CN1562995A - Left ofloxacin and Pidotimod compound preparation tech and its appts. - Google Patents
Left ofloxacin and Pidotimod compound preparation tech and its appts. Download PDFInfo
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- CN1562995A CN1562995A CN 200410023065 CN200410023065A CN1562995A CN 1562995 A CN1562995 A CN 1562995A CN 200410023065 CN200410023065 CN 200410023065 CN 200410023065 A CN200410023065 A CN 200410023065A CN 1562995 A CN1562995 A CN 1562995A
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Abstract
Tea leaves is used as raw material, by using water or solvent, to extract tea-polyphenol, then settle, centrifugal separation, column absorbing, extracting by ethyl acetate, vacuum concentrating, drying to obtain crude tea-polyphenol. Said crude product is then dissolved in water, absorbed by resin column, washed-off by agent gradient adding-in, based-on standard flowing curve to obtain 7 monomer catechins with purity>99%. For this purpose, full automatic absorbing resin column is equiped with metering pump to adjust fed-in of water, solution and solvent, HPLC real-time monitoring and pick-correcting to washing-off liquid is achieved by proportional flow-splitter. Automatic back-wash and resin-exchanging are achieved by being equiped with over-flow hole, resin discharging hole and others.
Description
Technical field
The present invention relates to extract the technology and the extraction equipment thereof of tea-polyphenol and catechin, particularly adopt adsorption resin column to prepare the technology of high-purity tea polyphenol and high-purity monomer catechin and the adsorption resin column of employing by tealeaves.
Background technology
Tea-polyphenol is the class extracted from the tealeaves polyphenolic compound based on catechin, has antitumorly, and anti-curing cancers brings high blood pressure down and blood sugar, suppresses and kills effects such as pathogenic bacteria and virus.Isolated monomer NVP-XAA 723 (EGCG) from tea-polyphenol is because the drug effect performance such as anti-oxidant, anticancer of its excellence is thought " to be the ideal PTS of extracting in the world from plant after taxol." therefore, extracting the technical study of tea-polyphenol and separation and Extraction catechin and extracting equipment development becomes hot topic.What extract tea-polyphenol employing at present from tealeaves mainly is solvent-extraction process (comprising water and water-containing solvent), the heavy metallic salt precipitator method and resin absorption concentration method.Solvent-extraction process will remove pigment and caffeine with chloroform extraction filtrate; The precipitation rule adopts tea-polyphenol in the heavy metal ion precipitation filtrate, and it is separated with caffeine with pigment, and these two kinds of methods may cause organic solvent or the heavy-metal residual in the tea-polyphenol product, and the tea-polyphenol purity of preparation is not high.Method by thick tea-polyphenol separation and Extraction catechin has the supercritical CO 2 extraction process, and this method product purity is higher, but complex process, it is single to separate component, operation inconvenience, cost height; Liquid phantom preparing chromatogram and counter current chromatography, the tea polyphenol monomer isolate purity height of preparation, recovering effect is better, but the cost of investment height, and throughput is " gram magnitude ", is difficult to the expansion scale.Chinese patent 02113680.7 has proposed a kind of " extracting the production technique of pure catechin in the tea ", this patent has adopted the D101 macroporous adsorbent resin, transfers pH value precipitation fine particle after-filtration but only adopt before tea extract upper prop, and the molecule difficulty eliminates, can pollute resin column, influence adsorption effect; Through twice upper prop also can only output purity be 90% catechin mixture, has but increased cost; And adopted the noxious solvent chloroform.Chinese patent 00128567.x has proposed " separation method of catechin compounds in a kind of tea-polyphenol ", adopt glucose Sephadex LH-20 gel series of columns, can obtain monomeric ester dissolubility catechin EGCG, ECG, but monomer purity only reaches 90～95%, can not satisfy the pharmacy requirement, with acetone and ethanol binary solvent wash-out, the inconvenience solvent recuperation has strengthened production cost.Chinese patent 01201087.1 has proposed " a kind of macroporous adsorptive resins ", 02256069.6 proposed a kind of " macroporous resin ultrasonic wave natural drug fractionation by adsorption device ", the common issue with that they exist is that filter screen stops up or resin used in the time of will more renewing resin for a long time, can only be with manually digging out, waste time and energy, and these two kinds of equipment can not be used for the separation and Extraction of high-purity monomer catechin basically.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of and produce high-purity tea polyphenol and by the novel process and the device thereof of tea-polyphenol separation and Extraction high-purity monomer catechin with the resin column absorption method, this device can extract tea-polyphenol, separable again catechin, the separation efficiency height, the product purity height, production cost is low.
Realize that the technical scheme that the object of the invention adopts is:
Tea leaf powder is broken to granularity≤1mm, from tealeaves, extract thick tea-polyphenol with water extraction, control tealeaves and pure water weight ratio are 1: 8～15,90～95 ℃ of temperature, stir and extracted 10～20 minutes, be that 90～95 ℃ hot pure water is washed tealeaf residue once with temperature again after the filtration, control slag and hot pure water weight ratio are 1: 4～6; It is to carry out the sedimentation centrifugation after 3～4 that tea extract is adjusted the pH value with hydrochloric acid or acetic acid, removes oil slick, lipid and slag, obtains the clean liquid of tea extract;
Clean liquid is directly gone up adsorption resin column, and the control adsorption temp is 5～20 ℃, 8～16 liters/minute of post delivery flow; After the total clean liquid that the every batch of tealeaves extracts is adsorbed resin column and adsorbs fully, wash post with pure water and when liquid effluent does not have obvious color, stop to wash post; Add weight concentration and be 80% ethanol desorb wash-out tea-polyphenol from the resin column, and the collection ethanol eluate, 4～9 liters/minute of dominant discharge, the desorb wash-out is after 10～20 minutes, ultrasonic again wash-out 5～15 minutes, desorb stop wash-out when being eluted to the last the next gum blushing of resin column and solid colour;
The ethanol eluate that contains tea-polyphenol is after vacuum concentration reclaims ethanol, and water is 1: 1～3 to add vinyl acetic monomer and extract tea-polyphenol at normal temperatures twice by weight; Extraction liquid and water carry out the sedimentation centrifugation, and the ethyl acetate extraction liquid that must contain tea-polyphenol is cooled to 5～20 ℃ of preservations, reclaim vinyl acetic monomer through vacuum concentration again, and solution gets the thick product of flaxen tea-polyphenol through spraying or lyophilize;
Is 1: 30～50 to add the pure water stirring and dissolving with the thick product of tea-polyphenol by tea-polyphenol and pure water weight ratio, and after the sedimentation centrifugation, with adsorption resin column absorption on the thick tea-polyphenol aqueous solution, the control adsorption temp is 5～20 ℃, 8～16 liters/minute of post delivery flow; After every batch of tea-polyphenol aqueous solution is adsorbed resin column and adsorbs fully, wash post with pure water and when liquid effluent does not have obvious color, stop to wash post;
After washing post and finish, pure water carries out the extraction separation of catechin, eluting solvent by stages section or be regardless of the segment gradient and increase progressively to add and carry out the desorb wash-out, the elutriant flow is selected a value in 4～9 liters of/minute intervals constant, 5～20 ℃ of temperature, simultaneously catechin from the polymeric adsorbent by desorb time-the absolute content standard flows out peak of curve and resin column proportional diverting device and divides flow liquid to detect the purpose peak value of acquisition when synchronous through HPLC, regularly collect each monomer component peak liquid, last vacuum concentration reclaims solvent, and solution is sprayed mutually or each catechin is made in lyophilize.
The present invention can also extract thick tea-polyphenol with solvent method from tealeaves, be that 1: 5～8 adding weight concentrations are 80% ethanol or methyl alcohol by tealeaves and weight of solvent ratio, and 60～65 ℃ of controlled temperature stir and extracted 30 minutes, and the slag after the filtration extracts once again.
The polymeric adsorbent of filling can be from C in the resin column of the present invention
18Resin, dextran Sephadex LH-20 gel resin, D101, NKA-2 macroporous adsorbent resin are appointed in the polymeric amide sorbent material and are selected one.
It is 80% acetone that the present invention goes back used weight concentration, or methyl alcohol desorb wash-out tea-polyphenol from the resin column.
One of catechin of the present invention desorb eluting solvent from the adsorption resin column is preferred is acetone, adopt the by stages section to increase progressively 1% operational throughput gradient adding by per minute, in pure water, add 0.05% trifluoracetic acid simultaneously, the first gradient zones metacetone weight concentration increases to 45% by 15%, the weight concentration of the second gradient zones metacetone increases to 60% by 45%, receives the peak respectively and gets catechin monomers.
Catechin of the present invention from the adsorption resin column the desorb eluting solvent another be preferably methyl alcohol, employing is regardless of segment and increases progressively 1% operational throughput gradient adding by per minute, in pure water, add 0.05% trifluoracetic acid simultaneously, the methyl alcohol weight concentration increases to 55% by 15%, receives the peak and gets catechin monomers.
The solvent that catechin of the present invention desorb wash-out from the adsorption resin column is adopted can also be from vinyl acetic monomer, acetonitrile, and dimethyl formamide (DMF) is appointed in the trifluoroacetic acid (TFA) and is selected one.
The device of implementing process using of the present invention is that the tea-polyphenol extraction separates dual-purpose full-automatic adsorption resin column with catechin monomers, it comprises: the resin column column casing, be positioned at the post lid that column casing top and column casing are tightly connected, post covers and is provided with resin water liquid feed port and tensimeter, the annular water or the solvent injecting jet pipe that are provided with near post lid and column casing connecting portion in the column casing, liquid level visor in the post of installing successively from top to bottom on the column casing wall, the upper visor of resin, the next visor of resin, column casing wall top is provided with medullary ray and the overflow weir that filtering net be housed of liquid level visor medullary ray in same horizontal plane, the agitator motor that is connected with the stirring rachis that is provided with in the column casing that install at post lid center, stir on the rachis and between upper and the next visor of resin, upper strata paddle and lower floor's paddle are being installed, the inverted cone liquid discharging bucket of column casing bottom is provided with filtering net, column casing wall bottom is close to the filtering net top and is had the resin outlet orifice, the column casing wall is positioned at the filtering net top outward and is provided with water jacket, be respectively arranged with water jacket water inlet pipe and rising pipe in the bottom of water jacket one side and the top of opposite side, several ultrasonic transducer oscillators are installed on the outer wall of water jacket, the inverted cone liquid discharging bucket of column casing bottom is provided with wastewater discharge pipe, backwash pipeline valve and the under meter that is communicated with this vent pipe is set between wastewater discharge pipe valve and the inverted cone liquid discharging bucket symmetrically, before under meter, after the main valve of the dominant discharge meter of close wastewater discharge pipe the proportional diverting device is installed, with water or solvent injecting jet pipe and tank connected connecting tube of solvent and solvent jar outlet valve, the paddle motor that is installed in the solvent tank top connects a jar interior stirring rachis and a paddle that is provided with, the solvent tank top also has charging opening, its total output tube is connected the volume pump group that some the volume pumps by frequency modulation motor control of water or solvent injection mixing tank are formed with the solvent jar, and the industrial computer of controlling each volume pump running and the switching of each pipeline valve.
The interior diameter d of the adsorption resin column that apparatus of the present invention adopt is 1～30: 1 with the ratio of the cylinder clear height h that removes loam cake and bottom liquid discharging bucket, or 1: 1～30.
The volume pump group of apparatus of the present invention can use the under meter group identical with its composition platform number to replace.
Adopt the processing step and the process of dual-purpose full-automatic adsorption resin column of the present invention and processing method separation and Extraction high-purity tea polyphenol and high-purity monomer catechin to be: to add pure water or stirring solvent after tealeaves is pulverized and extract, again with insulation hot water or solvent washery slag, to extract and the back sedimentation centrifugation of washery slag filtrate adjustment pH value adsorption resin column on the clean liquid; Pure water was washed post after absorption was finished, earlier with solvent (ethanol etc.) desorb wash-out tea-polyphenol, ultrasonic again wash-out; The elutriant vacuum concentration reclaims solvent, and water adds the ethyl acetate extraction tea-polyphenol, and back sedimentation centrifugation is finished in extraction, and the extraction liquid vacuum concentration reclaims vinyl acetic monomer, and water is dry must thick tea-polyphenol; Thick tea-polyphenol adds the pure water dissolving, and clean liquid (in case of necessity through the sedimentation centrifugation) is gone up adsorption resin column; After absorption is finished solvent (as acetone) gradient increased progressively and adds the desorb wash-out, connects peak liquid by receiving the peak curve, caffeine, non-ester catechin monomer product CAF, EGC, DL-C, EC and ester catechin monomer product EGCG, GCG, ECG, CG.
The present invention purifies at tea extract, ethyl acetate extraction liquid and aqueous phase separation, and the thick tea-polyphenol aqueous solution all adopts the sedimentation centrifugation need purify the time, to select DHC-500 type decanter type disc separator for use is example, liquid to be separated flow to the bottom of the drum by rotary drum central upper portion opening for feed through filling tube, rafter flows to the rotary drum space under the video disc seat, under the effect of centrifugal force of high speed rotating rotary drum, the solid phase particles that proportion is bigger (slag) is heavy discharges from slag notch to rotatory drum wall, under taper video disc guiding, oil slick in the extracting solution, organic phase in lipid or the extraction liquid flows supreme portion by light liquid outlet discharge, aqueous phase stream in tea-polyphenol and caffeine or the extraction liquid upwards flows behind rotatory drum wall and is discharged by heavy liquid exit, realize the clean liquid of tea-polyphenol and sediment and oil slick, lipid, ethyl acetate extraction liquid and water, the thick tea-polyphenol aqueous solution separates with molecule.Adopt the horizontal type screw settling separating machine, three-dimensional high speed cartridge type putting-down machine separates, and effect is close.
The major technique measure of catechin separation and Extraction of the present invention is to adopt gradient to add solvent desorb wash-out catechin from the resin column; The purpose peak value of the branch flow liquid field monitoring of resin column proportional diverting device is received the peak when synchronous in certain catechin that pre-establishes desorb elution time-absolute content standard elution curve purpose peak value and HPLC UV-detector from certain polymeric adsorbent.With acetone desorb wash-out is that the concrete enforcement of example is:
Industrial computer regulates each volume pump automatically by design in advance and carries liquid proportional, and the acetone pump accounts for total conveying part by weight per minute by acetone and increases progressively 1% operational throughput, and pure water pump then accounts for successively decrease 1% operational throughput of total conveying part by weight per minute by pure water; As adopt mixed solvent (such as acetone and ethanol) desorb wash-out, then the ethanol pump accounts for successively decrease 1% operational throughput of total conveying part by weight per minute by ethanol, perhaps ethanol pump and pure water pump account for successively decrease 0.5% operational throughput of total conveying part by weight per minute separately by ethanol and pure water respectively, guarantee that two pumps or three pump per minute delivery solvent amount sums equal the resin column elutant and flow out total amount, and constant.Each volume pump carries liquid evenly to spray to resin column behind solvent jar stirring and evenly mixing.As long as guarantee that per minute delivery solvent total amount equals the resin column elutant and flows out total amount, and constant, can adopt to be different from 1% Grad.
Formulation standard elution curve is the solvent burden ratio according to used resin on this resin column, the characteristic of the thick product of tea-polyphenol, under equal or conditions of similarity, find out the best gradient proportioning of eluting solvent through trial test, wash-out under constant flow velocity and gradient condition, access some parts continuously with volume elutriant sample under meter, under UV278nm, 35 ℃ of conditions of column temperature, detect the content of various catechin monomers in every part of liquid with HPLC efficient liquid phase chromatographic analysis instrument.Then, be ordinate zou with certain catechin content (%), with the elution time (minute) be that X-coordinate is drawn its elution curve, promptly time-the absolute content curve, the receipts peak standard elution curve of this catechin during as the desorb wash-out.During actual receipts peak, with on the adsorption column by solvent elution get off through effusive certain catechin of under meter time-the absolute content standard flows out peak of curve and divides flow liquid to compare through the purpose peak value that HPLC detects acquisition with resin column proportional diverting device, regulate and proofread and correct, make the two synchronous, access and receive peak liquid, each the monomer component purity that guarantees to collect is all more than 99%.Adopt receipts peak monitoring in real time also to be convenient to realize accessing the liquid automatization of purpose peak.The unified receipts of two monomer component intersections honeybee is made mixture, i.e. the high-purity tea polyphenol elaboration on the gauged receipts peak typical curve.
Advantage of the present invention is: the tea extract purifies and adopts the sedimentation centrifugation, obviously is better than the precipitator method commonly used at present, and the separation efficiency height can effectively be removed microfine impurity, oil slick, lipid and sediment simultaneously, and the protection polymeric adsorbent is not contaminated; Ethyl acetate extraction liquid and water adopt the sedimentation centrifugation, and layering is saved time and equipment than putting only, prevents vinyl acetic monomer emulsification and the loss of being taken away by water, the product yield height, and solvent load is few, and loss is few.The clean liquid of tea is directly gone up adsorption resin column without concentrated or dry, saves heat energy, reduces cost.Absorption separates with catechin adopts the resin column water jacket to send cold water or water from ice, the eluting solvent gradient adds, pre-establish the standard elution curve of each monomer of catechin from the adsorption resin column desorb, and the HPLC field monitoring is proofreaied and correct technical measures such as elution curve, monomer in the complicated mixture is successively eluted one by one according to its polarity, than fixedly flow of solvent phase wash-out receipts peak effect is much better, do not trail and the repetition peak, can isolate 7 catechin products, the purity of catechin is reached more than 99%.The present invention also can comprehensively reclaim caffeine, and byproducts such as tealeaves polysaccharide, liquid tealeaves saponin, chlorophyll, flavones and the dried dreg fodder of tealeaves have brought economic benefit to factory.
Device of the present invention has designed the volume pump group that drags with frequency modulation motor by Industrial Computer Control, has guaranteed that gradient single or that mix eluting solvent adds.Liquid stream or filter screen are obstructed in the post, when not reaching constant rate, also can start volume pump and give pressurization in the post, and production can be carried out smoothly.Column casing different positions from top to bottom is equipped with liquid level visor, the upper visor of resin, the next visor of resin in the post, be convenient to observe liquid level in the regulation and control post, resin column height, the variation of resin column post look, also be provided with the proportional diverting device, introduce the HPLC detector and carry out field monitoring, help the high purity of the smooth implementation and the separating monomer of technology of the present invention.Column casing is equipped with backwash pipeline valve, overflow weir and the filter screen thereof that links to each other with pure water pump, is convenient to stir backwash resin regeneration and mediation lower filter screen, prolongs the resin column life cycle.The column casing bottom is provided with the resin outlet orifice, pumps into pure water when changing old resin, starts the double leaf agitator, resin and water can be discharged simultaneously, than manually dig resin save time, laborsaving.Apparatus of the present invention are the ultra-large type adsorption resin column, and processing power reaches " 10 kilograms of magnitudes ", and production cost is reduced greatly.
Device of the present invention and the gradient elution that uses this device to adopt pre-establish technique means such as the standard elution curve of effective monomer component and field monitoring correction and can be used for fully extracting separating of natural medicinal ingredients and effective monomer pharmaceutical cpd from other animal and plant.
Description of drawings
Fig. 1 is an adsorption resin column synoptic diagram of the present invention.
Embodiment
Below in conjunction with drawings and Examples device of the present invention and technology are elaborated.
The device of implementing process using of the present invention is that the tea-polyphenol extraction separates dual-purpose full-automatic adsorption resin column with catechin monomers, it comprises the column casing 21 of loaded resin, the post lid 3 of truncated-spherical shape is arranged at column casing 21 tops, it and column casing are tightly connected, post lid 3 is provided with resin water liquid feed port 2 and tensimeter 30, and the inverted cone liquid discharging bucket that column casing 21 bottoms connect is provided with wastewater discharge pipe 17.The below of covering 3 connecting portions near column casing and post in the column casing 21 is provided with annular water or ejection of solvent pipe 4, spray tube 4 is connected by the connecting tube solvent jar 25 bottom vent pipe valves 23 outer with being arranged at column casing 21, and pure water, the clean liquid of tea, the tea-polyphenol aqueous solution and eluting solvent all are to be sprayed to the polymeric adsorbent that fills in the column casing by spray tube 4 through solvent jar 25.Liquid level visor 5 in the post is installed on the column casing wall from top to bottom successively, the upper visor 9 of resin, the next visor 14 of resin, the next visor 14 is installed in filtering net 20 tops of column casing 21 and column casing bottom inverted cone liquid discharging bucket connecting portion near the bottom, by pure water in 3 visor coupled columns, clean liquid, eluting solvent, the liquid level of tea-polyphenol solution, and the last level position (loading height) of the interior loaded resin of post and the observation of bottommost resin colourity, it is constant to be convenient to the interior liquid level of post, make interior pressure of resin column and outflow liquid measure constant, being convenient to the resin column height is consistent, stablize desorb wash-out elution curve, observing the next post look of resin column during wash-out changes, connect peak liquid reference when being convenient to the separating monomer catechin, be beneficial to the high purity of the smooth implementation and the assurance separating monomer of technology of the present invention.The column casing upper portion side wall has overflow weir 6, the horizontal center line of the horizontal center line of overflow weir 6 and liquid level visor is located in the same horizontal plane, be close to the column casing wall on the overflow weir 6 filtering net is arranged, when the backwash resin column, filtering net can make the particulate of post internal adsorption and broken toner discharge from overflow weir 6, and the resin of cleaning is retained in the post, helps the cleaning and regeneration of resin column, prolongs the resin column life cycle.Column casing 21 inside center are provided with and stir rachis 12, stir and be connected with agitator motor 1 after post lid 3 is stretched out in rachis 12 upper ends, its middle part and lower end are installed a upper strata paddle 11 and lower floor's paddle 13 respectively, the resin submergence that paddle 11 and 13 is all loaded in the post, stir resin when helping turning round fully, when resin is cleaned in backwash, can thoroughly exclude the broken resin and the particulate of absorption, help resin from the resin outlet orifice 15 of filtering net 20 tops is close in column casing wall bottom, to discharge when changing resin.Column casing 21 walls are positioned at the filtering net top outward and are provided with water jacket 8, bottom in water jacket 8 one sides is provided with water inlet pipe 19, the top of symmetrical opposite side is provided with rising pipe 7, the top of water jacket 8 should be higher than the loading height of resin in the post, like this when water inlet pipe 19 input cold water or water from ice are lowered the temperature to resin column, just can guarantee that resin temperature is even up and down, help the stable of technological process.Several ultrasonic transducer oscillators 10 are installed on the outer wall of water jacket 8, during the tea-polyphenol wash-out, are made wash-out more complete, when resin regeneration is cleaned, make resin absorption particulate and broken resin clean more thorough through ultrasonic cleaning through ultrasonic wash-out.Be provided with backwash pipeline valve 16 and the under meter 18 that is communicated with this vent pipe 17 between the inverted cone liquid discharging bucket of the by-pass valve control of wastewater discharge pipe 17 and column casing 21, two valves are housed before under meter, foreline valve is near wastewater discharge pipe 17, second valve is near under meter 18, near proportional diverting device 29 is housed after the foreline valve, during each monomer component of extraction separation, branch flow liquid through proportional diverting device 29 enters the HPLC detector, the elution curve of the effusive monomer component of field monitoring under meter, be beneficial to compare and proofread and correct, make that to access purpose peak liquid more accurate with the standard elution curve.Carrying out pure water when washing operation such as post, close under meter 18 foreline valves, open wastewater discharge pipe 17, make the waste water that need not to reclaim discharge adsorption resin column; When resin was cleaned in backwash, the pure water pumps water entered through backwash pipeline valve 16 and cleans resin in the post; When carrying out operations such as solvent elution tea-polyphenol and catechin, activated resin, then close wastewater discharge pipe 17, drive 18 two valves of under meter, make eluate solvent enter special-purpose storage tank, be convenient to solvent recuperation.The present invention is provided with special high level solvent jar 25, paddle 24 is set in the solvent jar 25, the paddle motor 28 that is installed in solvent jar 25 tops drives paddle 24 rotations by stir shaft, make the solution or the solvent that add in the jar even, send on water or the solvent injecting jet pipe 4 adding resin column liquid levels by solvent jar outlet valve 23 and pipeline again.The solvent tank top also has charging opening 26, and the clean liquid of tea and the tea-polyphenol aqueous solution also can add on the resin column liquid level through solvent jar 25 thus again.Apparatus of the present invention are provided with a volume pump group 22, and Fig. 1 represents to be made up of 4 volume pumps, and 22-1 advances pure water, and 22-2 advances ethanol, and 22-3 advances methyl alcohol or the clean liquid of tea or the tea-polyphenol aqueous solution, and 22-4 advances acetone, also more or less volume pump can be set according to producing needs.Every volume pump is driven by frequency modulation motor, regulate solvent, solution, pure water operational throughput by changing motor speed, the gradient that particularly can realize eluting solvent adds, and the liquid that each volume pump is carried is imported in the resin column after solvent jar 25 mixes by total output tube of volume pump group.The volume pump that adopts can be a ram type pump, diaphragm pump, and the shell and tube METERING DIAPHRAGM PUMPS, mechanical diaphragm variable volume pump etc. has the various forms pump of output metering.Can also replace the volume pump group with forming the identical under meter group of platform number.The running of each volume pump frequency modulation motor, and the switching of wastewater discharge pipe, under meter, backwash pipeline valve, water jacket water inlet and rising pipe, overflow weir or the like pipeline valve 27 all by industrial computer according to processing step and requirement and predefined program is controlled, thereby realize the fully automatic operation of present device.
According to industrial scale and needs, the ratio of adsorption resin column column casing interior diameter d of the present invention and clear height (removing the height of loam cake and bottom liquid discharging bucket) h can be 1～30: 1, or select arbitrarily in 1: 1～30 the scope.Following examples column casing interior diameter d is 59cm, and clear height h is 160cm, and d: h is 1: 2.71, dress D101 macropore or C
18The high h of resin is 110cm, and D101 macropore or C once pack into
18Polymeric adsorbent 300L.
Embodiment 1 is undertaken by aforementioned extraction process step, DHC-500 type decanter type disc separator (following examples are identical) is adopted in the sedimentation centrifugation, take by weighing 150 kilograms of time dried green teas, be crushed to granularity≤1mm, by tealeaves and pure water weight ratio is 1: 8～15 (best 1: 10), 90～95 ℃ of temperature, add pure water and stir extraction 10～20 minutes minutes, press the tealeaf residue after filtering: hot pure water weight ratio is 1: 4～6 (best 1: 5), with 90～95 ℃ of hot pure water washery slags once, twice tea extract adds hydrochloric acid or acetic acid is adjusted pH value to 3～4, resin column absorption on the clean liquid in settlement separate back, pure water is washed behind the post alcohol desorption wash-out tea-polyphenol with weight concentration 80%, control 8～16 liters/minute of absorption flows (best 8 liters/minute), 5～20 ℃ of adsorption temps, 4～9 liters/minute of desorb wash-out flows (best 4 liters/minute), after the desorb 10～20 minutes, ultrasonic again wash-out 5～15 minutes (best 10 minutes), the elutriant vacuum concentration reclaims ethanol, water added vinyl acetic monomer with 1: 1 and extracts tea-polyphenol at normal temperatures twice, extraction liquid and water are settlement separate, vacuum concentration reclaims vinyl acetic monomer, solution gets the thick product of flaxen tea-polyphenol through spraying or lyophilize, analyze through HPLC, extraction yield is 11.65% of a stem tea, thick tea-polyphenol purity 〉=75%.
Take by weighing water and carry 25 kilograms of tea-polyphenol crude products, by the weight ratio of tea-polyphenol and pure water is to add the pure water dissolving at 1: 30, resin column absorption on the tea-polyphenol aqueous solution, 8 liters/minute of control absorption flows, 5～20 ℃ of adsorption temps, desorb eluting solvent acetone increases progressively 1% gradient adding by per minute, the first gradient interval is 15～45%, the second gradient interval is 45～60%, in pure water, add 0.05% trifluoracetic acid (TFA) simultaneously, by measuring in advance, and regularly collect each catechin peak liquid through the gauged wash-out standard elution curve of HPLC field monitoring: 4 liters/minute of control desorb flows are constant, 5～20 ℃ of desorption temperatures, the first gradient interval, between 9～12 minutes, collect CAF (caffeine) peak liquid, collect EGC peak liquid between 13～16 minutes, collect DL-C peak liquid between 18～22 minutes, collect EC peak liquid between 27～29 minutes; EGCG peak liquid is collected in the second gradient interval between 30～35 minutes, collect GCG peak liquid between 38～41 minutes, collects ECG peak liquid between 51～55 minutes.Each monomer elutriant vacuum concentration respectively reclaims acetone, and solution gets 0.168 kilogram of 3 kinds of monomer non-ester catechin EGC, 0.068 kilogram of DL-C, 0.536 kilogram of EC through spraying or lyophilize; 13.000 kilograms of 3 kinds of monomer ester catechin EGCG, 0.054 kilogram of GCG, ECG2.433 kilogram; 2.445 kilograms of tea-polyphenol elaboration.Catechin yield 65.036%.Through the HPLC efficient liquid phase chromatographic analysis, 6 kinds of catechin purity 〉=99.3%, tea-polyphenol elaboration purity 〉=95.41%.
Embodiment 2 takes by weighing time dried green tea and is crushed to granularity≤1mm for 150 kilograms, by tealeaves and 80% ethanol (or methyl alcohol) weight ratio is that 1: 5～8 (best 1: 7) add extractor, stirs and extracts 25～35 minutes (best 30 minutes), 60～65 ℃ of controlled temperature, extract twice.Press filtration gets extracting solution, settlement separate with hydrochloric acid (or acetic acid) adjust pH to 3～4 backs, clean liquid vacuum concentration reclaims ethanol, water added vinyl acetic monomer normal temperature with 1: 3 and extracts tea-polyphenol twice down, extraction liquid and water sedimentation centrifugation final vacuum concentrate to reclaim vinyl acetic monomer, and solution is analyzed through HPLC through spraying or lyophilize gets the thick product of tea-polyphenol of yellowish white, extraction yield is 13.21% of a stem tea, thick tea-polyphenol purity 〉=73.5%
Take by weighing 25 kilograms of the thick tea-polyphenol of alcohol extracting, added the pure water dissolving as embodiment 1 by 1: 40, resin column absorption on the clean liquid in the settlement separate back of the tea-polyphenol aqueous solution is used acetone desorb wash-out, is received the peak, 13 liters/minute of absorption flows, 6 liters/minute of desorb flows are constant, and all the other processing condition and receipts peak period get 1.0503 kilograms of 7 catechin: EGC with embodiment 1,0.0285 kilogram of DL-C, 0.0643 kilogram of EC, 12.36 kilograms of EGCG, 0.5803 kilogram of GCG; 1.74 kilograms of ECG; Collected 0.0448 kilogram of CG in 58～61 minutes, amount to 15.8682 kilograms, yield accounts for thick tea-polyphenol 63.472%, also receive 2.1583 kilograms of tea-polyphenol elaboration, yield 8.633%.Analyze each catechin monomers purity 〉=99.1%, tea-polyphenol elaboration purity 〉=96.32% through HPLC.
Embodiment 3 takes by weighing 25 kilograms of commercially available thick tea-polyphenol, adds pure water as embodiment 1 by 1: 50 and dissolves settlement separate clean liquid, the carbon 18 (C on the clean liquid of getting in back
18) resin column absorption, the control absorption flow is 16 liters/minute, desorb eluent methyl alcohol increases progressively 1% gradient adding by per minute, the gradient interval is 15%～55%, only carry out wash-out one time, in pure water, add simultaneously 0.05%TFA, the desorb flow be 9 liters/minute constant, regularly collect each catechin peak liquid by the receipts peak technology of embodiment 1: collect EGC liquid between 11～13 minutes, collect DL-C liquid between 13.5～14.5 minutes, collect EGCG liquid between 15～19 minutes, 19.5 collect EC liquid between～21 minutes, 21.5 collect CAF liquid between～25 minutes, collect GCG liquid between 26～28 minutes, collect ECG liquid between 29～31 minutes.Get 0.155 kilogram of each catechin EGC after the drying, 0.068 kilogram of DL-C, 12.625 kilograms of EGCG, 0.411 kilogram of EC, 0.041 kilogram of GCG, 1.933 kilograms of ECG, amount to 15.233 kilograms, yield accounts for thick tea-polyphenol 60.932%, also receive 2.033 kilograms of tea-polyphenol elaboration, yield 8.132%.Analyze each catechin monomers purity 〉=99.06% through HPLC; Tea-polyphenol elaboration purity 〉=95.20%.
Claims (10)
1. the preparation technology of high-purity tea polyphenol and catechin comprises that tea leaf powder is broken to granularity is not more than 1mm, is characterized in that:
(1) extracts tea-polyphenol with water extraction, tealeaves and pure water weight ratio are 1: 8～15,90～95 ℃ of temperature, stir and extracted 10～20 minutes, filter the back with temperature be 90～95 ℃ hot pure water washery slag once, slag and water weight ratio are 1: 4～6, and it is to carry out the sedimentation centrifugation after 3～4 to get clean liquid that tea extract is adjusted the pH value with hydrochloric acid or acetic acid;
(2) clean liquid is directly gone up adsorption resin column, 5～20 ℃ of adsorption temps, 8～16 liters/minute of post delivery flow, absorption finishes and washes post with pure water, pure water the is washed post postemphasis amount concentration desorb wash-out tea-polyphenol that is 80% ethanol from the resin column, and collect elutriant, 4～9 liters/minute of wash-out flows, behind the alcohol desorption 10～20 minutes, ultrasonic again desorb wash-out 5～15 minutes;
(3) after the ethanol eluate vacuum concentration reclaims ethanol, water is 1: 1～3 to add vinyl acetic monomer normal temperature extraction tea-polyphenol by weight, after extraction liquid and the water sedimentation centrifugation, vacuum concentration reclaims vinyl acetic monomer, and solution gets the thick product of tea-polyphenol through spraying or lyophilize;
(4) be 1: 30～50 to add the pure water stirring and dissolving by thick product of tea-polyphenol and pure water weight ratio, adsorption resin column absorption on the aqueous solution, 5～20 ℃ of adsorption temps, 8～16 liters/minute of post delivery flow, absorption finishes and washes post with pure water;
(5) pure water is washed separation and Extraction catechin behind the post, eluting solvent by stages section or be regardless of the segment gradient and increase progressively to add and carry out the desorb wash-out, control elutriant flow is selected a value in 4～9 liters of/minute intervals constant, 5～20 ℃ of temperature, simultaneously catechin from the polymeric adsorbent by desorb time-the absolute content standard flows out peak of curve and resin column proportional diverting device and divides flow liquid to detect the purpose peak value of acquisition when synchronous through HPLC, regularly collect each monomer component peak liquid, last vacuum concentration reclaims solvent, and solution is sprayed mutually or each catechin is made in lyophilize.
2. the preparation technology of a kind of high-purity tea polyphenol according to claim 1 and catechin, it is characterized in that extracting tea-polyphenol with solvent method from tealeaves, the employing weight concentration is 80% ethanol (or methyl alcohol), 60～65 ℃ of controlled temperature, stir and extracted 25～35 minutes, filter residue extracts once again.
3. the preparation technology of a kind of high-purity tea polyphenol according to claim 1 and 2 and catechin is characterized in that the polymeric adsorbent of filling in the resin column is from D101, NKA-2 macroporous adsorbent resin, C
18Resin, dextran Sephadex LH-20 gel resin is appointed in the polymeric amide sorbent material and is selected one.
4. the preparation technology of a kind of high-purity tea polyphenol according to claim 1 and 2 and catechin is characterized in that from the resin column desorb wash-out tea-polyphenol weight concentration is 80% acetone, or methyl alcohol.
5. the preparation technology of a kind of high-purity tea polyphenol according to claim 1 and 2 and catechin, it is characterized in that catechin desorb eluting solvent from the adsorption resin column is an acetone, adopt the by stages section to increase progressively 1% operational throughput gradient adding by per minute, the first gradient zones metacetone weight concentration increases to 45% by 15%, the weight concentration of the second gradient zones metacetone increases to 60% by 45%, receives the peak respectively and gets catechin.
6. the preparation technology of a kind of high-purity tea polyphenol according to claim 1 and 2 and catechin, it is characterized in that catechin desorb eluting solvent from the adsorption resin column is a methyl alcohol, employing is regardless of segment and increases progressively 1% operational throughput gradient adding by per minute, the methyl alcohol weight concentration increases to 55% by 15%, receives the peak and gets catechin.
7. the preparation technology of a kind of high-purity tea polyphenol according to claim 1 and 2 and catechin, it is characterized in that the solvent that catechin desorb wash-out from the adsorption resin column is adopted can also be from vinyl acetic monomer, acetonitrile, dimethyl formamide is appointed in the trifluoroacetic acid and is selected one.
8. the adsorption resin column that adopts of the preparation technology of described high-purity tea polyphenol of claim 1 and catechin, it is characterized in that it comprises resin column column casing [21], the post lid [3] that is connected with the column casing top seal, post covers and has resin water liquid feed port [2] and tensimeter [30], the water or the solvent injecting jet pipe [4] that are provided with near post lid and column casing connecting portion in the column casing, liquid level visor [5] in the post of installing successively from top to bottom on the column casing wall, the upper visor of resin [9], the next visor of resin [14], the overflow weir that filtering net is housed [6] that column casing wall top is provided with, be installed on post cover with column casing in stir the agitator motor [1] that rachis [12] is connected, stir on the rachis at the upper strata paddle of between upper and the next visor of resin, installing [11] and lower floor's paddle [13], the filtering net [20] that is provided with on the inverted cone liquid discharging bucket of column casing bottom, the resin outlet orifice [15] of filtering net [20] top is close in column casing wall bottom, the column casing wall is positioned at the water jacket [8] that the filtering net top is provided with outward, the water jacket water inlet pipe [19] and the rising pipe [7] that are provided with respectively on the top of the bottom of water jacket one side and opposite side, several ultrasonic transducer oscillators [10] are installed on the outer wall of water jacket, the inverted cone liquid discharging bucket of column casing bottom is provided with wastewater discharge pipe [17], be provided with between wastewater discharge pipe valve and the inverted cone liquid discharging bucket with the backwash pipeline valve [16] of this vent pipe connection and link to each other and under meter [18] with [22-1] pump discharge, connecting tube and solvent jar outlet valve [23] that water or solvent injecting jet pipe [4] are connected with solvent jar [25], the paddle motor [28] that is installed in the solvent tank top connects a jar interior stirring rachis and a paddle [24] that is provided with, the solvent tank top also has charging opening [26], its total output tube is connected the volume pump group [22] that some the volume pumps by frequency modulation motor control of water or solvent injection resin column can be formed with solvent jar [25], install proportional diverting device [29] additional near behind the under meter control valve of wastewater discharge pipe, the industrial computer that divides flow liquid to enter HPLC detector field monitoring and control each volume pump running and each pipeline valve [27] switching.
9. the adsorption resin column that the preparation technology of high-purity tea polyphenol according to claim 8 and catechin adopts, the interior diameter d that it is characterized in that the adsorption resin column that adopts is 1～30: 1 with the ratio of the column casing clear height h that removes loam cake and bottom liquid discharging bucket, or 1: 1～30.
10. according to Claim 8 or the adsorption resin column that adopts of the preparation technology of 9 described high-purity tea polyphenols and catechin, it is characterized in that replacing the volume pump group with forming the identical under meter group of platform number.
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