US20120010379A1 - Catalyst carrier based on silica gel - Google Patents

Catalyst carrier based on silica gel Download PDF

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Publication number
US20120010379A1
US20120010379A1 US13/255,546 US201013255546A US2012010379A1 US 20120010379 A1 US20120010379 A1 US 20120010379A1 US 201013255546 A US201013255546 A US 201013255546A US 2012010379 A1 US2012010379 A1 US 2012010379A1
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range
spherical beads
metal
mixture
acid
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Angela Siegel
Tobias Eckardt
Andreas Braedikow
Thorsten Puvogel
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BASF SE
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BASF SE
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    • 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
    • B01J35/51—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/633—Pore volume less than 0.5 ml/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
    • C01B13/328—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process by processes making use of emulsions, e.g. the kerosine process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • C01B33/166—Preparation of silica xerogels by acidification of silicate in the presence of an inert organic phase
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F110/04—Monomers containing three or four carbon atoms
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
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    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to spherical beads comprising at least one metal and/or semimetal oxide, having a diameter in the range from 10 to 120 ⁇ m, a BET surface area in the range from 400 to 800 m 2 /g and a pore volume in the range from 0.3 to 3.0 cm 3 /g, wherein the diameter at no point of a given bead deviates by more than 10% from the average diameter of said bead and the surface of said bead is substantially smooth, to a process for producing these spherical beads and to the use of spherical beads as catalysts or catalyst carriers.
  • the present invention relates more particularly to spherical beads comprising SiO 2 (silica).
  • U.S. Pat. No. 2,921,839 discloses a method of producing finely divided silica particles by precipitation. To this end, an aqueous solution of an alkali metal silicate is admixed with an organic solvent and subsequently with an acid. After the organic phase has been separated off, the silica gel beads obtained are dried by azeotropic distillation. The method described in U.S. Pat. No. 2,921,839 provides silica gel particles having a diameter in the range from 10 to 1000 ⁇ m. U.S. Pat. No. 2,921,839 does not disclose any silica gel particles that are notable for a particularly high smoothness on their surface.
  • U.S. Pat. No. 3,489,516 discloses a method of producing silica beads by polymerization of xNa 2 O.ySiO 2 in a dispersed organic phase in an aqueous medium by addition of an acid.
  • the silica beads thus produced have a BET surface area in the range from 700 to 1100 m 2 /g or in the range from 300 to 600 m 2 /g. These silica beads can be used as catalysts.
  • silica particles, or their methods of making that display a combination of diameter, BET surface area, pore volume, polydispersity and surface smoothness that is particularly suitable according to the present invention and that appears to make these particles particularly suitable for use as catalysts in polymerization reactions, for example for producing polypropylene or polyethylene.
  • a process that provides spherical beads that display the recited advantageous combination of various parameters is not known in the art.
  • spherical beads comprising at least one metal and/or semimetal oxide, having a mean diameter in the range from 10 to 120 ⁇ m, a BET surface area in the range from 400 to 800 m 2 /g and a pore volume in the range from 0.3 to 3.0 cm 3 /g, wherein the diameter of a given bead at any one point of said bead deviates by less than 10% from the average diameter of said bead and the surface of said bead is substantially smooth.
  • the spherical beads of the present invention comprise at least one metal and/or semimetal oxide.
  • the at least one metal and/or semimetal oxide is selected from the group consisting of SiO 2 , Al 2 O 3 , TiO 2 , MgO and mixtures thereof.
  • the spherical beads of the present invention comprise SiO 2 . It is very particularly preferred for the spherical beads of the present invention to consist of SiO 2 to an extent of at least 96% by weight, particularly to an extent of at least 98% by weight. The remaining weight percentages can be accounted for by small amounts of further metals such as aluminum, sodium, iron and mixtures thereof, and also anions such as sulfate and/or chloride. These components in addition to SiO 2 are each present in an amount of less than 0.1% by weight.
  • the at least one metal and/or semimetal oxide is substantially amorphous; that is, the at least one metal and/or semimetal oxide is at least 80% amorphous and more preferably at least 90% amorphous.
  • the fraction of amorphous regions can be determined by following methods known to a person skilled in the art, for example by X-ray diffraction (XRD).
  • the BET surface area of the spherical beads of the present invention is generally in the range from 400 to 800 m 2 /g, preferably in the range from 500 to 600 m 2 /g and more preferably in the range from 520 to 580 m 2 /g.
  • the BET surface area can be determined by following methods known to a person skilled in the art, for example by N 2 physisorption measurements.
  • the mean diameter of the spherical beads of the present invention is generally in the range from 10 to 120 ⁇ m, preferably in the range from 30 to 100 ⁇ m, and most preferably in the range from 40 to 90 ⁇ m.
  • mean diameter is to be understood as the diameter averaged over all beads in a sample.
  • the D 10 value of the spherical particles of the present invention is generally in the range from 5 to 30 ⁇ m, preferably in the range from 10 to 25 ⁇ m and more preferably in the range from 12 to 20 ⁇ m.
  • the D 50 value of the spherical particles of the present invention is generally in the range from 30 to 70 ⁇ m, preferably in the range from 40 to 65 ⁇ m and more preferably in the range from 50 to 60 ⁇ m.
  • the D 90 value of the spherical particles of the present invention is generally in the range from 50 to 140 ⁇ m, preferably in the range from 75 to 120 ⁇ m and more preferably in the range from 80 to 100 ⁇ m.
  • the recited values D 10 , D 50 and D 90 indicate that 10%, 50% and 90%, respectively, of the particles measured have a smaller diameter than the recited diameter.
  • Methods of determining the mean diameter of the spherical beads are known to a person skilled in the art, for example Fraunhofer or Mie laser diffraction.
  • the pore volume of the spherical beads of the present invention is generally in the range from 0.3 to 3.0 cm 3 /g, preferably in the range from 0.8 to 2.5 cm 3 /g and most preferably in the range from 1.5 to 2.2 cm 3 /g.
  • Methods of determining the pore volume of the spherical beads are known to a person skilled in the art, for example N 2 -physisorption and Hg porosimetry measurements.
  • the spherical beads of the present invention are substantially monodisperse; that is, the spherical beads preferably have a narrow particle size distribution, as is clear from the recited D 10 , D 50 and D 90 values.
  • the spherical beads of the present invention are generally notable for a particularly pronounced and uniform shape.
  • the diameter of any one spherical bead of the present invention at any one point of this bead generally differs by less than 10%, preferably less than 5% and more preferably less than 2% from the average diameter of this bead.
  • average diameter is to be understood as meaning the diameter averaged over all diameters in a bead.
  • the ideal case of a perfectly uniform sphere would mean that there is only one diameter for every bead.
  • the spherical shape of the beads of the present invention can be determined by scanning electron micrographs.
  • the spherical beads of the present invention are further notable for the surface of these spherical beads being substantially smooth.
  • smooth is to be understood as meaning that the surface of the spherical beads of the present invention is free of any irregularities such as dents, fissures, faults, cracks, bulges, notches, etc.
  • the smoothness of the particles of the present invention can be determined by scanning electron micrographs for example.
  • the present invention also provides a process for producing the spherical beads of the present invention, said process comprising the steps (A) to (F).
  • Step (A) comprises providing a mixture comprising at least one at least partially water-miscible organic solvent, water and at least one precursor compound of the at least one metal and/or semimetal oxide as mixture A.
  • the at least one at least partially water-miscible organic solvent is not completely miscible with water in one preferred embodiment.
  • the at least one at least partially water-miscible organic solvent is selected from the group consisting of ketones, ethers, alcohols, for example butanols, such as n-butanol, isobutanol, tert-butanol, vegetable oils, silicone oils, mineral oils and mixtures thereof. n-Butanol is particularly preferred.
  • step (A) of the process of the present invention comprises using at least one at least partially water-miscible organic solvent which is water-saturated.
  • the mixture A provided in step (A) of the process of the present invention comprises water.
  • This water may be selected from tap water, drinking water, distilled water, demineralized water; preference is given to using distilled water.
  • the volume ratio of at least one at least partially water-miscible organic solvent to water in mixture A is generally in the range from 5:1 to 1:1 and preferably in the range from 4:1 to 2:1.
  • One particularly preferred embodiment comprises initially charging the at least one organic solvent and adding the at least one precursor compound to the at least one metal or semimetal oxide in aqueous solution to obtain mixture A.
  • the at least one compound used in step (A) of the process of the present invention as a precursor compound of the at least one metal and/or semimetal oxide can be any compound capable of conversion into the corresponding metal and/or semimetal oxide by reaction with at least one acid.
  • the precursor compound used is preferably sodium silicate xNa 2 O.ySiO 2 (water glass).
  • a further preferred embodiment of the process of the present invention uses a sodium silicate solution in step (A) in which the SiO 2 :Na 2 O molar ratio is generally in the range from 1 to 6, preferably in the range from 2 to 5 and more preferably in the range from 3 to 4, for example 3.4.
  • alkali metal silicates for example potassium silicate, alkaline earth metal silicates, colloidal silica sols and mixtures thereof.
  • the at least one precursor compound of the at least one metal and/or semimetal oxide is selected from the group consisting of alkali metal silicates, for example potassium silicate and/or sodium silicate, alkaline earth metal silicates, colloidal silica sols and mixtures thereof.
  • One particularly preferred embodiment utilizes an aqueous water glass solution, i.e., an aqueous solution of xNa 2 O.ySiO 2 in H 2 O, having a density ranging from 1.1 to 1.35 g/cm 3 , particularly from 1.14 to 1.32 g/cm 3 , in step (A) of the process of the present invention.
  • the at least one precursor compound of the at least one metal and/or semimetal oxide is used in mixture A in a concentration ranging from 1.5 to 4.5 mol*l ⁇ 1 .
  • Step (A) of the process of the present invention can generally be carried out at any temperature at which the individual components are processable or to be more precise soluble.
  • Step (A) preferably yields a two-phase mixture.
  • the temperature in step (A) is for example in the range from 10 to 80° C., preferably in the range from 15 to 40° C., more preferably equal to ambient temperature.
  • Step (B) of the process of the present invention comprises providing a mixture comprising at least one at least partially water-miscible organic solvent, water and at least one acid as mixture B.
  • Step (B) of the process of the present invention can utilize all at least partially water-miscible organic solvents already mentioned with regard to step (A); n-butanol is preferably used in step (B). It is further preferable to use in step (B) at least one at least partially water-miscible solvent which is water-saturated.
  • Mixture B comprises at least one acid.
  • any acid can be used that is soluble in a mixture comprising at least one at least partially water-miscible organic solvent and water and that is capable of converting the at least one compound used in step (A) as a precursor to the at least one metal and/or semimetal oxide, into the corresponding metal and/or semimetal oxide.
  • the at least one acid is selected from the group consisting of inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid or organic acids such as formic acid, acetic acid, propionic acid, butyric acid and mixtures thereof.
  • One particularly preferred embodiment uses sulfuric acid.
  • tap water, drinking water, distilled water or demineralized water can be used and preferably distilled water is used.
  • One preferred embodiment comprises preparing mixture B in step (B) by admixing an aqueous solution of the at least one acid with the at least one organic solvent.
  • This aqueous solution of the acid has an acid concentration in the range from 2% to 20% by weight, more preferably in the range from 3% to 15% by weight and particularly preferably in the range from 4% to 10% by weight.
  • the volume ratio of at least one at least partially water-miscible organic solvent to water in mixture B is generally in the range from 5:1 to 1:1 and preferably in the range from 4:1 to 2:1.
  • the temperature at which step (B) is carried out is generally in the range from 10 to 80° C., preferably in the range from 15 to 40° C. and more preferably equal to ambient temperature.
  • Step (C) comprises combining the mixtures A and B and reacting the at least one precursor compound of the at least one metal and/or semimetal oxide with the at least one acid to obtain a mixture C comprising an aqueous phase comprising the spherical beads and an organic phase.
  • step (C) of the process of the present invention can be effected by any method known to a person skilled in the art.
  • the mixtures A and B are introduced into a reactor, for example a flask or reaction tube, simultaneously and thereby combined.
  • the reaction of the at least one precursor compound to the at least one metal and/or semimetal oxide with the at least one acid results in the formation of the at least one metal and/or semimetal oxide.
  • the preferred case, where SiO 2 is formed from xNa 2 O.ySiO 2 and H 2 SO 4 (aq.) involves the following reaction taking place:
  • Step (C) of the process of the present invention is preferably carried out continuously, for example in a flow tube.
  • the temperature at which step (C) is carried out is generally in the range from 10 to 80° C., preferably in the range from 15 to 40° C. and more preferably equal to ambient temperature.
  • the spherical beads are present in dispersed form in mixture C.
  • Step (D) comprises separating the organic phase from the mixture C obtained in step (C) to obtain an aqueous phase comprising the spherical beads.
  • the separating of the organic phase from mixture C in step (D) of the process of the present invention can be carried out in any manner known to a person skilled in the art, for example by decanting off, sucking off, draining the lower phase off through a floor valve, etc.
  • the choice of the best method depends inter alia on whether the organic solvent used has a density above or below 1 g/ml, i.e., on whether the organic phase is above or below the aqueous phase.
  • the mixture C comprises an upper organic and a lower aqueous phase in which the spherical beads of the present invention are present in dispersed form.
  • step (D) is effected by sucking or pouring off the upper organic phase to obtain an aqueous phase comprising the spherical particles.
  • the aqueous phase obtained after step (D) may still comprise residues of the at least one organic solvent, for example up to 15% by weight and preferably up to 10% by weight.
  • step (D) is followed by adjusting the aqueous phase comprising the spherical beads to a neutral pH, i.e., pH 6-8, by addition of a suitable reagent.
  • a suitable reagent for example a mineral acid such as sulfuric acid.
  • the acid is preferably used as an aqueous solution having a concentration in the range from 20% to 60% by weight, preferably 30% to 50% by weight.
  • the neutralization is followed in one preferred embodiment by an aging step.
  • the spherical beads dispersed in water are heated to a temperature in the range from 40 to 95° C., preferably 50 to 90° C., for a certain period of time, for example 1 to 5 hours, preferably 2 to 4 hours.
  • step (E) of the process of the present invention comprises treating the spherical beads obtained in step (D) with at least one acid.
  • Step (E) of the process of the present invention has the purpose, inter alia, of removing salts resulting from the preparation of the spherical beads and present on and in the beads, for example Na 2 SO 4 .
  • the optional step (E) first comprises removing the water above the spherical particles in a manner known to a person skilled in the art, for example by decanting off, sucking off, etc.
  • the spherical particles are subsequently treated with an aqueous solution of an acid.
  • Suitable acids are selected from the group consisting of inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid or organic acids such as formic acid, acetic acid, propionic acid, butyric acid and mixtures thereof, particularly sulfuric acid.
  • the aqueous solution in the optional step (E) preferably has a low concentration, for example a concentration in the range from 0.1% to 5% by weight, and preferably in the range from 0.75% to 2% by weight.
  • the mixture obtained is preferably commixed until homogeneous, for example by stirring with apparatus known to a person skilled in the art. Subsequently, the mixture obtained is left to stand quiescently for a certain period of time, for example in the range from 0.25 to 2 h and preferably in the range from 0.25 to 1 h. Subsequently, the supernatant acidic solution is preferably removed again, for example by decanting off and/or sucking off. The sequence of acid addition-stirring-allowing to stand-acid removal is repeated two or more times, for example 2 to 10 times.
  • the spherical particles obtained are subsequently freed in a manner known to a person skilled in the art of disruptive components, for example acid, organic solvent and/or by-products formed in the formation of the at least one metal or semimetal oxide.
  • disruptive components for example acid, organic solvent and/or by-products formed in the formation of the at least one metal or semimetal oxide.
  • Step (F) of the process of the present invention comprises drying the spherical beads obtained in step (D) or (E).
  • the drying may be effected in any manner known to a person skilled in the art, for example in a drying cabinet at a temperature in the range from 100 to 300° C., preferably 150 to 250° C.
  • Step (F) of the process of the present invention can be carried out at atmospheric pressure or at a lower pressure, for example at less than 800 mbar and preferably at less than 600 mbar.
  • Step (F) is carried on until the spherical beads have a water content which is sufficiently low for the later use, for example in the range from 0.2% to 0.8% by weight. This water content can be determined as loss on drying at 200° C.
  • the spherical beads produced according to the present invention are notable for a particularly advantageous combination of features such as diameter, BET surface area, pore volume, smoothness and monodispersity. It is particularly the pronounced spherical shape and smoothness which, when the spherical beads are used as catalyst carriers in polymerizations, engender the formation of particularly monodisperse and spherical particles of polymer.
  • these spherical beads of the present invention are particularly useful as catalysts and catalyst carriers.
  • Catalytically active metals for example selected from the group consisting of chromium, magnesium, titanium, platinum, palladium, iridium, nickel, zirconium, zinc, copper, molybdenum, scandium and mixtures thereof, are applied to this end, if appropriate, to the particles of the present invention in amounts known to a person skilled in the art, for example 0.1% to 20% by weight, preferably 0.4% to 5% by weight, based on the overall particle.
  • the identity and amount of the catalytically active metal is generally dependent on the desired use and known to a person skilled in the art.
  • the present invention thus also provides a particulate catalyst comprising the spherical beads of the present invention and at least one catalytically active metal.
  • the amount which is present of the at least one catalytically active metal is preferably in a range from 0.1% to 20% by weight, preferably 0.4% to 5% by weight, all based on the overall particulate catalyst.
  • the present invention also provides for the use of the spherical beads of the present invention as catalysts or catalyst carriers, particularly in polymerization reactions, for example for producing polyethylene, polypropylene or other, specialty polymers.
  • FIG. 1 shows inventive spherical beads as a scanning electron micrograph.
  • FIG. 2 shows for comparison a typical spray-dried silica gel as per the prior art.
  • stirrer drives are adjusted to about 500 rpm. Then, the dilute sulfuric acid is introduced into one container and the water glass solution into the other. On completion of the addition and emulsification, stirrer speed is lowered to about 300 rpm in both cases. Using a pump, the emulsions thus prepared are converged from the receiving containers in a tube and subsequently emptied into a mobile receiver.
  • the mixture of n-butanol and silica gel is separated.
  • 40% sulfuric acid the pH of the silica gel mass is immediately adjusted to the range between 6.5 and 7.5.
  • the neutralized silica gel is placed in a 10 liter glass bottle and transferred into a warm water bath at 80° C. for about 2.5 hours.
  • a 1% H 2 SO 4 solution (a wide concentration range extending from 0.5% to 15% is possible) is added. An hour later, the supernatant solution is again sucked off and then the silica gel is again admixed with 1% H 2 SO 4 solution. This operation is repeated up to five times before the silica gel is admixed with water. This operation is repeated.
  • the spherical beads obtained are separated off by sucking off the supernatant liquid.
  • the silica gel is dried at 170° C. in a drying cabinet.

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  • Inorganic Chemistry (AREA)
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US13/255,546 2009-03-16 2010-03-09 Catalyst carrier based on silica gel Abandoned US20120010379A1 (en)

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CN103464216A (zh) * 2013-09-26 2013-12-25 中国海洋石油总公司 醋酸与丁烯合成醋酸仲丁酯杂多酸催化剂硅胶载体的制法
US9745201B2 (en) 2014-01-29 2017-08-29 Mitsubishi Materials Corporation Synthetic amorphous silica powder and process for manufacturing same
US10010871B2 (en) 2015-01-19 2018-07-03 Mitsui Mining & Smelting Co., Ltd. Carrier for exhaust gas purification catalyst and exhaust gas purification catalyst

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FR3065649B1 (fr) * 2017-04-28 2020-05-29 IFP Energies Nouvelles Monolithe poreux contenant du tio2 et son procede de preparation
JP6986908B2 (ja) 2017-09-05 2021-12-22 昭和電工株式会社 脂肪族カルボン酸エステルの製造方法
JP6910252B2 (ja) 2017-09-05 2021-07-28 昭和電工株式会社 シリカ担体の製造方法
WO2023178116A1 (en) * 2022-03-16 2023-09-21 W. R. Grace & Co.-Conn Silica-supported polyolefin catalyst system

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CN103464216A (zh) * 2013-09-26 2013-12-25 中国海洋石油总公司 醋酸与丁烯合成醋酸仲丁酯杂多酸催化剂硅胶载体的制法
US9745201B2 (en) 2014-01-29 2017-08-29 Mitsubishi Materials Corporation Synthetic amorphous silica powder and process for manufacturing same
US10010871B2 (en) 2015-01-19 2018-07-03 Mitsui Mining & Smelting Co., Ltd. Carrier for exhaust gas purification catalyst and exhaust gas purification catalyst

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CA2755648A1 (en) 2010-09-23
EP2408554A1 (de) 2012-01-25
RU2522595C2 (ru) 2014-07-20
JP2012520236A (ja) 2012-09-06
JP6035380B2 (ja) 2016-11-30
US8986642B2 (en) 2015-03-24
CN102355946B (zh) 2014-06-11
RU2011141701A (ru) 2013-04-27
JP2015221746A (ja) 2015-12-10
KR20110130450A (ko) 2011-12-05
US20130165608A1 (en) 2013-06-27
WO2010105941A1 (de) 2010-09-23
EP2408554B1 (de) 2016-12-14

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