DE936333C - Process for the production of oxygen-containing hydrocarbon compounds - Google Patents

Description

Process for the production of oxygen-containing hydrocarbon compounds It is known to use carbon monoxide and hydrogen at lower temperatures in the presence converting cobalt, nickel or iron containing catalysts into hydrocarbons. It is also known that higher contents of unsaturated, particularly low molecular weight, hydrocarbons can be obtained obtained if the temperatures are increased to over 400 ° and catalysts are used, which do not contain any metals of the iron group in a catalytically active form, but Oxides of metals of the a. to 7th group of the periodic table. On the other hand is it is known, from olefins after the so-called oxo synthesis, oxygen-containing compounds, especially aldehydes and alcohols. This is initially under increased Pressure and moderately elevated temperatures the olefin in the presence of metals of the iron group, especially cobalt, brought to reaction with carbon oxide-hydrogen mixtures, see above that aldehydes are formed from the olefins by the addition of C O + H2. these can are then reduced to alcohols in a special reduction stage.

It has now been found that this creates a significant technical Progress can be achieved by using the two processes known per se in the Way couples with each other that the first stage at temperatures above 400 °, preferably 55o to 7oo °, produced unsaturated hydrocarbons without being affected by the during gases present in their production are separated, then at reduced Temperatures in the presence of metals of the iron group, predominantly Cobalt, to be brought to further conversion with carbon oxide and hydrogen, whereby aldehydes are obtained immediately. This combination is significantly more advantageous than that known per se of the usual Fischer-Tropsch synthesis process or the like Process with the oxo process, because the invention is much more uniform and let defined products win. While the scale according to Fis ch e r-T r o p s c h hydrocarbons obtained comprises the range from Cl to C25 and higher, are preferably lower molecular weight from the reaction over oxidic catalysts Formed olefins, the number of which usually does not exceed five to ten, the The main part is accounted for by two to four oil fines.

The catalysts and temperatures to be used in the first stage of the new process can be the same as in the known processes already mentioned, e.g. B. one can as with the known under the name isosynthesis, by Pischler and Z iesecke, fuel chemistry 30, 1949, pp 13 and 6o, described method with pressures above 3o atmospheres, preferably 30o to 60o atmospheres, or as according to the British Patent specification 542 836, which prescribes pressures above = 0 at, preferably = 0 to 500 at. It is also known that such unsaturated hydrocarbons can be synthesized under normal pressure.

The pressures can be the same or the same in both stages of the process be different, e.g. B. can in the second stage a higher pressure than in the first Level prevail.

The gas composition can fluctuate within wide limits and the adapt to your needs. As after isosynthesis, there can be a relationship CO: H2 as i, 2: i or as according to British patent specification 542 836 of 3: i up to I: 4 are adhered to. In general, it is when you have both reaction stages considers, most advantageously, C 0-H2 ratios of 0.8: i to i: 1.3 apply.

Also the content of the components to be converted in the synthesis gas can be varied widely. Even if there are often high concentrations of the gas are the most favorable to reacting components, so can also in In some cases thinner gases can be processed with advantage, e.g. B. with 75, 6o% od. like. on CO - [- H2. Gas mixtures produced after Lurgi pressure gasification are particularly favorable were obtained, e.g. B. by gasifying solid fuels with oxygen or oxygen-enriched Air and water vapor under a pressure of about = 0 to 40 at about according to the German Patent 5g2 223 or 565 98i.

Another advantage of the process according to the invention is that the fine purification of the gases does not have to be carried out as far as in the Fischer-Tropsch synthesis with metallic catalysts. According to the invention, in many cases the gas can be used with its entire organic sulfur content, since the oxidic catalysts used are for the most part insensitive to sulfur. Also the second stage of the ver. Driving does not necessarily require removal of the organic sulfur. If the cleaning of the gas from undesired gas components is appropriate in special cases, z. B. the liberation of the gas from sulfur or carbonic acid, the rectisol process according to German patent specification g25 oo6, according to British patents 692 804, 728 444, 734 577, according to French patent I 024 585 and additional patent 64 004 as well as according to the Belgian patents 5o6 = 50 and 514 132 are used, after which at low temperatures below o ° with suitable detergents such. B. organic compounds of polar or polar character, which are in a liquid state at the respective treatment temperature, such as hydrocarbons and / or hydrocarbon derivatives, e.g. B. methanol, ethanol, propanol, acetals, ketones, e.g. B. methyl ethyl ketone, acetone, esters such as methyl, ethyl, propyl or butyl esters, ethers, z. B. diethyl ether, or their mixtures with one another, whereby water can also form a component of the detergent, is used.

Oxygen-containing compounds serve as catalysts in the first stage of metals of the 2nd to 7th group of the periodic table. In, many cases are the oxides are cheapest. Instead of using the oxides as such, you can corresponding other oxygen-containing compounds, such as nitrates or carbonates, use. It is usually advisable to use the catalysts with an activation or Subject to formation process. This is primarily a treatment the catalytic converters with hot gases or vapors, such as hydrogen or water vapor, or treatment with acids. The catalysts are advantageous in one for the Process favorable external shape, z. B. of great mechanical durability, brought, for example in spherical shape or cylindrical shape. They can be used for solidification with binders, such as clay, cement or aluminum gel.

Oxygen compounds are primarily used as catalytically active components of the following metals: zinc, manganese, chromium, aluminum, thorium, molybdenum, Tungsten, titanium, silicon, magnesium, cerium or the like. Of these substances you can one or more may be contained in the catalyst; in the latter case, the Metals of the chemical compounds used from the same or different groups belong to the periodic table. If mixtures of metal compounds are used, so these can already be used as a mixture, e.g. B. by cases of appropriately composed Solutions. In many cases it is also beneficial to use the ingredients of the catalyst or a part of it to manufacture for yourself and subsequently to mix. Particularly favorable combinations are z. B. Thorium Oxide-Aluminum Oxide, Thorium oxide-zinc oxide, aluminum oxide-zinc oxide, aluminum oxide-molybdenum oxide. In this the various metal compounds can be in somewhat the same order of magnitude be represented or one or more of them in subordinate quantities. she then act essentially as activators. For example, aluminum oxide, Zinc oxide, thorium oxide, magnesium oxide or silicon dioxide as predominant Ingredients and other ingredients such as oxides or oxygenated compounds of molybdenum, tungsten, cerium or chromium, use smaller amounts.

In many cases it is advantageous, in addition to the components mentioned, also to use small amounts of metal compounds from Group 1 of the Periodic Table, e.g. B. sodium, potassium, copper and / or silver to have in the catalysts. The addition of alkalis, e.g. B. up to 3 or 5 % K20, in the sense of the formation of higher molecular weight and oxygen-containing compounds.

In these and other cases it is beneficial to undergo further treatment of the catalysts for the purpose of activation, which is particularly important in connection with higher synthesis temperatures often in the sense of an increased formation of low molecular weight Olefins works. The catalysts can be used in pure form or with diluent, z. B. carriers, such as natural or artificial temperature-resistant masses, applied will. As such, for example: silica gel, kieselguhr, fuller's earth, Florida earth, high alumina cement, clay molded masses, and the like are advantageous is often a neutral or weakly alkaline character, as one with such Carriers avoids the reduction of the catalyst efficiency due to the formation of compounds. They can be arranged in a fixed manner in the reaction chamber, if appropriate in such a way that that you withdraw part of it continuously or discontinuously and can replace it with another.

The catalysts can be placed in one or more vessels be. Catalysts from can be used in the individual vessels or in the same vessel of the same or different types.

It can also be the gas to be converted together with dusty or fine-grain catalysts introduced into the lower part of the reaction vessel be, in which the gas is the catalyst in z. B. undulating or whirling motion holds. So it is kept in a floating state during the reaction and can then in the catalyst chamber itself or outside after removal with the gas mixture of the contact space are separated from the gases. The separated catalyst can be used again immediately for the synthesis. He will then again, if necessary replacing a part that has been eliminated, e.g. B. with the synthesis gas, in the catalyst room introduced. Is the catalyst, e.g. B. by mechanical stress, too fine or through approaches of carbon or higher molecular organic compounds Od. Like. Mechanically bonded or are its particles, z. B. by approach formation or sticking together, grown too large or otherwise due to the deposited products If its effectiveness is impaired, it can be subjected to a regeneration process will. This regeneration can take place continuously or discontinuously. Carbon compounds and carbon present on the catalyst can advantageously by oxidation with oxygen, e.g. B. by burning out can be eliminated. Included it is advisable to ensure that the catalyst activity is not too high Temperatures is affected. For example, gas is low first Oxygen content is oxidized and only when the content of combustible compounds has decreased on gases with a higher oxygen content, such as air or pure Oxygen, passed over.

However, there is also the possibility of carbon and carbon compounds get out of the catalyst in other ways, e.g. B. by reduction with Hydrogen, reaction with water vapor after the water gas reaction or similar process, in which the interfering substances are converted into gas or vapor form. Also can you combine the different cleaning methods with each other, e.g. B. with a Mixture of oxygen and water vapor work.

The temperatures of the synthesis of the olefins are essentially above 4oo °, with those above 55o ° being particularly favorable. When using thorium oxide containing Catalysts and very high pressures often come with much lower ones Temperatures off, e.g. B. at 450 °. The uppermost temperature limit is the same as with the known ones Move about 7oo °.

Depending on the catalyst activity, pressure, temperature and residence time and If necessary, circulation of the gases results in a variable conversion and different production yields. As with most others in the gas phase Processes, the use of circulating gases is also advantageous here, a more even gas distribution, especially in order to dissipate the heat of reaction in contact and the difference in the content of gases converted between reduce the beginning and end of contact. The upheaval is becoming better known in and of itself Way done with hot gas blower. You can use those formed in the synthesis Leave products in whole or in part in the cycle. Generally, yields from 3o to 17o g per Nm3 CO + H2 achieved in the inlet gas, of which a high proportion - mostly 50 to 90% - are olefins.

The gases coming from the first reaction stage are used for implementation the oxo reaction expediently directly after a corresponding lowering of the reaction temperature to between 6o and 25o °, advantageously 14o to 18o °, with a different catalyst, which contains metals of the iron group, predominantly cobalt. Here are pressures above 4o atü, z. B. 8o, 1oo and 15o atü, advantageous.

The catalysts can be metallic cobalt as well as others Contain cobalt compounds. So you can finely distribute the cobalt in a tower or slurried in liquid or in the form of a real solution. For example Soaps can be made of cobalt, as they are made by the action of pre-run fatty acids obtained from paraffin oxidation (fatty acids with a chain length of C5 to C11) or use other cobalt salts, possibly also water-soluble. Man can dissolve them in hydrocarbons or other solvents. In this second Reaction stages are formed by incorporation of carbon dioxide and Oxygen-containing hydrogen from the olefins formed in the first stage Compounds, especially aldehydes.

The gases containing carbon monoxide, hydrogen and olefins are conducted or vapors at the temperatures and pressures mentioned in the presence of cobalt compounds through the reaction vessel, a more or less large one is almost always formed Amount of volatile cobalt carbonyl compounds. These can be separated from the gas phase and the cobalt can be fed back into the process while the gas is removed from the process Process can be eliminated or returned to the first stage.

The oxo process can advantageously be carried out in the presence of liquids go, which are chosen so that they absorb the valuable reaction products and that they are expediently only required in small amounts. One obtains here the aldehydes produced are separated from the gases in dissolved form and practically quantitatively. In a subsequent stage, they are subjected to hydrogenation to give alcohols. The liquid is expediently chosen so that it is easy, for example through Distillation, separated from the synthesized oxygen-containing compounds can; z. B. is liquefied petroleum gas, i. H. liquefied propane and butane, well suited. In many cases it is expedient to use all or part of the liquids inherent in the reaction to use. The low-boiling fractions are particularly advantageous here. Man In this way, a separation from a non-reactive solvent is saved.

The catalysts can conveniently be used as slurries in an organic Liquid are used, which from the resulting reaction products easily can be separated e.g. B. boils either above or below this. So you can a finely divided cobalt-containing catalyst, such as that for the Fischer-Tropsch synthesis used cobalt-thorium-kieselguhr contact or thorium-cobalt-magnesium contact, Use slurried in hydrocarbons. This catalyst slurry can but also contain other ingredients, e.g. B. Catalyst carrier such as Mg0, Talc, carbon black or graphite. The slurries are e.g. B. in the printing system of Synthesis introduced by pumping the liquid by high pressure to at least one brings as high a pressure as there is in the system, and through appropriate valves smuggled in.

If you use the catalysts in a slurry, you can one the. No need to add solvents for the catalyst. If the catalyst is moved in the oxo synthesis, it can be parallel or countercurrent to the reaction gases be guided. If a catalyst slurry is finite, it is In many cases, direct current leads are particularly favorable.

The catalyst can also be in the form of volatile compounds, e.g. B. carbonyl compounds, such as cobalt carbonyl, are introduced such that cobalt carbonyl is added in small amounts to the gas to be converted, the carbonyl washed out after the reaction has ended, separated from the detergent and recycled again.

One can also proceed in such a way that one can determine the volatility of the cobalt compounds exploited after formation of carbonyl for the process, e.g. B. in the following way The high pressure tower, in which the oxo conversion takes place, is a porous carrier material filled, mixed with cobalt metal or other cobalt compounds, e.g. B. impregnated, is. In the oxo process, the cobalt is partially volatilized and appears as carbonyl partly in the liquid oxygen-containing reaction products withdrawn, partly in the outflowing reaction gases. The proportion contained in the liquid products precipitates in metallic form in the downstream hydrogenation vessel, in which converts the aldehydes contained in the liquid products into alcohols will. This is designed like the oxygenation vessel, namely with a porous one Filled with material that absorbs the precipitated cobalt. Is the deposition advanced so far that the tower threatens to become blocked, so you switch over and now use this tower for the oxidation reaction and the other one for the hydrogenation. The part of the cobalt carbonyl that is volatile with the gases is washed out by a detergent, z. B. with a part of the resulting after the hydrogenation is high in alcohol Fraction with which the cobalt carbonyl enters the first stage of the hydrogenation process can be traced back.

If necessary, you can choose between the first and the second stage of the method according to the invention part of the synthesized organic compounds remove, especially the higher-boiling part. For example, you can have a Arrange separator, which by cooling to the temperature of the second Stage collects liquefied compounds and allows them to be withdrawn.

Within the first stage, the second stage and then optionally the hydrogenation stage can maintain gas cycles in any known manner will. This can be used both to remove the heat of reaction and to achieve it the correct gas composition, cooling the contact, setting equilibria or happen from other points of view. In the first stage you can for example, maintain a 3 to 2-fold gas cycle. In the oxo level the use of a gas cycle is also appropriate in many cases, e.g. B. in order not to let the temperature rise undesirably or when in use of suspended catalyst this introduced in sufficient quantity To keep gas volume in suspension. The same considerations can also apply to the hydrogenation stage be authoritative.

The oxygenation and hydrogenation can take place in one or in different stages be performed; z. B. can in a first stage a partial oxidation and with the addition of a carbon oxide-hydrogen mixture in a second stage carry out the rest of the oxidation. One can do this in the first stage of the process convert a large part of the olefins and the rest of the olefins with freshly supplied gas react in the second stage. One achieves on this Way in many cases a more favorable conversion of the olefins.

A similar procedure can also be used for the hydrogenation of the aldehydes. So you can z. B. work first with hydrogen, which also contain carbon oxide can to drive off the carbon dioxide dissolved in the aldehydes and the cobalt carbonyl to decompose. If you use the interchangeable oven system outlined above works, is the use of a diluted or carbon dioxide-containing hydrogen therefore favorable because then the distribution of the precipitated cobalt metal is not but confined to a narrow zone near the entry of the liquid is pulled apart into another area. Switching over the catalyst vessels then needs to be carried out less frequently.

Example Water gas produced from coke with an organic content of 15 mg bound sulfur j e Nm3 gas and a carbon oxide-hydrogen ratio of about i: i was made in a synthesis stage using oxidic catalysts implemented. Then the gas with the reaction products contained therein treated further in an oxo stage. -After separation of the oxygen-containing products from the gas coming from the oxo stage, this became the first reaction stage recycled, while the separated oxygen-containing products, mainly Aldehydes, one consisting of two reaction stages with separate gas circuits Have been subjected to hydrogenation.

The synthesis furnace operated under 100 at was equipped with catalyst tubes from = o mm 1. W., which were surrounded by a molten salt. The molten salt was circulated in a known manner with the aid of a pump. At the beginning of operation the melt was heated electrically to get the reaction going (circulation and heating are not shown in the drawing). After the onset of the reaction the heating was turned off and the melt was used to discharge the resulting Heat of reaction that was withdrawn from it by cooling outside the furnace.

The catalyst was applied in molded pieces of 3 to 5 mm in diameter. It consisted essentially of aluminum oxide with additions of about 8% molybdenum oxide, 0.5 per cent. chromium oxide and 1.2 per cent. tungsten oxide. The fresh synthesis gas that is produced by the Line 33 arrived, was passed through the catalyst from top to bottom with a Gas load of around 5o Nm3 gas per hour per 6o 1 contact. The reaction temperature was about 58o °. At the same time were over the catalyst by means of the pump 2 and through lines 24 and 25 450 m3 of gas each 6o 1 contact and hour in the circuit circulated. A quantity of fresh gas corresponding to the amount of fresh gas was passed through lines 22 and 23 Amount of gas and reaction products transferred to the oxo stage.

The oxo stage operated under the same pressure as the synthesis furnace. It essentially consisted of a high-pressure furnace 3 at the head and foot end Connections for the discharge and supply of gases and liquids had. Of the The furnace was surrounded by a jacket for pressurized boiling water. There were cooling tubes in the furnace arranged, which also contained boiling pressurized water. When commissioning the The furnace was heated using the furnace system, for which purpose steam and pressurized water were introduced into the heat exchange rooms. When the reaction temperature is reached and the reaction started, the heat supply was turned off. The heat of reaction was then absorbed by the pressurized water with the formation of steam.

In the oxo stage, a saturated cobalt nitrate solution was used as a catalyst Soaked, coarse-pored pumice stone used. After the impregnation was the catalyst dried and reduced with hydrogen before being placed in the furnace became.

The gases and vapors coming from the synthesis furnace i were introduced into the lower part of the reaction vessel 3. The gas containing the reaction products of the oxo stage flowed off at the upper end of this reaction vessel and was passed through a tower 4 filled with Raschig rings in the direction from top to bottom. In the tower 4, cobalt carbonyl contained in the gases and vapors was washed out by sprinkling with a washing liquid supplied at 18. A fraction of the synthesis products boiling up to == o ° was used as the detergent. It came from the tower 4 through the line 26 into the reaction vessel 3, to which it was fed by means of a distributor plate arranged in the upper part of the vessel. In the reaction vessel 3, the washing liquid took up the aldehydes which were formed here from the olefins produced in the synthesis stage i, as well as other oxygen-containing compounds and a large part of the carbonic acid formed in the synthesis furnace i. This solution was drawn off from the lower part of the reaction vessel 3 through the line 27 into the vessel 5, in which it was cooled. It was then depressurized by means of the valve 6, releasing carbon dioxide, carbon dioxide and hydrogen and passed into the separating vessel 7. The gases separating from the solution in the separating vessel 7 were passed into the scrubber 8, in which small amounts of cobalt carbonyl contained in the gases were separated with a small portion of fresh washing liquid. The scrubbing liquid entered the scrubber 8 through the lines 18 and 30 and, after it had been used there to treat the gases, was conveyed through the lines 29 and 18 into the tower 4 by means of the pump = g.

The gases flowing out of the washing tower 4 were z. B. with a circulation pump g returned to the reaction vessel 3 of the oxo stage, namely 3oo Nm3 of gas circulated per hour. Part of the gas, the amount of which is that of the oxo stage Gas and steam volume corresponded, was through line 2i in the synthesis furnace i returned. By branching off a corresponding part of the gas at = o off the cycle became the Inert gases contained in the fresh gas removed from the system.

The solution freed from gases in the separation vessel 7 and containing the oxygen-containing Compounds -containing, was brought to 80 atm pressure by means of the pump ii and with this pressure is fed through line 31 to the hydrogenation vessel 12, which is in the same Was designed like the reaction vessel of Oxo level 3. It was also with Coarse-pored pumice stone, which, however, has not been previously impregnated with cobalt nitrate solution had been introduced into the vessel 12.

While the oxo reaction in vessel 3 proceeded at about 170 ° and there the reaction gases had a residence time of 18 seconds was used in the first hydrogenation stage 12 maintain a temperature of about 160 °. This were done by the pump 13 100 Nm3 hydrogen circulated every hour.

Gases, in particular, entered the hydrogen cycle from the liquid Carbonic acid and carbonic oxide, which are still in the liquid during relaxation in 6 were left behind, so that the hydrogen contained a few percent of these substances recorded.

The liquid and hydrogen were at the top of the reaction vessel 12 initiated. In 12, some of the aldehydes contained in the liquid converted into alcohols. Cobalt carbonyl still present in the liquid was completely destroyed, and the cobalt released from the carbonyl was found to be deflated on the carrier mass of the vessel 12 down.

Part of the gas cycle passed through vessel i2 Gas branched off through line 32 after the synthesis furnace i, the pump 2o brought the gas to the pressure required for the synthesis. To the extent that Hydrogen consumed in the hydrogenation stage 12 and discharged through line 32 was, the hydrogen from the last hydrogenation stage 14 was through line 37 added.

The liquid mixture leaving the reaction furnace 12 through the line 34 was fed by means of the pump 15 through the line 35 to a second hydrogenation vessel 14 at the top. In the hydrogenation vessel 14, the same pressure as in 12, but a temperature of 1g5 °, was maintained. The gas was passed through the hydrogenation vessel 14 from bottom to top in countercurrent to the liquid. 350 Nm3 of hydrogen per hour were circulated through the pump 16 and the circuit line 36. At 17, fresh hydrogen was introduced into the hydrogenation vessel 14, which was also charged with a cobalt-containing catalyst and was designed similarly to the vessel i2.

In the first hydrogenation vessel 12, the liquid was treated with the hydrogen in cocurrent so that cobalt carbonyl could not be flushed out of the liquid added above and removed with the reaction gases by the hydrogen; which would cause cobalt losses. This possibility of loss does not apply to the operation of the second furnace, so that it was possible to work in the countercurrent of gas and liquid. In the reaction products which left the second hydrogenation stage 14 through line 39 , the unsaturated hydrocarbons produced in the synthesis furnace i were present in a yield of about 90% in the form of alcohols, and 3% had been converted into higher molecular weight compounds.

Per Nm3 of that introduced into the first reaction stage with the fresh gas In the process according to the invention, carbon monoxide and hydrogen were the following reaction products obtained: i2o g propyl alcohols, 32 g butyl alcohols, 18 g amyl alcohols and about 32 g of a mixture of higher alcohols. Fetner produced 12 g of hydrocarbons.

After prolonged operation it was found that the formation of Koebalt carbonyl in reaction vessel 3 and the entrainment of the cobalt carbonyl from the liquid products in the first hydrogenation vessel 12 a depletion of catalytically active cobalt metal in reaction vessel 3 and an accumulation of cobalt on the catalyst in the hydrogenation vessel 12 took place, leading to a gradual increase in the flow resistance in the vessel 12 led. After the flow resistance that the gases in the first hydrogenation vessel i2 found had increased noticeably, the hydrogenation furnace 12 was used as an oxo furnace in place -The reaction vessel 3 switched, during this now as the first, hydrogenation stage served. This switchover was repeated from time to time when the impoverishment of the catalyst on cobalt in one vessel and the increase in flow resistance required this in the other vessel.

To regulate the gas ducts, the necessary known devices, such as valves, measuring devices and the like Positions 38 may be provided.

Claims (7)

PATENT CLAIMS: i. Process for the production of oxygen-containing hydrocarbon compounds by the addition of carbon oxide and hydrogen to hydrocarbon compounds containing double bonds in the presence of catalysts, the metals of the iron group; predominantly cobalt, characterized in that, in a first stage, unsaturated hydrocarbons, optionally in addition to oxygen-containing hydrocarbon compounds, are obtained by reacting gases containing carbon oxide and hydrogen at temperatures above 400 °, preferably from 55o to 700 °, in the presence of catalysts, which are essentially free of those compounds of the metals of the iron group which are catalytically active and which contain oxygen-containing compounds of the metals of the 2nd to 7th group of the periodic table which cannot be reduced under synthesis conditions or which can only be reduced to a lower valency, and then in a second 'Stage brings the reactants, after cooling to much lower temperatures, in the presence of catalysts containing metals of the iron group, predominantly cobalt, to convert with the formation of oxygen-containing compounds from the olefins. 2. Procedure according to Claim i, characterized in that temperatures between 6o and 25o ° and pressures above q.o atü can be selected. 3. The method according to claim i and 2, characterized in that a gas cycle is maintained that the converted gas of the first stage after lowering the temperature in the second stage and then, if necessary, in a deposition in which the two stages produced Liquefiable reaction products are deposited, whereupon the gas leads to first stage is returned, optionally with the addition of fresh carbon monoxide-hydrogen containing gas. q .. Method according to claims i to 3, characterized in that a complete or partial separation of higher molecular weight between the two stages Hydrocarbon compounds or optionally oxygen-containing hydrocarbon compounds by liquefaction, washing out or adsorption or combinations of these measures is effected and only the lower molecular compounds with the gas in the second Reaction stage are performed. 5. The method according to claim i to q., Characterized in, that the gases leaving the second reaction stage of compounds of the metals of the iron group before they are returned to the first stage. 6. The method according to claim i to 5, characterized in that the reactions in the first stage are carried out in apparatus in which the reaction gases do not come into contact with iron walls. 7. The method according to claim i to 6, characterized in that the aldehydes formed in the second stage are reduced in a third stage with hydrogen-containing gases to alcohols. B. The method according to claim i to 7, characterized in that the reaction in the second stage is carried out in the presence of a liquid preferably formed by the synthesis. G. Process according to Claims i to 8, characterized in that the reaction in the first stage is carried out with finely divided powdery catalyst in such a way that the solid, powdery catalyst is swirled upwards by the gas fed in at the bottom and kept in suspension or out of the Reaction chamber is carried out, whereby the parts of the catalyst damaged by transition into too small particles or carbon deposition or the like. Removed from the system and replaced by fresh catalyst. ok Process according to Claims i to g, characterized in that the heat of reaction is dissipated by heat-absorbing surfaces, circulation of gas or addition of heat-absorbing liquids. Referenced publications: German patent specification No. 896 338.