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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/20—Vanadium, niobium or tantalum
  • B01J23/22—Vanadium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0215—Coating
  • B01J37/0219—Coating the coating containing organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0215—Coating
  • B01J37/0221—Coating of particles
• • 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
  • B01J37/12—Oxidising
  • B01J37/14—Oxidising with gases containing free oxygen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
  • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
  • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
  • C07C57/13—Dicarboxylic acids
  • C07C57/145—Maleic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
  • C07C63/04—Monocyclic monocarboxylic acids
  • C07C63/06—Benzoic acid

Definitions

• the invention relates to a process for the preforming of oxidation catalysts, which is characterized in that the catalyst precursor in an atmosphere containing air with an air quantity of 0.05 to 4.0 Nm 3 / h heated to a temperature of at least 350 0 C. and the catalyst precursor is activated at least 350 ° C. for at least 9 hours.
• coated catalysts As oxidation catalysts so-called coated catalysts have proven in which the catalytically active material is cup-shaped on an inert carrier material, such as steatite applied.
• the catalytically active constituent of the catalytically active composition of these coated catalysts is, for example, in addition to titanium dioxide (in the form of its anatase modification) vanadium pentoxide.
• titanium dioxide in the form of its anatase modification
• vanadium pentoxide vanadium pentoxide.
• oxidic compounds which, as promoters, influence the activity and selectivity of the catalyst can be present in the catalytically active composition in small amounts.
• an aqueous solution and / or an organic solvent-containing solution or suspension of the active composition components and / or their precursor compounds is sprayed onto the support material at elevated temperature until the desired active mass fraction of the total catalyst weight has been reached.
• the suspension has been subjected to organic binders, preferably copolymers, advantageously in the form of an aqueous dispersion, of vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / ethylene or acrylic acid / maleic acid add.
• organic binders preferably copolymers, advantageously in the form of an aqueous dispersion, of vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / ethylene or acrylic acid / maleic acid add.
• the coating is usually carried out at temperatures from room temperature to 200 ° C.
• the addition of binder also has the advantage that the active material adheres well to the carrier, so that transport and filling of the catalyst are facilitated.
• the preactivation is usually carried out at temperatures above 200 to 500 0 C leads carried.
• the binder escapes from the applied layer by thermal decomposition and / or combustion. Most of the thermal treatment / preforming takes place in situ in the oxidation reactor.
• DE-A 25 50 686 describes a process for the preparation of catalysts for oxidation reaction in the gas phase.
• binders which are added to the coating solution, urea compounds such. Urea, thiourea, cyanamide compounds or dicyanamides. It is described that the duration of the activation treatment is not critical, with a minimum duration of 5 hours is to be adhered to.
• the coated carrier is heated evenly from 280 to 400 ° C. with air throughput and left at this temperature for 6 hours.
• US 4,489,204 discloses a process for the production of phthalic anhydride using annular support material.
• Example 1 it is disclosed that the catalyst using an air flow rate of 0.5 Nm 3 / h is heated to 300 0 C and the pre-formation is continued in the catalyst at a heating rate of 10 ° C / h to 39O 0 C is heated, the second phase of the heating takes 9 hours.
• DE-A 103 35 346 discloses catalysts for gas phase oxidations comprising an inert support and a catalytically active material containing transition metal oxides applied thereto.
• the binder there is disclosed a copolymer of an ⁇ -olefin and a vinyl-C 2 -C 4 -carboxylate whose vinyl-C 2 -C 4 -carboxylate content is at least 62 mol%. It is described that by thermal treatment of the catalyst at temperatures above 200 to 500 0 C, the binder escapes by thermal decomposition and / or combustion from the applied layer.
• EP-A 0 744 214 and DE-A 197 17 344 describe supported catalyst and a process for the preparation of catalysts in which a mixture of oxides is ground in the presence of water and then applied to the support body.
• Suitable organic binders are vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / maleate and also vinyl acetate / ethylene. It is described that after the catalyst has been introduced into the reactor, the binder burns out quantitatively within a short time in the air stream.
• US Pat. No. 4,397,768 describes a catalyst for phthalic anhydride production.
• the active composition is applied to an inert support by means of organic binders such as vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / maleate or vinyl acetate / ethylene.
• organic binders such as vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / maleate or vinyl acetate / ethylene.
• a binder for the production of coated catalysts which consists of a polymer of ethylenically unsaturated acid anhydrides and an alkanolamine having at least 2 OH groups, at most 2 nitrogen atoms and at most 8 carbon atoms.
• the catalyst was heated while passing air from 30 0 C to 610 0 C with a temperature increase of 5 ° C / min.
• the object of the present invention was to demonstrate an improved process for the preformation of oxidation catalysts.
• the Burn the binder used to be optimized Furthermore, by an improved combustion process, the formation of coke should be minimized and the starting behavior of the catalysts should be optimized.
• An optimization of the starting behavior can be achieved, for example, by forming a pronounced hot spot in the first catalytic converter position when starting up the reactor.
• a process for the preformation of oxidation catalysts is found, which is characterized in that the catalyst precursor in an atmosphere containing air with an input air amount of 0.05 to 5.0 Nm 3 / h heated to a temperature of at least 350 0 C. and the catalyst precursor is activated at least 350 ° C. for at least 9 hours.
• air as used in the context of the present invention is understood to mean a gas or a gas mixture consisting essentially of nitrogen, preferably with nitrogen contents of greater than 75% by volume, and of oxygen, preferably with oxygen contents greater than 15% by volume.
• nitrogen preferably with nitrogen contents of greater than 75% by volume
• oxygen preferably with oxygen contents greater than 15% by volume.
• their composition may vary within the limits known to those skilled in the art.
• the room air is suitably used.
• the catalyst precursor is heated to at least 37O 0 C, preferably at 390 to 470 0 C, heated.
• the temperature should suitably not exceed a value of 500 0 C.
• the catalyst precursor After reaching the desired temperature of the catalyst precursor is expediently for at least 9 hours at this temperature activated, ie at least 350 0 C, preferably at least 37o 0 C and in particular at 390-470 0 C.
• the catalyst precursor is activated for at least 12 hours, preferably for at least 15 hours, in particular for at least 24 hours at said temperature.
• the catalyst precursor is heated at a heating rate of 3 to 12 ° C / h, preferably at a heating rate of 5 to 10 ° C / h.
• the heating phase therefore expediently takes 25 to 120 hours, advantageously 40 to 70 hours.
• the amount of air used is expediently 0.05 to 5.0 Nm 3 / h during heating.
• the air may optionally be diluted with an inert gas.
• the air is diluted in a ratio of air to inert gas of 1: 0.1 to 1: 1, preferably in a ratio of 1: 0.1 to 1: 0.2.
• inert gases it is possible to use all those known to the person skilled in the art, for example nitrogen, carbon dioxide, argon and / or helium.
• the heating phase can be subdivided into a plurality of, advantageously from two to ten, sub-stages.
• the heating phase is divided into three sub-stages: In a first heating stage, the catalyst precursor at low temperatures of about room temperature to 80-12O 0 C using a small amount of air of advantageously 0.05 to 3 Nm 3 / h, preferably 0.1 to 1 Nm 3 / h, heated; in a second heating step, the catalyst precursor at average temperatures of about 80-120 0 C to 250-290 0 C using an average air amount of advantageously 1 to 4.5 Nm 3 / h, in particular from 2 to 4 Nm 3 / h, heated up; and in a third heating stage, the catalyst precursor at high temperatures of about 250-290 0 C to 350-470 0 C using a small amount of air of advantageously 0.05 to 2.5 Nm 3 / h, in particular from 0, 05 to 1.5 Nm 3 / h, heated.
• a first heating stage the catalyst precursor at low temperatures of about room temperature to 80-12O 0 C using a small amount of air of advantageously 0.05 to 3 Nm 3 / h,
• holding zones may be located after the individual stages or even within the individual stages, in which case the catalyst precursor is kept at the temperature reached for a certain time, for example for 10 to 120 minutes.
• This step can optionally with a smaller heating rate, for example, 3 to 10 0 C per hour, preferably 3 to 5 ° C per hour, to be heated.
• this stage may optionally contain several zones of constant temperature (temperature plateaus). In particular, temperature plateaus are advantageous in the temperature ranges of the thermal decomposition of the binders used.
• the air supply can be interrupted during heating of the catalyst precursor for a short period of time.
• the amount of air used is expediently 0.05 to 5.0 Nm 3 / h, preferably 0.05 to 3 Nm 3 / h and particularly preferably 0.05 to 1 Nm 3 / h.
• the air can also be diluted with inert gases when activated.
• the amount of air can be kept constant, increased or decreased.
• the amount of air is increased or kept constant during activation.
• the amount of air after two to four hours of advantageously 0.05 to 0.2 to 0.7 to 1 Nm 3 / h can be increased.
• the increase in the amount of air can optionally also be achieved by dilution with inert gases.
• the preforming is conveniently carried out in an air atmosphere without Edukt- loading. Usually, the preforming is carried out in an input overpressure range of 0 to 0.45 barg.
• the preforming is conveniently carried out in a salt bath heated / cooled fixed bed reactor.
• the fixed bed reactor suitably comprises a main reactor consisting of a multi-layered catalyst system and optionally a downstream finishing reactor.
• a gas cooler and a device for separating the product formed are expediently arranged, or after the gas cooler a finishing reactor, optionally a further gas cooler and a device for separating the product formed are arranged.
• the product formed is obtained, for example, by desublimation or by appropriate gas scrubbing from the reaction gas.
• the air flow is advantageously taken directly after the main reactor, i. in front of the gas cooler, separated. The separation can be carried out by all methods known to those skilled in the art.
• binders it is possible to use all binders known to the person skilled in the art.
• copolymers advantageously in the form of an aqueous dispersion of vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / ethylene and acrylic acid / maleic acid, or copolymers of an ⁇ -olefin and a vinyl-C2-C 4 - carboxylate, which Vinyl C 2 -C 4 carboxylate content is at least 62 mol%.
• copolymers of an ⁇ -olefin and a vinyl-C2-C 4 - carboxylate whose vinyl C 2 -C 4 -carboxylate content is at least 62 mol% are preferred.
• the binders are commercially available as aqueous dispersions, with a solids content of, for example, 35 to 65 wt .-%.
• the amount of such binder dispersions used is expediently from 1 to 30% by weight, based on the amount of the suspension used. Preferably 1 to 20 wt .-%, in particular 3 to 12 wt .-% are used.
• the amount of air in the second stage in the temperature range of 80-120 0 C to 250-290 0 C to 0.01 to 2 Nm 3 / h can be reduced.
• the amount of air in the third stage in the temperature range of 250-290 0 C to 350-470 0 C to 0.05 to 1 Nm 3 / h can be reduced.
• a high binder content of about 15 to 30 wt .-% can in a temperature range of 80-120 0 C to 250-290 0 C, a slow heating rate from 1 to 5 ° C per hour. Further, if necessary, the amount of air is diluted with inert gases.
• the preparation of the catalyst precursor is known to the person skilled in the art and is described, for example, in WO 2005 30380.
• the catalytic composition it is possible to use all the compositions known to the person skilled in the art, these are described, for example, in WO 2004 103944.
• coating the catalyst support with the catalytically active composition usually coating temperatures of 75 to 120 0 C are applied, wherein the coating can 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 wt .-%, usually 7 to 15 wt .-%.
• the invention relates to oxidation catalysts which are prepared by the process according to the invention.
• the invention relates to oxidation catalysts for the production of carboxylic acids and / or carboxylic anhydrides by a catalytic gas phase oxidation of aromatic hydrocarbons, such as benzene, the xylenes, naphthalene, toluene, durene or ß-picoline. You can in this way z.
• aromatic hydrocarbons such as benzene, the xylenes, naphthalene, toluene, durene or ß-picoline. You can in this way z.
• Phthalic anhydride, isophthalic acid, terephthalic acid, pyromellitic anhydride or niacin are well known.
• the preforming method according to the invention differs from the prior art in that precisely defined preforming steps are maintained.
• an improved burning off of the binder and thus an optimized starting behavior can be achieved.
• the catalyst according to the invention has the following advantages over the comparative catalyst (see Table 2): better product quality with respect to the phthalide concentration at low salt bath temperature, better phthalic anhydride (PSA) Yield and shorter start up time (time to achieve higher g / Nm 3 o XyloI loading).
• the suspension obtained was then sprayed onto 1200 g of steatite (magnesium silicate) in the form of rings with an outer diameter of 7 mm, a length of 7 mm and a wall thickness of 1.5 mm and dried.
• An analysis sample showed that the catalytically active composition applied in this manner after one hour calcination at 450 0 C 7.1 wt .-% vanadium (calculated as V2O5), 1, 8 wt .-% antimony (calculated as Sb 2 Oa) and 0.36 wt% cesium (calculated as Cs).
• the BET surface area of the TiO 2 mixture was 15.8 m 2 / g.
• the weight of the applied shell was 8% of the total weight of the finished catalyst.
• Second catalyst layer Layer 2.1 24.6 g of anatase (BET-OF 7 m 2 / g), 74.5 g of anatase (BET-OF 20 m 2 / g), 7.8 g of V 2 O 5 , 2.6 g of Sb 2 O 3, 0.35 g of Cs 2 CO 3 were suspended in 550 ml of deionized water and stirred for 18 hours. To this suspension was added 50 g of organic binder (ie 10% by weight of binder dispersion) consisting of a copolymer of vinyl acetate and vinyl laurate (weight ratio 75:25) in the form of a 50% by weight aqueous dispersion.
• organic binder ie 10% by weight of binder dispersion
• the suspension obtained was then sprayed onto 1200 g of steatite (magnesium silicate) in the form of rings with an outer diameter of 7 mm, a length of 7 mm and a wall thickness of 1, 5 mm and dried.
• An analytical sample showed that the catalytically active composition applied in this manner after one hour of calcination to 450 0 C 7.1 wt .-% vanadium (calculated as V 2 O 5 ), 2.4 wt .-% antimony (calculated as Sb 2 Oe) and 0.26 wt.% Cesium (calculated as Cs).
• the BET surface area of the TiO 2 mixture was 16.4 m 2 / g.
• the weight of the applied shell was 8% of the total weight of the finished catalyst.
• Third catalyst location location 3.1
• the suspension obtained was then sprayed onto 1200 g of steatite (magnesium silicate) in the form of rings with an outer diameter of 7 mm, a length of 7 mm and a wall thickness of 1, 5 mm and dried.
• An analysis sample showed that the catalytically active composition applied in this way after one hour of calcination to 45O 0 C 7.1 wt .-% vanadium (calculated as V 2 O 5 ), 2.4 wt .-% antimony (calculated as Sb 2 Oa) and 0.10 wt.% Cesium (calculated as Cs).
• the BET surface area of the TiO 2 mixture was 16.4 m 2 / g.
• the weight of the applied shell was 8% of the total weight of the finished catalyst.
• NH 4 H 2 PO 4 were suspended in 550 ml of deionized water and stirred for 18 h.
• organic binder ie 10% by weight of binder dispersion
• binder dispersion consisting of a copolymer of vinyl acetate and vinyl laurate (weight ratio 75:25) in the form of a 50% by weight aqueous dispersion.
• the suspension obtained was then sprayed onto 1200 g of steatite (magnesium silicate) in the form of rings with an outer diameter of 7 mm, a length of 7 mm and a wall thickness of 1, 5 mm and dried.
• Suspension 2 150 kg of the obtained coated catalyst were heated in a fluidized bed apparatus and treated with 24 kg of a suspension of 168.35 kg anatase having a BET surface area of 21 m 2 / g, 7.043 kg vanadium pentoxide, 19.080 kg oxalic acid, 0.990 g cesium sulfate, 238.920 kg Water and 66.386 kg of formamide, together with 37.5 kg of an organic binder in the form of a 48 wt .-% aqueous dispersion consisting of a copolymer of acrylic acid / maleic acid (weight ratio 75:25) sprayed (ie 7.5 wt. % Binder dispersion).
• Second catalyst location location 2.2
• % Binder dispersion 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 (analysis sample after heat treatment at 450 0 C).
• the catalytically active material applied in this manner ie 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 wt% antimony (calculated as Sb 2 O 3 ), 0.1 wt% cesium (calculated as Cs) and 89.05 wt% titanium dioxide.
• Table 1 illustrates the preforming of catalysts 1 and 2 according to the invention and the preforming of comparative catalyst 3.
• the catalysts were heated continuously in the tubular reactor, the amount of air used being changed in stages.
• the catalyst 1 were calcined at 400 ° C. for 24 hours under an air flow rate of 0.5 Nm 3 / h.
• Catalyst 2 was calcined at 390 ° C. for 24 hours under an air flow rate of 0.1 Nm 3 / h.
• the comparative catalyst 3 was calcined at 39O 0 C for 6 hours under a supplied air amount of 0.1 NnWh.
• PSA yield is an average PSA yield

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