EP2352635A2 - Corps moulé échangeur d'ions et son procédé de fabrication - Google Patents

Corps moulé échangeur d'ions et son procédé de fabrication

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Publication number
EP2352635A2
EP2352635A2 EP09744682A EP09744682A EP2352635A2 EP 2352635 A2 EP2352635 A2 EP 2352635A2 EP 09744682 A EP09744682 A EP 09744682A EP 09744682 A EP09744682 A EP 09744682A EP 2352635 A2 EP2352635 A2 EP 2352635A2
Authority
EP
European Patent Office
Prior art keywords
starting material
powder
ion exchanger
channels
adsorber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09744682A
Other languages
German (de)
English (en)
Inventor
Wolfgang Rohde
Veronika Wloka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09744682A priority Critical patent/EP2352635A2/fr
Publication of EP2352635A2 publication Critical patent/EP2352635A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2485—Monolithic reactors
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/327—Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing

Definitions

  • the invention relates to processes for the production of organic polymer moldings having ion exchanger or adsorber properties, moldings of this type and their use in heterogeneously catalyzed chemical reactions or as adsorbers for adsorbing ions or chemical compounds.
  • Ion exchangers are substances that are capable of exchanging ions bound to them for equivalent amounts of other ions from a surrounding solution. An exchange takes place between ions of the same direction.
  • Adsorber resins in contrast to the ion exchange resins, have a nonionic but, depending on the structure, a more or less polar character and non-stoichiometrically adsorb both anions, cations and uncharged compounds.
  • ion exchange resins and adsorbent resins are gel-based or macroreticular, spherical, porous synthetic resins based on styrene or acrylic resin.
  • three-dimensional crosslinking is achieved, typically by the inclusion of divinylbenzene.
  • the most commonly used ion exchangers today are polystyrene resins which are crosslinked with divinylbenzene (DVB) and thus show a high, high-molecular, three-dimensional structure and are usually in spherical form.
  • DVD divinylbenzene
  • a strong acidic cation exchanger By sulfonation of the crosslinked polystyrene resin, for. As with oleum, a strong acidic cation exchanger.
  • acrylic acid derivatives are cross-linked with divinylbenzene.
  • Anion exchangers can also be strongly basic or weakly basic. Exchanger resins with a quaternary ammonium group show a strongly basic character, while resins with tertiary amino groups have weak basic properties.
  • the ion exchangers are typically used as solid spheres, whereby flow reactors can be packed with them in the form of a fixed bed.
  • the object of the present invention is to provide a process for the production of organic polymer moldings with ion exchanger or adsorber properties, which allows the production of a large number of moldings geometries in a simple manner and thus the adaptation of the ion exchanger and adsorber to the respective application.
  • the object is achieved according to the invention by a process for the production of organic polymer moldings having ion exchanger or adsorber properties by means of a powder-based rapid prototyping process, in which a pulverulent organic polymer starting material or starting material mixture is applied to a substrate in a thin layer and then at selected points of that layer is added a binder and any necessary auxiliaries, or irradiated or otherwise treated, so that the powder is joined at these points, whereby the powder is bonded both within the layer and with the adjacent layers , and this process is repeated so many times that the desired shape of the shaped body is completely imaged in the powder bed formed, and subsequently the powder not bound by the binder is removed, so that the bonded powder in the desired shape z remains, wherein the starting material already exhibits the ion exchanger or adsorber properties or after shaping a corresponding functionalization of the shaped body takes place.
  • the ion exchanger or adsorber can serve as a catalyst for a variety of acidic or basic heterogeneously catalyzed reactions or for the purification or separation of chemical mixtures, eg. B. for wastewater treatment or in the analysis or as a guard bed.
  • the catalyst / adsorber is present in disorder in the reactor, aligned in a package and installed in the orderly manner in the reactor.
  • the most widespread is the use of catalysts in the form of granules, strands, tablets, rings or SpNt, which are introduced as a bed in the reactor.
  • a disadvantage of this type of use is that the beds described generally lead to a large pressure drop in the reactor.
  • it can easily lead to the formation of channels and the formation of zones with stagnant gas and / or liquid movement, so that the catalyst is only very unevenly loaded.
  • the required removal and installation of the moldings may be complex, for example in tube bundle reactors with a large number of tubes.
  • catalysts / adsorbers can also be used in the form of monoliths with continuous channels, honeycomb or rib structure, as described, for example, in DE-A-2709003.
  • the process according to the invention allows the preparation of organic polymer moldings having ion exchanger or adsorber properties in any suitable geometry. The preparation is carried out by the rapid prototyping method, which is explained below.
  • RP rapid prototyping
  • SLS Selective Laser Sintering
  • SLA Stereolithography
  • EP-A-0431 924 One of the rapid prototyping methods is described in EP-A-0431 924 and comprises the layered construction of three-dimensional components made of powder and binder. Unbound powder is removed at the end and the workpiece remains in the desired geometry.
  • the object is thus achieved according to the invention by the use of moldings which are optimized in terms of their geometry for the respective flow and reaction conditions in the reactor or adsorber bed, etc.
  • the reactor internals can be tailored for the application, as is not possible with conventional techniques.
  • the advantage of rapid prototyping technology over conventional manufacturing techniques is that theoretically any geometry, even complex components, for example, with cavities or microchannels, computer-controlled in the corresponding three-dimensional component without previous molding in molds, without cutting, using a CAD data set, Milling, grinding, etc. can be implemented.
  • the production of reactor internals possible because of their optimized geometry advantages for the mass and heat transport in chemical reactions compared to conventional reactor internals. This process intensification results in higher yields, conversions and selectivities as well as a safe reaction procedure and can lead to cost savings for existing or new processes in the chemical industry through reduced apparatus sizes or reduced amounts of catalyst.
  • organic polymer moldings having ion exchanger or adsorber properties are produced. These are usually gel or macroreticular porous resins.
  • the powdery starting materials are based on optionally crosslinked polystyrene, poly (meth) acrylates or poly (meth) acrylic acids.
  • the synthetic resins are based on styrene or acrylic resins.
  • a three-dimensional crosslinking or linking by crosslinking monomers, in particular divinylbenzene is achieved.
  • the exchange resins are not deformable in the heat and at the same time free of plasticizers. The release of soluble fractions is virtually eliminated.
  • B. can be crosslinked with electron radiation in the finished molding.
  • Crosslinkers can already be incorporated in the polymer and be brought to harden after shaping. So can be z.
  • Suitable molecular weights and the preparation of the polymer resins in particular polystyrene resins or polyacrylic resins, is known to the person skilled in the art.
  • the resins used in the rapid prototyping process according to the invention do not differ in this respect from the typical ion exchanger or adsorber resins.
  • Pulp-shaped starting materials which can be used with or without a binder are used in the rapid prototyping method to be used according to the invention.
  • the other versions apply to both variants. Both monodisperse and polydisperse powders can be used. Naturally, thinner layers can be realized with finer particles, whereby a larger number of layers and thus a higher spatial resolution is possible for the construction of a desired shaped body than with coarser particles. Preference is given to powders having an average particle size in the range from about 0.5 ⁇ m to about 450 ⁇ m, particularly preferably from about 1 ⁇ m to about 300 ⁇ m, and very particularly preferably from 10 to 100 ⁇ m. The powder to be used, if necessary, can also be specifically pretreated, for.
  • the rapid prototyping method to be used according to the invention consists of the following steps, which are repeated until the desired shaped body is completely composed of the individual layers.
  • a powdery starting material or starting material mixture is applied in a thin layer on a substrate and then added at selected points of this layer with a binder and any necessary auxiliaries, or irradiated or otherwise treated, so that the powder is connected at these locations, whereby the powder is combined both within the layer and with the adjacent layers.
  • the powder not bound by the binder is removed and the bonded powder remains in the desired shape.
  • any material suitable for bonding together adjacent particles of the powdery starting material can be used as the binder.
  • organic materials especially those which can be crosslinked or otherwise covalent bond with each other, for example, phenolic resins, polyisocyanates, polyurethanes, epoxy resins, furan resins, urea-aldehyde condensates, furfuryl alcohol, acrylic acid and Acrylate dispersions, polymeric alcohols, peroxides, carbohydrates, sugars, sugar alcohols, proteins, starch, carboxymethylcellulose, xanthan, gelatin, polyethylene glycol, poly- vinyl alcohols, polyvinylpyrrolidone or mixtures thereof.
  • the binders are used in liquid form either in dissolved or dispersed form, whereby both organic solvents (eg toluene) and water can be used.
  • the binder is a solvent which at least superficially dissolves the polymer starting material and thus produces a connection between the powder particles.
  • the dissolved polymer particles stick together so that a firm connection is formed.
  • the powdered starting material contains a reactive compound which is reacted with an applied activator compound to produce a compound of the polymer starting materials.
  • the reactive compound may be, for example, a monomer which is also included in the structure of the polymer starting material. This may be, for example, styrene, acrylates or acrylic acid.
  • the application of the binders takes place, for example, via a nozzle, a printhead or another apparatus which permits precise placement of the smallest possible drops of the binder on the powder layer.
  • the ratio of powder amount to binder amount varies depending on the substances used, and is usually in the range of about 40:60 to about 99: 1 parts by weight, preferably in the range of about 70:30 to about 99: 1 parts by weight, especially preferably in the range of about 85:15 to about 98: 2 parts by weight.
  • auxiliaries may be used which may, for example, have an influence on the crosslinking of the binders or serve as hardeners.
  • the adjuvants can be applied separately, but if appropriate they can also be added to the powder bed and / or the binder or the binder solution.
  • the bond by radiation treatment for. In the UV or IR range, see also the above description of the surface treatment.
  • the shaping may be followed by a heat treatment in order to obtain better crosslinking or conversion of the binder.
  • the polymeric starting material according to the invention can be functionalized before or after shaping with acidic groups, basic groups or chelating groups.
  • the functionalization takes place in the same way as in the production of ion exchange or adsorber resins. It is thus possible to use ready-to-use ion exchange resin powders or adsorber resin powders in the rapid prototyping process, or initially unfunctionalized resins are used, and the molded articles produced are subsequently functionalized.
  • Strongly acidic ion exchangers are typically based on polystyrene and are sulfonated with sulfuric acid (oleum), so that sulfonic acid groups are bound to the phenyl group in the molded body.
  • the reaction with perfluorosulfonic acid is also possible, cf. Applied Catalysis A: General 221 (2001) 45-62.
  • Low-acid ion exchangers are typically based on polyacrylates which have free carboxyl groups. These can be obtained by basic hydrolysis of the ester groups. Furthermore, phenol-formaldehyde gels can also be used.
  • Basic ion exchangers can be distinguished into strongly basic and weakly basic ion exchanger resins, depending on the presence of the fixed ions.
  • Exchanger resins with a quaternary ammonium group show a strongly basic character, while the resins with tertiary amino groups have weakly basic properties.
  • Basic ion exchangers can, for. B.
  • the organic polymers preferably have surface areas in the range from 5 to 200 m 2 / g, more preferably 10 to 100 m 2 / g, in particular 20 to 70 m 2 / g.
  • the average pore diameter is preferably 2 to 200 nm, in particular 10 to 100 nm.
  • In a functionalization are preferably 0.1 to 15 eq / kg, more preferably 0.5 to 10 eq / kg, especially 1 to 7 eq / kg, especially 2 to 6 eq / kg of functional or ionic groups.
  • the degree of functionalization determines inter alia the total capacity of the ion exchanger resins. Geometry of the moldings
  • the geometry of the shaped body depends on the requirements of the respective field of application and can be varied within wide limits due to the flexibility of the powder-based rapid prototyping method.
  • the organic polymer moldings having ion exchanger or adsorber properties can have one or more channels extending through the mold body and open to the outside.
  • an ion exchange medium can flow through these channels.
  • Such a shaped body preferably has from two to 100, particularly preferably from 4 to 50, channels. The channels pass through the molding and are open at the entrance and exit points.
  • the organic polymer shaped body having ion exchanger or adsorber properties may alternatively or additionally have a surface / volume ratio which is at least twice as large, preferably at least three times as large as the surface area / volume ratio of a sphere of the same volume , So far, organic ion exchangers were usually used in spherical form.
  • the moldings according to the invention allow a substantially improved ion exchange by increasing the surface available for the exchange.
  • the organic polymer moldings having ion exchanger or adsorber properties can also be in the form of a monolith through which a fluid medium can flow, the monoliths having channels which are at an angle in the range of 0 ° to 70 °, preferably 30 ° to 60 ° inclined to the main flow direction.
  • the monoliths may additionally have the specified number of channels and the specified surface / volume ratio.
  • the packs may preferably be embodied as multi-channel packs which have channels in which the chemical reaction preferably takes place and additionally contain channels in which the convective heat transport preferably takes place.
  • the channels for the heat transport are preferably more inclined and preferably have a hydraulic diameter which is larger by a factor of 2 to 10 than the diameter of the channels for catalysis. But even monolithic structures with advantageously arranged holes and / or openings, which connect the individual channels together and thus intensify cross-mixing, have significant advantages over the existing forms. Installation of the moldings in reactors, adsorption beds, cleaning beds The moldings used according to the invention are used as reactor internals.
  • the moldings used according to the invention can extend to the edge of the (column-shaped) reactor.
  • the incorporation of the structured catalysts in the reactor can be carried out in various ways, for. B. in a tube (bundle) reactor by arranging the cylindrical components on top of each other, wherein not necessarily all catalyst parts have the same shape, structure, functionalization, etc., but also vertical / longitudinal segmentation are possible.
  • installation may also be segmented in the transverse direction (such as with pie chunks through 4 quarter cylinders or through a number of hexagonal honeycomb-like components placed side by side).
  • Each packing element may be constructed of a plurality of longitudinally oriented layers, each layer containing closely spaced channels, the channels of adjacent layers crossing each other and the channels within a packing element having side walls which are permeable or impermeable to the fluids.
  • the packs are preferably either a) equipped with an edge seal to ensure a uniform flow over the entire packing cross-section to suppress the Randauerkeit, or b) preferably have a structure that has no higher porosity at the edge.
  • the invention also relates to corresponding packing elements.
  • Suitable forms or structures of the moldings used according to the invention are described, for example, in the following documents by the companies Montz and Sulzer.
  • the structures which are described in WO 2006/056419, WO 2005/037429, WO 2005/037428, EP-A-1 362 636, WO 01/52980 and EP-B-1 251 958, respectively A-38 18 917, DE-A-32 22 892, DE-A-29 21 270, DE-A-29 21 269, CA-A-10 28 903, CN-A-1 550 258, GB-A- 1 186 647, WO 97/02880, EP-A-1 477 224, EP-A-1 308 204, EP-A-1 254 705, EP-A-1 145 761, US 6,409,378, EP-A-1 029 588, EP-A-1 022 057 and WO 98/55221.
  • Another suitable molding is in the form of a cross-channel packing, the packing being composed of vertical layers consisting of corrugated or pleated metal oxides forming flow channels, the flow channels of adjacent layers crossing open, and the angle between the intersecting channels being less than about 100 ° is.
  • a cross-channel package is described for example in EP-A-1 477 224, see also the angle definition there.
  • packs which can be used as moldings are Sulzer BX tissue packs, Sulzer lamellar packs Mellapak, high-performance packs such as Mellapak Plus, structured packings from Sulzer (Optiflow), Montz (BSH) and Kühni (Rombopak) and packs from Emitec (www.emitec.com).
  • the moldings may, for example, have the shape of the packing types A3, B1, BSH, C1 and M of Montz.
  • the packing bodies are composed of corrugated webs (lamellae). The waves are inclined to the vertical and form with the adjacent lamellae intersecting flow channels.
  • Monolith sizes can be chosen freely. Typical preferred monolith sizes are in the range of 0.5 to 20 cm, in particular 1 to 10 cm. It is also possible to produce larger monolith monoliths.
  • the moldings of the invention are particularly preferably applicable when the available from known ion exchangers balls are too small, too large pressure losses or bypasses occur.
  • the ion exchangers or adsorbers produced according to the invention can be used in a large number of applications. First, they can be used as adsorber for a variety of different ions and chemical compounds. All metal ions contained in aqueous or organic liquid systems can be bound here, for example alkali metal or alkaline earth metal ions or heavy metal ions, but also metal ions, ammonium ions or anions.
  • the adsorber resins can be used for the purification of waste water.
  • the geometry is chosen so that an optimal adsorption of the metal ions from the flowing through solution is achieved at an optimum throughput. The adsorption properties can change with the pH.
  • the ion exchangers can also be used to reduce the water hardness.
  • Anion exchangers can be used to remove unwanted anions from liquid systems, for example sulfates, nitrates, halides such as chlorides or iodides.
  • Trace enrichment is possible with the help of chelating ion exchangers.
  • the total salt content of solutions and waters can be determined, interfering cations or anions can be removed with cation or anion exchangers, and chromatographic separation is possible.
  • the shaped bodies can be used to break up poorly soluble compounds.
  • the molded article After ion exchange, the molded article is typically washed and regenerated or eluted to be usable for other applications.
  • Preferred areas of application are water treatment such as water softening, desalination, partial desalination, the separation of rare earths, the separation of amino acids and their use in analytics.
  • the separation of high molecular weight organic compounds or dyes is preferred.
  • Other preferred applications are the purification and recovery of antibiotics, vitamins and alkaloids, the purification of enzymes and the adsorption of dyes.
  • the isolation and determination of acids and alkalis as well as the removal of interfering cations and anions is a preferred field of application.
  • mineral acids such as hydrochloric or sulfuric acid and alkalis, such as caustic soda and potassium hydroxide solution for the catalysis of esterifications, saponifications, condensations, rearrangements, hydrolyses, polymerizations, dehydration or Cyclizations has long been known. Due to the moldings according to the invention, products are available which, as carriers of exchangeable counterions as well as mineral acids or alkali solutions, contain catalytically active hydrogen or hydroxyl ions and likewise exhibit an immediate catalytic activity.
  • strongly acidic cation exchangers in the H + form can be used. In the case of base-catalyzed reactions, strongly basic ion exchangers in the OH " form can be used.
  • the present as a shaped body catalysts have many advantages over homogeneous acid or base catalysts: they can be easily separated from the reaction product, since they are present as moldings. They can be reused immediately without regeneration in most cases. Selectivity for large or small molecules is possible. Their use in continuous reaction is possible. They prevent the entrainment of foreign ions in the reaction product. They avoid interfering secondary or secondary reactions, so that the product purity increases.
  • the novel moldings are particularly preferably used as catalysts in esterifications, saponifications, dehydration, hydration, dehydration, aldol condensation, polymerizations, di- and oligomerization, alkylation.
  • cyanohydrin syntheses acetate formation, acylation, nitration, epoxidation, sugar inversion, rearrangement, isomerization, etherification, crosslinking.
  • the reaction is preferably follows at a temperature of up to 180 0 C, in particular at most 150 0 C.
  • the moldings of the invention can also be used as a guard bed to remove unwanted impurities from fluids.
  • Polymer powders having a mean particle size in the range from about 0.5 .mu.m to about 450 .mu.m, particularly preferably from about 1 .mu.m to about 300 .mu.m, and very particularly preferably from 10 to 100 .mu.m, are used for producing the shaped bodies according to the invention.
  • the powder may, as described, additionally contain one or more activators.
  • connection between the polymer powder particles may be by treatment with a solvent, by irradiation, or by applying a reactive compound which is applied as an activator compound to produce a compound of the polymer particles.
  • the functionalization of the resulting resin moldings can be carried out both in the starting powder and in the molding. In this case, for example, a sulfonation, as described above, carried out. Accordingly, the polymer is functionalized before or after shaping with acidic groups, basic groups or chelating groups.
  • the invention also relates to organic polymer moldings having ion exchanger or adsorber properties which can be prepared by the process described.
  • the organic moldings are preferably used as reactor internals in heterogeneously catalyzed chemical reactions or as adsorbers for adsorbing ions or chemical compounds.
  • a three-dimensionally structured "cross-channel structure" of polystyrene spheres is produced according to FIG. 1.
  • the length of the polymer moldings is 50 mm, the diameter is 14 mm.
  • the shaping takes place as three-dimensional printing on the ProMetal RCT S15 (ProMetal RCT GmbH, 86167 Augsburg). After printing, the green compact is blown free from unbonded polystyrene beads and the polystyrene molded body is then treated with oleum to give a strongly acidic ion exchanger.
  • a three-dimensionally structured "cross-channel structure" of polystyrene is produced as shown in Figure 2.
  • the length is 100 mm, the diameter is 80 mm, and shaping by means of rapid prototyping takes place on the ProMetal RCT S15 (ProMetal RCT GmbH, 86167 Augsburg) Blowing is treated with oleum to produce a strong acid ion exchanger of the polystyrene moldings.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Catalysts (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

L'invention porte sur la fabrication de corps moulés de polymères organiques avec des propriétés d'échange d'ions ou d'absorption au moyen d'un procédé de prototypage rapide à base de poudre, suivant lequel une matière de départ ou un mélange de matières de départ de polymère organique pulvérulent est appliqué en couche mince sur une sous-couche puis est mélangé à des emplacements choisis de cette couche avec un liant et des adjuvants éventuellement nécessaires, ou est irradié ou traité d'une autre manière, de telle sorte que la poudre est liée à ces endroits, ce par quoi la poudre est liée non seulement à l'intérieur de la couche mais encore aux couches adjacentes, et ce processus est répété autant de fois qu'il le faut pour que la forme souhaitée du corps moulé soit représentée complètement dans le lit de poudre formé, et ensuite la poudre non liée par le liant est enlevée, de telle sorte que la poudre liée reste dans la forme souhaitée, et la matière de départ présente déjà les propriétés d'échange d'ions ou d'absorption ou, après le façonnage, a lieu une fonctionnalisation correspondante du corps moulé.
EP09744682A 2008-10-31 2009-10-30 Corps moulé échangeur d'ions et son procédé de fabrication Withdrawn EP2352635A2 (fr)

Priority Applications (1)

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EP09744682A EP2352635A2 (fr) 2008-10-31 2009-10-30 Corps moulé échangeur d'ions et son procédé de fabrication

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EP08168021 2008-10-31
EP09744682A EP2352635A2 (fr) 2008-10-31 2009-10-30 Corps moulé échangeur d'ions et son procédé de fabrication
PCT/EP2009/064350 WO2010049515A2 (fr) 2008-10-31 2009-10-30 Corps moulé échangeur d'ions et son procédé de fabrication

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EP2352635A2 true EP2352635A2 (fr) 2011-08-10

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EP (1) EP2352635A2 (fr)
JP (1) JP2012506799A (fr)
KR (1) KR20110097797A (fr)
CN (1) CN102202870A (fr)
CA (1) CA2742235A1 (fr)
WO (1) WO2010049515A2 (fr)

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JP2012506799A (ja) 2012-03-22
CN102202870A (zh) 2011-09-28
WO2010049515A2 (fr) 2010-05-06
KR20110097797A (ko) 2011-08-31
US20110206569A1 (en) 2011-08-25
WO2010049515A3 (fr) 2010-12-29
CA2742235A1 (fr) 2010-05-06

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