EP1129029A1 - Oxyde de silicium a mesopores et micropores - Google Patents

Oxyde de silicium a mesopores et micropores

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Publication number
EP1129029A1
EP1129029A1 EP99948990A EP99948990A EP1129029A1 EP 1129029 A1 EP1129029 A1 EP 1129029A1 EP 99948990 A EP99948990 A EP 99948990A EP 99948990 A EP99948990 A EP 99948990A EP 1129029 A1 EP1129029 A1 EP 1129029A1
Authority
EP
European Patent Office
Prior art keywords
silicon dioxide
mesopores
polymer dispersion
water
micro
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Withdrawn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
EP99948990A
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German (de)
English (en)
Inventor
Ulrich Müller
Harald RÖCKEL
Roger Ruetz
Rainer Senk
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1129029A1 publication Critical patent/EP1129029A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic 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
    • 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
    • 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
    • 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
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm

Definitions

  • the present invention relates to a silicon dioxide which has meso and micro pores.
  • the invention further relates to methods for producing such a silicon dioxide, its use, and moldings and catalysts which contain the same.
  • wide-pore silica gels with a pore volume of more than 0.8 ml / g, a specific surface area of 200 - 400 m 2 / g and a pore diameter of 8 - 10 nm as well as narrow-pore silica gels with a pore volume of less than 0.5 ml / g g, a specific surface area of 600-800 m 2 / g and a pore diameter of 2-2.5 nm.
  • MCM-41 aluminosilicates with a large surface area and a sharp pore size distribution, which are referred to as MCM-41.
  • a BET surface area of more than 1000 m 2 / g and a pore volume of 0.79 cmVg were found for an aluminosilicate with a pore diameter of 4.5 nm. Further aluminosilicates with pore sizes of 3 nm and 4 nm are mentioned.
  • the aluminosilicates are synthesized using hexadecyltrimethylammonium salts as cationic surfactants.
  • EP-A 0 831 059 describes a mesoporous silicon dioxide and its production with the aid of a polymer dispersion as a pore former.
  • a microporous silicon dioxide and a process for its production is described in DE-A 197 32 865. According to this document, a polyethyleneimine is added to a silicon dioxide precursor to produce such a silicon dioxide.
  • the silicas described above each have the disadvantage that they are unable to take advantage of the mesopores, such as. B. good mass transport with which the micropores, in particular the good fixation z. B. to combine an active metal in catalysis.
  • the object of the present invention is accordingly to provide a silicon dioxide which has both mesopores and micropores and thus represents a combination of the desirable properties of excellent mass transfer and the fixation of the active component.
  • the present invention thus relates to a silicon dioxide which has both meso and micropores.
  • the proportion of micropores in the silicon dioxide according to the invention is 5 to 95%, preferably 10 to 60%, in particular 10 to 40% of the total pore volume.
  • the proportion of mesopores is 95 to 5%, preferably 90 to 40%, in particular 90 to 60% of the total pore volume, the total pore volume being determined in each case by adsorption with nitrogen up to 77 K and a relative pressure p / p 0 of 0.98.
  • Characteristic porosity data can be determined from gas adsorption measurements according to DIN 66131 and DIN 66134.
  • the silicon dioxide according to the invention have a specific surface area of the sum of micro and
  • the pore volume of the sum of micro and mesopores is preferably at least 0.2, preferably at least 0.3, in particular at least 0.4 ml / g.
  • Mesopores means pores with one
  • the pore surface can be measured using the BJH model (DIN
  • the pore volume becomes at a relative pressure of p / p 0
  • the silicas according to the invention preferably have a maximum of the pore diameter distribution of the mesopores of at least 3, preferably at least 5, in particular at least 8 nm and up to 50 nm.
  • the pore diameter distribution can in turn be determined by nitrogen adsorption at 77 K from the desorption branch of the isotherm.
  • the present invention thus also relates to a silicon dioxide with one or more of the features:
  • the main part of the mesopores preferably has a diameter in the range from 2 to 50, particularly preferably 4 to 30, in particular 6 to 20 nm.
  • the main part relates to the main part of the pore volume, the pore diameter being determined by nitrogen adsorption at 77 K.
  • Pore sizes, pore volumes and surfaces relate to calcined silicon dioxide.
  • the silicas according to the invention are clearly visible in the adsorption-desorption isotherm and have a proportion of type I isotherms in the relative pressure range below 0.5 p / p 0 (nitrogen 77 K), which is characteristic of the micropore fraction, and at the same time above 0.5 p / p 0 via a pronounced hysteresis between adsorption and desorption, as is characteristic of mesoporous substances according to the BJH (DIN 66134).
  • Both the adsorption curve and the desorption curve preferably each have only one step or a strong increase.
  • the X-ray diffractogram preferably shows a sharp increase in line intensity in the range 2 ⁇ ⁇ 6 °, in particular 2 ⁇ ⁇ 4 °. The largest part of the area of the X-ray diffractogram lies in the range 2 ° ⁇ 6 °.
  • the silicon dioxides according to the invention can be prepared by reacting silicon dioxide precursors in a water-containing medium which contains a polymer dispersion, the water-containing medium having a pH ⁇ 7.
  • the silicas produced in this way are preferably calcined.
  • the molecular weights of the polymers present in the polymer dispersion are adjusted so that as many pores as possible are obtained in the mesopore range in order to obtain the desired surface.
  • any polymer obtainable by radical, anionic or cationic polymerization can be used as the polymer dispersion. In general, it will be a polymer obtained by emulsion polymerization. In the same way, however, it is also possible to use polymers which are obtainable by a different type of polymerization, for example by suspension polymerization.
  • the polymer is preferably used in the form of a dispersion which in particular has a polymer content in the range from 20 to 60% by weight, in particular 30 to 50% by weight.
  • a primary dispersion ie a dispersion as it is obtained in emulsion polymerization
  • a secondary dispersion ie a dispersion which is obtained by subsequently dispersing an already isolated polymer in the dispersion medium.
  • the dispersion medium is usually water.
  • water-miscible organic solvents such as alcohols and ketones, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, acetone or methyl ethyl ketone, can also be present.
  • the polymers are preferably prepared by radical polymerization of ethylenically unsaturated monomers.
  • Particularly suitable monomers are e.g. B .:
  • ethylenically preferably ⁇ .ß-ethylenically unsaturated mono- and dicarboxylic acids, especially those with 3 to 6 carbon atoms.
  • examples include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid or itaconic acid and half-esters of ethylenically unsaturated dicarboxylic acids, such as maleic acid monoalkyl esters of C 1 -C 8 -alkanols;
  • vinyl aromatic compounds such as styrene, ⁇ -methylstyrene and vinyl toluenes
  • linear 1-olefins branched-chain 1-olefins or cyclic olefins, such as.
  • B. can carry a hydroxyl group, an amino or dialkylamino group or one or more alkoxylate groups, such as. B.
  • Acrylamides and alkyl substituted acrylamides such as. B. acrylamide, methacrylamide, N-tert-butylacrylamide, N-methyl- (meth) acrylamide;
  • sulfo groups such as, for. B. allylsulfonic acid, methallylsulfonic acid, styrene sulfonate, vinyl sulfonic acid, allyloxybenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, their corresponding alkali metal or ammonium salts or mixtures thereof;
  • C 1 to C 8 alkyl esters or C 1 to C 4 hydroxyalkyl esters of C 3 to C 6 mono- or dicarboxylic acids in particular acrylic acid, methacrylic acid or maleic acid or esters of with 2 to 50 moles of ethylene oxide, Propylene oxide, butylene oxide or mixtures thereof, alkoxylated C, - to C 18 alcohols with the acids mentioned, such as. B.
  • Alkylaminoalkyl (meth) acrylates or alkylaminoalkyl (meth) acrylamides such as.
  • Quaternization products e.g. B. with dimethyl sulfate, diethyl sulfate or other alkylating agents, vinyl and allyl esters of C, - to C 30 monocarboxylic acids, such as. B. vinyl formate, vinyl 2-ethylhexanoate, vinyl nonanoate, vinyl decanoate, vinyl pivalate, vinyl palmitate, vinyl stearate, vinyl laurate.
  • Vinylformamide N-vinyl-N-methylformamide, styrene, 2-methylstyrene, 3-methylstyrene, butadiene, N-vinylpyrrolidone, N-vinylimidazole, l-vinyl-2-methylimidazole, l-vinyl-2-methylimidazoline, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, allyl alcohol, 2-vinylpyridine, 4-vinylpyridine, diallyldimethylammonium chloride, vinylidene chloride, vinyl chloride, acrolein, methacrolein and vinyl carbazole or mixtures thereof. Quaternization products of the N-vinylimidazole monomers mentioned with dimethyl sulfate, diethyl sulfate or other alkylation agents.
  • Preferred monomers are esters of acrylic acid and methacrylic acid, vinylaromatic compounds, butadiene, vinyl esters, (meth) acrylonitrile and (meth) acrylamides.
  • Particularly preferred monomers are methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, styrene, butadiene, vinyl acetate, acrylonitrile or methacrylonitrile and acrylamide, and acrylamide.
  • the polymers can be prepared by customary polymerization processes, for. B. by radical substance, emulsion, suspension, dispersion, Solution and precipitation polymerization.
  • the polymerization processes mentioned are preferably carried out in the absence of oxygen, preferably in a stream of nitrogen.
  • the usual equipment is used for all polymerization methods, e.g. B. stirred tanks, stirred tank cascades, autoclaves, tubular reactors and kneaders.
  • the method of emulsion, precipitation or suspension polymerization is preferred.
  • the method of radical emulsion polymerization in an aqueous medium is particularly preferred.
  • polymers having a weight-average molecular weight of 1000 to 2,000,000, preferably 5000 to 500,000, are obtained.
  • the K values are generally in the range from 15 to 150 (1% by weight in dimethylformamide).
  • the mean particle size (determined by means of light scattering (autosizer)) is in the range from 20 to 1000 nm, preferably 30 to 700 nm, particularly preferably 40 to 400 nm.
  • the dispersion can have a monomodal or polymodal particle size distribution.
  • the emulsion polymerization can be carried out in such a way that the solids volume content is in the range from 10 to 70%, preferably 20 to 60%.
  • the polymerization is preferably carried out in the presence of radical-forming compounds (initiators). These compounds preferably require 0.05 to 15, particularly preferably 0.2 to 8% by weight, based on the monomers used in the polymerization.
  • Suitable polymerization initiators are the known initiators described in EP-A 0 831 059, for example peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxoesters, hydrogen peroxide and azo compounds.
  • initiators which can be water-soluble or water-insoluble are hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxidicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert.-butyl peroxide, acetylacetone peroxide, tert.-butyl hydroperoxide, cumene hydroperyl peroxide, tert-butyl peroxide, tert-butyl peroxide, tert-butyl peroxide, tert-butyl peroxide, tert-butyl peroxide, tert-butyl peroxide , tert-butyl perpivalate, tert-butyl perneohexanoate, tert-butyl per-2-ethylhexanoate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxodisul
  • the initiators can be used alone or in a mixture with one another, e.g. B. Mixtures of hydrogen peroxide and sodium peroxydisulfate. Water-soluble initiators are preferably used for the polymerization in an aqueous medium.
  • regulators can be used for this, such as, for example, compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan, C 1 -C 2 4- Aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, hydroxylammonium salts such as hydroxylammonium sulfate, formic acid, sodium bisulfite or isopropanol.
  • the polymerization regulators are generally used in amounts of 0.1 to 10% by weight, based on the monomers.
  • crosslinking agents are compounds with two or more ethylenically unsaturated groups, such as diacrylates or dimethacrylates of at least dihydric saturated alcohols, such as.
  • B ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1, 2-propylene glycol diacrylate, 1, 2-propylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol dimethacrylate.
  • the acrylic acid and methacrylic acid esters of alcohols with more than 2 OH groups can be used as crosslinkers, for.
  • Another class of crosslinking agents are diacrylates or dimethacrylates of polyethylene glycols or polypropylene glycols with molecular weights of 200 to 9,000 each.
  • block copolymers of ethylene oxide and propylene oxide or copolymers of ethylene oxide and propylene oxide which contain the ethylene oxide and propylene oxide units in a statistically distributed manner can also be used.
  • the oligomers of ethylene oxide or propylene oxide are suitable for the preparation of the crosslinkers, for. B. diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate.
  • crosslinking agents are vinyl acrylate, vinyl methacrylate, vinyl itaconate, adipic acid divinyl ester, butanediol divinyl ether, trimethylolpropane trivinyl ether, allyl acrylate. Allyl methacrylate, pentaallylsucrose, methylenebis (meth) acrylamide, divinylethyleneurea, divinylpropyleneurea, divinylbenzene, divinyldioxane, an, triallylcyanurate, tetraallylsilane, tetravinylsilane and bis- or polyacrylsiloxanes (e.g. Tegomere ®) from Th.
  • the crosslinking agents are preferably used in amounts of 0.05 to 50% by weight, preferably 0.1 to 20% by weight, in particular 0.5 to 10% by weight, based on the monomers to be polymerized.
  • emulsifiers or protective colloids are used for this.
  • Anionic, nonionic, cationic and amphoteric emulsifiers can be used.
  • Anionic emulsifiers for example alkylbenzenesulfonic acids, sulfonated fatty acids, sulfosuccinates, fatty alcohol sulfates, alkylphenolsulfates and fatty alcohol ether sulfates, are preferred.
  • nonionic emulsifiers which can be used are alkylphenol ethoxylates, primary alcohol ethoxylates, Fatty acid ethoxylates, alkanolamide ethoxylates, fatty amine ethoxylates, EO / PO block copolymers and alkyl polyglucosides can be used.
  • cationic or amphoteric emulsifiers such as B. used: quaternized aminoalkoxylates, alkylbetaines, alkylamidobetaines and sulfobetaines. Long-chain quaternary amines, such as. B. fatty amines quaternized with dimethyl sulfate.
  • Typical protective collodes are, for example, cellulose derivatives, polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, polyvinyl acetate, polyvinyl alcohol, polyvinyl ether, starch and starch derivatives, dextran, polyvinylpyrrolidone, polyvinylpyridine, polyethyleneimine, polyvinylamine, polyvinylformamide, polyvinylimidiminolimide, polyvinylimidiminolimide, Polyvinyl-1, 3-oxazolidone-2, polyvinyl-2-methylimidazoline as well as copolymers containing acrylic acid, methacrylic acid, maleic acid or maleic anhydride.
  • the emulsifiers or protective colloids are usually used in concentrations of 0.05 to 20% by weight, based on the monomers.
  • the monomers and emulsifiers can be neutralized in whole or in part by conventional, inorganic or organic bases or acids before or during the polymerization.
  • Suitable bases are e.g. B. alkali or alkaline earth metal compounds, such as sodium, potassium or calcium hydroxide, sodium carbonate, ammonia and primary, secondary or tertiary amines, such as di- or triethanolamine.
  • Suitable acids are e.g. As hydrochloric acid, sulfuric acid, phosphoric acid, formic acid and acetic acid.
  • Cationic aqueous polymer dispersions which are stabilized with cationic emulsifiers and / or cationic auxiliary monomers (emulsifiers or ⁇ , ⁇ -ethylenically unsaturated monomers which contain quaternary amine or ammonium structures) are particularly preferably used.
  • These emulsion polymers are preferably prepared with radical images containing cationic groups.
  • Particularly preferred monomers are methyl methacrylate, styrene, n-butyl acrylate, butanediol diacrylate and N, N-dimethylaminoethyl methacrylate quaternized with diethyl sulfate.
  • the polymer dispersion preferably contains polymers with basic building blocks of methyl methacrylate, butanediol diacrylate and / or dimethylaminoethyl methacrylate quaternized with diethyl sulfate.
  • the polymerization can be carried out continuously or batchwise in a customary manner according to a large number of variants. If the polymer is prepared by the method of solution, precipitation or suspension polymerization in a steam-volatile solvent or solvent mixture, the solvent can be separated off by introducing steam in order to obtain an aqueous solution or dispersion. The polymer can also be separated from the organic diluent by a drying process.
  • the polymer can be, for example, a rubber, such as an epichlorohydrin rubber, ethylene-vinyl acetate rubber,
  • Polyethylene chlorosulfone rubber silicone rubber, polyether rubber, diene rubber, such as butadiene rubber, acrylate rubber,
  • Ethylene propylene rubber ethylene propylene diene rubber, butyl rubber or a similar rubber.
  • polymers not prepared via free-radical polymerization such as, for. B. polysiloxanes, polyurethanes and polyesters can be used.
  • the glass transition temperature of the polymer dispersions used according to the invention is between -50 ° C. and +150 ° C., preferably between 0 and 110 ° C.
  • the concentration of the polymer in the reaction medium is preferably 0.05 to 20, particularly preferably 0.25 to 10, in particular 0.5 to 10, especially 0.5 to 5% by weight, based on the entire reaction mixture.
  • the polymer dispersion is particularly preferably present in a two-phase reaction medium in the water-containing or aqueous phase.
  • any suitable water-containing reaction medium can be used as the reaction medium.
  • water can be used as the reaction medium.
  • a mixture of water with a water-soluble organic solvent, such as a lower alcohol, such as ethanol or isopropanol can be used.
  • the reaction can also take place in a two-phase reaction medium which consists of an aqueous phase and an organic phase which is immiscible or only slightly miscible with water.
  • the organic phase should be inert with respect to the reaction.
  • the water-containing reaction medium or the two-phase mixture can be moved, in particular stirred, during the reaction, but a reaction can also take place in the non-moving phase, in particular at the phase boundary of a two-phase system.
  • the silicon dioxide can be obtained in the form of thin films or layers.
  • the oxide films or oxide layers obtained in this way can be used in membrane, separation and cleaning processes or also in applications for information storage. Corresponding films or layers can also be suitable for electronic, optical or electro-optical applications.
  • the membranes can also be used for catalytic reactions in membrane reactors or for reactive distillation.
  • silicon dioxide precursor All suitable compounds which result in silicon dioxide through physical or chemical treatment can be used as the silicon dioxide precursor.
  • organic silicon compounds in particular hydrolyzable organic silicon compounds, such as alcoholates or chelates.
  • the silicon dioxide precursor can be used in the form of an organic silicon compound, preferably a soluble salt or colloid, as well as in the form of water glass or pyrogenic silica.
  • Organic silicon compounds in the form of tetraalcoholates such as tetramethoxysilicon or tetraethoxysilicon, are preferably used.
  • the silicon tetraalkoxy compound in particular C M alkoxy compound, can be initially charged in the organic solvent and reacted at the phase boundary in a two-phase reaction medium.
  • the silicon dioxide according to the invention forms at the phase boundary of the immiscible phases.
  • an emulsion is formed either of the organic solvent in water or of water in the organic solvent.
  • the type and size of the silicon dioxide particles formed can be determined by varying the mixing intensity or the stirrer speed during mechanical stirring, so that shaped articles made of silicon dioxide are accessible.
  • the silicon dioxide according to the invention can be deposited on this carrier.
  • the carrier can be an inert porous carrier, such as a porous glass, aluminum oxide, silica gel or alumina, ceramic, metal or a metal packing, as is used for example for static mixers.
  • This inert carrier can thus be coated or impregnated with the silicon dioxide according to the invention, which results in composite materials which have good mechanical, anic stability, in particular in comparison to carrier-free mesoporous oxide shaped bodies.
  • Moldings made from the silicon dioxide according to the invention can also be produced after the reaction.
  • Silicon dioxide obtained in the reaction, in particular in powder form, is obtained by suitable
  • Suitable Processes are known, for example the silicon dioxide according to the invention can be mixed with a binder and pressed into tablets. Shaping by extrusion is also possible.
  • the reaction medium can contain other additives, such as metal or noble metal ions.
  • metal or noble metal ions for example, ions of the elements Al, B, Ge, of the groups lilac, Ilb, F / b, Vb, VIb of the periodic table of the elements, Be, Sn, Pb, Bi, Cu, Fe, Co, Ni, Ce, Mn or are suitable their mixtures.
  • the metal ions can be present in one of the two phases or in both phases. This makes it possible to introduce catalytically active metals into the silicon dioxide according to the invention or shaped bodies produced therefrom, for example in applications as a catalyst.
  • enzymes can also be introduced into the water-containing reaction medium or the aqueous phase of a two-phase reaction medium, which are then also condensed.
  • pharmacologically active substances such as active pharmaceutical ingredients, is also possible due to the mild reaction conditions. It is thus possible to produce silicon dioxides according to the invention or corresponding shaped articles which release a pharmaceutical active ingredient in a delayed manner in a specific application.
  • pigments can be introduced into the reaction medium, which are then present in the silicon dioxide according to the invention or molded articles thereof. It is thus possible to produce colored silicon dioxide or molded articles therefrom.
  • the reaction is preferably carried out at a temperature in the range from -10 to +150 ° C., preferably 10 to 90 ° C., particularly preferably 20 to 65 ° C.
  • the reaction can be carried out at atmospheric pressure, negative pressure or positive pressure, such as at a pressure in the range from 0.4 to 300 bar.
  • the reaction is preferably carried out at atmospheric pressure.
  • the process according to the invention must be in the acidic pH range, ie at a pH Value ⁇ 7.
  • the pH range is preferably from 5 to 1.
  • the acidification by all acids, such as. B. mineral acids, such as. B. HC1, HNO 3 , H 2 SO 4 and HF, but also heteropolyacids, such as. B. heteropoly tungstates are carried out.
  • SiO 2 can also be dissolved directly with HF, and an acid medium per se can thus be obtained, as is described in WO 97/16374.
  • the silicas according to the invention obtained after the reaction or shaped articles produced therefrom can be calcined according to the invention, for example in order to use them as catalysts or catalyst supports.
  • the calcination is preferably carried out at a temperature in the range from 300 to 600 ° C., preferably 400 to 450 ° C.
  • the period for the calcination can be 0.5 to 20 hours, preferably 2 to 8 hours.
  • a drying step can be added before calcination to obtain a dry silica.
  • the silicas used for calcination according to the invention have only a small proportion of polymer from the polymer dispersion.
  • the proportion of polymer dispersion in the dried silicon dioxide before calcination is preferably from 5 to 200, particularly preferably from 30 to 150,% by weight, based on the total mass of silicon dioxide and polymer.
  • the silicon dioxides according to the invention or shaped bodies produced therefrom or coated therewith or coated therewith can be used in a large number of applications.
  • the oxide films or layers formed in the synthesis in a stationary two-phase reaction medium can be used as self-supporting membranes.
  • the silicon dioxide according to the invention or molded articles produced therefrom can be used as catalysts or catalyst supports.
  • the Catalysts contain the silicon dioxide according to the invention as a carrier or as an active substance.
  • suitable catalytic reactions are the oxifunctionalization of hydrocarbons, the oxidation of olefins to oxiranes, aromatic alkylations, hydrogenations, dehydrogenations, hydrations, dehydrations, isomerizations, addition and elimination reactions, nucleophilic and electrophilic substitution reactions, dehydrocyclizations, hydroxylations of hydroxylations Aromatics, epoxy-aldehyde rearrangements, aminations of monomeric and oligomeric olefins, condensation reactions of the aldol type, polymerization reactions, esterifications and etherification reactions, as well as catalytic reactions of exhaust gases and flue gases or nitrogen oxide removal.
  • the use for the absorption and delayed release of medicaments and also for the absorption of pigments, which are then encapsulated in the mesoporous oxide molded body, for example, has already been described above.
  • Use as sorbents and for the production of oxide ceramics or use in material separation is also possible.
  • the surface quality of the silicon dioxide or molded articles thereof can be controlled by the type of dispersion used.
  • the dispersion can serve as a kind of stamp or form for the pore structure to be obtained.
  • Quat 311 dimethylaminoethyl methylacrylamide, quaternized with diethyl sulfate
  • the absorption curve shown in FIG. 1 was measured by means of nitrogen adsorption at 77 K.
  • the curve marked with crosses represents the adsorption, the curve marked with an asterisk represents the desorption.
  • the abscissa shows the cumulative adsorbed gas volume under standard temperature and pressure (V).
  • the surface of the mesopores was determined for the pores in the pore diameter range from approx. 2 to 200 nm
  • Deso ⁇ tionsast the hysteresis was 3.6 nm.
  • the surface calculated according to Langmuir in the relative pressure range up to 0.2 p / p 0 was 720 m 2 / g.
  • This example describes the production of a titanium-containing silicon dioxide according to the invention.
  • 7.4 g was placed in a 2 1 four-necked flask
  • Tetraisopropyl orthotitanate 209 g tetraethoxysilane (Merck), 300 g ethanol and 61 g of isopropanol mixed with stirring.
  • the resulting white suspension was stirred for one hour at room temperature.
  • the mixture was then rotated in at 60 ° C in a water jet vacuum.
  • the dried material was then calcined in air for 5 hours at 500 ° C. 63 g of product were obtained.
  • the material contained 2.1% by weight of titanium.
  • the typical absorption curve shown in FIG. 1 was again observed using nitrogen adsorption at 77 K.
  • a surface of the mesopores of 243 m 2 / g was determined for the pores in the pore diameter range from approx. 2 to 200 nm.
  • the corresponding pore volume of the mesopores was 0.24 ml / g
  • the total pore volume from micro and mesopores, determined at p / p 0 0.98, was 0.34 ml / g.
  • the surface calculated according to Langmuir in the relative pressure range up to 0.2 p / p 0 was 633 m 2 / g.
  • a capacity of 7.9% by weight was measured at room temperature (20 ° C.) and a propene partial pressure of 699 mbar in a microgravimetric determination of the propellant's propellant power.
  • This example describes the production of an iron-containing silicon dioxide according to the invention.
  • 209 g of tetraethoxysilane (Merck), 300 g of ethanol and 61 g of isopropanol were mixed with stirring in a 21-neck four-necked flask.
  • a mixture of 50 g of polymer dispersion in 650 g of deionized water with an addition of 7.5 g of hydrochloric acid (10% by weight) and 3.2 g of iron (II) sulfate was added dropwise to this mixture.
  • the resulting brown-yellow suspension was stirred for one hour at room temperature.
  • the mixture was then rotated in at 60 ° C in a water jet vacuum.
  • the dried material was then calcined in air for 5 hours at 500 ° C. 60 g of product were obtained.
  • the material contained 1.1% by weight of iron.
  • the typical absorption curve shown in FIG. 1 was again observed using nitrogen adsorption at 77 K.
  • a surface area of the mesopores of 215 m 2 / g was determined for the pores in the pore diameter range from approx. 2 to 200 nm.
  • the corresponding pore volume of the mesopores was 0.21 ml / g.
  • the surface area calculated according to Langmuir in the relative pressure range up to 0.2 p / p 0 was 444 m 2 / g.

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Abstract

L'invention concerne un oxyde de silicium qui présente des mésopores et des micropores.
EP99948990A 1998-10-15 1999-10-14 Oxyde de silicium a mesopores et micropores Withdrawn EP1129029A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19847630 1998-10-15
DE19847630A DE19847630A1 (de) 1998-10-15 1998-10-15 Siliciumdioxid mit Meso- und Mikroporen
PCT/EP1999/007737 WO2000021883A1 (fr) 1998-10-15 1999-10-14 Oxyde de silicium a mesopores et micropores

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EP1129029A1 true EP1129029A1 (fr) 2001-09-05

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KR (1) KR20010080175A (fr)
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AU (1) AU6202699A (fr)
BR (1) BR9914444A (fr)
CA (1) CA2346892A1 (fr)
DE (1) DE19847630A1 (fr)
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WO (1) WO2000021883A1 (fr)

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DE19939416A1 (de) 1999-08-20 2001-02-22 Basf Ag Verfahren zur Herstellung eines kristallinen, zeolithischen Feststoffs
JP4841768B2 (ja) * 2001-08-21 2011-12-21 独立行政法人産業技術総合研究所 含クロム酸化物からなる窒素酸化物吸着剤及びその製造方法
CN100383042C (zh) * 2003-04-22 2008-04-23 上海化工研究院 介孔二氧化硅分子筛的制备方法
US7211239B2 (en) * 2005-04-22 2007-05-01 Basf Aktiengesellschaft Process for preparing a nanosized zeolitic material
WO2007145676A1 (fr) * 2006-01-17 2007-12-21 Exxonmobil Research And Engineering Company Procédé de fabrication de corps en forme en silice
CN101600443B (zh) 2006-12-05 2014-08-13 荷兰联合利华有限公司 口腔护理产品
JP5093647B2 (ja) * 2007-03-19 2012-12-12 株式会社豊田中央研究所 メソ孔及びマイクロ孔を有する金属酸化物多孔体の製造方法、メソ孔及びマイクロ孔を有する金属酸化物多孔体及びそれを用いたガス浄化材料
WO2012017846A1 (fr) * 2010-08-06 2012-02-09 Dic株式会社 Composition de revêtement monocomposant, photocatalyseur l'utilisant, film de revêtement composé de celle-ci, et procédé de fabrication associé
FR2984882A1 (fr) * 2011-12-23 2013-06-28 Saint Gobain Ct Recherches Procede de fabrication d'un produit mesoporeux.
CN102908982A (zh) * 2012-10-24 2013-02-06 陕西省石油化工研究设计院 一种吸附废水中重金属离子的新型介孔材料制备方法
CN104310409B (zh) * 2014-10-14 2016-02-17 厦门大学 功能化聚合物在纳米介孔二氧化硅表面组装及解组装方法
KR102400571B1 (ko) * 2017-03-16 2022-05-23 한국과학기술연구원 다공성 실리카의 제조방법 및 그에 의해 제조된 다공성 실리카
CN107008460B (zh) * 2017-04-21 2020-06-30 广州花语精细化工有限公司 一种合成双长链酯基季铵盐所用的固体催化剂及其制备方法

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US5538710A (en) * 1994-12-14 1996-07-23 Energy Mines And Resources-Canada Synthesis of mesoporous catalytic materials
US5840271A (en) * 1996-02-09 1998-11-24 Intevep, S.A. Synthetic material with high void volume associated with mesoporous tortuous channels having a narrow size distribution
US5849258A (en) * 1996-06-06 1998-12-15 Intevep, S.A. Material with microporous crystalline walls defining a narrow size distribution of mesopores, and process for preparing same
DE19639016A1 (de) * 1996-09-23 1998-03-26 Basf Ag Mesoporöses Siliciumdioxid, Verfahren zu seiner Herstellung und seiner Verwendung
DE19732865A1 (de) * 1997-07-30 1999-02-04 Basf Ag Siliciumdioxid enthaltender Feststoff mit großer Oberfläche

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AU6202699A (en) 2000-05-01
BR9914444A (pt) 2001-06-26
DE19847630A1 (de) 2000-04-20
CA2346892A1 (fr) 2000-04-20
CN1330610A (zh) 2002-01-09
JP2002527327A (ja) 2002-08-27
WO2000021883A1 (fr) 2000-04-20
KR20010080175A (ko) 2001-08-22
ID28614A (id) 2001-06-21

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