EP1039969A1 - Corps moule comprenant un support inerte et au moins un materiau poreux obtenu par voie d'oxydation - Google Patents

Corps moule comprenant un support inerte et au moins un materiau poreux obtenu par voie d'oxydation

Info

Publication number
EP1039969A1
EP1039969A1 EP98964440A EP98964440A EP1039969A1 EP 1039969 A1 EP1039969 A1 EP 1039969A1 EP 98964440 A EP98964440 A EP 98964440A EP 98964440 A EP98964440 A EP 98964440A EP 1039969 A1 EP1039969 A1 EP 1039969A1
Authority
EP
European Patent Office
Prior art keywords
mixture
acid ester
oxidic material
hydrolyzate
porous oxidic
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Withdrawn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
EP98964440A
Other languages
German (de)
English (en)
Inventor
Georg Heinrich Grosch
Ulrich Müller
Andreas Walch
Norbert Rieber
Wolfgang Harder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1039969A1 publication Critical patent/EP1039969A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • 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
    • B01J37/033—Using Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids

Definitions

  • Shaped body comprising an inert carrier and at least one porous oxidic material
  • the present invention relates to a shaped body comprising an inert carrier and applied to it at least one porous oxidic material, a process for its production and its use for the conversion of organic compounds, in particular for the epoxidation of organic compounds with at least one C-C double bond.
  • the molded body described here has excellent abrasion resistance and excellent mechanical properties and is inexpensive compared to catalysts previously used for these purposes.
  • Abrasion-resistant molded articles made from catalytically active compositions are used in many chemical processes, in particular in processes using a fixed bed.
  • the catalytically active mass ie the porous oxidic material
  • a binder an organic viscosity-increasing compound and a liquid to increase the mass and compacted in a mixing or kneading device or an extruder.
  • the resulting plastic mass is then deformed, in particular using an extruder or an extruder.
  • the resulting moldings are dried and calcined.
  • a number of inorganic compounds are used as binders.
  • titanium dioxide or titanium dioxide hydrate is used as the binder.
  • Other binders mentioned in the prior art include:
  • Such catalysts are also produced with zeolites as active components.
  • JP 07,241,471 describes the support of zeolite powder which is suspended in water and organic emulsifiers with an inorganic binder and then applied to the support by wash-coating. These catalysts are designed for exhaust gas purification.
  • JP 07,155,613 describes the application of zeolites and silica sol are suspended in water and applied to a cordierite monolith carrier as a wash-coat suspension.
  • JP 02,111,438 also describes the application of zeolites to monolith supports, aluminum sol being used as the binder. This catalytic converter is also used for exhaust gas purification. No.
  • 4,692,423 describes the support of porous supports with zeolites by first adding cyclic oxides, which are unstable to polymerization, to the zeolite, coating the surface of the porous support with this suspension and then stripping off the solvent.
  • No. 4,283,583 describes catalysts in which zeolite has been supported on spherical supports (diameter 0.5-10 mm).
  • Adhesion of the active component to the carrier is important for gas phase processes such as exhaust gas purification, but the forces that act on the supported layer in a gas phase process are much less abrasive than, for example, in a liquid phase process. This places far higher demands on the adhesion of the supported layer. In particular, the constant presence of liquid or solvent can lead to the destabilization of the anchoring of the active composition on the inert carrier.
  • An application for a liquid phase process is described in JP 08,103,659.
  • titanium silicalite is applied to balls with a diameter of 0.2 - 20 mm.
  • titanium silicalite is suspended in an aqueous solution of polyvinyl alcohol and sprayed onto the ball.
  • the ready-to-use catalyst is then generated by calcining the sprayed ball and used in the epoxidation of propylene with hydrogen peroxide.
  • the catalyst produced in this way still shows a clear abrasion of the active component.
  • US Pat. No. 5,523,426 describes the possibility of epoxidizing propylene over titanium silicalite catalysts, in which the titanium silicalite can be applied, inter alia, to inert supports. No further explanation of the application process is given.
  • the invention was therefore based on the object of developing a process which makes it possible to apply zeolite and, in particular, titanium silicalite to any shaped, preferably non-monolithic, supports so that they can be used as catalysts in chemical processes, in particular in liquid phase processes, and the provision of such a catalyst per se.
  • the present invention relates to moldings comprising an inert carrier and applied thereon at least one porous oxidic material, obtainable by applying a mixture comprising at least one porous oxidic material and at least one metal acid ester or a hydrolyzate thereof or a combination of metal acid ester and Hydrolyzate thereof on the inert carrier, and a method for producing such a shaped body, wherein a mixture containing at least one porous oxidic material and at least one metal acid ester or a hydrolyzate thereof or a combination of metal acid ester and hydrolyzate thereof is applied to an inert carrier.
  • the inert carriers which can be used according to the invention can consist of oxides, carbides, nitrides or other inorganic or organic materials, provided they do not show any decomposition, melting or other instabilities at the temperatures required in the production process.
  • int used according to the invention means that the materials used as supports have no or at most negligible catalytic activity.
  • Inert metals or metal alloys such as steel, Kanthai, aluminum, etc. can also be used as materials for the inert carrier.
  • the inert carrier preferably has an alkali metal or alkaline earth metal content of ⁇ 1,000 ppm, preferably ⁇ 100 ppm and in particular ⁇ 10 ppm.
  • the low alkali metal or alkaline earth metal contents of the support are particularly important when the catalyst according to the invention is used for epoxidation, in particular with a titanium silicalite as the porous oxidic material.
  • the external shape of the inert support or molded body is not critical and can be chosen freely depending on the fluid dynamic conditions in the reactor specified for the reaction.
  • the inert carrier or molded body can be in the form of strands, such as. B.
  • the carrier or the shaped body is preferably present in the form of a non-spherical granulate, a strand, a grit, a tablet, a band-shaped structure or a structure having holes.
  • porous oxidic materials which can be used to produce the shaped body according to the invention, as long as it is possible to produce a shaped body as described here starting from these materials and these materials have the necessary catalytic activity.
  • the porous oxidic material is preferably a zeolite, more preferably a zeolite containing titanium, zirconium, chromium, niobium, iron or vanadium and in particular a titanium silicalite.
  • Zeolites are known to be crystalline allumosilicates with ordered channel and cage structures that have micropores.
  • micropores as used in the context of the present invention corresponds to the definition in "Pure Appl. Chem.” 45, p. 71 ff., In particular p. 79 (1976), and designates pores with a pore diameter of less than 2 nm.
  • the network of such zeolites is composed of SiO 4 and AlO 4 tetrahedra which are connected via common oxygen bridges.
  • zeolites which do not contain aluminum and in which titanium (Ti) is partly present in the silicate lattice instead of Si (IV).
  • Ti titanium
  • the titanium zeolites in particular those with a crystal structure of the MFI type, and possibilities for their preparation are described, for example in EP-A 0 311 983 or EP-A 0 405 978.
  • silicon and titanium such materials can also contain additional elements such as Contain aluminum, zirconium, tin, iron, cobalt, nickel, gallium, boron or small amounts of fluorine.
  • the titanium thereof can be partially or completely replaced by vanadium, zirconium, chromium, niobium or iron.
  • the molar ratio of titanium and / or vanadium, zirconium, chromium, niobium or iron to the sum of silicon and titanium and / or vanadium, zirconium, chromium, niobium or iron is generally in the range from 0.001: 1 to 0.1: 1.
  • Titanium zeolites with an MFI structure are known for being able to be identified by a certain pattern in the determination of their X-ray diffraction recordings and also by means of a framework vibration band in the infrared region (IR) at about 960 cm “1 and are thus different from alkali metal titanates or crystalline and amorphous Distinguish TiO 2 phases.
  • the titanium, zirconium, chromium, niobium, iron and vanadium zeolites mentioned are prepared by adding an aqueous mixture of an SiO 2 source, a titanium, zirconium, chromium, niobium, iron or .
  • Vanadium source such as titanium dioxide or a corresponding vanadium oxide, zirconium alcoholate, chromium oxide, niobium oxide or iron oxide and a nitrogen-containing organic base as a template ("Schab ion compound"), such as tetrapropylammonium hydroxide, optionally with the addition of basic compounds, in one Pressure vessel under elevated temperature in the period of several hours to a few days, creating a crystalline product. This is filtered off, washed, dried and baked at elevated temperature to remove the organic nitrogen base.
  • a template such as tetrapropylammonium hydroxide
  • the titanium or the zirconium, chromium, niobium, iron and / or vanadium is present at least partially within the zeolite structure in varying proportions with 4-, 5- or 6-fold coordination.
  • a repeated washing treatment with sulfuric acid hydrogen peroxide solution can follow, after which the titanium or zirconium, chromium, niobium, iron, vanadium zeolite powder must be dried and fired again; this can be followed by treatment with alkali metal compounds in order to convert the zeolite from the H form to the cation form.
  • the titanium or zirconium, chromium, niobium, iron, vanadium zeolite powder thus produced is then processed into a shaped body as described below.
  • Preferred zeolites are titanium, zirconium, chromium, niobium or vanadium zeolites, more preferably those with a pentasil zeolite structure, in particular the types with X-ray assignment to BEA, MOR, TON, MTW, FER, MFI -, MEL, CHA, ERI, RHO, GIS, BOG, NON, EMT, HEU, KFI, FAU, DDR, MTT, LTL, MAZ, GME, NES, OFF, SGT, EUO, MFS, MCM-22 or MFI / MEL mixed structure.
  • Zeolite he of this type are described, for example, in the Meier and Olson reference cited above.
  • Titanium-containing zeolites with the structure of UTD-1, CIT-1 or CIT-5 are also conceivable for the present invention.
  • Such zeolites are described, inter alia, in US Pat. No. 5,430,000 and WO 94/29408, the content of which in this regard is incorporated in its entirety in the present application by reference.
  • the shaped body according to the invention can have micropores, mesopores, macropores, micropores and mesopores, micropore and macropores or micropores, mesopores and macropores, the definition of the terms “mesopores” and “macropores” likewise corresponding to those in the literature mentioned above Pure appl. Chem. Corresponds and designates pores with a diameter of> 2 nm to 50 nm or> 50 nm.
  • the shaped body according to the invention can be a material based on a mesoporous silicon-containing oxide and a silicon-containing xerogel.
  • Silicon-containing mesoporous oxides which also contain Ti, V, Zr, Sn, Cr, Nb or Fe, in particular Ti, V, Zr, Cr, Nb or a mixture of two or more thereof, are particularly preferred.
  • the porous oxidic material described in detail above is always mixed with at least one metal acid ester or a hydrolyzate thereof or a combination of at least one metal acid ester and a hydrolyzate thereof (hereinafter often referred to as "metal acid ester (hydrolyzate)" referred to) applied to the inert support.
  • acid esters can from III. and IV. main and III. to VI. Subgroup of the periodic table. Furthermore, their partial hydrolyzates can be used.
  • tetraalkoxysilanes are particularly preferably used as metal acid esters in the context of the present invention.
  • Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane and tetrabu-toxysilane the analogous tetraalkoxytitanium and zirconium compounds as well as trimethoxy, triethoxy, tripropoxy, triisopropoxy or tri-ethoxysiloxysiloxysiloxysiloxysilane are particularly preferred.
  • the content of metal oxide according to the invention from the metal acid ester or the hydrolyzate thereof is preferably up to approximately 80% by weight, more preferably approximately 1 to approximately 50% by weight and in particular approximately 3 to approximately 30% by weight, based on the amount porous oxide.
  • the content of the mixture applied is generally about 1 to about 80% by weight, preferably about 1 to about 50% by weight and in particular about 3 to about 30% by weight, based in each case on the total amount of mixture and inert carrier .
  • the at least one porous oxidic material is suspended and applied in the form of a powder or granulate in a liquid, or the porous oxidic material in powder or granular form and the liquid required for the adhesion of the porous oxidic material to the inert carrier can be metered simultaneously.
  • the oxidic material to be applied is preferably suspended in the liquid and sprayed onto the carrier.
  • the metallic acid ester (hydrolyzate) used according to the invention is mixed with the powdery or granular porous oxidic material. The mixture obtained is then allowed to trickle onto the inert carrier, which is simultaneously sprayed with an adhesive liquid.
  • the hydrolysates of the metal acid esters are preferably used.
  • the metal acid ester (hydrolyzate) is mixed with the adhesive liquid, and then this mixture together with the powdery or granular porous oxidic material is simultaneously applied to the inert carrier.
  • Another preferred embodiment consists in suspending the metal acid ester (hydrolyzate) together with the porous oxidic material in the adhesion-promoting liquid and spraying the suspension onto the inert carrier.
  • the alcohol used in the above mixture preferably corresponds to the alcohol component of the metal acid ester used or the hydrolyzate thereof, but it is also not critical to use a different alcohol.
  • a particularly rapid adhesion of the mixture can be achieved if the inert carrier is mixed with acidic substances, e.g. organic or inorganic acids such as e.g. Nitric acid, sulfuric acid, hydrochloric acid, acetic acid, oxalic acid or phosphoric acid.
  • acidic substances e.g. organic or inorganic acids such as e.g. Nitric acid, sulfuric acid, hydrochloric acid, acetic acid, oxalic acid or phosphoric acid.
  • the mixture to be applied to the inert carrier can contain further additives, e.g. contain organic viscosity-increasing substances and other additives, as defined below.
  • liquids are preferably chosen which are vaporized at the spraying temperatures of approximately 30 to approximately 200 ° C., preferably approximately 50 to approximately 150 ° C. and in particular approximately 60 to approximately 120 ° C. can. If these liquids are added at the same time as adhesion promoters separately from the porous oxidic material, one will choose a liquid that boils significantly higher than at the specified temperatures.
  • the porous oxidic material is in
  • Alcohols such as B. methanol, ethanol, propanol, isopropanol and n-, iso-, tert-butanol and mixtures of two or more thereof, suspended.
  • a mixture of an alcohol, preferably one, is further preferred alcohol mentioned above, used with water.
  • the alcohol content of such a mixture is generally about 1 to about 80% by weight, preferably about 5 to about 70% by weight and in particular about 10 to about 60% by weight, based in each case on the total weight of the mixture from alcohol and water.
  • High-boiling liquids are to be understood as those with a boiling point at atmospheric pressure of more than 150 ° C.
  • Propanediol, glycerol, ethanediol, polyether, polyester, dipropylene glycol or mixtures of two or more thereof can preferably be used as high-boiling liquids.
  • organic viscosity-increasing substance preferably organic, in particular hydrophilic polymers, such as e.g. Cellulose, starch, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinyl pyrrolidone, polyisobutene, polytetrahydrofuran.
  • hydrophilic polymers such as e.g. Cellulose, starch, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinyl pyrrolidone, polyisobutene, polytetrahydrofuran.
  • Amines or amine-like compounds such as e.g. Tetraalkylammonium compounds or amino alcohols
  • carbonate-containing substances such as e.g. Calcium carbonate
  • Such further additives are described in EP-A 0 389 041, EP-A 0 200 260 and in WO 95/19222, which in this respect are fully incorporated into the context of the present application by reference.
  • the shaped body thus obtained can be subjected to a calcination step.
  • This calcination step can are eliminated if the shaped body is used as a catalyst in a reaction which is carried out at high temperatures and in the presence of oxygen. In this case, the calcination takes place in situ in the reactor.
  • the moldings are subjected to calcination. This achieves the hardness and abrasion resistance desired for the molded body.
  • the calcination is carried out at temperatures of approximately 200 ° C. to 1000 ° C., preferably 250 ° C. to 900 ° C. and particularly preferably approximately 300 ° C. to approximately 800 ° C., preferably in the presence of an oxygen-containing gas.
  • the moldings are preferably dried before the calcination, temperatures of approximately 50 to approximately 200 ° C., preferably approximately 80 to approximately 150 ° C. being used for this.
  • the moldings according to the invention or produced according to the invention have very good catalytic activity and excellent mechanical abrasion resistance, which make them suitable for use in liquid phase reactions.
  • the moldings according to the invention contain practically no fine-grained fractions than those with approximately 0.1 mm minimum particle diameter.
  • the molded articles according to the invention or produced by the process according to the invention contain a porous oxidic material - compared to corresponding molded articles of the prior art - have improved mechanical stability while maintaining activity and selectivity.
  • the moldings according to the invention or produced according to the invention can be used for the catalytic conversion of organic molecules.
  • Examples of such reactions are oxidations, the epoxidation of olefins such as the production of propylene oxide from propylene and H 2 O 2 , the hydroxylation of aromatics such as phenol from benzene and H 2 O 2 and hydroquinone from phenol and H 2 O 2 , the conversion of alkanes to alcohols, aldehydes and acids, isomerization reactions, such as, for example, the conversion of epoxides to aldehydes, and further reactions described in the literature with moldings of this type, in particular zeolite catalysts, as described, for example, in W.
  • the moldings discussed in detail above are particularly suitable for the epoxidation of olefins, preferably those having 2 to 8 carbon atoms, more preferably ethylene, propylene or butene, and in particular propene to give the corresponding olefin oxides. Accordingly, the present invention relates in particular to the use of the shaped body described here for the production of propylene oxide starting from propylene and hydrogen peroxide, as described, for example, in EP-A 0 100 119.
  • the sealed autoclave (anchor stirrer, 200 rpm) was brought to a reaction temperature of 175 ° C. at a heating rate of 3 ° C./min. The reaction was complete after 92 hours.
  • the cooled reaction mixture (white suspension) was centrifuged off and washed neutral with water several times. The solid obtained was dried at 110 ° C. in the course of 24 hours (weight: 298 g).
  • the pure white product had a Ti content of 1.3% by weight and a residual alkali content below 100 ppm.
  • the yield on SiO 2 used was 97%.
  • the crystallites had a size of 0.05 to 0.25 ⁇ m and the product showed a typical band at approx. 960 cm "1 in the IR spectrum. Comparative Example 1
  • Aerosil 200 (Degussa) were compacted with 150 g of ammonia solution (30%), 100 g of potato starch and 3000 g of water in a kneader formed into 2 mm strands in an extrusion press.
  • the strands thus obtained were dried at 110 ° C. and calcined at 500 ° C. for 16 hours.
  • the strands thus obtained had an alkali content of 40 ppm.
  • half of the strands were processed into 1-1.6 mm chips.
  • abrasion-resistant molded articles were obtained which are suitable for liquid-phase reactions.
  • the titanium silicalite content of the shaped body was 5% by weight, according to the atomic emission spectroscopy analysis.
  • acetic acid By soaking the moldings with acetic acid, better adhesion of the TS-1 was achieved when sprayed on.
  • the epoxidation properties of the catalyst B obtained in this way were investigated in epoxidation experiments.
  • titanium silicalite powder from preparation example 1 10 g were suspended in 100 g of methanol and 4 g of tetramethoxysilane. 100 g of silicon dioxide balls (Siliperl AF-125, Engelhardt) were placed in a heated spray plate. The suspension of the titanium silicalite in methanol / tetramethoxysilane was slowly sprayed on while rotating the spray plate evenly. The spheres thus obtained were dried at 120 ° C., sieved briefly and calcined at 500 ° C. for 5 hours. When sieving after drying, about 7 g of TS-1 powder were recovered.
  • the titanium silicalite content of the shaped body was 2% by weight and the alkali content was 400 ppm.
  • the epoxidation properties of the catalyst V3 obtained in this way were investigated in epoxidation experiments.
  • the PO and hydrogen peroxide contents can be found in Table 1.
  • Catalyst VI (TS-1, 1 mm strands) is significantly more active than Catalyst V2 (TS-1, 3 mm strands). This suggests poor use of the TS-1 strand with a diameter of 3 mm (V2).
  • the supported catalysts A to C achieved a higher PO yield despite the lower amount of TS-1 used.
  • Catalyst V3 shows almost no epoxidation activity due to the high alkali content of 400 ppm.
  • supported TS-1 catalysts are significantly more reactive in relation to the amount of TS-1 used than the catalysts used in the form of full contact (strand).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Epoxy Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un corps moulé comprenant un support inerte et au moins un matériau poreux obtenu par voie d'oxydation, appliqué dessus. Ce corps moulé s'obtient par application d'un mélange contenant le matériau poreux obtenu par voie d'oxydation (au moins au nombre de un) et au moins un ester d'acide métallique ou un hydrolysat en résultant ou une combinaison d'ester d'acide métallique et d'hydrolysat en résultant sur un support inerte.
EP98964440A 1997-12-10 1998-11-25 Corps moule comprenant un support inerte et au moins un materiau poreux obtenu par voie d'oxydation Withdrawn EP1039969A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19754924 1997-12-10
DE19754924A DE19754924A1 (de) 1997-12-10 1997-12-10 Formkörper umfassend einen inerten Träger und mindestens ein poröses oxidisches Material
PCT/EP1998/007603 WO1999029426A1 (fr) 1997-12-10 1998-11-25 Corps moule comprenant un support inerte et au moins un materiau poreux obtenu par voie d'oxydation

Publications (1)

Publication Number Publication Date
EP1039969A1 true EP1039969A1 (fr) 2000-10-04

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EP98964440A Withdrawn EP1039969A1 (fr) 1997-12-10 1998-11-25 Corps moule comprenant un support inerte et au moins un materiau poreux obtenu par voie d'oxydation

Country Status (10)

Country Link
EP (1) EP1039969A1 (fr)
JP (1) JP2001525248A (fr)
KR (1) KR20010032966A (fr)
CN (1) CN1284899A (fr)
AU (1) AU1964099A (fr)
CA (1) CA2314233A1 (fr)
DE (1) DE19754924A1 (fr)
ID (1) ID25488A (fr)
WO (1) WO1999029426A1 (fr)
ZA (1) ZA9811261B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2289809T3 (es) * 1998-04-08 2008-02-01 Basf Aktiengesellschaft Metodo para producur un cuerpo conformado utilizando un sol de oxido de metal, el cuerpo conformado, el uso de este en la produccion de un oxido de alqueno.
JP4578602B2 (ja) * 1999-12-07 2010-11-10 株式会社クラレ ３−メチルテトラヒドロフランの製造方法
DE19939416A1 (de) 1999-08-20 2001-02-22 Basf Ag Verfahren zur Herstellung eines kristallinen, zeolithischen Feststoffs
US20040054199A1 (en) 2002-09-17 2004-03-18 Basf Aktiengesellschaft Process for epoxidation and catalyst to be used therein
US10780431B1 (en) * 2019-03-22 2020-09-22 Oriental Union Chemical Corp. Method of using biopolymer to synthesize titanium-containing silicon oxide material and applications thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2218138A1 (en) * 1973-02-20 1974-09-13 Corning Glass Works Honeycomb ceramic catalyst carrier - with metal oxide layer deposited from slurry contg. organic silicon cpd., giving firm bonding
US4559364A (en) * 1983-12-30 1985-12-17 The Dow Chemical Company Catalysts having alkoxide-modified supports
CA2020482C (fr) * 1990-07-05 1999-10-12 Sellathurai Suppiah Zeolites riches en silice pour cadres supports
US5210062A (en) * 1991-08-26 1993-05-11 Ford Motor Company Aluminum oxide catalyst supports from alumina sols
US5212130A (en) * 1992-03-09 1993-05-18 Corning Incorporated High surface area washcoated substrate and method for producing same
US5374747A (en) * 1993-12-23 1994-12-20 Arco Chemical Technology, L.P. Epoxidation process and catalyst therefore

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9929426A1 *

Also Published As

Publication number Publication date
JP2001525248A (ja) 2001-12-11
WO1999029426A1 (fr) 1999-06-17
CA2314233A1 (fr) 1999-06-17
KR20010032966A (ko) 2001-04-25
ZA9811261B (en) 2000-06-09
ID25488A (id) 2000-10-05
AU1964099A (en) 1999-06-28
DE19754924A1 (de) 1999-06-17
CN1284899A (zh) 2001-02-21

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