EP0000663B1 - Verfahren zur Oxydation von Olefinen unter Verwendung von Katalysatoren, die Molybdän und verschiedene Promotoren enthalten - Google Patents

Verfahren zur Oxydation von Olefinen unter Verwendung von Katalysatoren, die Molybdän und verschiedene Promotoren enthalten Download PDF

Info

Publication number
EP0000663B1
EP0000663B1 EP78300199A EP78300199A EP0000663B1 EP 0000663 B1 EP0000663 B1 EP 0000663B1 EP 78300199 A EP78300199 A EP 78300199A EP 78300199 A EP78300199 A EP 78300199A EP 0000663 B1 EP0000663 B1 EP 0000663B1
Authority
EP
European Patent Office
Prior art keywords
process according
catalysts
mixtures
catalyst
combinations
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78300199A
Other languages
English (en)
French (fr)
Other versions
EP0000663A1 (de
Inventor
Andrew Tytus Guttmann
Robert Karl Grasselli
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Standard Oil Co
Original Assignee
Standard Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Standard Oil Co filed Critical Standard Oil Co
Publication of EP0000663A1 publication Critical patent/EP0000663A1/de
Application granted granted Critical
Publication of EP0000663B1 publication Critical patent/EP0000663B1/de
Expired legal-status Critical Current

Links

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.

Landscapes

  • 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)

Claims (11)

1. Verfahren zur Herstellung von ungesättigten Aldehyden und Säuren aus Propylen oder Isobutylen durch Oxidation von Propylen oder Isobutylen in der Dampfphase mit molekularem Sauerstoff bei einer Temperatur von etwa 200 bis 600°C in Anwesenheit eines molybdänhaltigen Katalysators, dadurch gekennzeichnet, daß der molybdänhaltige Katalysator die Formel
Figure imgb0020
hat, wobei
A Alkalimetall, Thallium, Silber oder ein Gemisch derselben ist,
B Kobalt, Nickel, Zink, Cadmium, Beryllium, Calcium, Strontium, Barium, Radium oder ein Gemisch derselben ist,
X Wismut, Tellur oder ein Gemisch derselben ist und
M mindestens eins der folgenden Komponenten ist:
(1) ein aus zwei oder mehr Elementen bestehendes System ausgewählt aus Cr + W, Ge + W, Mn + Sb, Cr + P, Ge + P, Cu + W, Cu + Sn, Mn + Cr, Pr + W, Ce + W, Sn + Mn, Mn + Ge oder Kombinationen derselben,
(2) Pb, B, Cu oder Kombibationen derselben und
(3) ein aus zwei oder mehr Elementen bestehendes System ausgewählt aus Mg + P, Mg + Cu, Mg + Cr, Mg + Cr + W, Mg + W, Mg + Sn oder Kombinationen derselben, und 0 ≦ a ≦ 5, 0 ≦ b ≦ 20, 0 ≦ c ≦ 20, 0 ≦ d ≦ 20, 0,01 ≦ 2 ≦ 12 und wenn M Mn + Sb ist, a größer ist als 0.,
x eine solche Zahl ist, daß die Wertigkeitsanforderungen der anderen Elemente für Sauerstoff befriedigt sind, und die Mindestmenge jedes Elements von M, wenn M eine Kombination von zwei oder mehr elementen ist ein Atomprozent bezogen auf die Anzahl der Atome der Komponente M beträgt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Katalyst frei ist von den Verunreinigungen In, Ga, La und Al, wenn M B, Cr + W, Pb, Cu oder ein Gemisch derselben ist.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß M ausgewählt ist aus Cr + W, Ge + W, Cr + P, Ge + P, Cu + W, Cu + Sn, Mn + Cr, Sn + Mn, Mn + Ge, Pb, Bund Mg + Sn.
4. Verfahren nach einem der Ansprüche 1 + 3, dadurch gekennzeichnet, daß x Bi ist.
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennziechnet, daß die Elemente des genannten Katalysators in solchen Anteilen vorhanden sind, daß 0 ≦ a ≦ 0,5, 0,1 ≦ b ≦ 20, 0,1 ≦ c ≦ 20, 0,1 ≦ d ≦ 20 und 0,01 ≦ e ≦ 6, und daß, wenn M Mn + Sb ist, a größer ist als 0.
6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß A mindestens eines der Elemente K, Rb und Cs ist und daß B Ni + Co ist.
7. Verfahren nach einem der Ansprüche 1, 2, 4, 5 oder 6, dadurch gekennzeichnet, daß M Mn + Sb ist.
8. Verfahren nach einem der Ansprüche 1, 2, 4, 5 oder 6, dadurch gekennzeichnet, daß M Ge + W ist.
9. Verfahren nach Anspruch 1 oder 3, dadurch gekennzeichent, daß A Alkalimetall ist, B Co, Ni oder ein Gemisch derselben ist, X Bi ist,
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet; daß der genannte Katalysator frei ist von den Verunreinigungen In, Ga, La und Al.
11. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß M aus mindestens einem der folgenden aus mindestens zwei Elementen bestehenden Systeme ist, die ausgewählt sind aus
(1) Pr + W, Ce + W
(2) Mg + P, Mg + Cu, Mg + Cr, Mg + Cr + W, Mg + W oder Kombinationen derselben.
12. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß M Mg + W ist.
13. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß M Ge + P ist.
14. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß M Cr + W ist.
15. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß M Cr + P ist.
EP78300199A 1977-07-28 1978-07-25 Verfahren zur Oxydation von Olefinen unter Verwendung von Katalysatoren, die Molybdän und verschiedene Promotoren enthalten Expired EP0000663B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US81973377A 1977-07-28 1977-07-28
US819733 1977-07-28

Publications (2)

Publication Number Publication Date
EP0000663A1 EP0000663A1 (de) 1979-02-07
EP0000663B1 true EP0000663B1 (de) 1981-10-21

Family

ID=25228904

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78300199A Expired EP0000663B1 (de) 1977-07-28 1978-07-25 Verfahren zur Oxydation von Olefinen unter Verwendung von Katalysatoren, die Molybdän und verschiedene Promotoren enthalten

Country Status (13)

Country Link
EP (1) EP0000663B1 (de)
AT (1) AT359055B (de)
BR (1) BR7804848A (de)
CA (1) CA1133505A (de)
DD (1) DD140034A5 (de)
DE (1) DE2861192D1 (de)
ES (1) ES472082A1 (de)
IN (1) IN148201B (de)
IT (1) IT1118241B (de)
NO (1) NO151083C (de)
PT (1) PT68313A (de)
RO (1) RO75319A (de)
YU (1) YU182978A (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1127137A (en) * 1977-12-20 1982-07-06 Dev D. Suresh Ammoxidation of olefins with novel antimonate catalysts
GB2077257B (en) * 1980-05-19 1984-06-27 Asahi Chemical Ind Process for producing methacrolein
US4532365A (en) * 1982-09-20 1985-07-30 The Halcon Sd Group, Inc. Conversion of alkanes to unsaturated aldehydes
DE3867249D1 (de) * 1987-02-17 1992-02-13 Nippon Catalytic Chem Ind Katalysator zur oxydation von olefin oder tertiaerem alkohol und verfahren zu seiner herstellung.
US5162578A (en) * 1987-06-12 1992-11-10 Union Carbide Chemicals & Plastics Technology Corporation Acetic acid from ethane, ethylene and oxygen

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5112603B1 (de) * 1971-05-26 1976-04-21
CA1049553A (en) * 1973-04-30 1979-02-27 The Standard Oil Company Preparation of acrylic acid and methacrylic acid from propylene or isobutylene in a one-reactor, fluid-bed system
NL171440C (nl) * 1973-05-10 1983-04-05 Japan Synthetic Rubber Co Ltd Werkwijze voor het bereiden van methacroleien door katalytische oxydatie van isobuteen.
US3972920A (en) * 1973-06-11 1976-08-03 Mitsubishi Rayon Co., Ltd. Process for producing unsaturated aldehydes, unsaturated fatty acids or conjugated dienes
GB1523772A (en) * 1974-07-22 1978-09-06 Standard Oil Co Oxidation catalysts
US4001317A (en) * 1974-07-22 1977-01-04 Standard Oil Company Process for the oxidation of olefins using catalysts containing various promoter elements
GB1489559A (en) * 1975-03-03 1977-10-19 Mitsubishi Rayon Co Catalytic process for the preparation of acrylic acid or methacrylic acid
GB1490683A (en) * 1975-03-12 1977-11-02 Mitsubishi Rayon Co Process and a catalyst for producing unsaturated aldehydes unsaturated carboxylic acids or conjugated diene
IN142430B (de) * 1975-04-21 1977-07-09 Standard Oil Co
US4118419A (en) * 1975-12-03 1978-10-03 Mitsubishi Rayon Company, Ltd. Catalytic process for the preparation of an unsaturated carboxylic acid
DE2626887B2 (de) * 1976-06-16 1978-06-29 Basf Ag, 6700 Ludwigshafen Katalysator für die Oxadation von (Methacrolein zu (Meth)Acrylsäure
US4065507A (en) * 1976-08-02 1977-12-27 Standard Oil Company Preparation of methacrylic derivatives from tertiary butyl-containing compounds

Also Published As

Publication number Publication date
DE2861192D1 (en) 1981-12-24
RO75319A (ro) 1980-11-30
AT359055B (de) 1980-10-27
IT1118241B (it) 1986-02-24
NO782583L (no) 1979-01-30
NO151083C (no) 1985-02-06
BR7804848A (pt) 1979-04-10
ATA551778A (de) 1980-03-15
PT68313A (en) 1978-08-01
YU182978A (en) 1982-08-31
ES472082A1 (es) 1979-04-16
NO151083B (no) 1984-10-29
EP0000663A1 (de) 1979-02-07
CA1133505A (en) 1982-10-12
IT7826141A0 (it) 1978-07-26
DD140034A5 (de) 1980-02-06
IN148201B (de) 1980-11-29

Similar Documents

Publication Publication Date Title
US3875220A (en) Process for the preparation of methacrylic acid from methacrolein
US4001317A (en) Process for the oxidation of olefins using catalysts containing various promoter elements
US4155938A (en) Oxidation of olefins
EP0437056B2 (de) Katalysator und Verfahren zur Herstellung von Acrylonitril und Methacrylonitril
US5212137A (en) Catalyst for the manufacture of acrylonitrile and methacrylonitrile
US3956181A (en) Oxidation catalyst
US3932551A (en) Process for the preparation of diolefins from olefins
US3972920A (en) Process for producing unsaturated aldehydes, unsaturated fatty acids or conjugated dienes
CA2417987C (en) Improved catalyst for the manufacture of acrylonitrile
US4556731A (en) Process for the oxidation of olefins using catalysts containing various promoter elements
US4217309A (en) Process for producing methacrolein
US4017423A (en) Process for the preparation of unsaturated acids from unsaturated aldehydes
US4280928A (en) Catalyst compositions and their use for the preparation of methacrolein
US4272637A (en) Catalyst for oxidation of isobutylene
US4186152A (en) Oxidation of olefins
US4190608A (en) Process for the oxidation of olefins using catalysts containing various promoter elements
US4306090A (en) Catalyst compositions and their use for the preparation of methacrolein
EP0265733B1 (de) Verfahren zur Herstellung von Methacrylsäure
GB2038656A (en) Process for producing methacrolein
US4316855A (en) Multiply promoted Sn-Sb oxide catalysts
JPS5950667B2 (ja) 種々の金属を助触媒とした触媒を使う不飽和ニトリルの製造法
US4174354A (en) Oxidative dehydrogenation using chromium-containing catalysts
US4178464A (en) Process for producing methacrylic acid
US4209640A (en) Catalysts for the oxidation of unsaturated aldehydes
EP0000663B1 (de) Verfahren zur Oxydation von Olefinen unter Verwendung von Katalysatoren, die Molybdän und verschiedene Promotoren enthalten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE CH DE FR GB NL

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE CH DE FR GB NL

REF Corresponds to:

Ref document number: 2861192

Country of ref document: DE

Date of ref document: 19811224

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19910624

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19910721

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19910726

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19910731

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19910923

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19911106

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19920725

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19920731

Ref country code: BE

Effective date: 19920731

BERE Be: lapsed

Owner name: THE STANDARD OIL CY

Effective date: 19920731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19930201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19920725

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19930331

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19930401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT