DE628557C - Production of oxygen-containing organic compounds - Google Patents

Description

Production of Oxygen-Containing Organic Compounds Various processes are known in which, by catalytic conversion of the oxides of carbon by means of hydrogen, methyl alcohol and other, higher molecular weight, oxygen-containing organic compounds are obtained. To obtain the latter, alkaline contacts have been used so far, in particular in accordance with patent 625 757.

It has now been found that even with alkali-free contacts one can achieve considerable Quantities of higher molecular weight compounds can be obtained when using contact compounds, which contain hydrating and hydrating or dehydrating ingredients and works under conditions where the hydrating effect of the contacts exceeds the hydrogenating end.

Both metals, such as. B. copper, Silver, gold, tin, lead, antimony, bismuth, zinc, cadmium, thallium, as well as oxides, such as B. the oxides of the above metals are used. As hydrating ingredients are called the oxides of titanium, zircon, thor, vanadium, niobium, manganese, cerium, lanthanum, Tantalum, chromium, molybdenum, tungsten, uranium, didymes, beryllium, aluminum, etc.

In general, the above contacts increase the hydrating effect on mixtures of oxides of carbon and hydrogen with their content of hydrating Components, with the carbon dioxide content of the gas mixture and with the temperature. The hydrating effect of the contact masses generally exceeds the hydrating effect Effect when the components of the contact masses are used in such proportions chooses that both are calculated on oxides, on each mole of the hydrogenating more than one Moles of hydrating ingredients are omitted. However, even with contact masses, which do not have the mentioned proportions of the two components that hydrating effects exceed the hydrating when the contact masses at higher than that required in each case for the formation of methyl alcohol Temperatures are brought into effect. The latter contact masses can also show a predominantly hydrating active trough, if one gas mixtures used whose carbon dioxide or carbon dioxide-hydrogen ratio is greater than is the ratio calculated for the formation of methyl alcohol.

To avoid undesirable side reactions, such as carbon deposition, Formation of hydrocarbons and the like, it is necessary for the absence of metallic iron, cobalt and nickel in the contacts and the contact furnace and carefully remove iron carbonyl from the gas.

Applying a higher pressure than Zoo Atm. causes an improvement of the raw product by removing certain unpleasant smelling components Working at Zoo Atrü. or under it sometimes arise with, significantly diminished and in many cases even disappear completely. Example i One made from cadmium chromate Prepared contact, the one at 3! 50 ° and with one of 1 part carbon oxide and 3, parts Hydrogen compound gas mixture at Zoo Atm. almost exclusively methyl alcohol would deliver, gives at 420 ° and the same gas mixture, or at 35o ° and one gas mixture consisting of 3 parts of carbon oxide and 2 parts of hydrogen, considerable Amounts of higher alcohols, ketones, esters, acids, etc.

Almost the same products are obtained at 350 ° with a hydrogen-rich one Gas mixture, if the cadmium chromate also contains other hydrating constituents, e.g. B. 5oo; o manganese oxide, are added.

Instead of cadmium chromate, other compounds such as copper vanadinate, zinc manganate, lead molybdate, bismuth zirconate, silver aluminate, or mixtures of the corresponding oxides or z. B. Use contacts made from 3 parts zinc oxide and 2 parts tungstic acid, 2 parts thallium oxide and 1 part uranium oxide or from - parts zinc oxide, 1 part copper oxide, 1 part chromic acid and 1 part manganese oxide. EXAMPLE 2 A catalyst which was prepared by pasting with a small amount of water and subsequently drying a mixture consisting of copper oxide, vanadium pentoxide and manganese oxide in a molecular ratio, yields when a gas mixture consisting of 1 part carbon oxide and 2 parts hydrogen is passed over at a pressure of zoo atm . at q.30 ° considerable amounts of a mixture of higher alcohols, ketones, esters, acids, etc.

Example 3 When one is passed over from 1 part carbon oxide and 2 parts Hydrogen gas mixture under a pressure of Zoo Atm. at q.50 ° above Zinc molybdate is a mixture of oxygen-containing organic compounds, which in addition to about 450% methanol contains about 2o0 / 0 isobutyl alcohol and 15% water. The rest consists mainly of organic acids, ketones and esters. Same At 400 to 40 ° C, under otherwise identical conditions, the catalyst yields almost pure products Methanol. Example 4 Makes a carbon dioxide-hydrogen mixture containing about 5.5 / "carbon under a pressure from Zoo Atm. passed at 39o ° over a catalyst, which from one part of tungstic acid and two parts of copper oxide, there are copious amounts higher alcohols, ketones, aldehydes, esters and acids. If you use one out of 25% Gas mixture consisting of carbon oxide and 75% hydrogen under otherwise identical conditions, in contrast, methanol is produced almost exclusively.

Claims (3)

PATENT CLAIMS: i. Variant of the process according to Patent 625 757, additional patent 544,665, high molecular weight for producing organic compounds. in particular alcohols and the like, from the oxides of carbon, characterized in that contact materials are used which contain constituents with a hydrating and hydrating action in such a way that their hydrating effect exceeds the hydrating effect. 2. Embodiment of the method according to claim i, characterized in that that the proportions of the hydrogenating and hydrating constituents of the Contact masses are chosen such that, both calculated as oxides, to i = moles each of the hydrating more than one mole of the hydrating constituents is omitted. 3rd embodiment of the method according to claim i, characterized in ;. -that one when using of contact masses in which per i mole of hydrogenating not more than i mole of hydrating Components are omitted, works at temperatures, which are higher than that required for the formation of methyl alcohol by means of the same contacts required are. q .. embodiment of the method according to claim =, thereby characterized in that when using contact materials in which i mole of each Hydrogenating not more than 1 mole of the hydrating constituents is not required, gas mixtures are used in which the ratio of carbon oxide or carbon dioxide to hydrogen or hydrocarbon is greater than calculated for methyl alcohol formation.