EP2032517A1 - Utilisation et procédé d'utilisation d'un catalyseur contenant un dioxyde de titane, en particulier dans la production d'anhydride phtalique - Google Patents

Utilisation et procédé d'utilisation d'un catalyseur contenant un dioxyde de titane, en particulier dans la production d'anhydride phtalique

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Publication number
EP2032517A1
EP2032517A1 EP07725469A EP07725469A EP2032517A1 EP 2032517 A1 EP2032517 A1 EP 2032517A1 EP 07725469 A EP07725469 A EP 07725469A EP 07725469 A EP07725469 A EP 07725469A EP 2032517 A1 EP2032517 A1 EP 2032517A1
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European Patent Office
Prior art keywords
catalyst
catalyst layer
active material
content
ppm
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EP07725469A
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German (de)
English (en)
Inventor
Christian GÜCKEL
Marvin Estenfelder
Gerhard Mestl
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Sued Chemie IP GmbH and Co KG
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Sued Chemie AG
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Priority to EP07725469A priority Critical patent/EP2032517A1/fr
Publication of EP2032517A1 publication Critical patent/EP2032517A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • 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
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • 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
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J37/0219—Coating the coating containing organic 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
    • 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
    • B01J35/612—Surface area less than 10 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
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g

Definitions

  • the invention relates to a catalyst comprising titanium dioxide, in particular for the production of phthalic anhydride (PSA) by gas phase oxidation of o-xylene and / or naphthalene.
  • PSA phthalic anhydride
  • the present invention relates to the use of titanium dioxide with low impurities of sulfur, and preferably a minimum content of niobium for the preparation of catalysts for the gas phase oxidation of hydrocarbons.
  • a suitable catalyst for the reaction in a reactor preferably a so-called tube bundle reactor in which a plurality of tubes are arranged in parallel, filled and from above or below with a mixture of the hydrocarbon (s) and an oxygen-containing Gas, for example, air flows through.
  • a hot spots By virtue of the strong heat formation of such oxidation reactions, it is necessary to surround the reaction tubes to avoid so-called hot spots ("hot spots") with a heat transfer medium and thus dissipate the heat produced.
  • This energy can be used to produce steam.
  • the heat transfer medium used is usually a salt melt and here preferably a eutectic mixture of NaNC> 2 and KNO 3 .
  • the layered arrangement of the catalysts also has the purpose of reducing the content of undesired by-products, i. Compounds, which are in a possible reaction mechanism of o-xylene and / or naphthalene to phthalic anhydride before the actual value product to keep as low as possible in the raw PSA.
  • undesirable by-products mainly include the compounds o-tolualdehyde and phthalide.
  • the further oxidation of these compounds to phthalic anhydride also increases the selectivity with respect to the actual value product.
  • overoxidation products also occur in the reaction.
  • These include maleic anhydride, citraconic anhydride, benzoic acid and the carbon oxides.
  • Targeted suppression of the formation of these undesired by-products in favor of the value product leads to a further increase in the productivity and efficiency of the catalyst.
  • Corresponding considerations also apply to other catalysts, for example for the partial oxidation of other hydrocarbons.
  • An object of the present invention was therefore to develop a catalyst or a catalyst system which avoids the disadvantages of known catalysts of the prior art and allows an improvement in the activity, selectivity and / or lifetime of the catalyst.
  • a first aspect of the invention relates to the use of a titanium dioxide having a sulfur content, calculated as elemental sulfur, of less than about 1000 ppm for the preparation of a catalyst for the gas phase oxidation of hydrocarbons.
  • the catalyst preferably contains the titanium dioxide in the catalytically active composition.
  • WO03 / 081481 relates to titanium oxide purification processes for Fischer-Tropsch catalysts, i. for reactions under reductive conditions at high pressures, in which - in contrast to the present oxidation reactions - the formation of metal sulfides is a problem.
  • the content of the TiC> used is well 2 (calculated as elemental sulfur) of sulfur at less than about 900 ppm, more preferably less 750 ppm, preferably less than 500 ppm, more preferably less than about 300 ppm.
  • the advantages of the catalyst according to the invention containing TiO 2 with little contamination of sulfur are particularly evident when the TiO 2 has a BET surface area of at least 5 m 2 / g, in particular of at least 12 m 2 / g.
  • the BET surface area (DIN 66131) of the TiO 2 material used is preferably in the range between about 15 and 60 m 2 / g, in particular between 15 and 45 m 2 / g, more preferably between 15 and 35 m 2 / g.
  • niobium in the (low sulfur) titania used offers surprising advantages in catalysts for the gas phase oxidation of hydrocarbons.
  • the content of niobium (calculated as Nb) of the TiO 2 used is therefore more than about 500 ppm, in particular more than 1000 ppm.
  • a high activity can be achieved with high selectivity of the catalyst. This applies, for example, in the gas phase oxidation of o-xylene and / or naphthalene to phthalic anhydride with high catalyst activity and very high Ca selectivity or phthalic anhydride (PSA) selectivity.
  • PSA phthalic anhydride
  • niobium can be adjusted, for example, by the use of niobium acid or niobium oxal during the production of the TiO 2 . It has also been found in the context of the present invention that the low sulfur content and the high niobium content of the titanium dioxide interact favorably with the properties of the catalyst produced therewith.
  • the niobium is removed from the titanium dioxide in addition to the sulfur because of the selected treatment conditions, in particular the elevated temperature.
  • US Pat. No. 5,527,469 which also relates to a titanium dioxide precursor, titania hydrolyzate.
  • excessive removal of niobium is surprisingly disadvantageous according to the present invention.
  • the TiO 2 used has a content of phosphorus, calculated as elemental phosphorus, of a few - -
  • MSA maleic anhydride
  • the TiO 2 used according to the invention has both the low sulfur content and the above-described high niobium content and more preferably also the low P content as defined above.
  • TiC.sub.i materials having the above low P content exhibit better activity and selectivity than TiC.sub.3 even at a higher S content (more than about 1000 ppm) Materials which do not have the above low P content.
  • the TiO 2 used in the catalyst has the above specification with regard to the sulfur content and preferably also the niobium content and / or the phosphorus content.
  • the catalyst according to the invention is preferably predominantly, ie more than 50%, in particular more than 75%, more preferably more than 90%, in particular substantially or completely only TiO 2 material with the above specification included. Blends of various TiO 2 materials may also be used.
  • Suitable TiO 2 materials are commercially available or can be obtained by a person skilled in the art according to standard methods, provided that care is taken in the synthesis that the starting reagents or raw materials used contain correspondingly low impurities of sulfur (or preferably also phosphorus), and optionally already have a niobium content in the desired height.
  • the duration of the individual washing steps can also be varied. For example, a washing step may be carried out for 3 to 16 hours. After each washing step, the material may be separated from the respective washing solution in a conventional manner before the next washing step, for example by filtration. In order to reduce or avoid the removal of niobium, the washing steps are preferably not carried out at elevated temperature but, for example, at room temperature (20 ° C.) or below. After the last washing step, the material can be dried.
  • a method for determining the proportion of the impurities mentioned herein in the TiO 2 , in particular the S, P and Nb contents of the TiO 2 used is given below before the examples (DIN ISO 9964-3).
  • the active composition (catalytically active material) of the catalyst according to the invention contains titanium dioxide with a specific BET surface area and preferably a specific pore radius distribution, to which reference is made to the copending WO 2005/11615 A1 of the same applicant. Thereafter, it is preferred to use a titanium dioxide wherein at least 25%, more preferably at least about 40%, more preferably at least about 50%, most preferably at least about 60% of the total pore volume is formed by pores having a radius between 60 and 400 nm - -
  • a TiO 2 having a primary crystallite size (primary particle size) of greater than about 210 angstroms, preferably greater than about 250 angstroms, more preferably at least 300 angstroms, more preferably at least about 350 angstroms, more preferably at least 390 angstroms is used .
  • the primary crystallite size is preferably less than 900 angstroms, in particular less than 600 angstroms, more preferably less than 500 angstroms.
  • TiO 2 is used which has a bulk density of less than 1.0 g / ml, in particular less than 0.8 g / ml, more preferably less than about 0.6 g / ml. Most preferred are TiO 2 materials having a bulk density of not more than about 0.55 g / ml. A method for determining the bulk density is given in the method part below. It has thus been found that the use of a titanium dioxide having a bulk density as defined above enables the production of particularly powerful catalysts.
  • the bulk density here is a measure of a particularly favorable structure of the TiO 2 surface provided in the catalyst, whereby the looser, not too compact structure offers particularly favorable reaction spaces and feed and Ableitwege be provided for the reactants or reaction products.
  • the catalysts prepared using the titanium dioxide described herein can be used in various gas phase oxidation reactions of hydrocarbons.
  • gas phase oxidation also includes partial oxidation of the hydrocarbons. Particularly preferred is the use for the production of phthalic anhydride by gas phase oxidation of o-xylene, naphthalene or mixtures thereof.
  • a variety of other catalytic gas phase oxidations of aromatic hydrocarbons such as benzene, xylenes, naphthalene, toluene or durene are known in the art for the preparation of carboxylic acids and / or carboxylic anhydrides. For example, benzoic acid, maleic anhydride, isophthalic acid, terephthalic acid or pyromellitic anhydride are obtained. Also in such reactions, the catalyst of the invention can be used.
  • ammoxidation of alkanes and alkenes the ammoxidation of alkylaromatics and alkyl heteroaromatics to the corresponding cyano compounds, in particular the ammoxidation of 3-methylpyridine (b-picoline) to 3-cyano-pyridine, in the oxidation from 3-methylpyridine to nicotinic acid, in the oxidation of acenaphthene to naphthalic anhydride, or in the oxidation of durene to pyro- - -
  • a preferred use also includes the preparation of naphthalic anhydride from acenaphthene and the production of cyanopyridine from alkylpyridine (picoline) by ammoxidation, such as from 3-methylpyridine to 3-cyano-pyridine.
  • cyanopyridine alkylpyridine (picoline) by ammoxidation, such as from 3-methylpyridine to 3-cyano-pyridine.
  • suitable catalysts and reaction conditions can be found, for example, in Saurambaeva and Sembaev, Eurasian ChemTech Journal 5 (2003), S, 267-270.
  • An overview of the amm (oxidation) of methylpyridines can be found, for example, in R. Chuck , Applied Catalysis, A: General (2005), 280 (1), 75-82.
  • catalyst according to the invention or of the TiC> 2 as defined herein relate to oxidative dehydrogenations, for example of ethane, propane, butane, isobutane or longer-chain alkanes, to the respective alkenes.
  • the catalysts in particular for the above-described ammoxidation and oxidation reactions, can be unsupported catalysts or shell catalysts in the form of the shaped bodies and geometries known to the person skilled in the art. It is particularly advantageous if the active composition is applied to an inert carrier.
  • a tube bundle reactor which may consist of a plurality of parallel tubes, passed.
  • the reactor tubes is in each case a bed of at least one catalyst.
  • a bed of several (different) catalyst layers is advantageous.
  • the use of the catalysts according to the invention for the production of phthalic acid has been Anhydride by gas phase oxidation of o-xylene and / or naphthalene surprisingly found that the catalysts of the invention a high conversion with low formation of undesired by-products CO x , ie CO 2 and CO, is obtained. Furthermore, a very good C ⁇ ⁇ and PSA selectivities show, which in total increases the productivity of the catalyst. The low CO x - selectivity also results in an advantageous manner lower heat generation and lower hot spot temperatures. This leads to a slower deactivation of the catalyst in the hot spot area.
  • the indication of the total pore volume relates in each case to the total pore volume measured by means of mercury porosimetry between 7500 and 3.7 nm pore radius size.
  • titanium dioxide used for catalyst preparation may have the properties described herein, although this is not generally preferred.
  • the form of the catalyst or its homogeneous or heterogeneous structure is in principle not limited in the sense of the present invention and may include any embodiment familiar to the person skilled in the art and appearing suitable for the respective field of application.
  • inert carriers for example of quartz (SiO 2 ), porcelain, magnesium oxide, tin dioxide, silicon carbide, rutile, alumina (Al 2 O 3 ), aluminum silicate, magnesium silicate (steatite), zirconium silicate or cerium silicate, or of mixtures the above materials used.
  • the carrier may, for example, have the form of rings, balls, shells or hollow cylinders. Then the catalytically active material is applied in relatively thin layers (shells). It is also possible to apply two or more layers of the same or differently composed catalytically active composition.
  • the usual and conventional components in the active material of the catalyst may be included, wherein TiO 2 (including the impurities mentioned herein) preferably about 40 to 99 wt .-% of forms active mass of the catalyst.
  • the catalysts according to the invention preferably contain, in addition to TiO 2 , vanadium oxide.
  • oxides of niobium and / or antimony and / or further components such as Cs and / or P are included.
  • the catalysts or their active material contain:
  • V 2 O 5 0 - 30 wt .-%, in particular 1 - 30 wt .-%
  • TiO 2 (including the Ver40 to 99 wt .-%, impurities) in particular balance to 100 wt .-%
  • the prior art describes a number of promoters for increasing the productivity of the catalysts which can likewise be used in the catalyst according to the invention.
  • promoters for increasing the productivity of the catalysts which can likewise be used in the catalyst according to the invention.
  • These include, inter alia, the alkali and alkaline earth metals, thallium, antimony, phosphorus, iron, niobium, cobalt, molybdenum, silver, tungsten, tin, lead, zirconium, copper, gold and / or bismuth and mixtures of two or more of the above components.
  • DE 21 59 441 A describes a catalyst which, in addition to titanium dioxide of the anatase modification, consists of 1 to 30% by weight of vanadium pentoxide and zirconium dioxide.
  • the activity and selectivity of the catalysts can be influenced, in particular by lowering or increasing the activity.
  • the promoters which increase the selectivity include, for example, the alkali metal oxides, whereas oxidic phosphorus compounds, in particular phosphorus pentoxide, can lower the activity of the catalyst at the expense of selectivity, depending on the degree of promotion.
  • Shell catalysts can be referred, for example, to the process described in DE-A-16 42 938 or DE-A 17 69 998, in which an aqueous or organic solvent-containing solution or suspension of the components of the catalytically active material and / or their precursor compounds (often referred to as "mash") are sprayed onto the support material in a heated coating drum at elevated temperature until the desired level of catalytically active mass, based on the total catalyst weight, is reached.
  • an aqueous or organic solvent-containing solution or suspension of the components of the catalytically active material and / or their precursor compounds (often referred to as "mash") are sprayed onto the support material in a heated coating drum at elevated temperature until the desired level of catalytically active mass, based on the total catalyst weight, is reached.
  • so-called shell catalysts are prepared by applying a thin layer of 50 to 500 ⁇ m of the active components to an inert support (e.g., U.S. 2,035,606).
  • an inert support e.g., U.S. 2,035,606
  • balls or hollow cylinders have been proven.
  • the molten and sintered molded articles must be heat-resistant within the temperature range of the proceeding reaction.
  • the advantage of coating carrier bodies in a fluidized bed is the high uniformity of the layer thickness, which plays a decisive role for the catalytic performance of the catalyst.
  • a particularly uniform coating is obtained by spraying a suspension or solution of the active components on the heated support at 80 to 200 ° C in a fluidized bed, for example according to DE 12 80 756, DE 198 28 583 or DE 197 09 589.
  • Drag drums can be used
  • Use of hollow cylinders as a carrier in said fluidized bed process the inside of the hollow cylinder are uniformly coated.
  • the method according to DE 197 09 589 is of particular advantage since, in addition to a uniform coating, a slight abrasion of parts of the apparatus is achieved by the predominantly horizontal, circular movement of the carrier.
  • the aqueous solution or suspension of the active components and an organic binder preferably a copolymer of vinyl acetate / vinyl laurate, vinyl acetate / ethylene or styrene / acrylate, sprayed via one or more nozzles on the heated, fluidized carrier. It is particularly advantageous to give up the spray liquid at the place of the highest product speed, whereby the spray can be evenly distributed in the bed. The spraying process is continued until either the suspension has been consumed or the required amount of active components has been applied to the carrier.
  • an organic binder preferably a copolymer of vinyl acetate / vinyl laurate, vinyl acetate / ethylene or styrene / acrylate
  • the catalytically active composition of the catalyst according to the invention containing the TiO 2 as defined herein is applied in a fluidized bed or fluidized bed with the aid of suitable binders, so that a coated catalyst is produced.
  • suitable binders include organic binders known to the person skilled in the art, preferably copolymers, advantageously in the form of an aqueous dispersion, of vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / maleate and also vinyl acetate / ethylene.
  • an organic polymeric or copolymeric adhesive in particular a vinyl acetate copolymer adhesive, is used as the binder.
  • the binder used is added in conventional amounts of the catalytically active composition, for example about 10 to 20 _
  • Wt .-% based on the solids content of the catalytically active material.
  • application to the carrier is possible even without organic binders.
  • the binder used burn out during heating of the catalyst at startup of the filled reactor within a short time.
  • the binders serve primarily to enhance the adhesion of the catalytically active material to the carrier and to reduce abrasion during transport and filling of the catalyst.
  • a powder is first prepared from a solution and / or a suspension of the catalytically active metal oxides and / or their precursor compounds, optionally in the presence of auxiliaries for catalyst preparation, which is then used for catalyst preparation on the support, optionally after conditioning and optionally after heat treatment to produce the catalytically active metal oxides shell-shaped and subjected to the thus coated support a heat treatment to produce the catalytically active metal oxides or a treatment for devolatilization.
  • the catalysts in the reaction tubes of the reactor which are thermostated from the outside to the reaction temperature, for example by means of salt melts filled.
  • the reaction gas at temperatures of generally from 300 to 450 0 C, preferably 320 to 420 0 C, and particularly preferably from 340 to 400 0 C and at an overpressure of generally 0.1 to 2.5, preferably from 0.3 to 1.5 bar at a space velocity of generally 750 to 5000 h "1 passed .
  • the reaction gas supplied to the catalyst is preferably produced generally by mixing a molecular oxygen-containing gas which may contain, besides oxygen, still suitable reaction moderators and / or diluents such as steam, carbon dioxide and / or nitrogen, with the aromatic hydrocarbon to be oxidized, the molecular oxygen-containing gas generally 1 to 100, preferably 2 to 50 and particularly preferably 10 to 30 mol% oxygen, 0 to 30, preferably 0 to 10 mol% water vapor and 0 to 50, preferably 0 to 1 mol% Carbon dioxide, balance nitrogen, may contain.
  • the catalyst has an active composition content of between about 7 and 12% by weight, preferably between 8 and 10% by weight.
  • the active material (catalytically active composition) preferably contains between 5 to 15% by weight of V 2 O 5 , 0 to 4% by weight of Sb 2 O 3 , 0.2 to 0.75% by weight of Cs, 0 to 3% by weight .-% Nb 2 O 5 contains.
  • the remainder of the active composition is at least 90 wt .-%, preferably at least 95 wt .-%, more preferably at least 98 wt .-%, in particular at least 99 wt .-%, more preferably at least 99.5 wt. -%, In particular 100 wt .-% of TiO 2 .
  • Such a catalyst according to the invention can be used, for example, advantageously in a two- or multi-layer catalyst as the first catalyst layer located toward the gas inlet side.
  • the BET surface area of the catalyst is between 15 and about 25 m 2 / g. Furthermore, it is preferred that such a first catalyst layer has a length fraction of about 40 to 60% of the total length of all existing catalyst layers (total length of the existing catalyst bed).
  • the catalyst has an active composition content of about 6 to 11 wt .-%, in particular 7 to 9 wt .-% to.
  • the active composition preferably contains 5 to 15% by weight of V 2 O 5 , 0 to 4% by weight of Sb 2 O 3 , 0.05 to 0.3% by weight of Cs, 0 to 2% by weight of Nb 2 O contains 5 and 0 - 2 wt .-% phosphorus.
  • the remainder of the active composition is at least 90 wt .-%, preferably at least 95 wt .-%, more preferably at least 98 wt .-%, in particular at least 99 wt .-%, more preferably at least 99.5 Wt .-%, in particular 100 wt .-% of TiO 2 .
  • a catalyst according to the invention can be used, for example, advantageously as a second catalyst layer, ie downstream of the first catalyst layer located toward the gas inlet side (see above). It is preferred that the catalyst has a BET surface area between about 15 and 25 m 2 / g. Furthermore, it is preferred that this second layer occupies a length fraction of about 10 to 30% of the total length of all existing catalyst layers.
  • the catalyst has an active composition content of between about 5 and 10% by weight, in particular between 6 and 8% by weight.
  • the active composition (catalytically active composition) preferably contains 5 to 15% by weight of V 2 O 5 , 0 to 4% by weight of Sb 2 O 3 , 0 to 0.1% by weight of Cs, 0 to 1% by weight. % Nb 2 O 5 and 0-2 wt% phosphorus.
  • the remainder of the active composition is at least 90 wt .-%, preferably at least 95 wt .-%, more preferably at least 98 wt .-%, in particular at least 99 wt .-%, more preferably at least 99.5 wt.
  • such a catalyst can advantageously be used as the third, (or last) catalyst layer arranged downstream of the second catalyst layer described above.
  • a BET surface area of the catalyst which is somewhat higher than that of the layers closer to the gas inlet side, in particular in the range between about 25 to about 45 m 2 / g, is preferred.
  • such a third catalyst layer occupies a length fraction of about 10 to 50% of the total length of all existing catalyst layers.
  • the first catalyst layer located towards the gas inlet side has a length fraction, based on the total length of the catalyst bed, of at least 40%, in particular at least 45%, particularly preferably at least 50%. It is particularly preferred that the proportion of the first catalyst layer in the total length of the catalyst bed is between 40 and 70%, in particular between 40 and 55%, particularly preferably between 40 and 52%.
  • the first catalyst layer has a length fraction, based on the total length of the catalyst bed, between about 10% and 20%.
  • the length fraction of the second catalyst layer is preferably between about 40% and 60%, based on the total length of the catalyst bed.
  • the length fraction of the third or fourth catalyst layer is preferably between about 15% and 40%, based on the total length of the catalyst bed.
  • the second layer preferably occupies about 10 to 40%, in particular about 10 to 30% of the total length of the catalyst bed. Furthermore, it has surprisingly been found that a ratio of the length of the third catalyst layer to the length of the second catalyst layer is between about 1 and 2, in particular between 1.2 and 1.7, particularly preferably between 1.3 and 1.6, particularly good results with regard to the economy such as the efficiency of raw material utilization and productivity of the catalyst provides.
  • the content of alkali metals in the catalyst layers is preferred from the gas inlet side to the gas outlet side when using the catalyst prepared according to the invention in a multi-layer catalyst bed for the preparation of phthalic anhydride.
  • the alkali content, preferably the Cs content (calculated as Cs) in the second catalyst layer is smaller than in the first catalyst layer, and in the third catalyst layer smaller than in the second catalyst layer (and preferably, if necessary, on the third Location following locations).
  • the Cs content (calculated as Cs) in the catalyst therefore particularly preferably decreases from layer to layer in the gas flow direction.
  • the third (and preferably also optionally subsequent catalyst layers) contains no Cs.
  • the last catalyst layer has no Cs.
  • only the last catalyst layer has phosphorus.
  • the active composition in the 1st layer and in the 2nd layer, and in a 4-layer catalyst preferably also in the 3rd catalyst layer no phosphorus. (By "no phosphorus" is meant that in the preparation no P active was added to the active mass).
  • the active material content decreases from the first catalyst layer located towards the gas inlet side to the catalyst layer located toward the gas outlet side.
  • the first catalyst layer has an active material content between about 7 and 12 wt .-%, in particular between about 8 and 11 wt .-%
  • the second catalyst layer has an active material content between about 6 and 11 wt .-% , in particular between about 7 and 10 wt .-%
  • the third catalyst layer has an active material content of between about 5 and 10 wt .-%, in particular between about 6 and 9 wt .-%, having.
  • first, second and third catalyst layer are used in the context of the present invention as follows: as the first catalyst layer, the catalyst inlet to the gas inlet side is referred to. To the gas outlet side, two further catalyst layers are contained in the catalyst according to the invention, which are referred to as second or third catalyst layer. The third catalyst layer is closer to the gas outlet side than the second catalyst layer.
  • the catalyst has three or four catalyst layers.
  • the third catalyst layer is located on the gas outlet side.
  • additional catalyst layers downstream of the first catalyst layer is not excluded.
  • the third catalyst layer as defined herein may be followed by a fourth catalyst layer (preferably with an identical or even lower active material content than the third catalyst layer).
  • the active material content between the first and the second catalyst layer and / or between the second and the third catalyst layer may decrease.
  • the active material content decreases between the second and the third catalyst layer.
  • the BET surface area increases from the first catalyst layer located towards the gas inlet side to the third catalyst layer located toward the gas outlet side. Preferred ranges for the BET surface area are 15 to 25 m 2 / g for the first catalyst layer, 15 to 25 m 2 / g for the second catalyst layer and 25 to 45 m 2 / g for the third catalyst layer.
  • the BET surface area of the first catalyst layer is lower than the BET surface area of the third catalyst layer.
  • Particularly advantageous catalysts are also obtained when the BET surface areas of the first and the second catalyst layer are the same, whereas the BET surface area of the third catalyst layer is larger.
  • the catalyst activity to the gas inlet side is according to a preferred embodiment of the invention less than the catalyst activity towards the gas outlet side. It is further preferred that at least 0.05 wt .-% of the catalytically active material by at least one alkali metal, calculated as alkali metal (s), is formed. Particularly preferred cesium is used as the alkali metal.
  • the catalyst contains a total of niobium in an amount of 0.01 to 2 wt .-%, in particular 0.5 to 1 wt .-% of the catalytically active material.
  • the catalysts according to the invention are temperature-treated or calcined (conditioned) in the customary manner before use. It has been found to be advantageous if the catalyst for at least 24 hours at least 390 0 C, especially between 24 and 72 hours at least 400 0 C, in an oil-containing gas, especially in air, is calcined.
  • the temperatures should preferably not exceed about 500 ° C., in particular about 470 ° C. In principle, however, other calcination conditions which appear to the person skilled in the art are not excluded.
  • the present invention relates to a process for the preparation of a catalyst according to any one of the preceding claims, comprising the following steps:
  • the present invention also relates to the use of a titanium dioxide as defined above for the preparation of a catalyst, in particular for the gas phase oxidation of hydrocarbons, preferably for the gas phase oxidation of o-xylene and / or naphthalene to phthalic anhydride.
  • the present invention relates to a process for the gas phase oxidation of at least one hydrocarbon, wherein:
  • the catalyst is contacted with a gas stream containing the at least one hydrocarbon and oxygen
  • the process is a process for the production of phthalic anhydride from o-xylene and / or naphthalene.
  • the pore radius distribution and the pore volume of the TiO 2 used were determined by means of mercury porosimetry according to DIN 66133; maximum pressure: 2,000 bar, Porosimeter 4000 (Porotec, DE), according to the manufacturer's instructions.
  • the determination of the primary crystallite sizes was carried out by means of powder X-ray diffractometry.
  • the analysis was carried out with a device from Bruker, DE, type BRUKER AXS-D4 Endeavor.
  • the obtained X-ray diffractograms were recorded with the software package "DiffracPlus D4 Measurement” according to the manufacturer's instructions and the half-width of the 100% reflex was evaluated with the software "DiffracPlus Evaluation" according to the Debye-Scherrer formula according to the manufacturer's instructions Primary crystallite size to be determined.
  • the particle sizes were determined according to the laser diffraction method using a Fritsch Particle Sizer Analysette 22 Economy (Fritsch, DE) according to the manufacturer's instructions, also with regard to sample pretreatment: the sample is homogenized in deionized water without addition of auxiliaries and ultrasonically for 5 minutes treated.
  • the determination of the chemical impurities of the TiO 2 in particular the contents of S, P and Nb is carried out according to DIN ISO 9964-3.
  • the contents can be determined by means of ICP-AES (Inductively Coupled Plasma Atomic Emission Spectroscopy) and possibly added in the case of alkali to the total alkali content of TiO2. - -
  • the bulk density was (dried at 150 0 C in a vacuum, uncalcined) based on the used for preparing the catalyst TiO 2 determined. The values obtained from three determinations were averaged.
  • the bulk density was determined by placing 100 g of the TiO 2 material in a 1,000 ml can and shaking for about 30 seconds.
  • a measuring cylinder (capacity exactly 100ml) is weighed empty to 10 mg. Then the powder funnel with stand and clamp is fastened over the opening of the cylinder. After starting the stopwatch, the measuring cylinder is filled with the TiO 2 material within 15 seconds. With the spatula filling is poured continuously, so that the measuring cylinder is always filled slightly protruding. After 2 minutes, the supernatant is wiped off with the spatula, whereby it must be ensured that no pressing forces condense the material in the cylinder. The filled measuring cylinder is brushed off and weighed.
  • the determination of the BET surface area, the pore radius distribution or the pore volume as well as the primary crystallite sizes and the particle size distribution was carried out with respect to the titanium dioxide in each case at the uncalcined material dried at 150 ° C. under reduced pressure.
  • the data in the present specification with respect to the BET surface areas of the catalysts or catalyst layers refer to the BET surface areas of each TiO 2 material used (dried in vacuum at 150 0 C, uncalcined. See above).
  • the BET surface area of the catalyst is determined by the BET surface area of the TiC 2 used , wherein the BET surface area is changed to a certain extent by the addition of further catalytically active components. This is familiar to the expert.
  • the proportion of active mass (proportion of the catalytically active composition, without binder) in each case refers to the proportion (in% by weight) of the catalytically active composition in the total weight of the catalyst, including support in the respective catalyst layer, measured after conditioning for 4 hours at 400 ° C. ,
  • the catalyst B For the preparation of the catalyst B with an active material content of 8 wt .-% and the composition of 7.5 wt .-% vanadium pentoxide, 3.2 wt .-% antimony trioxide, 0.40 wt .-% cesium (calculated as cesium ), 0.2 wt .-% phosphorus (calculated as phosphorus) and the rest titanium dioxide were then in a so-called fluidized bed coater 2200 g steatite body in the form of hollow cylinders of size 8 x 6 x 5 mm with a suspension of 15.1 g vanadium pentoxide, 6.4 g antimony trioxide, 1.1 g cesium sulfate, 1.5 g ammonium dihydrogen phosphate, 178.6 g of the titanium dioxide washed as described above (BET surface area 19 m 2 / g), 120.5 g inland - -
  • TiC> 2 Before the actual preparation of the catalyst C were 200 g of TiC> 2 already washed in Example 2 TiC> 2 in each of several washing and Filtrier suitsen first with 1 molar nitric acid, bidistilled water, 1 molar ammonia water and finally again with bidistilled water for Washed with stirring for 12 h and filtered off. Finally, the sample was dried.
  • the washed TiO 2 material had the following chemical impurities:
  • the catalyst C with an active material content of 8 wt .-% and the composition of 7.5 wt .-% vanadium pentoxide, 3.2 wt .-% antimony trioxide, 0.40 wt .-% cesium (calculated as cesium ), 0.2 wt .-% phosphorus (calculated as phosphorus) and the rest titanium dioxide were then in a so-called fluidized bed coater 2200 g steatite body in the form of hollow cylinders of size 8 x 6 x 5 mm with a suspension of 15, 1 g vanadium pentoxide, 6.4 g antimony trioxide, 1.1 g cesium sulfate, 1.5 g ammonium dihydrogen phosphate, 178.6 g of the titanium dioxide washed as described above (BET surface area 19 m 2 / g), 120.5 g Binder from a 50% dispersion of water and vinyl acetate / ethylene copolymer
  • the catalyst D with an active material content of 8 wt .-% and the composition of 7.5 wt .-% vanadium pentoxide, 3.2 wt .-% antimony trioxide, 0.40 wt .-% cesium (calculated as cesium ), 0.2 wt .-% phosphorus (calculated as phosphorus) and the rest titanium dioxide were then in a so-called fluidized bed coater 2200 g steatite body in the form of hollow cylinders of size 8 x 6 x 5 mm with a suspension of 15.1 g vanadium pentoxide, 6.4 g antimony trioxide, 1.1 g cesium sulfate, 1.5 g ammonium dihydrogen phosphate, 178.6 g of the titanium dioxide washed as described above (BET surface area 19 m 2 / g), 120.5 g Binder from a 50% dispersion of water and vinyl acetate / ethylene copolymer
  • the catalysts B, C and D are used in parallel test runs.
  • the results of the test runs are listed in Table 1.
  • C 8 selectivity selectivity with respect to all valuable products with 8 carbon atoms (phthalic anhydride, phthalide, o-tolualdehyde, o-toluic acid)
  • the catalyst E For the preparation of the catalyst E with an active material content of 8 wt .-% and the composition of 7.5 wt .-% vanadium pentoxide, 3.2 wt .-% antimony trioxide, 0.40 wt .-% cesium (calculated as cesium ), 0.2 wt .-% phosphorus (calculated as phosphorus) and the rest titanium dioxide were in a so-called fluidized bed coater 2200 g Steatit stresses in the form of hollow cylinders of size 8 x 6 x 5 mm with a suspension of 15.1 g Vanadium pentoxide, 6.4 g antimony trioxide, 1.1 g cesium sulfate, 1.5 g ammonium dihydrogen phosphate, 178.6 g of a commercially available titanium dioxide having a BET surface area of 20 m 2 / g and the following chemical impurities
  • Example 7 Preparation of Catalyst F (Inventive)
  • the catalyst F For the preparation of the catalyst F with an active material content of 8 wt .-% and the composition of 7.5 wt .-% vanadium pentoxide, 3.2 wt .-% antimony trioxide, 0.40 wt .-% cesium (calculated as cesium ), 0.2 wt .-% phosphorus (calculated as phosphorus) and the rest titanium dioxide were in a so-called fluidized bed coater 2200 g Steatit stresses in the form of hollow cylinders of size 8 x 6 x 5 mm with a suspension of 15.1 g Vanadium pentoxide, 6, 4 g of antimony trioxide, 1.1 g of cesium sulfate, 1.5 g of ammonium dihydrogen phosphate, 178.6 g of titanium dioxide having a BET surface area of 19 m 2 / g (obtained by washing steps according to Example 2 from another commercially available TiO 2 ) and the following chemical impurities
  • the catalyst G with an active material content of 8% by weight and the composition of 7.5% by weight of vanadium pentoxide, 3.2% by weight of antimony trioxide, 0.40% by weight of cesium (calculated as cesium), 0.2% by weight of phosphorus (calculated as phosphorus) and the remainder titanium dioxide were in a so-called fluid bed coater 2200 g steatite body in the form of hollow cylinders of size 8 x 6 x 5 mm with a suspension of 15.1 g of vanadium pentoxide, 6 4 g antimony trioxide, 1.1 g cesium sulfate, 1.5 g ammonium dihydrogen phosphate, 178.6 g titanium dioxide with a BET surface area of 20 m 2 / g (obtained by washing steps according to Example 2 from another commercially available TiC> 2 ) and the following chemical impurities
  • the catalyst H For the preparation of the catalyst H with an active material content of 8 wt .-% and the composition of 7.5 wt .-% vanadium pentoxide, 3.2 wt .-% antimony trioxide, 0.40 wt .-% cesium (calculated as cesium ), 0.2% by weight of phosphorus (calculated as phosphorus) and the remainder of titanium dioxide 2200 g of steatite in the form of hollow cylinders of size 8 ⁇ 6 ⁇ 5 mm with a suspension of 15.1 g of vanadium pentoxide were used in a so-called fluid bed coater.
  • the catalysts F, G and H are used in parallel test runs.
  • the results of the test runs are listed in Table 2.
  • C 8 selectivity selectivity with respect to all value-added products with 8 carbon atoms (phthalic anhydride, phthalide, o-tolualdehyde, o-toluic acid)
  • CO x sum of carbon monoxide and dioxide in the exhaust gas stream
  • PSA phthalic anhydride
  • MSA maleic anhydride
  • Example 11 Preparation of a three-layer catalyst according to the invention
  • a three-layer catalyst according to the invention can be obtained, for example, as follows:
  • a catalyst K having an active composition content of 8% by weight and the composition of 7.5% by weight of vanadium pentoxide, 3.2% by weight of antimony trioxide, 0.20% by weight of cesium (calculated as cesium), 0.2% by weight of phosphorus (calculated as phosphorus) and the remainder of titanium dioxide (as in Example 3) were in a so-called fluidized bed coater 2200 g SteatitMech in the form of hollow cylinders of size 8 x 6 x 5 mm with a suspension of 15.1 g of vanadium pentoxide, 6.4 g of antimony trioxide, 0.5 g of cesium sulfate, 1.5 g of ammonium dihydrogen phosphate, 179 g of titanium dioxide having a BET surface area of 19 m 2 / g, 120 g of a 50% binder Dispersion of water and vinyl acetate / ethylene copolymer (Vinnapas ® EP 65 W, Wacker) and 1000
  • a catalyst L having an active composition content of 8% by weight and the composition of 11% by weight of vanadium pentoxide, 0.35% by weight of phosphorus (calculated as phosphorus) and the remainder titanium dioxide (as in Example 3) 2200 g of steatite body in the form of hollow cylinders of the size 8 ⁇ 6 ⁇ 5 mm with a suspension of 22.2 g of vanadium pentoxide, 2.6 g of ammonium dihydrogen phosphate, 178.5 g of titanium dioxide in a so-called fluidized-bed coater Surface of 19 m 2 / g, 120 g of binder from a 50% dispersion of water and vinyl acetate / ethylene copolymer (Vinnapas ® EP 65 W, Wacker) and 1000 g of water at a temperature of 70 0 C coated.
  • the active composition was applied in the form of thin layers.
  • the sequence of catalyst layers 140 cm of the catalyst J, 60 cm of the catalyst K, 90 cm of the catalyst L.
  • Example 12 Catalytic Performance Data of the Three-Layer Catalyst of the Invention
  • reaction tube 90 cm of the catalyst L 60 cm of the catalyst K and 140 cm of the catalyst J are successively filled.
  • the reaction tube is in a liquid molten salt, which can be heated to temperatures up to 450 0 C.
  • the catalyst bed is a 3 mm thermowell with built-in thermocouple, over which the catalyst temperature can be displayed over the complete catalyst combination.
  • 3 o-xylene purity 99.9% is added via this catalyst combination in the order of DEF from 0 to a maximum of 70 g / Nm 3.
  • the crude yield is determined as follows.
  • the catalyst according to the invention according to Example 12 shows a very good PSA yield and PSA quality.
  • the hot spot is advantageously positioned in the first catalyst layer.

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Abstract

La présente invention concerne l'utilisation d'un dioxyde de titane présentant une teneur en soufre, calculée en soufre élémentaire, inférieure à environ 1 000 ppm et une surface BET d'au moins 5 m<SUP>2</SUP>/g dans la production d'un catalyseur permettant l'oxydation en phase gazeuse d'hydrocarbures, en particulier l'oxydation en phase gazeuse d'o-xylène et/ou de naphtaline. Cette invention concerne également un procédé préféré de production d'un tel catalyseur.
EP07725469A 2006-05-23 2007-05-23 Utilisation et procédé d'utilisation d'un catalyseur contenant un dioxyde de titane, en particulier dans la production d'anhydride phtalique Withdrawn EP2032517A1 (fr)

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EP07725469A EP2032517A1 (fr) 2006-05-23 2007-05-23 Utilisation et procédé d'utilisation d'un catalyseur contenant un dioxyde de titane, en particulier dans la production d'anhydride phtalique

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EP06010681A EP1860091A1 (fr) 2006-05-23 2006-05-23 Catalyseur contenant de l'oxyde de titane, en particulier pour la production de l'acide phtalique
PCT/EP2007/004569 WO2007134849A1 (fr) 2006-05-23 2007-05-23 Utilisation et procédé d'utilisation d'un catalyseur contenant un dioxyde de titane, en particulier dans la production d'anhydride phtalique
EP07725469A EP2032517A1 (fr) 2006-05-23 2007-05-23 Utilisation et procédé d'utilisation d'un catalyseur contenant un dioxyde de titane, en particulier dans la production d'anhydride phtalique

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EP07725469A Withdrawn EP2032517A1 (fr) 2006-05-23 2007-05-23 Utilisation et procédé d'utilisation d'un catalyseur contenant un dioxyde de titane, en particulier dans la production d'anhydride phtalique

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TWI429623B (zh) 2014-03-11
TW200812954A (en) 2008-03-16
BRPI0712570A2 (pt) 2012-11-20
RU2434840C2 (ru) 2011-11-27
WO2007134849A1 (fr) 2007-11-29
JP5130450B2 (ja) 2013-01-30
EP1860091A1 (fr) 2007-11-28
CN101443304A (zh) 2009-05-27
ZA200807947B (en) 2009-11-25
CN101443304B (zh) 2013-10-16
KR101109381B1 (ko) 2012-01-30
JP2009537314A (ja) 2009-10-29
KR20090017630A (ko) 2009-02-18
RU2008150849A (ru) 2010-06-27
US20090312562A1 (en) 2009-12-17

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