DE1598555B2 - CHROMATOGRAPHIC SEPARATION PROCESS AND DEVICE FOR CARRYING OUT THE PROCESS - Google Patents

Description

45

The present invention relates to a chromatographic separation process with the aid of a separation tube, in which a substance to be separated is in the exchange of substances between a restrained and a funding phase is for which the function of the theoretical floor height against the total relative speed between the phases a first minimum of the floor height in the area of the laminar Has flow of the restrained phase, after which the floor level up to a maximum at considerably higher relative velocities, which essentially mark the beginning of turbulent flow conditions in the funding phase.

It has been known for a long time (see, for example, UhImann or Gas-Liquid Chromatography from St. Nο g a r e and R. J u ν e t, 1962, Interscience Publishers, New York, London, pp. 34 to 37) that for chromatographic separation processes usually a typical ratio between the relative Flow velocity between the phases on the one hand and the theoretical ground level on the other consists. In general, the height of the ground initially decreases with increasing speed and reaches a minimum at a relatively slow speed (which in this respect is an optimum in terms of separability of the system). At higher speeds, the height of the ground increases then constantly to.

So far it has been assumed that any increase in flow rate above this theoretical Optimum is inevitably paired with a corresponding increase in the theoretical floor height which will soon reach a value which is unacceptable for practical purposes. So it was previously for correct to adjust the relative flow velocity as close to this optimum as with can agree practically acceptable separation speeds. In gas chromatography these are Speeds pretty high. In liquid chromatography, the separations drag on for hours and sometimes days.

The object of the invention is to economically carry out chromatographic separations in significantly reduced time. In other words, in a given time the invention aims to do that Achieve vastly improved separations by applying a much larger one without wasting time theoretical plate number is made possible or that under the process conditions according to the invention a thorough radial mixing of the delivery phase perpendicular to the net flow direction and thereby a flattening of the flow profile in the separating tube is achieved.

The invention is based on the surprising discovery that, in contrast to the previous assumption, a reduction in the floor height is achieved again under certain conditions if the flow velocity is increased beyond a certain limit. In some cases one even reaches ground heights of the same order of magnitude as the minimum mentioned above, but at a much higher speed. Despite the mostly somewhat longer separation columns, the separation time in gas chromatography can be shortened by a factor of about 10, and in liquid chromatography by as much as 10 ⁴ times. The necessary conditions can be realized in practice and will also be discussed below.

The object is achieved in that the relative speed between the both phases above the speed corresponding to the maximum of the ground level, but below the speed is set at which the contribution to the ground level of the mass transfer resistance in the restrained phase the contribution to the ground level of the mass transfer resistance in the funding phase exceeds the order of magnitude, and that the reluctant Phase either kept completely stationary or moving linearly in countercurrent to the delivery phase or is adjusted so that the restrained phase assumes a whirled-up state, and that the mobility of the particles is limited to a fraction of the total length of the separation tube which does not exceed the order of magnitude of the cross-section of the separating tube.

The term "relative speed" is used because the invention is not only about Implementation of separations in the customary

intermittent operation, but also for countercurrent operation, especially for continuous Separations, suitable. For the same reason it is not possible in the broader sense of a "stationary" to speak in contrast to the "moving" phase, since both phases in continuous operation are movable. In all cases, however, it is the case that one phase retains the substances to be separated and seeks to delay, while the other phase promotes the substances to be separated.

In principle, the process can be applied to all common variants of chromatography, wherein the retaining phase is a solid or a liquid applied to a carrier or a gel (e.g. exchange resin), while the delivery phase can be gaseous or liquid.

The method is suitable for carrying out on a microanalytical scale, for carrying out Determinations in seconds (or even fractions of a second) or minutes, previously minutes or hours were required or even hardly feasible in terms of time. The time saving is in the large-scale operational monitoring is very valuable, as it enables immediate corrective measures ongoing production, for example in the oil and gas manufacturing or processing industry Industry, e.g. B. petrochemical, hydrocarbon synthesis, plastics manufacturing and other organic chemical industries. The procedure is suitable but also for the monitoring of various inorganic processes in which the raw materials or have products analyzed chromatographically, including the analysis of exhaust gases, e.g. Am metallurgical processes, e.g. B. in the oxygen inflation process in steelmaking.

Due to the increased throughput rate and the improvement in the flow profile, even at larger separating tube diameters, but in many cases it is also an economical preparative separation possible. Examples include the concentration or separation or purification of pharmaceuticals Active ingredients, e.g. B. hormones, vitamins, alkaloids, glycosides, antibiotics of essential oils and also inorganic substances, e.g. B. the extraction of rare earths, purification of fissile elements, Separation of cleavage products to obtain valuable by-products, separation of chromates, Extraction of precious metals, e.g. B. Gold, etc.

The method is both in unfilled and in uniformly or non-uniformly filled pipes, Pipes with internals and any other types of columns are possible, but of course apply not the same optimal conditions for all cases.

The invention also provides new or improved devices for performing the method.

A device according to the invention provides that a pipeline between two geographically different locations is designed as a chromatographic separation column, furthermore is a device with a pipeline set up as a separation column, characterized in that turbulence-inducing internals are provided.

Another device for carrying out the method according to the invention with a vertical separating tube with horizontal partition walls that are permeable to the conveying phase and impermeable to the restrained phase, the pipe sections between the partition walls being only partially filled with column filling material, is characterized according to the invention in that the pipe sections of the separating pipe are between the partition walls are designed as vortex chambers, the height of which does not exceed the size of the pipe diameter, the column filling material can be swirled and only partially fills the chambers in the non-swirled loose bed and that the inlet opening is attached at the lower end and the outlet opening at the upper end of the column.

If necessary, several of the separating tubes are connected in series via constrictions, and if necessary feed pumps are provided in the constrictions.

The invention also provides a device for the continuous implementation of the process with two columns, two removal points for fractions and a separate inlet port each for the delivery phase and the substance to be separated in the first column, which is characterized in that the first column to maintain a loosened ( powder state and for continuous gravity conveying of the column filling below a partition that is permeable to the conveying phase and impermeable to the restrained phase, such as a sieve plate or the like the inlet connection for the material to be separated and at the upper end of the column an outlet connection for the second fraction and a line for returning filling material from the upper end of the second column to the upper end of the first column, and that the second column le below has a device with a further partition and a chamber for the pneumatic or hydraulic conveyance of the column material by means of an eluant in the upper part of the column, which has a device for separating the filler from the eluent loaded with the first fraction and a further outlet port .

It shows

F i g. 1 a schematic curve of the relationship between the relative speed of the phases (U) and the theoretical ground level (H),

F i g. 2 shows a schematic view of a separation column in a special procedure according to the invention with loosened powder columns,

F i g. 3 shows a schematic view of a further development of the device according to FIG. 2 for continuous Implementation of the method according to the invention,

F i g. 4 shows a schematic view of a further device according to the invention for implementation of the process under fluidized bed conditions.

According to FIG. 1, section OA typically represents the ratio of H to U for filled or empty separation columns according to the prior art. It has now surprisingly been shown that the curve at B reaches a maximum and then decreases, provided that this effect is not masked by an excessive contribution of the restrained phase to the ground level. This contribution from the reluctant phase must be kept as low as possible under all circumstances. This is achieved by choosing the lowest possible effective

seed layer thickness of the restrained phase, which is further selected as possible so that the concentration distribution coefficient is high in the chromatographic system used, e.g. B. in the case of gas chromatography of the order of 1000 and in the case of liquid chromatography of the order of 100. The invention then provides that the chromatographic separation is carried out under the conditions which coincide with the leg of the curve to the right of B instead in the known manner in the area of the curve section a. It turns out that point B corresponds to the relative speed at which the flow form of the delivery phase assumes a turbulent character.

In typical examples, the relative speed at a, ie in the vicinity of the first curve minimum, is about 5 cm / sec when a gas is used as the delivery phase, and gas chromatograms are therefore also carried out at speeds of this order of magnitude. The speed in area b, which corresponds to the preferred conditions according to the invention, depends very strongly on the type of separating tube (and in certain respects also on the gas). If an empty, smooth-walled pipe with a diameter of 10 mm is used, the speed is of the order of magnitude of 2000 cm / sec. If a 1 mm capillary diameter is used, the speed is of the order of 100,000 cm / sec. In both cases, with thorough turbulence, the height of the floor approaches the size of the pipe diameter, provided that the resistance to the exchange of substances in the restrained phase is sufficiently low.

When using liquid delivery phases, completely different speed values apply, which are very strong depend on the viscosity of the liquid.

In filled columns the velocity at a is generally of the same order of magnitude as for empty separation tubes; for b , however, there are considerable differences, which largely depend on the type of filling.

") In the case of open (i.e. unfilled) separating tubes, the speed required to achieve the low floor height at b can be reduced under certain circumstances by appropriately spaced barriers in the flow path of the developer phase The turbulence-causing effect of the barriers lasts at least approximately from one barrier to the next. Struts, e.g. made of wire, can be provided in the pipe for this purpose. The barriers can also be attached to longitudinal wires, rods or threads inside the pipe, e.g. like the spikes of barbed wire. The obstructions can also be in the form of transversely stretched wire gauzes of a type similar to that in some known distillation columns.

The pipe walls can also be profiled to excite turbulence, in particular transversely to the Direction of flow, be provided.

The above measures increase at the same time the amount available for the reluctant phase standing surface.

Vibrations, in particular ultrasonic vibrations or also mechanical vibrations, can also be used to generate turbulence at lower flow speeds, if, for example, a very high speed is difficult, e.g. B. if in a given System that imposes exchange rate restrictions. Such vibrations also affect advantageous in other respects.

Part b of the curve does not decrease continuously, but increases again in the end, namely when the contribution of the mass transfer resistance in the restrained phase to the ground level begins to exceed the contribution of the conveying phase to the ground level. Since every increase in flow velocity is paired with (sometimes considerable) increases in pressure, it is usually uneconomical to increase the flow velocity beyond this point.

The individual contributions to the floor height can be measured separately. The contribution of the funding phase alone (including airfoil effects) can be measured in a known manner if the retarding effect the restrained phase is omitted. The total theoretical floor height can also be known in Wisely determine, and the difference between the two then equals the contribution of the reluctant Phase.

In order to keep the contribution of the restrained phase as low as possible, one preferably uses a restrained phase in which the substance exchange on the. the immediate vicinity of the surface remains limited. This condition is met, for example, by many solid adsorbents (in particular non-porous adsorbents such as metals, glass or porous materials essentially without blind pores, e.g. some types of activated carbon, aluminum oxide, silica gel, molecular sieves and even organic polymers, e.g. network polymers of styrene, divinylbenzene and their derivatives or copolymers); the same applies to thin liquid layers and thin ion exchange layers. If possible, the layer thickness should not exceed ^{10 ~ 3} cm, preferably 10 ~ ^{4 cm.} In the case of ion exchangers, monomolecular ion exchange layers are preferred. Ion exchange layers can also be applied to a carrier (e.g. by polymerizing divinylbenzene-styrene in the form of thin layers on the carrier material and subsequent sulfonation). It is also possible to use the surface of plastic capillaries or powders, e.g. B. made of polyethylene or polyvinyl chloride to sulfonate.

The above applies to both unfilled pipes and filled pipes. In both cases, the following also applies: that the turbulence of the funding phase should extend as possible over the entire width of the column. This not only ensures that all parts of the funding phase come into close contact with the whole restrained phase insured in the shortest possible time, but also results in a flattened flow profile of the conveying phase as a result of thorough radial Mixing. Preferably, there should be complete radial mixing, i. H. across the net flow direction, take place repeatedly at intervals that are on the order of the pipe diameter do not exceed. This can be achieved, for example, by thorough turbulence alone, but is the application of the vibrations mentioned above

209 549/476

a further aid and the use of mechanical aids is also possible, for example the already mentioned barriers or others, of which, for example, below in other things Context will be discussed. s

Because of the process-related higher speeds, it is now also practically possible perform the chromatographic separations in pipelines, especially long-distance lines, which according to the invention are particularly set up as chromatographic separation devices. Thus, the chromatographic separation, z. B. Cleaning of the material, simultaneously with the promotion of the material from one place to another. As already said, in the unfilled separating tube, whose wall is used as the stationary phase or carries it, the theoretical floor height the pipe diameter. It follows that a pipeline, e.g. B. 30 cm in diameter and several Kilometers long, corresponds to a considerable number of theoretical soils, and difficult separations allows large volumes of material in a short time. The evolution of the chromatogram by elution, for example, it can be carried out semi-continuously by introducing the material to be separated in the pipe in short bursts of addition. This can be compared achieve an efficiency of up to 85 percent for fully continuous operation. The proportionate low chromatographic capacity of pipelines in which only the inner surface for the Material exchange is available then, if a valuable one, is not necessarily a disadvantage Substance is present in low concentration and is to be enriched or separated, or if one wants to remove a minor contamination from the material. Such tasks come up frequently before. The pipe wall can also be used in a manner known per se to increase the specific Treat or coat the surface. Internals or coarse-grained pipe fillings to increase the Exchange capacities are also possible.

The enrichment or isolation of valuable components in low concentration is in pipelines possible through frontal analysis, for example, and then becomes particularly economically interesting, if the material used to wash out the pipe after each separation is also a substance that is to be conveyed from one end of the pipeline to the other. Leave these types of separation apply to the constituents of substances that have always been conveyed through pipelines were e.g. B. gas, steam, liquids such as natural or synthetic petroleum products, organic Solvents, coal distillates and pyrolysates, noble gas concentrates such as those enriched from natural gas Helium, air distillation fractions, etc.

The invention can in principle also be applied to isotope separation. When hydrogen gas is in conveyed in the manner described through appropriately prepared pipelines is up to arrival at the other end a complete or partial separation into isotopes is possible. In a similar way heavy water can be made from steam. Deuterium enrichments can also be found in achieve the promotion of hydrocarbon gases through pipelines in the manner described.

The mentioned separations can of course also be carried out on a large or small scale in specially designed devices (i.e. without the secondary purpose of conveying material from a Place to other).

A detailed description of the above-mentioned applications is unnecessary insofar as the restrained and conveying phases to be used essentially consist of chromatographic ones known per se Process for the same separations at low speed, i.e. H. in the laminar Flow area, are known. The novelty lies in the significantly higher flow velocities to achieve the typical turbulent flow form and the greater care of the choice or preparation of the restrained phase in order to minimize its contribution to the ground level restrict.

It also applies to the separation in pipelines that the turbulence is caused by internals and the like. Can be promoted in the manner described above, thereby for example with get by with lower pump outputs.

In some cases, the pipe material itself, e.g. B. use the metal as the stationary phase, if necessary after activation. An aluminum pipe surface can in itself oxidize in a known manner to produce an active aluminum oxide surface. The pipes can also in a known manner inside by applying a colloidal carbon layer, an ion exchange resin layer, silica gel or other active substances including liquid layers.

It is even possible to improve the separations or separating capacities, entire pipelines to be filled with a tube filling containing a stationary phase.

Here, too, it is again true that filled pipes for carrying out the method, regardless of their Size, do not require further description as essentially the same as for conventional ones Separating columns applies, apart from the fact that it may be necessary, the wall thickness for increased To increase operating pressures in order to enable the high flow velocities.

In this context it has also been found that the best overall results are achieved with filler material can be achieved whose grain size is at least 0.5 mm, preferably at least 1 mm, diameter amounts to.

F i g. 2, 3 and 4 show variants of the method to achieve high flow velocities in filled columns at lower pressure. this will achieved in that the retaining phase is present in a column filling made of granular material, which is a larger apparent due to the high speed of the delivery phase in turbulent flow Volume as the bulk volume of the granular material occupies in bulk.

In FIG. 2, a column has an inlet port 2 and an outlet port 3 which are separated from the interior of the column by means of partitions 4 and 5, respectively. The latter are permeable for the funding phase, but impermeable for granular filling material 6. In loose Filling, the filling material 6 fills the column up to the level 7. Before the actual separation, the Funding phase at 2 with a valve 8 set

introduced sufficiently high flow velocity to completely absorb the granular material Transferring the fluidized bed state without the material being dragged away from the production phase. In the fluidized bed state, i.e. H. the state in which when the filling material 6 is in a thoroughly fluidized state, the filling rises up to level 9. Then the flow rate of the delivery phase is reduced so far that the Turbulence of the filler material grains ceases and with a certain shrinkage of the filler material volume, z. B. up to level 10 takes place. In this state, the column filling has the following important ' Properties: It has a lower apparent density and greater porosity than the filling in the loose bed, the condition that the column filling when the flow of the conveying phase ceases completely would take. Thus, for a given pressure drop through column 1, there is a higher one Flow rate of the delivery phase than the corresponding flow rate at the same pressure drop through the column 1 before the just complete whirling described. The column filling also has free-flowing properties (Pourability), almost to the same extent as the fluidized bed. On the other hand, there is no turbulence of the particles that would have caused band broadening in the case of chromatography. Simultaneously the process conditions are set so that the turbulent flow form in the delivery phase prevails, with the funding phase unhindered in all directions of the highly porous column filling can flow. The substance to be separated is introduced at lla. The factions will be one after the other is caught with the eluate at 3.

In principle, the delivery phase can also be liquid in this example, with the column filling either completely solid material or solid particles with a layer of liquid or gel or beads of gel-like material, e.g. B. resinous or rubbery polymers, which have ion exchange properties, for example.

When using liquid delivery phases, a partition 4 is preferably provided with a minimum Flow resistance, e.g. B. a wire mesh is used. When using gas as the production phase A certain pressure drop through the partition 4 proves to be an advantage. One then uses, for example a tightly woven synthetic fiber filter cloth on a rigid, reticulated or perforated surface. Porous ceramic or sintered glass frits can also be used. Also metal plates with fine perforations are sometimes suitable. Felt is generally less suitable. The best pad it is relatively easy to determine empirically for a given column filling.

'. The filling material 6 is preferably made of rounded, z. B. approximately spherical particles which should be as free as possible from radial branches and the like, which easily cause the individual grains to get caught. Any tendency to clump is a disadvantage and should be avoided. The most suitable grain size depends, among other things, on the species, e.g. B. shape and density of the powder particles, from and is z. B. between 2 and 0.03 mm clear mesh size. The coarser grain size applies to low-density powders. The particles can consist, for example, of silica gel, aluminum oxide, magnesium silicate, a wide variety of metals, glass, activated carbon, a wide variety of organic and inorganic solid adsorbents, natural and synthetic polymers, solid and gel-like ion exchangers and other substances.

The calculation or estimation of the most favorable grain sizes for a certain system is known in Way possible. Suppose, for example, that a gas with the density and viscosity of air is below Normal conditions are to come into use as the funding phase and that the restrained phase the Has density of silica gel or glass beads and essentially consists of approximately spherical particles If there is the same grain size (which is favorable under all circumstances), the minimum is recommended Grain size around 0.5 mm, since with such a grain size a linear gas velocity of about 1 m / sec is possible without whirling up the powder. Such a flow rate is already clearly in the turbulent area. A powder with a grain size of at least 1 mm is more favorable.

Under turbulent flow conditions, the pressure drop described above cannot whirled up, but loosened column be twenty times less than the pressure drop for the same flow rate through a tightly packed column.

Because of the already mentioned high flowability or pourability of the filler material 6, it is suitable State also especially for the continuous conveyance of the filler material 6 through a tube in the Countercurrent with the delivery phase in continuous chromatography.

According to FIG. 3, the relaxed state described with reference to FIG. 2 is changed to the continuous one Chromatography applied. The actual separation column is denoted by 11 and contains the Column filling in the form just described, which is maintained by means of the conveying phase flowing in through inlet connection 12 and column support 13 will. The material to be separated is continuously introduced at an inlet connection 14. At the At the bottom of the column 11, the free-flowing, extremely free-flowing filler material 6 becomes continuous withdrawn under the action of gravity at an adjustable speed by means of a slide 15 and .flows essentially in the state of loose bedding through a connecting pipe 16 into a stripping column 17, the porous bottom 18 of which separates the scraper column 17 from a chamber 19 from which the Stripping agent, d. H. an eluent, introduced into the stripper column 17 at a fairly high rate will. The speed is sufficient to generate a strongly whirled, z. B. Dust cloud condition in the stripper column 17. Thus, the filler material 6 in the stripper column 17 has a substantial lower apparent density than the same material in column 11, and thereby becomes a Circuit management of the filler material 6 brought about, which is now in the stripper column 17 to a Extension 20 rises where the lower flow rate of the stripping agent causes settling causing filler particles. The settling filler material 6 flows from the extension 20 under gravity through a connecting pipe 21 and over a baffle plate 22 in the upper part of the Pillar 11. The cycle speed of the reverse

holding phase is adjusted in relation to the flow rate of the conveying phase in column 11 so that that the one desired material fraction, the column 11 with the delivery phase through an outlet port 23 leaves, while a further fraction the column 11 with the retaining phase at the slide 15 leaves. This second fraction is now eluted out of the restrained phase in the stripping column 17 and leaves the device with the eluent through a port 24. In the stripping column 17 a higher temperature than in column 11 can be set under certain circumstances.

The output connection 23 and 24 can optionally with dust collectors, for. B. cyclones provided be. Likewise, an extension 20 of the scraper column 17 can incorporate the design features of a dust separator device, ζ. Β. of a cyclone or the like. Own.

Of course, the circulation of the restrained phase can also be brought about mechanically or are funded. It is not absolutely necessary that gravity be entirely or even just partially takes effect, although in most cases this simplifies the device contributes. ,

The eluent in the stripping column 17 can be identical to the delivery phase. Then are located Under certain circumstances, the chambers below the column support 13 and the porous base 18 interrelate in connection. The porous bottom. 18 is then such that it allows the eluent to flow through it offers less resistance than the column support 13, thus a state of lower density in the stripper column 17 than to ensure in pillar 11.

Any other eluent to recover the retentive phase so that it is in the column 11 can be used again. For some purposes it is itself possible to use the starting material to be separated as an eluent, with the eluate whole or partially returns from the outlet connection 24 to the inlet connection 14. This version is suitable especially for cleaning materials, the contamination of which is present in low concentration. Further it is possible to gradually strip the retained material from the retaining phase and to be carried out in fractions, instead of the stripping column 17 being several one behind the other Pillars used.

The device is particularly suitable for gas chromatography, but in principle can also be used Use with a liquid delivery phase.

According to FIG. 4, pillars 25 and 26 are provided, any number of which are shown in FIG Way can be connected in series by means of much thinner tubes 27, where appropriate feed pumps 28 are mounted in the tubes 27. Each column 25, 26 is by means of sieve plates 29 of a type that the development phase (introduced at 30) offers little resistance, but the restrained phase does not let through, divided into a number of chambers. The heights of the individual chambers between successive sieve plates 29 are of the same order of magnitude and preferably at most as large as the optimal floor height for this system, i.e. H. of the same order of magnitude as that Column diameter. Each chamber contains fine-grained filler material containing the retaining phase 6, but not enough to completely fill the chamber with the material in bulk. at When using this device, the flow rate of the conveying phase is set in such a way that that the filling material 6 is whirled up completely in the chambers. This creates a complete radial mix not only in the funding phase, but also in the reluctant phase. Another utter one Mixing of the delivery phase takes place in the pumps 28 in each case.

The following examples illustrate a few of the large number of possible applications of the invention.

example 1

Separation of palmitic and stearic acid

The acids are separated by reverse phase chromatography. System: paraffin oil as restrained Phase, 70% aqueous acetone as the production phase, temperature 35 ° C. The alpha value in this Example is 1.7.

a) Conventional filled column, laminar flow

Diatomaceous earth is used as a carrier. The column length is 85 cm, the diameter 8 mm and the Pressure 50 cm solvent column. Analysis time: About 3 hours.

b) Filled column, turbulent flow

Glass beads, 1 mm in diameter, treated with dichlorodimethylsilane serve as carriers. The carrier is impregnated with a dilute ethereal solution of paraffin oil. After evaporation of the ether, an oil layer about 10 ~ ⁴ cm thick remains. The column length is 2.5 m and the pressure drop is 5 atm. The separation takes place in about 50 seconds.

c) Empty separation tube, laminar flow

A very large capillary, inner diameter 0.2 mm, is used (a larger diameter For example, 2 mm would mean ten times the required column length and the analysis time increase by a hundred times). The column length is 100 cm, the pressure 30 cm solvent column and the separation time 2 hours.

d) Empty separation pipe, turbulent flow

Here, a thicker separating tube, for example 2 mm in internal diameter, is preferred because one A 0.2 mm capillary would theoretically allow a separation in less than 1 second, for that but would require a pressure of about 3000 atm, which is too high for practical purposes. the The column length is 40 m, the pressure drop is 35 atm and the separation time is 4 minutes.

. Example 2

Separation of transbutene-2 and butene-1
by gas-liquid chromatography

This example shows a separation as it is used in the field of petrochemicals can.

The following system is used: Reticent phase: Diisodecyl phthalate; Funding phase: Nitrogen; 50 ° C. Alpha for this system is about 1.3.

a) Empty separation tube, laminar flow

Tube diameter 0.2 mm

Separation time about 10 seconds

Column length 10 m

Pressure drop about 10 atm ^;

or ' ^:

Column diameter ..... 2mm

Separation time about 4 minutes

Column length 50 m

Pressure 30 cm solvent column ■: ■ '.' ■

b) Empty separation pipe, turbulent flow

Tube diameter 0.2 mm

Separation time less than 1 second

Column length 10 m

Pressure drop about 200 atm

Pipe diameter 2 mm

Separation time about 10 seconds

Column length 200 m

Pressure drop about 90 atm

c) device according to FIG. 4th

Grain size 0.5 mm

Total column length .... 25 m

Diameter 10 cm

250 sieve plates 10 cm apart, flow speed 5 m / sec

Separation time about a minute

d) device according to FIG. 2

Grain size 1 mm

Column length 10 m (5 sections of

each 2 m connected in series)

Column diameter 20 cm

Flow velocity. 1 m / sec

Separation time about 1 minute

Note: In c) and d) the exact flow rate becomes empirical for each filler material determined, as this depends critically on slight differences in grain size and shape.

e) device according to FIG. 3

Grain size 1 mm

Length of the column 11 .... 10 m The inlet connection 14 is located halfway Height,

Downward movement of the
Filling 20 cm / sec

Upward flow velocity of the
Gas 70 cm / sec

(relative to the column wall)

Pillar is vibrating,

Flow speed in the stripping column 17 about 20 m / sec

The diameter of the stripper column 17 is one third that of the column 11 in this example, and in the case of the porous bottom 18, conveying nozzles can be used be attached in a manner known per se from pneumatic conveying devices.

Example3

Separation of codeine and heroin

This example is typical of alkaloid separations.

The following system is used: Retention phase: silica gel; Funding phase: methanol - n-butanol - benzene - water 60:15: 10:15. Alpha for this system is around 1.4.

a) Filled column, laminar flow (fine particles)

Separation time about 25 hours

Column length 2 m

Pressure 30 cm liquid column

b) Filled column, turbulent flow

(Filling material 1 mm grain size)

Separation time 2Va minutes

Column length 4 m

Pressure drop 15 atm

c) Empty separation tube, laminar flow

Separation time 8 hours

Column length 4 m

Pressure 40 cm liquid column

Column diameter 0.2 mm

d) Empty separation pipe, turbulent flow

Separation time 8 minutes

Column length 50 m

Pressure drop 40 atm

Column diameter 2 mm

Example 4
Separation of atropine and morphine

Reticent phase: silica gel; Funding phase: benzene - acetone - ether - 10% aqueous ammonia: 4: 6: 1: 0.3. Alpha for this system is approximately 1.45.

a) Filled column, laminar flow (fine filling, conventional type)

Separation time about 15 hours

Column length 1.5 m

Pressure 30 cm solvent column

b) Filled column, turbulent flow (filling material 1 mm grain size)

Separation time 2 minutes

Column length 3 m

Pressure drop 10 atm

c) Empty pipe, laminar flow

Column diameter 0.2 mm

Column length 4 m

Pressure 40 cm solvent column, separation time 9 hours

209 549/476

1 5ÖÖ 555

17 18

- d) Empty pipe, turbulent flow Example- 5

Column diameter 2 mm separation of sodium and potassium ions

Column length 40 m Restrained phase: ion exchanger; Delivery pressure drop 35 atm _{5 has} . _{Q1 normal Ha}

Separation time about 5 minutes _{AIpha for this system is about 2} , ₃ .

e) Device according to FIG. 4 _a ) Filled column, laminar flow

The separation requires (for 99% purity) about the usual fine-pored column of 40 cm length,

100 theoretical floors. With a column diameter of 1 cm diameter is used; Pressure: 30 cm

ser of 10 cm, the column length is 10 m and eluent.

holds 100 sieve plates and enough silica gel beads, separation time: 11 hours,

half fill each chamber. The pearl through,. _. , _, ·,

knife is chosen so that the material in a ^b ) Gelullte column, turbulent flow

Flow velocity of 2 m / sec completely 15 lmm particles in a column of 1.5 m

is whirled up. Height. The pressure drop is 30 atm, the separation

The separation is then complete in about 1 minute. takes about 30 seconds.

1 sheet of drawings

Claims (17)

Patent claims: 1. Chromatographic separation process with the help of a separation tube, in which a to separating substance is in the exchange of substances between a restrained and a funding phase, for the function of the theoretical ground level against the total relative speed between the phases a first minimum of the floor height in the area of laminar flow the restrained phase, after which the floor level up to a maximum at considerably higher relative velocities, which essentially mark the beginning of turbulent flow conditions corresponds in the moving phase, characterized in that the relative speed between the both phases above the speed corresponding to the maximum of the ground level, yes is set below the speed at which the contribution to the ground level of the mass transfer resistance in the restrained phase the contribution to the ground level of the mass transfer resistance in the delivery phase exceeds the order of magnitude, and that the restrained phase either entirely kept stationary or moving linearly in countercurrent to the conveying phase or so set is that the restrained phase assumes a whirled up state and that the The mobility of the particles is limited to a fraction of the total length of the separating tube which does not exceed the order of magnitude of the cross-section of the separating tube. 2. The method according to claim 1, characterized in that the delivery phase in the turbulent State is passed through an unfilled separating tube, the inner surface of which is known per se Way is used as a stationary phase or as a carrier for the stationary phase. 3. The method according to claim 1 and 2, characterized in that the separation is carried out simultaneously carried out with the transport of the material to be separated through a pipeline will. :. 4. The method according to claim 2 or 3, characterized in that by internals, Vibration, sound radiation facilitates or increases the formation of turbulence. 5. The method according to claim 1, characterized in that that in filled columns the formation of turbulence is facilitated or increased by vibration and sound radiation. 6. The method according to any one of claims 1 to 5, characterized in that the funding phase by setting the turbulence accordingly, using vibrations or mechanical aids repeatedly and at intervals of at most the same order of magnitude as the pipe diameter is completely mixed in the direction transverse to the direction of flow will. 7. The method according to any one of claims 1 to 6, characterized in that the delivery phase with a restrained phase with a layer thickness of at most 10 ~ ' ^! cm, preferably 10 ~ ⁴ cm, is brought into chromatographic mass transfer. 8. The method according to any one of claims 1 to 7, characterized in that in the funding phase the turbulent flow prevails. 9. The method according to any one of claims 1 or 5 to 8, characterized in that the Funding phase with a flow velocity in the turbulent flow range through a die Retaining phase containing pipe filling with a grain size of at least 0.5 mm, preferably 1 mm diameter is passed. 10. The method according to any one of claims 1 or 5 to 9, characterized in that in a powder column containing the retaining phase, the flow rate of the The delivery phase is adjusted so that the powder column has a larger volume than that of the loose Bulk occupies, without substantial movement of the powder particles relative to one another, in particular without vortex motion, and that the ratio of flow velocity, particle size, Shape and density is adjusted to the properties of the funding phase so that in the Delivery phase turbulence prevails, and that preferably as a column filling approximately spherical Particles are used. 11. The method according to claim 1 and 10, characterized in that in the continuous Functioning of the powder column in the loosened, free-flowing state under the action of gravity in countercurrent to the delivery phase by removing powder at the lower end of the column gradually and evenly downwards is promoted that so much powder is applied at the top of the column that the column height remains essentially constant and that the mixture to be separated in a manner known per se is continuously introduced between the bottom and top of the column and the Ratio of the speeds of the two phases is set so that a fraction upwards and the other downwards. 12. The method according to claim 1 and 11, characterized characterized in that the removed powder elutes in a second tube and simultaneously from the eluent up to at least the top of the first column is conveyed, from where the powder is returned to the first column. 13. The method according to claim 1 and 12, characterized in that the first column and the second tube can be sealed against one another by means of the powder in the poured state. 14. Device for performing the method according to claim 1 and 3, characterized in that that a pipeline between two geographically different locations called chromatographic Separation column is formed. 15. Device for performing the method according to claims 1 and 4 with a . pipeline set up as a separation column, thereby characterized in that ,, turbulence-inducing internals are provided. 16. Apparatus for performing the method according to claim 1 with a vertical Separating tube with permeable for the delivery phase and impermeable for the restrained phase horizontal partition walls, with the pipe sections between the partition walls which are only partially filled with column filling material, characterized in that the pipe sections of the separating tube (25, 26) between the partition walls (29) in each case as vortex chambers, the height of which does not exceed the order of magnitude of the pipe diameter are, the column filling material can be swirled and only in the non-swirled loose bulk state partially fills the chambers and that the inlet opening at the lower end and the outlet opening attached to the top of the column. 17. Apparatus for continuously carrying out the method according to claim 1 and 11 with two columns, two extraction points for fractions and each with a separate inlet connection for the funding phase and the substance to be separated in the first column, characterized in that that the first column (11) to maintain a loosened powder state and for continuous gravity conveying of the column filling below a permeable for the conveying phase and an intermediate wall (13) impermeable to the retaining phase, such as a sieve plate Od. Like. To blow in the delivery phase and immediately above a drain pipe (16) for which has the column packing material containing a fraction, further above the inlet port (14) for the material to be separated and an outlet nozzle at the top of the column (23) for the second fraction and a line (21) for returning filler material the upper end of the second column (17) into the upper end of the first column (11), and that the second column (17) below a device with a further partition (18) and one Chamber (19) for the pneumatic or hydraulic conveyance of the column material by means of an eluent in the upper part (2) of the column (17), which has a device for demixing of the filler from the eluent loaded with the first fraction and one has further outlet nozzle (24).