CN107096251A - Multistage supercritical fluid rectification separation and continuous flow elution preparation chromatographic separation device - Google Patents
Multistage supercritical fluid rectification separation and continuous flow elution preparation chromatographic separation device Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/40—Selective adsorption, e.g. chromatography characterised by the separation mechanism using supercritical fluid as mobile phase or eluent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The multi-stage supercritical fluid rectification separation and continuous flow elution preparative chromatographic separation device consists of a supercritical fluid rectification separation mechanism and a supercritical continuous flow elution preparative chromatographic separation mechanism, wherein the supercritical fluid rectification separation mechanism consists of three stages of rectification units and has a pressure gradient and a temperature gradient. The invention can ensure that the supercritical fluid rectification is operated and operated under the pressure gradient and the temperature gradient, has wider and more accurate adjustment range on the properties of the supercritical fluid such as solubility, permeability and volatility, and improves the rectification separation effect; the pressure gradient control adjustment is added, so that the defects that the supercritical fluid rectification tower is easy to overflow when the temperature at the bottom is low and the material is easy to agglomerate when the temperature at the top is high, which are caused by temperature adjustment; compared with temperature regulation, pressure regulation has timely response, no lag and easy realization of intelligent control.
Description
Technical field
Chromatographic separation device is prepared the present invention relates to a kind of multi-stage supercritical fluid rectifying separation and continuous stream elution.
Background technology
With the enhancing of people's environmental consciousness, Green Chemistry has become the study hotspot of current many sciemtifec and technical spheres, and
As new technology, new method, the main flow of development of new techniques theory.Supercritical fluid is as material higher than critical pressure and critical
A kind of special state during temperature, the high density and the diffusion coefficient between air-liquid of low viscosity, liquid with gas
Etc. feature, the solubility height, permeability to material are strong, nontoxic, non-ignitable, no chemical corrosivity；Abundance, it is cheap；Only
Phase can just occur by pressure change to change and realize the quick separating with solute, applied to biological medicine, fine chemistry industry
Field, with typical Green Chemistry feature, especially in the extraction and preparation of heat sensitivity target compound, shows wide
And tempting application prospect.
From 1978 in the world First supercritical fluid extraction equipment for the first time in the industrialization of caffeine removing caffeine
After, supercritical fluid extraction, supercritical fluid rectifying, supercritical fluid chromatography application grow up in succession, respectively should
For different separation purposes.The application of supercritical fluid extraction bioactive substance is earliest, and the patent of application is most, for example：
CN93106143.1、CN98113267.7、CN01108503.7、CN01123601.9、CN02138911.X、
CN03113953.1、CN03151456.1、CN200510057385.6、CN200410100584.6、CN200310117437.5、
CN200610083872.4、CN200980101373.5、CN201510148508.0、CN201110301357.X、
CN201510480636.5、CN201510480655.8、CN201610345648.1、CN201610688537.0、
CN201610909805.7, CN201621076358.3, CN20161084625.4 etc., individually disclose qinghaosu, Chinese yam
Active ingredient, olive yellow in saponin, chinaberry element medicinal extract, lycopene oil, pumpkin seeds anti-proliferate factor active material, Chinese medicine Resina draconis
It is active in ketone, carrotene concentrate, vitamin E concentrate, natural medicinal plant active ingredient, bee pollen grease, kenaf seeds
Material, dysmenorrhoea effective component of chinese medicine, tobacco aromaticss, linseed oil, pecan oil, Herba Hyperici Japonici total flavones, rhodioside, shiny-leaved yellowhorn
The supercritical fluid extraction method of seed kernel oil, micro- plan ball algae omega-3 polyunsaturated fatty acids isoreactivity material, supercritical fluid extraction
The purpose taken is to extract target product as fully as possible.
In order to improve the economic benefit of supercritical fluid extraction operation, people have done very on supercritical fluid extraction equipment
Many researchs and improvement, such as：Patent CN99113167.3, CN97220110.6, CN00103059.0, CN200920277420.9,
CN201220267677.8、CN201120146207.1、CN201110051925.5、CN201120055100.6、
CN201110051925.5、CN201510182295.3、CN201420692299.7、CN201410461204.5、
CN201510182295.3, CN201520486893.5, CN201611054608.8, patent CN201420432742.7,
CN201420434179.7、CN201420433968.9、CN201420434231.9、CN201420434474.2、
CN201420442024.8、CN201420443019.9、CN201420443071.4、CN201420442434.2、
CN201420434511.X, CN201620422853.9, CN02228379.X etc. individually disclose various supercritical fluid extractions
Device, such as band expect the combined type extraction equipment, the extracting system with supersonic generator reinforcing, band supercritical fluid hair of hand basket admittedly
The extracting system without high-pressure pump, the extracting system with cold source heat pump unit, double tower extracting system, the horizontal supercritical fluid of raw device
Extraction device, etc., reach quick, energy-conservation, easily section consumption, purpose.
The product composition that supercritical fluid extraction is obtained all is mixture, and particularly natural products composition is more complicated, is
The concentration and purity of object are improved, people have further developed the combination of supercritical fluid extraction and other technologies, example
Such as：Patent CN01805533.8 discloses a kind of supercritical fluid extraction added under cosolvent and liquid chromatography separation knot
The taxol of conjunction and its preparation method of derivative；Patent CN201310410867.X discloses a kind of supercritical fluid extraction
The method that momordica glycoside V is produced with macroporous resin adsorption partition method；Patent CN201210118989.7 discloses a kind of super face
The method that boundary's extraction prepares cured myricinic acid A with silica gel chromatography, the mixture that supercritical fluid extraction is obtained, then enter one
Step is purified with other separation methods, the object of purity needed for obtaining.
For the material of the favorable solubility in supercritical fluid, step can be separated with extract without supercritical fluid
Suddenly, it is sent directly into rectifying column and carries out rectifying separation, plays a part of to concentrate and improve purity.Patent 98111424.5 discloses one kind
The method that supercritical fluid extraction is combined separation wheat embryo oil with rectifying, the material that supercritical fluid extraction is obtained imports essence
In fractional distillation column, wheat-germ oil is separated in the rectifying column of several sections of different holding temperatures to be distributed, and is collected specific cut, is realized dimension life
The concentration of the target components such as plain E.Patent CN0010326.7 discloses a kind of supercritical fluid extraction and concentrated natural vitamin E
Method, the fatty acid ester containing VE that supercritical fluid extraction is obtained, material is imported into rectifying column, material and supercritical fluid
In reverse movement, in the VE concentrate feeds of the continuous collection 50 ~ 60% in rectifying column bottom, the aliphatic acid that purity is more than 99% is isolated from tower top
Ester.Patent 201610134812.4 discloses a kind of supercritical fluid extraction, rectifying, chromatogram preparation facilities, and the device is by changing
Become the switch and path direction of valve to reach supercritical extract, overcritical rectifying, Supercritical fluid chromatography, supercritical extract+rectifying group
Close the individually operated or combination operation of supercritical extract+Supercritical fluid chromatography.These methods are supercritical fluid technique
Applications expanding thinking.
Supercritical fluid chromatography is also developed as a kind of high-purity separation means, patent CN201610564045.0,
CN201510658485.8、CN201510711100.X、CN201380073443.7、CN201310568685.5、
CN201410062862.7、CN200980159732.2、CN200510049524.0、CN200510049491.X、
CN201420390019.7, CN200980159732.2, CN201610121712.8 individually disclose supercritical fluid chromatography skill
Art splits optical isomer, separation and prepares tobacco sequiterpene, purification of carboxylic acids compound, flavone compound, preparation how unsaturated
The method of the monomer of fatty acid ester, patent CN200510049524.0, CN200510049491.X, CN201420390019.7,
CN201511023539.X、CN200980159732.2、CN201410062862.7、CN201480044773.8、
CN201280029719.7, individually disclose supercritical fluid chromatography device.These patents apply supercritical fluid well
The characteristics of chromatographic technique, positive effect is served in the separation of high-purity compound.
Compared with conventional liq, dissolubility, permeability, volatility of supercritical fluid etc. except being strongly depend on temperature,
Pressure is also strongly depend on simultaneously, disclosed supercritical fluid rectifying patent, is the rectifying in a pressure system at present
Tower segmentation insulation forms thermograde, and component dissolubility is correspondingly formed inside rectifying column or the distribution of volatile gradient reaches point
From purpose.Thermograde regulation is depended merely in supercritical fluid rectifying separation, and adjustable extent is limited, using limited；Shooting flow
Body rectifying column bottom temperature easy flash when too low, easy ramming material when tower top temperature is high, does not reach the purpose of rectifying；For major diameter
Rectifying column, tower external heat ecto-entad formation thermograde, easily causes with layer temperature distributing disproportionation in tower, influences separating effect；
For the material that composition is complicated, supercritical fluid rectifying separation is typically up to less than the effect of monomer separation, with other chromatographic processes
With reference to being also difficult to reach industrialization quantity-produced purpose.
The content of the invention
The purpose of the present invention, is to provide for a kind of multi-stage supercritical fluid rectifying separation and continuous stream elution prepares chromatogram point
From device, i.e., the multi-stage supercritical fluid distillation system and supercritical fluid controlled by thermograde and barometric gradient double base is continuous
The separator of stream elution preparing chromatography system coupling, the characteristics of being strongly depend on temperature and pressure using supercritical fluid,
The control system of thermograde and barometric gradient can be formed by being set in rectifier unit, make supercritical fluid rectifying separation controllable
Carried out under the conditions of thermograde and barometric gradient.Influence to increase the influence of barometric gradient on the basis of control separation in thermograde
Control, improves supercritical fluid changes to operating condition in rectification system response promptness and wide area, improves rectifying separation
The controllability of efficiency.The multi-stage supercritical fluid rectifying isolation technics of double base control prepares color with supercritical fluid continuous stream elution
Compose isolation technics coupling, it is possible to use the quick continuous separation function of supercritical fluid rectifying, the material of complexity composition is advance
The simple cut of composition is separated into, recycles the elution of supercritical fluid continuous stream to prepare the fine separation function of chromatogram and further will
The fraction seperation simply constituted is into monomeric substance.Realize and continuously, scale finely separate preparation monomeric substance.
The present invention is achieved in that the multi-stage supercritical fluid rectifying separation and continuous stream elution prepare chromatographic isolation
Device, it is prepared chromatographic fractionation system and constituted by supercritical fluid rectifying piece-rate system and supercritical fluid continuous stream elution, institute
The supercritical fluid rectifying piece-rate system stated is made up of three-level rectification cell, with barometric gradient and thermograde；
First order rectification cell：The inlet end of the capital of first order rectifying column 11 connection first order counterbalance valve 21, first order back pressure
The exit end of valve 21 is connected with the lower inlet of second level rectifying column 12；First order rectifying column post bottom fraction outlets are defeated by fluid
Measuring pump 61b is sent to be connected with end entrance on the first separating still 31；The bottom end outlet of first separating still 31 and the gate out switch valve of cut 1
1 connection；First pressure limiting control valve 41 is connected with the top export of the first separating still 31；Fluid conveys measuring pump 61c imports and faced with super
Boundary's fluid input port connection, fluid conveys post bottom of the measuring pump 61c ports of export by check valve 71c and first order rectifying column 11
Supercritical carbon dioxide fluid entrance is connected；Fluid conveying measuring pump 61d entrances are connected with fluid mechanics input port, fluid conveying
The measuring pump 61d ports of export are connected by check valve 71d with the upper end material inlet of first order rectifying column 11；Fluid conveys measuring pump
61a outlets are connected with the upper end refluxing opening of first order rectifying column 11；The column outer wall of first order rectifying column 11 has heater T1a and T1b；
Second level rectification cell：The capital of second level rectifying column 12 is connected with the inlet end of second level counterbalance valve 22, the second level back of the body
The exit end of pressure valve 22 is connected with the lower inlet of third level rectifying column 13；The bottom fraction outlets of second level rectifying column 12 pass through stream
Body conveying measuring pump 62b is connected with end entrance on the second separating still 32；The bottom end outlet of second separating still 32 successively through switching valve 52,
The feed liquid fluid conveying measuring pump 64a that check valve 72 prepares chromatographic separation device with continuous stream elution is connected, the second separating still 32
Lower end is exported to be connected with fluid conveying measuring pump 61a imports；Second pressure limiting control valve 42 and the top export of the second separating still 32 connect
Connect；Any switching laws between the second separating still 32 is exported to check valve 72, to cut 2, extremely closed of switching valve 52；Fluid conveying meter
Amount pump 62a outlets are connected with the upper end refluxing opening of second level rectifying column 12；The column outer wall of second level rectifying column 12 with heater T2a and
T2b；
Third level rectification cell：The inlet end of the capital of third level rectifying column 13 connection third level counterbalance valve 23, third level back pressure
The exit end of valve 23 is connected with end entrance on the 4th separating still 34；4th pressure limiting control valve 44 goes out with the top of the 4th separating still 34
Mouth connection；The outlet of the lower end of 4th separating still 34 prepares chromatographic isolation dress through switching valve 54, check valve 74 and continuous stream elution successively
The feed liquid fluid conveying measuring pump 64a connections put；Switching valve 54 is exported, extremely in the 4th separating still 34 to check valve 74, to cut 4
Any switching laws between closing；The outlet of the lower end of 4th separating still 34 is conveyed on measuring pump 63a and third level rectifying column 13 by fluid
Hold refluxing opening connection；The lower end fraction outlets of third level rectifying column 13 are conveyed on measuring pump 63b and the 3rd separating still 33 by fluid
End entrance is connected, and the 3rd pressure limiting control valve 43 is connected with the top export of the 3rd separating still 33；The bottom end outlet of 3rd separating still 33 according to
The secondary feed liquid fluid conveying measuring pump 64a for preparing chromatographic separation device with continuous stream elution through switching valve 53, check valve 73 is connected；
Any switching laws between the 3rd separating still 33 is exported to check valve 73, to cut 3, extremely closed of switching valve 53；3rd separating still 33
Lower end is exported to be connected with fluid conveying measuring pump 62a entrances, and the column outer wall of third level rectifying column 13 has heater T3a and T3b；
Described overcritical continuous stream elution prepares chromatographic fractionation system and is：
The supercritical fluid eluent conveying measuring pump 64b ports of export are connected with the arrival end of IV area's chromatographic column 84；IV area's chromatographic column
84 port of export is connected with the arrival end of III area's chromatographic column 83；The port of export of IV area's chromatographic column 84 is conveyed with the fluid of component 1 and measured
The arrival end of pump 65 is connected；The outlet of the fluid of component 1 conveying measuring pump 65 is connected with the entrance of the upper end of 1 fluid separating still of component 35, group
The top of 1 fluid separating still 35 is divided to be connected with the 5th pressure limiting control valve 45, the bottom connection fluid discharge outlet switch valve 3 of component 1；IIIth area
The port of export of chromatographic column 83 is connected with the arrival end of II area's chromatographic column 82；Connect the feed liquid fluid conveying metering of three-level rectification cell
The pump 64a port of export is connected by check valve 75 with the arrival end of II area's chromatographic column 82；The port of export of II area's chromatographic column 82 and Ith area
The arrival end of chromatographic column 81 is connected, and the port of export of II area's chromatographic column 82 also conveys the entrance point company of measuring pump 66 with the fluid of component 2
Connect；The fluid of the component 2 conveying port of export of measuring pump 66 is connected with the entrance of the upper end of 2 fluid separating still of component 36；The fluid of component 2 is separated
The top of kettle 36 is connected with the 6th pressure limiting control valve 46, the bottom of 2 fluid separating still of component 36 and the fluid discharge outlet switch valve 2 of component 2
Connection；The port of export of I area's chromatographic column 81 is connected with check valve 76, and check valve 76 is connected with the arrival end of IV area's chromatographic column 84.
Fluid of the present invention conveys measuring pump（61a、61b、61c、61d、62a、62b、63a、63b、64a、64b）、
Counterbalance valve（21、22、23）, pressure limiting control valve（41、42、43、44、45、46）, switching valve（52、53、54）And rectifying column（11、
12、13）Separating still（31、32、33、34、35、36）Temperature sensor, the pressure sensor of interior setting are connected with computer respectively.
First order counterbalance valve 21 of the present invention, second level counterbalance valve 22, third level counterbalance valve 23 control respectively
One-level rectifying column 11, second level rectifying column 12, the pressure in the post of third level rectifying column 13 to lower and upper distribution gradient, to lower and
Upper pressure is lower.
First order rectifying column 11 of the present invention, second level rectifying column 12, the heater of the column outer wall of third level rectifying 13
Thermal source is preferably radiant heating thermal source or Heated by Far-Infrared Radiation thermal source.
First order rectifying column 11 of the present invention, second level rectifying column 12, the column outer wall of third level rectifying column 13 heating temperature
Spend distribution gradient.
First, second and third grade of rectifying column of the present invention（11、12、13）It is packed column；Filling out in described packed column
Material specific surface area is 400 ~ 4000m2/m3, porosity be 0.60 ~ 0.95 solid packing, preferably specific surface area be 1000 ~
3000m2/m3, porosity is 0.80 ~ 0.90 solid packing.
Arbitrary extension is more stages rectification cell to supercritical fluid rectifying piece-rate system of the present invention according to actual needs
System.
It is a kind of continuous feed, the separation of continuous discharge preparation chromatogram that continuous stream elution of the present invention, which prepares chromatogram,.
Cut 2 of the present invention, cut 3, cut 4 are separated again, are added as needed on continuous stream elution and are prepared chromatogram
Device quantity, makes each cut while being separated again.
Ith area of the present invention chromatographic column 81, II area's chromatographic column 82, III area's chromatographic column 83, IV area's chromatographic column 84 according to point
Increase post number from needing to connect.
Ith area of the present invention chromatographic column 81, II area's chromatographic column 82, III area's chromatographic column 83, IV area's chromatographic column 84 are fillings
Chromatographic column or integral post or bundling capillary pipe post.
The beneficial effects of the invention are as follows it can be such that supercritical fluid rectifying is grasped simultaneously under barometric gradient and thermograde
Run, it is wider also more accurate to Supercritical Fluids such as dissolubility, permeability, volatile adjustable range, improve rectifying
Separating effect；Increase barometric gradient to control to adjust, the supercritical fluid rectifying column bottom brought by temperature adjustment merely can be avoided
The disadvantage of easy ramming material when easy flash, tower top temperature are high when temperature is low；Pressure is adjusted compared with temperature adjustment, and response is timely,
Without delayed, intelligentized control method is easily realized.Using radiant type mode of heating, it will not be returned in same reflux layer formation thermograde
Fluid layer is without temperature difference, and rectifying separation is more efficient；Multistage supercritical fluid rectifying can cut rectification layer thin, and rectifying separation evaporates
It is grouped into simple, greatly reduces the burden that follow-up supercritical fluid continuous stream prepares chromatogram；Washed with supercritical fluid continuous stream
The de- chromatogram for preparing is combined, and can continuously, scale separate preparation thermal sensitivity bioactive substance monomer, it is easy to form work
Industry metaplasia is produced.
Brief description of the drawings
Fig. 1 is structural representation of the invention.
Embodiment
1 the present invention is described in further detail with embodiment below in conjunction with the accompanying drawings.
Multi-stage supercritical fluid rectifying separation and continuous stream elution of the present invention prepare chromatographic separation device, and it is separated
Process comprises the following steps：
1st, allow all fluid delivery pumps, switch valve, switching valve to be closed first, open all pressure limiting control valves and
Back pressure control valve 21,22.
2nd, open fluid and convey measuring pump 61c by supercritical fluid from the lower inlet of first order rectifying column 11 is pumped into rectifying column,
And it is full of after the first order, the second level, third level rectifying column, regulation counterbalance valve 23 to back pressure is more than 80MPa.3rd, first is opened
Level rectifying column 11, second level rectifying column 12, the heater power source of third level rectifying column 13, set heating-up temperature to predetermined value, make
Temperature puts in order distribution gradient by T1a, T1b, T2a, T2b, T3a, T3b, and it is constant to temperature to be incubated a period of time.
4th, the first order, the second level, third level counterbalance valve 21,22,23 to certain value are adjusted respectively and do not make pressure from bottom to up not
Disconnected reduction distribution gradient, and reach stable state；Regulation pressure limiting control valve 41,42,43,44 is opened to certain value；Open stream
Body conveys measuring pump 61d, by material from the upper end entrance of first order rectifying column 11 is pumped into rectifying column, allows supercritical fluid and thing
Material in first order rectifying column 11, second level rectifying column 12, third level rectifying column 13 with different pressure, temperature conditionss under link
Rectifying is flowed back, and backflow is exchanged to stable state.
5th, fluid conveying measuring pump 61b, 62b, 63b are opened from bottom to up, take cut 1, cut 2, cut 3, the inspection of the sample of cut 4
Survey, fluid is adjusted on demand and conveys measuring pump 61a, 62a, 63a to certain reflux ratio, reach rectifying backflow steady.
6th, according to the composition and yield of the cut 1 of detection feedback, pressure and the fluid of fine setting first order counterbalance valve 21 are conveyed
Measuring pump 61a flow, allows into the material stream in first order rectifying column 11 with supercritical fluid in first order pressure and temperature
Under the conditions of fully after exchange equilibrium, heavy constituent is collected in the first separating still 31 by regulation fluid conveying measuring pump 61b flow,
The first pressure limiting control valve 41 is finely tuned to certain value, heavy constituent is separated out after separation, discharged by switch valve 1, collects the cut 1 obtained
For heavy constituent.
7th, according to the composition and yield of the cut 2 of detection feedback, the pressure and fluid for finely tuning second level counterbalance valve 22 are conveyed
Measuring pump 62a flow, allows the lighter component into second level rectifying column 12 to continue back under the conditions of the pressure and temperature of the second level
Stream is reached after balance, opens fluid conveying measuring pump 62b and light component is collected in the second separating still 32, finely tune the second pressure limiting control
Valve 42 processed obtains cut 2 to certain value（Light component）.
8th, the composition result detected according to cut 2 is judged, will switching if cut 2 needs to be further separated
Valve 52 is set to the second separating still 32 and is in connected state with feed liquid fluid conveying measuring pump 64a entrances, opens feed liquid fluid defeated
Send measuring pump 64a to send into cut 2 in continuous stream elution preparing chromatography system to be further separated；Further divide if need not do
From switching valve 52 then be set into the second separating still 32 collecting outlet with cut 2 to be in connected state, according to the second separating still 32
The cut amount batch (-type) discharge of collection, it is light component to collect the cut 2 obtained.
9th, according to the composition and yield of the cut 3 of detection feedback, pressure and the fluid of fine setting third level counterbalance valve 23 are conveyed
Measuring pump 63a flow, allow into the more light component in third level rectifying column 13 under the conditions of the pressure and temperature of the third level after
Continuous backflow reached after balance, is opened fluid and is conveyed measuring pump 63b by lighter Fraction collection in the 3rd separating still 33, fine setting the
Three pressure limiting control valves 43 obtain cut 3 to certain value（More light component）.
10th, the composition result detected according to cut 3 is judged, will switching if cut 3 needs to be further separated
Valve 53 is set to the 3rd separating still 33 and is in connected state with feed liquid fluid conveying measuring pump 64a entrances, opens feed liquid fluid defeated
Send measuring pump 64a to send into cut 3 in continuous stream elution preparing chromatography system to be further separated；Further divide if need not do
From switching valve 53 then be set into the 3rd separating still 33 collecting outlet with cut 3 to be in connected state, according to the 3rd separating still 33
The cut amount batch (-type) discharge of collection, it is more light component to collect the cut 3 obtained.
11st, feed liquid stream is constituted in the 4th separating still 34 of detection, if the cut 4 in the 4th separating still 34 needs further to divide
From switching valve 54 then be set into the 4th separating still 34 conveying measuring pump 64a entrances with feed liquid fluid to be in connected state, will evaporate
Points 4, which are conveyed into continuous stream elution, prepares in chromatographic fractionation system and is further separated., will if cut 4 is without further separating
Switching valve 54 is set to the 4th separating still 34 and cut 4 collects outlet and is in connected state, is collected according to the 4th separating still 34
Cut amount batch (-type) is discharged, and it is most light component to collect the cut 4 obtained.
12nd, supercritical fluid eluent conveying measuring pump 64b is opened, supercritical fluid eluent is delivered to IV area's chromatogram
The entrance of post 84, and it is sequentially sent to IV area's chromatographic column 84, III area's chromatographic column 83, II area's chromatographic column 82, I area's chromatographic column 81；Faced with super
Boundary's fluid driven discharges bubble that may be remaining in all pipelines and chromatographic column, is conveyed after after system balancing, opening feed liquid fluid
Measuring pump 64a, it would be desirable to the cut 2 further separated（Or cut 3, or cut 4）It is pumped into from the entrance of II area's chromatographic column 82；Evaporate
Divide 2（Or cut 3, or cut 4）In each component brought into II area's chromatographic column 82, I area's chromatographic column 81, IV successively by supercritical fluid
Separated in the area's chromatographic column 83 of area's chromatographic column 84 and III, each component with different retention times will be in chromatographic column filler
Gradually be separated distribution in II chromatographic column 82, I chromatographic column 81, IV chromatographic column 84, III area's chromatographic column 83, adjustment control feed liquid fluid
（Cut）Flow velocity, flow and the column temperature being pumped into supercritical fluid are to optimal released state.
13rd, continuous operation to each component be distributed in each chromatographic column it is constant after, unlatching is arranged at II area's chromatographic column 82 and Ith area
The fluid of component 2 conveying measuring pump 66 between chromatographic column 81, continuously pumps out the fluid of component 2（Strong retained fraction）And collect
In the 6th separating still 36, the fluid of component 2 is exported from switch valve 2, and the component obtained after further gas-liquid separation is strong reservation
Component；The fluid of the component 1 conveying measuring pump 65 being arranged between IV area's chromatographic column 84 and III area's chromatographic column 83 is opened, successively
Ground pumps out the fluid of component 1（Weak retained fraction）And be collected in the 5th separating still 35, the fluid of component 1 is exported from switch valve 3, through entering
The component obtained after one step gas-liquid separation is weak retained fraction；According to the strong and weak of the retention time of target compound, it can distinguish
Collected from the fluid issuing of component 1 and the fluid issuing of component 2 and obtain required pure component.
Dotted arrow in Fig. 1 represents the moving direction of switching port.
In Fig. 1：1st, the gate out switch valve of cut 1；2nd, the fluid issuing switch valve of component 2；3rd, the fluid issuing switch valve of component 1；
11st, first order rectifying column；12nd, second level rectifying column；13rd, third level rectifying column；21st, first order counterbalance valve；22nd, second level back pressure
Valve；23rd, third level counterbalance valve；31st, the first separating still；32nd, the second separating still；33rd, the 3rd separating still；34th, the 4th separating still；
35th, the fluid separating still of component 1；36th, the fluid separating still of component 2；41st, the first pressure limiting control valve；42nd, the second pressure limiting control valve；43、
3rd pressure limiting control valve；44th, the 4th pressure limiting control valve；45th, the 5th pressure limiting control valve；46th, the 6th pressure limiting control valve；52、53、
54th, switching valve；61a, 61b, 61c, 61d, 62a, 62b, 63a, 63b, fluid conveying measuring pump；64a, the conveying of feed liquid cut fluid
Measuring pump；64b, supercritical fluid eluent conveying measuring pump；65th, the fluid of component 1 conveying measuring pump；66th, the fluid of component 2 is conveyed
Measuring pump；71c, 71d, 72,73,74,75,76, check valve；81st, I area's chromatographic column；82nd, II area's chromatographic column；83rd, III area's chromatogram
Post；84th, IV area's chromatographic column；T1a, T1b, first order rectifying column outer wall heater；T2a, T2b, the heating of second level rectifying column outer wall
Device；T3a, T3b, third level rectifying column outer wall heater.
Claims (10)
1. multi-stage supercritical fluid rectifying separation and continuous stream elution prepare chromatographic separation device, it is by supercritical fluid rectifying point
Chromatographic fractionation system composition is prepared from system and overcritical continuous stream elution, it is characterized in that：Described supercritical fluid rectifying point
It is made up of from system three-level rectification cell, with barometric gradient and thermograde；
First order rectification cell：The inlet end of the capital of first order rectifying column 11 connection first order counterbalance valve 21, first order back pressure
The exit end of valve 21 is connected with the lower inlet of second level rectifying column 12；First order rectifying column post bottom fraction outlets are defeated by fluid
Measuring pump 61b is sent to be connected with end entrance on the first separating still 31；The bottom end outlet of first separating still 31 and the gate out switch valve of cut 1
1 connection；First pressure limiting control valve 41 is connected with the top export of the first separating still 31；Fluid conveys measuring pump 61c imports and faced with super
Boundary's fluid input port connection, fluid conveys post bottom of the measuring pump 61c ports of export by check valve 71c and first order rectifying column 11
Supercritical carbon dioxide fluid entrance is connected；Fluid conveying measuring pump 61d entrances are connected with fluid mechanics input port, fluid conveying
The measuring pump 61d ports of export are connected by check valve 71d with the upper end material inlet of first order rectifying column 11；Fluid conveys measuring pump
61a outlets are connected with the upper end refluxing opening of first order rectifying column 11；The column outer wall of first order rectifying column 11 has heater T1a and T1b；
Second level rectification cell：The capital of second level rectifying column 12 is connected with the inlet end of second level counterbalance valve 22, the second level back of the body
The exit end of pressure valve 22 is connected with the lower inlet of third level rectifying column 13；The bottom fraction outlets of second level rectifying column 12 pass through stream
Body conveying measuring pump 62b is connected with end entrance on the second separating still 32；The bottom end outlet of second separating still 32 successively through switching valve 52,
The feed liquid fluid conveying measuring pump 64a that check valve 72 prepares chromatographic separation device with continuous stream elution is connected, the second separating still 32
Lower end is exported to be connected with fluid conveying measuring pump 61a entrances；Second pressure limiting control valve 42 and the top export of the second separating still 32 connect
Connect；Any switching laws between the second separating still 32 is exported to check valve 72, to cut 2, extremely closed of switching valve 52；Fluid conveying meter
Amount pump 62a outlets are connected with the upper end refluxing opening of second level rectifying column 12；The column outer wall of second level rectifying column 12 with heater T2a and
T2b；
Third level rectification cell：The inlet end of the capital of third level rectifying column 13 connection third level counterbalance valve 23, third level back pressure
The exit end of valve 23 is connected with end entrance on the 4th separating still 34；4th pressure limiting control valve 44 goes out with the top of the 4th separating still 34
Mouth connection；The outlet of the lower end of 4th separating still 34 prepares chromatographic isolation dress through switching valve 54, check valve 74 and continuous stream elution successively
The feed liquid fluid conveying measuring pump 64a connections put；Switching valve 54 is exported, extremely in the 4th separating still 34 to check valve 74, to cut 4
Any switching laws between closing；The outlet of the lower end of 4th separating still 34 is conveyed on measuring pump 63a and third level rectifying column 13 by fluid
Hold refluxing opening connection；The lower end fraction outlets of third level rectifying column 13 are conveyed on measuring pump 63b and the 3rd separating still 33 by fluid
End entrance is connected, and the supercritical fluid outlet that the 3rd pressure limiting control valve 43 gasifies with the top of the 3rd separating still 33 is connected；3rd
The bottom end outlet of separating still 33 prepares the feed liquid fluid of chromatographic separation device through switching valve 53, check valve 73 with continuous stream elution successively
Convey measuring pump 64a connections；Switching valve 53 is any between the 3rd separating still 33 is exported to check valve 73, to cut 3, extremely closed
Switching；The lower end of 3rd separating still 33 is exported to be connected with fluid conveying measuring pump 62a entrances, and the column outer wall of third level rectifying column 13 has
Heater T3a and T3b；
Described overcritical continuous stream elution prepares chromatographic fractionation system and is：
The supercritical fluid eluent conveying measuring pump 64b ports of export are connected with the arrival end of IV area's chromatographic column 84；IV area's chromatographic column
84 port of export is connected with the arrival end of III area's chromatographic column 83；The port of export of IV area's chromatographic column 84 is conveyed with the fluid of component 1 and measured
The arrival end of pump 65 is connected；The outlet of the fluid of component 1 conveying measuring pump 65 is connected with the entrance of the upper end of 1 fluid separating still of component 35, group
The top of 1 fluid separating still 35 is divided to be connected with the 5th pressure limiting control valve 45, the bottom connection fluid discharge outlet switch valve 3 of component 1；IIIth area
The port of export of chromatographic column 83 is connected with the arrival end of II area's chromatographic column 82；Connect the feed liquid fluid conveying metering of three-level rectification cell
The pump 64a port of export is connected by check valve 75 with the arrival end of II area's chromatographic column 82；The port of export of II area's chromatographic column 82 and Ith area
The arrival end of chromatographic column 81 is connected, and the port of export of II area's chromatographic column 82 also conveys the entrance point company of measuring pump 66 with the fluid of component 2
Connect；The fluid of the component 2 conveying port of export of measuring pump 66 is connected with the entrance of the upper end of 2 fluid separating still of component 36；The fluid of component 2 is separated
The top of kettle 36 is connected with the 6th pressure limiting control valve 46, the bottom of 2 fluid separating still of component 36 and the fluid discharge outlet switch valve 2 of component 2
Connection；The port of export of I area's chromatographic column 81 is connected with check valve 76, and check valve 76 is connected with the arrival end of IV area's chromatographic column 84.
2. multi-stage supercritical fluid rectifying separation and continuous stream elution prepare chromatographic separation device according to claim 1, its
It is characterized in：Described fluid conveying measuring pump（61a、61b、61c、61d、62a、62b、63a、63b、64a、64b）, counterbalance valve
（21、22、23）, pressure limiting control valve（41、42、43、44、45、46）, switching valve（52、53、54）And rectifying column（11、12、13）Point
From kettle（31、32、33、34、35、36）Temperature sensor, the pressure sensor of interior setting are connected with computer respectively.
3. multi-stage supercritical fluid rectifying separation and continuous stream elution prepare chromatographic separation device according to claim 1, its
It is characterized in：The first order rectifying that described first order counterbalance valve 21, second level counterbalance valve 22, third level counterbalance valve 23 are controlled respectively
Post 11, second level rectifying column 12, the pressure in the post of third level rectifying column 13 are got over to lower and upper distribution gradient to lower and upper pressure
Come lower.
4. multi-stage supercritical fluid rectifying separation and continuous stream elution prepare chromatographic separation device according to claim 1, its
It is characterized in：Described first order rectifying column 11, second level rectifying column 12, the column outer wall of third level rectifying 13 heater thermal source it is preferred
For radiant heating thermal source or Heated by Far-Infrared Radiation thermal source；Described first order rectifying column 11, second level rectifying column 12, the third level
The column outer wall heating-up temperature distribution gradient of rectifying column 13.
5. multi-stage supercritical fluid rectifying separation and continuous stream elution prepare chromatographic separation device according to claim 1, its
It is characterized in：First, second and third grade of rectifying column（11、12、13）It is packed column；Packing specific area in described packed column is
400~4000m2/m3, porosity be 0.60 ~ 0.95 solid packing, preferably specific surface area be 1000 ~ 3000m2/m3, porosity
For 0.80 ~ 0.90 solid packing.
6. multi-stage supercritical fluid rectifying separation and continuous stream elution prepare chromatographic separation device according to claim 1, its
It is characterized in：Supercritical fluid distillation system expands to more stages rectification cell system according to actual needs.
7. multi-stage supercritical fluid rectifying separation and continuous stream elution prepare chromatographic separation device according to claim 1, its
It is characterized in：It is a kind of continuous feed, the separation of continuous discharge preparation chromatogram that described continuous stream elution, which prepares chromatogram,.
8. multi-stage supercritical fluid rectifying separation and continuous stream elution prepare chromatographic separation device according to claim 1, its
It is characterized in：Described cut 2, cut 3, cut 4 are separated again, are added as needed on continuous stream elution and are prepared chromatogram arrangement number
Amount, makes each cut while being separated again.
9. multi-stage supercritical fluid rectifying separation and continuous stream elution prepare chromatographic separation device according to claim 1, its
It is characterized in：Described I area's chromatographic column 81, II area's chromatographic column 82, III area's chromatographic column 83, IV area's chromatographic column 84 need string according to separation
Connection increase post number.
10. multi-stage supercritical fluid rectifying separation and continuous stream elution prepare chromatographic separation device according to claim 1, its
It is characterized in：Described I area's chromatographic column 81, II area's chromatographic column 82, III area's chromatographic column 83, IV area's chromatographic column 84 be chromatography column or
Integral post or bundling capillary pipe post.
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| CN111372895A (en) * | 2017-09-05 | 2020-07-03 | 森馨自然提取有限公司 | Purification process using adsorbent and pressurized low polarity water extraction |
| CN111887329A (en) * | 2020-08-12 | 2020-11-06 | 广州市浩立生物科技有限公司 | Method for efficiently extracting caffeine in deep processing of coffee |
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| CN1528487A (en) * | 2003-10-10 | 2004-09-15 | 大连理工大学 | Basic process flow of semicontinuous supercritical fluid extraction |
| CN203447813U (en) * | 2013-07-22 | 2014-02-26 | 曹庸 | Multifunctional continuous phase-changing extraction device |
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| CN1253951A (en) * | 1999-11-19 | 2000-05-24 | 上海交通大学 | Supercritical fluid extraction process for extracting concentrated natural vitamin E |
| CN1528487A (en) * | 2003-10-10 | 2004-09-15 | 大连理工大学 | Basic process flow of semicontinuous supercritical fluid extraction |
| CN203447813U (en) * | 2013-07-22 | 2014-02-26 | 曹庸 | Multifunctional continuous phase-changing extraction device |
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