WO1997047387A1 - Procede de production d'un catalyseur compose d'un corps porteur et d'une matiere a activite catalytique appliquee sur la surface dudit support - Google Patents

Procede de production d'un catalyseur compose d'un corps porteur et d'une matiere a activite catalytique appliquee sur la surface dudit support Download PDF

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Publication number
WO1997047387A1
WO1997047387A1 PCT/EP1997/002819 EP9702819W WO9747387A1 WO 1997047387 A1 WO1997047387 A1 WO 1997047387A1 EP 9702819 W EP9702819 W EP 9702819W WO 9747387 A1 WO9747387 A1 WO 9747387A1
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Prior art keywords
movement
catalytically active
carrier
amount
mass
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Application number
PCT/EP1997/002819
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German (de)
English (en)
Inventor
Hartmut Hibst
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Basf Aktiengesellschaft
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU31699/97A priority Critical patent/AU3169997A/en
Publication of WO1997047387A1 publication Critical patent/WO1997047387A1/fr

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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B01J37/0223—Coating of particles by rotation
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to a process for producing a catalyst which consists of a support body and a catalytically active composition applied to the surface of the support body.
  • the present invention further relates to catalysts which consist of a support body and a catalytically active composition applied to the surface of the support body and are referred to as shell catalysts, and to the use of such shell catalysts.
  • DE-A 2 351 151 relates to catalytic oxidation, ammoxidation and the oxidative dehydrogenation of olefins containing 3 to 5 carbon atoms on catalytically active oxide materials in the gas phase.
  • Exemplary embodiments form the conversion of butadiene to maleic anhydride, from propene to acrolein, from acrolein to
  • Acrylic acid from propene to acrylonitrile and from 2-butene to butadiene.
  • DE-A 16 42 921 and DE-A 21 06 796 teach the catalytic gas phase oxidation of aromatic and unsaturated hydrocarbons, naphthalene, o-xylene, benzene or n-butene to carboxylic acids or their anhydrides. Exemplary embodiments form the conversion of o-xylene to phthalic anhydride and of butadiene to maleic anhydride. From DE-A 25 26 238 it is known to produce acrylic acid or methacrylic acid by catalytic gas phase oxidation of acrolein or methacrolein on catalytically active oxide materials.
  • DE-A 20 25 430 relates to the catalytic gas phase oxidation of indanes to, for example, anthraquinone.
  • the catalytically active oxide mass can only contain another element or more than another element (multi-element oxide masses).
  • Catalytically active oxide compositions which comprise more than one metallic, in particular transition, metallic element are used particularly frequently.
  • metallic, in particular transition, metallic element are used particularly frequently.
  • Multielement oxide materials are usually not simple physical mixtures of oxides of the elemental constituents, but rather heterogeneous mixtures of complex poly compounds of these elements.
  • shaped bodies are usually formed from the catalytically active oxide mass, the longitudinal dimension of which, as a function of the inside diameter of the contact tube, is generally a few millimeters.
  • a disadvantage of shaped bodies which consist exclusively of the catalytically active oxide composition is that on the one hand they have to have a certain thickness in order to meet the requirement for satisfactory mechanical stability.
  • a disadvantage of larger active material thicknesses, however, is that they involve an extension of the diffusion path out of the reaction zone, which promotes undesired subsequent reactions and thus reduces the target product selectivity.
  • the mechanical stability is ensured by the carrier and the oxidic active material can be applied in the desired layer thickness on the carrier surface.
  • the carrier bodies are preferably hollow or fully cylindrical or spherical.
  • the oxidic active composition can be applied as such or in the form of a catalyst precursor composition which, after application, is then converted into the actual oxidic active composition by thermal treatment (calcination).
  • shell catalysts based on catalytically active oxide materials can be produced by applying the catalytically active material to the carrier body with the aid of the plasma spraying or flame spraying process.
  • a disadvantage of the applicability of this process is that the meltability of at least one main component must be given at the working temperature of the flame spray or plasma torch.
  • Another disadvantage of this method is that the size of the specific catalytically active surface is generally unsatisfactory.
  • DE-A 20 25 430 contains a process for the preparation of a spherical coated catalyst in which an aqueous solution containing oxalic acid and the catalytically active oxide composition is sprayed onto hot carrier balls.
  • a disadvantage of this procedure is that it can only be used with water-soluble catalytically active oxide compositions.
  • DE-A 16 42 921 relates to the production of spherical oxidic coated catalysts by spraying a liquid containing the oxidic active composition in dissolved or suspended form onto hot spherical support bodies.
  • DE-A 16 42 921 recommends water or an organic solvent such as alcohol or formamide as the solvent or suspending medium.
  • a disadvantage here is also that the water or solvent evaporates practically in one fell swoop as soon as the sprayed-on mass comes into contact with the hot carrier, which reduces the adhesive strength of the shell.
  • DE-A 25 10 994 corresponds essentially to the teaching of DE-A 16 42 921 with the difference that it also includes ring-shaped carriers.
  • DE-A 21 06 796 discloses the preparation of coated catalysts by spraying aqueous suspensions of the catalytically active oxidic material onto the moving support bodies. This procedure has the same disadvantages as for the spraying of the oxidic Described active composition dissolved aqueous solutions. This applies in particular to spraying onto heated carrier bodies. The recommendation that an aqueous polymer dispersion be used as a binder cannot remedy this disadvantage, but rather the presence of one makes it difficult
  • DE-A 26 26 887 attempts to alleviate the disadvantages of DE-A 21 06 796 by spraying the aqueous suspension onto carrier balls having a temperature of only 25 to 80 ° C. According to DE-A 29 09 671, page 5, line 10, this procedure can lead to sticking of the sprayed carrier bodies. To increase the adhesive strength of the oxidic catalytically active shell on the surface of the
  • Carrier body recommends DE-A 26 26 887 to incorporate inorganic hydroxy salts into the aqueous suspension to be sprayed on, which hydrolyze to hydroxides in aqueous solution and, after the shell catalyst has been produced, form catalytically indifferent constituents of the catalytically active oxide composition.
  • a disadvantage of this measure is that it requires a dilution of the oxidic active composition.
  • DE-A 29 09 670 corresponds essentially to that of DE-A 26 26 887. According to the description of DE-A 29 09 670, mixtures of water and alcohol can also be used as the suspension medium. After the suspension of the catalytically active oxide composition has been sprayed on, the moisture content is removed by passing hot air over it.
  • GB-1 331 423 relates to a process for the preparation of spherical oxide coated catalysts which is characterized in that an aqueous suspension or solution is formed from catalyst precursors and an organic auxiliary substance which is soluble in water , mixed with the carrier bodies and, with occasional stirring, the liquid constituents removed by evaporation.
  • the coated support bodies obtained in this way are then calcined and the catalyst precursor layer is converted into active oxide.
  • a disadvantage here is the need to have to evaporate the liquid components after the coating is finished and the possible reactive interaction of the organic auxiliary substance with the catalyst precursor.
  • EP-A 284 448 and EP-A 37 492 recommend the production of coated catalysts by the spray process already described, or by the process of GB-1 331 423, with the disadvantages already mentioned.
  • EP-B 293 859 discloses a method for producing spherical coated catalysts by using a centrifugal flow coating device. The coating takes place by means of a catalyst precursor mass.
  • EP-B 293 859 recommends e.g. Water, alcohol and acetone.
  • EP-B 293 859 A disadvantage of the teaching of EP-B 293 859 is again the need to use a binder.
  • DE-A 25 26 238 and US Pat. No. 3,956,377 disclose a process for producing spherical oxide coated catalysts in which the carrier balls are first moistened with water or other liquids such as petroleum ether as binders. Subsequently, the catalytically active oxide mass is applied to the carrier material moistened with binder by rolling the moist carrier material in the powdery catalytically active oxide mass.
  • a disadvantage of this procedure is again the requirement that the binder be used and that the achievable shell thickness is limited by the binder absorption capacity of the carrier, since this amount of binder absorbed by the carrier is responsible for binding the entire powdery oxide mass to be absorbed.
  • Another disadvantage of the method is that the degree of moistening of the respective surface layer varies continuously during the coating process.
  • the base layer meets the moisture of the uncoated substrate. Subsequently, the moisture first has to migrate through the base layer to its surface in order to be able to adhere further active composition, etc. As a result, an onion-like shell structure is obtained, the adherence of successive layers in particular not being satisfactory.
  • DE-A 29 09 671 tries to alleviate the disadvantages of the procedure described above by filling the spherical carrier bodies into an inclined rotating turntable.
  • the rotating turntable guides the spherical carrier bodies periodically under two metering devices arranged one after the other at a certain distance.
  • the first of the two metering devices corresponds to a nozzle through which the Carrier balls are sprayed with water and moistened in a controlled manner.
  • the second metering device is located outside the atomizing cone of the sprayed-in water and is used to supply finely divided oxidic active material.
  • the controlled moistened carrier balls take up the supplied catalyst powder, which is compacted into a coherent shell by the rolling movement on the outer surface of the carrier balls.
  • the carrier ball coated in this way as it were a new carrier body, again passes through the spray nozzle in the course of the subsequent rotation, is moistened in a controlled manner in the same way in order to be able to take up a further layer of finely divided oxidic active material in the course of the further movement etc.
  • a disadvantage of this procedure is that the water used as a binder must finally be removed by introducing hot air.
  • the teaching of DE-A 44 32 795 is a further development of the teaching of DE-A 29 09 671 and differs from the latter in that an aqueous solution of an organic substance boiling at normal pressure above 100 ° C. is used as the liquid binder .
  • the object of the present invention was therefore to provide a process for producing a catalyst consisting of a support body and a catalytically active composition applied to the surface of the support body, which on the one hand does not require the use of a liquid binder and on the other hand does not have the disadvantages of the plasma spraying or flame spraying process of DE-A 20 25 430.
  • a process for the preparation of a catalyst consisting of a support body and a catalytically active composition applied to the surface of the support body which is characterized in that the catalytically active composition or a precursor composition thereof, together with the support bodies, is placed in a cylindrical container there and moves it so that its total movement is a suspension of a rotary movement of the cylindrical container about its own (central) longitudinal axis (movement 1) and a circular movement of this longitudinal axis (movement 2), with the proviso that the direction of the vector of the angular velocity of the movement 1 [ ⁇ lj is opposite to the direction of the vector of the angular velocity of the movement 2 ⁇ ⁇ 2 j, 5 - the amount of the smaller of the two angular speeds is at least 50%, preferably at least 75%, the amount of the larger of the two angular velocities,
  • the amount of the smaller of the two angular speeds is preferably at least 90, advantageously at least 95% of the amount of the larger of the two angular speeds.
  • the amounts of the two angular velocities ⁇ 1 , ⁇ 2 are of particular advantage with the same magnitude. Furthermore, it is favorable if the
  • centrifugal acceleration of movement 2 is at least three times or five times, advantageously at least ten times the acceleration due to gravity.
  • the centrifugal acceleration of movement 2 will be at least twenty or at least thirty times the acceleration due to gravity.
  • the inner diameter of the cylindrical container is usually 10 to 50, usually 20 to
  • the inner diameter of the cylindrical container is a multiple of the longest dimension (in the case of a ball, its diameter) of the carrier body (typically 10 to 100 times).
  • the form of movement according to the invention of the carrier body and the catalytically active composition to be applied to it is guaranteed between the two
  • the base-coated carrier body acts as a new carrier body, etc.
  • the targeted choice of the ratio of the total surface to be coated and the amount of material to be applied to the same can be adjusted essentially as required.
  • the uniformly coated carrier bodies can be removed from the same.
  • the form of movement of the cylindrical container according to the invention can be realized in a simple manner by attaching the cylindrical container to a horizontally rotating sun disk and rotating it in the opposite direction to its rotating longitudinal disk about its own longitudinal axis.
  • Such an arrangement is e.g. commercially available in the form of high-speed planetary mills (see SPRECHSAAL, Vol. 125, No. 7, 1992, p. 397 ff; cav 1993, June, p. 98 ff; planetary high-speed mill, company publication of
  • the sun disk of such a high-speed planetary mill carries four cylindrical cups in an arrangement according to FIGS. 1 and 2 (taken from SPRECHSAAL, Vol. 125, No. 7, 1992, p. 398 and p. 399).
  • FIGS. 1 and 2 have the following meaning:
  • ri radius of movement of the spherical support body in point A through the rotation of the sun disk
  • r 2 radius of movement of the spherical support body in point B through the rotation of the sun disk
  • the centrifugal forces act alternately in the same and opposite directions. This results in successive running of the support bodies on the inner wall of the cup and lifting and free passage through the coating material and support bodies through the interior of the cup.
  • the cylinder cup is normally closed by a cover.
  • the materials of the support bodies are preferably chemically inert, ie they essentially do not intervene in the course of the chemical reaction, for example gas phase oxidation, which is catalyzed by the coated catalysts produced according to the invention.
  • aluminum oxide, silicon dioxide, silicates such as clay, kaolin, steatite, pumice, aluminum silicate and magnesium silicate, silicon carbide, zirconium dioxide and thorium dioxide are particularly suitable as materials for the carrier bodies.
  • the surface of the carrier body is advantageously rough, since an increased surface roughness generally causes an increased adhesive strength of the applied shell to oxidic active material.
  • the surface roughness R z of the carrier body is preferably in the range from 40 to 500 ⁇ m, preferably 40 to 200 ⁇ m (determined in accordance with DIN 4768 Sheet 1 using a “Hommel Tester for DIN-ISO surface measurement parameters” from Hommelwerke).
  • the carrier materials can be porous or non-porous.
  • the carrier material is often non-porous (total volume of the pores based on the volume of the carrier body ⁇ 1% by volume).
  • any geometries of the carrier bodies can be considered for the method according to the invention.
  • Their longest dimension is usually 1 to 10 mm.
  • balls or cylinders, in particular hollow cylinders, are preferably used as carrier bodies.
  • cylinders are used as carrier bodies, their length is preferably 2 to 10 mm and their outside diameter is preferably 4 to 10 mm.
  • the wall thickness is usually 1 to 4 mm.
  • Particularly preferred ring-shaped carrier bodies have a length of 3 to 6 mm, an outer diameter of 4 to 8 mm and a wall thickness of 1 to 2 mm. Rings of geometry 7 mm x 3 mm x 4 mm (outer diameter x length x inner diameter) are very particularly preferred.
  • the thickness of the catalytically active composition is expediently as a rule from 5 nm to 1000 ⁇ m. 10 nm to 500 ⁇ m, particularly preferably 100 nm to 500 ⁇ m and very particularly preferably 200 nm to 300 ⁇ m, are preferred, in particular in the case of ring-shaped carrier bodies.
  • the fineness of the catalytically active mass to be applied to the surface of the carrier body, such as the catalytically active oxide mass is of course applied to the desired shell. adjusted thickness.
  • the method according to the invention can be repeated periodically to achieve an increased shell thickness.
  • Binder does not need, which excludes a reaction with the mostly organic binder.
  • the material used for coating does not necessarily have to be used in finely divided form. Rather, it can be assumed that the starting material is of a coarse particle size, that if the carrier body is selected appropriately, the process according to the invention is subject to a milling process until the Van der Waals forces that are developed enable the force to be drawn up onto the surface of the carrier body. An otherwise required separate grinding process can be omitted.
  • a further essential feature of the method according to the invention is that both the catalytically active oxidic mass as such and also a preliminary discharge of the same can be applied to the carrier body.
  • catalytically active oxidic masses For the production of catalytically active oxidic masses, it is customary to start from sources of the catalytically active, oxidic masses which are suitable in a manner known per se and to produce an intimate, preferably finely divided,
  • Dry mixture (which can be applied as a precursor mass to the surface of the carrier body), which is then subjected to the calcination (thermal treatment) and, if appropriate, converted into finely divided form by grinding. If the pre-discharge is already applied, the application is calculated after the application has been completed. This usually leads to coated catalysts with an increased specific surface area of the active composition.
  • the sources are either already oxides or such
  • the intimate mixing of the starting compounds can take place in dry or in wet form. If it is carried out in dry form, the starting compounds are expediently used as finely divided powders and, after mixing and optionally pressing, are subjected to the calcination. However, the intimate mixing is preferably carried out in wet form.
  • the starting compounds are usually in the form of an aqueous solution or S uspension mixed together.
  • the aqueous mass is then dried and, after drying, calcined.
  • the drying process is preferably carried out by spray drying.
  • the case anfal ⁇ loin powder turns out for immediate further processing often be too finely divided. In these cases, it can be kneaded with the addition of water.
  • the modeling clay obtained is then subjected to the calcination and then ground to a finely divided oxidic active composition.
  • the process according to the invention is favorable in the case of multimetal oxide compositions containing Mo and V or Mo, Fe and Bi.
  • X 4 at least one or more alkali metals
  • X 5 at least one or more alkaline earth metals, X 6 Si, Al, Ti and / or Zr, a 1 to 6, b 0.2 to 4, c 0.5 to 18, d 0 to 40, e 0 to 2, f 0 to 4, g 0 to 40 and n a number which is determined by the valency and frequency of the elements other than oxygen in I.
  • DE-A 43 35 973 describes the preparation of active multimetal oxides I, including the calcination conditions.
  • DE-A 43 35 973 also discloses preferred embodiments within active multimetal oxides I. These include, for example, those multimetal oxides I that are described below Meanings of the variables of the general formula I are recorded: ⁇ i W, Nb and / or Cr,
  • n is a number which is determined by the valency and frequency of the elements in I other than oxygen.
  • multimetal oxides I are those of the general formula I '
  • X 6 Si and / or AI a 3 to 4.5, b 1 to 1.5, c 0.75 to 2.5, f 0 to 0.5, g 0 to 8 and n a number represented by the Value and frequency of elements other than oxygen is determined in I '.
  • Shell catalysts produced according to the invention with the active multimetal oxides I are particularly suitable for the gas-phase catalytically oxidative production of acrylic acid from acrolein. This applies in particular to spherical or ring-shaped shell catalysts. Especially if they have the characteristics (geometry, shell thickness, etc.) described as preferred in this document.
  • the general reaction conditions for the gas phase catalytic oxidation of acrolein to acrylic acid can also be found in DE-A 43 35 973.
  • the process according to the invention is also suitable in the case of active multimetal oxides as are used for the catalytic gas phase oxidation of methacrolein to methacrylic acid and are described, for example, in DE-A 40 22 212.
  • the method according to the invention proves itself in the case of active multimetal oxides of general stoichiometry II to be applied as a shell
  • Tungsten X 4 silicon, aluminum, titanium and / or zirconium, a 0.5 to 5, b 0, 01 to 3, c 3 to 10, d 0.02 to 2, e 0 to 5, f 0 to 10 and n a number, which is determined by the valency and frequency of the elements other than oxygen in II, as suitable.
  • DE-A 40 23 239 describes the production of active multimetal oxides II, including the calcination conditions.
  • Shell catalysts produced according to the invention with the active multimetal oxides II are particularly suitable for the gas-phase catalytic oxidative production of acrolein from propene. This applies in particular to spherical or ring-shaped coated catalysts. Especially if they have the characteristic (geometry, shell thickness, etc.) described as preferred in this document.
  • the general reaction conditions for the gas-phase catalytic oxidation of propene to acrolein can also be found in DE-A 40 23 239 and in DE-A 44 31 957.
  • the aforementioned shell catalysts of the active multimetal oxides II are also suitable for the gas-phase catalytically oxidative production of methacrolein from tert. -Butanol, isobutane, isobutene or tert. -Butyl methyl ether.
  • the general Reaction conditions for this catalytic gas phase oxidation can be found, for example, in DE-A 40 23 239 and in DE-A 43 35 172.
  • the method according to the invention is suitable in the case of the active oxide compositions of DE-A 44 05 514.
  • the process according to the invention is very generally suitable for producing coated catalysts based on active compositions, in particular for the catalyzed reactions listed in this document in the context of the assessment of the prior art.
  • the active composition is an oxidic active composition which only comprises another element in addition to oxygen.
  • the method according to the invention is suitable for the production of shell catalyst test quantities for shell catalyst screening.
  • FIGS. 1, 2 An arrangement according to FIGS. 1, 2 was used to apply the method according to the invention
  • Either smooth steatite spheres with a diameter of 1 mm or surface-rough stateite spheres (surface roughness R z 0.5 mm due to splitting) with a diameter of 2 mm were used as carrier bodies.
  • Carrier body duration of movement and revolutions per minute of the sun disk. All information relates to one (1) cylinder cup.
  • the amount of the oxide layer applied is given in% by weight, based on the weight of the carrier ball.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé permettant de produire un catalyseur cupuliforme, selon lequel la matière à activité catalytique ou un précurseur de ladite matière est placé(e) conjointement avec les corps porteurs dans un bécher cylindrique et sont agités de manière que le mouvement global consiste en une superposition résultant d'un mouvement rotatif du bécher cylindrique autour de son propre axe longitudinal et d'un mouvement circulaire de son axe longitudinal.
PCT/EP1997/002819 1996-06-12 1997-05-30 Procede de production d'un catalyseur compose d'un corps porteur et d'une matiere a activite catalytique appliquee sur la surface dudit support WO1997047387A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU31699/97A AU3169997A (en) 1996-06-12 1997-05-30 Process for producing a catalyst consisting of a substrate and a catalytically active compound applied to the upper surface of said substrate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19623413.1 1996-06-12
DE1996123413 DE19623413A1 (de) 1996-06-12 1996-06-12 Verfahren zur Herstellung eines Katalysators, bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Masse

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Publication Number Publication Date
WO1997047387A1 true WO1997047387A1 (fr) 1997-12-18

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DE (1) DE19623413A1 (fr)
ID (1) ID17197A (fr)
WO (1) WO1997047387A1 (fr)

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DE10059922A1 (de) * 2000-12-01 2002-06-20 Hte Ag The High Throughput Exp Verfahren zum Aufbringen von Materiallagen auf Formkörpern
DE10061555A1 (de) 2000-12-11 2002-06-20 Basf Ag Schalenkatalysator für die Hydrierung von Maleinsäureanhydrid und verwandten Verbindungen zu gamma-Butyrolacton und Tetrahydrofuran und Derivaten davon
DE10208113A1 (de) * 2002-02-26 2003-09-04 Basf Ag Verfahren zur Herstellung von Schalenkatalysatoren
US7022643B2 (en) 2002-08-20 2006-04-04 Nippon Shokubai Co., Ltd. Production process for catalyst
US20040038820A1 (en) * 2002-08-20 2004-02-26 Nippon Shokubai Co., Ltd. Production process for catalyst
JP4295521B2 (ja) 2003-02-13 2009-07-15 株式会社日本触媒 アクリル酸製造用触媒およびアクリル酸の製造方法
JP5096486B2 (ja) 2006-12-13 2012-12-12 ビーエーエスエフ ソシエタス・ヨーロピア マイクロカプセル
WO2009112467A1 (fr) 2008-03-11 2009-09-17 Basf Se Microcapsules à parois en acylurée
EP2442901A2 (fr) 2009-06-15 2012-04-25 Basf Se Microcapsules contenant des polymères fortement ramifiés en tant que réticulants
KR101812351B1 (ko) 2009-07-10 2017-12-26 바스프 에스이 가교제로서 폴리비닐 단량체를 갖는 마이크로캡슐
EP2528959A1 (fr) 2010-01-25 2012-12-05 Basf Se Procédé de préparation de produits de condensation d'acide phénolsulfonique et d'aldéhyde et leur utilisation en tant qu'agents dessicatifs
JP6005067B2 (ja) 2011-02-16 2016-10-12 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ カプセルコアとしてパラフィン組成物を有するマイクロカプセル
US9181466B2 (en) 2011-02-16 2015-11-10 Basf Se Microcapsules with a paraffin composition as capsule core

Citations (3)

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Publication number Priority date Publication date Assignee Title
DE2909671A1 (de) * 1979-03-12 1980-10-02 Basf Ag Verfahren zur herstellung von schalenkatalysatoren
JPS6295141A (ja) * 1985-10-18 1987-05-01 Daicel Chem Ind Ltd 被覆触媒の製造方法
EP0294775A1 (fr) * 1987-06-12 1988-12-14 BASF Aktiengesellschaft Procédé de préparation de catalyseurs à couche superficielle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2909671A1 (de) * 1979-03-12 1980-10-02 Basf Ag Verfahren zur herstellung von schalenkatalysatoren
JPS6295141A (ja) * 1985-10-18 1987-05-01 Daicel Chem Ind Ltd 被覆触媒の製造方法
EP0294775A1 (fr) * 1987-06-12 1988-12-14 BASF Aktiengesellschaft Procédé de préparation de catalyseurs à couche superficielle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 011, no. 300 (C - 449) 29 September 1987 (1987-09-29) *

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ID17197A (id) 1997-12-11
AU3169997A (en) 1998-01-07

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