WO2000072962A1 - Procede d'amelioration de l'activite et de la selectivite d'un catalyseur d'ammoxydation - Google Patents

Procede d'amelioration de l'activite et de la selectivite d'un catalyseur d'ammoxydation Download PDF

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WO2000072962A1
WO2000072962A1 PCT/US2000/014529 US0014529W WO0072962A1 WO 2000072962 A1 WO2000072962 A1 WO 2000072962A1 US 0014529 W US0014529 W US 0014529W WO 0072962 A1 WO0072962 A1 WO 0072962A1
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mixed oxides
particles
catalyst
mixture
heating
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PCT/US2000/014529
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English (en)
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Mary Jennifer Young
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Solutia Inc.
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Priority to AU51656/00A priority Critical patent/AU5165600A/en
Publication of WO2000072962A1 publication Critical patent/WO2000072962A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8871—Rare earth metals or actinides
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • 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
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • 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
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates generally to a process for producing oxidation and/or ammoxidation catalysts containing the elements iron, antimony, uranium, bismuth, and molybdenum in a catalytically active oxidized state.
  • Description of Related Art It is well known that olefins can be oxidized to oxygenated hydrocarbons such as unsaturated aldehydes and acids, for example, acrolein and methacrolein, and acrylic acid and methacrylic acid. Olefins can also be ammoxidized to unsaturated nitriles such as acrylonitrile and methacrylonitrile. Acrylonitrile is a valuable monomer used to produce a variety of polymeric products.
  • 4,487,850 discloses catalysts containing the elements iron, antimony, uranium, bismuth, and molybdenum in a catalytically active oxidized state.
  • the yield and selectivity of the above catalyst and other catalysts are generally satisfactory, the commercial utility of a catalyst system is highly dependent upon the cost of the system, the conversion of the reactant(s), the yield of the desired product(s), and the stability of the catalyst during operation. In many cases, a reduction in the cost of a catalyst system on the order of a few cents per pound or a small percent increase in the yield of the desired product represents a tremendous commercial advantage.
  • the present invention provides an improved process for producing a catalyst containing the elements iron, antimony, uranium, bismuth and molybdenum in a catalytically active oxidized state useful in the preparation of unsaturated nitriles by ammoxidation of olefins and in the oxidation of olefins to the corresponding unsaturated aldehydes.
  • One embodiment of the present invention is a process for producing a catalyst, comprising the steps of:
  • the temperature used for heating in step (c) preferably is at least about 100°C, and the duration of the heating preferably is at least about 4 hours. In one especially preferred embodiment, the heating in step (c) is done at between about 100°C and about 105°C for about 4 hours.
  • the mixed oxides component can suitably be formed into particles in step (b) by milling the mixed oxides component in the form of an aqueous slurry.
  • Another embodiment of the present invention is a process for producing a catalyst, which comprises the steps of:
  • step (ii) heating the mixture of step (i) at a temperature and for a time sufficient to induce formation of crystalline oxides of antimony; (iii) adding an aqueous solution of ferric nitrate to the mixed oxides mixture;
  • step (c) forming the combination of step (b) into particles, which may be part of a slurry; (d) heating the particles at a temperature between about 40°C and about 120°C for at least about 1 hour;
  • This process can further comprise the step of adding a support material comprising from about 10% to about 90% by weight of the total weight of the catalyst prior to the heating of step (d).
  • a support material comprising from about 10% to about 90% by weight of the total weight of the catalyst prior to the heating of step (d).
  • the support material is added prior to step (c).
  • the support material most preferably comprises from about 35% to about 65%> by weight of the total weight of the catalyst.
  • a suitable support material is silica.
  • the drying in step (e) of the embodiment of the invention is done by spray drying a slurry.
  • the process for producing the catalyst comprises:
  • aspects of the present invention are (1) the catalysts prepared by any of the above-described processes, (2) processes for the oxidation of an olefin to a corresponding unsaturated aldehyde or acid, comprising contacting the olefin with oxygen in the presence of a catalyst prepared by any of the above-described processes, and (3) processes for the ammoxidation of an olefin to a corresponding unsaturated nitrile comprising contacting the olefin with oxygen and ammonia in the presence of a catalyst prepared by any of the above-described processes.
  • the catalysts produced by the present invention exhibit improved characteristics in oxidation and ammoxidation processes, including yield and selectivity, as compared to prior catalysts. Therefore, the present invention makes the production of the end products of the oxidation and ammoxidation processes more economical.
  • the catalysts produced by the processes of the present invention contain antimony, uranium, iron, bismuth, and molybdenum in a catalytically active oxidized state useful for the oxidation and/or ammoxidation of olefins. These catalysts are represented by the empirical formula:
  • the catalysts can be prepared in the following manner.
  • a hydrated mixed oxides component containing antimony, uranium, iron, and bismuth is intimately mixed with a ferric molybdate or ammonium molybdate component (the preparation of each of these components is described below).
  • the mixing of the components is accomplished in an aqueous slurry at a pH of about 9.
  • the hydrated mixed oxides component is first slurried in water at the prescribed pH.
  • a catalyst support may be added, if desired, along with the hydrated mixed oxides component. In either case, whether a support is present or absent, a molybdate is then added to the slurry.
  • the resultant slurry is ball milled for about 18 hours or until the solid particles are reduced to a size less than 10 microns in diameter. Thereafter, the pH of the slurry is adjusted, if necessary to about 8- 9.
  • the mixed slurry is then heat-treated at a temperature between about 40 °C and 120 °C, preferably at a temperature of about 100 °C.
  • the slurry is suitably heat-treated for at least 1 hour, preferably between about 1 hour and about 6 hours, more preferably for about 4 hours.
  • the slurry may be mixed during the heat-treating process to aid in heat transfer and assure a well-mixed slurry. Other combinations of heating times and temperatures can be used if they improve the activity and/or selectivity of the catalyst.
  • the heat-treated slurry is then dried to remove the bulk (e.g., at least about 70-
  • the concentrated slurry contains a certain amount of water and it is desirable to remove this water by some form of drying process to form a dry catalyst precursor.
  • This can take the form of a simple oven drying process in which the water-containing solid phase is subjected to a temperature that is sufficiently high to vaporize the water and completely dry the solid phase.
  • An alternate drying process which may be employed is the so-called spray-drying process. In this process, which is preferred for use in the present invention, water- containing solid phase particles are sprayed into contact with hot gas (usually air) so as to vaporize the water. The drying is controlled by the temperature of the gas and the distance the particles travel in contact with the gas.
  • the catalyst precursor is calcined to form the active catalyst.
  • the calcination is usually conducted in air at essentially atmospheric pressure and at a temperature of about 500 °C to about 1150 °C, preferably from about 750 °C to about 900 °C.
  • the time to complete the calcination can vary and will depend upon the temperature employed. In general the time can be anything up to 24 hours, but for most purposes, a time period from about 1 hour to about 3 hours at the designated temperatures is sufficient.
  • the catalyst can be employed without a support and will display excellent activity.
  • a support material which functions by providing a large surface area for the catalyst and by creating a harder and more durable catalyst for use in the highly abrasive environment of a fluidized bed reactor.
  • This support material can be any of those commonly proposed for such use, such as silica, zirconia, alumina, titania, antimony pentoxide sol, or other oxide substrates. From the point of view of availability, cost, and performance, silica is usually a satisfactory support material and is preferably in the form of silica sol for easy dispersion.
  • the proportions in which the components of the supported catalysts are present can vary widely, but it is usually preferred that the support provides from about 10%> to about 90% and more preferably about 35% to about 65% by weight of the total combined weight of the catalyst and the support.
  • the support material is preferably slurried along with the hydrated mixed oxide component in water at a pH of 9 while maintaining slurry fluidity.
  • the hydrated mixed oxides component contains antimony, uranium, iron, and bismuth. It is prepared by mixing the oxides or nitrates of bismuth and uranium and an oxide of antimony (usually antimony trioxide) with nitric acid. The antimony trioxide is heated in the nitric acid. By so doing, the initially amorphous antimony trioxide is converted to crystalline oxides of antimony. In addition, at least a portion of the antimony trioxide is converted to higher oxidation states such as antimony tetroxide and antimony pentoxide.
  • the time required to induce the formation of the desired crystalline oxides of antimony can vary and will depend, at least in part, on the temperature employed. Generally, a time period of about 2 hours to about 6 hours at temperatures from about 90°C to about 110 °C, preferably at least 100 °C is sufficient. After the heating period is completed, an aqueous solution of ferric nitrate
  • the molybdate may be introduced as any compound which does not interfere with catalysis or neutralize the catalyst.
  • Ferric molybdate and ammonium molybdate have been successfully employed to introduce the molybdate.
  • Ammonium molybdate is preferred, being the simplest to prepare (from molybdenum trioxide and aqueous ammonia).
  • Ferric molybdate may be prepared by combining stoichiometric amounts of aqueous solutions of ammonium molybdate and ferric nitrate.
  • the catalyst preparation process of this invention yields an improved catalyst that exhibits exceptional utility in the production of nitriles from olefins.
  • Olefins suitable for use in this invention include those characterized by having at least one methyl group attached to a trigonal carbon atom.
  • Nonlimiting representatives of such olefins include propylene, isobutylene, 2-methyl-l-pentene, 1 ,4-hexadiene, and the like.
  • Of particular importance is the production of acrylonitrile from propylene, although it should be understood that the described catalyst is also useful for ammoxidation of other suitable olefins and for oxidation of such olefins to aldehydes and acids.
  • a mixture of olefin, ammonia, and oxygen (or air) is fed into a reactor and through a bed of catalyst particles at elevated temperatures.
  • Such temperatures are usually in the range of about 400° C to about 550° C, and preferably about 425° C to about 500° C, and the pressure is from about 1 atmosphere to about 6 atmospheres (100 kPa to about 600 kPa).
  • the ammonia and olefin are required stoichiometrically in equimolar amounts, but it is usually necessary to operate with a molar ratio of ammonia to olefin in excess of 1 to reduce the incidence of side reactions.
  • the stoichiometric oxygen requirement is 1.5 times the molar amount of olefin.
  • the feed mixture is commonly introduced into the catalyst bed at a W/F (defined as the weight of the catalyst in grams divided by the flow of reactant stream in ml/sec at standard temperature and pressure) in the range of about 2 g- sec/ml to about 15 g-sec/ml, preferably from about 4 g-sec/ml to about 10 g-sec/ml.
  • the ammoxidation reaction is exothermic and for convenience in heat distribution and removal, the catalyst bed is desirably fluidized.
  • fixed catalyst beds may also be employed with alternative heat removal means such as cooling coils within the bed.
  • the catalyst as prepared by the process of this invention is particularly well adapted for use in such a process in that improved yields of and selectivities to the desired product(s) are experienced due to the unique and novel preparation procedures employed herein.
  • the following examples illustrating the best presently-known methods of practicing this invention are described in order to facilitate a clear understanding of the invention. It should be understood, however, that these examples, while indicating preferred embodiments, are given by way of illustration only and are not to be construed as limiting the invention since various changes and modifications within the spirit of the invention will become apparent to those skilled in the art from this description. As used herein, the following terms are defined in the following manner:
  • WTF is defined as the weight of the catalyst in grams divided by the flow rate of the reactant stream in ml/sec measured at STP, the units being g-sec/ml.
  • AN yield is defined as: [(mols AN formed)/(mols C 3 H 6 feed)] x 100
  • the amount of catalyst used in the evaluation ranged between 295 grams and 460 grams and was adjusted in order to get a propylene conversion between 98.5 - 99.2%>.
  • the solution was diluted with 300mL of water followed by the addition of 612.0g (2.1 mole) of antimony trioxide Sb 2 O 3 .
  • the resulting mixture was heated to 100-105°C and maintained at this temperature for a period of time sufficient to convert the amorphous antimony trioxide to crystalline oxides of antimony, usually four hours.
  • a solution of 606g (1.5 mole) of ferric nitrate nonahydrate [Fe(NO 3 ) 3 -9H 2 O] in 5.6 liters of water was added to the mixture and the mixture was allowed to cool to room temperature.
  • the pH of the mixture was adjusted to 8.0 using about 1900ml of a 14%> by weight solution of aqueous ammonia (prepared by mixing equal volumes of concentrated aqueous ammonia and water) causing the precipitation of the hydrated mixed oxides.
  • the precipitate was removed from the mother liquor using a filter press and the wet cake of the precipitate was reslurried in 20 liters of water and filtered again to remove the ammonium nitrate formed during precipitation as well as occluded impurities.
  • Catalyst 1 A Formation of Catalyst 1 A.
  • the catalyst cake from step (A) and the ferric molybdate cake from step (B) were mixed in a ball mill jar. To this was added 2127g of SiO 2 suspension (40%> by weight), 40mL concentrated NH 4 OH and 200mL water and the mixture was milled for 20 hours. The milled slurry was divided into two equal portions. One portion of the slurry, portion "1 A”, was spray dried at a temperature of 83-85°C. The dried particles were then calcined at 850°C for one hour to give catalyst 1 A.
  • Catalyst Reactor Charge g 368 350
  • Two catalysts of the composition Sb 225 U 050 Fe 0 50 Bi 002 Mo 004 O r 50%SiO 2 were prepared in the following manner to illustrate the improved heat-treated catalysts.
  • Bismuth trioxide (10.08g, 0.022mol) was added to 1098g of 70% HNO 3 in a 11 -liter stainless steel reactor. The mixture was heated to 60°C before 302.4g (0.359mol) of U 3 O 8 was added over a period of 5 to 10 minutes. The temperature of the mixture was raised to 90 ° C and maintained between 90-95°C.
  • step (A) Formation of Catalyst 2A.
  • the filter cake obtained from step (A) was mixed with 3010g of SiO 2 sol (40% by weight) in a ball mill. After milling for 30 minutes, an ammonium heptamolybdate solution prepared by dissolving 12.5g (0.087mol) of MoO 3 in 200mL of water and 40mL concentrated NH 4 OH was added to the slurry.
  • Catalyst Charge g 350g 310g
  • Example 3 Two catalysts of the composition: Sb, 86 U 033 Fe 066 Bi 002 Mo 004 O r 60%SiO 2 were prepared in the following manner to illustrate the improved heat-treated catalyst: A) Hydrated Mixed Oxides (Sb, 86 U 033 Fe 066 Bi 002 O r xH 2 O) - Bismuth oxide, Bi 2 O 3 (10.6g, 0.023 mole) was added with stirring to 975g of 70% concentrated nitric acid in an 11 -liter stainless steel reactor. The solution was heated to about 60°C before 210.3g (0.25 mole) of uranium octoxide U 3 O 8 was added within five to ten minutes. The mixture was then heated to and kept at 90°C for 30 minutes.
  • A) Hydrated Mixed Oxides (Sb, 86 U 033 Fe 066 Bi 002 O r xH 2 O) - Bismuth oxide, Bi 2 O 3 (10.6g, 0.023 mole) was added with stirring to 975g of 70%
  • the solution was diluted with 300 mL of water followed by the addition of 612. Og (2.1 mil) of antimony trioxide Sb 2 O 3 .
  • the resulting mixture was heated to 100-105°C and maintained at this temperature for 4 hours.
  • a solution of 606g (1.5 mole) of ferric nitrate nonahydrate [Fe(NO 3 ) 3 *9H 2 O] in 5.6 liters of water was added to the mixture and the mixture was allowed to cool to room temperature with mixing.
  • the pH of the mixture was then adjusted to 8.0 with the addition of about 1900 mL of a 14% by weight solution of aqueous ammonia (prepared by mixing equal volumes of concentrated aqueous ammonia and water) causing the precipitation of the hydrated mixed oxides.
  • aqueous ammonia prepared by mixing equal volumes of concentrated aqueous ammonia and water
  • the precipitate was removed from the mother liquor using the filter press and the wet cake of the precipitate was reslurried in 20 liters of water and filtered again to remove the ammonium nitrate formed during the precipitation as well as occluded impurities.
  • step (A) The wet cake from step (A) was mixed with 3840g of SiO 2 sol (40%) by weight) in a ball mill jar. After milling for 30 minutes, a solution of ammonium heptamolybdate, prepared by dissolving 12.9g (0.09 mole) of MoO 3 in 200 mL water and 40 mL of concentrated aqueous ammonia, was added to the slurry. The pH of the slurry was adjusted to pH 9.0 with additional concentrated aqueous ammonia before milling the slurry for 20 hours. The milled slurry was then divided into two equal portions.
  • Catalyst 3B The other portion of the milled slurry, was heated in a glass reactor with mixing for 4 hours at 102 °C. After cooling the mixture to room temperature, the mixture was transferred to the ball mill jar and milled for 20 hours. The milled slurry was spray dried and calcined as in step (b) to give catalyst 3B.

Abstract

La présente invention concerne un procédé amélioré de production d'un catalyseur contenant du fer, de l'antimoine, de l'uranium, du bismuth et du molybdène dans un état oxydé actif sur le plan catalytique, ce catalyseur étant utile dans la préparation de nitriles insaturés par ammoxydation d'oléfines et dans l'oxydation d'oléfines pour obtenir les aldéhydes insaturés correspondants. Un des modes de réalisation consiste à: (a) former un composant d'oxydes mélangés contenant des oxydes d'antimoines, de bismuth, de fer et d'uranium; (b) combiner les oxydes mélangés avec un molybdate; (c) former le composant d'oxydes mélangés en particules; (d) chauffer les particules à une température comprise entre environ 40 °C et environ 120 °C pendant au moins une heure; (e) sécher les particules; et enfin, (f) calciner les particules.
PCT/US2000/014529 1999-05-27 2000-05-26 Procede d'amelioration de l'activite et de la selectivite d'un catalyseur d'ammoxydation WO2000072962A1 (fr)

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AU51656/00A AU5165600A (en) 1999-05-27 2000-05-26 Process for improving activity and selectivity of ammoxidation catalyst

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US13625899P 1999-05-27 1999-05-27
US60/136,258 1999-05-27
US13646399P 1999-05-28 1999-05-28
US60/136,463 1999-05-28

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EP1424125A1 (fr) * 2002-11-27 2004-06-02 Solutia Inc. Catalyseur et procédé d'oxidation ou d'ammoxidation d'oléfines
EP3744418A1 (fr) 2016-01-09 2020-12-02 Ascend Performance Materials Operations LLC Compositions et procédés catalytiques pour la production directe de cyanure d'hydrogène dans un flux d'alimentation de réacteur d'acrylonitrile

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US5132269A (en) * 1990-09-10 1992-07-21 Nitto Chemical Industry Co., Ltd. Iron-antimony-molybdenum-containing oxide catalyst composition and process for preparing the same
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US4487850A (en) * 1984-01-06 1984-12-11 Monsanto Company Catalysts for the oxidation and ammoxidation of olefins
US5079379A (en) * 1988-12-29 1992-01-07 Monsanto Company Fluid bed process
US5132269A (en) * 1990-09-10 1992-07-21 Nitto Chemical Industry Co., Ltd. Iron-antimony-molybdenum-containing oxide catalyst composition and process for preparing the same
US5364825A (en) * 1992-06-25 1994-11-15 Basf Aktiengesellschaft Multimetal oxide compositions and process of preparing same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1424125A1 (fr) * 2002-11-27 2004-06-02 Solutia Inc. Catalyseur et procédé d'oxidation ou d'ammoxidation d'oléfines
US6916763B2 (en) 2002-11-27 2005-07-12 Solutia Inc. Process for preparing a catalyst for the oxidation and ammoxidation of olefins
KR101003340B1 (ko) 2002-11-27 2010-12-23 솔루티아인코포레이티드 올레핀의 산화 및 가암모니아 산화용 촉매의 제조 방법
EP3744418A1 (fr) 2016-01-09 2020-12-02 Ascend Performance Materials Operations LLC Compositions et procédés catalytiques pour la production directe de cyanure d'hydrogène dans un flux d'alimentation de réacteur d'acrylonitrile

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