EP0000835B1 - Process for forming multicomponent oxide complex catalysts - Google Patents

Process for forming multicomponent oxide complex catalysts Download PDF

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Publication number
EP0000835B1
EP0000835B1 EP78300247A EP78300247A EP0000835B1 EP 0000835 B1 EP0000835 B1 EP 0000835B1 EP 78300247 A EP78300247 A EP 78300247A EP 78300247 A EP78300247 A EP 78300247A EP 0000835 B1 EP0000835 B1 EP 0000835B1
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Prior art keywords
catalyst
phase
host
elements
key catalytic
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German (de)
English (en)
French (fr)
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EP0000835A1 (en
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James Frank Brazdil
Robert Karl Grasselli
Dev Dhanaraj Suresh
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Standard Oil Co
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Standard Oil Co
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Priority claimed from JP9775978A external-priority patent/JPS5547144A/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/8872—Alkali or alkaline earth metals
    • 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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0576—Tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B01J27/192—Molybdenum with 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • 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
    • 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 to catalysts useful in the oxidation and/or ammoxidation of olefins. More specifically, the present invention relates to a novel process for producing oxidation and/or ammoxidation catalysts having superior properties.
  • olefins can be oxidized to oxygenated hydrocarbons such as unsaturated aldehydes and acids, for example, acrolein and methacrolein, and acrylic and methacrylic acids. It is also well known that olefins can be ammoxidized to unsaturated nitriles such as acrylonitrile and methacrylonitrile. The value of such oxygenated hydrocarbons and unsaturated nitriles is generally well recognized with acrylonitrile being among the most valuable monomers available to the polymer industry for producing useful polymeric products.
  • olefins Various catalytic processes are known for the oxidation and/or ammoxidation of olefins. In such processes it is common to react an olefin or an olefin-ammonia mixture with oxygen in the vapour phase in the presence of a catalyst.
  • acrolein and acr / lonitrile propylene is generally used as the olefin reactant and for the production of methacrolein and methacrylonitrile, isobutylene is generally used as the olefin reactant.
  • catalysts have been disclosed as useful in the oxidation and ammoxidation of olefins.
  • examples of such catalysts are those disclosed in United States Patents Nos. 3,882,159 and 3,746,657, US Patent Application Serial Number 748,609, filed December 7, 1976.
  • Catalysts based on bismuth and molybdenum, that is bismuth molybdate catalysts, promoted with various additional elements such as iron, cobalt, nickel, potassium, phosphorus, chromium and manganese demonstrate particular utility in these reactions.
  • Bismuth molybdate catalysts have been prepared in the past by a number of different techniques.
  • Example III of U.S. 3,746,657 shows a method of preparation which comprises forming a mixture of potassium hydroxide, ammonium molybdate and silica, adding to the mixture phosphoric acid, solutions in nitric acid of the nitrates of cobalt, iron, nickel and bismuth, and more silica to form a slurry, then spray drying and calcining to form the catalyst.
  • US Application Serial Number 748,609 discloses a catalyst preparation technique in which an aqueous solution of cobalt nitrate and nickel nitrate, an aqueous solution of potassium nitrate and iron nitrate, an aqueous nitric acid solution of bismuth nitrate and a silica sol are added in order to an aqueous solution of ammonium heptamolybdate and phosphoric acid, and the composition so obtained spray dried and calcined to form the catalyst.
  • This application also discloses another catalyst preparation technique in which an aqueous nitric acid solution of ferric nitrate and bismuth nitrate is added to a previously formed aqueous slurry containing ammonium heptamolybdate, phosphoric acid, arsenic acid, silica sol, nickel nitrate and cobalt nitrate, the composition so obtained heated until a gel forms, and the gel dried and calcined to produce the ultimate catalyst.
  • the catalytic activity of multi-component oxidation and ammoxidation catalysts can be significantly enhanced if the key catalytic phase (for example, bismuth molybdate in the case of a bismuth molybdate-type catalyst) is pre-formed prior to combining it with the remaining elements of the desired catalyst.
  • This procedure not only enhances the activity of the catalyst, but is simple and easy to carry out.
  • the portion denoted by is denoted as the key catalytic phase, while the portion of the catalyst defined by is the host-, promotor-, and/or co-catalyst phase (hereinafter referred to as the host-catalyst phase).
  • M is preferably Bi and N is Mo.
  • these catalysts those containing nickel, cobalt and iron and optionally phosphorous or antimony, are preferred, and of these catalysts those containing an alkali metal, most preferably potassium, rubidium and/or cesium, are especially preferred.
  • the catalyst contains a Group IIA or IIB metal, it is preferably Mg, Cd or Zn.
  • the key catalytic phase of the catalyst for example bismuth molybdate
  • the key catalytic phase can be made in accordance with any conventional technique.
  • bismuth molybdate can be conveniently prepared by adding ammonium heptamolybdate, (NH 4 ) I M OI O 14 .4H,O, to an aqueous solution of bismuth nitrate, preferably in a nitric acid solution, and then adjusting the pH to form a precipitate of bismuth molybdate.
  • other bismuth salts having decomposable anions can be employed.
  • acetate, triphenyl and citrate salts of bismuth can be employed to form bismuth molybdate.
  • decomposable salts of the other M elements can be used to supply the M component of the key catalytic phase, while ammonium tungstate, or tungstic acid can be used to supply tungsten in the case in which N is W.
  • Still another technique for forming the key catalytic phase is by known metallurgical techniques, for example, by reacting bismuth oxide and molybdenum oxide together in the solid phase.
  • the amount of M and N components combined together is, of course, dependent upon the ultimate composition of the objective catalyst as well as the amount of N element in the co-catalyst phase.
  • the ratio M/N in forming the key catalytic phase be maintained within the range of 1:9 to 9:1, preferably 2:1 to 1:3 and most preferably 2:1 to 2:3.
  • the M/N ratio be 2:1 to 1 :3 and most preferably 2:1 to 2:3.
  • the remaining elements of the desired catalyst which form the host-catalyst phase can be combined with the preformed key catalytic phase in any manner.
  • a single solution or.slurry containing all of the ingredients of the host-catalyst phase can be added to the pre-formed key catalytic phase and the composition so obtained dried and calcined to produce the desired catalyst.
  • one or more of the elements in the host-catalyst phase can also be pre-formed into a molybdate and/or tungstate prior to admixing with the pre-formed key catalytic phase.
  • the chromium content of the host-catalyst phase can be formed into chromium molybdate (in the case of a molybdate catalyst) prior to addition to the key catalytic phase. Since, however, it is desirable that the process of the invention be as simple as possible, it is preferred to form the host-catalyst phase in a single operation. In any event, it is necessary in order to keep the process of the invention simple that none of the Group VIII elements in the catalyst, if any, is individually pre-formed into a molybdate or tungstate since to do so would make the preparation procedure unduly and unnecessarily complex.
  • the host-catalytic phase can be combined with the key catalytic phase in the form of a solution or slurry, the solution or slurry preferably being aqueous. If a host-catalyst phase in the form of a solution is employed, the solution is added to the key catalytic phase (either in the form of a solid or a slurry) and the composition so obtained heated to dryness. In accordance with well known chemical phenomena, heating, pH adjustment or other appropriate treatment of the aqueous composition causes precipitation of the components dissolved in the liquid phase of the slurry, thereby producing a precipitate which together with the pre-formed key catalytic phase forms a pre-catalyst of appropriate composition. Drying and calcination of the pre-catalyst in accordance with conventional procedures causes decomposition of decomposable anions and cations thereby yielding an activated catalyst of the desired composition.
  • the host-catalyst phase is in the form of a slurry rather than a solution
  • this slurry is admixed with the key catalytic phase (either in the form of a slurry or a solid) and the composition so obtained dried and calcined in the same manner as discussed above to produce a catalyst of the desired composition.
  • an aqueous solution or slurry containing less than all of the elements in the host-catalyst phase can be added to the key catalytic phase.
  • one or more additional solutions or slurries containing the remaining elements constituting the host-catalyst phase must also be added to the key catalytic phase to produce the desired catalyst.
  • the manner in which the elements of the co-catalyst phase are combined with the key catalytic phase is unimportant so long as none of the Group VIII elements in the catalyst, if any, are preformed into molybdates and/or tungstates individually.
  • the starting materials used to supply particular elements for forming the host-catalyst phase can be any materials conventionally employed in the manufacture of oxidation catalysts. Normally, decomposable salts which will yield the desired elements upon heating to elevated temperatures are employed, although oxides and even free acids can be employed as can salts in which both the anion and cation contribute elements to the final catalyst such as KH Z PO 4 .
  • decomposable salts which will yield the desired elements upon heating to elevated temperatures are employed, although oxides and even free acids can be employed as can salts in which both the anion and cation contribute elements to the final catalyst such as KH Z PO 4 .
  • nitrate, acetate, triphenyl and citrate salts of the elements in question can be employed as can phosphoric acid, antimony oxide and chromium trioxide.
  • Nitrate salts find particular applicability in prior art processes and are especially useful in the process according to the invention.
  • the desired catalyst is most simply made by combining together an aqueous slurry of the key catalytic phase and an aqueous slurry of the host-catalyst phase, drying the composition so obtained to yield a solid pre-catalyst precipitate and calcining the precipitate to form a catalyst of the desired composition.
  • the key catalytic phase aqueous slurry is preferably made by co-precipitation techniques using decomposable salts (preferably nitrates and ammonium salts) and if desired, oxides and free acids and the aqueous slurry of the host-catalyst phase is similarly made by co-precipitation with decomposable salts (preferably nitrates and ammonium salts) and if desired oxides and free acids.
  • decomposable salts preferably nitrates and ammonium salts
  • the starting materials used for supplying the elements of the host-catalyst phase e.g. nitrate salts, free acids, oxides, etc.
  • the starting materials used for supplying the elements of the host-catalyst phase can be individually added (either in the form of a solid or a slurry) to an aqueous slurry of the key catalytic phase, and the precipitate obtained on drying calcined in the usual manner.
  • the key catalytic phase of the desired catalyst once pre-formed can be combined in essentially any form with the remaining ingredients of the catalyst.
  • the key catalytic phase which is normally derived in the form of an aqueous slurry, can be combined with the other elements of the catalyst still in the form of this aqueous slurry.
  • no filtering of the key catalytic phase slurry to remove the mother liquor therefrom is necessary in accordance with the present invention. Indeed, filtering is undesirable since it complicates the preparation procedure.
  • the pre-formed key catalytic phase can be separated from the mother liquor, as by filtration, and combined with the other ingredients of the catalyst in this form.
  • the key catalytic phase can be subjected to calcination with or without previous filtration in a conventional manner before admixing with the other ingredients of the catalyst, although this is unnecessary. And, if calcination is carried out it is preferably accomplished under conditions insufficient to cause significant crystallization. Furthermore, if the key catalytic phase is formed by techniques other than co-precipitation, such as, for example, metallurgical techniques, it can be combined with the other ingredients of the catalyst in the form derived.
  • the order in which the various phases of the catalyst are added to one another is also not critical. More specifically, one or more components of the host-catalyst phase (either preformed or unpreformed) can be added to the key catalyst phase, or conversely the key catalytic phase can be added to one or more of the components (either preformed or unpreformed) of the host-catalyst phase. Furthermore, if all of the ingredients of the host-catalyst phase are not simultaneously combined with the key catalytic phase, the order in which the different elements of the host-catalyst phase are combined with the key catalytic phase is also unimportant.
  • the catalysts of the present invention are calcined prior to use.
  • calcination of oxide complex catalysts serves to activate the catalysts, i.e. increase their catalytic activity.
  • calcination serves to drive off decomposable anions and cations which may be present in the pre-catalyst.
  • calcination can be accomplished in the presence of oxygen, preferably air, or other gas in a conventional manner.
  • the catalyst can be calcined for a period of 4 to 48 hours at temperatures of 200 to 800°C in the presence of air.
  • the catalyst of the present invention may include significant amounts of essentially inert supports such as silica, alumina, alundum, pumice, titania and zirconia.
  • essentially inert supports such as silica, alumina, alundum, pumice, titania and zirconia.
  • Such support materials are well known in the art for supporting oxide complex type catalysts, and any conventional support material can be employed in any conventional amount.
  • a support material can be added to the remaining ingredients of the desired catalyst at any time and in any manner.
  • the support material can be added to the key catalytic phase prior to the addition of the host-catalyst phase or it can be added to the catalyst once formed before or even after calcination.
  • the support material is added to the host-catalyst prior to combining the host-catalyst phase with the key catalytic phase.
  • an important feature of the present invention is that the key catalytic phase of the objective catalyst is preformed prior to admixing with other ingredients of the catalyst.
  • the element or elements M e.g. Bi
  • the other elements in the catalyst e.g. Ni, Co or Fe
  • the M element is allowed to form a molydate and/or tungstate without competition from competing elements so that the key catalytic phase can properly form.
  • the catalysts produced by the process of the present invention have superior catalytic activity compared to catalysts produced by prior art techniques.
  • a catalyst of the formula: was prepared by a conventional catalyst preparation technique in the following manner:
  • composition B 63.56g (NH 4 ) 6 MO 7 O 24 .4H 2 O was dissolved in 65cc H 2 0 at 60°C. 205.49g of 40 percent silica sol (Nalco) was added to the dissolved ammonium heptamolybdate. Next 3.46g of a 42 percent H 3 P0 4 aqueous solution was added to form a slurry denoted as composition B.
  • Nitrate solution A was then slowly added with stirring to composition B and as a result a light yellow slurry was formed.
  • the slurry was heated and stirred until it thickened.
  • the thickened material was dried at 120°C and then denitrified by heating in air at 290°C for three hours followed by heating in air at 425°C for three hours.
  • the catalyst was then ground to a particle size between 0.833 mm and 0.417 mm mesh and the ground catalyst was calcined in air at 610°C for three hours to yield the desired catalyst.
  • a catalyst having the following chemical formula was prepared by the process of the present invention: The chemical composition of this catalyst is identical to the chemical composition of the catalyst made in Comparative Example A.
  • the previously prepared bismuth molybdate slurry was then added to the host-catalyst slurry with stirring.
  • the mixture obtained was evaporated to dryness with constant stirring on a hot plate and finally in a drying oven at 120°C.
  • the dried material was then calcined in air at 290°C for three hours, then 425°C for three hours, then ground and screened to a particle size between 0.833 mm and 0.417 mm mesh.
  • the ground material was then finally calcined at 610°C for a period of three hours to yield the desired catalyst.
  • Example 1 was repeated except that the bismuth molybdate slurry was filtered to remove the preformed bismuth molybdate from the mother liquor. The bismuth molybdate was then dried overnight, calcined in the air at 290°C for one hour and ball milled before being added to the host-catalyst slurry.
  • the yield of acrylic acid significantly increases when a catalyst of the present invention is used.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP78300247A 1977-08-10 1978-08-04 Process for forming multicomponent oxide complex catalysts Expired EP0000835B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US823319 1977-08-10
US05/823,319 US4148757A (en) 1977-08-10 1977-08-10 Process for forming multi-component oxide complex catalysts
CS785206A CS216809B2 (en) 1977-08-10 1978-08-09 Method of making the molybdate oxide komplex catalyser
JP9775978A JPS5547144A (en) 1977-08-10 1978-08-10 Multiple component oxide complex catalyst forming technique

Publications (2)

Publication Number Publication Date
EP0000835A1 EP0000835A1 (en) 1979-02-21
EP0000835B1 true EP0000835B1 (en) 1981-09-30

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US (1) US4148757A (xx)
EP (1) EP0000835B1 (xx)
AT (1) AT362751B (xx)
AU (1) AU3800078A (xx)
BR (1) BR7805113A (xx)
CS (1) CS216809B2 (xx)
DD (1) DD138280A5 (xx)
DE (1) DE2861229D1 (xx)
DK (1) DK328678A (xx)
ES (1) ES472344A1 (xx)
FI (1) FI782425A (xx)
GR (1) GR71850B (xx)
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DE2861229D1 (en) 1981-12-10
RO76127A (ro) 1981-03-30
FI782425A (fi) 1979-02-11
TR20371A (tr) 1981-05-04
CS216809B2 (en) 1982-11-26
AT362751B (de) 1981-06-10
NO782715L (no) 1979-02-13
DK328678A (da) 1979-02-11
IT7826337A0 (it) 1978-07-31
BR7805113A (pt) 1979-04-10
PT68387A (en) 1978-09-01
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US4148757A (en) 1979-04-10
DD138280A5 (de) 1979-10-24
ES472344A1 (es) 1979-10-01
ATA584578A (de) 1980-11-15
GR71850B (xx) 1983-06-29
EP0000835A1 (en) 1979-02-21
IL55125A0 (en) 1978-09-29
ZA784157B (en) 1979-07-25

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