• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    1295386 Continuous cyclic chromatography BOEHRINGER MANNHEIM GmbH 19 July 1971 [23 July 1970 13 March 1971] 33784/71. Heading B1X A process for the continuous cyclic chromatographic separation of a multicomponent mixture utilising two columns connectable in series and which may be packed with ion exchangers comprises alternately passing the mixture and element, e.g. H 2 O to the first column 3 from sources S and W respectively by means of dosing pumps 1, 4 and switching clock 6. Eluent then passes to the second column 10. Any predetermined undesirable fraction emerging from the first column is detected by a detector 7, e.g. a flow through refractometer, which causes control 12 to switch a valve 8 to its Fig. 1 position so that the fraction is diverted to drain, and the connection between the columns is broken. During this time H 2 O is supplied to the second column 10 via pump 9. The fractions emerging from the second column are detected by detector 13, e.g. for measuring angle of rotation or refractive index, and diverted by valve 15 and its control 14 to the appropriate vessels. The columns may be packed with polystyrene sulphonate resin cross-linked with divinylbenzene and loaded with calcium ions. The multicomponent mixtures may be epimerised or non-epimerised starch syrup, or a salt free solution of starch hydrolysate which are to be split into glucose and fructose, and the impurities may be oligosaccharides.
    公开号:SU797547A3
    申请号:SU711686010
    申请日:1971-07-22
    公开日:1981-01-15
    发明作者:Лауер Карл；Вудка Хейнц-Гюнтер；Штек Георг
    申请人:Берингер Маннхайм Гмбх (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF CHROMATOGRAPHIC SEPARATION OF MULTICOMPONENT MIXTURES
    one
    This invention relates to an improved method for the technical separation of multicomponent mixtures using continuous cyclic column chromatography.
    There is a known method for separating a multicomponent mixture containing, for example, fructose, glucose and sucrose, by cyclic column chromatography using adsorbents and eluents known for these mixtures. This column is a system of 6 serially connected glass tubes each 2 m; fl.
    The disadvantage of this method is the low selectivity of the separation of the high-quality component of the crumbly molasses - fructose, which is caused by a long cycle period and a higher rate of movement of the contaminants in comparison with the speed of the main component.
    . The purpose of the invention is to increase the separation capacity of the above method.
    The goal is achieved in the manner that the separation column is divided into two sections, the mixture BetjecTB is introduced into,
    the first section, washed with eluent, the fractions not separated at the end of the first section of the separation column are fed to the second section, while
    the separated fractions are removed at the end of the first section of the column, at the same time an eluent liquid is supplied to the second section in an amount equivalent to the selected fraction,
    after separation of the fraction in the second section, both sections of the column are reconnected until the newly separated fraction of the next cycle is opened.
    A preferred embodiment of the method is: separation of glucose-fructose molasses contaminated with disaccharides and polysaccharides into cation-exchange
    resins in the form of alkaline or alkaline earth metal meta-salts with ic: using water as an eluent, separating starch hydrolysates on cation-exchange resins in the form
    alkaline or alkaline-earth metal salts using water as eluent, column areas usually have a ratio of 1: (2-3). The proposed method can be used in all large-scale separation processes, where the transit time of contaminants differs from the transit time of the separated main components. The description of the method is illustrated in FIGS. 1 and 2. From the tank S, the multicomponent mixture solution is pumped by pump 1 via line 2 to the first section of the column. After a certain time, the pump 1 is turned off and at the same time from the tank with the eluting medium W by the pump 4 through the pipeline 5 to the first section 3 of the column, the elution liquid is pumped over, and the capacity of both pumps 1 and 4 is the same. At the end of the elution phase, the pump 4 is turned off and the pump 1 is switched on again. Pumps 1 and 4 are controlled by a clockwork 6 with empirically determined and fixed time intervals. The liquid leaving the section 3 of the column flows through the analyzer 7, which, depending on the concentration of the individual fractions, turns on valve 8 through the regulating device 12. When the fraction containing only contaminants reaches the analyzer 7, valve 8 is turned on so that the liquid leaving section 3 The columns are directed to the tank D. At the same time, the pump 9 is switched on, transferring fluid from the tank W. to the column section 10, and the capacity of this pump is exactly the same as the capacity of pumps 1 and 4. Start with a certain concentration of the fluid flowing through the analyzer 7, i.e. after removing the contamination and reaching a certain level of concentration of the first main fraction, the valve 8 is switched in such a way that the analyzer 7 is directly connected to the supply pipe (see Fig.2). The pump is turned off in this position, so that there is no connection between tank D and tank W The logic / element in the analyzer 12 remains unchanged until the concentration of the liquid flowing out of the analyzer 7 increases from zero to some small value. This occurs when, after the intermediate pass of the pure eluent, analyzers 7 again get contaminated in the next cycle. The proposed method ensures that only the main fractions get into the longer section of the column 1, which lie under further separation. Further separation is made with the following. The analyzer 13 switches the valve 15 through the regulating device 14 in such a way that the first fraction accumulates in reservoir G and the second fraction in reservoir G. The gap between the exact fractions containing both components is directed to the G / F tank. The separator plant has three regulating units, formed in Figures 1 and 2 by dashed lines. Unit 1, which includes a clock mechanism 6 and pumps 1 and 4, operates completely independently and is set up empirically at the start of the separator system so that the node L1 fraction followed without a break with as little overlap as possible. Unit II, consisting of an analyzer 7 with a regulating device 12, a valve 8 and a pump 9, is designed to remove the fraction containing contaminants. The analyzer consists of a simple concentration meter, such as a flow refractometer, the results of which are communicated as a proportional to the measured voltage parameter of the regulating device 12. The latter has a so-called logic element, which is, for example, a tracking relay, through which the valve 8 and the pump 9 they are turned on at a certain concentration only if at the moment of switching on the concentration of the liquid flowing through the analyzer is in the increase stage. The control device shuts off the water pump 9 k during the collection of contaminated fractions. The unit 11, designed to separate fructose and glucose, consists of an analyzer 13 with a control device 14 and a valve 15. The unit is designed to direct the main fractions into the respective tanks G, G / F and F. The analyzer 13 consists of one measuring device for the angle of rotation and one for the index of refraction. Measuring instruments are equipped with flow cells and their measurement results are reported to the device 14 in the form of voltage proportional to the parameter. Control device 14 contains a computing device that calculates partial concentrations of glucose and fructose. If there is a deviation from the permissible concentration limits, valve 15 is turned on. To control the separation process, a multi-color chart recorder can be connected to the computing device of the regulating device 14, recording the concentrations of glucose and fructose in the form of a continuous elution pattern. In Fig. 2, node II is connected in such a way that section 3 of the column is directly connected by valve 8 and inlet pipe 11 with a section of the column 10.
    Example 1, Production of pure fructose from epimerized starch syrup.
    Dimensions of the column: section 3 of the column: diameter 10 cm, length 4.5 m,
    section 10 of the column: diameter 10 cm length 9.0 m.
    At a rate of movement of 1 l / h 2 l of 3.5% by weight, it is epimerized. A solution of starch syrup is fed to section 3 of the column. After 20 minutes, pump 1 is turned off and pump 4 is supplied with a flow of 2.6 liters / hour from tank W to section 3 of the column for 2.6 hours. Pumps 1 and 4 provide alternately in the same rhythm of loading section 3 of the column. After about 90 minutes, analyzer 12 measures the first changes in the index of refraction. Valve 8 is activated so that the eluate drains into reservoir O. Now in section 10 of the column, the pump 9 supplies water. After another 90 minutes, the column will be cleared of contamination. At a concentration of about 190 g of glucose / liter, the valve 8 is switched and the section 3 of the column is connected to the section 10 of the column. The eluate is further divided in section 10 of the column and sent to tanks G, G / F and F. For fructose, the rotation angle is approximately 92 °, which corresponds to the purity requirement of German Pharmacology (OAB 7)
    Example 2. Getting pure dextrose from starch hydrolysates.
    Dimensions of COLUMN: 1st section of the column: diameter 1.2 m, length 5.0 m,
    2nd section of the column: diameter 1.2 m, length 10.0 m.
    Filling the column: DOWEKC50WX4 in Ca form. (polystyrenesulfonate resin, the mesh structure of the molecules in which created divilbenzene).
    50% w / w desalted starch hydrolyzate is fed to the column at a rate of 1200 l / h. After 60 minutes, the feed is stopped and another pump 4 is supplied with water at a speed equal to 1200 l / h for 3 hours. The column is loaded hundreds of times without interruption with this 4-hour time cycle. After 80-90 minutes after the feeding of the starch hydrolyzate, the analyzer detects at the end of the first part. The formation of fast moving contaminants (oligosaccharides). The eluate is taken up for 30-40 minutes in the corresponding tank and replaced with the same amount of water. After the first dextrose enters the analyzer, section 3 of the column is connected to section 10 of the column and, according to the readings of the second analyzer at the end of the second section of the column, the eluate is divided into oligosaccharide fraction and dextrose fraction.
    After evaporation, the zlyuata is obtained. based on the amount of starch hydrolyzate added, about 5 to 90% dextrose, 98-99% pure, 8-10% oligosaccharides selected at the end of the first section of the column, and 1-3% oligosaccharides selected at the end of the second section of the column. Cyclic loading with starch hydrolyzate makes it possible to divide 7200 liters of starch hydrolyzate per day, i.e., to obtain about 3500-4000 kg of dextrose per day.
    Example 3. Preparation of albu min, lactose and calcium lactate from serum.
    Column Size:
    1st section of the column: diameter
    10 cm, length 1 m, 0 2nd section of the column: diameter
    10 cm, length 3 m.
    Filling the column: Lefatit
    TSW-iiO in calcium form (polystyrene resin with sulfonic acid groups).
    Acidic serum is concentrated in vacuo at 40 ° C to 6 times the solids content. The resulting concentrate is fed in portions of 1 liter Q at a temperature of 20 ° C to the top of the separation column and elution with distilled water at 20 ° C.
    After every 10 liters of eluting agent, 1 l of concentrate is reintroduced into the column. At the exit of both sections of the column, the solids content is continuously determined using a flow-through refractometer.
    权利要求:
    Claims (1)
    [1]
    After the introduction of 2.5-3 l, elute-. At the exit of the first column, the appearance of rapidly moving fractions containing protein and lactose is observed. After adding approximately 6 liters, these fractions completely pass into the second part of the column, after which the second part of the column is directly connected to the pipeline-eluting agent, and the liquid, which then exits from the first part of the column, is discharged to obtain calcium lactate. The bulk of the calcium lactate is obtained during the addition of the 8-11th liter of eluent into the first part of the column. Between the 12th and the 13th liter of the liquefying liquid, the following fraction of protein and lactose appears, so that both columns re-connect with each other and carry out further work accordingly. 0 At the end of the second section of the column, after adding 10 liters of elution liquid, a protein fraction is obtained. After the addition of 13.5-19 liters, a fraction containing lactose is obtained. Besides the daily fractions, before the appearance of the next protein fraction after 20 liters of the calcium lactate residues contained, are discarded. Protein fractions are collected and carefully evaporated in vacuo at 4 ° C., The product is obtained in the form of colorless flakes. The fractions containing lactose and calcium lactate are evaporated, and crystalline products are obtained after recrystallization from water. As a result, 50 g of protein, 280 g of lactose and 80 g of calcium lactate are obtained from each liter of whey concentrate. Example 4. Method for the continuous production of pure steroids from a mixture obtained by reducing testosterone. Filler for the column: Sephadex LH20. Eluent; methylene chloride / methanol 96/4. Dimensions of the column: section of the column, 3: diameter 3 cm, length 50 cm, section of the column 10, diameter 3 cm, length 100 cm. At a speed of 300 ml / h, 30 ml of a steroid solution (obtained by restoring 5 g of testosterone) in the flux. After b min, pump 1 is turned off, and pump 4 supplies eluent from the tank for 9 hours. Then pumps 1 and 4 alternately in a constant rhythm feed the indicated substances into column section 3. After 3 hours analyzer 7 shows the first changes based on the testosterone content in the solution and the valve 8 ovits in a position to zlyuat flowed into the vessel about. Now, an eluate is supplied to the section of the column 10 by means of the pump 9. After a further 3 hours, the untreated test is removed from the column 3 and the incompletely separated recovery products are determined using an analyzer 7 (4-10 hours). Valve 8 is switched off and column 3 is connected to column 10 until testosterone is again detected with the analyzer 7 (12-15th hour), after which valve 8 is restored to its original position. Then, the eluate is again divided into a regular section of the column section 10, after which pure ILR, 17 | b-androstan diol (12-15th hours) are obtained; Sp |, 171-androstanediol (15-18th hours) and 3 | 4 , drostenediol {18-21st hours). At the task rhythm at 9 o'clock all activities and factions are repeated after a specified time. Without the separation of testosterone, which flows through the column 3-4 times faster than androst andiol, the task must be extended to at least 27 hours in order to avoid merging the two consecutive cycles. Example 5. Chromatographic production of purine bases from a mixture of crude (unpurified) bases of nucleosides. The filler for the column-exchange resin OowexSO in acid form. Eluent: methanol / 2m aqueous solution of hydrochloric acid 1/9. Sizes of the column: section of the column 3, diameter 9 cm, length 1 m, section of the column 10, diameter, length 3 m. 300 ml of a 2% solution of uracil, cytosine, guanine and adenine are fed into the section of column 3 at a rate of 6 l / h with the help of pump 1. After 3 min, the pump 1 is turned off and with the help of the pump 4 over the next 4 hours, the eluate from the tank W is fed into the column 3. Pumps 1 and 4 are then fed alternately with the indicated substances in column 3. After about 1.2 hours, the first changes are noted on the analyzer, and valve 8 is turned on so that the slush flows into the container O. At this time, the pump 9 supplies the eluate to the portion of the column 10. For a further 2.8 hours, the pyrimidine bases are completely flushed out of the portion of the column and the valve 8 is switched so that the COLUMNS 3 and 10 are re-connected together. The eluate is separated in the usual manner in the region of the column 10 and consistently pure guanine and adenine are obtained. Claim 1. The method of chromatographic separation of multicomponent mixtures by cyclic chromatography, in order that, in order to increase the separation ability of the method, the separation column is divided into two sections, the mixture of substances is introduced into the first section, washed with eluent, not separated at the end of the first section of the separation column, the fractions are fed to the second section, while the separated fractions are removed at the end of the first section of the column; at the same time, eluent liquid is fed to the second section lichestve equivalent to the selected fraction, after separation of fractions in the second section are both connected to the column again until yet not re Vits section EMA fraction sledukvdego cycle. 2, POP.1 method, characterized in that glucoe-fructose molasses, contaminated with scarsharides and sex, are separated by isahavids, n-exchangeable resins in the form of alkali or alkaline-earth metal salts, using as eluent.
    3. Method POP1, characterized in that the starch hydroliesates are separated into cation exchange resins in the form of their alkali or alkaline earth metal salts, using water as eluent.
    4. The method according to claims 1 to 3, of which the plots
    columns have a ratio of 1: (2-3). Priority on item m:
    07.23.70p.1,2 and 4;
    03.13.71 p.Z. Information sources,
    taken into account in examinations
    1. Patent of Germany No. 1567325, class, C 23 to 11/00, VYLOZH 16.04.70 (prototype).
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2362211C3|1973-12-14|1978-05-11|Sueddeutsche Zucker Ag, 6800 Mannheim|Process for processing molasses|
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    US4718405A|1986-07-25|1988-01-12|Uop Inc.|Enhancing L-glucose yield: epimerization of L-mannose by molybdate in presence of epimerization inhibitors|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2036525A|DE2036525B2|1970-07-23|1970-07-23|Method and device for the chromatographic separation of multicomponent mixtures|
    DE19712112176|DE2112176A1|1971-03-13|1971-03-13|Chromatographic separation process - with impurities removed at intermediate point from two section column|
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