EP2501472A1 - Multilayer catalyst for producing carboxylic acids and/or carboxylic acid anhydrides with vanadium antimonate in at least one catalyst layer, and method for producing phthalic acid anhydride with a low hot-spot temperature - Google Patents

Multilayer catalyst for producing carboxylic acids and/or carboxylic acid anhydrides with vanadium antimonate in at least one catalyst layer, and method for producing phthalic acid anhydride with a low hot-spot temperature

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Publication number
EP2501472A1
EP2501472A1 EP10781485A EP10781485A EP2501472A1 EP 2501472 A1 EP2501472 A1 EP 2501472A1 EP 10781485 A EP10781485 A EP 10781485A EP 10781485 A EP10781485 A EP 10781485A EP 2501472 A1 EP2501472 A1 EP 2501472A1
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EP
European Patent Office
Prior art keywords
catalyst
vanadium
producing
carboxylic acids
xylene
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.)
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EP10781485A
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German (de)
French (fr)
Inventor
Stefan Altwasser
Jürgen ZÜHLKE
Frank Rosowski
Cornelia Katharina Dobner
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BASF SE
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BASF SE
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Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J35/19—
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to a catalyst system for the production of
  • Carboxylic acids and / or carboxylic anhydrides which has a plurality of catalyst layers arranged one above the other in the reaction tube, wherein in at least one of the catalyst layers Vanadiumantimonat is introduced into the active composition.
  • the present invention relates to a process for gas phase oxidation in which a gaseous stream comprising at least one hydrocarbon and molecular oxygen, passes through several catalyst layers and the maximum
  • Hotspot temperature is below 425 ° C.
  • carboxylic acids and / or carboxylic anhydrides are produced industrially by the catalytic gas phase oxidation of hydrocarbons such as benzene, the xylenes, naphthalene, toluene or durene in fixed bed reactors. You can in this way z.
  • a mixture of an oxygen-containing gas and the one to be oxidized is passed
  • the catalysts used in the process according to the invention are generally coated catalysts in which the catalytically active composition is applied in the form of a dish on an inert support.
  • the layer thickness of the catalytically active composition is generally 0.02 to 0.25 mm, preferably 0.05 to 0.15 mm.
  • the proportion of the active material in the catalyst is usually 5 to 25 wt .-%, usually 7 to 15 wt .-%.
  • the catalysts have a cup-shaped active mass layer of substantially homogeneous chemical composition. Further, on a carrier can also
  • Steatite is preferred in the form of spheres with a diameter of 3 to 6 mm or of rings with an outer diameter of 5 used to 9 mm, a length of 4 to 7 mm and an inner diameter of 3 to 7 mm.
  • titanium dioxide is used in the anatase form for catalytically active material.
  • 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 may consist of a single titanium dioxide or a mixture of titanium dioxides. In the latter case, the value of the BET surface area is determined as a weighted average of the contributions of the individual titanium dioxides.
  • the titanium dioxide used is z. B. advantageous from a mixture of a T1O2 with a BET surface area of 5 to 15 m 2 / g and a T1O2 with a BET surface area of 15 to 50 m 2 / g.
  • vanadium sources are vanadium pentoxide or ammonium meta vanadate.
  • Antimony sources are various antimony oxides.
  • Phosphorus source are in particular phosphoric acid, phosphorous acid, hypophosphorous acid, ammonium phosphate or phosphoric acid esters and especially ammonium dihydrogen phosphate into consideration.
  • the sources of cesium are the oxides or hydroxide or the salts which can be thermally converted into the oxide, such as
  • Carboxylates in particular the acetate, malonate or oxalate, carbonate,
  • a small number of other oxidic compounds which, as promoters, influence the activity and selectivity of the catalyst, for example by lowering or increasing its activity, can be present in the catalytically active composition in small amounts.
  • promoters are the alkali metals, in particular other than said cesium, lithium, potassium and rubidium, which are usually used in the form of their oxides or hydroxides, thallium (I) oxide, alumina, zirconium oxide,
  • the oxides of niobium and tungsten in amounts of from 0.01 to 0.50% by weight, based on the catalytically active composition, are also suitable as additives.
  • suspensions are organic binders, preferably copolymers, advantageously in the form of an aqueous dispersion of acrylic acid / maleic acid,
  • the binders are commercially available as aqueous dispersions, with a
  • Binder dispersions is generally 2 to 45 wt .-%, preferably 5 to 35 wt .-%, particularly preferably 7 to 20 wt .-%, based on the weight of
  • the carrier is in z.
  • a fluidized bed or fluidized bed apparatus in an ascending gas stream, in particular air, fluidized.
  • the apparatuses usually consist of a conical or spherical container in which the fluidizing gas is introduced from below or from above via a dip tube.
  • the suspension is sprayed via nozzles from above, from the side or from below into the fluidized bed.
  • a centrally or concentrically arranged around the dip tube riser Within the riser, there is a higher gas velocity, the
  • a suitable fluidized bed apparatus is z. As described in DE-A 4006935.
  • coating temperatures of 20 to 500 ° C are used, whereby the coating can be carried out under atmospheric pressure or under reduced pressure.
  • the coating is carried out at 0 ° C to 200 ° C, preferably at 20 to 150 ° C, especially at 60 to 120 ° C.
  • thermal treatment of the pre-catalyst thus obtained at temperatures above 200 to 500 ° C escapes the binder by thermal decomposition and / or combustion of the applied layer.
  • the thermal treatment takes place in situ in the gas phase oxidation reactor.
  • Japanese Patent Laid-Open No. 180430/82 discloses two-layer catalysts for the oxidation of o-xylene to phthalic anhydride, which include titanium dioxide and titanium dioxide
  • Vanadium antimonate as catalytically active components.
  • the possible o-xylene loadings as well as the space velocities are at these
  • the hotspot temperatures for example, in the oxidation of o-xylene too
  • Phthalic anhydride are at loadings between 80 and 100 g o-xylene / Nm 3 usually above 440 ° C.
  • High hotspot temperatures are an expression of an excessive increase in the total oxidation of o-xylene to CO, CO2 and water and are associated with increased damage to the catalyst. The aim is therefore to have the lowest possible hotspot temperatures.
  • the object of the present invention was to provide an improved catalyst for the production of carboxylic acids and / or carboxylic anhydrides, in particular to develop an improved catalyst for the partial oxidation of o-xylene to PSA for o-xylene loadings of at least 80 g / Nm 3 .
  • the solution of the problem is a multi-layer catalyst for the production of
  • the hotspot temperature of such a catalyst is significantly lower than in the case of a comparative catalyst prepared without the addition of vanadium antimonate; the carboxylic acid or carboxylic acid anhydride yields are significantly higher.
  • the vanadium antimonate introduced in the active composition of at least one layer can be prepared by reacting any vanadium and antimony compounds.
  • Vanadium antimonate may have different molarity
  • Antimony compounds are used.
  • the preparation of the vanadium antimonate can be characterized, for example, by reaction of the oxides in aqueous solution or else by the use of hydrogen peroxide. In the latter case, for.
  • Connection can be reacted with antimony trioxide to Vanadiumantimonat.
  • the catalysts of the invention comprise in a preferred
  • Embodiment three, four or five layers can, for example, to avoid high hotspot temperatures in conjunction with suitable pre and / or
  • the pre and / or reposting and the intermediate layers can usually consist of catalytically inactive or less active material.
  • Another object of the invention is a method for producing a
  • Carboxylic anhydrides with at least 3 layers characterized in that at least one catalyst layer, a vanadium antimonate is added.
  • Another object of the invention is a process for the gas phase oxidation of hydrocarbons in a multi-layer catalyst with at least 3 layers, at whose preparation at least one catalyst layer, a vanadium antimonate is added.
  • the inventive method is preferably suitable for
  • a preferred embodiment of the method according to the invention is characterized in that the hotspot temperature is above 425 ° C in any of the catalyst layers.
  • Another object of the invention is the use of a
  • Multi-layer catalyst with at least 3 layers in the preparation of which at least one catalyst layer, a vanadium antimonate is added, for the production of carboxylic acids and / or carboxylic anhydrides.
  • Example 1 (according to the invention):
  • Catalyst layer 1 (KL1) (vanadium antimonate as V and Sb source):
  • the suspension is heated with stirring to 100 ° C and stirred after reaching 100 ° C for 16 hours at this temperature. Subsequently, the suspension was cooled to 80 ° C and dried by spray drying. The inlet temperature was at 340 ° C, the outlet temperature at 1 10 ° C.
  • the spray powder thus obtained had a content of vanadium of 32% by weight and an antimony content of 30% by weight. The so produced
  • Vanadium antimonate had a vanadium oxidation state of 4.24 and a BET surface area of 95 m 2 / g.
  • the applied to the steatite rings active mass was 8.4%.
  • the analyzed composition of the active composition consisted of 7.1% V 2 0 5 , 4.5% Sb 2 0 3 , 0.50% Cs, remainder TiO 2 .
  • vanadium pentoxide and antimony trioxide were used instead of vanadium antimonate in the preparation of KL2, KL3, KL4 and KL5 as source of V or Sb in the suspension batch.
  • Catalyst layer 2 (KL2) (vanadium pentoxide and antimony trioxide as V or Sb source): Preparation analogous to KL1 with variation of the composition of the suspension. After calcination of the catalyst for one hour at 450 ° C, the applied to the steatite rings active mass was 9.1%. The analyzed composition of the active composition consisted of 7.1% V 2 0 5 , 1, 8% Sb 2 0 3 , 0.38% Cs, balance Ti0 2 with a
  • Catalyst layer 3 (KL3) (vanadium pentoxide and antimony trioxide as V or Sb source): Preparation analogous to KL1 with variation of the composition of the suspension. After calcination of the catalyst for one hour at 450 ° C, the applied to the steatite rings active composition was 8.5%. The analyzed composition of the active composition consisted of 7.95% V 2 0 5 , 2.7% Sb 2 0 3 , 0.31% Cs, balance Ti0 2 with a
  • Catalyst layer 4 (vanadium pentoxide and antimony trioxide as V or Sb source): Preparation analogous to KL1 with variation of the composition of the suspension. After calcination of the catalyst for one hour at 450 ° C, the applied to the steatite rings active composition was 8.5%. The analyzed composition of the active composition consisted of 7.1% V 2 0 5 , 2.4% Sb 2 0 3 , 0.10% Cs, balance Ti0 2 with a
  • Oxidation of o-xylene to phthalic anhydride The catalytic oxidation of o-xylene to phthalic anhydride was carried out in a salt bath-cooled tubular reactor with an inner diameter of the tubes of 25 mm. From reactor inlet to reactor outlet, 80 cm KL1, 60 cm KL2, 70 cm KL3, 50 cm KL4 and 60 cm KL5 were introduced into a 3.5 m long iron tube with a clear width of 25 mm. The iron tube was surrounded by a salt melt for temperature control, a 4 mm outer diameter thermowell with built-in tension element was the catalyst temperature measurement.
  • Example 2 (not according to the invention):
  • Example 1 the proportion of xylene and phthalide in the reactor exit gas was below 0.10 and below 0.15 wt%, respectively.
  • the PSA yield in Example 1 is significantly higher than that in Example 2, the hotspot temperature in Example 1 is significantly lower than in Example 2.
  • Catalyst layer 6 (KL6) (vanadium pentoxide and antimony trioxide as V or Sb source): Preparation analogous to KL1 with variation of the composition of the suspension. After calcination of the catalyst for one hour at 450 ° C was on the steatite rings applied active mass 8.5%. The analyzed composition of the active composition consisted of 1 1, 0% V 2 0 5 , 2.4% Sb 2 0 3 , 0.22% Cs, balance Ti0 2 with a
  • Catalyst layer 7 (vanadium antimonate as V and Sb source):
  • the vanadium antimonate was prepared analogously to Example 1 while varying the V / Sb ratio.
  • the spray powder thus obtained had a vanadium content of 28.5% by weight and an antimony content of 36% by weight.
  • Active mass consisted of 7.1% V 2 0 5 , 6.0% Sb 2 0 3 , 0.50% Cs, balance Ti0 2 with an average BET surface area of 20 m 2 / g.
  • Catalyst layer 8 (KL8) (vanadium antimonate as V and Sb source):
  • the vanadium antimonate was prepared analogously to Example 1 while varying the V / Sb ratio.
  • the spray powder thus obtained had a vanadium content of 35% by weight and an antimony content of 25.5% by weight.
  • the applied to the steatite rings active composition was 8.3%.
  • the analyzed composition of the active composition consisted of 7.1% V 2 0 5 , 3.5% Sb 2 0 3 , 0.55% Cs, remainder TiO 2 with an average BET surface area of 20 m 2 / g.
  • Catalyst layer 9 (KL9) (vanadium pentoxide and antimony trioxide as source of V or Sb): Preparation analogous to KL1 with variation of the composition of the suspension.
  • KL9 vanadium pentoxide and antimony trioxide as source of V or Sb
  • the analyzed composition of the active composition consisted of 7.1% V 2 0 5 , 6.0% Sb 2 0 3 , 0.38% Cs, balance Ti0 2 with a
  • PSA amount means the resulting phthalic anhydride in weight percent based on 100% o-xylene).

Abstract

The invention relates to a catalyst system for producing carboxylic acids and/or carboxylic acid anhydrides, having several catalyst layers lying one above the other in the reaction tube, wherein vanadium antimonate is introduced into the active mass in at least one of the catalyst layers. The invention further relates to a method for gas-phase oxidation in which a gaseous flow comprising at least one hydrocarbon and molecular oxygen is conducted through several catalyst layers, and the maximum hot-spot temperature is under 425 °C.

Description

Mehrlagenkatalysator zur Herstellung von Carbonsäuren und/oder Carbonsäureanhydriden mit Vanadiumantimonat in wenigstens einer Katalysatorlage und Verfahren zur Herstellung von Phthalsäureanhydrid mit niedriger Hotspottemperatur Beschreibung  Multi-layer catalyst for the preparation of carboxylic acids and / or carboxylic anhydrides with vanadium antimonate in at least one catalyst layer and method for the preparation of phthalic anhydride with a low hotspot temperature Description
Die vorliegende Erfindung betrifft ein Katalysatorsystem zur Herstellung von The present invention relates to a catalyst system for the production of
Carbonsäuren und/oder Carbonsäureanhydriden, das mehrere im Reaktionsrohr übereinander angeordnete Katalysatorlagen aufweist, wobei bei mindestens einer der Katalysatorlagen Vanadiumantimonat in die Aktivmasse eingebracht wird. Ferner betrifft die vorliegende Erfindung ein Verfahren zur Gasphasenoxidation, bei dem man einen gasförmigen Strom, der mindestens einen Kohlenwasserstoff und molekularen Sauerstoff umfasst, durch mehrere Katalysatorlagen leitet und die maximale Carboxylic acids and / or carboxylic anhydrides, which has a plurality of catalyst layers arranged one above the other in the reaction tube, wherein in at least one of the catalyst layers Vanadiumantimonat is introduced into the active composition. Furthermore, the present invention relates to a process for gas phase oxidation in which a gaseous stream comprising at least one hydrocarbon and molecular oxygen, passes through several catalyst layers and the maximum
Hotspottemperatur dabei unter 425 °C liegt. Hotspot temperature is below 425 ° C.
Eine Vielzahl von Carbonsäuren und/oder Carbonsäureanhydriden wird technisch durch die katalytische Gasphasenoxidation von Kohlenwasserstoffen, wie Benzol, den Xylolen, Naphthalin, Toluol oder Durol in Festbettreaktoren hergestellt. Man kann auf diese Weise z. B. Benzoesäure, Maleinsäureanhydrid, Phthalsäureanhydrid, Isophthal- säure, Terephthalsäure oder Pyromellithsäure-anhydrid erhalten. Im Allgemeinen leitet man ein Gemisch aus einem sauerstoffhaltigen Gas und dem zu oxidierenden A variety of carboxylic acids and / or carboxylic anhydrides are produced industrially by the catalytic gas phase oxidation of hydrocarbons such as benzene, the xylenes, naphthalene, toluene or durene in fixed bed reactors. You can in this way z. B. benzoic acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid or pyromellitic anhydride. Generally, a mixture of an oxygen-containing gas and the one to be oxidized is passed
Ausgangsmaterial durch Rohre, in denen sich eine Schüttung eines Katalysators befindet. Zur Temperaturregelung sind die Rohre von einem Wärmeträgermedium, beispielsweise einer Salzschmelze, umgeben. Starting material through pipes, in which there is a bed of catalyst. For temperature control, the tubes are surrounded by a heat transfer medium, for example a molten salt.
Bei den im erfindungsgemäßen Verfahren verwendeten Katalysatoren handelt es sich im Allgemeinen um Schalenkatalysatoren, bei denen die katalytisch aktive Masse schalenförmig auf einem inerten Träger aufgebracht ist. Die Schichtdicke der katalytisch aktiven Masse beträgt in der Regel 0,02 bis 0,25 mm, vorzugsweise 0,05 bis 0,15 mm. Der Anteil der Aktivmasse am Katalysator beträgt üblicherweise 5 bis 25 Gew.-%, meist 7 bis 15 Gew.-%. Im Allgemeinen weisen die Katalysatoren eine schalenförmig aufgebrachte Aktivmasseschicht mit im wesentlichen homogener chemischer Zusammensetzung auf. Ferner können auf einen Träger auch The catalysts used in the process according to the invention are generally coated catalysts in which the catalytically active composition is applied in the form of a dish on an inert support. The layer thickness of the catalytically active composition is generally 0.02 to 0.25 mm, preferably 0.05 to 0.15 mm. The proportion of the active material in the catalyst is usually 5 to 25 wt .-%, usually 7 to 15 wt .-%. Generally, the catalysts have a cup-shaped active mass layer of substantially homogeneous chemical composition. Further, on a carrier can also
nacheinander zwei oder mehrere unterschiedliche Aktivmassenschichten aufgebracht werden. Es wird dann von einem Zwei- oder Mehr-Schichten-Katalysator gesprochen (siehe beispielsweise DE 19839001 A1 ). two or more different active mass layers are applied successively. It is then spoken of a two- or multi-layer catalyst (see, for example, DE 19839001 A1).
Als inertes Trägermaterial können praktisch alle Trägermaterialien des Standes der Technik, wie sie vorteilhaft bei der Herstellung von Schalenkatalysatoren für die Oxidation aromatischer Kohlenwasserstoffe zu Aldehyden, Carbonsäuren und/oder Carbonsäureanhydriden eingesetzt werden, Verwendung finden, wie beispielsweise in WO 2004/103561 beschrieben. Bevorzugt wird Steatit in Form von Kugeln mit einem Durchmesser von 3 bis 6 mm oder von Ringen mit einem äußeren Durchmesser von 5 bis 9 mm, einer Länge von 4 bis 7 mm und einem Innendurchmesser von 3 bis 7 mm verwendet. Virtually all support materials of the prior art, as are advantageously used in the preparation of shell catalysts for the oxidation of aromatic hydrocarbons to form aldehydes, carboxylic acids and / or carboxylic anhydrides, can be used as the inert support material, as described, for example, in WO 2004/103561. Steatite is preferred in the form of spheres with a diameter of 3 to 6 mm or of rings with an outer diameter of 5 used to 9 mm, a length of 4 to 7 mm and an inner diameter of 3 to 7 mm.
Üblicherweise wird Titandioxid in der Anatas-Form für katalytisch aktive Masse verwendet. Das Titandioxid weist vorzugsweise eine BET-Oberfläche von 15 bis 60 m2/g, insbesondere 15 bis 45 m2/g, besonders bevorzugt 13 bis 28 m2/g auf. Das eingesetzte Titandioxid kann aus einem einzelnen Titandioxid oder einem Gemisch von Titandioxiden bestehen. In letzterem Fall bestimmt sich der Wert der BET-Oberfläche als gewichteter Mittelwert der Beiträge der einzelnen Titandioxide. Das eingesetzte Titandioxid besteht z. B. vorteilhaft aus einem Gemisch eines T1O2 mit einer BET- Oberfläche von 5 bis 15 m2/g und eines T1O2 mit einer BET-Oberfläche von 15 bis 50 m2/g. Typically, titanium dioxide is used in the anatase form for catalytically active material. 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 may consist of a single titanium dioxide or a mixture of titanium dioxides. In the latter case, the value of the BET surface area is determined as a weighted average of the contributions of the individual titanium dioxides. The titanium dioxide used is z. B. advantageous from a mixture of a T1O2 with a BET surface area of 5 to 15 m 2 / g and a T1O2 with a BET surface area of 15 to 50 m 2 / g.
Als Vanadiumquelle eignen sich besonders Vanadiumpentoxid oder Ammoniummeta- vanadat. Als Antimonquelle eignen sich verschiedene Antimonoxide. Als Particularly suitable vanadium sources are vanadium pentoxide or ammonium meta vanadate. Antimony sources are various antimony oxides. When
Phosphorquelle kommen insbesondere Phosphorsäure, phosphorige Säure, hypophosphorige Säure, Ammoniumphosphat oder Phosphorsäureester und vor allem Ammoniumdihydrogenphosphat in Betracht. Als Quellen von Cäsium kommen das Oxide oder Hydroxid oder die thermisch in das Oxid überführbare Salze wie Phosphorus source are in particular phosphoric acid, phosphorous acid, hypophosphorous acid, ammonium phosphate or phosphoric acid esters and especially ammonium dihydrogen phosphate into consideration. The sources of cesium are the oxides or hydroxide or the salts which can be thermally converted into the oxide, such as
Carboxylate, insbesondere das Acetat, Malonat oder Oxalat, Carbonat, Carboxylates, in particular the acetate, malonate or oxalate, carbonate,
Hydrogencarbonat, Sulfat oder Nitrat in Betracht. Hydrogen carbonate, sulfate or nitrate into consideration.
Neben den optionalen Zusätzen an Cäsium und Phosphor können in der katalytisch aktiven Masse in geringen Mengen eine Vielzahl anderer oxidischer Verbindungen enthalten sein, die als Promotoren die Aktivität und Selektivität des Katalysators beeinflussen, beispielsweise indem sie seine Aktivität absenken oder erhöhen. Als solche Promotoren seien beispielhaft die Alkalimetalle, insbesondere außer dem genannten Cäsium, Lithium, Kalium und Rubidium, die meist in Form ihrer Oxide oder Hydroxide eingesetzt werden, Thallium(l)oxid, Aluminiumoxid, Zirkoniumoxid, In addition to the optional additions of cesium and phosphorus, a small number of other oxidic compounds which, as promoters, influence the activity and selectivity of the catalyst, for example by lowering or increasing its activity, can be present in the catalytically active composition in small amounts. Examples of such promoters are the alkali metals, in particular other than said cesium, lithium, potassium and rubidium, which are usually used in the form of their oxides or hydroxides, thallium (I) oxide, alumina, zirconium oxide,
Eisenoxid, Nickeloxid, Kobaltoxid, Manganoxid, Zinnoxid, Silberoxid, Kupferoxid,Iron oxide, nickel oxide, cobalt oxide, manganese oxide, tin oxide, silver oxide, copper oxide,
Chromoxid, Molybdänoxid, Wolframoxid, Iridiumoxid, Tantaloxid, Nioboxid, Arsenoxid, Antimontetroxid, Antimonpentoxid und Ceroxid genannt. Chromium oxide, molybdenum oxide, tungsten oxide, iridium oxide, tantalum oxide, niobium oxide, arsenic oxide, antimony tetroxide, antimony pentoxide and ceria.
Ferner kommen von den genannten Promotoren noch bevorzugt als Zusätze die Oxide von Niob und Wolfram in Mengen von 0,01 bis 0,50 Gew.-%, bezogen auf die katalytisch wirksame Masse in Betracht. Furthermore, of the promoters mentioned, the oxides of niobium and tungsten in amounts of from 0.01 to 0.50% by weight, based on the catalytically active composition, are also suitable as additives.
Die Aufbringung der einzelnen Schichten des Schalenkatalysators kann mit beliebigen an sich bekannten Methoden erfolgen, z. B. durch Aufsprühen von Lösungen oder Suspensionen in der Dragiertrommel oder Beschichtung mit einer Lösung oder Suspension in einer Wirbelschicht, wie beispielsweise in WO 2005/030388, DE 4006935 A1 , DE 19824532 A1 , EP 0966324 B1 beschrieben. Den verwendeten Suspensionen werden in der Regel organische Binder, bevorzugt Copolymere, vorteilhaft in Form einer wässrigen Dispersion, von Acrylsäure/Maleinsäure, The application of the individual layers of the coated catalyst can be carried out by any known methods, for. Example by spraying solutions or suspensions in the coating drum or coating with a solution or suspension in a fluidized bed, as described for example in WO 2005/030388, DE 4006935 A1, DE 19824532 A1, EP 0966324 B1. The used As a rule, suspensions are organic binders, preferably copolymers, advantageously in the form of an aqueous dispersion of acrylic acid / maleic acid,
Vinylacetat/Vinyllaurat, Vinylacetat/Acrylat, Styrol/Acrylat sowie Vinylacetat/Ethylen zugesetzt. Die Binder sind als wässrige Dispersionen handelsüblich, mit einem Vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate and vinyl acetate / ethylene added. The binders are commercially available as aqueous dispersions, with a
Feststoffgehalt von z. B. 35 bis 65 Gew.-%. Die eingesetzte Menge solcher Solids content of z. B. 35 to 65 wt .-%. The amount used such
Binderdispersionen beträgt im Allgemeinen 2 bis 45 Gew.-%, vorzugsweise 5 bis 35 Gew.-%, besonders bevorzugt 7 bis 20 Gew.-%, bezogen auf das Gewicht der  Binder dispersions is generally 2 to 45 wt .-%, preferably 5 to 35 wt .-%, particularly preferably 7 to 20 wt .-%, based on the weight of
Suspension. Der Träger wird in z. B. einer Wirbelschicht- bzw. Fließbettapparatur in einem aufsteigenden Gasstrom, insbesondere Luft, fluidisiert. Die Apparate bestehen meist aus einem konischen oder kugelförmigen Behälter, bei dem das fluidisierende Gas von unten oder von oben über ein Tauchrohr eingeführt wird. Die Suspension wird über Düsen von oben, seitlich oder von unten in die Wirbelschicht eingesprüht. Vorteilhaft ist der Einsatz eines mittig bzw. konzentrisch um das Tauchrohr angeordneten Steigrohrs. Innerhalb des Steigrohres herrscht eine höhere Gasgeschwindigkeit, die die Suspension. The carrier is in z. As a fluidized bed or fluidized bed apparatus in an ascending gas stream, in particular air, fluidized. The apparatuses usually consist of a conical or spherical container in which the fluidizing gas is introduced from below or from above via a dip tube. The suspension is sprayed via nozzles from above, from the side or from below into the fluidized bed. Advantageously, the use of a centrally or concentrically arranged around the dip tube riser. Within the riser, there is a higher gas velocity, the
Trägerpartikel nach oben transportiert. Im äußeren Ring liegt die Gasgeschwindigkeit nur wenig oberhalb der Lockerungsgeschwindigkeit. So werden die Partikel kreisförmig vertikal bewegt. Eine geeignete Fließbettvorrichtung ist z. B. in der DE-A 4006935 beschrieben. Carrier particles transported upwards. In the outer ring, the gas velocity is only slightly above the loosening speed. So the particles are moved vertically in a circle. A suitable fluidized bed apparatus is z. As described in DE-A 4006935.
Bei der Beschichtung des Katalysatorträgers mit der katalytisch aktiven Masse werden im Allgemeinen Beschichtungstemperaturen von 20 bis 500 °C angewandt, wobei die Beschichtung unter Atmosphärendruck oder unter reduziertem Druck erfolgen kann. Im Allgemeinen erfolgt die Beschichtung bei 0 °C bis 200 °C, vorzugsweise bei 20 bis 150 °C, insbesondere bei 60 bis 120 °C durchgeführt. In coating the catalyst support with the catalytically active composition, generally coating temperatures of 20 to 500 ° C are used, whereby the coating can be carried out under atmospheric pressure or under reduced pressure. In general, the coating is carried out at 0 ° C to 200 ° C, preferably at 20 to 150 ° C, especially at 60 to 120 ° C.
Durch thermische Behandlung des so erhaltenen Präkatalysators bei Temperaturen über 200 bis 500 °C entweicht das Bindemittel durch thermische Zersetzung und/oder Verbrennung aus der aufgetragenen Schicht. Vorzugsweise erfolgt die thermische Behandlung in situ im Gasphasenoxidationsreaktor. By thermal treatment of the pre-catalyst thus obtained at temperatures above 200 to 500 ° C escapes the binder by thermal decomposition and / or combustion of the applied layer. Preferably, the thermal treatment takes place in situ in the gas phase oxidation reactor.
Die Japanische Offenlegungsschrift Nr. 180430/82 offenbart Zweilagenkatalysatoren zur Oxidation von o-Xylol zu Phthalsäureanhydrid, welche Titandioxid und Japanese Patent Laid-Open No. 180430/82 discloses two-layer catalysts for the oxidation of o-xylene to phthalic anhydride, which include titanium dioxide and titanium dioxide
Vanadiumantimonat als katalytisch aktive Komponenten enthalten. Allerdings sind die möglichen o-Xylolbeladungen sowie die Raumgeschwindigkeiten bei diesen Vanadium antimonate as catalytically active components. However, the possible o-xylene loadings as well as the space velocities are at these
Katalysatoren limitiert. Catalysts limited.
Die Hotspottemperaturen beispielsweise bei der Oxidation von o-Xylol zu The hotspot temperatures, for example, in the oxidation of o-xylene too
Phthalsäureanhydrid (PSA) liegen bei Beladungen zwischen 80 und 100 g o-Xylol/Nm3 üblicherweise bei über 440 °C. Hohe Hotspottemperaturen sind Ausdruck einer zu starken Zunahme der Totaloxidation des o-Xylols zu CO, CO2 und Wasser und sind verbunden mit einer verstärkten Schädigung des Katalysators. Anzustreben sind demzufolge möglichst niedrige Hotspottemperaturen. Phthalic anhydride (PSA) are at loadings between 80 and 100 g o-xylene / Nm 3 usually above 440 ° C. High hotspot temperatures are an expression of an excessive increase in the total oxidation of o-xylene to CO, CO2 and water and are associated with increased damage to the catalyst. The aim is therefore to have the lowest possible hotspot temperatures.
Die Aufgabe der vorliegenden Erfindung bestand darin, einen verbesserten Katalysator zur Herstellung von Carbonsäuren und/oder Carbonsäureanhydriden bereitzustellen, insbesondere einen verbesserten Katalysator zur partiellen Oxidation von o-Xylol zu PSA für o-Xylolbeladungen von mindestens 80 g/Nm3 zu entwickeln. The object of the present invention was to provide an improved catalyst for the production of carboxylic acids and / or carboxylic anhydrides, in particular to develop an improved catalyst for the partial oxidation of o-xylene to PSA for o-xylene loadings of at least 80 g / Nm 3 .
Die Lösung der Aufgabe ist ein Mehrlagenkatalysator zur Herstellung von The solution of the problem is a multi-layer catalyst for the production of
Carbonsäuren und/oder Carbonsäureanhydriden mit mindestens 3 Lagen, bei dessen Herstellung mindestens einer Katalysatorlage ein Vanadiumantimonat zugegeben wird. Die Hotspottemperatur eines solchen Katalysators ist insgesamt signifikant niedriger als bei einem Vergleichskatalysator, der ohne Zugabe von Vanadiumantimonat hergestellt wurde, die Carbonsäure bzw. Carbonsäureanhydride-Ausbeuten liegen signifikant höher. Carboxylic acids and / or carboxylic anhydrides with at least 3 layers, in the production of at least one catalyst layer, a vanadium antimonate is added. Overall, the hotspot temperature of such a catalyst is significantly lower than in the case of a comparative catalyst prepared without the addition of vanadium antimonate; the carboxylic acid or carboxylic acid anhydride yields are significantly higher.
Das in der Aktivmasse mindestens einer Lage eingebrachte Vanadiumantimonat kann durch Umsetzung beliebiger Vanadium- und Antimonverbindungen hergestellt werden. Bevorzugt ist die direkte Umsetzung der Oxide zu einem Mischoxid bzw. The vanadium antimonate introduced in the active composition of at least one layer can be prepared by reacting any vanadium and antimony compounds. Preferably, the direct reaction of the oxides to a mixed oxide or
Vanadiumantimonat. Das Vanadiumantimonat kann unterschiedliche molare Vanadium antimonate. The vanadium antimonate may have different molar
Verhältnisse von V/Sb aufweisen sowie ggf. auch weitere Vanadium- bzw. Have ratios of V / Sb and possibly also more vanadium or
Antimonverbindungen enthalten und in Mischung mit weiteren Vanadium- bzw. Contain antimony compounds and mixed with other vanadium or
Antimonverbindungen eingesetzt werden. Die Herstellung des Vanadiumantimonats kann beispielsweise durch Umsetzung der Oxide in wässriger Lösung oder auch durch den Einsatz von Wasserstoffperoxid gekennzeichnet sein. In letzterem Fall kann z. B. Vanadiumpentoxid in einer wässrigen Wasserstoffperoxidlösung gelöst und im Antimony compounds are used. The preparation of the vanadium antimonate can be characterized, for example, by reaction of the oxides in aqueous solution or else by the use of hydrogen peroxide. In the latter case, for. B. vanadium pentoxide dissolved in an aqueous hydrogen peroxide solution and in
Anschluss mit Antimontrioxid zu Vanadiumantimonat umgesetzt werden. Connection can be reacted with antimony trioxide to Vanadiumantimonat.
Die erfindungsgemäßen Katalysatoren umfassen in einer bevorzugten The catalysts of the invention comprise in a preferred
Ausführungsform drei, vier oder fünf Lagen und können beispielsweise zur Vermeidung hoher Hotspottemperaturen auch in Verbindung mit geeigneten Vor- und/oder Embodiment three, four or five layers and can, for example, to avoid high hotspot temperatures in conjunction with suitable pre and / or
Nachschüttungen sowie zusammen mit Zwischenlagen eingesetzt werden, wobei die Vor- und/oder Nachschüttungen sowie die Zwischenlagen in der Regel aus katalytisch inaktivem oder weniger aktivem Material bestehen können. Emptying and together with intermediate layers are used, the pre and / or reposting and the intermediate layers can usually consist of catalytically inactive or less active material.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung eines Another object of the invention is a method for producing a
Mehrlagenkatalysators zur Herstellung von Carbonsäuren und/oder Multi-layer catalyst for the production of carboxylic acids and / or
Carbonsäureanhydriden mit mindestens 3 Lagen, dadurch gekennzeichnet, dass mindestens einer Katalysatorlage ein Vanadiumantimonat zugegeben wird. Carboxylic anhydrides with at least 3 layers, characterized in that at least one catalyst layer, a vanadium antimonate is added.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Gasphasenoxidation von Kohlenwasserstoffen an einem Mehrlagenkatalysator mit mindestens 3 Lagen, bei dessen Herstellung mindestens einer Katalysatorlage ein Vanadiumantimonat zugegeben wird. Das erfindungsgemäße Verfahren eignet sich bevorzugt zur Another object of the invention is a process for the gas phase oxidation of hydrocarbons in a multi-layer catalyst with at least 3 layers, at whose preparation at least one catalyst layer, a vanadium antimonate is added. The inventive method is preferably suitable for
Gasphasenoxidation aromatischer C6- bis Cio-Kohlenwasserstoffe, wie Benzol, den Xylolen, Toluol, Naphthalin oder Durol (1 ,2,4,5-Tetramethylbenzol) zu Carbonsäuren und/oder Carbonsäureanhydriden wie Maleinsäureanhydrid, Phthalsäureanhydrid, Benzoesäure und/oder Pyromellithsäuredianhyrid. Das Verfahren eignet sich besonders zur Herstellung von Phthalsäureanhydrid aus o-Xylol und/oder Naphthalin. Gasphasenreaktionen zur Herstellung von Phthalsäureanhydrid sind allgemein bekannt und beispielsweise in WO 2004/103561 beschrieben. Gas phase oxidation of aromatic C6 to Cio hydrocarbons, such as benzene, the xylenes, toluene, naphthalene or Durol (1, 2,4,5-tetramethylbenzene) to carboxylic acids and / or carboxylic anhydrides such as maleic anhydride, phthalic anhydride, benzoic acid and / or pyromellitic dianhydride. The process is particularly suitable for the preparation of phthalic anhydride from o-xylene and / or naphthalene. Gas-phase reactions for the preparation of phthalic anhydride are generally known and are described, for example, in WO 2004/103561.
Eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, dass die Hotspottemperatur in keiner der Katalysatorlagen über 425 °C liegt. Ein weiterer Gegenstand der Erfindung ist die Verwendung eines A preferred embodiment of the method according to the invention is characterized in that the hotspot temperature is above 425 ° C in any of the catalyst layers. Another object of the invention is the use of a
Mehrlagenkatalysators mit mindestens 3 Lagen, bei dessen Herstellung mindestens einer Katalysatorlage ein Vanadiumantimonat zugegeben wird, zur Herstellung von Carbonsäuren und/oder Carbonsäureanhydriden. Beispiele  Multi-layer catalyst with at least 3 layers, in the preparation of which at least one catalyst layer, a vanadium antimonate is added, for the production of carboxylic acids and / or carboxylic anhydrides. Examples
Beispiel 1 (erfindungsgemäß): Example 1 (according to the invention):
Katalysatorlage 1 (KL1 ) (Vanadiumantimonat als V- und Sb-Quelle):  Catalyst layer 1 (KL1) (vanadium antimonate as V and Sb source):
Herstellung des Vanadiumantimonats: Preparation of vanadium antimonate:
In einem thermostatisierten Doppelmantelglasgefäß wurden 6 I demineralisiertes Wasser vorgelegt. Darin wurden 2855,1 g Vanadiumpentoxid und 1827,5 g 6 l of demineralized water were placed in a thermostated double-walled glass vessel. There were 2855.1 g of vanadium pentoxide and 1827.5 g
Antimontrioxid suspendiert. Anschließend wurde mit einem weiteren Liter Antimony trioxide suspended. Subsequently, with another liter
demineralisiertem Wasser nachgespült, die Suspension unter Rühren auf 100 °C erhitzt und nach Erreichen von 100 °C 16 Stunden bei dieser Temperatur gerührt. Im Anschluss wurde die Suspension auf 80 °C abgekühlt und per Sprühtrocknung getrocknet. Die Eingangstemperatur lag dabei bei 340 °C, die Austrittstemperatur bei 1 10 °C. Das so erhaltene Sprühpulver wies einen Gehalt an Vanadium von 32 Gew.-% sowie einen Gehalt an Antimon von 30 Gew.-% auf. Das so hergestellte rinsed with demineralized water, the suspension is heated with stirring to 100 ° C and stirred after reaching 100 ° C for 16 hours at this temperature. Subsequently, the suspension was cooled to 80 ° C and dried by spray drying. The inlet temperature was at 340 ° C, the outlet temperature at 1 10 ° C. The spray powder thus obtained had a content of vanadium of 32% by weight and an antimony content of 30% by weight. The so produced
Vanadiumantimonat wies eine Vanadiumoxidationsstufe von 4,24 und eine BET- Oberfläche von 95 m2/g auf. Vanadium antimonate had a vanadium oxidation state of 4.24 and a BET surface area of 95 m 2 / g.
Suspensionsansatz und Beschichtung: Suspension batch and coating:
4,44 g Cäsiumcarbonat, 413,7 Titandioxid (Typ Fuji TA 100CT, Anatas, BET- Oberfläche 27 m2/g), 222,1 g Titandioxid (Typ Fuji TA 100, Anatas, BET-Oberfläche 7 m2/g) und 91 ,6 g Vanadiumantimonat wurden in 1869 g demineralisiertem Wasser suspendiert und 18 Stunden gerührt, um eine homogene Verteilung zu erzielen. Zu dieser Suspension wurden 78,4 g organischer Binder, bestehend aus einem Copolymer aus Vinylacetat und Vinyllaurat in Form einer 50 Gew.-%igen wässrigen Dispersion zugegeben. In einer Fließbettapparatur wurden 768 g dieser Suspension auf 2 kg Steatit (Magnesiumsilikat) in Form von Ringen mit Abmessungen von 7 mm x 7 mm x 4 mm aufgesprüht und getrocknet. 4.44 g of cesium carbonate, 413.7 of titanium dioxide (Fuji TA 100CT type, anatase, BET surface area 27 m 2 / g), 222.1 g of titanium dioxide (Fuji TA 100 type, anatase, BET surface area 7 m 2 / g) and 91.6 g of vanadium antimonate were suspended in 1869 g of demineralized water and stirred for 18 hours to obtain a homogeneous distribution. To this suspension, 78.4 g of organic binder consisting of a Copolymer of vinyl acetate and vinyl laurate added in the form of a 50 wt .-% aqueous dispersion. In a fluidized bed apparatus, 768 g of this suspension were sprayed onto 2 kg of steatite (magnesium silicate) in the form of rings with dimensions of 7 mm × 7 mm × 4 mm and dried.
Nach Kalzination des Katalysators für eine Stunde bei 450 °C betrug die auf die Steatitringe aufgebrachte Aktivmasse 8,4 %. Die analysierte Zusammensetzung der Aktivmasse bestand aus 7,1 % V205, 4,5 % Sb203, 0,50 % Cs, Rest Ti02. Im Gegensatz zu KL1 wurde bei der Herstellung von KL2, KL3, KL4 und KL5 statt Vanadiumantimonat Vanadiumpentoxid und Antimontrioxid als V- bzw. Sb-Quelle im Suspensionsansatz eingesetzt. After calcination of the catalyst for one hour at 450 ° C, the applied to the steatite rings active mass was 8.4%. The analyzed composition of the active composition consisted of 7.1% V 2 0 5 , 4.5% Sb 2 0 3 , 0.50% Cs, remainder TiO 2 . In contrast to KL1, vanadium pentoxide and antimony trioxide were used instead of vanadium antimonate in the preparation of KL2, KL3, KL4 and KL5 as source of V or Sb in the suspension batch.
Katalysatorlage 2 (KL2) (Vanadiumpentoxid und Antimontrioxid als V- bzw. Sb-Quelle): Herstellung analog KL1 unter Variation der Zusammensetzung der Suspension. Nach Kalzination des Katalysators für eine Stunde bei 450 °C betrug die auf die Steatitringe aufgebrachte Aktivmasse 9,1 %. Die analysierte Zusammensetzung der Aktivmasse bestand aus 7,1 % V205, 1 ,8 % Sb203, 0,38 % Cs, Rest Ti02 mit einer Catalyst layer 2 (KL2) (vanadium pentoxide and antimony trioxide as V or Sb source): Preparation analogous to KL1 with variation of the composition of the suspension. After calcination of the catalyst for one hour at 450 ° C, the applied to the steatite rings active mass was 9.1%. The analyzed composition of the active composition consisted of 7.1% V 2 0 5 , 1, 8% Sb 2 0 3 , 0.38% Cs, balance Ti0 2 with a
durchschnittlichen BET-Oberfläche von 16 m2/g. average BET surface area of 16 m 2 / g.
Katalysatorlage 3 (KL3) (Vanadiumpentoxid und Antimontrioxid als V- bzw. Sb-Quelle): Herstellung analog KL1 unter Variation der Zusammensetzung der Suspension. Nach Kalzination des Katalysators für eine Stunde bei 450 °C betrug die auf die Steatitringe aufgebrachte Aktivmasse 8,5 %. Die analysierte Zusammensetzung der Aktivmasse bestand aus 7,95 % V205, 2,7 % Sb203, 0,31 % Cs, Rest Ti02 mit einer Catalyst layer 3 (KL3) (vanadium pentoxide and antimony trioxide as V or Sb source): Preparation analogous to KL1 with variation of the composition of the suspension. After calcination of the catalyst for one hour at 450 ° C, the applied to the steatite rings active composition was 8.5%. The analyzed composition of the active composition consisted of 7.95% V 2 0 5 , 2.7% Sb 2 0 3 , 0.31% Cs, balance Ti0 2 with a
durchschnittlichen BET-Oberfläche von 18 m2/g. average BET surface area of 18 m 2 / g.
Katalysatorlage 4 (KL4) (Vanadiumpentoxid und Antimontrioxid als V- bzw. Sb-Quelle): Herstellung analog KL1 unter Variation der Zusammensetzung der Suspension. Nach Kalzination des Katalysators für eine Stunde bei 450 °C betrug die auf die Steatitringe aufgebrachte Aktivmasse 8,5 %. Die analysierte Zusammensetzung der Aktivmasse bestand aus 7,1 % V205, 2,4 % Sb203, 0,10 % Cs, Rest Ti02 mit einer Catalyst layer 4 (KL4) (vanadium pentoxide and antimony trioxide as V or Sb source): Preparation analogous to KL1 with variation of the composition of the suspension. After calcination of the catalyst for one hour at 450 ° C, the applied to the steatite rings active composition was 8.5%. The analyzed composition of the active composition consisted of 7.1% V 2 0 5 , 2.4% Sb 2 0 3 , 0.10% Cs, balance Ti0 2 with a
durchschnittlichen BET-Oberfläche von 17 m2/g. average BET surface area of 17 m 2 / g.
Katalysatorlage 5 (KL5): Catalyst layer 5 (KL5):
Herstellung analog KL1 unter Variation der Zusammensetzung der Suspension. Nach Kalzination des Katalysators für eine Stunde bei 450 °C betrug die auf die Steatitringe aufgebrachte Aktivmasse 9,1 %. Die analysierte Zusammensetzung der Aktivmasse bestand aus 20 % V205, 0,38 % P, Rest Ti02 mit einer durchschnittlichen BET- Oberfläche von 23 m2/g. Preparation analogous to KL1 with variation of the composition of the suspension. After calcination of the catalyst for one hour at 450 ° C, the applied to the steatite rings active mass was 9.1%. The analyzed composition of the active composition consisted of 20% V 2 0 5 , 0.38% P, balance TiO 2 with an average BET surface area of 23 m 2 / g.
Oxidation von o-Xylol zu Phthalsäureanhydrid: Die katalytische Oxidation von o-Xylol zu Phthalsäureanhydrid wurde in einem salzbadgekühlten Rohrreaktor mit einem Innendurchmesser der Rohre von 25 mm durchgeführt. Von Reaktoreingang zu Reaktorausgang wurden 80 cm KL1 , 60 cm KL2, 70 cm KL3, 50 cm KL4 und 60 cm KL5 in ein 3,5 m langes Eisenrohr mit einer lichten Weite von 25 mm eingefüllt. Das Eisenrohr war zur Temperaturregelung von einer Salzschmelze umgeben, eine 4 mm Außendurchmesser Thermohülse mit eingebautem Zugelement diente der Katalysatortemperaturmessung. Oxidation of o-xylene to phthalic anhydride: The catalytic oxidation of o-xylene to phthalic anhydride was carried out in a salt bath-cooled tubular reactor with an inner diameter of the tubes of 25 mm. From reactor inlet to reactor outlet, 80 cm KL1, 60 cm KL2, 70 cm KL3, 50 cm KL4 and 60 cm KL5 were introduced into a 3.5 m long iron tube with a clear width of 25 mm. The iron tube was surrounded by a salt melt for temperature control, a 4 mm outer diameter thermowell with built-in tension element was the catalyst temperature measurement.
Durch das Rohr wurden stündlich von oben nach unten 4,0 Nm3-Luft mit Beladungen an 99,2 Gew.-%igem o-Xylol von 30 bis 100 g/Nm3 geleitet. Dabei wurden bei 80 g o- Xylol/Nm3 die in Tabelle 1 zusammengefassten Ergebnisse erhalten ("PSA-Aubeute" bedeutet das erhaltene Phthalsäure-anhydrid in Gewichtprozent, bezogen auf Through the tube, 4.0 Nm 3 of air with loadings of 99.2% by weight o-xylene of 30 to 100 g / Nm 3 were passed hourly from top to bottom. In this case, the results summarized in Table 1 were obtained at 80 g o-xylene / Nm 3 ("PSA-Aubeute" means the obtained phthalic anhydride in weight percent, based on
100%iges o-Xylol). Beispiel 2 (nicht erfindungsgemäß):  100% o-xylene). Example 2 (not according to the invention):
Von Reaktoreingang zu Reaktorausgang wurden 130 cm KL2, 70 cm KL3, 60 cm KL4, 60 cm KL5 in ein 3,5 m langes Eisenrohr mit einer lichten Weite von 25 mm eingefüllt. Im Gegensatz zu Beispiel 1 wurde in keiner der Katalysatorlagen Vanadiumantimonat zugegeben.  From reactor inlet to reactor outlet, 130 cm KL2, 70 cm KL3, 60 cm KL4, 60 cm KL5 were introduced into a 3.5 m long iron tube with a clear width of 25 mm. In contrast to Example 1, vanadium antimonate was not added to any of the catalyst layers.
Tabelle 1 : Table 1 :
In beiden Beispielen lag der Anteil an Xylol und Phthalid im Reaktorausgangsgas unter 0,10 bzw. unter 0,15 Gew.-%. Die PSA-Ausbeute in Beispiel 1 liegt signifikant höher als die in Beispiel 2, die Hotspottemperatur in Beispiel 1 ist signifikant niedriger als bei Beispiel 2. In both examples, the proportion of xylene and phthalide in the reactor exit gas was below 0.10 and below 0.15 wt%, respectively. The PSA yield in Example 1 is significantly higher than that in Example 2, the hotspot temperature in Example 1 is significantly lower than in Example 2.
Beispiel 3 (erfindungsgemäß): Example 3 (according to the invention):
Katalysatorlage 6 (KL6) (Vanadiumpentoxid und Antimontrioxid als V- bzw. Sb-Quelle): Herstellung analog KL1 unter Variation der Zusammensetzung der Suspension. Nach Kalzination des Katalysators für eine Stunde bei 450 °C betrug die auf die Steatitringe aufgebrachte Aktivmasse 8,5 %. Die analysierte Zusammensetzung der Aktivmasse bestand aus 1 1 ,0 % V205, 2,4 % Sb203, 0,22 % Cs, Rest Ti02 mit einer Catalyst layer 6 (KL6) (vanadium pentoxide and antimony trioxide as V or Sb source): Preparation analogous to KL1 with variation of the composition of the suspension. After calcination of the catalyst for one hour at 450 ° C was on the steatite rings applied active mass 8.5%. The analyzed composition of the active composition consisted of 1 1, 0% V 2 0 5 , 2.4% Sb 2 0 3 , 0.22% Cs, balance Ti0 2 with a
durchschnittlichen BET-Oberfläche von 21 m2/g. Oxidation von o-Xylol zu Phthalsäureanhydrid: average BET surface area of 21 m 2 / g. Oxidation of o-xylene to phthalic anhydride:
Von Reaktoreingang zu Reaktorausgang wurden 80 cm KL1 , 60 cm KL2, 70 cm KL3, 50 cm KL6 und 60 cm KL5 eingefüllt. Durch das Rohr wurden stündlich von oben nach unten 4,0 Nm3-Luft mit Beladungen an 99,2 Gew.-%igem o-Xylol von 30 bis 100 g/Nm3 geleitet. Dabei wurden bei 80 bzw. 100 g o-Xylol/Nm3 die in Tabelle 2 zusammenge- fassten Ergebnisse erhalten ("PSA-Aubeute" bedeutet das erhaltene Phthalsäureanhydrid in Gewichtprozent, bezogen auf 100%iges o-Xylol). From reactor inlet to reactor outlet 80 cm KL1, 60 cm KL2, 70 cm KL3, 50 cm KL6 and 60 cm KL5 were filled. Through the tube, 4.0 Nm 3 of air with loadings of 99.2% by weight o-xylene of 30 to 100 g / Nm 3 were passed hourly from top to bottom. In this at 80 and 100 g o-xylene / m 3, the zusammenge- summarized in Table 2. Results ( "PSA yield" is the phthalic anhydride obtained in percent by weight based on 100% -pure o-xylene).
Tabelle 2: Table 2:
Beispiel 4 (erfindungsgemäß): Example 4 (according to the invention):
Katalysatorlage 7 (KL7) (Vanadiumantimonat als V- und Sb-Quelle):  Catalyst layer 7 (KL7) (vanadium antimonate as V and Sb source):
Die Herstellung des Vanadiumantimonats erfolgte analog Beispiel 1 unter Variation des V/Sb-Verhältnisses. Das so erhaltene Sprühpulver wies einen Gehalt an Vanadium von 28,5 Gew.-% sowie einen Gehalt an Antimon von 36 Gew.-% auf.  The vanadium antimonate was prepared analogously to Example 1 while varying the V / Sb ratio. The spray powder thus obtained had a vanadium content of 28.5% by weight and an antimony content of 36% by weight.
Suspensionsansatz und Beschichtung: Suspension batch and coating:
Siehe Beispiel 1 unter Variation der Zusammensetzung der Suspension mit Einsatz des Vanadiumantimonats aus Beispiel 4.  See Example 1 with variation of the composition of the suspension using the vanadium antimonate from Example 4.
Nach Kalzination des Katalysators für eine Stunde bei 450 °C betrug die auf die Steatitringe aufgebrachte Aktivmasse 8,3 %. Die analysierte Zusammensetzung der After calcination of the catalyst for one hour at 450 ° C, the applied to the steatite rings active composition was 8.3%. The analyzed composition of
Aktivmasse bestand aus 7,1 % V205, 6,0 % Sb203, 0,50 % Cs, Rest Ti02 mit einer durchschnittlichen BET-Oberfläche von 20 m2/g. Active mass consisted of 7.1% V 2 0 5 , 6.0% Sb 2 0 3 , 0.50% Cs, balance Ti0 2 with an average BET surface area of 20 m 2 / g.
Oxidation von o-Xylol zu Phthalsäureanhydrid: Oxidation of o-xylene to phthalic anhydride:
Von Reaktoreingang zu Reaktorausgang wurden 80 cm KL7, 60 cm KL2, 70 cm KL3, 50 cm KL6 und 60 cm KL5 eingefüllt. Durch das Rohr wurden stündlich von oben nach unten 4,0 Nm3-Luft mit Beladungen an 99,2 Gew.-%igem o-Xylol von 30 bis 100 g/Nm3 geleitet. Dabei wurden die in Tabelle 3 zusammengefassten Ergebnisse erhalten ("PSA-Aubeute" bedeutet das erhaltene Phthalsäureanhydrid in Gewichtprozent, bezogen auf 100%iges o-Xylol). Beispiel 5 (erfindungsgemäß): From reactor inlet to reactor outlet 80 cm KL7, 60 cm KL2, 70 cm KL3, 50 cm KL6 and 60 cm KL5 were filled. Every hour from top to bottom, 4.0 Nm 3 of air through the tube with loadings of 99.2% by weight of o-xylene of 30 to 100 g / Nm 3 directed. The results summarized in Table 3 were obtained ("PSA-Aubeute" means the resulting phthalic anhydride in weight percent, based on 100% o-xylene). Example 5 (according to the invention):
Katalysatorlage 8 (KL8) (Vanadiumantimonat als V- und Sb-Quelle):  Catalyst layer 8 (KL8) (vanadium antimonate as V and Sb source):
Die Herstellung des Vanadiumantimonats erfolgte analog Beispiel 1 unter Variation des V/Sb-Verhältnisses. Das so erhaltene Sprühpulver wies einen Gehalt an Vanadium von 35 Gew.-% sowie einen Gehalt an Antimon von 25,5 Gew.-% auf.  The vanadium antimonate was prepared analogously to Example 1 while varying the V / Sb ratio. The spray powder thus obtained had a vanadium content of 35% by weight and an antimony content of 25.5% by weight.
Suspensionsansatz und Beschichtung: Suspension batch and coating:
Siehe Beispiel 1 unter Variation der Zusammensetzung der Suspension mit Einsatz des Vanadiumantimonats aus Beispiel 5.  See Example 1 with variation of the composition of the suspension using the vanadium antimonate from Example 5.
Nach Kalzination des Katalysators für eine Stunde bei 450 °C betrug die auf die Steatitringe aufgebrachte Aktivmasse 8,3 %. Die analysierte Zusammensetzung der Aktivmasse bestand aus 7,1 % V205, 3,5 % Sb203, 0,55 % Cs, Rest Ti02 mit einer durchschnittlichen BET-Oberfläche von 20 m2/g. After calcination of the catalyst for one hour at 450 ° C, the applied to the steatite rings active composition was 8.3%. The analyzed composition of the active composition consisted of 7.1% V 2 0 5 , 3.5% Sb 2 0 3 , 0.55% Cs, remainder TiO 2 with an average BET surface area of 20 m 2 / g.
Oxidation von o-Xylol zu Phthalsäureanhydrid: Oxidation of o-xylene to phthalic anhydride:
Von Reaktoreingang zu Reaktorausgang wurden 80 cm KL8, 60 cm KL2, 70 cm KL3, 50 cm KL6 und 60 cm KL5 eingefüllt. Durch das Rohr wurden stündlich von oben nach unten 4,0 Nm3-Luft mit Beladungen an 99,2 Gew.-%igem o-Xylol von 30 bis 100 g/Nm3 geleitet. Dabei wurden die in Tabelle 3 zusammengefassten Ergebnisse erhalten ("PSA-Aubeute" bedeutet das erhaltene Phthalsäureanhydrid in Gewichtprozent, bezo- gen auf 100%iges o-Xylol). From reactor inlet to reactor outlet 80 cm KL8, 60 cm KL2, 70 cm KL3, 50 cm KL6 and 60 cm KL5 were filled. Through the tube, 4.0 Nm 3 of air with loadings of 99.2% by weight o-xylene of 30 to 100 g / Nm 3 were passed hourly from top to bottom. The results summarized in Table 3 were obtained ("PSA yield" means the phthalic anhydride obtained in percent by weight, based on 100% strength o-xylene).
Tabelle 3 Table 3
Beispiel 6 (nicht erfindungsgemäß): Example 6 (not according to the invention):
Katalysatorlage 9 (KL9) (Vanadiumpentoxid und Antimontrioxid als V- bzw. Sb-Quelle): Herstellung analog KL1 unter Variation der Zusammensetzung der Suspension. Nach Kalzination des Katalysators für eine Stunde bei 450 °C betrug die auf die Steatitringe aufgebrachte Aktivmasse 8,5 %. Die analysierte Zusammensetzung der Aktivmasse bestand aus 7,1 % V205, 6,0 % Sb203, 0,38 % Cs, Rest Ti02 mit einer Catalyst layer 9 (KL9) (vanadium pentoxide and antimony trioxide as source of V or Sb): Preparation analogous to KL1 with variation of the composition of the suspension. To Calcination of the catalyst for one hour at 450 ° C, the applied to the steatite rings active composition was 8.5%. The analyzed composition of the active composition consisted of 7.1% V 2 0 5 , 6.0% Sb 2 0 3 , 0.38% Cs, balance Ti0 2 with a
durchschnittlichen BET-Oberfläche von 20 m2/g. average BET surface area of 20 m 2 / g.
Oxidation von o-Xylol zu Phthalsaureanhydrid: Oxidation of o-xylene to phthalic anhydride:
Von Reaktoreingang zu Reaktorausgang wurden 80 cm KL9, 60 cm KL2, 60 cm KL3, 60 cm KL6 und 60 cm KL5 eingefüllt. Durch das Rohr wurden stündlich von oben nach unten 4,0 Nm3-Luft mit Beladungen an 99,2 Gew.-%igem o-Xylol von 30 bis 100 g/Nm3 geleitet. Dabei wurden die in Tabelle 4 zusammengefassten Ergebnisse erhaltenFrom reactor inlet to reactor outlet, 80 cm KL9, 60 cm KL2, 60 cm KL3, 60 cm KL6 and 60 cm KL5 were filled. Through the tube, 4.0 Nm 3 of air with loadings of 99.2% by weight o-xylene of 30 to 100 g / Nm 3 were passed hourly from top to bottom. The results summarized in Table 4 were obtained
("PSA-Aubeute" bedeutet das erhaltene Phthalsaureanhydrid in Gewichtprozent, bezogen auf 100%iges o-Xylol). ("PSA amount" means the resulting phthalic anhydride in weight percent based on 100% o-xylene).
Tabelle 4 Table 4
Modellrohrergebnisse Beispiel 6 (nicht erfindungsgemäß)  Model tube results Example 6 (not according to the invention)
Luftmenge [Nm3/h] 4,0 Air volume [Nm 3 / h] 4.0
Beladung [g/Nm3] 75 Load [g / Nm 3 ] 75
Laufzeit [Tage] 29  Duration [days] 29
Salzbadtemperatur [°C] 361  Salt bath temperature [° C] 361
Hotspottemperatur [°C] 448  Hotspot temperature [° C] 448
PSA-Ausbeute [Gew.-%] 1 12,4  PSA yield [wt%] 1 12.4

Claims

Ansprüche claims
1 . Mehrlagenkatalysator zur Herstellung von Carbonsäuren und/oder 1 . Multi-layer catalyst for the production of carboxylic acids and / or
Carbonsäureanhydriden mit mindestens 3 Lagen, dadurch gekennzeichnet, dass bei der Herstellung des Katalysators mindestens einer Katalysatorlage ein  Carboxylic acid anhydrides with at least 3 layers, characterized in that in the preparation of the catalyst at least one catalyst layer
Vanadiumantimonat zugegeben wird.  Vanadiumantimonat is added.
2. Verfahren zur Oxidation von o-Xylol zu Phthalsäureanhydrid an einem 2. A process for the oxidation of o-xylene to phthalic anhydride on a
Mehrlagenkatalysator gemäß Anspruch 1 .  Multi-layer catalyst according to claim 1.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die Hotspottemperatur in keiner der Katalysatorlagen über 425 °C liegt. 3. The method according to claim 2, characterized in that the hotspot temperature in any of the catalyst layers is above 425 ° C.
4. Verwendung eines Katalysators gemäß Anspruch 1 zur Herstellung von 4. Use of a catalyst according to claim 1 for the preparation of
Carbonsäuren und/oder Carbonsäureanhydriden.  Carboxylic acids and / or carboxylic anhydrides.
5. Verfahren zur Herstellung eines Mehrlagenkatalysators zur Herstellung von 5. A process for the preparation of a multilayer catalyst for the production of
Carbonsäuren und/oder Carbonsäureanhydriden mit mindestens 3 Lagen, dadurch gekennzeichnet, dass mindestens einer Katalysatorlage ein Vanadiumantimonat zugegeben wird.  Carboxylic acids and / or carboxylic anhydrides with at least 3 layers, characterized in that at least one catalyst layer, a vanadium antimonate is added.
EP10781485A 2009-11-20 2010-11-15 Multilayer catalyst for producing carboxylic acids and/or carboxylic acid anhydrides with vanadium antimonate in at least one catalyst layer, and method for producing phthalic acid anhydride with a low hot-spot temperature Withdrawn EP2501472A1 (en)

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