EP1814660A1 - Utilisation de melanges d'oxyde de titane pour produire des catalyseurs - Google Patents

Utilisation de melanges d'oxyde de titane pour produire des catalyseurs

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Publication number
EP1814660A1
EP1814660A1 EP05815892A EP05815892A EP1814660A1 EP 1814660 A1 EP1814660 A1 EP 1814660A1 EP 05815892 A EP05815892 A EP 05815892A EP 05815892 A EP05815892 A EP 05815892A EP 1814660 A1 EP1814660 A1 EP 1814660A1
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EP
European Patent Office
Prior art keywords
weight
catalyst
titanium dioxide
layer
anatase
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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Application number
EP05815892A
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German (de)
English (en)
Inventor
Samuel Neto
Sebastian Storck
Jürgen ZÜHLKE
Frank Rosowski
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BASF SE
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BASF SE
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Publication date
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Publication of EP1814660A1 publication Critical patent/EP1814660A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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—
    • B01J35/60—
    • B01J35/613—
    • 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
    • B01J37/0232—Coating by pulverisation
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to the use of titanium dioxide mixtures of the anatase form with defined physical properties for the preparation of catalysts which are particularly suitable for phthalic anhydride synthesis. Furthermore, the invention relates to catalysts which contain titanium dioxide mixtures of the anatase form with defined physical properties.
  • Titanium dioxide in the anatase modification is the main constituent of the active composition of the phthalic anhydride catalysts and serves to support the catalytically active and selective vanadium pentoxide components.
  • DE-A 2 106 796 describes the preparation of supported catalysts for the oxidation of o-xylene to phthalic anhydride, wherein the titanium dioxide has a BET surface area of 15 to 100 m 2 / g, preferably 25 to 50 m 2 / g. Particularly suitable is a mixture of anatase of the BET surface area of 7 to 11 m 2 / g and titanium dioxide hydrate of BET surface area> 100 m 2 / g, wherein the components alone would not be suitable.
  • EP-A 522 871 describes a relationship between the BET surface area of the titanium dioxide and the catalyst activity.
  • the catalyst activity is when titanium dioxide having BET surface areas of below
  • BET surface areas are preferably from 15 to 40 m 2 / g.
  • the individual catalyst layers are structured so that in general the activity of the individual layers increases from the reactor inlet to the reactor outlet.
  • EP-A 985 648 describes the preparation of phthalic anhydride by catalytic gas phase oxidation of o-xylene and / or naphthalene with a catalyst system which is structured so that the porosity of the catalyst and thus the activity from the reactor inlet to the reactor outlet increases quasi-continuously.
  • the porosity is defined by the free volume between the coated moldings of the bed in the reaction tube.
  • the specific surface area of the active components changed by the variation of the specific surface of titanium dioxide, this was between 40 and 140 m 2 / g.
  • the BET surface area of the titanium dioxide should be between 10 and 60 m 2 / g. In the examples of EP-A1 063 222, the BET surface area is constant at 22 m 2 / g.
  • the decrease in the activity of the first catalyst layer with respect to the life of the catalyst has a negative effect.
  • sales decline in the range of the first highly selective layer.
  • the main reaction zone migrates deeper and deeper into the catalyst bed over the course of the catalyst life, i.
  • the o-xylene or Naphthalinfeed is increasingly implemented only in the subsequent less selective layers.
  • the result is reduced Phthalcicreanhydridausbeuten and an increased concentration of by-products or unreacted starting materials.
  • the salt bath temperature can be raised steadily. As the catalyst life increases, however, this measure also leads to a reduction in the phthalic anhydride yield.
  • the object was therefore to show catalysts with improved properties, in particular with respect to the yield. Above all, it is intended to show oxidation catalysts, in particular phthalic anhydride catalysts having improved activity, selectivity and yield.
  • the object further consisted of finding oxidation catalysts which, when used in an activity-structured multilayer catalyst system, combine the advantages thereof with those of a high service life and high selectivity in the first catalyst layers.
  • titanium dioxide (s) A in anatase modification which has a BET surface area greater than 15 m 2 / g and a hydrogen uptake for the reduction of Ti 4+ to Ti 3+ from 5 to 20 ⁇ mol / m 2
  • titanium dioxide (s) B in anatase modification which has a BET surface area of less than or equal to 15 m 2 / g and a hydrogen uptake for the reduction of Ti 4+ Ti 3+ from 0.6 to 7 ⁇ mol / m 2
  • titanium dioxide (s) A which has a BET surface area of 18 to 90 m 2 / g, in particular from 18 to 55 m 2 / g. Titanium dioxide A preferably has a hydrogen uptake for the reduction of Ti 4+ to Ti 3+ from 5 to 17 ⁇ mol / m 2 .
  • Titanium dioxide B 1 which has a BET surface area of 3 to 15 m 2 / g. Titanium dioxide B preferably has a hydrogen uptake for the reduction of Ti 4+ to Ti 3+ from 0.6 to 5 ⁇ mol / m 2 .
  • the BET surface area of the titanium dioxide mixture of A and B advantageously has a value of from 5 to 50 m 2 / g, in particular from 10 to 30 m 2 / g.
  • the mixture is advantageously carried out with a ratio of titanium dioxide (s) A to titanium oxides (B) of from 0.5: 1 to 6: 1, in particular from 1: 1 to 5: 1.
  • titanium dioxide mixture used according to the invention particularly preferably consists of one titanium dioxide each from group A and B.
  • the titanium dioxide mixture used according to the invention is suitable for the preparation of catalysts which are used in an activity-structured at least two-phase, preferably at least three-layered catalyst system in the uppermost or the upper, in particular in the upper, catalyst entrance to the reactor entrance.
  • An activity-structured catalyst system is understood as meaning a system of different catalyst layers, the activity of the catalysts changing from one layer to the next. In general, preference is given to catalyst systems whose activity increases virtually continuously from the reactor inlet to the reactor outlet. However, one or more intermediate or intermediate catalyst layers which have a higher activity than the subsequent layers can be used.
  • titanium dioxide mixture used according to the invention when using the titanium dioxide mixture used according to the invention in a multilayer catalyst system, it is advantageous in the uppermost layer with a ratio of titanium dioxide (e) A to titanium dioxide (s) B of 0.8: 1 to 3: 1, in particular 1 : 1 to 2.5: 1 used. Titanium dioxide mixtures or pure titanium dioxides of the anatase modification can be used in the further layers. When using titanium dioxide mixtures, the ratio of A to B in the next lower layer is advantageously 2: 1 to 5: 1.
  • the titanium dioxide mixture mentioned is particularly suitable for the preparation of oxidation catalysts for the synthesis of aldehydes, carboxylic acids and / or carboxylic acid anhydrides.
  • the titanium dioxide mixture mentioned is particularly suitable for the preparation of phthalic anhydride catalysts which are prepared in an activity-structured at least two-layer, preferably at least three-day catalyst system in the uppermost (in a two-layer catalyst system) or in the two uppermost or in the uppermost lysator für used (in a three- or multi-layer catalyst system) were ⁇ the.
  • the catalyst top layer according to the invention may contain one or more catalyst layers as a precursor to said titanium dioxide mixture.
  • benzaldehyde, benzoic acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, pyromellitic anhydride or nicotinic acid can advantageously be prepared using the catalyst according to the invention, which is described below.
  • a mixture of a gas comprising molecular oxygen, for example air, and the starting material to be oxidized is generally passed through tubes in which there is a charge of the catalyst according to the invention.
  • the oxidation is carried out using the catalyst according to the invention in an activity-structured catalyst system.
  • Suitable catalysts are oxidic supported catalysts.
  • coated catalysts in which the catalytically active composition has been applied to the carrier in the form of a dish have proven particularly useful.
  • the catalytically active constituent used is preferably vanadium pentoxide.
  • promoters are, for example, the alkali metal oxides, thallium (I) oxide, aluminum oxide, zirconium oxide, iron oxide, nickel oxide, cobalt baltoxid, manganese oxide, tin oxide, silver oxide, copper oxide, chromium oxide, molybdenum oxide, tungsten oxide, iridium oxide, tantalum oxide, niobium oxide, arsenic oxide, antimony oxide, cerium oxide and phosphorus pentoxide.
  • promoters are, for example, the alkali metal oxides, thallium (I) oxide, aluminum oxide, zirconium oxide, iron oxide, nickel oxide, cobalt baltoxid, manganese oxide, tin oxide, silver oxide, copper oxide, chromium oxide, molybdenum oxide, tungsten oxide, iridium oxide, tantalum oxide, niobium oxide, arsenic oxide, antimony oxide, cerium oxide and phosphorus pentoxide.
  • the alkali metal oxides act, for example, as promoters which reduce the activity and increase the selectivity.
  • organic binders preferably copolymers, advantageously in the form of an aqueous dispersion, of vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / maleate, vinyl acetate / ethylene and hydroxyethyl cellulose can be added to the catalytically active composition, with binder amounts of from 3 to 20 % By weight, based on the solids content of the solution of the active ingredient components, were used (EP-A 744 214).
  • Organic binders are preferably used as described in DE-A 198 24 532.
  • coating temperatures above 15O 0 C is advantageous.
  • the surrounded angege ⁇ usable coating temperatures depending on ver ⁇ dietarytem binder comprises between 50 and 45O 0 C (DE-A 2106796).
  • the applied binders burn out after filling the catalyst and starting up the reactor within a short time.
  • the binder additive has the advantage that the active material adheres well to the carrier, so that transport and filling of the catalyst are facilitated.
  • the catalyst for the Phthalcicreanhydrisynthese has on porous and / or non-porous support material advantageously 5 to 15 wt .-% based on the total catalyst, active composition, said active composition 3 to 30 wt .-% V 2 O 5 , 0 to 4 Wt .-% Sb 2 O 3 , 0 to 1, 0 wt .-% P, 0 to 1, 5 wt .-% alkali (calc.
  • titanium dioxide (s) A in anatase modification which has a BET surface area of greater than 15 m 2 / g and a hydrogen uptake for the reduction of Ti 4+ to Ti 3+ from 5 to 20 ⁇ mol / m 2
  • titanium dioxide (e) B in anatase modification which has a BET surface area of less than or equal to 15 m 2 / g and a Wasserstoffauf ⁇ assumption for the reduction of Ti 4+ to Ti 3+ from 0.6 to 7 mol / m 2 .
  • the catalyst on carrier material has from 5 to 12% by weight, based on the total catalyst, of active composition, this active composition being from 3 to 20% by weight of V 2 O 5 , 0 to 4 Wt .-% Sb 2 O 3 , 0 to 0.5 wt .-% P, 0.1 to 1, 5 wt .-% alkali (calc.
  • titanium dioxide (e) A in Anatase modification which has a BET surface area of greater than 15 m 2 / g and a hydrogen uptake for the reduction of Ti 4+ to Ti 3+ from 5 to 20 ⁇ mol / m 2
  • titanium dioxide (e) B in anatase modification which has a BET surface area of less than or equal to 15 m 2 / g and a hydrogen uptake for the reduction of Ti 4+ to Ti 3+ from 0.6 to 7 ⁇ mol / m 2 .
  • multilayer catalyst systems are used in which the less active catalyst is placed in a fixed bed such that the reaction gas first with this catalyst and only then with the more active catalyst in the second layer comes into contact. If appropriate, pre-or intermediate-layer catalyst layers which have a higher activity than the subsequent catalyst layer can be used. Subsequently, the reaction gas comes into contact with the still more active catalyst layers.
  • the differently active catalysts can be thermostated to the same or different temperatures.
  • three- to five-day catalyst systems are used, in particular three- and four-layer catalyst systems.
  • catalyst systems whose catalyst activity increases quasi-continuously from layer to layer are preferred.
  • the catalysts for the synthesis of phthalic anhydride have the following composition:
  • an alkali (calculated as alkali metal), in particular cesium oxide, and the remainder to 100% by weight of a mixture of titanium dioxide (s) A in anatase modification which has a BET surface area greater than than 15 m 2 / g and a hydrogen uptake for the reduction of Ti 4+ to Ti 3+ from 5 to 20 ⁇ mol / m 2
  • titanium dioxide (e) B in anatase modification which has a BET surface area of less than or equal to 15 m 2 / g and a hydrogen uptake for the reduction of Ti 4+ to Ti 3+ from 0.6 to 7 ⁇ mol / m 2
  • an alkali (calculated as the alkali metal), in particular cesium oxide 0 to 0.4 wt .-% phosphorus pentoxide (calculated as P) and the remainder to 100 wt .-% titanium dioxide in anatase, given Where appropriate as in layer a)
  • Active composition 5 to 30% by weight of vanadium (calculated as V 2 O 5 ) 0 to 3 wt .-% antimony trioxide
  • an alkali (calculated as the alkali metal), in particular cesium oxide 0.05 to 0.4 wt .-% phosphorus pentoxide (calculated as P) and the balance to 100 wt .-% titanium dioxide, in particular in anatase modification, if appropriate as in layer a).
  • the catalysts have the following composition:
  • From 6 to 11% by weight of vanadium (calculated as V 2 O 5 ) from 0 to 3% by weight of antimony trioxide contains from 0.1 to 1% by weight of an alkali (calculated as alkali metal), in particular cesium oxide, and the remainder to 100 %
  • a mixture of titanium dioxide (s) A in anatase modification which has a BET surface area of greater than 15 m 2 / g and a hydrogen absorption for the reduction of Ti 4+ to Ti 3+ from 5 to 20 micromol / m 2 has auf ⁇
  • titanium dioxide (s) B in the anatase modification the m a BET surface area of less than or equal to 15 2 / g and an absorption of hydrogen for the reduction of Ti 4+ to Ti 3+ 0.6 to 7 has ⁇ mol / m 2
  • active composition based on the total catalyst, this active composition being:
  • an alkali (calculated as alkali metal), in particular cesium oxide 0 to 0.4% by weight of phosphorus pentoxide (calculated as P) and the remainder to 100% by weight of titanium dioxide in anatase modification Where appropriate as in layer a)
  • active composition based on the total catalyst, this active composition being:
  • an alkali (calculated as the alkali metal), in particular cesium oxide 0 to 0.4 wt .-% phosphorus pentoxide (calculated as P) and the remainder to 100 wt .-% titanium dioxide in anatase, given Where appropriate as in layer a) for the fourth layer (layer c, towards the reactor exit)): 8 to 12% by weight of active composition based on the total catalyst, this active compound being:
  • the catalyst layers a), b1), b2) and / or c) can also be arranged so that they each consist of two or more layers. These interlayers advantageously have intermediate catalyst compositions.
  • a quasi-continuous transition of the layers and a quasi-uniform increase in the activity can be effected by forming a zone with a mixing of the following catalysts in the transition from one layer to the next layer performs.
  • the catalysts are filled in layers to react in the tubes of a Rohrbündelre ⁇ actuator.
  • the reaction gas at salt bath temperatures of generally 300 to 45O 0 C, preferably 320 to 42O 0 C and more preferably 340 to 400 0 C, passed.
  • the different catalyst beds can also be thermostated to different temperatures.
  • the bed length of the first catalyst layer preferably accounts for more than 20 to 80% of the total catalyst fill level in the reactor.
  • the bed height of the first two, or the first three catalyst layers advantageously makes up more than 60 to 95% of the total Katalysator collliere. If appropriate, one or more catalyst layers, which preferably make up less than 20% of the total catalyst charge height, may be disposed upstream of the first catalyst layer mentioned.
  • Typical reactors have a filling height of 250 cm to 350 cm.
  • the Katalysator ⁇ layers can also be optionally distributed to several reactors.
  • the reaction gas (starting gas mixture) fed to the catalyst is generally accompanied by mixing a gas containing molecular oxygen, which may also contain suitable reaction moderators, such as nitrogen, and / or diluents, such as steam and / or carbon dioxide, besides oxygen the oxidized o-xylene or naphthalene produced.
  • the reaction gas generally contains 1 to 100 mol%, preferably 2 to 50 mol%, and particularly preferably 10 to 30 mol% of oxygen.
  • the reaction gas is mixed with 5 to 140 g / Nm 3 gas, preferential Example 60 to 120 g / Nm 3 and more preferably 80 to 120 g / Nm 3 o-xylene and / or naphthalene loaded.
  • the catalyst used is preferably an even more active catalyst in comparison to the catalyst of the last layer.
  • the catalysts of the invention have the advantage of improved performance. This improvement can be observed even at high loadings with o-xylene and / or naphthalene, eg at 100 g / Nm 3 .
  • the resulting suspension was then sprayed onto 1200 g of steatite (magnesium silicate) in the form of rings with an outer diameter of 7 mm, a length of 7 mm and a wall thickness of 1.5 mm and dried.
  • the weight of the applied shell was 8% of the total weight of the finished catalyst.
  • the catalytically active composition applied in this manner after one hour of calcination at 450 ° C., contained 7.1% by weight of vanadium (calculated as V 2 O 5 ), 1.8% by weight of anti-mon (calculated as Sb 2 O) 3 ), 0.36 wt% cesium (calculated as Cs).
  • the BET surface area of the TiO 2 mixture was 15.8 m 2 / g.
  • the resulting suspension was then sprayed onto 1200 g of steatite (magnesium silicate) in the form of rings with an outer diameter of 7 mm, a length of 7 mm and a wall thickness of 1.5 mm and dried.
  • the weight of the applied shell was 8% of the total weight of the finished catalyst.
  • the thus applied catalytically active material, ie the catalyst shell comprised one hour calcination at 45O 0 C 7.1 wt .-% of vanadium (calculated as V 2 O 5), 2.4 wt .-% antimony (calculated as Sb 2 O 3 ), 0.26 wt% cesium (calculated as Cs).
  • the BET surface area of the TiO 2 mixture was 16.4 m 2 / g.
  • organic binder consisting of a copolymer of vinyl acetate and vinyl laurate in the form of a 50 wt .-% aqueous dispersion.
  • the resulting suspension was then sprayed onto 1200 g of steatite (magnesium silicate) in the form of rings with an outer diameter of 7 mm, a length of 7 mm and a wall thickness of 1.5 mm and dried.
  • the weight of the applied shell was 8% of the total weight of the finished catalyst.
  • the catalytically active material applied in this manner ie the catalyst shell, contained, after one hour of calcination at 450 ° C., 7.1% by weight of vanadium (calculated as V 2 O 5 ), 2.4% by weight of antimony (calculated as Sb 2 O 3 ), 0.10% by weight of cesium (calculated as Cs).
  • the BET surface area of the TiO 2 mixture was 16.4 m 2 / g.
  • the resulting suspension was subsequently sprayed onto 1200 g of steatite (magnesium silicate) in the form of rings with an outer diameter of 7 mm, a length of 7 mm and a wall thickness of 1.5 mm and dried.
  • the weight of the applied shell was 8% of the total weight of the finished catalyst.
  • the catalytically active material applied in this manner ie the catalyst shell, contained, after one hour of calcination at 450 ° C., 20.00% by weight of vanadium (calculated as V 2 O 5 ), 0.38% by weight of phosphorus (calculated as P).
  • the BET surface area of the TiO 2 mixture was 20.9 m 2 / g.
  • the suspension was applied to 1200 g of steatite molded article (magnesium silicate) in the form of rings (7 ⁇ 7 ⁇ 4 mm, OD ⁇ L ⁇ ID) by spraying.
  • the weight of the applied Aktivmassen ⁇ shell was 8% of the total weight of the finished catalyst.
  • the catalytically active composition applied in this manner after calcination at 400 ° C. for 4 hours, contained 7.1% by weight of V 2 O 5 , 2.4% by weight of Sb 2 O 3 , 0.36% by weight of Cs.
  • the BET surface area was 14.7 m 2 / g.
  • the suspension was applied to 1200 g of steatite molded article (magnesium silicate) in the form of rings (7 ⁇ 7 ⁇ 4 mm, OD ⁇ L ⁇ ID) by spraying.
  • the weight of the applied Aktivmassen ⁇ shell was 9% of the total weight of the finished catalyst.
  • the catalytically active composition applied in this manner after calcination at 400 ° C. for 4 hours contained 8.6% by weight of V 2 O 5 , 2.6% by weight of Sb 2 O 3 , 0.10% by weight of Cs.
  • the BET surface area was 20.8 m 2 / g.
  • Undercoat (c) 24.6 g anatase (BET-OF 7 m 2 / g, H 2 uptake: 4.9 ⁇ mol / m 2 ), 73.7 g anatase (BET-OF 30 m 2 / g, H 2 Uptake: 2.8 ⁇ mol / m 2 ), 25.0 g of V 2 O 5 , 1.7 g of NH 4 H 2 PO 4 were suspended in 650 ml of deionized water and stirred for 15 hours. To this suspension was then added 62 g of an aqueous dispersion (50% by weight) of vinyl acetate and vinyl laurate.
  • the suspension was applied to 1200 g of steatite molded article (magnesium silicate) in the form of rings (7 ⁇ 7 ⁇ 4 mm, AD ⁇ L ⁇ ID) by spraying.
  • the weight of the applied active mass shell was 10% of the total weight of the finished catalyst.
  • the catalytically active composition applied in this manner after calcination at 400 ° C. for 4 hours contained 20.0% by weight of V 2 O 5 , 0.4% by weight of P.
  • the BET surface area was 24.2 m 2 / gA 2
  • the suspension was applied to 1200 g of steatite molded body (magnesium silicate) in the form of rings (7 ⁇ 7 ⁇ 4 mm, outside diameter (AD) ⁇ length (L) ⁇ inside diameter (ID)) by spraying.
  • the weight of the applied active composition shell was 8% of the total weight of the finished catalyst.
  • the catalytically active composition applied in this manner after calcining at 400 ° C. for 4 hours, contained 7.1% by weight of V 2 O 5 , 2.4% by weight of Sb 2 O 3 , 0.33% by weight of Cs.
  • the BET surface area was 18.4 m 2 / g.
  • the suspension was applied to 1200 g of steatite molded article (magnesium silicate) in the form of rings (7 ⁇ 7 ⁇ 4 mm, AD ⁇ L ⁇ ID) by spraying.
  • the weight of the applied active mass shell was 9% of the total weight of the finished catalyst.
  • the catalytically active composition applied in this manner contained 11.5% by weight of V 2 O 5 , 0.4% by weight of P.
  • the BET surface area was 21. 3 m 2 / g ,
  • the suspension was applied to 1200 g of steatite molded article (magnesium silicate) in the form of rings (7 ⁇ 7 ⁇ 4 mm, AD ⁇ L ⁇ ID) by spraying.
  • the weight of the applied active mass shell was 9% of the total weight of the finished catalyst.
  • the catalytically active composition applied in this manner after calcining at 400 ° C. for 4 h, contained 20.0% by weight of V 2 O 5 , 0.4% by weight of P.
  • the BET surface area was 19.9 m 2 / g ,
  • the suspension was applied to 1200 g of steatite molded article (magnesium silicate) in the form of rings (7 ⁇ 7 ⁇ 4 mm, OD ⁇ L ⁇ ID) by spraying.
  • the weight of the applied Aktivmassen ⁇ shell was 8% of the total weight of the finished catalyst.
  • the catalytically active composition applied in this manner after calcination at 400 ° C. for 4 hours, contained 7.1% by weight of V 2 O 5 , 2.4% by weight of Sb 2 O 3 , 0.36% by weight of Cs.
  • the BET surface area was 16.1 m 2 / g.
  • the suspension was applied to 1200 g of steatite molded article (magnesium silicate) in the form of rings (7 ⁇ 7 ⁇ 4 mm, AD ⁇ L ⁇ ID) by spraying.
  • the weight of the applied active mass shell was 9% of the total weight of the finished catalyst.
  • the catalytically active composition applied in this manner after calcination at 400 ° C. for 4 hours contained 7.1% by weight of V 2 O 5 , 2.4% by weight of Sb 2 O 3 , 0.10% by weight of Cs, 0.4 wt.% P.
  • the BET surface area was 17.3 m 2 / g.
  • the suspension was applied to 1200 g of steatite molded article (magnesium silicate) in the form of rings (7 ⁇ 7 ⁇ 4 mm, AD ⁇ L ⁇ ID) by spraying.
  • the weight of the applied active mass shell was 10% of the total weight of the finished catalyst.
  • the BET surface area was
  • the suspension obtained was then sprayed onto 1200 g of steatite (magnesium silicate) in the form of rings (7 ⁇ 7 ⁇ 4 mm, (AD) ⁇ (L) ⁇ (ID)) and dried.
  • the weight of the applied shell was 8% of the total weight of the finished catalyst.
  • the catalytically active mass applied in this way ie the catalyst shell, after one hour of calcination to 450 0 C contained 7.12 wt .-% vanadium (calculated as V 2 O 5 ), 2.37 wt .-% antimony (calculated as Sb 2 O 3 ), 0.36 wt Cesium (calculated as Cs), 27.20% by weight of titanium dioxide (TiO 2 -I) and 63.46% by weight of titanium dioxide (TiO 2 -2).
  • the catalytically active material applied in this manner ie the catalyst shell, contained, after one hour of calcination at 450 ° C., 7.12% by weight of vanadium (calculated as V 2 O 5 ), 2.37% by weight of antimony (calculated as Sb 2 O 3 ), 0.26 wt.% Cesium (calculated as Cs), 22.60 wt.% Titanium dioxide (TiO 2 -I) and 67.79 wt.% Titanium dioxide (TiO 2 -2).
  • the suspension obtained was then sprayed onto 1200 g of steatite (magnesium silicate) in the form of rings (7 ⁇ 7 ⁇ 4 mm, (AD) ⁇ (L) ⁇ (ID)) and dried.
  • the weight of the applied shell was 8% of the total weight of the finished catalyst.
  • the catalytically active material applied in this manner ie the catalyst shell, contained, after one hour of calcination at 450 ° C., 7.12% by weight of vanadium (calculated as V 2 O 5 ), 2.37% by weight of antimony (calculated as Sb 2 O 3 ), 0.10% by weight of cesium (calculated as Cs), 22.60% by weight of titanium dioxide (TiO 2 -I) and 67.79% by weight of titanium dioxide (TiO 2 -2).
  • the catalytically active material applied in this manner ie the catalyst shell, contained, after one hour of calcination at 450 ° C., 20.0% by weight of vanadium (calculated as V 2 O 5 ), 0.38% by weight of phosphorus (calculated as P), 15.73% by weight of titanium dioxide (TiO 2 -I) and 62.90% by weight of titanium dioxide (TiO 2 -3).
  • 200 mg of the TiO 2 in the anatase modification were positioned as a powdery bed in the reactor.
  • a pretreatment was carried out to remove adsorbed water.
  • the sample was heated in helium at 20 K / min to 673 K and left for one hour at this temperature. After cooling to below 232 K and purging in helium, the experiment was carried out.
  • the sample was heated with a ramp of 15 K / min to a final temperature of 1373 K in H 2 / He stream (10% H 2 in He, flow: 30 Nml / min).
  • the hydrogen consumption was determined by gas chromatography (thermal conductivity detector) and then normalized to the amount / surface area of the sample.

Abstract

L'invention se rapporte à l'utilisation de mélanges d'oxyde de titane de forme anatase présentant des propriétés physiques définies pour produire des catalyseurs qui sont en particulier utilisés pour la synthèse d'anhydride phtalique. Cette invention concerne également des catalyseurs qui contiennent de l'oxyde de titane de forme anatase présentant des propriétés physiques définies.
EP05815892A 2004-11-18 2005-11-16 Utilisation de melanges d'oxyde de titane pour produire des catalyseurs Withdrawn EP1814660A1 (fr)

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PCT/EP2005/012283 WO2006053732A1 (fr) 2004-11-18 2005-11-16 Utilisation de melanges d'oxyde de titane pour produire des catalyseurs

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RU2007122282A (ru) 2008-12-27
TW200626232A (en) 2006-08-01
MX2007005850A (es) 2007-06-15
JP2008520418A (ja) 2008-06-19
US20080064594A1 (en) 2008-03-13
KR101308197B1 (ko) 2013-09-13
WO2006053732A1 (fr) 2006-05-26
KR20070086369A (ko) 2007-08-27
TWI378823B (en) 2012-12-11
BRPI0517850A (pt) 2008-10-21
CN101060927A (zh) 2007-10-24
US7851398B2 (en) 2010-12-14
CN101060927B (zh) 2011-05-11

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