CN107163618A - Supercritical fluid column chromatography prepares the method and device of high-purity capsochrome Capsaicin - Google Patents
Supercritical fluid column chromatography prepares the method and device of high-purity capsochrome Capsaicin Download PDFInfo
- Publication number
- CN107163618A CN107163618A CN201710445174.2A CN201710445174A CN107163618A CN 107163618 A CN107163618 A CN 107163618A CN 201710445174 A CN201710445174 A CN 201710445174A CN 107163618 A CN107163618 A CN 107163618A
- Authority
- CN
- China
- Prior art keywords
- capsaicin
- supercritical fluid
- capsochrome
- carbon dioxide
- capsorubin
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
-
- 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
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/17—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/18—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/17—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/20—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/62—Three oxygen atoms, e.g. ascorbic acid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
Supercritical fluid pillar layer separation prepares the method and apparatus of high-purity capsochrome Capsaicin, and its step includes：Supercritical carbon dioxide or modifying supercritical carbon dioxide in charging tank with after capsicum oleoresin or the miscible filtering of their saponification resultant, separation is adsorbed and is desorbed by the preparative chromatographic column of filled solid sorbent particles, according to the signal of detector, the eluent containing different solutes is collected to corresponding collector, then solute component is separated with carbon dioxide equal solvent in the separator, tail gas is compressed into liquid after dust removal by filtration, the de- liquid of condensation and absorption column purification and returns to storage tank recycling.This technique can prepare extremely low molten residual or even without the high sterling of the Capsaicin such as the high sterling of the pigment such as molten residual capsorubin, capsorubin, bata-carotene, β kryptoxanthins, luteole, capsorubin ester, capsorubin ester, kryptoxanthin ester and nordihydrocapsaicin, capsaicine, dihydrocapsaicin.
Description
Technical field
Chromatographic technique is prepared the present invention relates to supercritical fluid, more particularly to is prepared using supercritical fluid pillar layer separation
The technique of high-purity natural product, belongs to natural products purifying and preparation field.
Background technology
Supercritical fluid column chromatography, is also supercritical fluid column chromatography, is the solia particle using supercritical fluid as mobile phase
Adsorbent is the chromatographic column isolation technics of stationary phase.Supercritical fluid have similar liquids density and similar organic solvent it is molten
Agent power, and diffusion coefficient is higher than 1-2 order of magnitude of liquid.Near critical-temperature, the minor variations of pressure can cause density
Large change.And density influences the solvability of supercritical fluid with being changed significantly, therefore pass through and change influence density
Technological parameter (mainly pressure and temperature) relatively easily can prepare material of different nature by chromatography separation.Currently,
It is supercritical carbon dioxide to study most ripe supercritical medium.
Capsicum oleoresin be it is a kind of extracted from capsicum be made up of capsochrome, Capsaicin, vitamin, polyphenol etc.
Mixture.Wherein pigment composition includes double hydroxyl carotenoid such as capsorubin, capsorubin, luteole, violaxanthin
The mono fatty acid ester and double acid ester of monomer and its a variety of straight chain saturations and unrighted acid；The monohydroxy such as kryptoxanthin class is recklessly
The mono fatty acid ester of radish element monomer and its a variety of straight chain saturations and unrighted acid；And beta carotene etc..Capsaicin composition
Including 12 kinds of 9-11 carbon branched chain fatty acid vanilla amide compounds, i.e. capsaicine, dihydrocapsaicin, nordihydrocapsaicin, high by two
Hydrogen capsaicine etc..In addition, the also ascorbic acid containing high level in capsicum oleoresin.
Because the polarity spectrum of capsochrome and Capsaicin is larger, and two class components show to the maximum absorption wavelength of ultraviolet
Write different, respectively in 450-480nm and 260-290nm scopes, therefore quantitatively divide in high performance liquid chromatography and Supercritical fluid chromatography
When analysing capsochrome and Capsaicin, detected respectively usually using different chromatographic conditions.In Overcritical prepared chromatographic, it is possible to use
This nature difference, in regular hour node, pressure and the inspection of polarity and overcritical mobile phase by regulating and controlling eluant, eluent
The Detection wavelength of device is surveyed, two class materials are disposably separated step by step.And the polarity of ascorbic acid is compared with the serial chemical combination of capsaicine
Thing is higher, and maximum absorption wavelength is also different from capsochrome, Capsaicin, typically in 245nm or so.By the acidity for adjusting mobile phase
It can be separated from series capsicum alkali.
Either common organic solvent extractionprocess, or supercritical extraction process, can not all produce no solvent residue
Capsochrome or Capsaicin product, it is more difficult to obtain capsorubin, capsorubin, capsaicine, dihydrocapsaicin, drop dihydro capsicum
The sterling of the single compounds such as alkali.Although and can accomplish that fine separation is each using organic solvent for the high performance liquid chromatography of mobile phase
Kind of pigment and Capsaicin compound, it can be difficult to be fully solved problem of solvent residual, and deposit and use inflammable and explosive solvent under high pressure
Excessive risk problem.
Supercritical carbon dioxide can be used as most of nonpolar, middle polarity the molecules of flowing phase separation.Overcritical dioxy
Change carbon, which need to only reduce pressure, can be converted into gas and be kept completely separate with solute, without problem of solvent residual.So, overcritical two
Carbonoxide prepares chromatogram has its unique and irreplaceable advantage in fields such as food, pharmaceutical raw materials.And carbon dioxide is nontoxic
Harmless, incombustible, plant-scale supercritical carbon dioxide preparing chromatography system has organic solvent to be the efficient of mobile phase
The unrivaled security of liquid phantom preparing chromatogram.
Using the medium above polarity such as the similar capsaicine of the dynamic mutually elution separation of stream of supercritical carbon dioxide, ascorbic acid
, it is necessary to which adding polar solvent as polar modifier of mobile phase or acid-base property compound improves flowing as additive during compound
The eluting power of highly polar material in relatively.Methanol, ethanol are to use most polarity modifiers.When separating ascorbic acid,
In addition to methanol polar solvent, the inorganic acidic materials such as phosphoric acid can also be added to accelerate elution process.Many analysis skills
Art research shows that overcritical analysis chromatogram is analyzing capsaicine, dihydrocapsaicin isopolarity Capsaicin or capsicum in quantifying capsicum
It is more efficient all than high performance liquid chromatography in terms of the low polarity pigment such as red pigment and its ester, capsorubin and its ester.
There is researcher to invent some incomplete supercritical carbon dioxide preparing chromatography systems, but in these inventions
Mentioned preparing chromatography system is without reference to tail gas recycle, also without crucial accurate separated collection system, the work used
Skill technical scheme is not suitable for preparing the high-purity Capsaicin pigment product involved by this patent from capsicum or pepper extract.
Patent document CN201010591082.3 discloses a kind of Supercritical fluid chromatography separation dress of orange oil element in sweet shaddock oil
Put and its method.The device is exclusively used in the separation from sweet shaddock oil and prepares orange oil element, because being with supercritical carbon dioxide only
Working medium, is not suitable for compound highly polar in the similar capsaicine of separation, ascorbic acid etc..The device is not provided with tail gas recycle and followed
Loop system, is not suitable for commercial Application.
Patent document CN201310289339.3 discloses the super of oxygenatedchemicals in a kind of separation concentration tangerine oil and faced
Boundary's extraction-chromatography process integration.The technique is same only with supercritical carbon dioxide as working medium, is also not suitable for separating polar higher
The compound such as capsaicine, dihydrocapsaicin.Due to the limitation of technique, operation every time is required for opening equipment paraffin removal, it is impossible to
Realize continuous operation.The device is not provided with the tail gas recycle circulatory system as other invented, unfavorable to environment, no
It is adapted to commercial Application.
Patent document CN201610121712.8 discloses a kind of supercritical fluid chromatograph with multiple-way valve and for making
Standby isolation and purification method.Switched by the switch of multiple-way valve so that blending ingredients to be separated pass through the pre-separation of pre-separation post, caught more
Clustered column trapping, the clastotype of how main separation post separation are separated.This design cycle is excessively complicated, it is not easy to realize scale
Change operation, the technique also has no the separation and recovery equipment and flow for setting carbon dioxide tail gas and solvent composition.And the device
Without accurate sterling separation and recovery system, separation analysis is suitable only for, and high-purity capsochrome, Capsaicin compound can not be realized
Separation prepare.
At present, there is not yet separation prepares high-purity capsaicin, dihydrocapsaicin, capsorubin, capsorubin, kryptoxanthin
Overcritical prepared chromatographic technology report.Also have no and collect piece-rate system and the tail gas recycle circulatory system with commercial viability
Supercritical fluid chromatography piece-rate system related invention.Device of the present invention, is both to be used to realize that chili ingredient is divided entirely
From supercritical fluid column chromatography preparation system, be also the overcritical post color that the feasible separation of industry prepares high-purity pigment, Capsaicin
Spectra system.
The content of the invention
It is used for the invention discloses one kind from thick capsicum oleoresin, or the capsicum oleoresin Jing Guo initial gross separation, or they
Saponified middle separation prepare high-purity capsorubin, capsorubin ester, capsorubin, capsorubin ester, β-carrot
The supercritical fluid chromatography method and apparatus of the native compounds such as element, kryptoxanthin, kryptoxanthin ester, capsaicine, dihydrocapsaicin.Its
Step includes：By the liquid carbon dioxide in storage tank by passing through high-pressure pump respectively with polarity modifier after pump head cooler precooling
It is passed through after premixing according to a certain percentage in interval charging tank, heating pressurization reaches specific supercriticality.Supercritical fluid exists
It is miscible with capsicum oleoresin or its saponification resultant in charging tank, chromatographed after filtering by the preparative of filled solid sorbent particles
Post is adsorbed and is desorbed separation.According to the concentration signal of detector, singly separate target components at each or each group specific
Target components are flowed completely through controls supercritical fluid directly to pass to detector from the bypass before charging tank at once after detector, by
Through being loaded into the corresponding collector of collection system by the corresponding simple target component of detector or the combination of specific target components,
Then target solute component is separated with carbon dioxide equal solvent in the separator.Tail gas by dust removal by filtration, the de- liquid of condensation and
Liquid is compressed into after absorption column purification and returns to storage tank recycling.
This method can prepare extremely low molten residual or even without molten residual capsorubin, capsorubin, beta carotene, β-hidden Huang
The high sterling of the pigment such as matter, capsorubin ester, capsorubin ester, kryptoxanthin ester, nordihydrocapsaicin, capsaicine, dihydro capsicum
The high sterling of the Capsaicins such as alkali, and other chili ingredients such as ascorbic acid high sterling.
The supercritical fluid column chromatography of the present invention, which prepares capsochrome Capsaicin technique and device characteristic, is：
Device contains the one or more groups of charging systems fed for interval.When interval charging tank reaches more than two,
Interval charging-continuous separating operation pattern without shutting down can be used, by the rotation interval between different charging tanks plus
Material, maintains supercritical fluid persistent loop mass transfer, and separation prepares target product.
Charging tank operating pressure is 8-100MPa, chuck heating-up temperature room temperature to 90 DEG C it is controllable, sample cell is detachable, two
There is the sealing of 0 type circle, 1-200 μm of aperture sieve plate is capped, for retaining solid impurity and insoluble matter in raw material.
Device contains many logical detectors, and detector is constructively at least up to three-dimensional intercommunication, so as to can be directly from charging tank
Preceding supercritical fluid passage bypass imports the supercritical fluid without solute to detector, is leading to the shooting flow of chromatographic column
Body stops not being collected into the target fraction for flowing through detector eluted impurely controllably suitably in the state of flowing
Collector in.
Detector can be containing more than one group of ultra-violet absorption spectrum sample cell, if necessary using the purple of multigroup different wave length
Outside line monitors the separation situation of the different type material such as capsaicine, capsochrome simultaneously.Detector can also be photodiode
Array detector (PAD or DAD), differential refraction detector (RID), EISD (ELSD), fluorescence detector
(FLD) in one or more or used simultaneously with UV detectors.
Using supercritical carbon dioxide fluid or based on supercritical carbon dioxide, a certain proportion of polarity modifier is added
Fluid-mixing be eluant, eluent.Polarity modifier can be water, methanol, ethanol, isopropanol, ethyl acetate, n-hexane, acetone,
Acetonitrile, tetrahydrofuran, ethylene glycol monomethyl ether, butyl glycol ether, petroleum ether, dichloromethane, chloroform, carbon tetrachloride, can also
It is their mixture.As needed, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, ammoniacal liquor, isopropylamine, triethanolamine can be added
Improve eluting power of the CO 2 supercritical mobile phase to highly polar soda acid compound Deng acid-base property compound.
Adsorbent stationary phase is the silica gel particle of silica gel particle or surface chemistry β-cyclodextrin used in device, also may be used
To be alundum (Al2O3), activated carbon, magnesium silicate, polyamide, diatomaceous earth particle, or they press the mixture of certain ratio.Such as
It is necessary, the chromatographic column that can connect same or different strengthens the separation to a certain product.As needed, once fail to separate
The component combination come can continue to be passed through next stage chromatography column progress secondary separation, make after can also directly collecting separation mobile phase
For product.
The piece-rate system of device performs operation according to the signal of detector.Detector is flowed completely through detecting target product
The mobile phase for not carrying solute is bypassed before charging tank at once afterwards and is passed directly into detector, target product is brought into segregative line
System, promotes and cleans the corresponding cut separated directly after detector, realize that technical grade is other and be precisely separated.
The present invention uses the adsorbents such as filling gel, bonded silica gel, activated carbon, bonded silica gel, aluminum oxide or calcium silicates
Chromatographic column, disposably separation can prepare the classes such as capsorubin, capsorubin, zeaxanthin, kryptoxanthin under suitable condition
The dye compound such as carrotene monomer and its aliphatic acid list (double) ester and beta carotene, capsaicine, dihydrocapsaicin, drop two
The Capsaicin compound such as hydrogen capsaicine and homodihydrocapsaicin, if it is necessary, separation simultaneously prepares the vitamins such as ascorbic acid
Compound.The technique can be fed intake intermittently operated by single channel, it would however also be possible to employ the feeding system of binary channels or more is at two
Or alternately fed intake in two or more charging tank, the continuous closed-loop flowing of supercritical fluid is realized, separation incessantly prepares product.
Its characterization step includes：The natural capsicum such as capsicum oleoresin extract or its saponification resultant are added to by charge pipe and fed intake
Carbon dioxide, is compressed to more than critical pressure and is passed through charging tank by tank by the high-pressure pump with pump head cooling system from liquid
Middle dissolving raw material, as needed, appropriate polarity modifier and additive and overcritical dioxy is conveyed by another high-pressure pump
Change carbon mixing, fluid-mixing is brought the raw material in charging tank into chromatographic column with temperature control system and separated.According to
The signal of thread detector, controls corresponding acquisition channel, by the isolated target components being dissolved in supercritical fluid point
It is not collected into different collectors, then by the decompression that heats up in each separator provided with temperature control system and pressure regulating system
Middle release carbon dioxide equal solvent component, obtains corresponding product.At each group, back pressure control is set between collector and separator
Valve processed, the operating pressure before maintaining separator is on the critical pressure of carbon dioxide.Two separated from separator
Carbonoxide tail gas pressurizes into liquid again after purification in condensation decompression is except residual tank and active carbon adsorption column, and two are returned with pump conveying
Recycled in carbonoxide flow container.
Entered respectively as needed according to the different and isolated colour components and Capsaicin component of raw material and separating technology
Enter corresponding collector.In order to ensure the purity of product, in specific production process, each product uses a special receipts
Storage, depending on the quantity of collector is according to the type and quantity of target product.The need for this technique can be according to production, adjust
The composition and ratio of whole eluant, eluent, the filler composition of chromatographic column, size, to prepare capsaicin, the capsochrome of various purity
With vitamin etc..The cooling that the carbon dioxide separated with solute removes residual tank by the dust removal by filtration in separator, condensation decompression is removed
Solvent and adsorption column absorption except it is molten it is residual after, it is again pressurized liquefied, recycle.This technique close loop maneuver, environmental pollution is minimum；
Material treatment temperature is low, can retained product to greatest extent bioactivity；Can a step separation prepare i.e. obtain at a relatively high purity
Specific products, it might even be possible to prepared by way of section is without any organic solvent at the beginning of in pigment separated completely solvent-free
Pigment product.
This technique can go out polarity spectrum very remote pigment and Capsaicin composition using timesharing gradient elution technique first separation.
Under the conditions of certain stationary phase, only by the polarity of gradient change mobile phase, add appropriate Mobile Phase Additives and promote elution
And separation, prepare capsochrome, Capsaicin, ascorbic acid in a separation circulation separation simultaneously.
The charging system of the present invention can be using double tanks pattern in parallel, alternate intermittent charging, so as to one of wherein interval
When charging, another head tank can be used normally to produce.
In order to which further raising prepares the efficiency of post, it is to avoid frequently dismantle main splitter, the present invention is after charging tank, color
One section of replaceable Filter column is set up in position before spectrum post.Filter column can use the filler with chromatographic column same type,
Can also be different fillers, particle diameter can be consistent with splitter fixation, can also be smaller.Before separation will be insoluble miscellaneous
Matter and the material of most of difficult elution are filtered out, and can play a part of the space availability ratio that raising prepares post.Filter column institute every
From difficult elution component, can behind heat up and gradually be eluted in the case of increasing modifying agent and isolate component therein
Come, insoluble matter is then cleared up when up to significantly affecting filter efficiency by changing Filter column.
After column outlet, high pressure resistant on-line checking device is installed close to product collection system, for example with ultraviolet point
Light photometer component, the change in concentration of monitoring kinds of ingredients is scanned with 260nm-480nm absorbing wavelengths scope online.Detector is also
Can be photodiode array detector (PAD or DAD), differential refraction detector (RID), EISD
(ELSD), in fluorescence detector (FLD) one or more or used simultaneously with UV detectors.The valve of product collection system is opened
Conjunction can be triggered by detector signal, and corresponding electrically executing agency performs automatically.Also can be by manually according to real-time signal data
Directly control.
This technique can produce needs according to the separation of product, adjust pressure, temperature and the flow velocity of supercritical carbon dioxide,
Or the flow velocity and species of adjustment polarity modifier and additive, or the adjustment filler composition of chromatographic column, size, the quantity connected
With type, (colourless) mixing capsaicin, (without peppery) mixing capsochrome or single capsorubin (ester), peppery can be prepared respectively
Green pepper rubine element (ester), beta carotene, kryptoxanthin (ester), zeaxanthin (ester), capsaicine, dihydrocapsaicin, nordihydrocapsaicin
Deng product.
It is used to prepare capsorubin, capsicum jade from capsicum oleoresin or from its saponified middle separation the invention discloses one kind
The Overcritical prepared chromatographic device of the compounds such as red pigment, beta carotene, capsaicine, dihydrocapsaicin, ascorbic acid.In device
Contain：Liquid phase carbon dioxide storage tank (1), modifying agent storage tank (2), high-pressure pump (3), pump head cooler (4), high-pressure pump (5), interval
Charging tank (6), Filter column (7), chromatographic column (8), on-line checking device (9), collector (10), Back pressure control valve (11), separator
(12), airflow filtering device (13), condensation decompression except residual tank (14), adsorption column (15), compressor (16), gas-liquid surge tank (17),
Pump head cooler (18), high-pressure pump (19).
As the carbon dioxide carrier of mobile phase, first from liquid phase carbon dioxide storage tank, (1) passed through pump head cooler
(4) after precooling, the pressure of needs is gradually forced into using high-pressure pump (3), the pressure limit of the liquid CO 2 exported can
In 8-100Mpa scopes.As needed, appropriate flow velocity is pressed to height from modifying agent storage tank (2) by an other high-pressure pump (5)
Pressure carbon dioxide liquid is mixed into polarity modifier, and fluid-mixing enters interval charging tank (6) by valve, be previously added it is peppery
The saponified mixing of green pepper oleoresin or capsicum oleoresin.Interval charging tank can be 1 group or more than 2 groups rotation chargings
With dissolving circulation.Appropriate heating medium is passed through in charging tank chuck feed liquid in tank is heated to 35-80 DEG C, make carbon dioxide stream
Body is in supercriticality.After capsicum oleoresin is dissolved into supercritical carbon dioxide, outlet valve is opened, feed liquid is passed through
Cross Filter column (7) and enter the chromatographic column (8) for being filled with a diameter of 1-100 μm of solid sorbent particles afterwards, with appropriate flow velocity
Separation is adsorbed and eluted, the chromatography under supercriticality is realized.According to the on-line checking device being arranged on after chromatographic column
(9) scan data, cut chromatographic column end separated is collected by the period to corresponding collector (10), collector and its
Mobile phase is in highdensity overcritical before Back pressure control valve (11), maintenance separator are provided between separator (12) afterwards
State.Cut, which enters, depressurizes heating after separator, carbon dioxide removal equal solvent component just obtains corresponding product.In order to true
The purity of product is protected, every kind of specific target product uses one group of special collector and separator.Separated through separator, dedusting
Carbon dioxide by condensation decompression except residual tank (14) and adsorption column (15) purification etc. are after step, produced carbon dioxide tail gas
Gas-liquid mixture phase is forced into through compressor (16), by gas-liquid surge tank (17), its liquid portion is through pump head cooler (18)
The middle recycling of liquid phase carbon dioxide storage tank (1) is transported to by high-pressure pump (19) after cooling.
When the low polarity dye compound for being used to separate preparation high-purity using only the present apparatus, and misalign highly polar Capsaicin
And highly polar ascorbic acid is when being finely divided, supercritical carbon dioxide fluid or and supercritical carbon dioxide can be only used
Appropriate polarity modifier is pumped into simultaneously, to elute the dye compound for separating relatively low polarity.On a silica gel column, dye compound
Capsorubin monomer, capsorubin monomer, zeaxanthin monomer, capsorubin mono fatty acid ester, capsorubin monoester fat
Acid esters, beta carotene, capsorubin double acid ester, capsorubin double acid ester, zeaxanthin double acid ester etc. according to
This elution, separation can be collected respectively.If the use of the saponification resultant of treated capsicum oleoresin being raw material, height can be prepared
Capsorubin, capsorubin, zeaxanthin, beta carotene of purity etc..After dye compound collection is finished, silica gel is improved
The temperature of post, and increase the ratio of polarity modifier, adding the soda acid additives such as phosphoric acid, triethanolamine if necessary can be faster
Ground cleans up pillar, and Capsaicin and ascorbic acid are rich in eluent, can be long by a set product collector and separator
Time, which collects, separates the eluent, produces colourless capsaicin mixed crystal.
While polarity spectrum very remote low polarity carotenoid pigment is produced in separation in needing to circulate in same first separation
With in when highly polar amide-type Capsaicin compound and highly polar ascorbic acid or two class therein, gradient elution skill need to be applied
Art.For example, in the column chromatography system that silica gel is stationary phase, first having on a small quantity with low polarity supercritical carbon dioxide fluid or addition
The supercritical carbon dioxide fluid that solvent modified dose of machine is mobile phase, and elution separates carotenoid contained in capsicum oleoresin
The dye compounds such as monomer, carotenoid ester and beta carotene.The flow velocity and temperature of control material, can be realized peppery substantially
Green pepper red pigment monomer and its single (double) ester, capsorubin monomer and its single primary pigments chemical combination such as (double) ester and beta carotene
It is prepared by the separation of thing.Pigment product separation prepare after the completion of, adjustment mobile phase in supercritical carbon dioxide and modifying agent flow velocity,
Adjust the ratio of modifying agent and additive, or improve chromatographic column operating temperature, can smoothly separate the higher capsaicine of polarity,
The compounds such as dihydrocapsaicin, nordihydrocapsaicin, homodihydrocapsaicin and ascorbic acid.
Supercritical carbon dioxide polarity modifier used in the present invention can be water, methanol, ethanol, isopropanol, acetic acid second
Ester, n-hexane, acetone, acetonitrile, tetrahydrofuran, ethylene glycol monomethyl ether, butyl glycol ether, petroleum ether, dichloromethane, chloroform,
Carbon tetrachloride or their mixture.As needed, can add phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, ammoniacal liquor,
The acid-base property such as isopropylamine, triethanolamine compound improves mobile phase to highly polar soda acid compound, such as Vitamin C as additive
Acid, eluting power.
Adsorbent stationary phase used in the present invention is the silica gel particle of silica gel particle or surface chemistry β-cyclodextrin,
Can be alundum (Al2O3), activated carbon, magnesium silicate, polyamide, diatomaceous earth particle, or they are by the mixture of certain ratio.
If it is necessary, the same or different chromatographic column that can connect, the component combination for once failing to separate continues to be passed through next section
Chromatographic column carries out secondary separation.This technique can produce needs according to the separation of product, adjust the pressure of supercritical carbon dioxide
And flow velocity, or the flow velocity and species of polarity modifier and additive are adjusted, or adjust filler composition, size, the string of chromatographic column
The quantity and type of connection, mixing decolouring capsaicin, mixing de- peppery capsochrome or capsorubin (ester), capsicum can be prepared respectively
The products such as rubine element (ester), beta carotene, kryptoxanthin (ester), zeaxanthin (ester), capsaicine, dihydrocapsaicin.This technique is pacified
Overall height is imitated, and environmentally safe, operation temperature is low, and product bioactivity is not influenceed, and products obtained therefrom purity is high, without further adding
Work is the level that can reach solvent-free or extremely low solvent.
It is an object of the invention to overcome conventional solvent extraction process, supercritical extraction process can not separate preparation high-purity
Dye compound and the capsicums such as capsorubin, capsorubin, capsorubin fatty acid ester, capsorubin fatty acid ester
The deficiency of the Capsaicin compound such as alkali, dihydrocapsaicin and nordihydrocapsaicin；The efficient liquid phase that solvent is mobile phase is overcome to prepare
The high risk of chromatogram, overcome solvent process purification system products obtained therefrom still residual solvent the shortcomings of.The present invention provides a kind of
Using the fluid of supercritical carbon dioxide or supercritical carbon dioxide as eluant, eluent, capsaicine is efficiently quickly completely separated
With the method for capsicum red pigment.This method retains the advantage of supercritical extract, and opposed polarity is completely separated while can realize
Product, the separating effect of the supercritical carbon dioxide separator greatly enhanced.Tail gas recycle and pressurized circulation system ensure that
The economy of operating cost and the environment friendly of system.
Efficiently, environmentally safe, operation temperature is low, and product bioactivity is not influenceed, and products obtained therefrom is pure for this process safety
Degree is high, the level without being processed further can reach solvent-free or extremely low solvent.
Brief description of the drawings
Two, this specification accompanying drawing, is half fed using single-throw batch can interval feed pattern and the rotation of double-throw batch can respectively
The process chart of continuous preparation mode.The collection piece-rate system being made up of two groups of collectors and separator is only drawn in figure, it is real
Border can be as needed when implementing, and mutually isostructural collection piece-rate system is extended to and can guarantee that various products are all preferably divided
From the quantity required for purity.Wherein：
Fig. 1 --- the overcritical column chromatography of single channel batch (-type) prepares capsochrome Capsaicin process chart；
Fig. 2 --- the semicontinuous overcritical column chromatography of binary channels prepares capsochrome Capsaicin process chart.
Specific device title representated by the Arabic numerals marked in accompanying drawing is as follows：
1 --- liquid phase carbon dioxide storage tank,
2 --- modifying agent storage tank,
3 --- high-pressure pump,
4 --- pump head cooler,
5 --- high-pressure pump,
6 --- charging tank,
7 --- Filter column,
8 --- chromatographic column,
9 --- on-line checking device,
10 --- collector,
11 --- Back pressure control valve,
12 --- separator,
13 --- airflow filtering device,
14 --- condensation decompression removes residual tank,
15 --- adsorption column,
16 --- compressor,
17 --- gas-liquid surge tank,
18 --- pump head cooler,
19 --- high-pressure pump.
Embodiment
Embodiment 1：
The various pigments of separation are extracted as raw material, therefrom using the pigment green pepper extract that hoirzontally rotating organic solvent counter-current extraction is produced
Compound.Total capsaicin content 0.08%, color value 235 in raw material.Filter column is using 20 μm of silica fillers, and its is a diameter of
100mm, column length 200mm, splitter is using 50 μm of silica fillers, diameter 200mm, column length 1800mm.It is activity to adsorb column packing
Charcoal.Fractional composition, setting Detection wavelength 460nm are monitored using online UV-detector.Charging tank is provided with pre-heating system, chromatographic column
Provided with temperature control and balance system.
Use single channel batch (-type) Supercritical fluid chromatography preparation technology.
This example mainly prepares solvent-free high-purity dye compound, for the dye compound of low polarity, passes through merely
Supercritical carbon dioxide can elute separation, therefore can manufacture solvent-free high-purity capsochrome using this technique.Work as detection
Device monitor target product completely by or according to predetermined ratio by detector after, start control at once, make mobile phase straight
Connect from the bypass before charging tank and be passed directly into detector, target product is continued to bring corresponding collector into and after collector
Lock out operation is performed in separator.It is automatic after setting 10min to recover post flowing, at the same detector outlet flow switch to it is new
Collector.
The of a relatively high Capsaicin impurity of polarity is easily easier to and pigment separated by silica gel absorption.By the raw material used
Capsaicin content is low, and Capsaicin is only collected as impurity and separated.In wash phase, CO 2 fluid gradient be pumped into 5%-10% without
Water-ethanol, can receive the Capsaicin compound elution based on dihydrocapsaicin, capsaicine, nordihydrocapsaicin as accessory substance
Collection.
The capsicum crude extract of the above-mentioned color values 235 of 900g is added into charging tank by charge pipe, will by high-pressure pump after sealing
The boost in pressure of liquid CO 2 is warming up to 35 DEG C to 30MPa.Raw material is carried through pure supercritical carbon dioxide, with 200ml/
Min flow velocity carries out chromatography, and (time that switching runner leads directly to detector is not counted in it for timing since charging tank enters post
In), 21 points monitored that first solute cut zeaxanthin dipalmitate passes through detector after 46 seconds, now, opened corresponding
Collection channel, allows fluid to enter one group of collection-piece-rate system.24 points of 06 second first cuts by detector, now, are stood completely
Carve and start control, allow mobile phase to be directly passed directly into detector from the bypass before charging tank, target product is continued to bring into accordingly
Collector and lock out operation is performed from the separator after collector.It is automatic after 10min to recover post flowing, close first group
Collection channel, while runner switches to new collector.
And then, second solute cut capsorubin dipalmitate (29 points and 27 seconds -33 points and 19 seconds) passes through detector,
It is collected into second group of collection channel and separates in the separator.Operate according to this, the obvious solute group being collected into order
Dividing is successively：The myristinate of capsorubin two (36 points and 02 second -38 points and 24 seconds), capsorubin lauric myristic ester (40
Points 25 seconds -43 points 04 second), capsorubin dilaurate (46 points and 10 seconds -49 points and 24 seconds), (51 point 14 of capsorubin dibasic acid esters
Seconds -53 points 09 second), it is beta-cryptoxanthin monoesters (54 points and 24 seconds -55 points and 07 second), beta carotene (56 points and 22 seconds -58 points and 39 seconds), peppery
Green pepper pigment monoesters (58 points 56 seconds -68 points 35 seconds, be consecutively detected 6 groups of mixing solute components, it is unified to collect separation, mainly by peppery
Green pepper red pigment, zeaxanthin, capsorubin monoesters composition), beta-cryptoxanthin (69 points and 13 seconds -70 points and 17 seconds), (72 points of hidden capsanthin
00 second -72 points 49 seconds), zeaxanthin (73 points and 25 seconds -74 points and 24 seconds), capsorubin (76 points and 21 seconds -77 points and 12 seconds), violaxanthin
(79 points 51 seconds 81 points 06 second), capsorubin (82 points and 43 seconds -83 points and 24 seconds).
The isolated capsorubin monomer of capsorubin weighs 4.8 grams, and HPLC measures purity and reaches 97.8%.Capsicum
5.6 grams of red pigment monomer, HPLC purity reaches 97.5%.Due to not using solvent, so separated product is solvent-free
The product of residual.
Complete after main component separation, synchronously supplied into supercritical carbon dioxide fluid by high-pressure pump 50ml/min without
Water-ethanol is polarity modifier, and Filter column, chromatogram column temperature are increased to 60 DEG C, coordinate supercritical carbon dioxide to follow system
Ring cleans 120min.The solute of this cleaning process elution is collected separately and separated, and resulting product can be used as carrying after merging
Ascorbic acid and polyphenol is taken to be used.120min cleans wax-like filtrate 132.6g before oily gleanings 302.1g, Filter column, filtering
Post weightening 160.2g.
In separation process, separator temperature is set as 50 DEG C, pressure 5-8MPa.Under the conditions of in this, product and dioxy
Change carbon separation, mouth releases product under separator, carbon dioxide then subtracts from separator adjusted valve suitable for reading, filter into condensation
Pressure removes residual tank, adjusts its temperature to -10 DEG C, pressure is 0.5-1MPa, and the solvent of carbon dioxide and residual is separated, then leads to
Solvent micro in adsorption column absorbing carbon dioxide is crossed, clean carbon dioxide is obtained and is liquefied by compressor compresses, uses high pressure
Pump is transmitted back to storage tank recycling.
Each pigment products weight and purity are as shown in the table：
Embodiment 2：
Capsicum crude extract (capsaicin content 10%, color value 62) that 20Kg flat rotary extractor counter-current extractions are obtained with
20Kg50% ethanol/waters are mixed, and heating saponification is carried out to it with 4Kg10% sodium hydroxides, and saponification temperature is controlled at 40-60 DEG C,
Cooling and standings after saponification 1-2h, isolated upper strata saponification resultant 2.6Kg.It is super using binary channels using this saponification resultant as raw material
Critical fluids column chromatography preparation system (Fig. 2) continuously prepares high-purity capsochrome and Capsaicin.
The above-mentioned saponification resultants of 1Kg are put into one group of interval charging tank, chromatographic column filler is 50 μm of silica gel particles, adsorption column
Filler is activated carbon.By charging tank temperature adjustment to 32 DEG C, pressure brings up to 28MPa, and raw material is dissolved by supercritical carbon dioxide
Chromatographic column is carried along into, column temperature is set as 35 DEG C, and regulation chromatogram column pressure is 25MPa.Flow rate of mobile phase is set as 200ml/
min.Meter was recorded the post separation time and (rejects the time that midway switching runner collects product) since being opened the valve after charging tank.
Using UV absorption spectrum detectors, separation prepares pigment stage default absorbing wavelength 460nm.When detector monitors to target product
Completely by or according to predetermined ratio by detector after, start control at once, allow mobile phase directly from the side before charging tank
Road is passed directly into detector, and target product is continued to bring corresponding collector into and separation is performed from the separator after collector
Operation.It is automatic after 10min to recover post flowing, while detector outlet flow switches to new collector.
In separation process, separator temperature is set as 50 DEG C, pressure 5-8MPa.Under the conditions of in this, product and dioxy
Change carbon separation, mouth releases product under separator, carbon dioxide then subtracts from separator adjusted valve suitable for reading, filter into condensation
Pressure removes residual tank, adjusts its temperature to -10 DEG C, pressure is 0.5-1MPa, and the solvent of carbon dioxide and residual is separated, then leads to
Solvent micro in adsorption column absorbing carbon dioxide is crossed, clean carbon dioxide is obtained and is liquefied by compressor compresses, uses high pressure
Pump is transmitted back to storage tank recycling.
It is beta carotene (26 points and 12 seconds -28 points and 09 second) to take the lead in by detector, passes through one group of collector, separator
Collect and separate.It is more obvious due to distinguishing, determine beta carotene purity through HPLC and reach 98.1%, impurity is cis
Beta carotene.
After one substantially and is clearly spaced, high-purity beta-cryptoxanthin (33 points and 14 seconds -35 points and 16 seconds) is separated
Come, determining beta carotene purity through HPLC reaches 99.1%.
Be subsequently isolated out is the hidden capsanthin (36 points and 05 second -36 points and 31 seconds) of relatively small amount.
Then what is separated is zeaxanthin (38 points and 26 seconds -41 points and 02 second), and purity is 96%.
Next what is separated is a small amount of mutatoxanthin (42 points and 21 seconds -43 points and 04 second), (43 point 46 of cis capsorubin
Seconds -44 points 19 seconds), antheraxanthin (44 points and 31 seconds -45 points and 09 second).
Then pass through detector is relative amount highest capsorubin (46 points and 7 seconds -48 points and 55 seconds), and HPLC purity is high
Up to 98.2%, impurity is a small amount of epoxy capsorubin.
Subsequent pass through detector is violaxanthin (50 points and 02 second -50 points and 57 seconds), (51 point 30 of capsorubin respectively
Seconds -52 points 11 seconds).
So far, high-purity is separated without residual molten series capsicum pigment product.
Capsaicine series compound is adsorbed on a silica gel column, because polarity is higher, it is difficult to be washed by supercritical carbon dioxide
It is de-.So, 20ml/min absolute ethyl alcohols are next added in mobile phase and improve the polarity of mobile phase, to elute prepare it is peppery
Green pepper alkali product.The measure wavelength of UV detectors is adjusted to 280nm.
Dihydrocapsaicin 71 points 16 seconds -73 points pass through detector within 24 seconds.Followed by capsaicine (76 points 12 seconds -81 points 09
Second) and nordihydrocapsaicin (83 points and 12 seconds -84 points and 52 seconds).Separating degree is excellent.
The collection method in this stage is identical with the first stage.After monitoring that target product flows completely through detector, cut
Change of current road, allows mobile phase to be passed directly into detector from the bypass before charging tank, and target product is continued to bring corresponding collector into
And lock out operation is performed from the separator after collector.It is automatic after 10min to recover post flowing, while detector outlet flow
Switch to new collector.
After the separation of first 1kg raw material is finished, the same flowing phase composition of maintenance and flow velocity (200ml/min overcritical two
Carbonoxide and 20ml/min absolute ethyl alcohols), rise column temperature to 60 DEG C, purging system.Cleaning fluid through same collection separation process,
Extract first separation thing per 30min to weigh, second is to be washed out without new material.29 grams of solid powder is recovered to altogether.Through
Determine regenerant and mainly contain ascorbic acid, polyphenol and a small amount of capsaicine.
During cleaning systems, in the interval charging tank that another 1Kg raw material is put into another group of independence.Cleaning is finished
Afterwards, column temperature is recovered to normal temperature, stops absolute ethyl alcohol high-pressure pump, and by supercritical carbon dioxide switch to it is corresponding feed intake it is logical
Road, the measure wavelength of UV detectors is adjusted to 460nm, and second batch separation preparation is started using identical chromatographic condition.
The same zero point that the time for opening charging tank outlet valve is set as to this batch-wise chromatography disengaging time.
Beta carotene (26 points and 29 seconds -28 points and 18 seconds), beta-cryptoxanthin (33 points and 28 seconds -35 points and 33 seconds), hidden capsanthin (36
Points 21 seconds -36 points 48 seconds), zeaxanthin (38 points and 42 seconds -41 points and 20 seconds), mutatoxanthin (42 points and 38 seconds -43 points and 20 seconds),
Cis capsorubin (44 points and 00 second -44 points and 34 seconds), antheraxanthin (44 points and 47 seconds -45 points and 26 seconds), (46 points of capsorubin
23 seconds -49 points 11 seconds), violaxanthin (50 points and 18 seconds -51 points and 13 seconds), capsorubin (51 points and 47 seconds -52 points and 29 seconds) lead to according to this
Cross detector and collect and separate.
Then, the measure wavelength of UV detectors is adjusted to 280nm.With 20ml/min flow velocity in supercritical carbon dioxide
Add absolute ethyl alcohol.
Dihydrocapsaicin (73 points and 26 seconds -75 points and 35 seconds), capsaicine (78 points and 23 seconds -83 points and 17 seconds), nordihydrocapsaicin
(85 points 21 seconds -87 points 03 second) collect separation successively.
Continuous operation two batches separation prepare obtained by products weight be respectively：
Claims (11)
1. a kind of method that supercritical fluid pillar layer separation prepares capsochrome Capsaicin, it is characterized in that：By liquid carbon dioxide
Premixed according to a certain percentage by high-pressure pump respectively with polarity modifier after precooling, heating is forced into after specific supercriticality
It is miscible with the capsicum oleoresin or its saponification resultant that are previously added charging tank, the system of filled solid sorbent particles is passed through after filtering
Standby type chromatographic column carries out mass transfer separation；Controlled at once after each or each group of target components flow completely through on-line checking device super
Critical fluids are passed directly into detector from the bypass before feeder, will be loaded into corresponding receive by the target components of detector
Storage, then realizes the separation of target components and carbon dioxide equal solvent in connected separator；Carbon dioxide tail gas passes through
Liquid, which is compressed into, after dust removal by filtration, the de- liquid of condensation and absorption column purification returns to storage tank recycling.
Contain 2. prepared by a kind of supercritical fluid pillar layer separation in capsochrome Capsaicin process unit, device：Liquid phase titanium dioxide
Carbon storage tank, modifying agent storage tank, high-pressure pump, pump head cooler, high-pressure pump, interval charging tank, Filter column, chromatographic column, on-line checking
Device, collector, Back pressure control valve, separator, airflow filtering device, condensation decompression are except residual tank, adsorption column, compressor, gas-liquid buffering
Tank, pump head cooler, high-pressure pump.
3. a kind of supercritical fluid pillar layer separation prepares capsochrome Capsaicin process unit, it is characterized in that：Device, which contains, to be used for
One or more groups of feeding systems that interval feeds intake, when interval charging tank reaches more than two, can use the interval without shutting down
Charging-continuous separating operation pattern, rotation feeds between different charging tanks, maintains supercritical fluid persistent loop.
4. a kind of supercritical fluid pillar layer separation prepares capsochrome Capsaicin process unit, it is characterized in that：Charging tank work pressure
Power is 8-100MPa, and chuck heating-up temperature is controllable.
5. a kind of supercritical fluid pillar layer separation prepares capsochrome Capsaicin process unit, it is characterized in that：Contain many logical detections
Device, detector is constructively at least up to three-dimensional intercommunication, directly can directly to be led from the supercritical fluid passage before feeder
Enter to be free of the supercritical fluid of solute, stop that in the state of flowing detection will be had passed through in the supercritical fluid for leading to chromatographic column
The target fraction of device is controllably collected into appropriate collector.
6. a kind of method that supercritical fluid pillar layer separation prepares capsochrome Capsaicin, with supercritical carbon dioxide fluid or with
Supercritical carbon dioxide is main body, and the fluid-mixing for adding a certain proportion of polarity modifier is eluant, eluent.
7. a kind of method that supercritical fluid pillar layer separation prepares capsochrome Capsaicin, used polar modifier of mobile phase
Can be water, methanol, ethanol, isopropanol, ethyl acetate, n-hexane, acetone, acetonitrile, tetrahydrofuran, ethylene glycol monomethyl ether, second two
Alcohol butyl ether, petroleum ether, dichloromethane, chloroform, carbon tetrachloride or their mixture.As needed, Ke Yitian
Phosphorate the acid-base property compound such as acid, formic acid, acetic acid, trifluoroacetic acid, ammoniacal liquor, isopropylamine, triethanolamine.
8. a kind of supercritical fluid pillar layer separation prepares capsochrome Capsaicin process unit, used adsorbent stationary phase is
Silica gel particle or alundum (Al2O3), activated carbon, magnesium silicate, the polyamides of silica gel particle or surface chemistry β-cyclodextrin
Amine, diatomaceous earth particle, or they are by the mixture of certain ratio.
9. a kind of supercritical fluid pillar layer separation prepares capsochrome Capsaicin process unit, its piece-rate system is according to detector
Signal performs operation, and the mobile phase of solute will not be carried at once from charging tank detecting after target product flows completely through detector
Preceding bypass is passed directly into detector, brings target product into piece-rate system.
10. a kind of supercritical fluid pillar layer separation prepares capsochrome Capsaicin process unit, in each group of collector and separation
Back pressure control valve is set between device, and the operating pressure before maintaining separator is on the critical pressure of carbon dioxide.
11. a kind of supercritical fluid pillar layer separation prepares capsochrome Capsaicin process unit, after charging tank, chromatographic column it
It is preceding to be provided with replaceable filtering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710445174.2A CN107163618A (en) | 2017-06-02 | 2017-06-02 | Supercritical fluid column chromatography prepares the method and device of high-purity capsochrome Capsaicin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710445174.2A CN107163618A (en) | 2017-06-02 | 2017-06-02 | Supercritical fluid column chromatography prepares the method and device of high-purity capsochrome Capsaicin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107163618A true CN107163618A (en) | 2017-09-15 |
Family
ID=59825905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710445174.2A Pending CN107163618A (en) | 2017-06-02 | 2017-06-02 | Supercritical fluid column chromatography prepares the method and device of high-purity capsochrome Capsaicin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107163618A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108148445A (en) * | 2018-01-16 | 2018-06-12 | 邯郸市美康生物科技有限公司 | A kind of production method for improving capsicum red pigment absorption ratio |
| US20210392927A1 (en) * | 2020-06-22 | 2021-12-23 | Henan Zhongda Hengyuan Biotechnology Stock Co., Ltd. | Method of preparing paprika red pigment with low polycyclic aromatic hydrocarbons |
| NL2033813A (en) * | 2021-12-30 | 2023-07-04 | Jiangsu Hanbon Sci & Tech Co | High-efficiency supercritical equipment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099899C (en) * | 1997-12-31 | 2003-01-29 | 孙传经 | Commercial scale supercritical carbon dioxide prepn. chromatography and use thereof |
| CN1698925A (en) * | 2005-03-28 | 2005-11-23 | 浙江大学 | Chromatogram arrangement of supercritical fluid imitation moving bed with four subareas |
| CN1936572A (en) * | 2005-09-23 | 2007-03-28 | 中国科学院大连化学物理研究所 | Super-critical flow extraction-efficient liquid-phase colour spectrum combined system |
| CN102879482A (en) * | 2011-07-13 | 2013-01-16 | 江苏汉邦科技有限公司 | Supercutical fluid chromatograph (SFC) instrument and automatic back pressure apparatus used therein |
| CN106457103A (en) * | 2014-05-15 | 2017-02-22 | Ykk株式会社 | Method and device for separating and recovering supercritical fluid |
-
2017
- 2017-06-02 CN CN201710445174.2A patent/CN107163618A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099899C (en) * | 1997-12-31 | 2003-01-29 | 孙传经 | Commercial scale supercritical carbon dioxide prepn. chromatography and use thereof |
| CN1698925A (en) * | 2005-03-28 | 2005-11-23 | 浙江大学 | Chromatogram arrangement of supercritical fluid imitation moving bed with four subareas |
| CN1936572A (en) * | 2005-09-23 | 2007-03-28 | 中国科学院大连化学物理研究所 | Super-critical flow extraction-efficient liquid-phase colour spectrum combined system |
| CN102879482A (en) * | 2011-07-13 | 2013-01-16 | 江苏汉邦科技有限公司 | Supercutical fluid chromatograph (SFC) instrument and automatic back pressure apparatus used therein |
| CN106457103A (en) * | 2014-05-15 | 2017-02-22 | Ykk株式会社 | Method and device for separating and recovering supercritical fluid |
Non-Patent Citations (2)
| Title |
|---|
| IVANA BONACCORSI等: "《Characterization of the pigment fraction in sweet bell peppers (Capsicum annuum L.) harvested at green and overripe yellow and red stages by offline multidimensional convergence chromatography/liquid chromatography-mass spectrometry》", 《J. SEP. SCI.》 * |
| T. A. BERGER等: "《Separation of Natural Food Pigments in Saponified and Un-Saponified Paprika Oleoresin by Ultra High Performance Supercritical Fluid Chromatography (UHPSFC)》", 《CHROMATOGRAPHIA》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108148445A (en) * | 2018-01-16 | 2018-06-12 | 邯郸市美康生物科技有限公司 | A kind of production method for improving capsicum red pigment absorption ratio |
| US20210392927A1 (en) * | 2020-06-22 | 2021-12-23 | Henan Zhongda Hengyuan Biotechnology Stock Co., Ltd. | Method of preparing paprika red pigment with low polycyclic aromatic hydrocarbons |
| US11969004B2 (en) * | 2020-06-22 | 2024-04-30 | Henan Zhongda Hengyuan Biotechnology Stock Co., Ltd. | Method of preparing paprika red pigment with low polycyclic aromatic hydrocarbons |
| NL2033813A (en) * | 2021-12-30 | 2023-07-04 | Jiangsu Hanbon Sci & Tech Co | High-efficiency supercritical equipment |
| BE1029711B1 (en) * | 2021-12-30 | 2023-10-18 | Jiangsu Hanbon Sci & Tech Co | HIGH EFFICIENCY SUPERCRITICAL EQUIPMENT |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111960926B (en) | Preparation method of cannabidiol crystal | |
| CN106831353B (en) | Method for extracting cannabidiol from cannabis sativa | |
| CN107163618A (en) | Supercritical fluid column chromatography prepares the method and device of high-purity capsochrome Capsaicin | |
| US20060074254A1 (en) | Process for extracting taxanes | |
| CN111153843B (en) | Method for separating lycium barbarum pigment monomers | |
| CN111039761B (en) | Method for purifying cannabidiol | |
| Viganó et al. | Comprehensive analysis of phenolic compounds from natural products: Integrating sample preparation and analysis | |
| CN105566414B (en) | The method that four kinds of flavone glycosides are isolated and purified from waxberry flesh | |
| CN105859803B (en) | A kind of preparation method of galloyl glucose | |
| CN112661612A (en) | Method for large-scale preparation of high-purity CBD through post-decarboxylation and supercritical extraction | |
| Assimopoulou et al. | Preparative isolation and purification of alkannin/shikonin derivatives from natural products by high‐speed counter‐current chromatography | |
| CN108033993A (en) | A kind of method for preparing triptonide | |
| CN102321135A (en) | Method for separating and purifying cordycepin by utilizing high-speed counter-current chromatography | |
| Xu et al. | D-limonene as an alternative for the extraction and purification of nuciferine from lotus leaf via multi-stage vortex assisted two-phase solvent extraction integrated with solid phase extraction using mesoporous material SBA-15 as adsorbent | |
| CN108129545B (en) | A method of preparing triptolide | |
| CN105973683A (en) | Pretreatment device as well as use method and application thereof | |
| CN107573255A (en) | A kind of method that capsaicine and dihydrocapsaicin are isolated and purified from pepper fruit | |
| CN110922439A (en) | Method for separating and preparing gram-grade high-purity natural product | |
| CN110684001A (en) | Method for purifying sheep crispin A from sheep crispin root bark by column chromatography-high-speed countercurrent chromatography | |
| CN100427174C (en) | Integrated process and apparatus for extracting and separating effective Chinese medicine components | |
| CN112029312B (en) | Preparation method of capsorubin with high light absorption ratio and capsorubin with high content | |
| CN109651301A (en) | A kind of purification process of orlistat | |
| CN110229089B (en) | Method for separating and purifying high-purity canthaxanthin by using double solvents in combination with medium-pressure liquid chromatography | |
| CN107376420A (en) | Disperse mobile phase countercurrent chromatography separation method | |
| Lasoń-Rydel et al. | Methods of purification of raw polyphenol extract for chromatographic analysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170915 |
|
| WD01 | Invention patent application deemed withdrawn after publication |