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  • B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
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  • 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
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  • 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
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  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
  • B01J27/198—Vanadium
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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  • B01J37/02—Impregnation, coating or precipitation
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  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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  • Y02P20/00—Technologies relating to chemical industry
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  • Y02P20/584—Recycling of catalysts

Definitions

• the invention relates to a process for the conversion of a multimetal oxide precatalyst lysators in a gas phase oxidation catalyst with a catalytically active silver vanadium oxide bronze, in particular a catalyst for gas phase partial oxidation of aromatic hydrocarbons, aldehydes, carboxylic acids and / or bonTexreanhydriden Carbon Acid.
• aldehydes, carboxylic acids and / or carboxylic anhydrides is technically by the catalytic gas phase oxidation of aromatic hydrocarbons such as benzene, o-, m- or p-xylene, naphthalene, toluene or Durol (1, 2,4,5-tetramethylbenzene) in fixed bed reactors produced.
• aromatic hydrocarbons such as benzene, o-, m- or p-xylene, naphthalene, toluene or Durol (1, 2,4,5-tetramethylbenzene) in fixed bed reactors produced.
• aromatic hydrocarbons such as benzene, o-, m- or p-xylene, naphthalene, toluene or Durol (1, 2,4,5-tetramethylbenzene) in fixed bed reactors produced.
• WO 00/27753, WO 01/85337 and WO 2005/012216 describe multimetal oxides containing silver and vanadium oxide.
• the multimetal oxides are converted into silver vanadium oxide bronzes, which catalyze the partial oxidation of aromatic hydrocarbons.
• Silver vanadium oxide bronzes mean silver vanadium oxide compounds having an average Ag: V ratio of less than 1. They are generally semiconducting or metallically conductive, oxidic solids which preferentially crystallize in layer or tunnel structures, whereby the vanadium in the [V 2 O 5 ] host lattice is partially reduced to V (IV).
• the thermal transformation of the multimetal oxides into silver vanadium oxide bronzes proceeds via a series of reduction and oxidation reactions, which are not yet understood in detail.
• the multimetal oxide is applied as a layer to an inert support to obtain a so-called precatalyst.
• the conversion of the precatalyst into the active catalyst is usually carried out in situ in the oxidation reactor under the conditions of the oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic anhydrides.
• the hydrocarbon loading of the gas stream with the hydrocarbon to be oxidized must be increased slowly from very low values, the hot spot temperature in the catalyst is controlled. It usually lasts for several days or weeks until the final load is reached at which productive hydrocarbon oxidation occurs.
• WO 00/27753 discloses that the conversion of the precatalyst can also take place outside the oxidation reactor by thermal treatment at temperatures above 200 to 650 ° C, influencing factors, such as the composition of the gas atmosphere, presence or absence of a binder and type and amount of a Binders are to be considered.
• the optimal conditions should be determined in a preliminary test. More detailed information about these conditions does not make the document.
• the invention is based on the object to provide a convenient method by which the precatalysts outside the oxidation reactor can be converted into the active gas phase oxidation catalysts.
• the object is achieved in accordance with the invention by a process for converting a precatalyst comprising an inert support, an organic carbon source and a silver and vanadium-containing multimetal oxide into a gas phase oxidation catalyst comprising the inert support and a catalytically active silver vanadium oxide bronze in which the precatalyst is thermally treated in a gaseous atmosphere containing less than 10% by volume of oxygen at a temperature of at least 350 ° C, the amount of carbon source in the precatalyst prior to the thermal treatment being varied from zero ) Value below a critical level and the critical amount is defined as the amount of carbon source above which reduction to elemental silver occurs during thermal treatment of the precatalyst.
• the vanadium is present in the oxidation state 5 (vanadium ⁇ )); in the silver vanadium oxide bronze, the average vanadium oxidation state is typically 4.5 to 4.9, especially 4.6 to 4.7.
• the catalysts obtained by the thermal treatment according to the invention show sufficient abrasion resistance and can be easily handled, transported and filled into reaction tubes.
• the gas atmosphere in which the thermal treatment takes place contains less than 10% by volume, preferably less than 3% by volume and in particular less than 1% by volume of (molecular) oxygen.
• an inert gas preferably nitrogen, which is essentially free of oxygen.
• the thermal treatment is expediently carried out in a gas stream, preferably an inert gas stream.
• the thermal treatment can be carried out in any suitable apparatus, for. B. in Hordenöfen, Drehkugelöfen, heated reactors in which a bed of precatalyst is flowed through by the gas stream, and the like.
• the thermal treatment is carried out at a temperature of at least 350 ° C, preferably at least 400 ° C, in particular 400 to 600 ° C. Higher temperatures within the specified range usually result in higher crystallinity and lower BET surface area of the silver vanadium oxide bronze.
• the heating rate is not particularly critical, 1 to 10 ° C / min are generally suitable.
• the duration of the thermal treatment is generally 0.5 to 12 hours, preferably 1 to 5 hours.
• the precatalyst contains an organic carbon source.
• the carbon source is used in the thermal treatment of the precatalyst probably as a reducing agent for a partial reduction of vanadium contained in the multimetal (V) to V (IV) is present.
• Suitable carbon sources include, for example, ethylene glycol, propylene glycol, glycerine, pentaerythritol, pentoses, hexoses, oxalic acid, ammonium oxalate, malonic acid, maleic acid, fumaric acid, succinic acid, ascorbic acid, benzoic acid, o-, m- and p-toluic acid, phthalic acid, phthalic anhydride, Isophthalic acid, terephthalic acid, dimethylformamide, dimethylacetamide, N-methylpyrrolidone;
• Suitable carbon sources include polymers such as polyalkylene glycols, polyalkyleneamines, polysaccharides, polyvinyl alcohol, vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / maleate or vinyl acetate / ethylene copolymers. It has been found that the amount of carbon source in the precatalyst must be controlled. If the amount of the carbon source is too high, no silver vanadium oxide bronze is formed during the thermal treatment of the precatalyst, but the silver ions contained in the multimetal oxide are reduced to elemental silver. While the silver vanadium oxide bronze has a dark green color, the elemental silver deposited on the catalyst appears black.
• the presence of elemental silver can also be detected in the powder X-ray diffraction pattern by the occurrence of diffraction reflections attributable to the cubic silver lattice. Surprisingly, the reduction to elemental silver abruptly occurs from a limit of the amount of carbon source. The limit is referred to for the purposes of the present application as a "critical amount of carbon source”.
• the critical amount depends on the chemical nature of the carbon source. It can easily be determined by the expert in preliminary tests. For example, a sample amount of a precatalyst having a given carbon source content may be subjected to the thermal treatment (eg, 4 hours at 490 ° C in a nitrogen stream), and the resulting catalyst is examined for the occurrence of elemental silver. If a reduction to elemental silver occurs, the skilled artisan (in a fresh sample of the precatalyst) can gradually lower the carbon content (according to the procedure described below) and re-subject the precatalyst to thermal treatment. In this way, the critical amount can be readily limited by means of a few experiments.
• the amount of carbon source in the pre-catalyst before the thermal treatment to a value of less than 2 wt .-% (calculated as carbon based on the weight of the multimetal), z.
• the amount of carbon source in the precatalyst before the thermal treatment is generally at least 0.1% by weight, usually at least 0.5% by weight, based on the weight of the multimetal oxide.
• the carbon content can be determined by burning an accurately weighed sample of the active mass of the (pre) catalyst in the oxygen stream and quantitatively detecting the carbon dioxide formed, e.g. B. by means of an IR cell.
• the person skilled in the art can consistently select pore patterns, binders and other auxiliaries with low carbon content or only use carbonaceous auxiliaries in minor amounts during the preparation of the precatalyst. In general, however, in view of a reasonable adhesion of the multimetal oxide to the support, a desired pore structure, and other factors, it is essential to use larger amounts of carbonaceous adjuvants in precatalyst production.
• the precatalyst initially contains an amount of carbon source that is greater than or equal to the critical amount.
• the untreated precatalyst will hold amounts of carbon sources corresponding to 3 to 10 weight percent carbon based on the weight of the multimetal oxide. It is possible to adjust the amount of carbon source to a value below the critical amount by tempering the pre-catalyst in an oxygen-containing atmosphere at a temperature of 80 to 200 ° C or burns.
• burning off is meant a reduction in carbon content, whereby a portion of the carbon source is vaporized, sublimated and / or oxidatively decomposed to gaseous products such as carbon dioxide.
• the burning can be carried out in any suitable apparatus, for. As such as those used for the subsequent thermal treatment of the pre-catalyst.
• the burning preferably comprises at least one heating phase during which the temperature of the precatalyst is reduced at a rate of less than 5 ° C / min (especially less as 1. 5 ° C / min) and at least one plateau phase during which the temperature of the precatalyst is maintained substantially constant.
• the burning takes place in an oxygen-containing atmosphere; the atmosphere preferably contains at least 5% by volume, e.g. at least 12.5 vol.%, and up to 25 vol.% (molecular) oxygen.
• the atmosphere preferably contains at least 5% by volume, e.g. at least 12.5 vol.%, and up to 25 vol.% (molecular) oxygen.
• air is used.
• the burning is carried out in an air stream.
• the burning is carried out at a temperature of 80 to 200 ° C, preferably 120 to 190 ° C.
• Suitable multimetal oxides their preparation and their application to inert carriers are known per se and z.
• the multimetal oxide has the general formula I:
• a has a value of 0.3 to 1.9, preferably 0.5 to 1.0, and more preferably 0.6 to 0.9;
• Q is an element selected from P, As, Sb and / or Bi,
• b has a value of 0 to 0.3, preferably 0 to 0.1
• M for at least one of alkali and alkaline earth metals, Bi, Tl, Cu, Zn, Cd, Pb, Cr, Au, Al, Fe, Co, Ni, Mo, Nb, Ce, W, Mn, Ta, Pd, Pt, Ru and / or Rh selected Metal is, preferably Nb, Ce, W, Mn and Ta, in particular Ce and Mn, of which Ce is most preferred
• c has a value of 0 to 0.5, preferably 0.005 to 0.2, in particular 0.01 to 0.1; with the proviso that (a-c) is> 0.1,
• d is a number which is determined by the valency and frequency of the elements other than oxygen in the formula I, and
• e has a value of 0 to 20, preferably 0 to 5.
• the multimetal oxide is preferably present in a crystal structure whose powder X-ray diagram shows diffraction reflections at the interplanar spacings d 15.23 ⁇ 0.6, 12.16 ⁇ 0.4, 10.68 ⁇ 0.3, 3.41 ⁇ 0.04 , 3.09 ⁇ 0.04, 3.02 ⁇ 0.04, 2.36 ⁇ 0.04 and 1.80 ⁇ 0.04 ⁇ .
• the complete powder X-ray diffraction pattern of the multimetal oxide of the formula I has, inter alia, the 17 diffraction peaks listed in Table 1. Less intense diffraction reflections of the powder X-ray diagram of the multimetal oxides of the formula I were not taken into account in Table 1.
• the indication of the X-ray diffraction reflexes in this application takes place in the form of the lattice plane spacings d [ ⁇ ] which are independent of the wavelength of the X-radiation used and which can be calculated from the measured diffraction angle by means of the Bragg equation.
• the BET specific surface area measured according to DIN 66 131, which is based on the "Commendations 1984" of the IUPAC International Union of Pure and Applied Chemistry (see Pure & Appl. Chem. 57, 603 (1985)), is in usually more than 1 m 2 / g, preferably 3 to 250 m 2 / g, in particular 10 to 250 m 2 / g and particularly preferably 20 to 80 m 2 / g.
• a suspension of vanadium pentoxide (V 2 O 5 ) is generally heated with the solution of a silver compound and a solution of a compound of the metal component M and optionally the solution of a compound of Q.
• a solvent for this reaction can serve polar organic solvents, preferably water is used as the solvent.
• silver salt silver nitrate is preferably used.
• the element or elements Q from the group P, As, Sb and / or Bi can be used in elemental form or as oxides or hydroxides.
• their partially neutralized or free acids are used, such as phosphoric acid, arsenic acid, antimonic acid, the ammonium hydrogen phosphates, arsenates, antimonates and bismuthates, and the alkali metal hydrogenphosphates, arsenates, antimonates and bismuthates.
• salts of metal component M water-soluble salts are generally used, for example the perchlorates or carboxylates, in particular the acetates.
• the nitrates of the relevant metal component M are preferably used, in particular cerium nitrate or manganese nitrate.
• the reaction of the V 2 O 5 with the silver compound, the compound of the metal component M and optionally Q may be carried out generally at room temperature or at elevated temperature.
• the reaction is carried out at temperatures of 20 to 375 0 C, preferably at 20 to 100 0 C and particularly preferably at 60 to 100 0 C.
• the reaction is carried out expediently under the autogenous pressure of the reaction system in a pressure vessel.
• the reaction conditions are chosen so that the reaction can be carried out at atmospheric pressure.
• the duration of this reaction may be 10 minutes to 3 days, depending on the nature of the starting materials reacted and the temperature conditions used.
• reaction time of the reaction for example to 5 days or more.
• reaction of the V 2 O 5 with the silver compound, the compound of the metal component M to the multimetal oxide is carried out for a period of 6 to 24 hours.
• the orange-red color of the V 2 O 5 suspension changes and it forms the new compound in the form of a dark brown suspension.
• the multimetal oxide thus formed can be isolated from the reaction mixture.
• the resulting multimetal oxide suspension is spray-dried.
• the spray drying is generally carried out under atmospheric pressure or reduced pressure.
• the inlet temperature of the drying gas is determined - generally air is used as such, but of course other drying gases such as nitrogen or argon can also be used.
• the inlet temperature of the drying gas is determined - generally air is used as such, but of course other drying gases such as nitrogen or argon can also be used.
• Drying gas in the spray dryer is advantageously chosen so that the starting temperature of the cooled by evaporation of the solvent drying gas 200 0 C for a longer period does not exceed.
• the starting temperature of the drying gas is set to 50 to 150 ° C., preferably 100 to 140 ° C.
• the precatalyst is a precursor of the catalyst, which consists of an inert carrier material and at least one layer applied to it in a dish-shaped manner, this layer preferably containing from 30 to 100% by weight, in particular from 50 to 100% by weight to the total weight of this layer, a muimetimalloxids according to formula I.
• the layer consists entirely of a multimetal oxide according to formula I. If the catalytically active layer contains, in addition to the multimetal oxide according to formula I, further components, this can be achieved, for example.
• the precatalyst contains 5 to 25 wt .-%, based on the total weight of the pre-catalyst, multimetal.
• inert carrier material for the pre-catalysts and coated catalysts virtually all support materials of the prior art, as they are advantageous in the Production of shell catalysts for the oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic anhydrides are used, for example, quartz (SiO 2 ), porcelain, magnesium oxide, tin dioxide, silicon carbide, rutile, alumina (Al 2 O 3 ), aluminum silicate, steatite ( Magnesium silicate), zirconium silicate, cerium silicate or mixtures of these support materials.
• the carrier is generally "non-porous".
• support materials are steatite and silicon carbide.
• the shape of the support material is generally not critical to the precatalysts and shell catalysts of the present invention.
• catalyst supports in the form of spheres, rings, tablets, spirals, tubes, extrudates or chippings can be used.
• the dimensions of these catalyst supports correspond to the catalyst supports conventionally used for the preparation of shell catalysts for the gas phase partial oxidation of aromatic hydrocarbons.
• the abovementioned carrier materials in powder form can also be admixed with the catalytically active composition of the coated catalysts according to the invention.
• the shell-shaped coating of the inert carrier material with the multimetal oxide known methods can be used. For example, a slurry of the powder of the multimetal oxide obtained after isolation and drying can be sprayed onto the catalyst support in a heated coating drum. It is also fluid bed coater for cup-shaped application of the multimetal oxide are used on the catalyst support.
• the suspension of the multimetal oxide may be dissolved in water, an organic solvent such as higher alcohols, polyhydric alcohols, e.g.
• Organic binders, preferably copolymers can be dissolved or advantageously added in the form of an aqueous dispersion, with binder contents generally being from 10 to 20% by weight, based on the solids content of the suspension or slurry of the multimetal oxide according to the invention. Suitable binders are z. As vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / maleate or vinyl acetate / ethylene copolymers.
• the shell catalysts are used for the partial oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic anhydrides, in particular for the gas phase partial oxidation of o-xylene and / or naphthalene to phthalic anhydride or of toluene to benzoic acid and / or benzaldehyde, with a molecular used oxygen-containing gas.
• the catalysts may be used for this purpose alone or in combination with other differently active catalysts, for example vanadium oxide / anatase-based catalysts of the prior art, the different catalysts generally being arranged in separate catalyst beds arranged in one or more fixed catalyst beds can be arranged in the reactor.
• the shell catalysts or precatalysts are for this purpose filled in the reaction tubes of a tubular reactor, which from the outside, z. B. by means of a molten salt, are thermostated to the reaction temperature.
• About the thus prepared catalyst charge is the reaction gas at temperatures of 100 to 650 0 C and preferably 250 to 480 0 C and at an overpressure of generally 0.1 to 2.5 bar, preferably from 0.3 to 1, 5 Bar with a space velocity of generally 750 to 5000 h "1 passed .
• the reaction gas supplied to the catalyst is generally produced by mixing a molecular oxygen-containing gas which may contain, besides oxygen, still suitable reaction moderators and / or diluents such as water vapor, carbon dioxide and / or nitrogen with the aromatic hydrocarbon to be oxidized
• the molecular oxygen-containing gas is generally 1 to 100% by volume, preferably 2 to 50% by volume and particularly preferably 10 to 30% by volume of oxygen, 0 to 30% by volume, preferably 0 to 20% by volume.
• the gas containing molecular oxygen is generally charged with 30 to 300 g per Nm 3 , preferably with 70 to 150 g per Nm 3 gas of the aromatic hydrocarbon to be oxidized. It is particularly advantageous to use air as the molecular oxygen-containing gas.
• the aromatic hydrocarbon is first on a bed the shell-type catalyst of the invention reacted under partial conversion to a reaction mixture.
• the resulting reaction mixture or a fraction thereof may then be brought into contact with at least one further catalyst whose catalytically active composition contains vanadium pentoxide and anatase.
• the gaseous stream is passed sequentially over a bed of an upstream catalyst and a bed of a downstream one Catalyst directs, wherein the bed of the upstream catalyst comprises a catalyst according to the invention and the bed of the downstream catalyst contains at least one catalyst whose catalytically active material contains vanadium pentoxide and anatase.
• the catalytically active mass of the downstream catalyst contains from 1 to 40% by weight of vanadium oxide, calculated as V 2 O 5 , from 60 to 99% by weight of titanium dioxide, calculated as TiO 2 , up to 1% by weight of a cesium compound calculated as Cs, up to 1% by weight of a phosphorus compound, calculated as P, and up to 10% by weight of antimony oxide, calculated as Sb 2 ⁇ 3.
• the bed of the downstream catalyst comprises at least two layers of catalysts whose catalytically active composition has different Cs content, the Cs content decreasing in the flow direction of the gaseous stream.
• the invention is illustrated by the following examples and comparative examples.
• the resulting powder had a BET specific surface area of 61 m 2 / g.
• a powder X-ray diagram was recorded with the aid of a D 5000 diffractometer from Siemens using Cu-K ⁇ radiation (40 kV, 30 mA).
• the diffractometer was equipped with an automatic primary and secondary glare system as well as a secondary monochromator and scintillation detector.
• the powder such as magnesium silicate rings follows: 350 g of steatite rings having an outer diameter of 7 mm, a length of 3 mm and a wall thickness of 1 5 mm were placed in a coating drum at 20 0 C for 20 min with 85 g of the powder and 8.5 g of oxalic acid with the addition of 50 ml of a 12.5 wt .-% aqueous glycerol solution coated and then dried.
• the weight of the catalytically active composition thus applied determined on a sample of the pre-catalyst obtained, was, after heat treatment at 450 ° C. for 1 hour, 18% by weight, based on the total weight of the finished catalyst.
• the carbon content was about 4 Ge. -% (based on the active mass).
• the precatalyst was heated to 140 ° C. in a forced air oven under an air atmosphere at a heating rate of 0.33 ° C./min and held at this temperature for 4 hours. After this treatment, the carbon content in the precatalyst was about 1% by weight (based on the active composition). Thereafter, the precatalyst was heated in a rotary ball furnace (500 ml ball) under a N 2 - atmosphere (1 NI / hg A kt ⁇ vmasse N 2 ) at a heating rate of 2 ° C / min to 490 ° C and 4 hours at this temperature held.
• the active mass appeared dark green; the carbon content was 0.007 wt .-% (based on the active mass).
• X-ray diffraction showed that it was a crystalline ⁇ -bronze.
• the BET surface area was 3.9 m 2 / g, the average vanadium oxidation level 4.67.
• the gas phase oxidation of o-xylene to phthalic anhydride could be started with an initial loading of about 30 g / Nm 3 air, the could be increased rapidly to about 80 g / Nm 3 .
• an upgraded sample of a catalyst prepared in situ had a carbon content of 0.005 wt .-% (based on the active composition).
• the extension sample was a crystalline ⁇ -bronze (from the powder X-ray diagram, the following interplanar spacings d [ ⁇ ] with the corresponding relative intensities l re ⁇ [%] were obtained: 4.85 (9.8), 3, 50 (14.8), 3.25
• the BET surface area was 6.7 m 2 / g, the average vanadium oxidation level 4.63.
• Example 1 was repeated, but the pre-catalyst was heated in the first treatment step only for 2 hours at 100 ° C in air.
• the carbon content in the Precatalyst was 2.6% by weight.
• the pre-catalyst was kept at 450 ° C for 4 hours in a stream of nitrogen.
• the obtained catalyst was black;
• the powder diffractogram revealed a single intense peak attributable to the cubic lattice of silver. No peaks were observed which are attributable to the ⁇ bronze.
• the BET surface area was 30 m 2 / g, the average vanadium oxidation state 4.1-4.2 (the catalyst was overreduced).
• the carbon content was less than 0.02 wt%.
• Comparative Example 2 was repeated; However, the thermal treatment was carried out at 450 ° C in the air stream.
• the active composition of the catalyst obtained comprised a mixture of ⁇ -Ag 0 33V 2 O 5 and Ag 1 2 V 3 Oe.
• the average vanadium oxidation state was 4.8.

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