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
  • 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
  • B01J23/888—Tungsten
• • 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
• • 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
  • B01J23/888—Tungsten
  • B01J23/8885—Tungsten containing also molybdenum
• • 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
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
• • 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
• • 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

Definitions

• the catalysts described in these patents are indeed very desirable for the oxidation of olefins to unsaturated aldehydes and acids.
• some of these catalysts exhibit a less than desired redox stability when subjected to stressful conditions. More specifically, it occasionally happens in a commercial facility that the amount of oxygen fed to the reactor along with the olefin feed is either much greater or much less than the desired value. When this happens, it has been found that the catalysts may exhibit a significant decrease in catalytic activity. This, of course, is very disadvantageous.
• the present invention provides a new process for the catalytic oxidation of olefins to unsaturated aldehydes and acids which employs catalysts having high redox stability so that the catalysts can withstand major deviations in redox conditions without significant decrease in catalytic activity.
• the process of the invention produces unsaturated aldehydes and acids by the vapor phase oxidation of propylene or isobutylene with molecular oxygen at a temperature of about 200° to 600°C. in the presence of a catalyst represented by the following formula: wherein A is alkali metal, thallium, silver or mixtures thereof;
• the catalyst is free of indium, gallium, lanthanum and aluminium impurities when M is B, Cr + W, Pb, and/or Cu.
• the catalyst described is free of indium, gallium, lanthanum and aluminum impurities.
• the relative amounts of the various ingredients in the foregoing catalysts are such that the following inequalities apply: 0 ⁇ a ⁇ 0.5, 0.1 ⁇ b ⁇ 20, 0.1 ⁇ c ⁇ 20, 0.1 ⁇ d ⁇ 20 and 0.01 ⁇ e ⁇ 6.
• the catalysts of this invention preferably contain K, Rb and/or Cs. Also, in the catalysts of the invention X is preferably Bi.
• the catalysts employed in the inventive process are represented by the formula: wherein A is an alkali metal, preferably K, Rb, Cs or mixtures thereof,
• the minimum amount of each element in the system is 1, preferably 5, atom percent based on the total number of atoms in the system.
• a mixture of the olefin and molecular oxygen is contacted with a catalyst at an elevated temperature of about 200° to 600°C. for a contact time sufficient to convert the olefin to the desired aldehydes and/or acids.
• a contact time may vary widely from a few seconds to ten or twenty seconds or more.
• the reaction can be conducted under atmospheric, superatmospheric or subatmospheic pressure with the use of a superatmospheric pressure normally being used on a commercial scale.
• the catalyst employed may be any of the catalysts delineated by the formula described above. Preferred are those catalysts falling within the foregoing generic description which contain potassium, rubidium, cesium or mixtures thereof and those contain cobalt or nickel or mixtures thereof, and catalysts containing potassium, rubidium, cesium or mixtures thereof as well as nickel or cobalt or mixtures thereof are particularly preferred.
• the catalysts of the present invention can be prepared by techniques well known in the art. In this connection, techniques for preparing analogous catalysts are thoroughly described in the patents and application referred to abovce. Such catalysts are most conveniently prepared by the co-precipitation of soluble salts, although any other conventional technique can be employed. More specific information on the preparation of catalysts is given in the following examples.
• the catalysts of the present invention may be employed in unsupported form or they may be supported on a suitable carrier.
• Suitable carriers include silica, alumina, Alundum, titania, zirconia, silicon carbide and the like.
• the catalysts may also be used in various physical forms.
• the catalysts can be employed in a form suitable for carrying out the invention reaction in a fixed-bed mode or the catalyst can be employed in a form suitable for carrying out the invention reaction in a fluid-bed form.
• a remarkable feature of the present invention is that the catalysts employed exhibit significant redox stability.
• mishaps inevitably occur. If the amount of molecular oxygen relative to the amount of olefin contacting the catalysts at any particular time significantly drops below the desired value, a noticeable decrease in catalytic activity of the catalyst may occur.
• the catalysts employed exhibit a far reduced tendency to lose their catalytic activity when subjected to unfavourable reaction conditions. From a commercial-standpoint, therefore, the inventive process using the catalysts described herein has significant advantages over presently commercially practiced processes.
• aqueous slurry (referred to a solution A) containing 37.00 grams (NH 4 ) 6 Mo 7 O 24 .4H 2 O, 8.56 grams of a 0.10 g./ml. aqueous solution of H 3 PO 4 , 38 ml. of water and 25.43 grams of a 40% silica sol was prepared.
• solution B An aqueous solution (referred to as solution B) containing 21.17 grams Fe(N0 3 ) 3 .9H 2 0, 8.47 grams Bi(N0 3 ) 3 .5H 2 0, 12.7 grams Ni(NO 3 ) 2 ⁇ 6H 2 O, 22.87 grams Co(N0 3 ) 2 .6H 2 0 and 1.75 ml. ⁇ of a 0.10 g./ml. aqueous solution of KN0 3 was separately prepared. Solution A was then heated initially to 45-55°C. and solution B added dropwise to solution A with stirring. During addition of solution B, the temperature of the composition was increased so as to reach 75-80°C. at the end of the solution B addition. Stirring was continued and the temperature of the composition maintained between about 80 and 85°C. until sufficient water had evaporated so that a thick paste was obtained.
• the thick paste was placed in an oven at 120°C. and heated for about 2t hours, the paste being stirred every hour. Heating was then continued until the paste was dry.
• the dried paste was then heated in air at 290°C. for 3 hours and then at 425°C. for 3 hours. The heated paste was then additionally heated in air at 550°C. for 16 hours to produce the indicated catalyst.
• each of the catalysts described in Table I was subjected to a redox test in the following manner. 5 cc. of each catalyst prepared above was charged into a fixed-bed reactor. The temperature of the catalyst in the reactor was raised to a predetermined value and a feed comprising propylene/oxygen (in the form of air)/water in a ratio of 1/2.3/4 was fed to the reactor at a rate such that the apparent contact time was 3 seconds and a WWH of about 0.07. Once the reaction had commenced, a sample of the product was recovered and analyzed for acrolein and acrylic acid so that the initial catalytic activity of the catalyst could be determined.
• the ratio of the ingredients in the feed as indicated above was changed to 1/0.7/4, and the temperature of the catalyst was raised to 400°C. This low oxygen was fed to the reactor under these conditions for a period of 2 hours.
• the catalyst was reoxidized by feeding a feed of oxygen (in the form of air)/stem in a ratio of 2.3/4 to the catalyst at the reaction temperature indicated in Table I for 1 hour. Thereafter, the propylene flow was resumed to its initial value, and a product sample taken after the reaction had proceeded to steady state.
• ACR is acrolein
• AA is acrylic acid.
• the performance number as defined above is a measure of the catalytic activity of a catalyst in that it is a function of both the selectivity and per pass conversion.
• the catalysts of the present invention in the inventive reaction show a much smaller loss in performance number (and indeed some of the catalysts even show an improvement in performance number) over the reference catalysts.
• the inventive catalysts when employed in the inventive reaction exhibit a far greater redox stability when subjected to unfavorable reaction conditions as compared to conventional catalysts.

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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)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 1978
  • 1978-06-28 CA CA306,381A patent/CA1133505A/en not_active Expired
  • 1978-07-11 IN IN516/DEL/78A patent/IN148201B/en unknown
  • 1978-07-18 PT PT68313A patent/PT68313A/pt unknown
  • 1978-07-24 DD DD78206895A patent/DD140034A5/de unknown
  • 1978-07-25 DE DE7878300199T patent/DE2861192D1/de not_active Expired
  • 1978-07-25 EP EP78300199A patent/EP0000663B1/en not_active Expired
  • 1978-07-26 IT IT26141/78A patent/IT1118241B/it active
  • 1978-07-27 BR BR7804848A patent/BR7804848A/pt unknown
  • 1978-07-27 ES ES472082A patent/ES472082A1/es not_active Expired
  • 1978-07-27 RO RO7894818A patent/RO75319A/ro unknown
  • 1978-07-27 NO NO782583A patent/NO151083C/no unknown
  • 1978-07-28 YU YU01829/78A patent/YU182978A/xx unknown
  • 1978-07-28 AT AT551778A patent/AT359055B/de not_active IP Right Cessation

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