DE3103410A1 - Process for the oxidative dehydrogenation of isobutyric acid to methacrylic acid - Google Patents

Process for the oxidative dehydrogenation of isobutyric acid to methacrylic acid

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Publication number
DE3103410A1
DE3103410A1 DE19813103410 DE3103410A DE3103410A1 DE 3103410 A1 DE3103410 A1 DE 3103410A1 DE 19813103410 DE19813103410 DE 19813103410 DE 3103410 A DE3103410 A DE 3103410A DE 3103410 A1 DE3103410 A1 DE 3103410A1
Authority
DE
Germany
Prior art keywords
acid
metal
methacrylic acid
isobutyric acid
oxidative dehydrogenation
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.)
Withdrawn
Application number
DE19813103410
Other languages
German (de)
Inventor
Wilhelm Dr. 6100 Darmstadt Gruber
Günter Dipl.-Chem. Dr. 6105 Ober-Ramstadt Schröder
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.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
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 Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Priority to DE19813103410 priority Critical patent/DE3103410A1/en
Priority to EP81102670A priority patent/EP0046840B1/en
Priority to DE8181102670T priority patent/DE3161102D1/en
Priority to ES503035A priority patent/ES8203322A1/en
Priority to US06/297,279 priority patent/US4370490A/en
Publication of DE3103410A1 publication Critical patent/DE3103410A1/en
Withdrawn legal-status Critical Current

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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
    • B01J23/002—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
    • 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
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • 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

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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)

Abstract

Isobutyric acid is dehydrogenated oxidatively according to the invention in the gas phase using an essentially sulphate-free metal oxide catalyst based on molybdenum oxide which contains additionally vanadium, phosphorus and a metal from the group comprising the alkali metals, alkaline earth metals, Zn, Ag, Al, Ti, Pb and Sn and, besides or instead of the abovementioned metals, a metal from amongst the group comprising Mn, Fe, Co and Ni, to give methacrylic acid.

Description

Verfahren zur oxydativen Dehydrierung von IsobuttersäureProcess for the oxidative dehydrogenation of isobutyric acid

zu Methacyrl säur9~~~~~~~~~~~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Die Erfindung gemäß der Hauptanmeldung P 30 32 423.3 betrifft ein Verfahren zur oxydativen Dehydrierung von Isobuttersäure zu Methacrylsäure nach dem Oberbegriff des Patentanspruches. Die vorliegende Erfindung bezweckt eine weitere Ausgestaltung des Verfahrens gemäß der Hauptanmeldung unter Verwendung eines Katalysators auf Basis von Molybdänoxid, Vanadin und Phosphor, wobei erfindungsgemäß als weiteres Metall in dem Katalysator ein Metall aus der Gruppe Mangan, Eisen, Kobalt und Nickel enthalten ist.to Methacyrl säur9 ~~~~~~~~~~~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~ The invention according to the main application P 30 32 423.3 relates to a process for oxidative dehydrogenation from isobutyric acid to methacrylic acid according to the preamble of the patent claim. The present invention aims at a further embodiment of the method according to FIG of the main application using a catalyst based on molybdenum oxide, Vanadium and phosphorus, according to the invention as a further metal in the catalyst contains a metal from the group consisting of manganese, iron, cobalt and nickel.

Es war schon aus der japanischen Patentanmeldung 75/4014 bekannt, zur oxydativen Dehydrierung von Isobuttersäure zu Methacrylsäure in der Gasphase einen Katalysator zu verwenden, der durch Zugabe von Nickel- oder Kobaltsulfat zu einer Molybdovanadophosphorsäure hergestellt worden ist. Bei einem hohen Ihnwandlungsgrad der eingesetzten Isobuttersäure von 80 bis 90 % erreicht man mit diesem Katalysator nur Selektivitäten zwischen 45 und 50 %, was für eine wirtschaftliche Herstellung von Methacrylsäure nicht ausreichend ist.It was already known from Japanese patent application 75/4014, for the oxidative dehydrogenation of isobutyric acid to methacrylic acid in the gas phase to use a catalyst made by adding nickel or cobalt sulfate to it a molybdovanadophosphoric acid. With a high degree of change 80 to 90% of the isobutyric acid used is achieved with this catalyst only selectivities between 45 and 50%, what an economical production methacrylic acid is not sufficient.

Oberraschenderweise gelingt es, die Selektivität bei gleichem Umsatzgrad erheblich zu steigern, wenn man nicht die Sulfate der genannten Metalle einsetzt, sondern Katalysatoren, die sich mit der allgemeinen Formel MaMobVcPdOe umschreiben lassen, wobei M ein Metall der Gruppe Mn, Fe, Co und Ni bedeutet und a einen Wert von 0,4 bis 2,5, b etwa 12, c einen Wert von 1 bis 2 und d einen Wert von 0,5 bis 3 haben und e sich aus den Wertigkeiten und Anteilen der anderen Elemente von selbst ergibt.Surprisingly, it succeeds in the selectivity same To increase the degree of conversion considerably, if one does not use the sulfates of the metals mentioned uses, but catalysts that deal with the general formula MaMobVcPdOe let circumscribe, where M is a metal from the group Mn, Fe, Co and Ni and a has a value from 0.4 to 2.5, b about 12, c a value from 1 to 2 and d a value from 0.5 to 3 and e result from the valencies and proportions of the other elements results by itself.

Ebenso wie beim Verfahren der 14.luptanlneldung werden die Katalysatoren bevorzugt in Verbindung mit einem festen Träger, etwa auf Basis von Siliciumdioxid, angewendet. Sie können ebenfalls den Katalysator in einem Gewichtsanteil von 5 bis 80 %, vorzugsweise von 20 bis 70 %, enthalten und bei Temperaturen zwischen 200 und 4000C calciniert worden sein.As in the procedure of the 14th main registration, the catalytic converters preferably in connection with a solid support, e.g. based on silicon dioxide, applied. You can also use the catalyst in a weight proportion of 5 to 80%, preferably from 20 to 70%, and at temperatures between 200 and calcined at 4000C.

Das Dehydrierungsverfahren wird wie in der H.luptanmeldung beschrieben durchgeführt und läßt - wie dort - Selektivitäten für Isobuttersäure von 60 bis 74 % bei Umsatzgraden von 80 bis 100% erreichen.The dehydration process is as described in the H.lupt application carried out and leaves - as there - selectivities for isobutyric acid from 60 to Achieve 74% at conversion levels of 80 to 100%.

Die bevorzugten Verfahrensweisen gemäß der Hauptanmeldung gelten auch für die vorliegende Erfindung.The preferred procedures according to the parent application also apply for the present invention.

Beispiele Analog der Arbeit-sweise gemäß A3 in der Hauptanmeldung werden vier Katalysatoren A bis D mit folgender Zusammensetzung hergestellt: A) Mn Mo12 V1,5 P2O45,8 B) Fe0,67 Mo12 V1,5 P2O45,8 C) Co Mo12 V1,5 P2O45,8 C) Ni Mo12 V1,5 P2O45,8 Im Temperaturbercich von 320 - 350°C wurden über die Katalysatoren A bis D Gemische von Isobuttersäure, Wasser und Luftsauerstoff im Molverhältnis 1 : 2 : 1,7 und einer Verweilzeit von 0,3 sec geleitet. In der nachfolgenden Tabelle sind die erreichten Werte für den Isobuttersäureumsatz und die Selektivität an Methacrylsäure verzeichnet: Beisp. Katalysator Katalysator- Umsatz an Selektivität Nr. temperatur Isobutter- an Methacryl-°C säure (%) säure (t) 1 A 330 84,8 64,9 2 A 340 93,0 62,3 3 B 330 81,8 66,1 4 B 350 95,9 62,3 5 C 340 91,1 65,5 6 c 350 96,1 64,5 7 D 350 93,6 58,4 Beispiel 8 Uber 13 ml eines auf Kieselgur niedergeschlagenen Katalysators der Zusammensetzung C wurde bei 3600C mit einer Verweilzeit von 0,5 sec ein Gasgemisch aus Isobuttersäure, Wasser, Sauerstoff und Stickstoff im Molverhältnis 1 : 2 : 1,5 : 20 geleitet. Bei einem Umsatz von 99,8 eO der eingesetzten Isobuttersäure wurde Methacrylsäure in einer Selektivität von 74,1 % erzeugt.Examples Analogous to the procedure according to A3 in the main application four catalysts A to D are produced with the following composition: A) Mn Mo12 V1.5 P2O45.8 B) Fe0.67 Mo12 V1.5 P2O45.8 C) Co Mo12 V1.5 P2O45.8 C) Ni Mo12 V1.5 P2O45.8 In the temperature range of 320-350 ° C, the catalysts A to D Mixtures of isobutyric acid, water and atmospheric oxygen in a molar ratio 1: 2: 1.7 and a residence time of 0.3 sec. In the table below are the values achieved for the isobutyric acid conversion and the selectivity of methacrylic acid recorded: Example catalyst catalyst conversion to selectivity No. temperature Isobutyric acid in methacrylic acid (%) acid (t) 1 A 330 84.8 64.9 2 A 340 93.0 62.3 3 B 330 81.8 66.1 4 B 350 95.9 62.3 5 C 340 91.1 65.5 6 c 350 96.1 64.5 7 D 350 93.6 58.4 Example 8 About 13 ml of a precipitated on diatomaceous earth Composition C catalyst was at 3600C with a residence time of 0.5 sec a gas mixture of isobutyric acid, water, oxygen and nitrogen in a molar ratio 1: 2: 1.5: 20 passed. With a conversion of 99.8 eO of the isobutyric acid used methacrylic acid was produced with a selectivity of 74.1%.

Claims (1)

Patentanspruch Verfahren zur oxydativen Dehydrierung von Isobuttersäure zu Methacrylsäure unter Verwendung eines im wesentlichen sulfatfreien Metalloxid-Katalysators auf der Basis von Molybdänoxid, der zusätzlich Vanadin, Phosphor und ein Metall aus der Gruppe der Alkalimetalle, Erdalkalimetalle, Zink, Silber, Aluminium, Titan, Blei und Zinn enthält, nach Patentanmeldung P 30 32 423.3, dadurch gekennzeichnet, daß der Katalysator neben oder alxstelle der genanntes0 Metalle ein Metall der Gruppe Mangan, Eisen, Kobalt und Nickel enthält.Claim Process for the oxidative dehydrogenation of isobutyric acid to methacrylic acid using an essentially sulfate-free metal oxide catalyst based on molybdenum oxide, which also contains vanadium, phosphorus and a metal from the group of alkali metals, alkaline earth metals, zinc, silver, aluminum, titanium, Contains lead and tin, according to patent application P 30 32 423.3, characterized in that that the catalyst, in addition to or as a substitute for the metals mentioned, is a metal of the group Contains manganese, iron, cobalt and nickel.
DE19813103410 1980-08-28 1981-02-02 Process for the oxidative dehydrogenation of isobutyric acid to methacrylic acid Withdrawn DE3103410A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE19813103410 DE3103410A1 (en) 1981-02-02 1981-02-02 Process for the oxidative dehydrogenation of isobutyric acid to methacrylic acid
EP81102670A EP0046840B1 (en) 1980-08-28 1981-04-09 Process for the oxidizing dehydrogenation of isobutyric acid to methacrylic acid
DE8181102670T DE3161102D1 (en) 1980-08-28 1981-04-09 Process for the oxidizing dehydrogenation of isobutyric acid to methacrylic acid
ES503035A ES8203322A1 (en) 1980-08-28 1981-06-13 Process for the oxidizing dehydrogenation of isobutyric acid to methacrylic acid.
US06/297,279 US4370490A (en) 1980-08-28 1981-08-28 Process for producing methacrylic acid by oxidative dehydration of isobutyric acid and catalyst therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19813103410 DE3103410A1 (en) 1981-02-02 1981-02-02 Process for the oxidative dehydrogenation of isobutyric acid to methacrylic acid

Publications (1)

Publication Number Publication Date
DE3103410A1 true DE3103410A1 (en) 1982-08-26

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DE (1) DE3103410A1 (en)

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