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WO2012014154A1 - Catalyseur pour l'oxydation de o-xylène et/ou de naphthalène en anhydride phtalique - Google Patents

Catalyseur pour l'oxydation de o-xylène et/ou de naphthalène en anhydride phtalique Download PDF

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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
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WO
WIPO (PCT)
Prior art keywords
catalyst
xylene
oxidation
oxide
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2011/053327
Other languages
English (en)
Inventor
Stefan Altwasser
Jürgen ZÜHLKE
Frank Rosowski
Michael Krämer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF China Co Ltd
BASF SE
Original Assignee
BASF China Co Ltd
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF China Co Ltd, BASF SE filed Critical BASF China Co Ltd
Priority to CN201180035813.9A priority Critical patent/CN103025424B/zh
Priority to BR112013001388A priority patent/BR112013001388A2/pt
Priority to KR1020137004810A priority patent/KR20130131306A/ko
Priority to EP11811912.2A priority patent/EP2598238A4/fr
Priority to JP2013522327A priority patent/JP5973436B2/ja
Publication of WO2012014154A1 publication Critical patent/WO2012014154A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/395—Thickness of the active catalytic layer
    • 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).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Furan Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un catalyseur pour l'oxydation de o-xylène et/ou de naphtalène en anhydride phtalique, lequel catalyseur comprend une pluralité de zones disposées en série dans le tube de réaction et est obtenu au moyen d'un trioxyde d'antimoine renfermant une proportion importante de valentinite. Par ailleurs, l'invention concerne un procédé d'oxydation en phase gazeuse, selon lequel un courant gazeux contenant au moins un hydrocarbure et de l'oxygène moléculaire est amené à traverser un catalyseur obtenu à l'aide d'un trioxyde d'antimoine renfermant une proportion importante de valentinite.
PCT/IB2011/053327 2010-07-30 2011-07-26 Catalyseur pour l'oxydation de o-xylène et/ou de naphthalène en anhydride phtalique Ceased WO2012014154A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201180035813.9A CN103025424B (zh) 2010-07-30 2011-07-26 用于使邻二甲苯和/或萘氧化成邻苯二甲酸酐的催化剂
BR112013001388A BR112013001388A2 (pt) 2010-07-30 2011-07-26 catalisador para a oxidação de o-xileno e/ou naftaleno para anidrido ftálico, e, processo para a oxidação em fase gasosa
KR1020137004810A KR20130131306A (ko) 2010-07-30 2011-07-26 o-자일렌 및/또는 나프탈렌의 프탈산 무수물로의 산화를 위한 촉매
EP11811912.2A EP2598238A4 (fr) 2010-07-30 2011-07-26 Catalyseur pour l'oxydation de o-xylène et/ou de naphthalène en anhydride phtalique
JP2013522327A JP5973436B2 (ja) 2010-07-30 2011-07-26 ｏ−キシレン及び／又はナフタレンを無水フタル酸に酸化するための触媒

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 (fr) 2012-02-02

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PCT/IB2011/053327 Ceased WO2012014154A1 (fr) 2010-07-30 2011-07-26 Catalyseur pour l'oxydation de o-xylène et/ou de naphthalène en anhydride phtalique

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

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
WO2015121485A1 (fr) * 2014-02-17 2015-08-20 Basf Se Système catalyseur pour l'oxydation de l'o-xylène et/ou du naphtalène en anhydride phtalique
WO2015121483A1 (fr) * 2014-02-17 2015-08-20 Basf Se Système catalyseur pour l'oxydation d'o-xylène et/ou de naphtalène en anhydride phtalique
DE102014203725A1 (de) 2014-02-28 2015-09-03 Basf Se Oxidationskatalysator mit sattelförmigem Trägerformkörper
JP2015530228A (ja) * 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 カルボン酸および／またはカルボン酸無水物を製造するための触媒
EP2987552A1 (fr) * 2014-08-22 2016-02-24 Basf Se Système catalyseur pour oxydation d'o-xylène et/ou naphtalène pour produire de l'anhydride phtalique
WO2019018567A1 (fr) * 2017-07-18 2019-01-24 Ha-International, Llc Compositions et procédés pour revêtements réfractaires à porteurs d'esters
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 (zh) * 2019-10-12 2021-04-13 中国石油化工股份有限公司 一种邻二甲苯氧化制苯酐的催化剂及其制备方法

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JP6466429B2 (ja) * 2013-06-26 2019-02-06 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 気相酸化反応器を始動するための方法
DE102017202351A1 (de) * 2017-02-14 2018-08-16 Clariant International Ltd Katalysatormaterial zur Oxidation von Kohlenwasserstoffen mit antimondotiertem Titandioxid
CN116059995A (zh) * 2021-11-01 2023-05-05 中国石油化工股份有限公司 均四甲苯制均酐的催化剂及其制备方法和应用

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EP0522871A1 (fr) 1991-07-10 1993-01-13 Nippon Shokubai Co., Ltd. Catalyseur et procédé pour la préparation de l'anhydride phtalique
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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
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EP2598238A1 (fr) 2013-06-05
JP2013539407A (ja) 2013-10-24
JP5973436B2 (ja) 2016-08-23
TW201219112A (en) 2012-05-16
CN103025424B (zh) 2016-01-20
BR112013001388A2 (pt) 2016-05-24
KR20130131306A (ko) 2013-12-03
CN103025424A (zh) 2013-04-03

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