Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
  • G01N30/50—Conditioning of the sorbent material or stationary liquid
  • G01N30/58—Conditioning of the sorbent material or stationary liquid the sorbent moving as a whole
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
  • B01D15/08—Selective adsorption, e.g. chromatography
  • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
  • B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
  • B01D15/1892—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns the sorbent material moving as a whole, e.g. continuous annular chromatography, true moving beds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
  • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
  • B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
  • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
  • B01J8/0257—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical annular shaped bed
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
  • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
  • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
  • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
  • B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
  • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
  • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
  • B01J8/0461—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds
  • B01J8/0469—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds the beds being superimposed one above the other
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2215/00—Separating processes involving the treatment of liquids with adsorbents
  • B01D2215/02—Separating processes involving the treatment of liquids with adsorbents with moving adsorbents
  • B01D2215/022—Physically moving the adsorbent as a whole, e.g. belts, discs or sheets
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
  • G01N30/50—Conditioning of the sorbent material or stationary liquid
  • G01N30/58—Conditioning of the sorbent material or stationary liquid the sorbent moving as a whole
  • G01N2030/587—Continuous annular chromatography

Definitions

• the present invention relates to an annular chromatograph with a particle bed in its annular gap.
• Annular chromatography has been a variant of preparative chromatographic separations that has been recognized for a number of years and is increasingly being used. Annular chromatography is preferably used when large amounts of substance mixtures have to be separated, since this type of chromatography can be operated continuously, and with a relatively high degree of resolution.
• P-CAC preparative continuous annular chromatography
• Such cleaning processes are largely carried out in separate apparatus and in batch operation, ie the cleaning of the starting products and the end product takes place, for example, chromatographically in pre-columns or in downstream separating cleaners. len, which prevents continuous operation, since the release agents have to be rinsed, regenerated or equilibrated after the substance mixtures have been separated. In the best case, an intermittent feed stream is possible in a semi-continuous process. However, this limits the throughput of such systems, the outlay in terms of equipment, time and money for such processes, and consequently also the price for products produced in this way is high.
• the aim of the invention was therefore to provide an annular chromatographic system for the continuous implementation of chemical reactions and upstream and downstream cleaning steps in a continuous and thus more economical procedure. Another goal was to optimize the residence times of the substances in the individual sections of the plant.
• annular chromatograph with a particle bed in its annular gap, which is characterized in that at least one reaction zone is provided for carrying out chemical reactions with at least one associated separation zone for chromatographic separation.
• Such an arrangement of the reaction and separation zone in a single annular chromatographic graphic column (in any order) enables successive reactions) and separation (s) or pre-treatment (s) and reaction (s) in completely continuous operation, ie not just semi-continuously with intermittent feeding of the feed stream, since in the case of annular chromatographs the desired one or more Products at desired local positions along the circumference of the column from the column or in the present case from the corresponding zone and enter the next zone.
• Another advantage of this system is that in such a reaction chromatograph, the reaction products formed in the reaction zones continuously from the reaction zone are subtracted, which shifts the reaction weight to the product side, which results in rapid and generally quantitative conversions
• At least one reaction zone is arranged above at least one separation zone for separating reaction mixtures obtained in such a "fixed bed reactor” and separating and / or purifying reaction products formed in an alternative reaction zone chemical reaction (s) taking place, also according to the invention, preferably at least one tienn zone above at least one reaction zone
• reaction and separation zones in almost any number and sequence are also possible according to the invention.
• one or more reaction zones can follow one another or one after the other after a separation zone for pre-purification, which in turn is followed by one or more separation zones for splitting the reaction products and by-products.
• a separation zone for pre-purification which in turn is followed by one or more separation zones for splitting the reaction products and by-products.
• the material for the separation zone (s) can consist of anion exchange resins, cation exchange resins, exclusion gels, gel permeation gels, affinity gels, hydrophobic chromatography (HIC) gels, displacement (resins), reversed phase (reversed phase) gels and electrophoresis gels or any other separating agents commonly used in chromatographic separation processes. Depending on the separation problem, any combination of such separation gels and resins can be used.
• electrophoresis gels electrodes are arranged at the top and bottom of the electrophoretic separation layer in order to apply voltage. The electrical connection is made, for example, via slip ring contact to the axis of rotation of the column. Details can be found in the also pending, on 1 December 1 997 filed Austrian patent application with the application number A 2030/97.
• the material for the reaction zone (s) can generally be made from the same materials as the separation zone (s) and from material which is inert to the reactions taking place therein, depending on the type of reaction, e.g. Glass beads, activated carbon, (optionally modified) polymers, aluminum oxide, silica gel, etc. can be selected. Glass beads and activated carbon are preferred according to the invention.
• the material for the reaction zone (s) can be reacted with one or more reaction catalysts, e.g. Metals, metal complexes or enzymes, impregnated or coated, e.g. Pd / C, Pt / C etc. This measure enables, for example, the simultaneous supply of several reactants in a single feed stream, the actual reaction only coming into contact with a catalyst immobilized in the reaction zone.
• the material for the at least one reaction zone can also preferably be coated according to the invention with at least one reactant, ie one or more further reactants can be fed together with catalyst (s) in a feed stream, but the reaction in turn occurs only in the reaction zone in the Chromatographs; According to the invention, however, all reactants can also be immobilized on the particle material of the reaction zone and only the required catalyst (s) can be fed in with the feed, if one or more Components of the feed stream displaced at least one reactant from the solid phase in order to bring it into contact with the other reactant (s)
• the particle bed in the annular chromatograph according to the invention can consist of a single material or different materials for the reaction and separation zone, wherein the reaction zone material can optionally be impregnated or coated as described above and the two particle materials can, if appropriate, continuously merge into one another.
• all are in Zones containing chromatographs are spatially separated from one another by separating layers in order to prevent mixing of both the particle materials and the individual currents between the respective zones.
• Such separating layers can be composed of membranes, non-porous, inert particle material and - especially when electrophoresis is used - of electrical be selected non-conductive material glass beads are preferred here, which are both inert for a large part of the reactions in question and electrically non-conductive
• the particle bed is covered with a cover layer and / or is underlaid with a base layer, the cover and base layers preferably being made of the same material as the separating layer (s), in particular glass beads.
• the top or bottom zone For electrophoretic separation, the provision of a top or base layer is always advisable in order to keep the electric field as constant as possible
• the particle bed in the cylinder jacket is usually of uniform thickness, which has the consequence that the flow rate of the liquid phase is essentially constant or is determined by the packing density of the particle bed.
• the inner cylinder and / or the outer cylinder of the reactor can be designed to run away from the other at least over part of the height of the particle bed, preferably conically.This reduces the flow velocity in the particle bed, which is e.g. Separation zones results in an increase in the resolution
• the narrowing i.e. the points with converging column walls, according to the invention preferably at the end of reaction zones with a subsequent separation zone, in order to feed the feed at the beginning of the separation zone as concentrated as possible, while extensions are preferably to be found in the area of separation zones, where - as mentioned above - they further increase the separation performance of the column improve
• a temperature jacket is provided on the chromatograph according to the invention in the area of at least one zone on the inner and / or outer cylinder in order to be able to heat or cool the solutions transported in the column. This can be particularly important in reaction zones where a certain reaction temperature has to be maintained , the chromatographic separation in separation zones can also be influenced by the temperature, which is why temperature jacket at both reaction and separation zones are within the scope of the invention
• a radiation source is provided as a heat source and / or as a reaction catalyst or initiator in the area of at least one zone on the inner and / or outer cylinder.
• FIGS. 1 a) and 1 b) are schematic views of embodiments of the annular chromatograph of the invention
• 2a) and 2b) are schematic views of further embodiments of the annular chromatograph of the invention
• FIG. 3 is a schematic sectional view of an embodiment of an annular chromatograph according to the invention with radiation source and temperature jacket
• FIG. 4 is a schematic sectional view of an inventive annular chromatograph with flow cross-section modifications
• FIG. 5a) -5f) shows sketches of possible embodiments of the inventive annular chromatograph with constrictions or extensions of the liquid flow
• Fig. 1 shows schematically two embodiments of the present invention, namely an annular chromatograph with a reaction zone 1 and one or two separation zones 2, 3 in an annular column made of inert material to the components of the reaction and separation solutions, preferably glass, consisting of an inner cylinder 8 and one Outer cylinder 9 (only the outer cylinder 9 can be seen in FIG. 1).
• the column (driven by a motor, not shown) is rotatably supported about an axis 1 2 and is continuously fed via connecting lines 1 3 for feed and solvent, a distributor head 14 and feed channels 1 5.
• the channels 1 5 can have the customary configurations, ie individual , Multiple or Slot nozzles or the like, of course, for the invention, however, curved slot nozzles of different widths which are adapted to the column circumference are preferred in order to be able to match the feed and eluent flows as closely as possible to one another.
• outlet channels or tubes 16 are provided for collecting the eluates. These outlets 16 can either be connected to the column (i.e. they rotate with it about axis 1 2) or can be fixed to axis 1 2 and e.g. are in contact with the column rotating relative to it via a slip ring, the latter embodiment being preferred.
• the particle material of the uppermost zone 1 or 2 is covered in each case with a cover layer 6, into which the feed channels 15 are preferably immersed, in order to ensure an even task.
• 1 a) additionally shows a base layer 7 which (in addition to a - not shown - porous base plate, for example a filter, membrane disc, etc.) serves to prevent particle material from escaping at the bottom of the column. and separation zones are usually separated by separation layers 5 in order to prevent mixing of the particle materials of the two zones.
• the material for the separation, cover and base layers 5, 8, 9 is selected from membranes and non-porous particle material inert to all components of the respective reaction and separation solutions and can be the same or different for all three layers, where but it must not be electrically conductive, especially for electrophoretic separations.
• Glass beads are preferred according to the invention, since they are inert and easy to apply in practically all common applications
• a single reaction zone 1 and a separation zone 2 are provided.
• the material for the reaction zone can be selected from any particle materials which are inert to the reactions then taking place, such as, for example, glass beads, preferably those with diameters of approximately 1 50-240 ⁇ m, and also from material with a separating action, such as ion exchange resins, exclusion resins, etc. , the Particle material itself can take part in the reaction (eg ion exchanger, H ⁇ catalysis or the like) or not.
• the material of reaction zone 1 can also be coated with one or more reactants and / or catalyst (for example metal complexes, enzymes, pH modifiers etc.), so that the reaction takes place on the solid phase. In theory, all reactants can even be immobolized on the support if at least one component supplied together with the feed solvent (eg the solvent itself) displaces at least one reaction partner from the binding to the solid phase, ie strips it.
• a feed solution which contains at least one of the reactants and / or catalyst is fed into the column via the feed channels 15 and from there into the reaction zone 1, where the desired chemical reaction of the reactants occurs. These enter the separation layer 5 at the lower end of zone 1 and then into separation zone 2, where the mixture of substances is separated and purified.
• the height and the diameter of the individual zones is influenced by the type of reaction and separation, the intended residence time of the substances in the column, the type of particle materials, the packing density of the respective zones, the desired resolution of the separation and other factors are well known in the field.
• the average trained specialist is able to carry out the dimensioning according to the specific problem, eg empirically or through preliminary tests.
• Fig. 1 b three zones 1, 2, 3 separated from each other by separating layers 5 are provided. Zones 2 and 3 are designed as separation zones and zone 1 in between as a reaction zone.
• One or more components of the feed solution fed in via the feed tubes 15 can thus be pre-cleaned in the separation zone 2 before the desired reaction can take place in zone 1. This is followed in a manner similar to that described with reference to FIG. 1 a), a separation of the reaction products in separation zone 3.
• FIG. 2a) and 2b) further embodiments of the invention are shown schematically.
• Fig. 2a) two separation and reaction zones 2, 3 and 1, 4 are shown.
• a multistage synthesis can be carried out continuously, with an intermediate purification in separation zone 2 then following a first reaction step in reaction zone 1 a second reaction step in reaction zone 4 and finally the final cleaning in separation zone 3 can be carried out.
• reaction zone 1 shows an embodiment with a reaction zone and two separation zones 1 or 2, 3, in which a mixture emerging from reaction zone 1 can be cleaned in two stages, which enables high-purity products at column outlet 16.
• Fig. 3 a partial section of a particularly preferred embodiment of the invention is shown schematically.
• Two separation and reaction zones are provided, namely a zone 2 for pre-cleaning, similar to Fig. 1 b), two successive reaction zones 1, 4 for performing a two-stage synthesis, and again a separation zone 3 for a final cleaning step.
• the first reaction zone 1 is here provided with a radiation source 11, which is arranged along the inner circumference of the inner cylinder 8 and the outer circumference of the outer cylinder 9 in order to make the entire volume of the zone as uniform as possible.
• a radiation source 11 which is arranged along the inner circumference of the inner cylinder 8 and the outer circumference of the outer cylinder 9 in order to make the entire volume of the zone as uniform as possible.
• Any type of electromagnetic radiation can be considered as radiation, for example visible light and UV light as reaction catalysts, IR and microwave radiation as a heat source; UV and microwave radiation are preferred.
• reaction zone 4 for the second reaction step which is equipped with a temperature jacket, i.e. Heating or cooling jacket is provided, which either serves to bring the reaction mixture to the required reaction temperature or (as in this case) to cool it after exposure to radiation in zone 1 before the subsequent separation.
• a temperature jacket i.e. Heating or cooling jacket is provided, which either serves to bring the reaction mixture to the required reaction temperature or (as in this case) to cool it after exposure to radiation in zone 1 before the subsequent separation.
• tempering jackets can of course also be attached to separation zones in order to directly temper the separation mixtures, i.e. mostly to cool.
• the radiation source and the temperature jacket can be supplied from the inside - via axis 1 2 - or from the outside.
• zone 4 shows a possible modification at the transition from a reaction zone 1 to a separation zone 2
• the cross section of the column narrows, in the figure to V ⁇ of the original value, which leads to an increase in the flow rate (here, for example, on the 1 6-fold) and thus leads to a concentration of the mixture emerging from the reaction zone, which subsequently flows through a separating layer 5, for example made of glass beads, which includes an area with a narrowed cross section but parallel cylinder walls, which is referred to as concentration zone 17 .
• concentration zone 17 the mixture enters separation zone 2.
• the cross section widens (and the flow rate decreases) to the initial value, the interactions with the solid phase become stronger again and the dissolution of the mixture into its components is thus improved.
• An expansion of the cross-section to higher values than in zone 1 would result in a further improvement in the separation performance.
• the constriction or expansion as a cone ensures the uniformity of the flow in these areas, which means that there are hardly any undesirable congestion or side flows at these points or jerky mixes can occur as flow turbulence is minimized in this way
• the ratio between the maximum and the minimum annular gap width is preferably between 10 1 and 1.5: 1, in particular between 5. 1 and 1, 5 • 1.
• the height of the concentration zones 17 or zones with improved resolution can preferably extend over a value corresponding to the minimum width of the annular gap up to 2/3 of the bed height, a value corresponding to the maximum width of the annular gap being particularly preferred.
• 5 shows schematically different embodiments of the column cross section, with FIGS. 5a) and 5e) representing a narrowing or widening which are formed by inclination of only one cylinder wall (optionally inner or outer cylinder) toward the other or away from it.
• FIGS. 5b) and 5f) show, in an analogous manner, a narrowing or widening due to inclination of the cylinder walls on both sides, and in FIGS. 5c) and 5d) a one-sided or bilateral narrowing with the preceding concentration zone 17 is shown. From this - as also already from Fig. 4 - it can be seen that several constrictions and / or extensions can follow one another in order to gradually regulate the liquid flow up or down to very rapid or slow flow rates, if this corresponds to the respective requirements of the annular chromatograph of the invention is useful.
• annular chromatographs The number of possible uses of the annular chromatographs according to the invention is almost unlimited, which is why only here in general and in general for diverse homo- and heterogeneous catalysis processes, various hydrogenations, dehydrogenations, redox reactions, hydro- and other solvolyses, enzyme reactions and much more. is referred.
• a concrete example is the hydrolysis and subsequent separation of oligomeric carbohydrates, e.g. through acid catalysis:

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• Organic Chemistry (AREA)
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• 1997
  • 1997-12-09 AT AT0207697A patent/AT405026B/de not_active IP Right Cessation
• 1998
  • 1998-12-09 JP JP52945499A patent/JP2001512370A/ja active Pending
  • 1998-12-09 CA CA002279942A patent/CA2279942A1/en not_active Abandoned
  • 1998-12-09 EP EP98958721A patent/EP0963227A1/de not_active Withdrawn
  • 1998-12-09 EA EA199900732A patent/EA001580B1/ru not_active IP Right Cessation
  • 1998-12-09 CN CN98804030A patent/CN1252009A/zh active Pending
  • 1998-12-09 WO PCT/AT1998/000299 patent/WO1999029388A1/de not_active Application Discontinuation
  • 1998-12-09 BR BR9807203-0A patent/BR9807203A/pt not_active Application Discontinuation
  • 1998-12-09 AU AU14747/99A patent/AU740246B2/en not_active Ceased

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