EP1670582A1 - Process for preparing a catalyst for use in oxidation reactions in the gas phase by coating carrier material in a fluidised bed apparatus - Google Patents

Process for preparing a catalyst for use in oxidation reactions in the gas phase by coating carrier material in a fluidised bed apparatus

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Publication number
EP1670582A1
EP1670582A1 EP04765591A EP04765591A EP1670582A1 EP 1670582 A1 EP1670582 A1 EP 1670582A1 EP 04765591 A EP04765591 A EP 04765591A EP 04765591 A EP04765591 A EP 04765591A EP 1670582 A1 EP1670582 A1 EP 1670582A1
Authority
EP
European Patent Office
Prior art keywords
gas
suspension
catalyst
susp
carrier
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.)
Withdrawn
Application number
EP04765591A
Other languages
German (de)
French (fr)
Inventor
Samuel Neto
Wolfgang Rummel
Sebastian Storck
Jürgen ZÜHLKE
Frank Rosowski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Priority claimed from DE10344844A external-priority patent/DE10344844A1/en
Priority claimed from EP04003444A external-priority patent/EP1563905A1/en
Application filed by BASF SE filed Critical BASF SE
Priority to EP04765591A priority Critical patent/EP1670582A1/en
Publication of EP1670582A1 publication Critical patent/EP1670582A1/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/16—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by suspending the powder material in a gas, e.g. in fluidised beds or as a falling curtain
    • 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
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/006—Coating of the granules without description of the process or the device by which the granules are obtained
    • 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—
    • B01J35/30—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • 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
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst

Definitions

  • benzoic acid maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid or pyromellitic anhydride.
  • a mixture of an oxygen-containing gas and the starting material to be oxidized is passed through pipes in which there is a bed of catalyst.
  • the tubes are surrounded by a heat transfer medium, for example a molten salt.
  • shell catalysts in which the catalytically active composition is applied in a shell-like manner to an inert support material, such as steatite, have proven to be useful as catalysts for these oxidation reactions.
  • Different catalytically active materials can be applied in one or more shells.
  • vanadium pentoxide is generally used as the catalytically active component of the catalytically active composition of these coated catalysts.
  • the catalytically active composition can contain a large number of other oxidic compounds in small amounts, which as promoters influence the activity and selectivity of the catalyst.
  • an aqueous suspension of the active composition constituents and / or their precursor compounds or sources is sprayed onto the support material at elevated temperature until the desired proportion of active composition in the total catalyst weight is reached, e.g. DE-A 40 06 935.
  • the carrier material is fluidized in an ascending gas stream, in particular air.
  • the devices usually consist of a conical or spherical container, in which the fluidizing gas is introduced from below or from above via a central tube. The suspension is sprayed from above, from the side or from the nozzle
  • a suitable fluid bed apparatus is described for example in DE-A 40 06 935.
  • organic binders preferably copolymers, advantageously in the form of an aqueous dispersion, of vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate and vinyl acetate / ethylene to the suspension.
  • the addition of binder also has the advantage that the active composition adheres well to the support, so that the catalyst can be transported and filled in more easily.
  • the binder escapes from the applied layer through thermal decomposition and / or combustion.
  • the thermal treatment is usually carried out in situ in the oxidation reactor.
  • the quality of the supported catalysts obtainable in this way depends crucially on the operating parameters of the fluidized bed apparatus, in particular on the total mass of the carrier material in the apparatus, the binder content of the sprayed-in suspension, the flow rate and the temperature of the gas stream blown in for swirling and Dosing rate at which the suspension is sprayed onto the fluidized inert carrier.
  • the most important operating parameters of the fluid bed apparatus for coating the carrier materials are set by means of complex empirical test series, which must already be carried out on a production scale, since scaling from the laboratory or pilot plant scale to the production scale is practically impossible due to the lack of or inadequate theoretical models.
  • WO 98 14274 describes a process for producing a supported catalyst in a fluidized bed apparatus, in which a less thin 100 ⁇ m layer of an active composition is applied in aqueous suspension to an inert support of 5 ⁇ m to 20 mm diameter.
  • WO 02 096557 describes a process for the production in a fluidized bed apparatus of supported metallic nanoparticles as catalysts.
  • US 4 977 126 describes a process for the production of supported catalysts in a fluidized bed apparatus, in which the catalysts consist of a metallic cobalt layer on oxide supports.
  • FR 2791 905 describes a process for producing supported catalysts in which the suspension consists of fine particles with a diameter of 10-100 ⁇ m and a density of more than 1000 kg / m 3 and about 30% larger particles with a diameter of 0.4-1 mm contained.
  • the invention relates to a process for the preparation of a catalyst for gas phase oxidation, in which a particulate inert carrier of a total mass M ⁇ ra g er is weighed into a fluidized bed apparatus, at least one aqueous suspension of a catalytically active material or sources for it and binders with a binder content B Susp are provided, the inert carrier by supplying a fluidized heated to a temperature T opp gas stream at a flow rate Q gas, and spraying the suspension at a rate Q Susp onto the fluidized inert carrier.
  • one chooses Q Gas , Qsusp, B S u SP , M Trager , and T Ggs within the ranges 3000 ⁇ Q Gas [m 3 / h] ⁇ 9000, 1000 ⁇ Q Susp [g / min] ⁇ 3500, 2 ⁇ Bsusp [wt. %] ⁇ 18, 60 ⁇ M carrier [kg] ⁇ 240. 75 ⁇ 7 gas [° C] ⁇ 120 such that a parameter K, which is defined as K 0.020 Q gas - 0.055 Q susp + 7.500 ß Süsp - 0.667 M carrier + 2.069 T gas - 7 with the relation 127, 5 ⁇ K ⁇ 202 is sufficient.
  • the mechanical stability of the layer on the carrier is also improved.
  • the layer (s) of the coated catalyst are applied, for example, by spraying a suspension of TiO 2 and V 2 O 5 , which may contain sources of the promoter elements mentioned below, onto the fluidized support.
  • the catalytically active composition preferably contains 1 to 40 in the calcined state, based on the total amount of the catalytically active composition % By weight of vanadium oxide, calculated as V 2 O 5 , and 60 to 99% by weight of titanium dioxide, calculated as TiO 2 .
  • Suitable starting compounds for the element vanadium are, for example, vanadium oxides such as vanadium pentoxide (V 2 O 5 ), vanadates such as ammonium rnetavanadate, vanadium oxysulfate hydrate, vanadyl acetate tylacetonate, vanadium halides such as vanadium tetrachloride (VCI 4 ) and vanadium oxyhalogenides such as VOCI 3 .
  • vanadium oxides such as vanadium pentoxide (V 2 O 5 )
  • vanadates such as ammonium rnetavanadate
  • vanadium oxysulfate hydrate vanadyl acetate tylacetonate
  • vanadium halides such as vanadium te
  • the vanadium starting compounds used can also be those which contain vanadium in oxidation state +4 or which contain vanadium in oxidation state +5 and various reducing agents (for example NH 4 + or its decomposition product NH 3 ), the V 5+ can reduce to V 4+ .
  • a reducing agent can also be oxalic acid, oxalate, hydrazine dihydrochloride, hydrazine sulfate, hydrazine (monohydrate), hydroxylamine, hydroxylamine hydrochloride or their salts.
  • the catalytically active composition can also contain 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 O 3 ,
  • the catalytically active composition can in principle contain a small number of other oxidic compounds which, as promoters, influence the activity and selectivity of the catalyst, for example by reducing or increasing its activity.
  • promoters are the alkali metal oxide, in particular in addition to the cesium oxide, lithium, potassium and rubidium oxide, thallium (l) oxide, aluminum oxide, zirconium oxide, iron oxide, nickel oxide, cobalt oxide, manganese oxide, tin oxide, silver oxide, copper oxide, chromium oxide, Molybdenum oxide, tungsten oxide, iridium oxide, tantalum oxide, Ni oboxid, arsenic oxide, cerium oxide called.
  • cesium from this group is used as a promoter.
  • 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 preferred as additives.
  • Oxidic phosphorus compounds, in particular phosphorus pentoxide, are particularly suitable as an activity-increasing but selectivity-reducing additive.
  • the suspension Before coating, the suspension is preferably stirred for a sufficiently long time, for example 2 to 30 hours, in particular 12 to 25 hours, in order to break up agglomerates of the suspended solids and to obtain a homogeneous suspension.
  • the suspension typically has a solids content of 20 to 50% by weight.
  • the suspension medium is generally aqueous, e.g. B. water itself or an aqueous mixture with a water-miscible organic solvent, such as methanol, ethanol, isopropanol, formamide and the like.
  • first or second suspension of TiO 2 and V 2 O 5 particles as catalyst particles preferably have at least 90 % By volume of the V 2 O 5 particles have a diameter of 20 ⁇ m or less and at least 95% by volume of the V 2 O 5 particles have a diameter of 30 ⁇ m or less.
  • organic binders preferably copolymers, advantageously in the form of an aqueous dispersion, of vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate and vinyl acetate / ethylene are added to the suspension.
  • the binders are commercially available as aqueous dispersions with a solids content of e.g. B. 35 to 65 wt .-%. According to the invention, the amount of such binder dispersions used is 2 to 18% by weight. based on the weight of the suspension.
  • coating temperatures of 75 to 120 ° C. are used according to the invention, it being possible for the coating to be carried out under atmospheric pressure or under reduced pressure.
  • the layer thickness of the catalytically active composition is generally 0.02 to 0.25 mm, preferably 0.05 to 0.20 mm.
  • the active mass fraction of the catalyst is usually 5 to 25% by weight, usually 7 to 15% by weight.
  • the binder escapes from the applied layer by thermal decomposition and / or combustion.
  • the thermal treatment is preferably carried out in situ in the gas phase oxidation reactor.
  • the characteristic number is preferably in a range from 136.0 ⁇ K ⁇ 193.5 and there are 4500 ⁇ Q gas [m 3 / h] ⁇ 7500, 1500 ⁇ Q Susp [g / min] ⁇ 3000, 5 ⁇ B Susp [ % By weight] ⁇ 15, 100 ⁇ M mger [kg] ⁇ 200, and 80 ⁇ 7 gas [° C] ⁇ 115.
  • the characteristic number is particularly preferably in a range from 143 ⁇ K ⁇ 184.5 and there are 5500 ⁇ Q gas [m 3 / h] ⁇ 6500, 2000 ⁇ Q Susp [g / min] ⁇ 2500, 6 ⁇ B susp [ % By weight] ⁇ 11 120 ⁇ M carrier [kg] ⁇ 180, 90 ⁇ T gas [° C] ⁇ 115.
  • any gas or gas mixture which is inert under the operating conditions can be used for swirling and tempering the bed of carrier material in the fluidized bed apparatus.
  • the gas supplied is air, which enables the system to be operated particularly cost-effectively.
  • the catalytically active composition can also be applied in two or more layers.
  • the layers preferably have different selectivity and activity.
  • the inner layer or the inner layers can have an antimony oxide content of up to 15% by weight and the outer layer can have an antimony oxide content reduced by 50 to 100%.
  • the inner layer and outer layer can contain different amounts of P.
  • two layers are provided with a second aqueous suspension of catalytically active material and binder and sprayed onto the fluidized carrier coated with the first suspension.
  • carrier materials of the prior art such as are advantageously used in the production of coated catalysts for the oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic acid anhydrides
  • inert carrier material 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 carrier materials.
  • the carrier material is usually non-porous.
  • non-porous is to be understood in the sense of "except for technically ineffective amounts of pores non-porous", since technically inevitably a small number of pores can be present in the carrier material, which ideally should not contain any pores.
  • Steatite and silicon carbide are particularly worth mentioning as advantageous carrier materials.
  • the shape of the support material is generally not critical for the precatalysts and coated catalysts according to the invention.
  • catalyst supports in the form of spheres, rings, tablets, spirals, tubes, extrudates or grit can be used.
  • the dimensions of these catalyst carriers correspond to those of the catalyst carriers usually used for the production of shell catalysts for the gas phase partial oxidation of aromatic hydrocarbons.
  • Steatite in the form of balls with an outer diameter of 0.5 to 10 mm or rings with an outer diameter of 3 to 15 mm is preferably used.
  • the process according to the invention is particularly preferably carried out in a fluidized bed apparatus which has a container for receiving the particulate carrier, in the lower region of which a bowl-like depression is provided, a central tube for supplying the gas, which extends essentially axially downward in the container opens into the recess, a substantially ring-shaped deflector screen, which is fastened to the central tube in the upper region of the container, and a guide ring arranged in the lower region of the container, which surrounds the central tube substantially concentrically over part of its length, and means for spraying the first and optionally the second suspension.
  • a fluid bed apparatus is described, for example, in German patent application DE 4006935.
  • Commercially available fluid bed apparatuses which are suitable for carrying out the process according to the invention are, for example, the ball coaters HKC 150 and HKC 200 from Hüttlin, Steinen, Germany.
  • the catalysts according to the invention are generally suitable for the gas phase oxidation of aromatic C 6 to C 10 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 invention therefore also relates to the use of the catalyst prepared by the process according to the invention for the production of phthalic anhydride from o-xylene, naphthalene or mixtures thereof.
  • the catalysts prepared according to the invention are filled into reaction tubes thermostatically controlled from the outside to the reaction temperature, for example by means of molten salt, and the salt bath temperatures are generally from 300 to 450 ° C., preferably from 320 to 420 ° C. and particularly preferably from 340 to 400 ° C and at an overpressure of generally 0.1 to 2.5 bar, preferably 0.3 to 1.5 bar with a space velocity of generally 750 to 5000 h "1.
  • the reaction gas fed to the catalyst is generally generated by mixing a gas containing molecular oxygen, which in addition to oxygen can also contain suitable reaction moderators and / or diluents, such as steam, carbon dioxide and / or nitrogen, with the aromatic hydrocarbon to be oxidized, the molecular oxygen-containing gas in generally 1 to 100 mol%, preferably 2 to 50 mol% and particularly preferably 10 to 30 mol% oxygen, 0 to 30 mol%, preferably 0 to 10 mol% water vapor and 0 to 50 mol%, preferably 0 to 1 mol% carbon dioxide, the rest nitrogen.
  • a gas containing molecular oxygen which in addition to oxygen can also contain suitable reaction moderators and / or diluents, such as steam, carbon dioxide and / or nitrogen
  • the molecular oxygen-containing gas in generally 1 to 100 mol%, preferably 2 to 50 mol% and particularly preferably 10 to 30 mol% oxygen, 0 to 30 mol%, preferably 0 to 10 mol% water
  • the molecular oxygen-containing gas is generally charged with 30 g to 150 g per Nm 3 of gas of the aromatic hydrocarbon to be oxidized. It has proven to be particularly advantageous if catalysts are used in the catalyst bed which differ in their catalytic activity and / or chemical composition of their active composition. Usually, when using two reaction zones in the first reaction zone, i.e. towards the gas inlet of the reaction gas, a catalyst is used which has a somewhat lower catalytic activity compared to the catalyst which is located in the second reaction zone, i.e. towards the gas outlet , In general, the reaction is controlled by the temperature setting in such a way that in the first zone most of the aromatic hydrocarbons contained in the reaction gas are converted with maximum yield. Three- to five-layer catalyst systems are preferably used, in particular three- and four-layer catalyst systems.
  • Binder concentration 10% by weight of the total suspension used
  • the catalytically active composition applied in this way i.e. the catalyst shell, contained 7.12% by weight of vanadium (calculated as V 2 O 5 ), 1.8% by weight of antimony (calculated as Sb 2 O 3 ), 0.33% by weight of cesium (calculated as Cs), 90.75% by weight of titanium dioxide.
  • the weight of the shell applied was 8.0% of the total weight of the finished catalyst.
  • the key figure K which was calculated from the equation of claim 1, is 188.5.
  • the abrasion after a triple drop test was 25% by weight (after 1 h of calcination at 450 ° C.).
  • approx. 50 g of catalyst (calcined after heat treatment at 450 ° C. for one hour) were dropped through a 3 m long tube with an internal diameter of 25 mm. The catalyst falls into a bowl underneath the tube, is separated from the dust generated when it hits the ground, and is dropped again through the tube.
  • the total mass loss after three drop tests with respect to the amount of active mass applied, which corresponds to 100%, is a measure of the abrasion resistance of the catalyst.
  • the catalyst was prepared as in Example 1, the operating conditions of the fluid bed apparatus being set as follows:
  • Binder concentration 10% by weight of the total suspension used
  • the catalyst was prepared as in Example 1, the operating conditions of the fluid bed apparatus being set as follows: Air flow: 6000 m 3 / h
  • the key figure K which was calculated from the equation of claim 1, is 263.5.
  • the catalytically active composition applied in this way i.e. the catalyst shell, consisted on average of 0.15% by weight of phosphorus (calculated as P), 7.5% by weight of vanadium (calculated as V 2 O 5 ), 3, 2% by weight of antimony (calculated as Sb 2 O 3 ), 0.1% by weight of cesium (calculated as Cs) and 89.05% by weight of titanium dioxide.
  • the operating conditions of the fluid bed apparatus were:
  • Air flow 6500 m 3 / h
  • Binder concentration 7.5% by weight of the total suspension used, carrier weight 150 kg steatite rings (8 mm x 6 mm x 5 mm)
  • the characteristic number K which was calculated from the equation in claim 1, is 154.9.
  • the abrasion after a triple drop test (drop test as in Example 1) was 5% by weight (after 1 hour calcination at 450 ° C.).
  • Comparative Example 5 The catalyst was prepared as in Example 4, spraying 19 kg of the suspension and setting the operating conditions of the fluid bed apparatus as follows:
  • Air flow 6500 m 3 / h
  • Binder concentration 7.5% by weight of the total suspension used
  • Carrier weight 50 kg steatite rings (8 mm x 6 mm x 5 mm)
  • the key figure K which was calculated from the equation in claim 1, is 221.6.
  • the catalyst was prepared as in Example 4, the operating conditions of the fluid bed apparatus being set as follows:
  • Air flow 6500 m 3 / h dosing rate: 900 g / min
  • Binder concentration 7.5% by weight of the total suspension used, carrier weight 150 kg steatite rings (8 mm x 6 mm x 5 mm)
  • the key figure K which was calculated from the equation in claim 1, is 229.9.
  • 150 kg of the shell catalyst obtained were heated in a fluidized bed apparatus and with 24 kg of a suspension of 168.35 kg of anatase with a BET surface area of 21 m 2 / g, 7.043 kg of vanadium pentoxide, 19.080 kg of oxalic acid, 0.990 g of cesium sulfate, 238.920 kg of water and 66.386 kg of formamide, together with 37.5 kg of an organic binder consisting of a copolymer of acrylic acid / maleic acid (weight ratio 75:25) sprayed.
  • Air flow 6500 m 3 / h
  • Binder concentration 7.5% by weight of the total suspension used
  • the key figure K which was calculated from the equation in claim 1, is 154.9.
  • the weight of the applied layers was 9.3% of the total weight of the finished catalyst (after heat treatment at 450 ° C. for one hour).
  • the catalytically active composition applied in this way i.e. the catalyst shells, consisted on average of 0.08% by weight of phosphorus (calculated as P), 5.75% by weight of vanadium (calculated as V 2 O 5 ), 1, 6% by weight of antimony (calculated as Sb 2 O 3 ), 0.4% by weight of cesium (calculated as Cs) and 92.17% by weight of titanium dioxide.
  • the abrasion after a triple drop test was 10% by weight (after 1 hour calcination at 450 ° C.).
  • a clamshell catalyst was prepared as in Example 7, the operating conditions of the fluid bed apparatus being set as follows:
  • Air flow 2900 m 3 / h dosing rate: 2250 g / min
  • Binder concentration 7.5% by weight of the total suspension used
  • the key figure K which was calculated from the equation in claim 1, is 82.9.
  • a two-layer catalyst was prepared as in Example 7, the operating conditions of the fluidized bed apparatus being set as follows:
  • Air flow 6500 m 3 / h
  • Binder concentration 7.5% by weight of the total suspension used Weighing in 150 kg steatite rings (8 mm x 6 mm x 5 mm) Supply air temperature: 125 ° C
  • the key figure K which was calculated from the equation in claim 1, is 212.8.

Abstract

The invention relates to a method for the production of a catalyst for gas-phase oxidations, whereby a total mass MTrAger of a particulate inert support is weighed out into a fluid bed apparatus, at least one aqueous suspension of a catalytically-active material or a source thereof and binding agents with a binding agent content of BSusp is prepared, the inert support is fluidised by introduction of a gas flow with temperature controlled to TGas at a flow of QGas and the suspension sprayed on the fluidised inert support at a dosage rate of QSusp. By selection of QGas, QSusp, BSusp, MTräger, and TGas within the ranges 3000 <= QGas [m3/h] <= 9000, 1000 ≤ QSusp [g/min] <= 3500, 2≤ BSusp [wt. %] <= 18, 60 ≤ MTräger [kg] <= 240. 75 ≤ TGas [ °C] <= 120, such that for a parameter K, where K = 0.020 QGas - 0.055 QSusp + 7.500 BSusp - 0.667 MTräger + 2.069 TGas - 7, the relationship 127.5 <= K <= 202 is satisfied, qualitatively high quality coatings are generated and the formation of so-called twins from mutually-adhering support particles can be avoided.

Description

VERFAHREN ZUR HERSTELLUNG EINES KATALYSATORS FÜR GASPHASENOXIDATIONEN DURCH BESCHICHTEN VON TRÄGERMATERIAL IN EINER FLIESSBETTAPPARATURMETHOD FOR PRODUCING A CATALYST FOR GAS PHASE OXIDATION BY COATING CARRIER MATERIAL IN A FLUID BED APPARATUS
Beschreibungdescription
Verfahren zur Herstellung eines Katalysators für Gasphasenoxidationen, sowie die Verwendung des Katalysators zur katalytischen Gasphasenoxidation von aromatischen Kohlenwasserstoffen zu Carbonsäuren und/oder Carbonsäureanhydriden, insbesondere zur Herstellung von Phthalsäureanhydrid aus o-Xylol, Naphthalin oder Gemischen davon. 10 Eine Vielzahl von Carbonsäuren und/oder Carbonsäureanhydriden wird technisch durch die katalytische Gasphasenoxidation von aromatischen Kohlenwasserstoffen, wie Benzol, den Xylolen, Naphthalin, Toluol oder Durol, in Festbettreaktoren hergestellt. Man kann auf diese Weise z. B. Benzoesäure, Maleinsäureanhydrid, Phthalsäu- 15 reanhydrid, Isophthalsäure, Terephthalsäure oder Pyromellithsäureanhydrid erhalten. Im Allgemeinen leitet man ein Gemisch aus einem sauerstoffhaltigen Gas und dem zu oxidierenden Ausgangsmaterial durch Rohre, in denen sich eine Schüttung eines Katalysators befindet. Zur Temperaturregelung sind die Rohre von einem Wärmeträgermedium, beispielsweise einer Salzschmelze, umgeben.Process for the preparation of a catalyst for gas phase oxidations, and the use of the catalyst for the catalytic gas phase oxidation of aromatic hydrocarbons to carboxylic acids and / or carboxylic acid anhydrides, in particular for the production of phthalic anhydride from o-xylene, naphthalene or mixtures thereof. 10 A large number of carboxylic acids and / or carboxylic anhydrides is produced industrially by the catalytic gas phase oxidation of aromatic hydrocarbons, such as benzene, the xylenes, naphthalene, toluene or durol, in fixed bed reactors. You can z. B. benzoic acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid or pyromellitic anhydride. In general, a mixture of an oxygen-containing gas and the starting material to be oxidized is passed 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.
20 Als Katalysatoren haben sich für diese Oxidationsreaktionen so genannte Schalenkatalysatoren bewährt, bei denen die katalytisch aktive Masse schalenförmig auf einem inerten Trägermaterial, wie Steatit aufgebracht ist. Dabei können unterschiedliche katalytisch aktive Massen in einer oder mehreren Schalen aufgebracht werden. Als kataly- 25 tisch aktiver Bestandteil der katalytisch aktiven Masse dieser Schalenkatalysatoren dient im allgemeinen neben Titandioxid Vanadiumpentoxid. Des weiteren 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. 30 Zur Herstellung derartiger Schalenkatalysatoren wird eine wässrige Suspension der Aktivmassenbestandteile und/oder deren Vorläuferverbindungen oder Quellen auf das Trägermaterial bei erhöhter Temperatur aufgesprüht, bis der gewünschte Aktivmassenanteil am Katalysatorgesamtgewicht erreicht ist, z.B. die DE-A 40 06 935. Hierzu 35 eignen sich insbesondere sogenannte Wirbelschicht- bzw. Fließbettapparate. In diesen Vorrichtungen wird das Trägermaterial 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 Zentralrohr eingeführt wird. Die Suspension wird über Düsen von oben, seitlich oder vonSo-called shell catalysts, in which the catalytically active composition is applied in a shell-like manner to an inert support material, such as steatite, have proven to be useful as catalysts for these oxidation reactions. Different catalytically active materials can be applied in one or more shells. In addition to titanium dioxide, vanadium pentoxide is generally used as the catalytically active component of the catalytically active composition of these coated catalysts. In addition, the catalytically active composition can contain a large number of other oxidic compounds in small amounts, which as promoters influence the activity and selectivity of the catalyst. 30 To produce shell catalysts of this type, an aqueous suspension of the active composition constituents and / or their precursor compounds or sources is sprayed onto the support material at elevated temperature until the desired proportion of active composition in the total catalyst weight is reached, e.g. DE-A 40 06 935. For this 35 so-called fluidized bed or fluidized bed apparatuses are particularly suitable. In these devices, the carrier material is fluidized in an ascending gas stream, in particular air. The devices usually consist of a conical or spherical container, in which the fluidizing gas is introduced from below or from above via a central tube. The suspension is sprayed from above, from the side or from the nozzle
40 unten in die Wirbelschicht eingesprüht. Vorteilhaft ist der Einsatz eines mittig bzw. konzentrisch um das Zentralrohr angeordneten Leitrohrs. Innerhalb des Leitrohrs herrscht eine höhere Gasgeschwindigkeit, welche die Trägerpartikel nach oben transportiert. Im äußeren Ring liegt die Geschwindigkeit nur wenig oberhalb der Lockerungsgeschwindigkeit. So werden die Partikel kreisförmig vertikal bewegt.40 sprayed into the bottom of the fluidized bed. It is advantageous to use a guide tube arranged centrally or concentrically around the central tube. There is a higher gas velocity inside the guide tube, which transports the carrier particles upwards. In the outer ring the speed is only slightly above the loosening speed. The particles are moved vertically in a circular manner.
45 Ein geeigneter Fließbettapparat ist beispielsweise in der DE-A 40 06 935 beschrieben. Um die Qualität der Beschichtung zu verbessern, wurde in der Technik dazu übergegangen, der Suspension organische Binder, bevorzugt Copolymere, vorteilhaft in Form einer wässrigen Dispersion, von Vinylacetat/Vinyllaurat, Vinylacetat/Acrylat, Sty- rol/Acrylat sowie Vinylacetat/Ethylen zuzusetzen. Der Binderzusatz hat zudem den Vorteil, dass die Aktivmasse gut auf dem Träger haftet, so dass Transport und Einfüllen des Katalysators erleichtert werden.45 A suitable fluid bed apparatus is described for example in DE-A 40 06 935. In order to improve the quality of the coating, technology has been adopted to add organic binders, preferably copolymers, advantageously in the form of an aqueous dispersion, of vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate and vinyl acetate / ethylene to the suspension. The addition of binder also has the advantage that the active composition adheres well to the support, so that the catalyst can be transported and filled in more easily.
Bei der thermischen Behandlung bei Temperaturen über 80 bis 450 °C entweicht der Binder durch thermische Zersetzung und/oder Verbrennung aus der aufgetragenen Schicht. Meist erfolgt die thermische Behandlung in situ im Oxidationsreaktor.During thermal treatment at temperatures above 80 to 450 ° C, the binder escapes from the applied layer through thermal decomposition and / or combustion. The thermal treatment is usually carried out in situ in the oxidation reactor.
Die Qualität der so erhältlichen Trägerkatalysatoren, insbesondere die Beschichtungs- qualität, hängt entscheidend von Betriebsparameter der Fließbettapparatur ab, insbe- sondere von der Gesamtmasse des Trägermaterials in der Apparatur, des Bindemittelgehalts der eingesprühten Suspension, des Durchflusses und der Temperatur des zur Verwirbelung eingeblasenen Gasstroms und Dosierrate, mit der man die Suspension auf den fluidisierten inerten Träger aufsprüht. Die Einstellung der wichtigsten Betriebsparameter der Fließbettapparatur zur Beschichtung der Trägermaterialien erfolgt im Stand der Technik durch aufwändige empirische Testreihen, die bereits im Produktionsmaßstab erfolgen müssen, da eine Skalierung vom Labor- oder Technikumsmaßstab auf den Produktionsmaßstab wegen fehlender oder unzureichender theoretischer Modelle praktisch nicht möglich ist.The quality of the supported catalysts obtainable in this way, in particular the coating quality, depends crucially on the operating parameters of the fluidized bed apparatus, in particular on the total mass of the carrier material in the apparatus, the binder content of the sprayed-in suspension, the flow rate and the temperature of the gas stream blown in for swirling and Dosing rate at which the suspension is sprayed onto the fluidized inert carrier. In the state of the art, the most important operating parameters of the fluid bed apparatus for coating the carrier materials are set by means of complex empirical test series, which must already be carried out on a production scale, since scaling from the laboratory or pilot plant scale to the production scale is practically impossible due to the lack of or inadequate theoretical models.
In WO 98 14274 ist ein Verfahren zur Herstellung eines Trägerkatalysators in einer Fließbettappartur beschrieben, bei dem eine weniger dünne 100 μm Schicht einer Aktivmasse in wässrige Suspension auf einen inerten Träger von 5 μm - 20 mm Durchmesser aufgebracht wird.WO 98 14274 describes a process for producing a supported catalyst in a fluidized bed apparatus, in which a less thin 100 μm layer of an active composition is applied in aqueous suspension to an inert support of 5 μm to 20 mm diameter.
WO 02 096557 beschreibt ein Verfahren zur Herstellung in einer Fließbettapparatur von geträgerten metallischen Nanopartikeln als Katalysatoren.WO 02 096557 describes a process for the production in a fluidized bed apparatus of supported metallic nanoparticles as catalysts.
US 4 977 126 beschreibt ein Verfahren zur Herstellung von Trägerkatalysatoren in einer Fließbettapparatur, bei dem die Katalysatoren aus metallischer Cobalt-Schicht auf Oxid-Trägern besteht.US 4 977 126 describes a process for the production of supported catalysts in a fluidized bed apparatus, in which the catalysts consist of a metallic cobalt layer on oxide supports.
FR 2791 905 beschreibt ein Verfahren zur Herstellung von Trägerkatalysatoren, bei dem die Suspension aus feinen Partikeln mit 10-100 μm Durchmesser und einer Dichte von mehr als 1000 kg/m3 besteht und etwa 30% größerer Partikeln mit Durchmessern von 0,4 - 1 mm enthielt.FR 2791 905 describes a process for producing supported catalysts in which the suspension consists of fine particles with a diameter of 10-100 μm and a density of more than 1000 kg / m 3 and about 30% larger particles with a diameter of 0.4-1 mm contained.
Allerdings werden in diesen Dokumenten weder Katalysatoren für Gasphasenoxidatio- nen, noch die Beschichtung von Ringen beschrieben. Der Erfindung liegt daher das technische Problem zugrunde, ein Verfahren zur Herstellung eines Katalysators für Gasphasenoxidationen in einer Fließbettapparatur anzugeben, bei dem man ohne aufwändige Vorversuche eine gleichmäßige und reproduzierbare Beschichtung eines Trägermaterials erhält.However, these documents do not describe catalysts for gas phase oxidation or the coating of rings. The invention is therefore based on the technical problem of specifying a method for producing a catalyst for gas phase oxidations in a fluidized bed apparatus, in which a uniform and reproducible coating of a support material is obtained without complex preliminary tests.
Überraschend wurde gefunden, dass man dieses technische Problem lösen kann, wenn man die in die Apparatur eingewogene Menge an Trägermaterial, den Durchfluss und die Temperatur des zugeführten Gasstroms, sowie die Dosierrate und den Bindemittelgehalt der eingesprühten Suspension aus bestimmten vorgegeben Bereichen, so wählt, dass diese Parameter eine einfache empirisch ermittelte mathematische Relation erfüllen.Surprisingly, it was found that this technical problem can be solved by choosing the amount of carrier material weighed into the apparatus, the flow rate and the temperature of the gas stream supplied, and the metering rate and the binder content of the sprayed-in suspension from certain predetermined ranges, such that these parameters fulfill a simple empirically determined mathematical relation.
Die Erfindung betrifft ein Verfahren zur Herstellung eines Katalysators für Gasphasenoxidation, bei dem man einen teilchenförmigen inerten Träger einer Gesamtmasse Mτrager in eine Fließbettapparatur einwiegt, wenigstens eine wässrige Suspension eines katalytisch aktiven Materials oder Quellen dafür und Bindemittel mit einem Bindemittelgehalt BSusp bereitstellt, den inerten Träger durch Zufuhr eines auf eine Temperatur TGgs temperierten Gasstroms bei einem Durchfluss QGas fluidisiert, und die Suspension mit einer Dosierrate QSusp auf den fluidisierten inerten Träger aufsprüht.The invention relates to a process for the preparation of a catalyst for gas phase oxidation, in which a particulate inert carrier of a total mass Mτ ra g er is weighed into a fluidized bed apparatus, at least one aqueous suspension of a catalytically active material or sources for it and binders with a binder content B Susp are provided, the inert carrier by supplying a fluidized heated to a temperature T opp gas stream at a flow rate Q gas, and spraying the suspension at a rate Q Susp onto the fluidized inert carrier.
Erfindungsgemäß wählt man QGas, Qsusp , BSuSP , MTrager , und TGgs innerhalb der Bereiche 3000 < QGas [m3/h] ≤ 9000, 1000 < QSusp [g/min] < 3500, 2 < Bsusp [Gew. %] ≤ 18, 60 < MTräger [kg] ≤ 240. 75 < 7Gas [°C] < 120 so aus, dass eine Kenngröße K, die definiert ist als K = 0,020 QGas - 0,055 QSusp + 7,500 ßSüsp - 0,667 MTrager + 2,069 TGas - 7 der Relation 127, 5 < K≤ 202 genügt.According to the invention, one chooses Q Gas , Qsusp, B S u SP , M Trager , and T Ggs within the ranges 3000 <Q Gas [m 3 / h] ≤ 9000, 1000 <Q Susp [g / min] <3500, 2 <Bsusp [wt. %] ≤ 18, 60 <M carrier [kg] ≤ 240. 75 <7 gas [° C] <120 such that a parameter K, which is defined as K = 0.020 Q gas - 0.055 Q susp + 7.500 ß Süsp - 0.667 M carrier + 2.069 T gas - 7 with the relation 127, 5 <K≤ 202 is sufficient.
Wenn die Betriebsparameter diese Relation erfüllen, werden qualitativ hochwertige Schichten erzeugt. Insbesondere wird die Bildung von sogenannten Zwillingen vermeiden, d.h. von aneinanderhaftenden Trägerkörpern, die beispielsweise wegen unzureichender Trocknung oder zuviel Bindemittel entstehen können. Ferner tritt kein oder nur sehr geringer Abrieb durch aufgeplatzte Schichten auf. Auch die Schichten selbst sind sowohl bei Beschichtung der Träger mit einer Schicht als auch mit zwei Schichten gleichmäßiger, als bei einem Beschichtungsverfahren, bei dem ein oder mehre Parameter die obige Relation nicht erfüllen.If the operating parameters meet this relation, high-quality layers are produced. In particular, the formation of so-called twins will be avoided, i.e. of mutually adhering carrier bodies, which can arise, for example, due to insufficient drying or too much binder. Furthermore, no or only very little abrasion occurs due to burst layers. The layers themselves are more uniform both when coating the supports with one layer and with two layers than in a coating method in which one or more parameters do not meet the above relation.
Auch die mechanische Stabilität der Schicht auf dem Träger ist verbessert.The mechanical stability of the layer on the carrier is also improved.
Beim erfindungsgemäßen Verfahren erfolgt das Aufbringen der Schicht(en) des Schalenkatalysators durch beispielsweise durch Aufsprühen einer Suspension von TiO2 und V2O5, die gegebenenfalls Quellen der unten genannten Promotorelemente enthält, auf den fluidisierten Träger. Vorzugsweise enthält die katalytisch aktive Masse im calcinier- ten Zustand, bezogen auf die Gesamtmenge der katalytisch aktiven Masse, 1 bis 40 Gew.-% Vanadiumoxid, berechnet als V2O5, und 60 bis 99 Gew.-% Titandioxid, berechnet als TiO2.In the process according to the invention, the layer (s) of the coated catalyst are applied, for example, by spraying a suspension of TiO 2 and V 2 O 5 , which may contain sources of the promoter elements mentioned below, onto the fluidized support. The catalytically active composition preferably contains 1 to 40 in the calcined state, based on the total amount of the catalytically active composition % By weight of vanadium oxide, calculated as V 2 O 5 , and 60 to 99% by weight of titanium dioxide, calculated as TiO 2 .
Als Vanadium-Quelle wird vorzugsweise pulveriges Vanadiumpentoxid (V5+) sowie ge- löstes Vanadium, z. B. Vanadyloxalat (V4+) verwendet. Geeignete Ausgangsverbindungen für das Element Vanadium sind z.B. Vanadiumoxide wie Vanadiumpentoxid (V2O5), Vanadate wie Ammoniumrnetavanadat, Vanadiumoxysulfathydrat, Vanadylace- tylacetonat, Vanadinhalogenide wie Vanadintetrachlorid (VCI4) und Vanadinoxyhaloge- nide wie VOCI3. Dabei können als Vanadiumausgangsverbindungen auch solche mit- verwendet werden, die Vanadium in der Oxidationsstufe +4 enthalten, oder die Vanadium in der Oxidationsstufe +5 und verschiedene Reduktionsmittel enthalten (z.B. NH4 +, bzw. dessen Zersetzungsprodukt NH3), die V5+ zu V4+ reduzieren können. Ein solches Reduktionsmittel können auch Oxalsäure, Oxalat, Hydrazindihydrochlorid, Hydrazinsulfat, Hydrazin(Monohydrat), Hydroxylamin, Hydroxylaminhydrochlorid oder deren Salze sein.Powdery vanadium pentoxide (V 5+ ) and dissolved vanadium, eg. B. vanadyl oxalate (V 4+ ) used. Suitable starting compounds for the element vanadium are, for example, vanadium oxides such as vanadium pentoxide (V 2 O 5 ), vanadates such as ammonium rnetavanadate, vanadium oxysulfate hydrate, vanadyl acetate tylacetonate, vanadium halides such as vanadium tetrachloride (VCI 4 ) and vanadium oxyhalogenides such as VOCI 3 . The vanadium starting compounds used can also be those which contain vanadium in oxidation state +4 or which contain vanadium in oxidation state +5 and various reducing agents (for example NH 4 + or its decomposition product NH 3 ), the V 5+ can reduce to V 4+ . Such a reducing agent can also be oxalic acid, oxalate, hydrazine dihydrochloride, hydrazine sulfate, hydrazine (monohydrate), hydroxylamine, hydroxylamine hydrochloride or their salts.
Die katalytisch aktive Masse kann daneben bis zu 1 Gew.-% einer Cäsiumverbindung, berechnet als Cs, bis zu 1 Gew.-% einer Phosphorverbindung, berechnet als P und bis zu 10 Gew.-% Antimonoxid, berechnet als Sb2O3 enthalten.The catalytically active composition can also contain 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 O 3 ,
Neben den fakultativen an Zusätzen Cäsium und Phosphor können im Prinzip 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, beispielweise indem sie seine Aktivität absenken oder erhöhen. Als solche Promotoren seien beispielhaft die Alkalimetalloxid, insbesondere außer dem genannten Cäsiumoxid, Lithium-, Kalium- und Rubidiumoxid, Thallium(l)oxid, Aluminiu- oxid, Zirkoniumoxid, Eisenoxid, Nickeloxid, Kobaltoxid, Manganoxid, Zinnoxid, Silberoxid, Kupferoxid, Chromoxid, Molybdänoxid, Wolframoxid, Iridiumoxid, Tantaloxid, Ni- oboxid, Arsenoxid, Ceroxid genannt. In der Regel wird aus dieser Gruppe Cäsium als Promotor verwendet.In addition to the optional cesium and phosphorus additives, the catalytically active composition can in principle contain a small number of other oxidic compounds which, as promoters, influence the activity and selectivity of the catalyst, for example by reducing or increasing its activity. Examples of such promoters are the alkali metal oxide, in particular in addition to the cesium oxide, lithium, potassium and rubidium oxide, thallium (l) oxide, aluminum oxide, zirconium oxide, iron oxide, nickel oxide, cobalt oxide, manganese oxide, tin oxide, silver oxide, copper oxide, chromium oxide, Molybdenum oxide, tungsten oxide, iridium oxide, tantalum oxide, Ni oboxid, arsenic oxide, cerium oxide called. As a rule, cesium from this group is used as a promoter.
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. Als die Aktivität erhöhenden aber die Selektivität vermindernden Zusatz kommen vor allem oxidische Phosphorverbindungen insbesondere Phosphorpentoxid in Betracht.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 preferred as additives. Oxidic phosphorus compounds, in particular phosphorus pentoxide, are particularly suitable as an activity-increasing but selectivity-reducing additive.
Vor der Beschichtung wird die Suspension vorzugsweise ausreichend lange, z.B. 2 bis 30 Stunden, insbesondere 12 bis 25 Stunden, gerührt, um Agglomerate der suspen- dierten Feststoffe aufzubrechen und eine homogene Suspension zu erhalten. Die Suspension hat typischerweise einen Feststoffgehalt von 20 bis 50 Gew.-%. Das Suspensionsmedium ist im Allgemeinen wässrig, z. B. Wasser selbst oder ein wässriges Gemisch mit einem wassermischbaren organischen Lösungsmittel, wie Methanol, Etha- nol, Isopropanol, Formamid und dergleichen. Wenn die erste oder zweite Suspension TiO2- und V2O5-Teilchen als Katalysatorteilchen weisen vorzugsweise wenigstens 90 Vol.-% der V2O5-Teilchen einen Durchmesser von 20 μm oder weniger und wenigstens 95 Vol.-% der V2O5-Teilchen einen Durchmesser von 30 μm oder weniger auf.Before coating, the suspension is preferably stirred for a sufficiently long time, for example 2 to 30 hours, in particular 12 to 25 hours, in order to break up agglomerates of the suspended solids and to obtain a homogeneous suspension. The suspension typically has a solids content of 20 to 50% by weight. The suspension medium is generally aqueous, e.g. B. water itself or an aqueous mixture with a water-miscible organic solvent, such as methanol, ethanol, isopropanol, formamide and the like. If the first or second suspension of TiO 2 and V 2 O 5 particles as catalyst particles preferably have at least 90 % By volume of the V 2 O 5 particles have a diameter of 20 μm or less and at least 95% by volume of the V 2 O 5 particles have a diameter of 30 μm or less.
In der Regel werden der Suspension organische Binder, bevorzugt Copolymere, vorteilhaft in Form einer wässrigen Dispersion, von Vinylacetat/Vinyllaurat, Vinylace- tat/Acrylat, Styrol/Acrylat sowie Vinylacetat/Ethylen zugesetzt. Die Binder sind als wässrige Dispersionen handelsüblich, mit einem Feststoffgehalt von z. B. 35 bis 65 Gew.-%. Die eingesetzte Menge solcher Binderdispersionen beträgt erfindungsgemäß 2 bis 18 Gew.-%. bezogen auf das Gewicht der Suspension.As a rule, organic binders, preferably copolymers, advantageously in the form of an aqueous dispersion, of vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate and vinyl acetate / ethylene are added to the suspension. The binders are commercially available as aqueous dispersions with a solids content of e.g. B. 35 to 65 wt .-%. According to the invention, the amount of such binder dispersions used is 2 to 18% by weight. based on the weight of the suspension.
Bei der Beschichtung des Katalysatorträgers mit der katalytisch aktiven Masse werden erfindungsgemäß Beschichtungstemperaturen von 75 bis 120 °C angewandt, wobei die Beschichtung unter Atmosphärendruck oder unter reduziertem Druck erfolgen kann.When coating the catalyst support with the catalytically active composition, coating temperatures of 75 to 120 ° C. are used according to the invention, it being possible for the coating to be carried out under atmospheric pressure or under reduced pressure.
Die Schichtdicke der katalytisch aktiven Masse beträgt in der Regel 0,02 bis 0,25 mm, vorzugsweise 0,05 bis 0,20 mm. Der Aktivmasseanteil am Katalysator beträgt üblicherweise 5 bis 25 Gew.-%, meist 7 bis 15 Gew.-%.The layer thickness of the catalytically active composition is generally 0.02 to 0.25 mm, preferably 0.05 to 0.20 mm. The active mass fraction of the catalyst is usually 5 to 25% by weight, usually 7 to 15% by weight.
Durch thermische Behandlung des so erhaltenen Präkatalysators bei Temperaturen über 80 bis 450 °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 precatalyst obtained in this way at temperatures above 80 to 450 ° C., the binder escapes from the applied layer by thermal decomposition and / or combustion. The thermal treatment is preferably carried out in situ in the gas phase oxidation reactor.
Bevorzugt liegt die Kennzahl in einem Bereich von136,0 ≤ K≤ 193,5 liegt und es sind 4500 < QGas [m3/h] < 7500, 1500 < QSusp [g/min] < 3000, 5 < BSusp [Gew.%] < 15, 100 < Mmger [kg] < 200, und 80 < 7Gas [°C] < 115.The characteristic number is preferably in a range from 136.0 ≤ K ≤ 193.5 and there are 4500 <Q gas [m 3 / h] <7500, 1500 <Q Susp [g / min] <3000, 5 <B Susp [ % By weight] <15, 100 <M mger [kg] <200, and 80 <7 gas [° C] <115.
Besonders bevorzugt liegt die Kennzahl in einem Bereich von 143 < K≤ 184,5 liegt und es sind 5500 < QGas [m3/h] < 6500, 2000 < QSusp [g/min] < 2500, 6 ≤ Bsusp [Gew.%] < 11 120 < MTräger [kg] < 180, 90 < TGas [°C] < 115.The characteristic number is particularly preferably in a range from 143 <K≤ 184.5 and there are 5500 <Q gas [m 3 / h] <6500, 2000 <Q Susp [g / min] <2500, 6 ≤ B susp [ % By weight] <11 120 <M carrier [kg] <180, 90 <T gas [° C] <115.
Zum Verwirbeln und temperieren der Trägermaterialschüttung in der Fließbettapparatur kann jedes bei den Betriebbedingungen inertes Gas oder Gasgemisch verwendet werden. Vorteilhaft ist das zugeführte Gas aber Luft, was einen besonders kostengünstigen Betrieb der Anlage ermöglicht.Any gas or gas mixture which is inert under the operating conditions can be used for swirling and tempering the bed of carrier material in the fluidized bed apparatus. However, the gas supplied is air, which enables the system to be operated particularly cost-effectively.
Die katalytisch aktive Masse kann auch in zwei oder mehreren Schichten aufgebracht sein. Vorzugsweise besitzen die Schichten unterschiedliche Selektivität und Aktivität. Beispielsweise kann die innere Schicht oder die inneren Schichten einen Antimonoxidgehalt von bis zu 15 Gew.-% und die äußere Schicht einen um 50 bis 100% verringerten Antimonoxidgehalt aufweisen. Beispielsweise kann die innere Schicht und äußere Schicht unterschiedliche P-Menge enthalten. Zu Herstellung von Katalysatoren mit zwei Schichten stellt man erfindungsgemäß eine zweite wässrige Suspension aus katalytisch aktivem Material und Bindemittel bereit und sprüht sie auf den mit der ersten Suspension beschichteten fluidisierten Träger auf.The catalytically active composition can also be applied in two or more layers. The layers preferably have different selectivity and activity. For example, the inner layer or the inner layers can have an antimony oxide content of up to 15% by weight and the outer layer can have an antimony oxide content reduced by 50 to 100%. For example, the inner layer and outer layer can contain different amounts of P. For the production of catalysts with According to the invention, two layers are provided with a second aqueous suspension of catalytically active material and binder and sprayed onto the fluidized carrier coated with the first suspension.
Als inertes Trägermaterial können praktisch alle Trägermaterialien des Standes der Technik, wie sie vorteilhaft bei der Herstellung von Schalenkatalysatoren für die Oxida- tion aromatischer Kohlenwasserstoffe zu Aldehyden, Carbonsäuren und/oder Carbonsäureanhydriden eingesetzt werden, Verwendung finden, beispielsweise Quarz (SiO2), Porzellan, Magnesiumoxid, Zinndioxid, Siliciumcarbid, Rutil, Tonerde (AI2O3), Alumini- umsilikat, Steatit (Magnesiumsilikat), Zirkoniumsilikat, Cersilikat oder Mischungen dieser Trägermaterialien. Das Trägermaterial ist in der Regel nicht-porös. Der Ausdruck "nicht-porös" ist dabei im Sinne von "bis auf technisch unwirksame Mengen an Poren nicht-porös" zu verstehen, da technisch unvermeidlich eine geringe Anzahl Poren im Trägermaterial, das idealerweise keine Poren enthalten sollte, vorhanden sein können. Als vorteilhafte Trägermaterialien sind insbesondere Steatit und Siliciumcarbid hervorzuheben. Die Form des Trägermaterials ist für die erfindungsgemäßen Präkatalysatoren und Schalenkatalysatoren im Allgemeinen nicht kritisch. Beispielsweise können Katalysatorträger in Form von Kugeln, Ringen, Tabletten, Spiralen, Röhren, Extrudaten oder Splitt verwendet werden. Die Dimensionen dieser Katalysatorträger entsprechen denen üblicherweise zur Herstellung von Schalenkatalysatoren für die Gasphasenpar- tialoxidation von aromatischen Kohlenwasserstoffen verwendeten Katalysatorträgern. Bevorzugt wird Steatit in Form von Kugeln mit einem äußeren Durchmesser von 0,5 bis 10 mm oder Ringen mit einem äußeren Durchmesser von 3 bis 15 mm verwendet.Practically all carrier materials of the prior art, such as are advantageously used in the production of coated catalysts for the oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic acid anhydrides, can be used as the inert carrier material, 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 carrier materials. The carrier material is usually non-porous. The expression "non-porous" is to be understood in the sense of "except for technically ineffective amounts of pores non-porous", since technically inevitably a small number of pores can be present in the carrier material, which ideally should not contain any pores. Steatite and silicon carbide are particularly worth mentioning as advantageous carrier materials. The shape of the support material is generally not critical for the precatalysts and coated catalysts according to the invention. For example, catalyst supports in the form of spheres, rings, tablets, spirals, tubes, extrudates or grit can be used. The dimensions of these catalyst carriers correspond to those of the catalyst carriers usually used for the production of shell catalysts for the gas phase partial oxidation of aromatic hydrocarbons. Steatite in the form of balls with an outer diameter of 0.5 to 10 mm or rings with an outer diameter of 3 to 15 mm is preferably used.
Besonders bevorzugt führt man das erfindungsgemäße Verfahren in einer Fließbettapparatur durch, die einen Behälter zu Aufnahme des teilchenförmigen Trägers, in dessen unterem Bereich eine schüsselartige Vertiefung vorgesehen ist, ein Zentralrohr zur Zufuhr des Gases, das sich in dem Behälter im wesentlichen axial nach unten erstreckt und in die Vertiefung mündet, einen im wesentlichen ringförmigen Abweisschirm, der in dem oberen Bereich des Behälters an dem Zentralrohr befestigt ist, und einen in dem unteren Bereich des Behälters angeordneten Leitring, der das Zentralrohr auf einem Teil seiner Länge im wesentlich konzentrisch umgibt, und Mitteln zum Einsprühen der ersten und gegebenenfalls zweiten Suspension umfasst. Eine solche Fließbettapparatur ist beispielsweise in der deutschen Patentanmeldung DE 4006935 beschrieben. Kommerziell erhältliche Fließbettapparturen, die sich zur Durchführung des erfindungsgemäßen Verfahrens eigenen sind beispielsweise die Kugel-Coater HKC 150 und HKC 200 der Fa. Hüttlin, Steinen, Deutschland.The process according to the invention is particularly preferably carried out in a fluidized bed apparatus which has a container for receiving the particulate carrier, in the lower region of which a bowl-like depression is provided, a central tube for supplying the gas, which extends essentially axially downward in the container opens into the recess, a substantially ring-shaped deflector screen, which is fastened to the central tube in the upper region of the container, and a guide ring arranged in the lower region of the container, which surrounds the central tube substantially concentrically over part of its length, and means for spraying the first and optionally the second suspension. Such a fluid bed apparatus is described, for example, in German patent application DE 4006935. Commercially available fluid bed apparatuses which are suitable for carrying out the process according to the invention are, for example, the ball coaters HKC 150 and HKC 200 from Hüttlin, Steinen, Germany.
Die erfindungsgemäßen Katalysatoren eignen sich generell zur Gasphasenoxidation aromatischer C6- bis C10-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 Pyromellithsäuredianhydrid. Gegenstand der Erfindung ist daher auch die Verwendung des nach dem erfindungsgemäßen Verfahren hergestellten Katalysators zur Herstel- lung von Phthalsäureanhydrid aus o-Xyloi, Naphthalin oder Gemischen davon. Zu diesem Zweck werden die erfindungsgemäß hergestellten Katalysatoren in von außen auf die Reaktionstemperatur, beispielsweise mittels Salzschmelzen, thermostati- sierte Reaktionsrohre gefüllt und die SalzbadTemperaturen von im allgemeinen 300 bis 450 °C, vorzugsweise von 320 bis 420 °C und besonders bevorzugt von 340 bis 400 °C und bei einem Überdruck von im allgemeinen 0,1 bis 2,5 bar, vorzugsweise von 0,3 bis 1,5 bar mit einer Raumgeschwindigkeit von im allgemeinen 750 bis 5000 h"1 geleitet. Das dem Katalysator zugeführte Reaktionsgas wird im allgemeinen durch Vermischen von einem molekularen Sauerstoff enthaltenden Gas, das außer Sauer- stoff noch geeignete Reaktionsmoderatoren und/oder Verdünnungsmittel, wie Dampf, Kohlendioxid und/oder Stickstoff, enthalten kann, mit dem zu oxidierenden, aromatischen Kohlenwasserstoff erzeugt, wobei das molekularen Sauerstoff enthaltende Gas im allgemeinen 1 bis 100 mol-%, vorzugsweise 2 bis 50 mol-% und besonders bevorzugt 10 bis 30 mol-% Sauerstoff, 0 bis 30 mol-%, vorzugsweise 0 bis 10 mol-% Was- serdampf sowie 0 bis 50 mol-%, vorzugsweise 0 bis 1 mol-% Kohlendioxid, Rest Stickstoff, enthalten kann. Zur Erzeugung des Reaktionsgases wird das molekularen Sauerstoff enthaltende Gas im allgemeinen mit 30 g bis 150 g je Nm3 Gas des zu oxidierenden, aromatischen Kohlenwasserstoffs beschickt. Es hat sich als besonders vorteilhaft erwiesen, wenn in der Katalysatorschüttung Katalysatoren eingesetzt werden, die sich in ihrer katalytischen Aktivität und/oder chemischen Zusammensetzung ihrer Aktivmasse unterscheiden. Üblicherweise wird bei Anwendung zweier Reaktionszonen in der ersten, also zum Gaseintritt des Reaktionsgases hin gelegenen Reaktionszone, ein Katalysator eingesetzt, der in Vergleich zum Katalysator, welcher sich in der zweiten, also zum Gasaustritt hin gelegenen Reaktionszone, befindet, eine etwas geringere katalytische Aktivität hat. Im allgemeinen wird die Umsetzung durch die Temperatureinstellung so gesteuert, dass in der ersten Zone der größte Teil der im Reaktionsgas enthaltenen aromatischen Kohlenwasserstoff bei maximaler Ausbeute umgesetzt wird. Vorzugsweise werden drei- bis fünflagige Katalysatorsysteme verwendet, insbesondere drei- und vierlagige Katalysatorsysteme.The catalysts according to the invention are generally suitable for the gas phase oxidation of aromatic C 6 to C 10 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 invention therefore also relates to the use of the catalyst prepared by the process according to the invention for the production of phthalic anhydride from o-xylene, naphthalene or mixtures thereof. For this purpose, the catalysts prepared according to the invention are filled into reaction tubes thermostatically controlled from the outside to the reaction temperature, for example by means of molten salt, and the salt bath temperatures are generally from 300 to 450 ° C., preferably from 320 to 420 ° C. and particularly preferably from 340 to 400 ° C and at an overpressure of generally 0.1 to 2.5 bar, preferably 0.3 to 1.5 bar with a space velocity of generally 750 to 5000 h "1. The reaction gas fed to the catalyst is generally generated by mixing a gas containing molecular oxygen, which in addition to oxygen can also contain suitable reaction moderators and / or diluents, such as steam, carbon dioxide and / or nitrogen, with the aromatic hydrocarbon to be oxidized, the molecular oxygen-containing gas in generally 1 to 100 mol%, preferably 2 to 50 mol% and particularly preferably 10 to 30 mol% oxygen, 0 to 30 mol%, preferably 0 to 10 mol% water vapor and 0 to 50 mol%, preferably 0 to 1 mol% carbon dioxide, the rest nitrogen. To generate the reaction gas, the molecular oxygen-containing gas is generally charged with 30 g to 150 g per Nm 3 of gas of the aromatic hydrocarbon to be oxidized. It has proven to be particularly advantageous if catalysts are used in the catalyst bed which differ in their catalytic activity and / or chemical composition of their active composition. Usually, when using two reaction zones in the first reaction zone, i.e. towards the gas inlet of the reaction gas, a catalyst is used which has a somewhat lower catalytic activity compared to the catalyst which is located in the second reaction zone, i.e. towards the gas outlet , In general, the reaction is controlled by the temperature setting in such a way that in the first zone most of the aromatic hydrocarbons contained in the reaction gas are converted with maximum yield. Three- to five-layer catalyst systems are preferably used, in particular three- and four-layer catalyst systems.
Die Erfindung wird durch die folgenden Beispiele näher veranschaulicht.The invention is illustrated in more detail by the following examples.
Beispiel 1 (Einschalenkatalysator auf herkömmlichen Trägerringen):Example 1 (single-shell catalyst on conventional carrier rings):
47,44 kg Anatas (BET- Oberfläche 9 m2/g), 20,34 kg Anatas (BET- Oberfläche 20 m2/g), 5,32 kg Vanadiumpentoxid, 1 ,33 kg Antimonoxid, 0,30 kg Cäsiumcarbonat wurden in 195 I entionisiertem Wasser suspendiert und 18 Stunden gerührt, um eine homogene Verteilung zu erzielen. Zu dieser Suspension wurden 30,6 kg organischer Binder, bestehend aus einem Copolymer aus Vinylacetat und Vinyllaurat in Form einer 50 Gew.-%igen wäßerigen Dispersion zugegeben.47.44 kg anatase (BET surface area 9 m 2 / g), 20.34 kg anatase (BET surface area 20 m 2 / g), 5.32 kg vanadium pentoxide, 1.33 kg antimony oxide, 0.30 kg cesium carbonate suspended in 195 l of deionized water and stirred for 18 hours to achieve a homogeneous distribution. 30.6 kg of organic binder consisting of a copolymer of vinyl acetate and vinyl laurate in the form of a 50% by weight aqueous dispersion were added to this suspension.
In einer Fließbettapparatur (Hüttlin HKC 150) wurden 60 kg dieser Suspension auf 150 kg Steatit (Magnesiumsilikat) in Form von Ringen mit Abmessungen von 7 mm x 7 mm x 4 mm (Außendurchmesser x Höhe x Innendurchmesser) aufgesprüht und getrocknet. Die Betriebsparameter waren Luftdurchfluss; 6000 m3/hIn a fluid bed apparatus (Hüttlin HKC 150), 60 kg of this suspension were sprayed onto 150 kg of steatite (magnesium silicate) in the form of rings with dimensions of 7 mm x 7 mm x 4 mm (outer diameter x height x inner diameter) and dried. The operating parameters were Air flow; 6000 m 3 / h
Dosierrate: 2250 g / minDosing rate: 2250 g / min
Bindemittelkonzentration 10 Gew.-% der gesamten eingesetzten SuspensionBinder concentration 10% by weight of the total suspension used
Trägereinwaage 150 kg Steatit-Ringe (7 mm x 7 mm x 4 mm) Zulufttemperatur: 109°CCarrier weight 150 kg steatite rings (7 mm x 7 mm x 4 mm) supply air temperature: 109 ° C
Die auf diese Weise aufgebrachte katalytisch aktive Masse, also die Katalysatorschale, enthielt nach einer Stunde Calcination auf 450°C 7,12 Gew.-% Vanadium (berechnet als V2O5), 1 ,8 Gew.-% Antimon (berechnet als Sb2O3), 0,33 Gew.-% Cäsium (berech- net als Cs), 90,75 Gew.-% Titandioxid. Das Gewicht der aufgetragenen Schale betrug 8,0 % des Gesamtgewichtes des fertigen Katalysators.The catalytically active composition applied in this way, i.e. the catalyst shell, contained 7.12% by weight of vanadium (calculated as V 2 O 5 ), 1.8% by weight of antimony (calculated as Sb 2 O 3 ), 0.33% by weight of cesium (calculated as Cs), 90.75% by weight of titanium dioxide. The weight of the shell applied was 8.0% of the total weight of the finished catalyst.
Die Kennzahl K, die aus der Gleichung des Anspruchs 1 berechnet wurde, beträgt 188,5.The key figure K, which was calculated from the equation of claim 1, is 188.5.
Der Abrieb nach dreifachem Falltest betrug 25 Gew.-% (nach 1 h Calcination bei 450°C). Bei dem Falltest wurden ca. 50 g Katalysator (calciniert nach einstündiger Wärmebehandlung bei 450°C) durch ein 3 m langes Rohr mit lichtem Durchmesser von 25 mm fallengelassen. Der Katalysator fällt in eine unter dem Rohr stehende Schale, wird von dem bei Aufschlag entstehenden Staub abgetrennt und wieder durch das Rohr fallengelassen. Der Gesamtmassenverlust nach dreimaligem Falltest bzgl. der aufgetragenen Aktivmassenmenge, die 100% entspricht ist ein Maß für die Abriebsfestigkeit des Katalysators.The abrasion after a triple drop test was 25% by weight (after 1 h of calcination at 450 ° C.). In the drop test, approx. 50 g of catalyst (calcined after heat treatment at 450 ° C. for one hour) were dropped through a 3 m long tube with an internal diameter of 25 mm. The catalyst falls into a bowl underneath the tube, is separated from the dust generated when it hits the ground, and is dropped again through the tube. The total mass loss after three drop tests with respect to the amount of active mass applied, which corresponds to 100%, is a measure of the abrasion resistance of the catalyst.
Verqleichsbeispiel 2:Comparative example 2:
Der Katalysator wurde präpariert wie in Beispiel 1 , wobei die Betriebsbedingungen der Fließbettapparatur wie folgt eingestellt wurden:The catalyst was prepared as in Example 1, the operating conditions of the fluid bed apparatus being set as follows:
Luftdurchfluss: 6000 m3/hAir flow: 6000 m 3 / h
Dosierrate: 2250 g / minDosing rate: 2250 g / min
Bindemittelkonzentration 10 Gew.-% der gesamten eingesetzten SuspensionBinder concentration 10% by weight of the total suspension used
Trägereinwaage 150 kg Steatit-Ringe (7 mm x 7 mm x 4 mm)Carrier weight 150 kg steatite rings (7 mm x 7 mm x 4 mm)
Zulufttemperatur: 70°C Die Kennzahl , die aus der Gleichung des Anspruchs 1 berechnet wurde, beträgtSupply air temperature: 70 ° C The key figure, which was calculated from the equation of claim 1, is
107,8.107.8.
Bei einer Zulufttemperatur, die unterhalb des erfindungsgemäßen Bereichs lag, wurden viele Zwillingsringe gefunden, die offenbar wegen unzureichender Trocknung entstan- den sind. Der Abrieb nach dreifachem Falltest (Falltest wie in Beispiel 1 ) betrug 40%.At an inlet air temperature that was below the range according to the invention, many twin rings were found, which apparently resulted from inadequate drying. The abrasion after a triple drop test (drop test as in Example 1) was 40%.
Verqleichsbeispiel 3:Comparative example 3:
Der Katalysator wurde präpariert wie in Beispiel 1 , wobei die Betriebsbedingungen der Fließbettapparatur wie folgt eingestellt wurden: Luftdurchfluss: 6000 m3/hThe catalyst was prepared as in Example 1, the operating conditions of the fluid bed apparatus being set as follows: Air flow: 6000 m 3 / h
Dosierrate: 2250 g / minDosing rate: 2250 g / min
Bindemittelkonzentration 20 Gew.-% der gesamten eingesetzten Suspension Trägereinwaage 150 kg Steatit-Ringe (7 mm x 7 mm x 4 mm)Binder concentration 20% by weight of the total suspension used, carrier weight 150 kg steatite rings (7 mm x 7 mm x 4 mm)
Zulufttemperatur: 109°CSupply air temperature: 109 ° C
Die Kennzahl K, die aus der Gleichung des Anspruchs 1 berechnet wurde, beträgt 263,5.The key figure K, which was calculated from the equation of claim 1, is 263.5.
Auch bei einer Bindemittelkonzentration, die über dem erfindungsgemäß vorgesehenen Bereich lag, fand man vielen Zwillingsringe. Der Abrieb nach dreifachem Falltest (Falltest wie in Beispiel 1 ) betrug 40%.Many twin rings were also found at a binder concentration which was above the range envisaged according to the invention. The abrasion after a triple drop test (drop test as in Example 1) was 40%.
Beispiel 4 (Einschalenkatalysator auf größeren Trägerringen):Example 4 (single-shell catalyst on larger support rings):
150 kg Steatit in Form von Ringen mit Abmessungen von 8 mm x 6 mm x 5 mm (Außendurchmesser x Höhe x Innendurchmesser) wurden in einer Fließbettapparatur (Hüttlin HKC 150) erhitzt und mit 57 kg einer Suspension aus 140,02 kg Anatas mit einer BET-Oberfläche von 21 m2/g, 11 ,776 kg Vanadiumpentoxid, 31 ,505 kg Oxalsäure, 5,153 kg Antimontrioxid, 0,868 kg Ammoniumhydrogenphosphat, 0,238 g Cäsiumsulfat, 215,637 kg Wasser und 44,808 kg Formamid, zusammen mit 33,75 kg eines organischen Binders, bestehend aus einem Copolymer von Acrylsäure/Maleinsäure (Gewichtsverhältnis 75:25) besprüht, bis das Gewicht der aufgetragenen Schicht 10,5 % des Gesamtgewichts des fertigen Katalysators betrug (nach einstündiger Wärmebehandlung bei 450 °C). Die auf diese Weise aufgebrachte katalytisch aktive Masse, also die Katalysatorschale, bestand im Mittel aus 0,15 Gew.-% Phosphor (berechnet als P), 7,5 Gew.-% Vanadium (berechnet als V2O5), 3,2 Gew.-% Antimon (berechnet als Sb2O3), 0,1 Gew.-% Cäsium (berechnet als Cs) und 89,05 Gew.-% Titandioxid. Die Betriebsbedingungen der Fließbettapparatur waren:150 kg steatite in the form of rings with dimensions of 8 mm x 6 mm x 5 mm (outer diameter x height x inner diameter) were heated in a fluidized bed apparatus (Hüttlin HKC 150) and with 57 kg of a suspension of 140.02 kg of anatase with a BET -Surface of 21 m 2 / g, 11, 776 kg vanadium pentoxide, 31, 505 kg oxalic acid, 5.153 kg antimony trioxide, 0.868 kg ammonium hydrogen phosphate, 0.238 g cesium sulfate, 215.637 kg water and 44.808 kg formamide, together with 33.75 kg of an organic binder consisting of a copolymer of acrylic acid / maleic acid (weight ratio 75:25) sprayed until the weight of the applied layer was 10.5% of the total weight of the finished catalyst (after heat treatment at 450 ° C for 1 hour). The catalytically active composition applied in this way, i.e. the catalyst shell, consisted on average of 0.15% by weight of phosphorus (calculated as P), 7.5% by weight of vanadium (calculated as V 2 O 5 ), 3, 2% by weight of antimony (calculated as Sb 2 O 3 ), 0.1% by weight of cesium (calculated as Cs) and 89.05% by weight of titanium dioxide. The operating conditions of the fluid bed apparatus were:
Luftdurchfluss: 6500 m3/hAir flow: 6500 m 3 / h
Dosierrate: 2250 g / minDosing rate: 2250 g / min
Bindemittelkonzentration 7,5 Gew.-% der gesamten eingesetzten Suspension Trägereinwaage 150 kg Steatit-Ringe (8 mm x 6 mm x 5 mm)Binder concentration 7.5% by weight of the total suspension used, carrier weight 150 kg steatite rings (8 mm x 6 mm x 5 mm)
Zulufttemperatur: 97°CSupply air temperature: 97 ° C
Die Kennzahl K, die aus der Gleichung im Anspruch 1 berechnet wurde, beträgt 154,9.Der Abrieb nach dreifachem Falltest (Falltest wie in Beispiel 1) betrug 5 Gew.-% (nach 1h Calcination bei 450°C).The characteristic number K, which was calculated from the equation in claim 1, is 154.9. The abrasion after a triple drop test (drop test as in Example 1) was 5% by weight (after 1 hour calcination at 450 ° C.).
Vergleichsbeispiel 5: Der Katalysator wurde präpariert wie in Beispiel 4, wobei 19 kg von der Suspension besprüht wurde und die Betriebsbedingungen der Fließbettapparatur wie folgt eingestellt wurden:Comparative Example 5: The catalyst was prepared as in Example 4, spraying 19 kg of the suspension and setting the operating conditions of the fluid bed apparatus as follows:
Luftdurchfluss: 6500 m3/hAir flow: 6500 m 3 / h
Dosierrate: 2250 g / minDosing rate: 2250 g / min
Bindemittelkonzentration 7,5 Gew.-% der gesamten eingesetzten SuspensionBinder concentration 7.5% by weight of the total suspension used
Trägereinwaage 50 kg Steatit-Ringe (8 mm x 6 mm x 5 mm)Carrier weight 50 kg steatite rings (8 mm x 6 mm x 5 mm)
Zulufttemperatur: 97°CSupply air temperature: 97 ° C
Die Kennzahl K, die aus der Gleichung im Anspruch 1 berechnet wurde, beträgt 221 ,6.The key figure K, which was calculated from the equation in claim 1, is 221.6.
In diesem Vergleichsbeispiel, bei dem die Einwage an Trägermaterial unterhalb des erfindungsgemäß vorgesehenen Bereichs lag, wurden wieder vielen Zwillingsringe gefunden. Der Abrieb nach dreifachem Falltest (Falltest wie in Beispiel 1) betrug 34%.In this comparative example, in which the weight of carrier material was below the range provided according to the invention, many twin rings were found again. The abrasion after triple drop test (drop test as in Example 1) was 34%.
Vergleichsbeispiel 6:Comparative Example 6:
Der Katalysator wurde präpariert wie in Beispiel 4, wobei die Betriebsbedingungen der Fließbettapparatur wie folgt eingestellt wurden:The catalyst was prepared as in Example 4, the operating conditions of the fluid bed apparatus being set as follows:
Luftdurchfluss: 6500 m3/h Dosierrate: 900 g / minAir flow: 6500 m 3 / h dosing rate: 900 g / min
Bindemittelkonzentration 7,5 Gew.-% der gesamten eingesetzten Suspension Trägereinwaage 150 kg Steatit-Ringe (8 mm x 6 mm x 5 mm)Binder concentration 7.5% by weight of the total suspension used, carrier weight 150 kg steatite rings (8 mm x 6 mm x 5 mm)
Zulufttemperatur: 97°CSupply air temperature: 97 ° C
Die Kennzahl K, die aus der Gleichung im Anspruch 1 berechnet wurde, beträgt 229,9.The key figure K, which was calculated from the equation in claim 1, is 229.9.
Bei zu geringer Dosierrate der Suspension wurden vielen abgeplatzte Schichtkatalysatoren gefunden. Der Abrieb nach dreifachem Falltest (Falltest wie in Beispiel 1 ) betrug 51%.If the dosing rate of the suspension was too low, many flaked-off layer catalysts were found. The abrasion after triple drop test (drop test as in Example 1) was 51%.
Beispiel 7: ZweischalenkatalysatorExample 7: Two-shell catalyst
Suspension 1 :Suspension 1:
150 kg Steatit in Form von Ringen mit Abmessungen von 8 mm x 6 mm x 5 mm (Außendurchmesser x Höhe x Innendurchmesser) wurden in einer Fließbettapparatur (Hüttlin HKC 150) erhitzt und mit 24 kg einer Suspension aus 155,948 kg Anatas mit einer BET-Oberfläche von 21 m2/g, 13,193 kg Vanadiumpentoxid, 35,088 kg Oxalsäure, 5,715 kg Antimontrioxid, 0,933 kg Ammoniumhydrogenphosphat, 0,991 g Cäsiumsulfat, 240,160 kg Wasser und 49,903 kg Formamid, zusammen mit 37,5 kg eines organischen Binders, bestehend aus einem Copolymer von Acrylsäure/Maleinsäure (Gewichtsverhältnis 75:25) besprüht. Suspension 2:150 kg steatite in the form of rings with dimensions of 8 mm x 6 mm x 5 mm (outer diameter x height x inner diameter) were heated in a fluid bed apparatus (Hüttlin HKC 150) and with 24 kg of a suspension of 155.948 kg of anatase with a BET surface of 21 m 2 / g, 13.193 kg vanadium pentoxide, 35.088 kg oxalic acid, 5.715 kg antimony trioxide, 0.933 kg ammonium hydrogen phosphate, 0.991 g cesium sulfate, 240.160 kg water and 49.903 kg formamide, together with 37.5 kg of an organic binder consisting of a copolymer of Sprayed acrylic acid / maleic acid (weight ratio 75:25). Suspension 2:
150 kg des erhaltenen Schalenkatalysators wurden in Fließbettapparatur erhitzt und mit 24 kg einer Suspension aus 168,35 kg Anatas mit einer BET-Oberfläche von 21 m2/g, 7,043 kg Vanadiumpentoxid, 19,080 kg Oxalsäure, 0,990 g Cäsiumsulfat, 238,920 kg Wasser und 66,386 kg Formamid, zusammen mit 37,5 kg eines organischen Binders, bestehend aus einem Copolymer von Acrylsäure/Maleinsäure (Gewichtsverhältnis 75:25) besprüht.150 kg of the shell catalyst obtained were heated in a fluidized bed apparatus and with 24 kg of a suspension of 168.35 kg of anatase with a BET surface area of 21 m 2 / g, 7.043 kg of vanadium pentoxide, 19.080 kg of oxalic acid, 0.990 g of cesium sulfate, 238.920 kg of water and 66.386 kg of formamide, together with 37.5 kg of an organic binder consisting of a copolymer of acrylic acid / maleic acid (weight ratio 75:25) sprayed.
Betriebsbedingungen der Fließbettapparatur beim Aufsprühen beider Schichten:Operating conditions of the fluid bed apparatus when spraying both layers:
Luftdurchfluss: 6500 m3/hAir flow: 6500 m 3 / h
Dosierraten: jeweils 2250 g / minDosing rates: 2250 g / min each
Bindemittelkonzentration 7,5 Gew.-% der gesamten eingesetzten SuspensionBinder concentration 7.5% by weight of the total suspension used
Trägereinwaage 150 kg Steatit-Ringe (8 mm x 6 mm x 5 mm) Zulufttemperatur: 97°CCarrier weight 150 kg steatite rings (8 mm x 6 mm x 5 mm) supply air temperature: 97 ° C
Die Kennzahl K, die aus der Gleichung im Anspruch 1 berechnet wurde, beträgt 154,9.The key figure K, which was calculated from the equation in claim 1, is 154.9.
Das Gewicht der aufgetragenen Schichten betrug 9,3 % des Gesamtgewichts des fer- tigen Katalysators (nach einstündiger Wärmebehandlung bei 450 °C). Die auf diese Weise aufgebrachte katalytisch aktive Masse, also die Katalysatorschalen, bestand im Mittel aus 0,08 Gew.-% Phosphor (berechnet als P), 5,75 Gew.-% Vanadium (berechnet als V2O5), 1 ,6 Gew.-% Antimon (berechnet als Sb2O3), 0,4 Gew.-% Cäsium (berechnet als Cs) und 92,17 Gew.-% Titandioxid.The weight of the applied layers was 9.3% of the total weight of the finished catalyst (after heat treatment at 450 ° C. for one hour). The catalytically active composition applied in this way, i.e. the catalyst shells, consisted on average of 0.08% by weight of phosphorus (calculated as P), 5.75% by weight of vanadium (calculated as V 2 O 5 ), 1, 6% by weight of antimony (calculated as Sb 2 O 3 ), 0.4% by weight of cesium (calculated as Cs) and 92.17% by weight of titanium dioxide.
Der Abrieb nach dreifachem Falltest (Falltest wie in Beispiel 1 ) betrug 10 Gew.-% (nach 1h Calcination bei 450°C).The abrasion after a triple drop test (drop test as in Example 1) was 10% by weight (after 1 hour calcination at 450 ° C.).
Vergleichsbeispiel 8:Comparative Example 8:
Ein Zweischalenkatalysator wurde präpariert wie in Beispiel 7, wobei die Betriebsbedingungen der Fließbettapparatur wie folgt eingestellt wurden:A clamshell catalyst was prepared as in Example 7, the operating conditions of the fluid bed apparatus being set as follows:
Luftdurchfluss: 2900 m3/h Dosierrate: 2250 g / minAir flow: 2900 m 3 / h dosing rate: 2250 g / min
Bindemittelkonzentration 7,5 Gew.-% der gesamte eingesetzten SuspensionBinder concentration 7.5% by weight of the total suspension used
Einwaage 150 kg Steatit-Ringen (8 x 6 x 5 mm)Weight 150 kg steatite rings (8 x 6 x 5 mm)
Zulufttemperatur: 97°CSupply air temperature: 97 ° C
Die Kennzahl K, die aus der Gleichung im Anspruch 1 berechnet wurde, beträgt 82,9.The key figure K, which was calculated from the equation in claim 1, is 82.9.
Bei zu geringem Luftdurchfluss wurden vielen Zwillingsringe und Katalysatoren mit abgeplatzten Schichten gefunden. Der Abrieb nach dreifachem Falltest (Falltest wie in Beispiel 1) betrug 64%. Verqleichsbeispiel 9:If the air flow was too low, many twin rings and catalysts with chipped layers were found. The abrasion after triple drop test (drop test as in Example 1) was 64%. Comparative Example 9:
Ein Zweischichtkatalysator wurde präpariert wie in Beispiel 7, wobei die Betriebsbedingungen der Fließbettapparatur wie folgt eingestellt wurden:A two-layer catalyst was prepared as in Example 7, the operating conditions of the fluidized bed apparatus being set as follows:
Luftdurchfluss: 6500 m3/hAir flow: 6500 m 3 / h
Dosierrate: 2250 g / minDosing rate: 2250 g / min
Bindemittelkonzentration 7,5 Gew.-% der gesamten eingesetzten Suspension Trägereinwaage 150 kg Steatit-Ringe (8 mm x 6 mm x 5 mm) Zulufttemperatur: 125°CBinder concentration 7.5% by weight of the total suspension used Weighing in 150 kg steatite rings (8 mm x 6 mm x 5 mm) Supply air temperature: 125 ° C
Die Kennzahl K, die aus der Gleichung im Anspruch 1 berechnet wurde, beträgt 212,8.The key figure K, which was calculated from the equation in claim 1, is 212.8.
Bei zu hoher Temperatur der zugeführten Luft fand man viele Katalysatoren mit abge- platzten Schichten gefunden. Der Abrieb nach dreifachem Falltest (Falltest wie in Beispiel 1) betrug 65%. If the temperature of the supplied air was too high, many catalysts with chipped layers were found. The abrasion after a triple drop test (drop test as in Example 1) was 65%.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung eines Katalysators für Gasphasenoxidationen, bei dem man einen teilchenförmigen inerten Träger einer Gesamtmasse MTrager in eine Fließbettapparatur einwiegt, wenigstens eine wässrige Suspension eines katalytisch aktiven Materials oder Quellen dafür und Bindemittel mit einem Bindemittelgehalt BSusp bereitstellt, den inerten Träger durch Zufuhr eines auf eine Temperatur 7Gas temperierten Gasstroms bei einem Durchfluss QGas fluidisiert, und die Suspension mit einer Dosierrate QSusp auf den fluidisierten inerten Träger aufsprüht, wobei man QGas, QsusP , Bsusp , Mτräger , und TGas innerhalb der Bereiche1. A process for the preparation of a catalyst for gas phase oxidations, in which a particulate inert carrier of a total mass M carrier r is weighed into a fluidized bed apparatus, at least one aqueous suspension of a catalytically active material or sources for it and binders with a binder content B Susp are provided, the inert carrier by supplying fluidizing a tempered to a temperature 7 gas gas stream at a flow rate Q gas, and spraying the suspension at a rate Q Susp onto the fluidized inert support, wherein one Q gas qsus P, Bs usp, Mτräger, and T gas within the areas
3000 ≤ QGas [m3/h] ≤ 9000, 1000 ≤ QSusp [g/min] < 3500, 2 < ßSusp [Gew.%] ≤ 18, 60 ≤ MTrager [kg] < 240. 75 ≤ TGas [°C] ≤ 120 so auswählt, dass eine Kenngröße K mit3000 ≤ Q Gas [m 3 / h] ≤ 9000, 1000 ≤ Q Susp [g / min] <3500, 2 <ß Susp [% by weight] ≤ 18, 60 ≤ M Carrier [kg] <240. 75 ≤ T Gas [° C] ≤ 120 so that a parameter K with
K = 0,020 QGas - 0,055 QSusp + 7,500 BSusp - 0,667 MTrgger + 2,069 TGas - 7 der Relation 127, 5 < K≤ 202 genügt.K = 0.020 Q Gas - 0.055 Q Susp + 7.500 B Susp - 0.667 M Trgger + 2.069 T Gas - 7 with the relation 127.5 <K≤ 202 is sufficient.
2. Verfahren gemäß Anspruch 1 , bei dem die Kennzahl K in einem Bereich von 136,0 ≤ K≤ 193,5 liegt und 4500 < QGas [m3/h] < 7500, 1500 < QSυsp [g/min] < 3000, 5 < ßSusp [Gew.%] < 15, 100 ≤ Mmger [kg] < 200, 80 < 7Gas [°C] < 115 sind.2. The method according to claim 1, wherein the characteristic number K is in a range of 136.0 ≤ K≤ 193.5 and 4500 <Q gas [m 3 / h] <7500, 1500 <Q Sυsp [g / min] < 3000, 5 <ß Susp [wt%] <15, 100 ≤ M mger [kg] <200, 80 <7 gas [° C] <115.
3. Verfahren gemäß Anspruch 2, bei dem die Kennzahl K in einem Bereich von 143 ≤ K≤ 184,5 liegt und 5500 ≤ QGas [m3/h] ≤ 6500, 2000 ≤ QSusp [g/min] ≤ 2500, 6 < BSυsp [Gew.%] ≤ 11 120 ≤ MTrager [kg] ≤ 180, 90 ≤ 7Gas [°C] ≤ 115 sind.3. The method according to claim 2, wherein the characteristic number K is in a range from 143 ≤ K≤ 184.5 and 5500 ≤ Q gas [m 3 / h] ≤ 6500, 2000 ≤ Q Susp [g / min] ≤ 2500, 6 <B Sυsp [wt%] ≤ 11 120 ≤ M carriers [kg] ≤ 180, 90 ≤ 7 gas [° C] ≤ 115.
4. Verfahren gemäß einem der Ansprüche 1 bis 3, wobei das zugeführte Gas Luft ist.4. The method according to any one of claims 1 to 3, wherein the gas supplied is air.
5. Verfahren gemäß einem der Ansprüche 1 bis 4, bei dem man eine zweite wässrige Suspension aus katalytisch aktivem Material und Bindemittel bereitstellt und auf den mit der ersten Suspension beschichteten fluidisierten Träger aufsprüht. 5. The method according to any one of claims 1 to 4, in which a second aqueous suspension of catalytically active material and binder is provided and sprayed onto the fluidized carrier coated with the first suspension.
6. Verfahren gemäß Anspruch 5, wobei man den mit der ersten Suspension beschichteten Träger vor dem Aufsprühen der zweiten Suspension trocknet.6. The method according to claim 5, wherein the carrier coated with the first suspension is dried before spraying on the second suspension.
7. Verfahren gemäß einem der Ansprüche 1 bis 6, wobei man den teilchenförmige inerte Träger in Form von Kugeln, Zylindern, Ringen oder Säulen, vorzugsweise mit Abmessungen von 5 bis 15 mm, bereitstellt.7. The method according to any one of claims 1 to 6, wherein one provides the particulate inert carrier in the form of balls, cylinders, rings or columns, preferably with dimensions of 5 to 15 mm.
8. Verfahren gemäß einem der Ansprüche 1 bis 7, bei dem die Fließbettapparatur einen Behälter zu Aufnahme des teilchenförmigen Trägers, in dessen unterem Bereich eine schüsselartige Vertiefung vorgesehen ist, ein Zentralrohr zur Zufuhr des Gases, das sich in dem Behälter im wesentlichen axial nach unten erstreckt und in die Vertiefung mündet, einen im wesentlichen ringförmigen Abweisschirm, der in dem oberen Bereich des Behälters an dem Zentralrohr befestigt ist, und einen in dem unteren Bereich des Behälters angeordneten Leitring, der das Zent- ralrohr auf einem Teil seiner Länge im wesentlich konzentrisch umgibt, und Mitteln zum Einsprühen der ersten und gegebenenfalls zweiten Suspension um- fasst.8. The method according to any one of claims 1 to 7, wherein the fluidized bed apparatus includes a container for receiving the particulate carrier, in the lower region of which a bowl-like depression is provided, a central tube for supplying the gas which is in the container substantially axially downward extends and opens into the depression, a substantially ring-shaped deflector screen which is fastened to the central tube in the upper region of the container, and a guide ring which is arranged in the lower region of the container and which is essentially concentric over part of its length surrounds, and comprises means for spraying the first and optionally second suspension.
9. Verfahren gemäß Anspruch 8, bei dem die erste oder zweite Suspension TiO2- und V2O5-Teilchen enthält, wobei wenigstens 90 Vol.-% der V2O5-Teilchen einen Durchmesser von 20 μ oder weniger und wenigstens 95 Vol.-% der V2O5- Teilchen einen Durchmesser von 30 μm oder weniger aufweisen.9. The method according to claim 8, wherein the first or second suspension contains TiO 2 and V 2 O 5 particles, at least 90% by volume of the V 2 O 5 particles having a diameter of 20 μ or less and at least 95 Vol .-% of the V 2 O 5 particles have a diameter of 30 μm or less.
10. Verfahren gemäß einem der Ansprüche 1 bis 7, wobei man für die erste oder zweite Suspension V2O5-Teilchen oder gelöstes Vanadium verwendet.10. The method according to any one of claims 1 to 7, wherein V 2 O 5 particles or dissolved vanadium are used for the first or second suspension.
11. Verwendung des nach einem der Ansprüche 1 bis 10 hergestellten Katalysators zur Herstellung von Phthalsäureanhydrid aus o-Xylol, Naphthalin oder Gemischen davon. 11. Use of the catalyst prepared according to one of claims 1 to 10 for the production of phthalic anhydride from o-xylene, naphthalene or mixtures thereof.
EP04765591A 2003-09-26 2004-09-24 Process for preparing a catalyst for use in oxidation reactions in the gas phase by coating carrier material in a fluidised bed apparatus Withdrawn EP1670582A1 (en)

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DE10344844A DE10344844A1 (en) 2003-09-26 2003-09-26 Preparation of a catalyst for gas phase oxidation, for the production of carboxylic acid from aromatic hydrocarbons, fluidizes inert carrier particles to be sprayed with a catalytic suspension
EP04003444A EP1563905A1 (en) 2004-02-16 2004-02-16 Process for preparing a catalyst for use in oxidation reactions in the gas phase by coating carrier material in a fluidised bed apparatus
EP04765591A EP1670582A1 (en) 2003-09-26 2004-09-24 Process for preparing a catalyst for use in oxidation reactions in the gas phase by coating carrier material in a fluidised bed apparatus
PCT/EP2004/010750 WO2005030388A1 (en) 2003-09-26 2004-09-24 Method for the production of a catalyst for gas-phase oxidations by the coating of support materials in a fluid bed apparatus

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