EP0513280A1 - Procede de fabrication de corps moules ayant une surface poreuse et une repartition etroite des rayons des pores superficiels - Google Patents

Procede de fabrication de corps moules ayant une surface poreuse et une repartition etroite des rayons des pores superficiels

Info

Publication number
EP0513280A1
EP0513280A1 EP91920271A EP91920271A EP0513280A1 EP 0513280 A1 EP0513280 A1 EP 0513280A1 EP 91920271 A EP91920271 A EP 91920271A EP 91920271 A EP91920271 A EP 91920271A EP 0513280 A1 EP0513280 A1 EP 0513280A1
Authority
EP
European Patent Office
Prior art keywords
coating particles
coating
moldings
particles
coated
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Withdrawn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
EP91920271A
Other languages
German (de)
English (en)
Inventor
Werner Hopp
Alfred Kaiser
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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 Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP0513280A1 publication Critical patent/EP0513280A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier

Definitions

  • the invention relates to a process for the production of moldings with a porous surface and a narrow surface pore radius distribution, and to the use of these moldings as supports for the fixation or immobilization of indicators, catalysts, biomass or parts of the biomass.
  • catalytically active substances are generally very expensive, the fixation of these substances, which is intended to prevent the catalyst from being removed with the reaction products, is of great importance.
  • Special catalyst carriers are developed for this purpose. The usability of such a catalyst support for a wide variety of catalytically active substances depends on its morphology and on its production process.
  • enzymes as a catalytic substance is becoming increasingly important. Enzymes are used, for example, in the industrial preparation of foods such as cheese or bread or in the production of alcoholic beverages. Since enzymes are generally water-soluble, they are easily transported away with the reaction medium and must therefore be constantly replaced. This increases the production costs and so a suitable immobilization of enzymes is of great economic importance.
  • One way of immobilizing enzymes is to use microbial cells as carriers for the enzyme. In this case, however, a suitable carrier material must be found for the immobilization of the microbial cells.
  • the immobilization of Mikroorga ⁇ mechanisms and 'cellular materials on solid supports is enrich a means Anlagen ⁇ spatially to such materials at desired locations. This is particularly important for biotechnological processes.
  • a wide variety of methods are known for modifying the surface of carrier materials. For example, inorganic or organic coatings are applied to the substrate materials, the bonding to the substrate generally being accomplished by chemical reactions.
  • the disadvantage of this method is that the desired pore size and the desired pore radius distribution can usually not be set or cannot be reproduced enough.
  • Another method is the application of fine, non-porous particles, which should contribute to a defined pore radius distribution due to the interstices between the particles at a given packing density.
  • binders For the stable fixation of such very fine particles on the carrier materials, however, the use of binders is necessary, but this causes an inaccurately reproducible narrowing of these intermediate spaces.
  • fillers or powders of small grain size can be applied to the surface of porous substrates and fixed with the aid of binders, condensable resins or by sintering, in order in this way to form a layer of smaller pore size, which is partially anchored in the substrate layer is to be obtained, and in order to create a body which has a smaller pore size than is possible with the production method of the substrate.
  • the disadvantage of this method is that with high filler proportions or with sintering the adhesion of the material in itself or on the substrate is imperfect, and so the substrates coated by this method are not mechanically strong. This manifests itself above all as sensitivity to vibrations and abrasion. If, on the other hand, high proportions of binder are used, there is a risk of creating completely dense areas on the substrate by locally too high concentrations, which are contrary to the intended use.
  • DE 34 10 650 AI supports bodies with a double pore structure of macro and micro pores with porosity-determining, continuous macro pores for the immobilization of microorganisms are known.
  • These carrier bodies are obtained by sintering a powder mixture of fine-grained, sinterable material and from a coarse-grained substance which can be extracted from the sintered product and which melts at a temperature higher than the sintering temperature, by cooling and by dissolving out the soluble component.
  • This is a technically very complex process for producing the surface porosity, because on the one hand high temperatures are required for the sintering process and on the other hand the final porosity only arises through post-treatment, namely by removing the soluble components.
  • a support material for chromatographic purposes based on silica which consists of a porous support, the surface of which is modified with a metal oxide to increase stability against alkaline media.
  • the modification takes place in such a way that the carrier body is treated with a solution of the metal in question.
  • the coating particles arise from the solution, which results in a change in size of these particles. This coating is not used to create or modify surface porosity.
  • GB-PS 1 581 993 a method for applying a water-containing metal oxide to a carrier and the carrier thus produced are known.
  • the coating does not serve to form a surface porosity, but is functional.
  • the object of the invention is to provide a method with which the surface of support bodies for the fixation or immobilization of indicators, of catalysts, of biomass or of parts of the biomass can be modified such that the surface of the support bodies is porous and that it shows a narrow pore radius distribution.
  • the size of the pore diameter should be varied over a wide range and should be able to be adapted exactly to the requirements of the respective application.
  • the process should be able to produce the surface of the above-mentioned carrier bodies quickly, easily, cheaply and universally on an industrial scale, and the manufacturing costs should be kept so low that the carrier bodies can be used for a wide range of applications.
  • the method should be universally applicable, and it is largely independent can be applied from the material of the support bodies used '.
  • the support bodies are coated with small, uniform particles with a narrow particle size distribution of an agglomeration-capable material without the application of pressure, without the addition of a binder and at temperatures below 120 ° C.
  • This forms the between the small, uniform particles The shape and size of the pore radii is determined by the shape and size of the small, uniform particles, and the pore radius distribution is determined by the particle size distribution agglomeration-capable particles, the smaller the spaces between these particles and the smaller the resulting pore radii, the more uniform the shape and the more uniform the size of the agglomeration-capable particles, the narrower the resulting pore Radius distribution.
  • the surface of support bodies for the fixation or immobilization of indicators, of catalysts, of biomass or of parts of the biomass be provided with a desired porosity, but it is also possible to provide the surface of other shaped bodies with a desired porosity, ie to be provided with a desired pore size and with a narrow pore radius distribution.
  • a desired porosity ie to be provided with a desired pore size and with a narrow pore radius distribution.
  • the coatings produced with the method according to the invention show an astonishing mechanical stability, for example when shaking, during transport or when decanting the shaped bodies, which is sufficient for many practical applications.
  • the substrates to be treated by the method according to the invention can be of diverse nature and they can have very different surface pores and sizes. The reason for this can be seen in the fact that the particle agglomerate which forms adapts to the pore shape of the substrate.
  • moldings with almost any surface texture can thus be coated.
  • the surface quality of the shaped bodies is only of minor importance, it was surprisingly found that even those shaped bodies can be coated that have a smooth, non-porous surface, so that these shaped bodies subsequently a defined surface porosity can be provided.
  • moldings with almost any shape can be coated. It is even possible to coat the inside of tubes using the method according to the invention. Surprisingly, it was found that not only flat structures can be provided with a defined surface porosity, but even very compact moldings, ie moldings with a small surface area compared to the volume. With the method according to the invention it is even possible to provide smooth, spherical shaped bodies with a defined surface porosity.
  • the shape of the substrate materials is preferably spherical, but an irregular shape is also possible.
  • granules with grain sizes in the range from 100 ⁇ m to 2 mm are coated, it having proven to be very advantageous if the diameter ratio of the spherical shaped body to the coating particles is chosen to be greater than 1000: 1.
  • coating particles with diameters ⁇ 100 nm are used.
  • molded articles made of nonmetallic-inorganic or of organically modified, nonmetallic-inorganic materials are coated without restricting generality.
  • Such materials are e.g. from ceramic or from glass-like single or multi-component systems such as made of silicate materials, e.g. Calcium silicate, made of fireclay or borosilicate glass. Particularly good results are achieved when coating shaped bodies made of aluminum oxide, soda-lime glass or silica glass.
  • coating particles are made from non-metallic-inorganic or from organically modified, non-metallic-inorganic materials used.
  • coating particles made of ceramic or glass-like one- or multi-component systems such as, for example, made of A1 2 0 3 or ZrO, can be used. Particularly good results are achieved when coating with particles made of SiO or TiO_.
  • Such coating particles can be synthesized, for example, using sol-gel methods or are described, for example, under the p
  • the particles used for coating can additionally be surface-modified before or during the production of the coating, e.g. be made hydrophobic.
  • hydrophobic aerosils can be used as coating particles with great success.
  • the moldings produced by the process according to the invention can be coated with the indicators or the catalysts after the coating process according to the invention. However, it is also possible to coat the particles used for the coating with indicators or with catalysts before or during the production of the coating.
  • suitable catalysts or indicators are, for example, vanadium pentoxide or bromophenol blue.
  • the moldings are to be coated dry, they can simply be mixed with the coating particles. Suitable devices for this are, for example, rotating drums. Surprisingly, this process results in very stable coatings. However, it is also possible for the coating particles to be moistened with a liquid before coating, or for the coating particles to be suspended in a liquid. The moldings for coating with the moist coating particles are then mixed and dried. This results in particularly stable and abrasion-resistant coatings. Suitable liquids for moistening the coating particles are, for example, water or water / alcohol mixtures. Suitable alcohols for this are, for example, ethanol or propanol. The moist, coated moldings can be dried, for example, by blowing dry with compressed air or thermally.
  • additives e.g. the indicators or the catalysts are added during the coating process in the form of solutions to the mixture of shaped body and coating particles.
  • the substrate material is coated together with the coating particles with a solution of the additive, e.g. of the indicator or the catalyst, mixed and then blown dry with compressed air.
  • thermal drying can also be carried out, it being important to ensure that, in the presence of additives, their thermal resistance limit is not exceeded. This has made it possible to provide the moldings with the required surface porosity in a single operation and at the same time to provide them with the desired indicators or catalysts.
  • the moldings produced by the process according to the invention can be used for a wide variety of purposes. Without restricting generality, they can be used as support materials for indicators, for catalysts, for immobilized enzymes or for immobilized microorganisms can be used, but also as test tubes or as filler material for test tubes. For example, the sensitivity and accuracy of detection of test tubes for harmful gases can be increased if glass beads coated with aerosil particles and impregnated with an appropriate reagent are used instead of the currently customary reagent-soaked silica gel particles. Further possible uses are catalytic reactions, for example of harmful gases in exhaust air streams or in chemical synthesis, preferably from the gas phase.
  • the 'mechanical stability of the coating is very Significant abrasion is not generated by the rubbing stress during the drying process or by subsequent transport and decanting processes.
  • the coating is stable even when gas streams of different humidity and temperature are passed through, as is necessary, for example, with different gas detection methods.
  • Stemalox balls material: A1_0; diameter: approx. 0.7 mm
  • Aerosil 200 o-tolidine in ethanol. Drying takes place at 50 ° C for 120 minutes. Then there is a free-flowing mixture that can be used after the transfer to test tubes for the detection of oxidizing gases (e.g. Cl or NO).
  • oxidizing gases e.g. Cl or NO.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Genetics & Genomics (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Microbiology (AREA)
  • Biotechnology (AREA)
  • Biomedical Technology (AREA)
  • Biochemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de fabrication de corps moulés ayant une surface poreuse et une répartition étroite des rayons des pores superficiels, ainsi que l'utilisation de ces corps moulés comme supports de fixation ou d'immobilisation d'indicateurs, de catalyseurs, d'une biomasse ou de parties de biomasse. Les corps moulés sont enduits avec des particules petites et uniformes, à répartition dimensionnelle étroite, d'un matériau susceptible de s'agglomérer, sans application de pression et sans adjonction de liant, à des températures inférieures à 120 °C, de sorte que les lacunes existant entre les particules petites et uniformes à la surface des corps moulés forment des pores avec des rayons étroitement répartis. La forme et les dimensions des rayons des pores sont déterminées par la forme et par les dimensions des particules petites et uniformes, alors que la répartition des rayons des pores est déterminée par la répartition dimensionnelle des particules.
EP91920271A 1990-11-29 1991-11-15 Procede de fabrication de corps moules ayant une surface poreuse et une repartition etroite des rayons des pores superficiels Withdrawn EP0513280A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4038109A DE4038109C2 (de) 1990-11-29 1990-11-29 Verfahren zur Herstellung von Formkörpern mit poröser Oberfläche und enger Oberflächenporenradienverteilung, nach dem Verfahren hergestellte Formkörper und Verwendung dieser Formkörper
DE4038109 1990-11-29

Publications (1)

Publication Number Publication Date
EP0513280A1 true EP0513280A1 (fr) 1992-11-19

Family

ID=6419235

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91920271A Withdrawn EP0513280A1 (fr) 1990-11-29 1991-11-15 Procede de fabrication de corps moules ayant une surface poreuse et une repartition etroite des rayons des pores superficiels

Country Status (3)

Country Link
EP (1) EP0513280A1 (fr)
DE (1) DE4038109C2 (fr)
WO (1) WO1992009364A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4411112C2 (de) * 1994-03-30 2002-06-20 Messer Griesheim Gmbh Absorptionsmasse für die Entsorgung von Fluor aus Gasgemischen und deren Verwendung
US6288273B1 (en) 1997-02-27 2001-09-11 Basf Aktiengesellschaft Method for producing shell catalysts for catalytic gas-phase oxidation of aromatic hydrocarbons
DE19938609C2 (de) * 1999-08-14 2002-11-14 Erhard Weber Kugelgel-Flächenlager
DE10208113A1 (de) * 2002-02-26 2003-09-04 Basf Ag Verfahren zur Herstellung von Schalenkatalysatoren

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1131512B (de) * 1954-12-30 1962-06-14 Dr Hugo Stoltzenberg Absorptionsmassen für transparente Atemfilter und Verfahren zu deren Herstellung
NL299290A (fr) * 1962-10-23
US3505785A (en) * 1967-06-20 1970-04-14 Du Pont Superficially porous supports for chromatography
US4070283A (en) * 1976-12-08 1978-01-24 E. I. Du Pont De Nemours And Company Controlled surface porosity particles and a method for their production
JPS53106682A (en) * 1977-03-01 1978-09-16 Hitachi Ltd Supporting method for hydrated metal oxide on carrier
US4594158A (en) * 1981-09-03 1986-06-10 Rohm And Haas Filter aid materials bearing anion exchange resins
EP0153937A4 (fr) * 1983-08-17 1986-11-06 Macedo Pedro Manuel Buarque De Supports chromatographiques ameliores a base de silice contenant des additifs.
DE3410650A1 (de) * 1984-03-23 1985-10-03 Kernforschungsanlage Jülich GmbH, 5170 Jülich Mit mikroorganismen bewachsene poroese anorganische traeger, verfahren zur immobilisierung von mikroorganismen und dafuer geeignete traegerkoerper
DE68900216D1 (de) * 1988-06-07 1991-09-26 Rohm & Haas Ionenaustauscherzusammenstellungen fuer die ionenaustauschchromatographie.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9209364A1 *

Also Published As

Publication number Publication date
DE4038109C2 (de) 1994-07-07
DE4038109A1 (de) 1992-06-04
WO1992009364A1 (fr) 1992-06-11

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