DE931405C - Process for the production of alcohol-like compounds from oxygen-containing carbon compounds, which are formed by the catalytic addition of carbon oxide and hydrogen to unsaturated carbon compounds - Google Patents

Description

Process for the production of alcohol-like compounds from oxygen-containing compounds Carbon compounds produced by the catalytic addition of carbon monoxide and hydrogen of unsaturated carbon compounds It is known that unsaturated carbon compounds especially olefin hydrocarbons, through catalytic addition of carbon monoxide and hydrogen at elevated pressure and temperature in so-called oxo compounds convict. The main conversion catalysts used here are iron, cobalt or nickel contacts use, expediently in connection with suitable carriers, such as B. kieselguhr, and activating additives, e.g. B. thorium, magnesium or manganese compounds. The accumulation of water gas forms on the existing olefinic double bonds essentially ketones and aldehydes, within the reaction mixture Saturated carbon compounds present in the starting mixture, in particular Paraffinic hydrocarbons, remain unaffected.

It has been found that the oxo compounds formed in this way easily and with good yield in corresponding alcohol links can be transferred if you use them using the water gas attachment used Contacts or other suitable catalysts with hydrogen-containing gases treated at temperatures and hydrogen partial pressures that are higher than those that were used in the previous catalytic water gas attachment found.

The reduction of aldehydes and ketones also mixed with paraffin hydrocarbons is known per se. From this, however, it was not evident that directly following the catalytic what sergasanlagung (oxo synthesis) without operational difficulties allows a smooth and satisfactory alcohol extraction to be carried out.

Despite various types of oxygen binding and extensive fluctuations in the mutual quantitative ratio of the oxo compounds, the reduction goes extremely well smoothly and clearly in front of you, so that without the formation of saturated hydrocarbons only alcohols are formed. With regard to achieving good yields, this is not the case Formation of paraffinic hydrocarbons is of particular importance. In particular This is because saturated hydrocarbons (e.g. ethane) are not or only under large losses can be converted back into the corresponding olefins.

As a catalyst for those following the carbon dioxide-hydrogen addition Reduction can use the usual hydrogenation catalysts, such as. B. finely divided nickel, Platinum or palladium can be used. But you can also use the same catalysts work that are used in water gas accumulation.

Furthermore, the following must be observed: The in the case of catalytic water gas accumulation resulting products always contain more or less large amounts of the used Catalyst in the form of organometallic compounds of unknown composition. When using cobalt-containing contacts, the starting product according to the invention maintains of alcohol production, Id. h. the end product of the catalytic olefin-water gas condensation, to be colored deep dark red-brown.

These metal compounds are used in a completely surprising manner the subsequent hydrogen addition decomposed, and on the one hand one obtains completely metal-free, colorless alcohols and, on the other hand, gains that for water gas attachment required reduced contact metal back in excellent activity. His Because of its fine distribution, it can be used again immediately for water gas storage will.

The new way of working combines alcohol production with one Purification of the water gas accumulation products and with a very efficient regeneration of the catalyst used.

In this way, the cumbersome work-up of the resulting oxygen-containing intermediates avoided. This is a significant fact Significance because the organometallic compounds that occur often only see each other difficult to remove and give rise to undesirable metal losses.

It should also be noted that the reaction products of the preceding Water gas deposits by no means only consist of defined aldehydes.

Depending on the type of olefins processed and depending on the Reaction conditions arise at the same time more or less large amounts of high molecular weight By-products of unknown constitution. One would use the aldehydes or aldehyde mixtures refine beforehand and only then treat with hydrogen, that would be the yield considerably less. In the new process, the yield is monomolecular However, alcohols are higher because the hydrogen attachment of the water gas attachment immediately follows, without any cleaning or removal of the Contact metal is made. The undesirable high molecular weight by-products unknown constitution are not in the procedure according to the invention in a predictable way degraded to simple aikd fetch, so that they have a corresponding Induce an increase in yield.

Further details can be found in the following exemplary embodiments evident.

Embodiment 1 It was slurried in 10 kg of a synthetic Light petrol, which boiled between 47 and 1450, contained 29 volume percent olefins and had a density of 0.667 (D20), 200 g of a cobalt-thoriuhi-nagnesium-kieselguhr catalyst which contained approximately 25 ovo cobalt. The suspension obtained was under vigorous stirring in an autoclave for 3 hours with water gas at one pressure of around 120 atü and treated at a temperature of 100 to 120 °. The reaction mixture absorbed approximately 1200 to 1300 normal liters of CO + H2. After attaching this The amount of gas with which CO and H2 were absorbed in an approximately 1: 1 ratio occurred no further gas uptake occurs at the specified maximum temperature of 120 °.

Then the carbon oxide-containing gas was replaced by hydrogen, the temperature increased and held at IgO ° for 3 hours. During this time took the reaction mixture has 1360 normal liters of hydrogen.

The obtained reaction product was removed by filtration from the catalyst severed. There were no aldehyde or ketone reactions and showed a density of 0.7in6. The start of boiling was 450, to 1450 680 / o, to 2300 900/0.

The decrease in volume with P2 O5 sulfuric acid was approximately 260/0. The olefins originally present were therefore with an increase in the Molecules have been converted into alcohols by one carbon atom at a time.

Embodiment 2 In 5 kg of a synthetically obtained, in the area from 243 to 21550 boiling, 420/0 olefins contain hydrocarbons of the density 0.770 300 g of a cobalt-thorium-alagnesium-kieselguhr catalyst were which contained 25 01 <> cobalt, slurried. Treated with vigorous stirring keep these suspensions in an autoclave at approximately 150 for 4 to 5 hours atü and at a temperature of I350 with water gas. This became approximately 1100 Normal liters of CO + H2 added. After this gas uptake had elapsed, no gas occurred at I350 more gas uptake.

The temperature was then increased to 190 ° and the water gas pressure to 400 atü increased. Now there was renewed uptake of gas, and that was among these Conditions within 5 hours of approximately 1000 liters of gas. The received and the reaction product separated off from the catalyst showed the following key figures: Start of boiling: 2430 to 255 °: 36% by volume to 282 °: 6 I, 5 -due to cleavage that occurred the boiling analysis is not pursued any further.

Density at 20 ° ............... 0.805 hydroxyl number ...... ......... 99 Neutralization number .. ............ I, 0 Saponification number .....: ............ I, 5 Carboxyl number .................... I, 0 As the analytical data above show, are the originally present olefins with an enlargement of the molecule by an I C atom have been converted into products with alcoholic hydroxyl groups with great purity. The boiling numbers and the hydroxyl number indicate that a wide range of pentadecyl alcohol was created.

Claims (1)

PATENT CLAIM: Process for the production of alcohol-like compounds from oxygen-containing carbon compounds, which are produced by catalytic addition from carbon oxide and hydrogen to unsaturated carbon compounds, characterized in that the catalytic addition of carbon monoxide and hydrogen on unsaturated carbon compounds obtained in accordance with patent 849,548 Immediate reaction mixtures, if appropriate after addition of hydrogenation catalysts with hydrogen-containing gases at higher temperatures and higher hydrogen partial pressures treated as those involved in catalytic water gas attachment to the unsaturated starting carbon compounds were used, whereby one the introduction of hydrogen is interrupted as soon as that required for alcohol formation Amount of hydrogen is absorbed. Cited publications: German Patent No. 660 61 9; french U.S. Patent No. 593,648; British Patent No. 4783I8; Journ. amer. chem. soc., 52, p. 3231.