DE600677C - Process for the preparation of methyl alcohol by reducing carbon oxide - Google Patents

Process for the preparation of methyl alcohol by reducing carbon oxide

Info

Publication number
DE600677C
DE600677C DEB108839D DEB0108839D DE600677C DE 600677 C DE600677 C DE 600677C DE B108839 D DEB108839 D DE B108839D DE B0108839 D DEB0108839 D DE B0108839D DE 600677 C DE600677 C DE 600677C
Authority
DE
Germany
Prior art keywords
methyl alcohol
hydrogen
elements
preparation
carbon oxide
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
DEB108839D
Other languages
German (de)
Inventor
Dr Otto Schmidt
Dr Hans Ufer
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.)
IG Farbenindustrie AG
Original Assignee
IG Farbenindustrie AG
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 IG Farbenindustrie AG filed Critical IG Farbenindustrie AG
Priority to DEB108839D priority Critical patent/DE600677C/en
Priority to AT105591D priority patent/AT105591B/en
Application granted granted Critical
Publication of DE600677C publication Critical patent/DE600677C/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof

Description

Verfahren zur Darstellung von Methylalkohol durch Reduktion von Kohlenoxyd Durch das Patent 54q.665 ist ein Verfahren zur Herstellung von Methylalkohol und anderen sauerstoffhaltigen organischen Verbindungen durch katalytische Hydrierung von Oxyden des Kohlenstoffs mit Wasserstoff unter Verwendung größerer Raummengen Wasserstoff als Kohlenoxyd bei Temperaturen von mindestens 450' und Drucken von zweckmäßig gegen Zoo Atm. und darüber geschützt, bei dem Katalysatoren verwendet werden, die unter den Arbeitsbedingungen nicht zum Metall reduzierbare Metalloxyde oder Verbindungen solcher für sich oder gemischt enthalten und in denen Eisen, Nickel oder Kobalt nicht oder nur in geringen Mengen vorhanden sind.Process for the preparation of methyl alcohol by reduction of carbon oxide By the patent 54q.665 is a process for the production of methyl alcohol and other oxygen-containing organic compounds by catalytic hydrogenation of oxides of carbon with hydrogen using larger amounts of space Hydrogen as carbon dioxide at temperatures of at least 450 'and pressures of useful against Zoo Atm. and protected by using catalysts the metal oxides which cannot be reduced to metal under the working conditions or compounds of such alone or mixed and in which iron, nickel or cobalt are not present or only in small quantities.

Im Patent 565 88o ist ferner gezeigt, daß man Methylalkohol auch dann mit guter Ausbeute und großer Reaktionsgeschwindigkeit erhält, wenn man das umzusetzende Gasgemisch bei verhältnismäßig niedrigen Temperaturen, etwa im Bereich von 22o bis 25o°, über solche Katalysatoren leitet, die außer einem oder mehreren katalytisch wirkenden Elementen noch Chrom oder diesem nahestehende Elemente der 6. Gruppe des periodischen Systems oder Bor oder mehrere solcher Elemente gleichzeitig enthalten.In the 565,880 patent it is also shown that methyl alcohol can also be used with good yield and high reaction rate, if you get what is to be converted Gas mixture at relatively low temperatures, for example in the range from 22o to 25o °, passes through such catalysts, which except one or more catalytically acting elements still chromium or related elements of the 6th group of periodic table or boron or contain several such elements at the same time.

Es wurde nun gefunden, daß die Darstellung von Methylalkohol durch katalytische Reduktion von Kohlenoxyd mittels Wasserstoffs oder mittels wasserstoffhaltiger Gase, wobei der Wasserstoff in überwiegender Raummenge angewandt wird, unter Druck und bei erhöhter Temperatur auch dann mit bestem Erfolg möglich ist, wenn man das Gasgemisch bei verhältnismäßig niedrigen Temperaturen, etwa im Bereich von Zoo bis 25o°, über solche Katalysatoren leitet, die außer einem oder mehreren katalytisch wirkenden Elementen noch Vanadin oder Mangan oder beide gleichzeitig, jedoch nicht gleichzeitig neben Mangan noch Chrom oder diesem nahestehende Elemente der 6. Gruppe des periodischen Systems oder Bor oder mehrere solcher Elemente, enthalten. Auch hier besitzt der gebildete Methylalkohol einen hohen Reinheitsgrad.It has now been found that the representation of methyl alcohol by catalytic reduction of carbon monoxide by means of hydrogen or by means of hydrogen Gases, in which the hydrogen is used in the predominant amount of space, under pressure and with the best possible success at elevated temperatures, if you do that Gas mixture at relatively low temperatures, for example in the range from Zoo to 25o °, passes through such catalysts, which except one or more catalytically acting elements nor vanadium or manganese or both at the same time, but not at the same time besides manganese also chromium or elements of the 6th group related to it of the periodic table or boron or several such elements. Even here the methyl alcohol formed has a high degree of purity.

Man kann die Kontaktmasse in der verschiedensten Weise herstellen. Günstige Resultate werden auch bei Verwendung der Sauerstoffsalze des Vanadins oder Mangans mit den katalytisch wirkenden Elementen erhalten; so sind z. B. günstig die Reduktionsprodukte von vanadinsaurem Kupfer oder Silber, mangansaurem Kupfer oder Silber.The contact compound can be produced in a wide variety of ways. Favorable results are also achieved when using the oxygen salts of vanadium or Manganese obtained with the catalytically active elements; so are z. B. cheap the reduction products of vanadium copper or silver, manganese copper or silver.

Beispiel i Ein Gemisch von io Teilen Kohlenoxyd und 9o Teilen Wasserstoff wird bei einer Temperatur von 22o° und einem Druck von etwa ioo Atm. über einen Kontakt geleitet, welcher aus Asbestwolle besteht, auf der ein inniges Gemisch von 5o Teilen Mangandioxyd, 3o Teilen Kupferoxyd, 15 Teilen Kobaltoxyd und 5 Teilen Silberoxyd aufgetragen ist; vor dem Gebrauch wird dieses bei etwa 20o° im Wasserstoffstrom reduziert. Das beim Überleiten des Kohlenoxyd-Wasserstoff-Gemisches austretende Reaktionsgas scheidet beim Abkühlen eine Flüssigkeit ab, welche in der Hauptsache- aus Methylalkohol besteht.Example i A mixture of 10 parts of carbon dioxide and 90 parts of hydrogen is at a temperature of 22o ° and a pressure of about 100 atm. about a Contact passed, which consists of asbestos wool, on which an intimate mixture of 50 parts manganese dioxide, 30 parts copper oxide, 15 parts cobalt oxide and 5 parts of silver oxide is applied; before use, this is about 20o ° reduced in the hydrogen stream. That is when the carbon oxide-hydrogen mixture is passed over exiting reaction gas separates a liquid on cooling, which is in the The main thing - consists of methyl alcohol.

Ein sehr gut wirksamer Katalysator kann auch in folgender Weise gewonnen werden: 17,2 Gewichtsteile Cadmiumcarbonat werden in Wasser unter Zusatz der nötigen Menge Salpetersäure gelöst; hierauf wird eine Lösung von 59,4 Gewichtsteilen Zinknitrat und 28,7 Gewichtsteilen Mangannitrat zugeführt und in der Siedehitze mit Kaliumcarbonatlösung gefällt. Die abfiltrierte Fällung wird gut mit .Wasser gewaschen und auf 25o Volumteile eines Kontaktträgers in erbsengroßen Stücken, z. B. Ton oder Bimsstein, durch gutes Mischen und Trocknen aufgetragen. Der Katalysator wird bei 250 bis 300° im Wasserstoffstrom reduziert.A very effective catalyst can also be obtained in the following way: 17.2 parts by weight of cadmium carbonate are dissolved in water with the addition of the necessary amount of nitric acid; a solution of 59.4 parts by weight of zinc nitrate and 28.7 parts by weight of manganese nitrate is then added and precipitated with potassium carbonate solution at the boiling point. The filtered precipitate is washed well with .Wasser and transferred to 250 parts by volume of a contact carrier in pea-sized pieces, e.g. B. clay or pumice stone, applied by mixing well and drying. The catalyst is reduced at 250 to 300 ° in a hydrogen stream.

Claims (1)

PATRNTANSPRUCH: Verfahren zur Darstellung von Methylalkohol durch Reduktion von Kohlenoxyd mittels Wasserstoffs oder mittels wasserstoffhaltiger Gase, wobei der Wasserstoff in überwiegender Raummenge angewandt wird, in Gegenwart von Katalysatoren unter Druck und bei erhöhter Temperatur, dadurch gekennzeichnet, daß man das Gasgemisch bei verhältnismäßig niedrigen Temperaturen, etwa im Bereich von Zoo bis 25o°, über solche Katalysatoren leitet, die außer einem oder mehreren katalytisch wirkenden Elementen noch Vanadin oder Mangan oder beide gleichzeitig, jedoch nicht gleichzeitig neben Mangan noch Chrom oder diesem nahestehende Elemente der 6. Gruppe des periodischen Systems oder Bor oder mehrere solcher Elemente,. enthalten.-PATENT CLAIM: Process for the preparation of methyl alcohol by Reduction of carbon oxide by means of hydrogen or by means of gases containing hydrogen, the hydrogen being used in a predominant amount of space, in the presence of Catalysts under pressure and at elevated temperature, characterized in that the gas mixture at relatively low temperatures, for example in the range of Zoo up to 25o °, via such catalysts, which except one or more catalytic acting elements nor vanadium or manganese or both at the same time, but not at the same time besides manganese also chromium or elements of the 6th group related to it of the periodic table or boron or several such elements ,. contain.-
DEB108839D 1923-03-03 1923-03-16 Process for the preparation of methyl alcohol by reducing carbon oxide Expired DE600677C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DEB108839D DE600677C (en) 1923-03-16 1923-03-16 Process for the preparation of methyl alcohol by reducing carbon oxide
AT105591D AT105591B (en) 1923-03-03 1923-09-26 Process for the preparation of methanol.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEB108839D DE600677C (en) 1923-03-16 1923-03-16 Process for the preparation of methyl alcohol by reducing carbon oxide

Publications (1)

Publication Number Publication Date
DE600677C true DE600677C (en) 1934-07-28

Family

ID=6992294

Family Applications (1)

Application Number Title Priority Date Filing Date
DEB108839D Expired DE600677C (en) 1923-03-03 1923-03-16 Process for the preparation of methyl alcohol by reducing carbon oxide

Country Status (1)

Country Link
DE (1) DE600677C (en)

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