WO2012014154A1 - Catalyst for oxidation of o-xylene and/or naphthalene to phthalic anhydride - Google Patents

Catalyst for oxidation of o-xylene and/or naphthalene to phthalic anhydride Download PDF

Info

Publication number
WO2012014154A1
WO2012014154A1 PCT/IB2011/053327 IB2011053327W WO2012014154A1 WO 2012014154 A1 WO2012014154 A1 WO 2012014154A1 IB 2011053327 W IB2011053327 W IB 2011053327W WO 2012014154 A1 WO2012014154 A1 WO 2012014154A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
xylene
oxidation
oxide
weight
Prior art date
Application number
PCT/IB2011/053327
Other languages
French (fr)
Inventor
Stefan Altwasser
Jürgen ZÜHLKE
Frank Rosowski
Michael Krämer
Original Assignee
Basf Se
Basf (China) Company Limited
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, Basf (China) Company Limited filed Critical Basf Se
Priority to EP11811912.2A priority Critical patent/EP2598238A4/en
Priority to CN201180035813.9A priority patent/CN103025424B/en
Priority to BR112013001388A priority patent/BR112013001388A2/en
Priority to KR1020137004810A priority patent/KR20130131306A/en
Priority to JP2013522327A priority patent/JP5973436B2/en
Publication of WO2012014154A1 publication Critical patent/WO2012014154A1/en

Links

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
    • 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
    • B01J23/18—Arsenic, antimony or bismuth
    • 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
    • B01J23/22—Vanadium
    • B01J35/30—
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
    • 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

Definitions

  • the present invention relates to a catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride, which has a plurality of catalyst zones which are arranged in series in the reaction tube and have been produced using an antimony trioxide which comprises a significant proportion of valentinite.
  • the present invention further relates to a process for gas-phase oxidation, in which a gas stream comprising at least one hydrocarbon and molecular oxygen is passed through a catalyst produced using an antimony trioxide which comprises a significant proportion of valentinite.
  • carboxylic acids and/or carboxylic anhydrides are prepared industrially by catalytic gas- phase oxidation of hydrocarbons such as benzene, xylenes, naphthalene, toluene or durene in fixed-bed reactors.
  • hydrocarbons such as benzene, xylenes, naphthalene, toluene or durene
  • benzoic acid maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid or pyromellitic anhydride.
  • a mixture of an oxygen-comprising gas and the starting material to be oxidized is passed through tubes in which a bed of a catalyst is present. To regulate the temperature, the tubes are surrounded by a heat transfer medium, for example a salt melt.
  • Coated catalysts in which the catalytically active composition has been applied in the form of a shell to an inert support material such as steatite have been found to be useful as catalysts for these oxidation reactions.
  • the catalysts have a layer of active composition which has an essentially homogeneous chemical constitution and has been applied in the form of a shell.
  • two or more different layers of active composition can be applied in succession to a support. These are then referred to as two-layer or multilayer catalysts (see, for example, DE 19839001 A1 ).
  • catalytically active constituents of the catalytically active composition of these coated catalysts use is generally made of titanium dioxide and vanadium pentoxide. Furthermore, small amounts of many other oxidic compounds which act as promoters to influence the activity and selectivity of the catalyst, including cesium oxide, phosphorus oxide and antimony oxide, can be present in the catalytically active composition. Catalysts giving a particularly high PAn yield can, according to EP 1636161 , be obtained when particular V20s Sb203 ratios are set and the antimony trioxide has a defined average particle size.
  • antimony oxides leads to an increase in the PAn selectivity; the effect is considered to be separation of the vanadium sites.
  • the antimony oxides used in the active composition of the catalysts can be various antimony oxides.
  • antimony(lll), antimony(IV) and antimony(V) compounds antimony trioxide or antimony pentoxide are usually used.
  • EP 522871 describes the use of antimony pentoxide, US
  • antimony trioxide Compared to antimony tetroxide and antimony pentoxide, antimony trioxide has the ability to spread better on titanium dioxide, so that significantly improved distribution of the catalyst is achieved. Antimony trioxide is typically used as pure senarmontite phase (cf. Schubert, U.-A. et al., Topics in Catalysis, 2001 , vol. 15(2-4), pages 195 to 200). Apart from the cubic
  • This object is achieved by a catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride, which has been produced using an antimony trioxide which comprises a significant proportion of valentinite.
  • the signal height is given by the difference between the maximum intensity of the respective signal and the background determined.
  • the antimony trioxide to be used according to the invention having a significant valentinite content can be used for producing one or more catalyst zones.
  • the catalyst has three, four or five zones, with antimony trioxide having a significant valentinite content having been used for producing at least one zone.
  • the catalysts of the invention can, for example to avoid high hot spot temperatures, also be used in combination with suitable upstream and/or downstream beds and also together with intermediate zones, with the upstream and/or downstream beds and the intermediate zones generally being able to comprise catalytically inactive or less active material.
  • the catalysts of the invention are generally coated catalysts in which the catalytically active composition has been applied in the form of a shell to an inert support material.
  • inert support material it is possible to use virtually all support materials of the prior art as are advantageously used in the production of coated catalysts for the oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and/or carboxylic anhydrides, for example quartz (S1O2), porcelain, magnesium oxide, tin dioxide, silicon carbide, rutile, alumina (AI2O3), aluminum silicate, steatite (magnesium silicate), zirconium silicate, cerium silicate or mixtures of these support materials.
  • the catalyst supports can, for example, be used in the form of spheres, rings, pellets, spirals, tubes, extrudates or crushed material.
  • These catalyst supports correspond to those of catalyst supports usually used for producing coated catalysts for gas-phase reactions of aromatic hydrocarbons. Preference is given to using steatite in the form of spheres having a diameter of from 3 to 6 mm or of rings having an external diameter of from 5 to 9 mm and a length of from 3 to 8 mm and a wall thickness of from 1 to 2 mm.
  • the catalysts of the invention comprise a catalytically active composition which comprises at least vanadium oxide and titanium dioxide and can be applied in one or more layers to the support material.
  • Various layers can in this case differ in terms of their chemical constitution.
  • the catalytically active composition preferably comprises, based on the total amount of the catalytically active composition, from 1 to 40% by weight of vanadium oxide, calculated as V2O5, and from 60 to 99% by weight of titanium dioxide, calculated as T1O2.
  • the catalytically active composition can, in preferred embodiments, additionally comprise up to 1 % by weight of a cesium compound, calculated as Cs, up to 1 % by weight of a phosphorus compound, calculated as P, and up to 10% by weight of antimony oxide, calculated as Sb2C"3. All figures relating to the chemical constitution of the catalytically active composition are based on the calcined state of the latter, e.g. after calcination of the catalyst for one hour at 450°C.
  • Titanium dioxide is usually used in the anatase form for the catalytically active composition.
  • the titanium dioxide preferably has a BET surface area of from 15 to 60 m 2 /g, in particular from 15 to 45 m 2 /g, particularly preferably from 13 to 28 m 2 /g.
  • the titanium dioxide used can be an individual titanium dioxide or a mixture of titanium dioxides. In the latter case, the magnitude of the BET surface area as weighted average determines the contributions of the individual titanium dioxides.
  • the titanium dioxide used is, for example, advantageously a mixture of a T1O2 having a BET surface area of from 5 to 15 m 2 /g and a T1O2 having a BET surface area of from 15 to 50 m 2 /g.
  • Suitable vanadium sources are, in particular, vanadium pentoxide or ammonium metavanadate.
  • Suitable antimony sources are various antimony trioxides which have a significant valentinite content.
  • Possible phosphorus sources are, in particular, phosphoric acid, phosphorous acid, hypophosphorous acid, ammonium phosphate or phosphoric esters and especially ammonium dihydrogenphosphate.
  • Suitable sources of cesium are the oxide or hydroxide or the salts which can be converted thermally into the oxide, e.g. carboxylates, in particular the acetate, malonate or oxalate, carbonate, hydrogencarbonate, sulfate or nitrate.
  • the catalytically active composition can comprise small amounts of many other oxidic compounds which act as promoters to influence the activity and selectivity of the catalyst, for example by decreasing or increasing its activity.
  • promoters are the alkali metals, in particular lithium, potassium and rubidium in addition to the abovementioned cesium, which are usually used in the form of their oxides or hydroxides, thallium(l) oxide, aluminum oxide, zirconium oxide, iron oxide, nickel oxide, cobalt oxide, manganese oxide, tin oxide, silver oxide, copper oxide, chromium oxide, molybdenum oxide, tungsten oxide, iridium oxide, tantalum oxide, niobium oxide, arsenic oxide, antimony tetroxide, antimony pentoxide and cerium oxide.
  • oxides of niobium and tungsten as additives in amounts of from 0.01 to 0.50% by weight, based on the catalytically active composition.
  • the application of the layer(s) of the coated catalyst is advantageously carried out by spraying a suspension of T1O2 and V2O5, which optionally comprises sources of the abovementioned promoter elements, onto the fluidized support.
  • the suspension is preferably stirred for a sufficiently long time, e.g. from 2 to 30 hours, in particular from 12 to 25 hours, in order to break up agglomerates of the suspended solids and obtain a homogeneous
  • the suspension typically has a solids content of from 20 to 50% by weight.
  • the suspension medium is generally aqueous, e.g. water itself or an aqueous mixture with a water- miscible organic solvent such as methanol, ethanol, isopropanol, formamide and the like.
  • organic binders preferably copolymers, advantageously in the form of an aqueous dispersion, of acrylic acid-maleic acid, vinyl acetate-vinyl laurate, vinyl acetate-acrylate, styrene- acrylate and vinyl acetate-ethylene, are added to the suspension.
  • the binders are commercially available as aqueous dispersions having a solids content of, for example, from 35 to 65% by weight.
  • the amount of such binder dispersions used is generally from 2 to 45% by weight, preferably from 5 to 35% by weight, particularly preferably from 7 to 20% by weight, based on the weight of the suspension.
  • the support is fluidized in an ascending gas stream, in particular air, in, for example, a fluidized- bed apparatus or a moving-bed apparatus.
  • the apparatuses usually comprise a conical or spherical vessel into which the fluidizing gas is introduced from below or from above via an immersed tube.
  • the suspension is sprayed through nozzles into the fluidized bed from above, from the side or from below.
  • the use of a riser pipe arranged centrically or concentrically around the immersed tube is advantageous.
  • a higher gas velocity which transports the support particles upward prevails within the riser pipe. In the outer ring, the gas velocity is only a little above the loosening velocity. As a result, the particles are moved vertically in a circular fashion.
  • a suitable fluidized-bed apparatus is described, for example, in DE-A 4006935.
  • Coating temperatures of from 20 to 500°C are generally employed in coating of the catalyst support with the catalytically active composition, with coating being able to be carried out under atmospheric pressure or under reduced pressure. In general, coating is carried out at from 0 ° C to 200°C, preferably from 20 to 150°C, in particular from 60 to 120°C.
  • the layer thickness of the catalytically active composition is generally from 0.02 to 0.2 mm, preferably from 0.05 to 0.15 mm.
  • the proportion of active composition in the catalyst is usually from 5 to 25% by weight, mostly from 7 to 15% by weight.
  • Thermal treatment at temperatures of from > 200 to 500°C of the precatalyst obtained in this way results in the binder being given off from the applied layer due to thermal decomposition and/or combustion.
  • the thermal treatment is preferably carried out in situ in the gas-phase oxidation reactor.
  • Determination of the valentinite content and the senarmontite content in antimony trioxide The determination was carried out by means of X-ray powder diffractometry. For this purpose, the antimony trioxide powder was measured in a "D5000 Theta/Theta" X-ray powder diffractometer from Siemens. The measurement parameters were as follows:
  • the signal height is given by the difference between the maximum intensity of the respective signal and the background determined.
  • the valentinite content is b/(a+b), and the senarmontite content is a/(a+b).
  • Example 1 (according to the invention):
  • Catalyst zone CZ1
  • the catalytic oxidation of o-xylene to phthalic anhydride was carried out in a salt bath-cooled tube reactor having an internal diameter of the tubes of 25 mm. From the reactor inlet to the reactor outlet, 130 cm of CZ1 , 70 cm of CZ2, 60 cm of CZ3 and 60 cm of CZ4 were introduced into an iron tube having a length of 3.5 m and an internal diameter of 25 mm. The iron tube was surrounded by a salt melt to regulate the temperature; a thermocouple sheath having an external diameter of 4 mm and a built-in withdrawable element served to measure the catalyst temperature. 4.0 standard m 3 /h of air having loadings of 99.2% strength by weight o-xylene of from 30 to
  • Example 4 (Oxidation of o-xylene to phthalic anhydride on the model tube scale, not according to the invention): See example 3, but with a catalyst bed comprising, from the reactor inlet to the reactor outlet, 130 cm of CZ5, 70 cm of CZ6, 60 cm of CZ7 and 60 cm of CZ4.
  • the catalytic oxidation of o-xylene to phthalic anhydride was carried out in a salt bath-cooled tube reactor having 15 105 tubes having an internal diameter of the tubes of 25 mm. From the reactor inlet to the reactor outlet, 130 cm of CZ1 , 90 cm of CZ2, 60 cm of CZ3 and 60 cm of
  • CZ4 were introduced.
  • some reactor tubes were equipped with a thermocouple.
  • 4.0 standard m 3 /h of air having an o-xylene loading (purity about 99% by weight) of from 0 to 100 g/standard m 3 were passed through the tubes.
  • the PAn yields were measured in the reactor outlet gas and are reported in table 2 in % by weight (kg of PAn per kg of o-xylene reacted) based on 100% strength o-xylene.
  • Example 6 (Oxidation of o-xylene to phthalic anhydride on an industrial scale, not according to the invention): See example 5, but with a catalyst bed from reactor inlet to reactor outlet comprising 130 cm of CZ5, 90 cm of CZ6, 60 cm of CZ7 and 60 cm of CZ4.
  • Comparison of examples 5 and 6 in table 2 shows that the catalyst activity of the catalyst in example 5 is higher than that in example 6.
  • the salt bath temperature in example 5 (according to the invention) can for this reason be lowered further, and the PAn yield with a low o-xylene and phthalide content is significantly higher than in example 6 (not according to the invention).

Abstract

Provided is a catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride, which has a plurality of catalyst zones which are arranged in series in the reaction tube and has been produced using an antimony trioxide which comprises a significant proportion of valentinite. Also disclosed is a process for gas-phase oxidation, in which a gas stream comprising at least one hydrocarbon and molecular oxygen is passed through a catalyst produced using an antimony trioxide which comprises a significant proportion of valentinite.

Description

CATALYST FOR OXIDATION OF O-XYLENE AND/OR NAPHTHALENE TO PHTHALIC ANHYDRIDE
Description The present invention relates to a catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride, which has a plurality of catalyst zones which are arranged in series in the reaction tube and have been produced using an antimony trioxide which comprises a significant proportion of valentinite. The present invention further relates to a process for gas-phase oxidation, in which a gas stream comprising at least one hydrocarbon and molecular oxygen is passed through a catalyst produced using an antimony trioxide which comprises a significant proportion of valentinite.
Many carboxylic acids and/or carboxylic anhydrides are prepared industrially by catalytic gas- phase oxidation of hydrocarbons such as benzene, xylenes, naphthalene, toluene or durene in fixed-bed reactors. In this way, it is possible to obtain, for example, benzoic acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid or pyromellitic anhydride. In general, a mixture of an oxygen-comprising gas and the starting material to be oxidized is passed through tubes in which a bed of a catalyst is present. To regulate the temperature, the tubes are surrounded by a heat transfer medium, for example a salt melt.
Coated catalysts in which the catalytically active composition has been applied in the form of a shell to an inert support material such as steatite have been found to be useful as catalysts for these oxidation reactions. In general, the catalysts have a layer of active composition which has an essentially homogeneous chemical constitution and has been applied in the form of a shell. Furthermore, two or more different layers of active composition can be applied in succession to a support. These are then referred to as two-layer or multilayer catalysts (see, for example, DE 19839001 A1 ).
As catalytically active constituents of the catalytically active composition of these coated catalysts, use is generally made of titanium dioxide and vanadium pentoxide. Furthermore, small amounts of many other oxidic compounds which act as promoters to influence the activity and selectivity of the catalyst, including cesium oxide, phosphorus oxide and antimony oxide, can be present in the catalytically active composition. Catalysts giving a particularly high PAn yield can, according to EP 1636161 , be obtained when particular V20s Sb203 ratios are set and the antimony trioxide has a defined average particle size.
The presence of antimony oxides leads to an increase in the PAn selectivity; the effect is considered to be separation of the vanadium sites.
The antimony oxides used in the active composition of the catalysts can be various
antimony(lll), antimony(IV) and antimony(V) compounds; antimony trioxide or antimony pentoxide are usually used. EP 522871 describes the use of antimony pentoxide, US
2009/306409 and EP 1636161 disclose the use of antimony trioxide. Compared to antimony tetroxide and antimony pentoxide, antimony trioxide has the ability to spread better on titanium dioxide, so that significantly improved distribution of the catalyst is achieved. Antimony trioxide is typically used as pure senarmontite phase (cf. Schubert, U.-A. et al., Topics in Catalysis, 2001 , vol. 15(2-4), pages 195 to 200). Apart from the cubic
senarmontite, there is also an orthorhombic modification of antimony trioxide, known as valentinite (Golunski, S. E. et al., Appl. Catal., 1989, vol. 48, pages 123 to 135).
There is a continual need for catalysts for gas-phase oxidations, which catalysts give a very high conversion at high selectivity.
It is an object of the present invention to develop a catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride, which catalyst makes possible a high phthalic anhydride yield with a low o-xylene and phthalide content at a low salt bath temperature. This object is achieved by a catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride, which has been produced using an antimony trioxide which comprises a significant proportion of valentinite.
It is an object of the invention to provide a catalyst for the oxidation of o-xylene and/or
naphthalene to phthalic anhydride, which has been produced using an antimony trioxide in which the ratio of signal height in the X-ray powder diffraction pattern at 2-theta = 28.4° to the sum of the signal heights at 2-theta = 27.7° and 28.4° is at least 0.02.
The signal at 2-theta = 27.7° is characteristic of senarmontite (cf. ASTM Index, No. 5-0534/7) and the signal at 2-theta = 28.4° for valentinite (cf. ASTM Index, No. 1 1 -689). The signal height is given by the difference between the maximum intensity of the respective signal and the background determined.
In a preferred embodiment of the invention, the catalyst has been produced using an antimony trioxide in which the ratio of the signal height in the X-ray powder diffraction pattern at 2-theta = 28.4° to the sum of the signal heights at 2-theta = 27.7° and 28.4° is at least 0.03, particularly preferably at least 0.05.
The antimony trioxide to be used according to the invention having a significant valentinite content can be used for producing one or more catalyst zones. In a preferred embodiment of the invention, the catalyst has three, four or five zones, with antimony trioxide having a significant valentinite content having been used for producing at least one zone.
The catalysts of the invention can, for example to avoid high hot spot temperatures, also be used in combination with suitable upstream and/or downstream beds and also together with intermediate zones, with the upstream and/or downstream beds and the intermediate zones generally being able to comprise catalytically inactive or less active material. The catalysts of the invention are generally coated catalysts in which the catalytically active composition has been applied in the form of a shell to an inert support material.
As inert support material, it is possible to use virtually all support materials of the prior art as are advantageously used in the production of coated catalysts for the oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and/or carboxylic anhydrides, for example quartz (S1O2), porcelain, magnesium oxide, tin dioxide, silicon carbide, rutile, alumina (AI2O3), aluminum silicate, steatite (magnesium silicate), zirconium silicate, cerium silicate or mixtures of these support materials. The catalyst supports can, for example, be used in the form of spheres, rings, pellets, spirals, tubes, extrudates or crushed material. The dimensions of these catalyst supports correspond to those of catalyst supports usually used for producing coated catalysts for gas-phase reactions of aromatic hydrocarbons. Preference is given to using steatite in the form of spheres having a diameter of from 3 to 6 mm or of rings having an external diameter of from 5 to 9 mm and a length of from 3 to 8 mm and a wall thickness of from 1 to 2 mm.
The catalysts of the invention comprise a catalytically active composition which comprises at least vanadium oxide and titanium dioxide and can be applied in one or more layers to the support material. Various layers can in this case differ in terms of their chemical constitution. The catalytically active composition preferably comprises, based on the total amount of the catalytically active composition, from 1 to 40% by weight of vanadium oxide, calculated as V2O5, and from 60 to 99% by weight of titanium dioxide, calculated as T1O2. The catalytically active composition can, in preferred embodiments, additionally comprise up to 1 % by weight of a cesium compound, calculated as Cs, up to 1 % by weight of a phosphorus compound, calculated as P, and up to 10% by weight of antimony oxide, calculated as Sb2C"3. All figures relating to the chemical constitution of the catalytically active composition are based on the calcined state of the latter, e.g. after calcination of the catalyst for one hour at 450°C.
Titanium dioxide is usually used in the anatase form for the catalytically active composition. The titanium dioxide preferably has a BET surface area of from 15 to 60 m2/g, in particular from 15 to 45 m2/g, particularly preferably from 13 to 28 m2/g. The titanium dioxide used can be an individual titanium dioxide or a mixture of titanium dioxides. In the latter case, the magnitude of the BET surface area as weighted average determines the contributions of the individual titanium dioxides. The titanium dioxide used is, for example, advantageously a mixture of a T1O2 having a BET surface area of from 5 to 15 m2/g and a T1O2 having a BET surface area of from 15 to 50 m2/g.
Suitable vanadium sources are, in particular, vanadium pentoxide or ammonium metavanadate. Suitable antimony sources are various antimony trioxides which have a significant valentinite content. Possible phosphorus sources are, in particular, phosphoric acid, phosphorous acid, hypophosphorous acid, ammonium phosphate or phosphoric esters and especially ammonium dihydrogenphosphate. Suitable sources of cesium are the oxide or hydroxide or the salts which can be converted thermally into the oxide, e.g. carboxylates, in particular the acetate, malonate or oxalate, carbonate, hydrogencarbonate, sulfate or nitrate.
Apart from the optional additions of cesium and phosphorus, the catalytically active composition can comprise small amounts of many other oxidic compounds which act as promoters to influence the activity and selectivity of the catalyst, for example by decreasing or increasing its activity. Examples of such promoters are the alkali metals, in particular lithium, potassium and rubidium in addition to the abovementioned cesium, which are usually used in the form of their oxides or hydroxides, thallium(l) oxide, aluminum oxide, zirconium oxide, iron oxide, nickel oxide, cobalt oxide, manganese oxide, tin oxide, silver oxide, copper oxide, chromium oxide, molybdenum oxide, tungsten oxide, iridium oxide, tantalum oxide, niobium oxide, arsenic oxide, antimony tetroxide, antimony pentoxide and cerium oxide.
Furthermore, among the abovementioned promoters, further preference is given to the oxides of niobium and tungsten as additives in amounts of from 0.01 to 0.50% by weight, based on the catalytically active composition.
The application of the layer(s) of the coated catalyst is advantageously carried out by spraying a suspension of T1O2 and V2O5, which optionally comprises sources of the abovementioned promoter elements, onto the fluidized support. Before coating, the suspension is preferably stirred for a sufficiently long time, e.g. from 2 to 30 hours, in particular from 12 to 25 hours, in order to break up agglomerates of the suspended solids and obtain a homogeneous
suspension. The suspension typically has a solids content of from 20 to 50% by weight. The suspension medium is generally aqueous, e.g. water itself or an aqueous mixture with a water- miscible organic solvent such as methanol, ethanol, isopropanol, formamide and the like.
In general, organic binders, preferably copolymers, advantageously in the form of an aqueous dispersion, of acrylic acid-maleic acid, vinyl acetate-vinyl laurate, vinyl acetate-acrylate, styrene- acrylate and vinyl acetate-ethylene, are added to the suspension. The binders are commercially available as aqueous dispersions having a solids content of, for example, from 35 to 65% by weight. The amount of such binder dispersions used is generally from 2 to 45% by weight, preferably from 5 to 35% by weight, particularly preferably from 7 to 20% by weight, based on the weight of the suspension. The support is fluidized in an ascending gas stream, in particular air, in, for example, a fluidized- bed apparatus or a moving-bed apparatus. The apparatuses usually comprise a conical or spherical vessel into which the fluidizing gas is introduced from below or from above via an immersed tube. The suspension is sprayed through nozzles into the fluidized bed from above, from the side or from below. The use of a riser pipe arranged centrically or concentrically around the immersed tube is advantageous. A higher gas velocity which transports the support particles upward prevails within the riser pipe. In the outer ring, the gas velocity is only a little above the loosening velocity. As a result, the particles are moved vertically in a circular fashion. A suitable fluidized-bed apparatus is described, for example, in DE-A 4006935. Coating temperatures of from 20 to 500°C are generally employed in coating of the catalyst support with the catalytically active composition, with coating being able to be carried out under atmospheric pressure or under reduced pressure. In general, coating is carried out at from 0°C to 200°C, preferably from 20 to 150°C, in particular from 60 to 120°C.
The layer thickness of the catalytically active composition is generally from 0.02 to 0.2 mm, preferably from 0.05 to 0.15 mm. The proportion of active composition in the catalyst is usually from 5 to 25% by weight, mostly from 7 to 15% by weight. Thermal treatment at temperatures of from > 200 to 500°C of the precatalyst obtained in this way results in the binder being given off from the applied layer due to thermal decomposition and/or combustion. The thermal treatment is preferably carried out in situ in the gas-phase oxidation reactor.
The invention further provides a process for gas-phase oxidation, wherein a gas stream comprising at least one hydrocarbon and molecular oxygen is passed through a catalyst produced using an antimony trioxide in which the ratio of the signal height in the X-ray powder diffraction pattern at 2-theta = 28.4° to the sum of the signal heights at 2-theta = 27.7° and 28.4° is at least 0.02.
A preferred embodiment of the invention is a process for the gas-phase oxidation of o-xylene and/or naphthalene to phthalic anhydride, wherein a gas stream comprising o-xylene and/or naphthalene and molecular oxygen is passed through a catalyst produced using an antimony trioxide in which the ratio of the signal height in the X-ray powder diffraction pattern at 2-theta = 28.4° to the sum of the signal heights at 2-theta = 27.7° and 28.4° is at least 0.02.
Examples
Determination of the valentinite content and the senarmontite content in antimony trioxide: The determination was carried out by means of X-ray powder diffractometry. For this purpose, the antimony trioxide powder was measured in a "D5000 Theta/Theta" X-ray powder diffractometer from Siemens. The measurement parameters were as follows:
Diameter 435 mm
X-radiation CuK-alpha (λ = 1 .54■ 10"10 m)
Tube voltage 40 kV
Tube current 30 mA
Aperture Variable V20
Scattered radiation orifice Variable V20
Secondary monochromator Graphite
Monochromator aperture 0.1 mm
Scintillation counter
Detector aperture 0.6 mm Step width 0.02° 2Θ
Step mode Continuous
Measurement time 2.4 s / step
Measurement rate 0.5° 20 / min
The signal height is given by the difference between the maximum intensity of the respective signal and the background determined. To determine the valentinite content, the signals at 2- theta = 27.7° (senarmontite, signal height a) and 28.4° (valentinite, signal height b) were employed. The valentinite content is b/(a+b), and the senarmontite content is a/(a+b).
Example 1 (according to the invention):
Catalyst zone CZ1 :
3.38 g of cesium carbonate, 459.3 g of titanium dioxide (Fuji TA 100C, anatase, BET surface area 20 m2/g), 196.9 g of titanium dioxide (Fuji TA 100, anatase, BET surface area 7 m2/g) and 51 .4 g of vanadium pentoxide and 13.2 g of antimony trioxide (Merck Selectipur 7835, valentinite content = 0.18, senarmontite content = 0.82, 99.5% Sb2C"3 content, 300 ppm by weight of As, 500 ppm by weight of Pb, 50 ppm by weight of Fe, average particle size 2 μηη) were suspended in 1869 g of demineralized water and stirred for 18 hours to achieve a homogeneous distribution. 78.4 g of organic binder comprising a copolymer of vinyl acetate and vinyl laurate were added in the form of a 50% strength by weight aqueous dispersion to this suspension. In a fluidized-bed apparatus, 820 g of this suspension were sprayed onto 2 kg of steatite (magnesium silicate) in the form of rings having dimensions of 7 mm x 7 mm x 4 mm and dried. After calcination of the catalyst for one hour at 450°C, the amount of active composition applied to the steatite rings was 9.1 %. The analyzed chemical constitution of the active composition was 7.1 % of V205, 1.8% of Sb2C>3, 0.38% of Cs, balance T1O2.
Catalyst zone CZ2:
Production analogous to CZ1 with variation of the chemical constitution of the suspension. After calcination of the catalyst for one hour at 450°C, the amount of active composition applied to the steatite rings was 8.5%. The analyzed chemical constitution of the active composition comprised 7.95% of V205, 2.7% of Sb2C>3, 0.31 % of Cs, balance T1O2 having an average BET surface area of 18 m2/g.
Catalyst zone CZ3:
Production analogous to CZ1 with variation of the chemical constitution of the suspension. After calcination of the catalyst for one hour at 450°C, the amount of active composition applied to the steatite rings was 8.5%. The analyzed chemical constitution of the active composition comprised 7.1 % of V205, 2.4% of Sb203, 0.10% of Cs, balance T1O2 having an average BET surface area of 17 m2/g. Catalyst zone CZ4:
Production analogous to CZ1 with variation of the chemical constitution of the suspension and using Fuji TA 100CT, anatase, BET surface area 27 m2/g, instead of Fuji TA 100C. After calcination of the catalyst for one hour at 450°C, the amount of active composition applied to the steatite rings was 9.1 %. The analyzed chemical constitution of the active composition comprised 20% of V2O5, 0.38% of P, balance Ti02 having an average BET surface area of 23 m2/g.
Example 2 (not according to the invention):
Catalyst zone CZ5:
Production analogous to CZ1 but using an antimony trioxide grade having a reduced valentinite content (e.g. Triox white from Antraco, valentinite content = 0.015, senarmontite content = 0.985, 99.3% Sb203 content, 0.3% by weight of As203, 0.18% by weight of PbO, 0.02% by weight of iron oxide, average particle size 1 .5 μηη).
Catalyst zone CZ6:
Production analogous to CZ2 but using an antimony trioxide grade having a reduced valentinite content (e.g. Triox white from Antraco, valentinite content = 0.015, senarmontite content = 0.985, 99.3% Sb203 content, 0.3% by weight of As203, 0.18% by weight of PbO, 0.02% by weight of iron oxide, average particle size 1 .5 μηη).
Catalyst zone CZ7:
Production analogous to CZ3 but using an antimony trioxide grade having a reduced valentinite content (e.g. Triox white from Antraco, valentinite content = 0.015, senarmontite content = 0.985, 99.3% Sb203 content, 0.3% by weight of As203, 0.18% by weight of PbO, 0.02% by weight of iron oxide, average particle size 1 .5 μηη).
Example 3 (Oxidation of o-xylene to phthalic anhydride on the model tube scale, according to the invention):
The catalytic oxidation of o-xylene to phthalic anhydride was carried out in a salt bath-cooled tube reactor having an internal diameter of the tubes of 25 mm. From the reactor inlet to the reactor outlet, 130 cm of CZ1 , 70 cm of CZ2, 60 cm of CZ3 and 60 cm of CZ4 were introduced into an iron tube having a length of 3.5 m and an internal diameter of 25 mm. The iron tube was surrounded by a salt melt to regulate the temperature; a thermocouple sheath having an external diameter of 4 mm and a built-in withdrawable element served to measure the catalyst temperature. 4.0 standard m3/h of air having loadings of 99.2% strength by weight o-xylene of from 30 to
100 g/standard m3 were passed through the tube from the top downward. This gave the results summarized in table 1 ("PAn yield" is the amount of phthalic anhydride obtained in percent by weight, based on 100% strength o-xylene). Example 4 (Oxidation of o-xylene to phthalic anhydride on the model tube scale, not according to the invention): See example 3, but with a catalyst bed comprising, from the reactor inlet to the reactor outlet, 130 cm of CZ5, 70 cm of CZ6, 60 cm of CZ7 and 60 cm of CZ4.
Table 1
Figure imgf000009_0001
Comparison of examples 3 and 4 in table 1 shows that the catalyst activity of the catalyst in example 3 is higher than that in example 4. The salt bath temperature in example 3 (according to the invention) can for this reason be lowered further, and the PSn yield with a low o-xylene and phthalide content is significantly higher than in example 4 (not according to the invention). Example 5 (Oxidation of o-xylene to phthalic anhydride on an industrial scale, according to the invention):
The catalytic oxidation of o-xylene to phthalic anhydride was carried out in a salt bath-cooled tube reactor having 15 105 tubes having an internal diameter of the tubes of 25 mm. From the reactor inlet to the reactor outlet, 130 cm of CZ1 , 90 cm of CZ2, 60 cm of CZ3 and 60 cm of
CZ4 were introduced. To record temperature profiles, some reactor tubes were equipped with a thermocouple. 4.0 standard m3/h of air having an o-xylene loading (purity about 99% by weight) of from 0 to 100 g/standard m3 were passed through the tubes. The PAn yields were measured in the reactor outlet gas and are reported in table 2 in % by weight (kg of PAn per kg of o-xylene reacted) based on 100% strength o-xylene.
Example 6 (Oxidation of o-xylene to phthalic anhydride on an industrial scale, not according to the invention): See example 5, but with a catalyst bed from reactor inlet to reactor outlet comprising 130 cm of CZ5, 90 cm of CZ6, 60 cm of CZ7 and 60 cm of CZ4.
Table 2
Figure imgf000010_0001
Comparison of examples 5 and 6 in table 2 shows that the catalyst activity of the catalyst in example 5 is higher than that in example 6. The salt bath temperature in example 5 (according to the invention) can for this reason be lowered further, and the PAn yield with a low o-xylene and phthalide content is significantly higher than in example 6 (not according to the invention).

Claims

Claims
1 . A catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride, which has been produced using an antimony trioxide in which the ratio of signal height in the X-ray powder diffraction pattern at 2-theta = 28.4° to the sum of the signal heights at 2-theta = 27.7° and 28.4° is at least 0.02.
2. A process for gas-phase oxidation, wherein a gas stream comprising at least one hydrocarbon and molecular oxygen is passed through a catalyst produced using an antimony trioxide in which the ratio of the signal height in the X-ray powder diffraction pattern at 2-theta = 28.4° to the sum of the signal heights at 2-theta = 27.7° and 28.4° is at least 0.02.
3. The process according to claim 2, wherein the hydrocarbon is o-xylene and/or
naphthalene.
PCT/IB2011/053327 2010-07-30 2011-07-26 Catalyst for oxidation of o-xylene and/or naphthalene to phthalic anhydride WO2012014154A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP11811912.2A EP2598238A4 (en) 2010-07-30 2011-07-26 Catalyst for oxidation of o-xylene and/or naphthalene to phthalic anhydride
CN201180035813.9A CN103025424B (en) 2010-07-30 2011-07-26 For the catalyst making ortho-xylene and/or Fluidized bed become phthalic anhydride
BR112013001388A BR112013001388A2 (en) 2010-07-30 2011-07-26 catalyst for the oxidation of o-xylene and / or naphthalene to phthalic anhydride, and process for gas phase oxidation
KR1020137004810A KR20130131306A (en) 2010-07-30 2011-07-26 Catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride
JP2013522327A JP5973436B2 (en) 2010-07-30 2011-07-26 Catalyst for oxidizing o-xylene and / or naphthalene to phthalic anhydride

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10171381.6 2010-07-30
EP10171381 2010-07-30

Publications (1)

Publication Number Publication Date
WO2012014154A1 true WO2012014154A1 (en) 2012-02-02

Family

ID=45529478

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2011/053327 WO2012014154A1 (en) 2010-07-30 2011-07-26 Catalyst for oxidation of o-xylene and/or naphthalene to phthalic anhydride

Country Status (7)

Country Link
EP (1) EP2598238A4 (en)
JP (1) JP5973436B2 (en)
KR (1) KR20130131306A (en)
CN (1) CN103025424B (en)
BR (1) BR112013001388A2 (en)
TW (1) TW201219112A (en)
WO (1) WO2012014154A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9029289B2 (en) 2012-07-16 2015-05-12 Basf Se Catalyst for preparing carboxylic acids and/or carboxylic anhydrides
WO2015121483A1 (en) * 2014-02-17 2015-08-20 Basf Se Catalyst system for oxidizing o-xylol and/or naphthalene into phthalic anhydride
WO2015121485A1 (en) * 2014-02-17 2015-08-20 Basf Se Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride
DE102014203725A1 (en) 2014-02-28 2015-09-03 Basf Se Oxidation catalyst with saddle-shaped carrier shaped body
JP2015530228A (en) * 2012-07-16 2015-10-15 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Catalyst for producing carboxylic acid and / or carboxylic anhydride
EP2987552A1 (en) * 2014-08-22 2016-02-24 Basf Se Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride
WO2019018567A1 (en) * 2017-07-18 2019-01-24 Ha-International, Llc Compositions and methods for refractory coatings with ester carriers
US10710054B2 (en) 2015-01-22 2020-07-14 Basf Se Multi-zoned catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride
CN112642454A (en) * 2019-10-12 2021-04-13 中国石油化工股份有限公司 Catalyst for preparing phthalic anhydride by oxidizing o-xylene and preparation method thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2717768T3 (en) * 2013-06-26 2019-06-25 Basf Se Procedure for starting a gas phase oxidation reactor
DE102017202351A1 (en) * 2017-02-14 2018-08-16 Clariant International Ltd Catalyst material for the oxidation of hydrocarbons with antimony-doped titanium dioxide

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4006935A1 (en) 1990-03-06 1991-09-12 Wacker Chemie Gmbh Fluidised bed appts. for mixing, drying and coating bulk solids - has support tube concentrically placed around down pipe to form ring shaped aperture in mixing chamber
EP0522871A1 (en) 1991-07-10 1993-01-13 Nippon Shokubai Co., Ltd. Catalyst and process for producing phthalic anhydride
DE19839001A1 (en) 1998-08-27 2000-03-02 Basf Ag Shell catalysts for the catalytic gas phase oxidation of aromatic hydrocarbons
US6362345B1 (en) * 1998-05-26 2002-03-26 Basf Aktiengesellschaft Method for producing phthalic anhydride by means of catalytic vapor-phase oxidation of o-xylol/naphthalene mixtures
EP1636161A1 (en) 2003-05-23 2006-03-22 Basf Aktiengesellschaft Production of aldehydes, carboxylic acids, and/or carboxylic acid anhydrides by means of catalysts containing vanadium oxide, titanium dioxide, and antimony oxide
US20060276661A1 (en) * 2003-05-23 2006-12-07 Basf Aktiengesellschaft Three-layered or four-layered catalyst systems for producing phthalic anhydride
US20090306409A1 (en) 2005-05-22 2009-12-10 Sud-Chemie Ag Multi-layer catalyst for producing phthalic anhydride

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60137438A (en) * 1983-09-28 1985-07-22 Nitto Chem Ind Co Ltd Manufacture of metal oxide catalyst containing antimony
DE19922156A1 (en) * 1999-05-12 2000-08-10 Basf Ag Multimetal oxide composition, useful as oxidation catalyst, especially for gas phase production of (meth)acrylic acid, is based on crystallites of constant composition
FR2855516B1 (en) * 2003-05-27 2005-07-08 Atofina OXIDATION OF ACRYLIC ACID PROPANE BY USING CATALYSTS MIXED WITH CRYSTALLINE PHASES
JP4442317B2 (en) * 2004-05-21 2010-03-31 三菱化学株式会社 Method for producing composite oxide catalyst
CN101130535B (en) * 2006-08-25 2010-10-13 中国石油化工股份有限公司 Method for producing phthallic anhydride
JP2009067621A (en) * 2007-09-12 2009-04-02 Nippon Shokubai Co Ltd Oxide particle, dispersion containing the particle, and catalyst using the particle
DE102008054586A1 (en) * 2008-12-12 2010-06-17 Basf Se Process for the continuous production of geometric shaped catalyst bodies K

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4006935A1 (en) 1990-03-06 1991-09-12 Wacker Chemie Gmbh Fluidised bed appts. for mixing, drying and coating bulk solids - has support tube concentrically placed around down pipe to form ring shaped aperture in mixing chamber
EP0522871A1 (en) 1991-07-10 1993-01-13 Nippon Shokubai Co., Ltd. Catalyst and process for producing phthalic anhydride
US6362345B1 (en) * 1998-05-26 2002-03-26 Basf Aktiengesellschaft Method for producing phthalic anhydride by means of catalytic vapor-phase oxidation of o-xylol/naphthalene mixtures
DE19839001A1 (en) 1998-08-27 2000-03-02 Basf Ag Shell catalysts for the catalytic gas phase oxidation of aromatic hydrocarbons
EP1636161A1 (en) 2003-05-23 2006-03-22 Basf Aktiengesellschaft Production of aldehydes, carboxylic acids, and/or carboxylic acid anhydrides by means of catalysts containing vanadium oxide, titanium dioxide, and antimony oxide
US20060276661A1 (en) * 2003-05-23 2006-12-07 Basf Aktiengesellschaft Three-layered or four-layered catalyst systems for producing phthalic anhydride
US20090306409A1 (en) 2005-05-22 2009-12-10 Sud-Chemie Ag Multi-layer catalyst for producing phthalic anhydride

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GOLUNSKI, S. E. ET AL., APPL. CATAL., vol. 48, 1989, pages 123 - 135
SCHUBERT, U.-A. ET AL., TOPICS IN CATALYSIS, vol. 15, no. 2-4, 2001, pages 195 - 200
See also references of EP2598238A4
U.-A.SCHUBERT ET AL.: "Possible effects of site isolation in antimony oxide-modifi ed vanadia/titania catalysts for selective oxidation of o-xylene.", TOPICS IN CATALYSIS, vol. 15, no. 2-4, 2001, pages 195 - 200, XP019291901 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015530228A (en) * 2012-07-16 2015-10-15 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Catalyst for producing carboxylic acid and / or carboxylic anhydride
US9029289B2 (en) 2012-07-16 2015-05-12 Basf Se Catalyst for preparing carboxylic acids and/or carboxylic anhydrides
US20170008866A1 (en) * 2014-02-17 2017-01-12 Basf Se Catalyst system for oxidizing o-xylol and/or naphthalene into phthalic anhydride
US9868713B2 (en) 2014-02-17 2018-01-16 Basf Se Catalyst system for oxidizing o-xylol and/or naphthalene into phthalic anhydride
WO2015121485A1 (en) * 2014-02-17 2015-08-20 Basf Se Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride
US9914716B2 (en) 2014-02-17 2018-03-13 Basf Se Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride
CN105992644A (en) * 2014-02-17 2016-10-05 巴斯夫欧洲公司 Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride
US20170008867A1 (en) * 2014-02-17 2017-01-12 Basf Se Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride
WO2015121483A1 (en) * 2014-02-17 2015-08-20 Basf Se Catalyst system for oxidizing o-xylol and/or naphthalene into phthalic anhydride
DE102014203725A1 (en) 2014-02-28 2015-09-03 Basf Se Oxidation catalyst with saddle-shaped carrier shaped body
US9925526B2 (en) 2014-02-28 2018-03-27 Basf Se Oxidation catalyst with saddle-shaped support body
RU2692807C2 (en) * 2014-02-28 2019-06-27 Басф Се Oxidation catalyst with saddle molded articles-carriers
EP2987552A1 (en) * 2014-08-22 2016-02-24 Basf Se Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride
US10710054B2 (en) 2015-01-22 2020-07-14 Basf Se Multi-zoned catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride
WO2019018567A1 (en) * 2017-07-18 2019-01-24 Ha-International, Llc Compositions and methods for refractory coatings with ester carriers
US11484935B2 (en) 2017-07-18 2022-11-01 Ha-International, Llc Compositions and methods for refractory coatings with ester carriers
US11712736B2 (en) 2017-07-18 2023-08-01 Ha-International, Llc Compositions and methods for refractory coatings with ester carriers
CN112642454A (en) * 2019-10-12 2021-04-13 中国石油化工股份有限公司 Catalyst for preparing phthalic anhydride by oxidizing o-xylene and preparation method thereof

Also Published As

Publication number Publication date
TW201219112A (en) 2012-05-16
EP2598238A4 (en) 2014-08-20
JP5973436B2 (en) 2016-08-23
EP2598238A1 (en) 2013-06-05
KR20130131306A (en) 2013-12-03
BR112013001388A2 (en) 2016-05-24
JP2013539407A (en) 2013-10-24
CN103025424A (en) 2013-04-03
CN103025424B (en) 2016-01-20

Similar Documents

Publication Publication Date Title
WO2012014154A1 (en) Catalyst for oxidation of o-xylene and/or naphthalene to phthalic anhydride
US9029289B2 (en) Catalyst for preparing carboxylic acids and/or carboxylic anhydrides
US20110124885A1 (en) Multilayer catalyst having vanadium antimonate in at least one catalyst layer for preparing carboxylic acids and/or carboxylic anhydrides and process for preparing phthalic anhydride having a low hot spot temperature
US8859459B2 (en) Multilayer catalyst for preparing phthalic anhydride and process for preparing phthalic anhydride
US9765046B2 (en) Process for preparing phthalic anhydride
US20110230668A1 (en) Catalyst for gas phase oxidations based on low-sulfur and low-calcium titanium dioxide
US9212157B2 (en) Catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride
US9914716B2 (en) Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride
KR20090010060A (en) Production of phthalic anhydride by gas phase oxidation of o-xylol in a primary and a secondary reactor
KR20060113888A (en) Gas phase oxidation catalyst with defined vanadium oxide particle size distribution
US9868713B2 (en) Catalyst system for oxidizing o-xylol and/or naphthalene into phthalic anhydride
US10710054B2 (en) Multi-zoned catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride
US9656983B2 (en) Process for starting up a gas phase oxidation reactor
JP5856089B2 (en) Titanium dioxide based gas phase oxidation catalyst with low sulfur and calcium content
EP2558453A1 (en) Process for controlling a gas phase oxidation reactor for preparation of phthalic anhydride
JP5879342B2 (en) Multilayer catalyst for producing phthalic anhydride and method for producing phthalic anhydride
JP2015530228A (en) Catalyst for producing carboxylic acid and / or carboxylic anhydride
EP2987552A1 (en) Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180035813.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11811912

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2011811912

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2013522327

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20137004810

Country of ref document: KR

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112013001388

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112013001388

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20130118