DE1165570B - Process for the production of methacrolein by the catalytic oxidation of isobutene - Google Patents

Process for the production of methacrolein by the catalytic oxidation of isobutene

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Publication number
DE1165570B
DE1165570B DEST19861A DEST019861A DE1165570B DE 1165570 B DE1165570 B DE 1165570B DE ST19861 A DEST19861 A DE ST19861A DE ST019861 A DEST019861 A DE ST019861A DE 1165570 B DE1165570 B DE 1165570B
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DE
Germany
Prior art keywords
isobutene
vanadium
bismuth
methacrolein
catalyst
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.)
Pending
Application number
DEST19861A
Other languages
German (de)
Inventor
Bernard Phielix
Jentje Ponnema
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Stamicarbon BV
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Stamicarbon BV
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Filing date
Publication date
Application filed by Stamicarbon BV filed Critical Stamicarbon BV
Publication of DE1165570B publication Critical patent/DE1165570B/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C47/22—Acryaldehyde; Methacryaldehyde
    • 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
    • B01J23/8876—Arsenic, antimony or bismuth
    • 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
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
    • 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
    • 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
    • B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
    • B01J2523/41—Silicon
    • 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
    • B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
    • B01J2523/54—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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/84—Metals of the iron group
    • B01J2523/842—Iron

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Internat. Kl.: C 07 cBoarding school Class: C 07 c

Deutsche KL: 12 ο-7/03 German KL: 12 ο -7/03

Nummer: 1165 570Number: 1165 570

Aktenzeichen: St 19861IV b / 12 οFile number: St 19861IV b / 12 ο

Anmeldetag: 18. Oktober 1962 Filing date: October 18, 1962

Auslegetag: 19. März 1964Opening day: March 19, 1964

In der Patentanmeldung St 18 888 IVb/12 ο (deutsche Auslegeschrift 1 160 839) wurde ein Verfahren beschrieben zur Herstellung von Methacrolein durch Oxydation von Isobuten mit sauerstoffhaltigen Gasen in der Gasphase bei erhöhter Temperatur in Anwesenheit von Katalysatoren, welches dadurch gekennzeichnet ist, daß man die Umsetzung bei 300 bis 8000C in Gegenwart eines Katalysators durchführt, der Gemische und/oder Verbindungen von Wismut- und Vanadiumoxyden oder von Wismut-, Vanadium- und Phosphoroxyden in einem Atomverhältnis von Wismut zu Vanadium bzw. Wismut zu der Summe von Vanadium und Phosphor von jeweils größer als 0,5:1 und kleiner als 1,5:1 enthält, bei Durchsatzgeschwindigkeiten von mindestens etwa 500 1 Isobuten je Liter Katalysator je Stunde unter Anwesenheit von 0,1 bis 1,0 Mol Sauerstoff je Mol Isobuten. Bei diesem Verfahren wird von reinem Isobuten ausgegangen, das beispielsweise erhalten werden kann, indem man aus einem bei thermischem und/oder katalytischem Kracken von Erdölfraktionen anfallenden Gemisch niedriger Kohlenwasserstoffe zuerst die im wesentlichen Kohlenwasserstoffe mit 4 C-Atomen enthaltende Fraktion ausscheidet und letztere anschließend einer weiteren Trennung unterzieht. Solche »C4-Fraktionen« enthalten außer Isobuten vorwiegend Buten-(l), eis- und trans-Buten-(2), Butadien, η-Butan und Isobutan; die Trennung dieser Bestandteile ist ziemlich kostspielig.In the patent application St 18 888 IVb / 12 o (German Auslegeschrift 1 160 839) a process was described for the production of methacrolein by oxidation of isobutene with oxygen-containing gases in the gas phase at elevated temperature in the presence of catalysts, which is characterized in that one carries out the reaction at 300 to 800 0 C in the presence of a catalyst, the mixtures and / or compounds of bismuth and vanadium oxides or of bismuth, vanadium and phosphorus oxides in an atomic ratio of bismuth to vanadium or bismuth to the sum of vanadium and Contains phosphorus of greater than 0.5: 1 and less than 1.5: 1, at throughput rates of at least about 500 liters of isobutene per liter of catalyst per hour in the presence of 0.1 to 1.0 mol of oxygen per mol of isobutene. This process is based on pure isobutene, which can be obtained, for example, by first separating the fraction containing essentially hydrocarbons with 4 carbon atoms from a mixture of low hydrocarbons obtained during thermal and / or catalytic cracking of petroleum fractions and then separating the latter from another Undergoes separation. Such “C 4 fractions” contain, besides isobutene, mainly butene- (1), cis- and trans-butene- (2), butadiene, η-butane and isobutane; the separation of these components is quite expensive.

Es wurde nunmehr gefunden, daß man beim Verfahren gemäß der Hauptpatentanmeldung nicht notwendigerweise von reinem Isobuten auszugehen braucht, sondern als Ausgangsprodukt auch die genannte, im wesentlichen Kohlenwasserstoffe mit 4 C-Atomen enthaltende Fraktion benutzen kann. Es hat sich herausgestellt, daß die Oxydation von Isobuten zu Methacrolein unter den für das Verfahren gemäß der Hauptpatentanmeldung zutreffenden Verfahrensbedingungen und Katalysatoren nicht durch die Anwesenheit der übrigen Q-Kohlenwasserstoffe beeinträchtigt wird und diese anderen Kohlenwasserstoffe nur in sehr geringem Umfang zu Aldehyden oder Säuren oxydiert werden. Wohl wird unter den gegebenen Bedingungen meistens ein Teil der vorhandenen Butene durch Dehydrogenierung in Butadien umgewandelt.It has now been found that the method according to the main patent application does not necessarily needs to start from pure isobutene, but also the above-mentioned, essentially hydrocarbons, as the starting product 4 carbon atoms containing fraction can use. It has been found that the oxidation of Isobutene to methacrolein under the process conditions applicable to the process according to the main patent application and catalysts not due to the presence of the remaining Q-hydrocarbons is impaired and these other hydrocarbons only to a very small extent to aldehydes or acids are oxidized. Under the given conditions, a part of the existing ones is likely Butenes converted to butadiene by dehydrogenation.

Das Verfahren der Erfindung besitzt gegenüber dem Verfahren der Hauptpatentanmeldung den Vorteil, daß jetzt die vorangehende Abtrennung von Isobuten aus der C4-Fraktion unterbleiben kann. Außerdem fällt auf diese Weise als wertvolles Nebenprodukt Butadien an.The process of the invention has the advantage over the process of the main patent application that the preceding separation of isobutene from the C 4 fraction can now be omitted. In addition, this produces butadiene as a valuable by-product.

Verfahren zur Herstellung von Methacrolein
durch katalytische Oxydation von IsobutenProcess for the production of methacrolein
by catalytic oxidation of isobutene

Zusatz zur Anmeldung: St 18888 IV b / 12 ο ■
Auslegeschrift 1 160 839Addition to registration: St 18888 IV b / 12 ο ■
Interpretation document 1 160 839

Anmelder:Applicant:

Stamicarbon N. V., Heerlen (Niederlande)Stamicarbon N.V., Heerlen (Netherlands)

Vertreter:Representative:

Dr. F. Zumstein,Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. AssmannDipl.-Chem. Dr. rer. nat. E. Assmann

und Dipl.-Cb.em. Dr. R. Koenigsberger,and Dipl.-Cb.em. Dr. R. Koenigsberger,

Patentanwälte, München 2, Bräuhausstr. 4Patent Attorneys, Munich 2, Bräuhausstr. 4th

Als Erfinder benannt:Named as inventor:

Bernard Phielix, Sittard,Bernard Phielix, Sittard,

Jentje Ponnema, Geleen (Niederlande)Jentje Ponnema, Geleen (Netherlands)

Beanspruchte Priorität:Claimed priority:

Niederlande vom 3. Juli 1962 (Nr. 280 494)Netherlands of July 3, 1962 (No. 280 494)

Die Durchführung des Verfahrens erfolgt weiter auf die in der Hauptpatentanmeldung erwähnte Weise, wobei man also ein aus der genannten Q-Fraktion und einem sauerstoffhaltigen Gas bestehendes Gemisch, gegebenenfalls in Anwesenheit inerter Gase oder Dämpfe, besonders von Wasserdampf, durch eine Ruheschicht der Katalysatormasse oder durch eine Katalysatorwirbelschicht leitet. Auch beim Verfahren der Erfindung kann es vorteilhaft sein, als Trägerstoff für die Katalysatoren Karborund zu benutzen.The process continues to be carried out in the manner mentioned in the main patent application, where one therefore consists of a mixture consisting of the said Q fraction and an oxygen-containing gas, possibly in the presence of inert gases or vapors, especially water vapor a resting layer of the catalyst mass or passes through a fluidized catalyst bed. Even with the procedure According to the invention, it can be advantageous to use carborundum as a carrier for the catalysts use.

Beispielexample

Für Vergleichszwecke wurden Kohlenwasserstofffraktionen, welche im wesentlichen Kohlenwasserstoffe mit 4 C-Atomen in wechselnden Mengen enthalten, über eine 50-ml-Katalysatorruheschicht geführt, welche Gemische und/oder Verbindungen von Wismut-, Vanadium- und Phosphoroxyden enthält in einem Atomarverhältnis Wismut zur Summe von Vanadium und Phosphor von 1:1 und Vanadium zu Phosphor von 3:1, also einer Zusammensetzung Bi(VO3)3 + BiPO4 + Bi2O3 entsprechend. Als Trägerstoff enthält der Katalysator Karborund; die MengeFor comparison purposes, hydrocarbon fractions, which essentially contain hydrocarbons with 4 carbon atoms in varying amounts, were passed over a 50 ml resting catalyst layer which contains mixtures and / or compounds of bismuth, vanadium and phosphorus oxides in an atomic ratio of bismuth to the sum of Vanadium and phosphorus of 1: 1 and vanadium to phosphorus of 3: 1, i.e. a composition of Bi (VO 3 ) 3 + BiPO 4 + Bi 2 O 3 . The catalyst contains carborundum as a carrier; the amount

._:·.,. 409 539/542._: ·.,. 409 539/542

der genannten Oxyde im Katalysator beläuft sich auf 25 Gewichtsprozent.of the oxides mentioned in the catalyst amounts to 25 percent by weight.

Eine 46 Volumprozent Isobuten, 25 Volumprozent Buten-(l), 10,5 Volumprozent trans-Buten-(2), 8 Volumprozent cis-Buten-(2), 1 Volumprozent Butadien und 9,5 Volumprozent Butan + Isobutan enthaltende Kohlenwasserstofffraktion wird, nach Vermischung mit Luft, unter Normaldruck mit einer Geschwindigkeit von 2800 1 der C4-Fraktion und 3500 1 Luft je Liter Katalysator je Stunde durch das Katalysatorbett geleitet. Der Reaktor wird auf einer Temperatur von 450c C gehalten. Aus den Analyseergebnissen des aus dem Reaktor austretenden Gasgemisches ergibt sich, daß die Umwandlung der C4-Fraktion zu Methacrolein 8,1 Molprozent und die Ausbeute der Methacroleinumsetzung, bezogen auf umgesetztes Isobuten, 78 Molprozent beträgt. Es wird mithin eine tägliche Methacroleinausbeute von 16,9 kg je Liter Katalysator erhalten. Es bildet sich daneben Butadien mit einer Ausbeute von 31 Molprozent, bezogen auf die Menge umgesetzter Butene.A hydrocarbon fraction containing 46 percent by volume isobutene, 25 percent by volume butene (1), 10.5 percent by volume trans-butene (2), 8 percent by volume cis-butene (2), 1 percent by volume butadiene and 9.5 percent by volume butane + isobutane is after mixing with air, passed through the catalyst bed under normal pressure at a rate of 2800 liters of the C 4 fraction and 3500 liters of air per liter of catalyst per hour. The reactor is maintained at a temperature of 450 C c. The analysis results of the gas mixture emerging from the reactor show that the conversion of the C 4 fraction to methacrolein is 8.1 mol percent and the yield of methacrolein conversion, based on isobutene converted, is 78 mol percent. A daily methacrolein yield of 16.9 kg per liter of catalyst is thus obtained. In addition, butadiene is formed with a yield of 31 mol percent, based on the amount of butenes reacted.

In einem anderen Versuch wird eine Kohlenwasserstofffraktion mit 23 Volumprozent Isobuten, 26 Volumprozent Buten-(l), 18 Volumprozent trans-Buten-(2), 27,5 Volumprozent cis-Buten-(2), 0,5 Volumprozent Butadien und 5,0 Volumprozent Butan + Isobutan durch dieselbe Katalysatormasse mit einer Geschwindigkeit von 2800 1 dieser C4-Fraktion und 3500 1 Luft je Liter Katalysator je Stunde geleitet. Die Reaktortemperatur wird auf 4700C gehalten. Von der C4-Fraktion werden jetzt 6,1 Molprozent in Methacrolein umgesetzt mit einer Ausbeute von 70 Molprozent, bezogen auf umgesetztes Isobuten. Die Tagesausbeute an Methacrolein beträgt also 12,8 kg je Liter Katalysator. Es bildet sich daneben Butadien mit einer Ausbeute von 28 Molprozent, bezogen auf die Menge umgesetzter Butene.In another experiment, a hydrocarbon fraction with 23 percent by volume isobutene, 26 percent by volume butene- (l), 18 percent by volume trans-butene- (2), 27.5 percent by volume cis-butene- (2), 0.5 percent by volume butadiene and 5, 0 percent by volume of butane + isobutane passed through the same catalyst mass at a rate of 2800 liters of this C 4 fraction and 3500 liters of air per liter of catalyst per hour. The reactor temperature is maintained at 470 0 C. 6.1 mol percent of the C 4 fraction is now converted into methacrolein with a yield of 70 mol percent, based on converted isobutene. The daily yield of methacrolein is therefore 12.8 kg per liter of catalyst. In addition, butadiene is formed with a yield of 28 mol percent, based on the amount of butenes reacted.

Claims (1)

Patentanspruch: , ^Claim:, ^ Weitere Ausbildung des Verfahrens nach Patentanmeldung St 18 888 IVb/12o zur Herstellung von Methacrolein durch Oxydation von Isobuten mit sauerstoffhaltigen Gasen in der Gasphase bei erhöhter Temperatur in Anwesenheit von Katalysatoren, wobei man die Umsetzung bei 300 bis 80O0C in Gegenwart eines Katalysators durchführt, der Gemische und/oder Verbindungen von Wismut- und Vanadiumoxyden oder von Wismut-, Vanadium- und Phosphoroxyden in einem Atomverhältnis von Wismut zu Vanadium bzw. Wismut zu der Summe von Vanadium und Phosphor von jeweils größer als 0,5:1 und kleiner als 1,5:1 enthält, bei Durchsatzgeschwindigkeiten von mindestens etwa 500 1 Isobuten je Liter Katalysator je Stunde unter Anwesenheit von 0,1 bis 1,0 Mol Sauerstoff je Mol Isobuten, dadurch gekennzeichnet, daß man statt reinem Isobuten als Ausgangsmaterial für das Verfahren eine Kohlenwasserstofffraktion verwendet, welche im wesentlichen Kohlenwasserstoffe mit 4 C-Atomen, und zwar außer Isobuten vorwiegend Buten-(l), eis- und trans-Buten-(2), Butadien, η-Butan und Isobutan enthält.Further development of the process according to patent application St 18 888 IVb / 12o for the production of methacrolein by oxidation of isobutene with oxygen-containing gases in the gas phase at elevated temperature in the presence of catalysts, the reaction being carried out at 300 to 80O 0 C in the presence of a catalyst, the mixtures and / or compounds of bismuth and vanadium oxides or of bismuth, vanadium and phosphorus oxides in an atomic ratio of bismuth to vanadium or bismuth to the sum of vanadium and phosphorus of in each case greater than 0.5: 1 and less than 1 , 5: 1, at throughput rates of at least about 500 liters of isobutene per liter of catalyst per hour in the presence of 0.1 to 1.0 mol of oxygen per mole of isobutene, characterized in that instead of pure isobutene, a hydrocarbon fraction is used as the starting material for the process used, which are essentially hydrocarbons with 4 carbon atoms, namely except for isobutene predominantly butene- (l), e Contains is- and trans-butene- (2), butadiene, η-butane and isobutane. In Betracht gezogene Druckschriften: Deutsche Auslegeschrift Nr. 1 114 474; französische Patentschriften Nr. 1 281 927, 1 287214.Documents considered: German Auslegeschrift No. 1 114 474; French patents nos. 1 281 927, 1 287214. 409 539/542 3.64 © Bundesdruclterei Berlin409 539/542 3.64 © Bundesdruclterei Berlin
DEST19861A 1962-07-03 1962-10-18 Process for the production of methacrolein by the catalytic oxidation of isobutene Pending DE1165570B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4413147A (en) * 1982-04-14 1983-11-01 The Halcon Sd Group, Inc. Conversion of isobutane to methacrolein
US4535188A (en) * 1982-04-14 1985-08-13 The Halcon Sd Group, Inc. Conversion of isobutane to methacrolein
USRE32082E (en) * 1982-04-14 1986-02-11 The Halcon Sd Group, Inc. Conversion of isobutane to methacrolein

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1114474B (en) * 1958-02-10 1961-10-05 Knapsack Ag Process for the production of isoprene or butadiene
FR1281927A (en) * 1960-10-27 1962-01-19 Shell Int Research Process for the dehydrogenation of organic compounds
FR1287214A (en) * 1960-04-26 1962-03-09 Distillers Co Yeast Ltd Process for preparing conjugated diolefins from olefins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1114474B (en) * 1958-02-10 1961-10-05 Knapsack Ag Process for the production of isoprene or butadiene
FR1287214A (en) * 1960-04-26 1962-03-09 Distillers Co Yeast Ltd Process for preparing conjugated diolefins from olefins
FR1281927A (en) * 1960-10-27 1962-01-19 Shell Int Research Process for the dehydrogenation of organic compounds

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4413147A (en) * 1982-04-14 1983-11-01 The Halcon Sd Group, Inc. Conversion of isobutane to methacrolein
US4535188A (en) * 1982-04-14 1985-08-13 The Halcon Sd Group, Inc. Conversion of isobutane to methacrolein
USRE32082E (en) * 1982-04-14 1986-02-11 The Halcon Sd Group, Inc. Conversion of isobutane to methacrolein

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