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WO1990006176A1 - Corps solide poreux synthetique - Google Patents

Corps solide poreux synthetique Download PDF

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Publication number
WO1990006176A1
WO1990006176A1 PCT/EP1989/001485 EP8901485W WO9006176A1 WO 1990006176 A1 WO1990006176 A1 WO 1990006176A1 EP 8901485 W EP8901485 W EP 8901485W WO 9006176 A1 WO9006176 A1 WO 9006176A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid body
body according
solid
density
bulk density
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.)
Ceased
Application number
PCT/EP1989/001485
Other languages
German (de)
English (en)
Inventor
Michael Durst
H. Henning Vollmer
Manfred Salinger
Kristian Franz
Heinz Bettmann
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.)
Schumacher & Co KG GmbH
Original Assignee
Schumacher & Co KG GmbH
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 Schumacher & Co KG GmbH filed Critical Schumacher & Co KG GmbH
Publication of WO1990006176A1 publication Critical patent/WO1990006176A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • B01J20/28—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
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • 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
    • B01J20/28002—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 physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/28002—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 physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • 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
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28088—Pore-size distribution
    • B01J20/28092—Bimodal, polymodal, different types of pores or different pore size distributions in different parts of the sorbent

Definitions

  • the invention relates to synthetic, porous solid bodies in the form of a granular, pourable material.
  • Such solid bodies can be used primarily as carrier bodies in biochemical and chemical reactions.
  • any bio- or chemical catalyst the type and application of which is not the subject of the invention, can be bound to the porous solid body, so that a composite of support body and catalyst results.
  • Such solid bodies can, however, also be used in a different way, in particular as a fluidizable medium, for example as an adsorbent in purely physical processes.
  • the following description of the invention relates essentially to the use of the solid body as a support for catalysts. However, this description is only to be understood as an example.
  • Known carrier bodies can be present as organic substances (e.g. polymer foams, synthetic fiber knits, ion exchange resins) or as an inorganic substance (e.g. sand, aluminum oxide, activated carbon).
  • organic substances e.g. polymer foams, synthetic fiber knits, ion exchange resins
  • inorganic substance e.g. sand, aluminum oxide, activated carbon.
  • a wide field of application of the known and the solid support bodies according to the invention is in particular in the field of biotechnology, including biological wastewater treatment.
  • the fixation of a catalyst (in the case of biocatalysts one speaks of an “immobilization”) on solid support bodies is always of procedural and economic advantage if the catalyst is washed out after a short time during continuous operation or when flowing through a reactor containing no support bodies threatens.
  • the recovery of the catalyst from the effluent stream which usually contains by-products and unreacted feedstocks in addition to the desired product, is generally complex and therefore more expensive than constantly using new, otherwise obtained or commercially available catalysts. Flushing occurs particularly in the case of finely dispersed catalysts, since these, as easily suspendable particles, easily follow a flow around them. In catalytic processes, the use of finely dispersed substances is the rule because, owing to the favorable ratio of catalyst surface to catalyst quantity, higher activities and yields are achieved than with coarser particles.
  • the retention of the catalyst by fixing it to support bodies ensures that the catalyst can be used over a longer period of time and has to be regenerated less frequently.
  • the catalyst has a density similar to that of the surrounding medium (carrier body), what has been said above applies to an increased degree.
  • the presence of a small density difference applies in particular to reactions in which the catalyst is of biological origin and is used in the form of free cells, in the form of cell fragments, cell extracts or as a pure enzyme.
  • a biocatalyst must be finely distributed in a mostly aqueous liquid phase that contains the substrate to be treated.
  • the accessibility of the catalyst to the substrate must not be significantly impaired by immobilization.
  • the resulting reaction products must be easy to remove.
  • Suitable viable cells are those of microorganisms (bacteria, yeasts, fungi) and those of animal or vegetable origin.
  • the fixing of catalysts to the solid bodies the following explanations also apply in principle to the use of conventional chemical catalysts.
  • the immobilization (or fixation) of a catalyst on a carrier body ideally brings about a complete retention of the catalyst, so that regular regeneration of the catalyst becomes superfluous. Regeneration can be completely dispensed with when working with living cells.
  • the loss of washed-out cells during continuous operation is continuously compensated for by the cell propagation after reaching a steady operating state.
  • a state of equilibrium is established between adsorption (colonization) and desorption (detachment): dead or only loosely adsorbed cells are carried out of the system and make room for fresh, active cells.
  • adsorption colonization
  • desorption detachment
  • the biocatalysts can be fixed right from the start, because this helps to shorten the start-up phase in terms of discharge losses.
  • the adhesion of the cells to the carrier body enables them to face the biological selection pressure more successfully and to establish themselves more quickly. This in turn has a positive effect in the form of faster product sales and a higher yield.
  • the solid body according to the invention is advantageously used in the form of fluidizable particles (carrier particles).
  • REPLACEMENT B L ATT Another possible application is to introduce the solid bodies in the form of a bed into a fixed bed reactor. However, this can cause procedural difficulties in gas-forming reactions (“gas embolism”, channel formation, constipation).
  • the carrier bodies suspended in a liquid phase can be retained, for example, by sieves with a mesh size adapted to the respective grain size.
  • the retention of the carrier bodies will be based on the principle of "gravity sedimentation” or "buoyancy sedimentation”.
  • the synthetic, porous solid bodies used as carrier materials according to the invention should be inert and stable over a longer period of time. This includes sufficient chemical and mechanical resistance. Porous carrier materials also have further advantages owing to their large usable surface area for colonization with microorganisms.
  • Special carrier bodies are known, for example, from the patents and patent applications mentioned below: DE 28 39 580, DE 33 23 078, DE 34 02 697, DE 36 11 582, DE 36 13 575, DE 36 15 103, DE 37 35 680, EP 0 046 901, EP 0 112 597, EP 0 131 251, EP 0 155 669, EP 0 158 909, EP 0 186 125, EP 0 200 486, EP 0 216 272 and EP 0 245 088.
  • the known methods for connecting a catalyst to a support can be divided into several groups. in the
  • REPLACEMENT LEAF In the simplest case, spontaneous adsorption occurs as soon as the catalyst comes into contact with the support surface. However, this does not lead to a sufficiently strong bond in all cases, so that sufficient stability of the adsorption is often only achieved by coating the support with coupling agents which have suitable functional groups. In some cases, cross-linking of the catalyst with glutar (di) aldehyde brings about better catalyst stability. However, it must be taken into account that such measures can at least partially block active centers of the catalyst, so that natural adsorption should always be given preference if possible. Surface treatments of substrates are described, for example, in patent applications EP 0 131 251, EP 0 158 909 and EP 0245 088.
  • Another known method consists in embedding the catalyst in a polymer matrix which is permeable to the liquid phase. This can also be done by soaking a porous substance with a polymer that contains whole cells or enzymes and then allowing the polymer to harden to a gel. This is described in patent application DE 36 13 575.
  • the carrier bodies are not to be used as a bed or packing in a fixed bed reactor, they have to be fluidized. This can be accomplished by means of a stationary or rotating fluidized bed.
  • the fluidized bed can be formed in a fluidized bed reactor (sometimes also referred to as a fluidized bed or fluidized bed reactor), in the second case a loop reactor with internal or external loop flow is to be used.
  • a fluidized bed reactor sometimes also referred to as a fluidized bed or fluidized bed reactor
  • a loop reactor with internal or external loop flow is to be used.
  • the design of such reactors which are also suitable for the solid bodies according to the invention and in which further functions, such as calming sections, separators, heat exchangers and
  • REPLACEMENT LEAF The like are integrated, can be done in different ways and is already described in part of the above-mentioned documents.
  • Knowing the speed of movement W p of the carrier particle is important for the design of fluidized bed reactors. It can be calculated approximately as follows:
  • the Reynolds number is defined here as:
  • the bulk density is to be used instead of the pure density g of the solid.
  • the bulk density ⁇ of the carrier formerly also called the density, represents the density of the
  • REPLACEMENT LEAF porous carrier body including its air-filled pores. It is calculated by neglecting the density of the air from the pure density of the material forming the framework ⁇ s and the porosity6 p according to the equation:
  • the bulk density is determined according to DIN 51065, the porosity according to DIN 51056. If the bulk density of a solid body varies from the inside to the outside, one also speaks of the local bulk density.
  • the bulk density is to be used for porous bodies in equations 1 and 2 instead of p g:
  • the density according to equation 5 is at the same time also approximately disregarded for the density of an overgrown carrier body (gas inclusions).
  • the reactor must be flowed through from bottom to top in order to fluidize the carrier.
  • Examples of such reactors are the patent applications EP 0 090 450 and EP 0 168 283.
  • the aim is to use cell organisms capable of reproduction and these by their natural adhesive properties, ie. H. to be fixed on supports as far as possible without the use of further aids.
  • H. natural adhesive properties
  • it is often only through the use of entire cell organisms that it is ensured that all the necessary cofactors are present in order to achieve a rapid, selective implementation.
  • these factors may be missing.
  • the adhesion can be supported by a change in the composition of the medium to be treated compared to the fermentation with unfixed cells or by a different pH value.
  • Possible impairments when operating a system with immobilized microorganisms can consist of the following:
  • the carrier material is not reusable if you want to switch to another process or the material has to be regenerated because contamination with foreign germs has occurred.
  • Porous, rigid solid support bodies with a large surface / volume ratio are used, since mechanical forces (abrasion) or hydraulic forces (relative speed of the particles to the fluid) can act less strongly on the cell organisms.
  • the porosity enables the cells to settle in protected cavities; by choosing a rigid body that becomes Avoid squeezing cells, as z. B. occurs with foams. If this does not yet sufficiently secure the settlement, there is the possibility, already mentioned, of using adhesion promoters.
  • the porosity of the carrier body must not be chosen too high, since otherwise the carrier body cannot be mechanically loaded.
  • pore diameter for optimal colonization can be, for example, 5 times the diameter of the cells.
  • maximum population density does not necessarily mean maximum activity of the organisms and maximum yield.
  • a free exchange of liquid and gas in the pores is just as important, so that larger pores or a juxtaposition of micro and macro pores should be sought.
  • a carrier material is used which can be annealed or leached chemically in order to remove unwanted growth and to sterilize the material.
  • G. A colonization enveloping the carrier particle is prevented, so that after an accident the biofilms of neighboring carrier particles do not grow together in the bed immediately.
  • the layer thickness of the biofilm on the outer contour of the particles as well as the abrasion of the carrier body itself, which, however, only starts with far higher forces, can be determined by using a fluidized bed in a narrower range by the selected space velocity, which however influences the expansion of the fluidized bed, control in a larger area by the selected particle diameter. Also for other reasons, such.
  • B. diffusion limits it may be necessary to limit the growth of microorganisms to a certain level.
  • the invention proposes synthetic, porous solid bodies in the form of a granular, pourable material which are distinguished by the fact that they have a bulk density which varies from the inside out, and the local one
  • Percentage changes in the local bulk density are related to the local bulk density in the core area (center).
  • the local bulk density can in principle increase or decrease from the inside to the outside.
  • carrier bodies with a relatively large volume fraction of pores for which no significant diffusion limitations are to be expected, the core of the carrier particle being used at the same time to set a desired overall bulk density in order to achieve precisely that To make sedimentation properties favorable.
  • This can take place in particular through a multilayer structure of the solid body, in which the local bulk density and / or preferably the local porosity changes abruptly from the inside to the outside.
  • the carrier bodies can also be constructed in such a way that the local bulk density and / or possibly the local porosity changes continuously from the inside to the outside.
  • the invention can also be understood as consisting in the method according to which, starting from a porosity which is favorable for the application in question, the bulk density of the solid bodies with regard to the reaction system to be operated is adjusted in accordance with the above-mentioned values such that give the best sedimentation properties of the solid body for the application.
  • FIG. 1 shows a porous solid body with a continuously decreasing solid density from the inside to the outside
  • FIG. 2 shows a solid body with a continuously increasing porosity from the inside out
  • FIG. 3 shows a multilayer structure of a porous solid body
  • Figure 4 shows a solid body similar to Figure 3 with an internal cavity
  • FIG. 5 shows a solid body similar to FIG. 4 with an intermediate layer surrounding the inner cavity.
  • Figures 1 to 5 each consist of three superimposed partial representations.
  • the solid body is realistically depicted on the left side of the representations in the top row, while it is more or less schematized on the right side of this representation.
  • the solid which forms the framework of the solid body is in each case denoted by the reference symbol 1, and the pores contained in it are identified by the reference symbol 2.
  • the reference number 3 denotes the material from which the core of the body is made
  • an inner cavity of the solid body is designated with the reference number 4
  • the graphic representations in the middle and lower row of FIGS. 1 to 5 show the dependence of the relative bulk density measured in the radial direction (r) of the respective solid body or porosity- (£ p ) »With $ g the average density of the substance from which the solid body is made up as a whole is assumed, or the average density of certain sections of the solid body (e.g. core 3) designated.
  • the radius of the respective solid body is assumed to be R.
  • the solid support bodies shown in FIGS. 1 to 5 are the most important limit cases of the invention.
  • the pores in the solid body are at least partially connected to one another and the fluid flows through them for the most part and can therefore be populated.
  • the solid body consisting of material 1 has a bulk density that decreases continuously from the inside to the outside (cf. the middle representation in FIG. 1).
  • the porosity (lower representation in FIG. 1) is constant or uniform. It could also vary (as assumed in Figure 2); H. have a gradient.
  • a porous solid support body according to FIG. 1 can be produced in the following way: in a pellet mixer or by means of a build-up granulation, the bodies can be produced by time-dependent addition of different raw materials with different densities in such a way that a density gradient is established within the body .
  • the bodies can be produced by time-dependent addition of different raw materials with different densities in such a way that a density gradient is established within the body .
  • a porosity that is constant over the cross-section (in the direction r) can be achieved either by an equal particle size distribution of the various raw materials added or - more advantageously - by the addition of pore formers of known size distribution during the entire production process, the pore formers subsequently being removed, e.g. B. be drained or burned out.
  • FIG. 2 shows a solid body with a continuously increasing porosity from the inside out, in such a way that either the number of pores or the pore size increases locally from the inside out.
  • the core can be non-porous, while the outer layer exposed to the medium to be treated can have a maximum porosity, which is only limited by the desired mechanical stability of the solid body.
  • the pores are advantageously connected to one another and open to the outside (pores through which they can flow).
  • FIG. 3 shows a multi-layer structure of a solid support body, the inner or core area of the body, provided that it is made of the same material as the outer area of the body, has a relatively low or no porosity compared to the outer area or, if the inner area differs materially from the material of the outer area, has at least a significantly higher bulk density than the outer area.
  • the outer area which is exposed to the medium to be treated, can have a maximum porosity, which in turn only by
  • FIG. 5 corresponds to that according to FIG. 4, but the cavity of the carrier body is additionally encased by a non-porous, impermeable intermediate layer made of the same or a different material as the material of the outer region.
  • the density gradient within a particle and thus the effective porosity can be varied within wide limits by corresponding process parameters during production.
  • the size (as well as the internal and external density) can be adjusted according to the fluid dynamic requirements of the reactor via the method of manufacture (e.g. mixing duration, speed of rotation of a mixing drum for solid bodies to be produced from several starting materials).
  • the method of manufacture e.g. mixing duration, speed of rotation of a mixing drum for solid bodies to be produced from several starting materials.
  • the porosity can be specifically changed so that the difference in bulk density is at least 20%.
  • the core of the solid body has a higher density than the bulk density of the porous outer layer (s).
  • the core has a lower density than the bulk density of the porous outer layer (s).
  • solid bodies according to the invention are compared with a comparative solid body of a known type, the comparative solid body being uniformly porous throughout and also having a constant density from the inside to the outside.
  • the aim of the calculation examples below is to demonstrate that a solid body according to the invention, with an improved range of usable pores, has the same good sedimentation properties as conventional comparative material with uniform porosity and density.
  • the solid according to the invention and the comparative solid are spherical.
  • the heavy core of the solid body according to the invention is spherical and lies concentrically in the interior of the particle.
  • the heavy core of the solid body according to the invention is non-porous, but consists of the same substance as
  • the porosity of the coating layer of the solid body according to the invention is uniform, i. H. it has no local gradient. The same applies to the comparative solid body as a whole.
  • the outer surface of both the inventive and the comparison carrier body and an underlying, spherical shell-shaped layer with a thickness of 6 D are open-pore. Diffusion no longer takes place in radially underlying layers (infinitely large diffusion limitation).
  • the comparative solid body thus comprises an external, effective spherical shell with the thickness c Q / in which diffusion processes and thus reactions take place between the medium to be treated and the microorganisms located in the pores.
  • the above assumption applies to the conditions in practice: no appreciable diffusion takes place in the porous core located within the spherical shell. The cells that settle there are undersupplied and not very productive.
  • the core which is ineffective in this regard, is usefully used in the case of the carrier body according to the invention to set a desired overall bulk density.
  • the outer spherical shell layer (cladding layer) of the solid body according to the invention which in turn encloses a solid core, is selected in its layer thickness H so that this value corresponds to the above-mentioned value D.
  • the solid volume fraction w of the fluidized beds is specified as a fixed value.
  • the core consists of a different solid than the porous coating layer.
  • Diameter of the solid body according to the invention with the validity of the requirements a. to i. d " 1000.10 " 6
  • the core consists of a different solid than the porous coating layer.
  • Diameter of the comparative solid body 2000.10 -6 ⁇ m
  • REPLACEMENT LEAF viewed this can also mean that the fluidized bed or reactor volume can be significantly smaller in order to achieve corresponding yields. This could not be achieved by using a finely dispersed fraction of particles with a smaller diameter alone, since the particles can only be reduced in size to a limited extent because of the risk of discharge.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)

Abstract

Des corps solides poreux synthétiques se présentent sous forme d'un matériau granulé en vrac et servent notamment de supports à des micro-organismes. La densité de ces corps varie de l'intérieur vers l'extérieur et leur masse volumique apparente locale varie d'au moins 20 % entre leur noyau (centre) et leur surface extérieure.
PCT/EP1989/001485 1988-12-08 1989-12-05 Corps solide poreux synthetique Ceased WO1990006176A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3841289A DE3841289A1 (de) 1988-12-08 1988-12-08 Synthetische, poroese feststoffkoerper
DEP3841289.6 1988-12-08

Publications (1)

Publication Number Publication Date
WO1990006176A1 true WO1990006176A1 (fr) 1990-06-14

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PCT/EP1989/001485 Ceased WO1990006176A1 (fr) 1988-12-08 1989-12-05 Corps solide poreux synthetique

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WO (1) WO1990006176A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11602120B2 (en) 2012-09-11 2023-03-14 Pioneer Pet Products, Llc Lightweight coated extruded granular absorbent
WO2015138821A1 (fr) 2014-03-12 2015-09-17 Pioneer Pet Products, Llc Absorbant granulaire extrudé

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3145183A (en) * 1958-12-16 1964-08-18 Norton Co Catalyst carrying balls
US3790475A (en) * 1972-03-27 1974-02-05 Corning Glass Works Porous glass support material
US3798176A (en) * 1968-07-19 1974-03-19 Osaka Yogyo Co Ltd Method for manufacturing a catalyst and its carrier having a vacant center or a dense center
US3875272A (en) * 1973-07-30 1975-04-01 Coors Porcelain Co Hollow pellets and method of making same
EP0123293A2 (fr) * 1983-04-22 1984-10-31 E.I. Du Pont De Nemours And Company Procédé pour préparer des supports superficiellement poreux pour chromatographie et catalyseurs
US4515906A (en) * 1983-02-28 1985-05-07 Bend Research, Inc. Anisotropic microporous supports impregnated with polymeric ion-exchange materials
US4576926A (en) * 1984-04-23 1986-03-18 California Institute Of Technology Catalytic hollow spheres

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3145183A (en) * 1958-12-16 1964-08-18 Norton Co Catalyst carrying balls
US3798176A (en) * 1968-07-19 1974-03-19 Osaka Yogyo Co Ltd Method for manufacturing a catalyst and its carrier having a vacant center or a dense center
US3790475A (en) * 1972-03-27 1974-02-05 Corning Glass Works Porous glass support material
US3875272A (en) * 1973-07-30 1975-04-01 Coors Porcelain Co Hollow pellets and method of making same
US4515906A (en) * 1983-02-28 1985-05-07 Bend Research, Inc. Anisotropic microporous supports impregnated with polymeric ion-exchange materials
EP0123293A2 (fr) * 1983-04-22 1984-10-31 E.I. Du Pont De Nemours And Company Procédé pour préparer des supports superficiellement poreux pour chromatographie et catalyseurs
US4576926A (en) * 1984-04-23 1986-03-18 California Institute Of Technology Catalytic hollow spheres

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DE3841289A1 (de) 1990-07-05

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