DE863654C - Process for the oxidation of methane or its homologues - Google Patents

Process for the oxidation of methane or its homologues

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Publication number
DE863654C
DE863654C DEG5346A DEG0005346A DE863654C DE 863654 C DE863654 C DE 863654C DE G5346 A DEG5346 A DE G5346A DE G0005346 A DEG0005346 A DE G0005346A DE 863654 C DE863654 C DE 863654C
Authority
DE
Germany
Prior art keywords
homologues
methane
oxidation
reaction
formaldehyde
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
DEG5346A
Other languages
German (de)
Inventor
Paul Nashan
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.)
Gutehoffnungshutte Oberhausen AG
Original Assignee
Gutehoffnungshutte Oberhausen 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 Gutehoffnungshutte Oberhausen AG filed Critical Gutehoffnungshutte Oberhausen AG
Priority to DEG5346A priority Critical patent/DE863654C/en
Application granted granted Critical
Publication of DE863654C publication Critical patent/DE863654C/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/04—Formaldehyde
    • 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
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • 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
    • 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
    • C07C45/37—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 >C—O—functional groups to >C=O groups
    • C07C45/38—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 >C—O—functional groups to >C=O groups being a primary hydroxyl group
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/75—Reactions with formaldehyde

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Oxydation von Methan oder seinen Homologen Die Erfindung betrifft ein Verfahren zur Oxydation von Methan und seinen Homologen zu Formaldehyd unter Verwendung von Sauerstoff oder Luft in Anwesenheit von Stickoxyden und Alkaliboraten als feste Katalysatoren, wobei die Reaktion des Gasgemisches unter erhöhtem Druck im Kreislaufprozeß durchgeführt wird. Praktische Versuche mit diesem Verfahren haben gezeigt, daß das an sich naheliegende und auch zunächst benu - tzte Verhältnis von 02: CH4 = i : i, also das stöchiometrische, praktisch gebraucht werden kann. Allerdings wurde beobachtet, daß ein Fahren der Reaktion unter Druck bei 'stöchiometrischem Verhältnis der Reaktionskomponenten niit Schwierigkeiten verbunden ist.Process for the oxidation of methane or its homologues The invention relates to a process for the oxidation of methane and its homologues to formaldehyde using oxygen or air in the presence of nitrogen oxides and alkali borates as solid catalysts, the reaction of the gas mixture being carried out under increased pressure in the circulation process . Practical tests with this method have shown that the nearby se and also first benu - assisted ratio of 02: CH4 = i: So the stoichiometric, can be practically used i. However, it has been observed that running the reaction under pressure at a stoichiometric ratio of the reaction components is associated with difficulties.

Das Reaktionsgemisch neigt zu spontanen Erhöhungen der Temperatur im Reaktionsraum. Dadurch treten lokale Überhitzungen auf, die zur Zersetzung des gebildeten Formaldehyds und zur Bildung von CO" CO und H, als Nebenprodukten führen. Diese Erscheinungen bessern sich, wenn das Verhältnis 0, : CH, oder seinen Homologen verkleinert wird.The reaction mixture tends to spontaneously increase the temperature in the reaction space. As a result, local overheating occurs, which leads to the decomposition of the formaldehyde formed and to the formation of CO "CO and H, as by-products. These phenomena improve when the ratio 0,: CH, or its homologues is reduced.

Es zeigte sich nun überraschenderweise, daß die Formaldehydbildung besonders dann begünstigt wird, wenn man dieses Verhältnis auf einen Wert im Gebiet zwischen 0,5 und 0,3 einstellt. Obwohl dadurch der 02-Partialdruck im Reaktionsgemisch, das dem Kreislaufgemisch zufließt, entscheidend verkleinert wird, wächst die unter denselben sonstigen Bedingungen erhaltene Menge Formaldehyd je Quadratzentimeter Querschnitt des Reaktionsraumes um 2o bis 25 "/, an. Es liegt auf der Hand, daß so bei der praktischen Durchführung des Verfahrens Energie sowohl für den Transport des notwendigen Oxydatiohsmittels als auch für- das -Aufheizen des Reaktionsgemisches gespart wird.It has now been found, surprisingly, that formaldehyde formation is particularly favored if this ratio is set to a value in the range between 0.5 and 0.3 . Although this significantly reduces the O2 partial pressure in the reaction mixture that flows into the circulation mixture, the amount of formaldehyde obtained under the same other conditions increases by 20 to 25 "per square centimeter of cross-section of the reaction chamber. It is obvious that this is the case the practice of the process energy for both the transport of the necessary Oxydatiohsmittels and by-the - the reaction mixture is heated saved.

Das erfindungsgemäße Verfahren ist sinngemäß auch auf die niederen, d. h. sowohl auf die gesättigten als auch auf die ungesättigten Glieder der Paraffinreihe anwendbar.-Beispiel Ein Gemisch von Methan, Luft und kleiner Menge Stickoxyden wurde im Kreislauf durch einen Reaktionsofen geführt, der mit einein aus Alkaliborat bestehenden Katalysator beschickt war und von außen erhitzt wurde. Die Geschwindigkeit des Reaktionsgernisches betrug etwa 40 cm/sec. Bei einem Volumenverhältnis von Sauerstoff'zu Methan gleich i. i betrug die stündliche Äusbeu'te 82,o g HCOH je Stunde. Bei einem Volumenv#rhältnis von Sattärstoff zu Methan gleich 0,5: 1 gemäß der Erfindung wurde dagegen eine stündliche Ausbeute von 98,9 g HC OH erhalten, das sind 2o,70/, mehr als bei Anwendung des stöchiometrischen Verhältnisses.The method according to the invention is analogously also applied to the lower, i.e. H. applicable to both the saturated and unsaturated members of the paraffin series. Example A mixture of methane, air and a small amount of nitrogen oxides was circulated through a reaction furnace charged with a catalyst consisting of alkali borate and externally heated. The speed of the reaction mixture was about 40 cm / sec. With a volume ratio of oxygen to methane equal to i. The hourly output was 82.0 g HCOH per hour. With a volume ratio of saturant to methane equal to 0.5: 1 according to the invention, on the other hand, an hourly yield of 98.9 g HC OH was obtained, that is 20.70 /, more than when the stoichiometric ratio was used.

Claims (1)

PATENTANSPRUCH: Verfahren zur Oxydation von Methan und seinen Homologen zu sauerstoffhaltigen Derivaten, vorzugsweise zu Formaldehyd, in Gegenwart von kleinen Mengen von Stickoxyden und festen, Alkaliborate enthaltenden Katalysatoren, bei Drücken zwischen i und 12 ata im Kreislaufverfahren', -dadurch gekennzeichnet, daß das Volumenverhältnis zwischen 0, und CH4 oder seinen Homologen bei etwa 0,5 und darunter liegt. PATENT CLAIM: Process for the oxidation of methane and its homologues to oxygen-containing derivatives, preferably to formaldehyde, in the presence of small amounts of nitrogen oxides and solid catalysts containing alkali borates, at pressures between 1 and 12 ata in the cycle process', characterized in that the volume ratio between 0 and CH4 or its homologues at about 0.5 and lower.
DEG5346A 1951-02-25 1951-02-25 Process for the oxidation of methane or its homologues Expired DE863654C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEG5346A DE863654C (en) 1951-02-25 1951-02-25 Process for the oxidation of methane or its homologues

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEG5346A DE863654C (en) 1951-02-25 1951-02-25 Process for the oxidation of methane or its homologues

Publications (1)

Publication Number Publication Date
DE863654C true DE863654C (en) 1953-01-19

Family

ID=7117743

Family Applications (1)

Application Number Title Priority Date Filing Date
DEG5346A Expired DE863654C (en) 1951-02-25 1951-02-25 Process for the oxidation of methane or its homologues

Country Status (1)

Country Link
DE (1) DE863654C (en)

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