phase is that volume ratio is normal hexane/aqueous isopropanol of 85/15; After separation, obtain four kinds of effective constituents of shizandra berry essential oil: deoxyschizandrin (Sin-A), Wuweizisu B (Sin-B), schisandrin (Sol-A), Wuweizichun B (Sol-B).
Further, when laboratory condition, should possess following condition: tubing string is 8 endowels, specification is internal diameter 21.2mm x length 100 mm, and the essential oil concentration of charging is 5025 mg/L, and flow velocity has respectively: it is 10 mL/min that scavenging solution enters discharging; It is 5.0 mL/min that agent pan feeding is washed in punching; Extract discharge port is 3.0 mL/min; Charging feeding mouth is 0.5 mL/min; Extraction Yu thing discharge port is 2.5 mL/min; It is 1.0 mL/min that agent reflux pump is washed in punching; Switching time is between 7.0～8.0 minutes.
Further, described shizandra berry essential oil is from shizandra berry, to extract the extraction of essential oil thing obtaining, and comprises Schisandra chinensis, kadsura longepedunculata, such as: from Schisandra chinensis fruit stone, extract and obtain shizandra berry essential oil.
Preferably, described shizandra berry essential oil prepares by the following method: get shizandra berry dry fruit, after soaked, fleshing, dry (water content is below 4.67%), obtain fruit stone, pulverize (being crushed to approximately 60 mesh left and right), carry out supercritical CO
2fluid extraction, extracting pressure is 10～70 MPa, extraction temperature is 35 DEG C～60 DEG C, obtains shizandra berry essential oil; In extraction process, can add in right amount ethanol, 0～25% (percent by volume) that the addition of ethanol is carbonic acid gas.
Further preferred, extracting pressure is 35MPa, and extraction temperature is 60 DEG C.
The present invention utilizes supercutical fluid to extract shizandra berry, obtain shizandra berry essential oil, and then adopt simulation moving-bed separation, activeconstituents in four in shizandra berry essential oil is carried out to separation and purification, effectively extract the activeconstituents having obtained in shizandra berry essential oil, be conducive to follow-up research.
Brief description of the drawings
Fig. 1: the HLC/UV collection of illustrative plates of shizandra berry fruit stone essential oil.
Fig. 2: supercritical carbon dioxide extraction equipment pipeline schema.
Fig. 3: the SMB layout diagram that configuration is 2/2/2/2.
Fig. 4: separable operational condition scope in trilateral theory.
Fig. 5: CIP-SMB schematic diagram.
Fig. 6: CIP-SMB separates three composition conceptual illustration.
The operational condition of Fig. 7: CIP-SMB.
Fig. 8: the HPLC collection of illustrative plates of four kinds of standard substance mixing solutionss.
Fig. 9: the HPLC collection of illustrative plates of shizandra berry essential oil.
Figure 10: be the separating experiment result of 5.0 minutes switching time.
Figure 11: be the separating experiment result of 5.5 minutes switching time.
Figure 12: be the separating experiment result of 6.5 minutes switching time.
Figure 13: be the separating experiment result of 7.0 minutes switching time.
Figure 14: be the separating experiment result of 7.5 minutes switching time.
Figure 15: be the separating experiment result of 8.0 minutes switching time.
Figure 16: be the separating experiment result of 8.5 minutes switching time.
Figure 17: be the separating experiment result of 10.0 minutes switching time.
Figure 18: experiment condition is in the sign of the theoretical defined plane of trilateral.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1 utilizes supercutical fluid and simulation moving-bed shizandra berry is extracted to separation
Method steps is as follows:
(1) essential oil raw material
1.1 raw material
Purchase the Schisandra chinensis of Taiwan Market of Chinese Materia Medica.Through soaked, fleshing, dry (water content is below 4.67%), then be crushed to about 60 mesh left and right with coffee bean grinder.
This research, except the yield of investigation extraction, is more analyzed and is monitored the content of four kinds of active ingredients.Four kinds of active ingredients selecting are deoxyschizandrin (Sin-A), Wuweizisu B (Sin-B), schisandrin (Sol-A), Wuweizichun B (Sol-B), and adopt the product (purity content is more than 98%) of Man Site bio tech ltd, Chengdu as standard reference material.
Acetonitrile, ethanol (95%) are purchased the closest friend and Trading Co., Ltd, and purity is LC level, as analyzing and extraction use, and adopt reagent level hexane and Virahol to use as simulation moving-bed research.Carbonic acid gas is provided by Jingde, Taiwan gas companies, and purity is more than 99.5%.
1.2 analytical procedure
This research is used HPLC/DAD to analyze four kinds of active ingredient content, and (250mm × 4.6 mm, m), and taking the acetonitrile of 1.0 mL/min and water as moving phase, its gradient operating method is as table 1 for 5 μ for Kromasil 100-5C18 for the tubing string of use.While carrying out quantitative analysis, this research adopt wavelength be the UV-light of 217 nm as quantitative criterion, typical HPLC/UV collection of illustrative plates is as shown in Figure 1.If adopting volume is the injection ring of 20 μ L, the inspection amount line of four kinds of standard substance is as follows respectively:
(1)
Table 1 shizandra berry essential oil is with the gradient design of HPLC analysis
| Time (min) | 0 | 30 | 40 | 45 | 55 |
| Acetonitrile ratio | 50 | 50 | 70 | 80 | 50 |
| Pure water ratio | 50 | 50 | 30 | 20 | 50 |
Four kinds of active component content comparisons in 1.3 shizandra berry positions
After the pulp of the shizandra berry of purchasing and fruit stone use respectively ethanol (95%) extraction, four kinds of active component contents in discovery fruit stone are much larger than the content of pulp.In each kilogram of dry weight raw material of digitized representation of table 2, the milligram of contained active ingredient is heavy.As shown in Table 2, the highest with the content of schisandrin (Sol-A) in four kinds of activeconstituentss, its excess-three kind is more or less the same, and in fruit stone, the content of activeconstituents is approximately 20～40 times of left and right of flesh-content.Therefore this research is only carried out supercritical fluid extraction to obtain essential oil for the fruit stone position of shizandra berry, and the essential oil obtaining is further as the raw material of using with SMB purifying.
The active component content of table 2 shizandra berry different sites
| Sample title | Sol-A (mg/kg) | Sol-B (mg/kg) | Sin-A (mg/kg) | Sin-B (mg/kg) |
| Fruit stone | 13746 | 7797 | 4100 | 5742 |
| Pulp | 369 | 358 | 190 | 270 |
1.4 supercritical carbon dioxide extraction equipment
Supercritical carbon dioxide extraction apparatus pipeline schema is as Fig. 2, and its general operation steps is as follows:
(1) opening device power supply, confirm that air compressor machine gaseous tension and relief valve pressure are more than 100 psi, and the temperature of confirming condenser C1 and the second condenser C2 is between-10 to-12 DEG C, primary heater H1 design temperature is the required temperature of extraction conditions, and secondary heater H2 is set as the required temperature of gas-liquid separation;
(2) respectively add a filter paper at inner bag upper cover and the lower cover of extraction tank, with the solid substance of filtered sample, after locking inner bag lower cover, then starting material to be extracted are placed in to inner bag, and lock inner bag upper cover, whole inner bag is placed in to extraction tank, cover extraction tank enclosing cover;
(3) open the first valve V1 and inject liquid carbon dioxide to storage tank WT, in observation liquid level window W, carbonic acid gas liquid level is that half is closed the first valve V1 when high;
(4) sequentially open the first liquid pump P1 and the 6th valve V6 refluxes carbonic acid gas, and temperature on liquid pump is shown drop to approximately-10 DEG C of left and right;
(5) after the temperature demonstration on liquid pump is stable, reads the pressure of storage tank WT, and confirm that carbonic acid gas was cold Liquid carbon dioxide;
(6) back pressure valve is all unclamped, then opening a little the second valve V2 makes carbonic acid gas enter extraction tank ET, in the time that gas-liquid separation groove S pressure is about 1.5 MPa, close again the second valve V2, progressively open the 5th valve V5 and allow the gas in extraction tank ET and gas-liquid separation groove S drain into atmosphere, until separator tank Pressure Drop to 0.2～0.3 MPa left and right;
(7) repeating step 6 several, to remove the air in extraction tank and separator tank as far as possible;
(8) by the second valve V2, the 4th valve V4 standard-sized sheet and close the 6th valve V6, slowly adjust back pressure valve BPR and set up system pressure, until extraction tank ET is while reaching the condition pressure setting, to be arranged on the carbonic acid gas flow velocity of mass flowmeter control the first liquid pump P1 after separator tank;
(9) in the time of system temperature, pressure, flow speed stability, open the 3rd valve V3, and utilize the second liquid pump P2 to pump in system according to the flow velocity setting auxiliary solvent, start to extract, and start timing simultaneously.If while not using auxiliary solvent extraction, before also the auxiliary solvent of pump enters separator tank Vent pressure, with the whole essential oils of complete collection, and ensure the normal prolonged operation of back pressure valve;
(10), after extraction 30 minutes, open the 5th valve V5 and collect the whole liquid in gas-liquid separation groove S.
Be 35MPa in extracting pressure, extraction temperature is 50 DEG C, adds after the supercritical carbon dioxide extraction of 25% (v/v) ethanol, obtains shizandra berry essential oil.Shizandra berry essential oil vacuum concentration that will extraction gained is removed after ethanol, and re-using Virahol and normal hexane (volume ratio of Virahol and normal hexane is 15:85), to be mixed with shizandra berry essential oil solution stand-by with the feedstock solution as SMB.Feedstock solution is carried out the analysis of HPLC simultaneously, to understand four kinds of active component contents wherein.The charging of this research using the essential oil concentration of 5025 mg/L as SMB, wherein the concentration of four kinds of activeconstituentss is respectively: 244.5 mg Sol-A/L, 108.2 mg Sol-B/L, 89.9 mg Sin-A/L, 89.7 mg Sin-A/L, all the other are mainly the grease of low hold-up, and the impurity of strong anelasticity.
(2) SMB technological overview
Because solid adsorbent has quite high selectivity, chromatographic technique is one of purification technique of industrial most critical always, preparation scale HPLC from the small-sized HPLC of development to the development phase, even arrives the chromatography of production use, at any time visible chromatographic technique institute roles all.But above-mentioned chromatography all belongs to batch operation, if can make the chromatography of batch into operate continuously, just effectively lift technique production capacity and sorbent material usefulness can reduce running cost and solvent consumption greatly.Simulated moving bed chromatography (simulated moving bed chromatography, be called for short SMB) technology is production technology the most continuously at present.
The configuration of SMB general device and principle of operation are as shown in Figure 3.A chromatography tubing string that has 8 series connection in Fig. 3, wherein C1, C2 are referred to as the first section; C3, C4 are referred to as the second section; C5, C6 are referred to as the 3rd section; C7, C8 are referred to as the 4th section.In Fig. 3, one has two entrances, is respectively the opening for feed of feed and desorbent; And 3 discharge ports, be respectively extract, raffinate, desorbent to recycle.Some designs directly just pump into the first section from the 4th section outlet by desorbent without processing again and recycle, and are referred to as loop design.If allow all opening for feeds and discharge port switch to clockwise next position after for some time, for example feed is by originally switching between C4 and C5 between C5 and C6, also move toward next tubing string simultaneously clockwise all the other gangways, after continuously switching, will form the similar mobile phenomenon of solid counterclockwise that allows.And at the same time, continuously clockwise is mobile for moving phase always, and reach the process that simulation solid contacts with the continuous countercurrent flow of liquid.
SMB system causes the solute generation of different retention intensity to separate because liquid is washed in punching with the relative velocity of solid, so if wish separates A and B,, in the middle of each section, the relative volume flow velocity of its liquid and solid must meet following condition:
(2)
Wherein K
awith K
bbe the Henry absorption constant of composition A and composition B, and m
jfor the ratio of mobile phase volume flow velocity in j section and solid volume flow velocity, be defined as:
(3)
Q
jfor liquid is at the flow velocity of j section, t
swfor tubing string switching time, V
cfor empty tube column volume, ε is tubing string total porosity, V
dfor the dead angle volume of each endowel.
If therefore with the m of the second section
2for transverse axis, the m of the 3rd section
3for the longitudinal axis, the operational condition that can separate completely is just in time located in trilateral, as shown in Figure 4.There is best separating effect and separation efficiency in vertex of a triangle.Except second and the relative velocity of the 3rd section will be seated in trilateral, first and the 4th section also must meet (2) formula simultaneously.
Traditional SMB is only suitable for the separation in two compositions, for multicomponent separation, needs more complicated design and accurate control.
The delay intensity of supposing A/B/C three component system system is sequentially A < B < C, and the design of Fig. 5 can make three compositions effectively separate.With the SMB of 8 tubing strings, and to set configuration be 1-3/1/3, composition B is identical with the method for traditional SMB with the separation of A, but the C composition of strong anelasticity, taken to the 0th section, carried out desorption with the strong desorbing agent of another kind or quite high relative volume flow velocity simultaneously.If with strong desorbing agent desorption, must recycle to rush to wash after agent is soaked and just can get back in SMB system.Therefore in operational design, the separation of A/B must meet (2) formula.
Because the anelasticity of composition C is stronger than B, so the C composition of turning left mobile is easy to extracting end (Extract) and flow out with work B composition, and pollute B product.For a TMB, such pollution also cannot be avoided, but for SMB, as long as utilize the concept of single tubing string, also can obtain at extraction end the product of pure B.In order to avoid C composition to pollute extraction end, in operation, need to be controlled especially.Fig. 6 has illustrated how to utilize the concept of single tubing string to avoid C composition end outflow from extracting.
After A/B/C tri-composition chargings, C composition is washed agent and takes to the 3rd section on the right by punching, blacking part in Fig. 6, then in the time of next switching time, it is the second section that the position of this tubing string is adjusted to, then continues after switching once again by migration the first section.As long as the number of switching time, flow velocity and each section tubing string can make the part of blacking can end outflow from extracting, just can allow C flow out from the 0th section completely.Therefore the operation of the second section and the 3rd section still must meet following restricted condition:
(4)
N in formula
2it is the tubing string number of the second section.
Except second and the restriction of the 3rd section, the operation of the 0th section also will meet following two conditions:
(5)
K in formula
c orepresent the Henry's constant of the composition C of the 0th section, m
orepresent the relative velocity of the 0th section.Because use different rushing to wash agent, so K
c owith K
cnot identical.If it is identical with SMB body that the 0th section rush washed agent, K
c owith K
cstill identical.
If at traditional (m
2, m
3) draw on coordinate plane, represent separable region as shown in Figure 7.The representative of right-angle triangle in figure can separate the trilateral of the two compositions of A/B and the equation of thick line representative (4) formula.Owing to must meet (2) formula and (4) formula simultaneously, be the K in way so can separate the operational condition of A/B/C completely
athe trilateral that-P-Q is linked to be, and P point also represents best operational condition.So, K
athe scope of-P-Q is larger, and the efficiency of SMB is higher.Therefore, except K
c-K
bmore better, in the design of SMB, n
2little.
(3) SMB design and description of equipment
3.1 SMB device configurations
This research is used the design of Fig. 5 to carry out schizandrin in shizandra berry essential oil and schizrol element to carry out the separation test of three compositions.In the middle of the design of Fig. 5, the 1st endowel is by the use as off-line cleaning, and 7 remaining endowels are designed to the SMB of four sections of loop, and its configuration can be write as 1-2/1/2/2.After shizandra berry essential oil solution is injected into system, if can separate completely, the weak composition that is detained will be flowed out by extraction Yu end (raffinate), be cleaned out (washed) and be detained into by force branch from washing outlet, be detained composition between of intensity and there will be and end (extract) extracting.
The SMB equipment of this research is produced by the manufacturing of Qiao Pu scientific & technical corporation, and the tubing string size that institute is used is 21.2 x 100 mm.
3.2 research method
Although the continuous separate that the separation of CIP-SMB belongs to three compositions from, for the separation of strong anelasticity composition, be still the separate mode of single tubing string, only have two weak compositions to be separated according to SMB continuous chromatography mode.Suppose that ternary delay intensity is sequentially A < B < C, in order to facilitate analysis and the interpretation of experimental result, therefore this research is still identical with separating of two compositions with the purity definition of extraction Yu end at extraction end, suc as formula (6) and formula (7), additionally define new index simultaneously, pollution level, extract end and extract the situation that Yu end is polluted by strong anelasticity composition with complete description, suc as formula (8) and formula (9).The purity of cleaning end defines suc as formula (10).
Purity at extract:
(6)
Purity at Raffinate:
(7)
Contamination level by Sorbitol at Extract:
(8)
Contamination level by Sorbitolat raffinate:
(9)
Purity at Washed:
(10)
In the design of operational condition, mainly taking Fig. 3 as foundation.Therefore can be distinguished into following several situation to the separation of three compositions:
(1) if A can effectively separate with B, but because the oversize C of causing switching time has polluted extraction end, P
ewith P
rpurity is high, but CL
enumerical value is also high.So CL
emainly be subject to the impact of switching time.
(2) if A can effectively separate with B, if but the 0th section rush that to wash agent volumetric flow rate relatively too low to the volumetric flow rate of solid, solid is not cleaned Qian Net completely and is just back to the 4th section, and therefore C will pollute extraction Yu end, so experimental result will show high P
ewith P
rbut, CL
rnumerical value also can raise.So CL
rmainly be subject to the relative velocity impact of the 0th section.
(3) if the relative volume flow velocity of the first section is too low, B even A may pollute the C of the 0th section.So P
wmainly be subject to the relative velocity impact of the first section.
Four kinds of activeconstituentss are held, are extracted the rate of recovery that end and clean three outlets of end and are defined as respectively extraction Yu:
(11)
(12)
(13)
3.2 stationary phase and operational condition
This research selects preparative scale silicon-dioxide as stationary phase, Merck LiChroprep Si 60 (40～63 um), and hexane/IPA solution taking volume ratio as 85/15 is as moving phase.Four kinds of standard substance mixing solutionss at the HPLC of 217 nm collection of illustrative plates as shown in Figure 8.Utilize the shizandra berry essential oil collection of illustrative plates of supercritical carbon dioxide extraction as shown in Figure 9.
This research is further used HPLC/RI, and with water as not being detained composition, the dead angle volume time that records HPLC is 0.47 minute, and t
0be 8.6 minutes, suppose that stationary phase is 0.41 at the porosity of tubing string simultaneously.If suppose that isothermal adsorption is linear absorption, the isothermal adsorption constant of four kinds of activeconstituentss is shown in table 2.
According to the collection of illustrative plates of Fig. 8 and 9, the Sin-A in four kinds of activeconstituentss in shizandra berry essential oil and Sin-B are considered as same composition Sin-A/B by this research, then utilize the technology of SMB that it is carried out to separating of two compositions with Sol-B, attempt utilizing the concept of CIP-SMB that Sol-A composition is given separating from cleaning end simultaneously.
Table 2 four kinds of activeconstituents residence times and Henry's constant
| Components | Sin B | Sin A | Sol B | Sol A |
| Retention time | 10.18 | 13.0 | 17.2/20.1 | 24.8 |
| Henry’s Constant | 0.135 | 0.376 | 0.735 | 1.385 |
(4) SMB separating experiment result
This research, under the flow conditions of fixing each gangway, changes the switching time of valve, and as table 3, the composition of then observing tri-exit end of CIP-SMB changes.It is 10 mL/min that the flow velocity setting has respectively scavenging solution to enter discharging; It is 5.0 mL/min that agent pan feeding is washed in punching; Extract discharge port is 3.0 mL/min; Charging feeding mouth is 0.5 mL/min; Extraction Yu thing discharge port is 2.5 mL/min; It is 1.0 mL/min that agent reflux pump is washed in punching.The essential oil concentration of charging is 5025 mg/L, and the concentration of four kinds of activeconstituentss is Csol-A=244.5; Csol-B=108.2; CSin-A=89.93; CSin-B=89.69 mg/L, also represents that the weight percent of these four kinds of activeconstituentss in essential oil is sequentially 4.87%, 2.15%, 1.79%, 1.79%.
The HPLC collection of illustrative plates of three outlet samples under each switching time under obtained stable state is as shown in Figure 10～17.Wherein the representative of collection of illustrative plates is from top to bottom cleaned end (Article 1 curve from top to bottom), extraction Yu end (Article 2 curve from top to bottom) and is extracted the collection of illustrative plates of three outlet samples that end (Article 3 curve from top to bottom).
Table 3 shizandra berry essential oil SMB separating experiment result
According to all HPLC collection of illustrative plates, and the inspection amount line of (1) formula, can calculate the concentration of four kinds of activeconstituentss in each outlet, and then can utilize (6), (7), the defined formula of (10) formula to calculate the purity of learning each composition, and the rate of recovery of utilizing (11)-(13) formula to calculate.The result of calculating gained arranges among table 3.
According to the result demonstration of Figure 10～17, between 7.0～8.0 minutes, have three best component separating effects switching time.Once, exceed 8.5 minutes switching time, all four kinds of activeconstituentss that enter from opening for feed all will can not be brought to cleaning section and bring out a mouthful outflow from cleaning.This representative is after being greater than 8.5 minutes switching time, and its operational condition all will no longer meet the condition of (4) formula.Once after being less than switching time 7 minutes,, because the defined relative velocity of (3) formula is too little, therefore extract the purity deficiency that end.
If suppose that the dead angle volume of SMB is 6% of tubing string volume, all operations condition of this research is located in the defined (m of trilateral theory
2, m
3) situation in plane as shown in figure 18.Circle points in Figure 18 is represented to the upper right corner that by the lower left corner switching time from short to long.By the result of HPLC collection of illustrative plates, be 7.5 to represent the region that can separate completely with Sol-B at Sin-B with 8.0 result switching time, and Figure 18 also roughly shows same result.
(6) long-time steady testing and each product concentrating degree
This research further operates for a long time under being the condition of 7.5 minutes switching time, the stability of test macro, and understand the content of each activeconstituents in three exit end products.Result shows, after operate continuously three days, the HPLC collection of illustrative plates of the sample of collection that sample every day is identical with Fig. 7, and whole samples of three days three collected exit end are after vacuum concentration, can record respectively the essential oil content of each exit end solution: extract that end be 0.1717 g/L; Extracting in end is 0.2993 g/L; Cleaning end is 0.0398 g/L.Under this condition, four kinds of activeconstituentss can be learnt by HPLC collection of illustrative plates in the concentration of each exit end, and therefore in each exit end product, the percentage composition of activeconstituents can be calculated and learn according to this, as table 4.
Active component content in the each exit end essential oil of table 4
| Oil content (mg/L) | Sol-A | Sol-B | Sin-A | Sin-B | |
| Feed | 5025 | 4.87% | 2.15% | 1.79% | 1.79% |
| Extract | 171.7 | 22.16% | 15.28% | 0.02% | 0 |
| Raffinate | 299.3 | 0 | 0 | 2.43% | 2.45% |
| Washed | 39.78 | 9.05% | 0 | 0 | 0 |
In charging, four kinds of activeconstituentss total content in essential oil reaches 10.6%, and all the other are most of taking grease as main.After the separation of CIP-SMB concentrates, the content of activeconstituents in product in the travel direction meeting leading product of these greases.Can be judged that by table 4 content of Sol-A and Sol-B is after separating of CIP-SMB is concentrated, can be increased to respectively 22.16% and can be increased to 2.43% and 2.45% extracting the content that Yu holds with 15.28%, Sin-A and Sin-B extracting the content that end.Although CIP-SMB effectively divides out Sol-A/B and Sin-A/B, but grease wherein and other impurity are still not yet separated, but the degree degree that content increases in essential oil far above Sin-A/B that the content of Sol-A/B in essential oil increases, therefore infer that most grease or impurity belong to low hold-up composition, so be sent to extraction Yu end, therefore reduced the content of Sin-A/B in extraction Yu end.
In table 4, also find that Sol-A is also increased to 9.05% at the content that cleans end simultaneously.Although it is very high to clean the Sol-A purity of end, the content in essential oil but only has 9.05%, and far away from 22.16% of end extracting, representative has many strong anelasticity compositions that do not appear in Fig. 1 also to be taken together toward cleaning to have held.
Claims (6)
1. a method of utilizing simulation moving-bed extraction shizandra berry essential oil, is characterized in that: get shizandra berry essential oil, carry out simulation moving-bed separation, condition is: stationary phase used is silicon-dioxide; Moving phase is that volume ratio is normal hexane/aqueous isopropanol of 85/15; After separation, obtain four kinds of effective constituents of shizandra berry essential oil: deoxyschizandrin (Sin-A), Wuweizisu B (Sin-B), schisandrin (Sol-A), Wuweizichun B (Sol-B).
2. the method for utilizing simulation moving-bed extraction shizandra berry essential oil according to claim 1, it is characterized in that: carry out simulation moving-bed separation, also possesses following condition: tubing string is 8 endowels, specification is internal diameter 21.2mm x length 100 mm, the essential oil concentration of charging is 5025 mg/L, and flow velocity has respectively: it is 10 mL/min that scavenging solution enters discharging; It is 5.0 mL/min that agent pan feeding is washed in punching; Extract discharge port is 3.0 mL/min; Charging feeding mouth is 0.5 mL/min; Extraction Yu thing discharge port is 2.5 mL/min; It is 1.0 mL/min that agent reflux pump is washed in punching; Switching time is between 7.0～8.0 minutes.
3. the method for utilizing simulation moving-bed extraction shizandra berry essential oil according to claim 1, is characterized in that: described shizandra berry essential oil is from shizandra berry, to extract the extraction of essential oil thing obtaining.
4. according to the method for utilizing simulation moving-bed extraction shizandra berry essential oil described in claim 1 or 3, it is characterized in that: described shizandra berry essential oil prepares by the following method: get shizandra berry dry fruit, through soaked, fleshing, dry after, obtain fruit stone, pulverize, carry out supercritical CO
2fluid extraction, extracting pressure is 10～70 MPa, extraction temperature is 35 DEG C～60 DEG C, obtains shizandra berry essential oil.
5. the method for utilizing simulation moving-bed extraction shizandra berry essential oil according to claim 4, is characterized in that: in extraction process, and appropriate ethanol, 0～25% (percent by volume) that the addition of ethanol is carbonic acid gas.
6. according to the method for utilizing simulation moving-bed extraction shizandra berry essential oil described in claim 4 or 5, it is characterized in that: extracting pressure is 35MPa, extraction temperature is 60 DEG C.
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| CN111803411B (en) * | 2020-06-04 | 2023-06-23 | 黑龙江澳利达奈德制药有限公司 | Skin care product containing schisandra chinensis extract and preparation method thereof |
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