DE1149123B - Process for the catalytic hydrogenating refining of hydrocarbon mixtures with substantial contents of aliphatic and cyclic diolefins and acetylene derivatives - Google Patents

Description

GERMAN

PATENT OFFICE

F 32070 IVd / 23b

REGISTRATION DATE: SEPTEMBER 8, 1960

NOTIFICATION
THE REGISTRATION
ANDOUTPUTE
EDITORIAL: MAY 22, 1963

When splitting petroleum, petroleum fractions or hydrocarbon mixtures, such as those from coal, Oil shale or other fuels are obtained at very high temperatures, e.g. B. 700 to 900 ° C, result in liquid hydrocarbon mixtures, which contain larger amounts of very reactive compounds, such as B. Diolefins with cumulative, conjugated and isolated double bonds, cyclodiolefins, aromatics in unsaturated side chains, acetylene derivatives and others. contain. These substances, for example which includes cyclopentadiene, diallyl, allene, 1,3-pentadiene and cyclohexadiene and derivatives thereof, tend to form polymers in the liquid phase, particularly at elevated temperatures. on the tendency of these substances to polymerize can be attributed to the difficulties encountered during heating of the input material to the evaporation temperature as well as the evaporation and the required subsequent heating of the gas-vapors mixture to reaction temperatures occur. Because of the tendency of these substances to polymerize, they form particularly in the devices for heating and evaporation of the hydrocarbon mixtures approaches or incrustations that are in can lead to clogging of the equipment for a short time. Furthermore, the catalysts that are used for the Hydrogen refining can be used, often in a very short time by loading with polymerization products or the effect of carbon is damaged. Numerous procedures have already been developed have been used to combat these difficulties.

Attempts have been made to overcome these disadvantages by dividing the hydrogen refining into two stages. This should in the first stage by adjusting the working conditions such as residence time and temperature, first the highly unsaturated hydrocarbons are hydrogenated to give high pressure and below 300 ⁰ C in the presence of catalysts, the oxides or sulfides of metals of the V to VIII Contained group of the periodic table, and was worked with supply of hydrogen. The gasolines prehydrogenated in this way were then subjected to further refining under normal or moderately increased pressure.

Similarly, in the case of mineral spirits and similar hydrocarbon fractions, a process also fails after which the starting material is first heated under pressure to at least 100 ° C. and combined with a small amount of hydrogen, e.g. B. 20 to 5001 per kilogram of starting material, in the Tempe process for catalytic hydrogenating

Refining of hydrocarbon mixtures with substantial aliphatic contents and cyclic diolefins and acetylene

derivatives

Applicant:

Farbwerke Hoechst Aktiengesellschaft formerly Master Lucius & Brüning,

Frankfurt / M., Brüningstr. 45

Dr. Wolfgang Kirschner,

Frankfurt / M.-Unterliederbach,

Dipl.-Ing. Dr. Günther Lipphardt

and Dr. Heinrich Haunschildt,

Frankfurt / M.-Höchst, have been named as inventors

The co-inventors have requested not to be named

Temperature range between 100 and 250 ° C in predominantly liquid phase pre-hydrogenated over a catalyst. The pre-hydrogenated starting material is then expediently under the same pressure in an evaporator with a larger amount of heated hydrogen, e.g. B.

0.5 to 3 m ³ per kilogram of starting material, largely evaporated. The evaporated fractions are then further heated together with hydrogen, catalytically refined in the temperature range between 300 and 450 ° C and the reaction products are cooled together with the hydrogen. After the gaseous and liquid components have been separated in a separator, the hydrogen-containing gas is fed back into the process and the liquid components are expanded.

In this process, the effectiveness of the prehydrogenation catalyst is relatively low quickly, even in the vaporizer difficulties arise due to deposits. The approach formation makes but are particularly noticeable when heating up the feed gasoline and in the pre-hydrogenation. Similar difficulties arise when heating the vaporized and pre-hydrogenated gasoline to

309 597/295

action temperature and catalytic refining on.

These difficulties are caused by the fact that in the evaporation a saturated Gas-vapor mixture is created, with which liquid droplets and foam are discharged from the evaporator which are only incomplete and very much in the course of the previously used procedures difficult to separate. It is especially these non-separable liquid particles that are then in the further course of the process, especially when heating to the reaction temperature and itself still on the hydrogenation catalyst due to the formation of high-boiling polymers and carbon Difficulties result and continuous, long-term operation is impossible do.

The catalytic, hydrogenating refining of hydrocarbon mixtures with substantial contents of aliphatic and cyclic diolefins and acetylene derivatives, in particular of those that arise from the cleavage of liquid hydrocarbons, over hydrogenation catalysts under elevated pressure and at elevated temperature with the separation of higher-boiling hydrocarbons takes place according to the invention in such a way that that the hydrocarbon mixtures are heated to temperatures between about 80 and 200 ⁰ C, expediently about 90 and 160 ⁰ C, and freed from the solid precipitates formed, that liquid particles from the gas-vapors mixture produced by evaporation with the addition of hydrogen or hydrogen-containing gases be deposited that the gas-vapors mixture in a heat exchanger, advantageously flowing downwards, heated to reaction temperature and passed from bottom to top through the catalyst, the lowest or the lower catalyst layers m be treated with raffinate, a raffinate fraction, the starting material or other washing liquids.

The invention combines the separation of the solid polymerization products that takes place at the beginning of the process with a repeated separation of liquid components from the gas-vapor stream and the extraction of the catalyst. This succeeds es, feedstocks with substantial amounts of highly reactive substances in continuous to process trouble-free operation to completely stable raffinates, which are also purer for the extraction Aromatics are suitable.

For example, hydrocarbon mixtures, such as mineral spirits, are advantageous in the heat exchange in known heat exchangers heated to temperatures of about 80 to 160 ° C and at these temperatures sent through filters. In these, about 0.01 to 0.3%, calculated on the input material, deposited solid polymers. About interruptions in continuous operation in the process Avoid according to the invention, are for this deposition of the solid polymers that are in the first Section of the heating of the starting materials takes place, two or more filters working in parallel are provided. These are alternately acted upon with the substances to be filtered in such a way that the one filter is freed from the nitrided solids, while the other is freed from that to be filtered Liquid flows through. To make it easier to switch the filters and also one in larger ones Expedient cleaning of the heat exchangers or heaters upstream of the filters without interrupting operation, heat exchangers working in parallel can advantageously be used or heater groups can be provided.

The filtered material contains not only unreacted unsaturated hydrocarbons but also soluble polymers contain. The filtrate goes into an evaporator, in which at the same time hydrogen or hydrogen-containing Gas is introduced. Appropriately, a circulation evaporator is used through which to evaporating good z. B. with a centrifugal pump or by pumping liquid by means of a gas stream, z. B. the applied hydrogen or hydrogen-containing gas is kept in circulation. Evaporation residue is taken from under the evaporator and branched off from the process, while the gas-vapors mixture is advantageous in one Separator freed from coarse liquid particles and then placed in a device for separation further liquid particles still entrained in the gas-vapor stream is passed. As useful Mechanical fine separation processes have proven to be effective for this purpose, provided they are highly efficient can be set.

A washing device for the gas-vapor mixture laden with liquid particles can also be used to good effect at this point.
The washing device can be designed in a known manner, for. B. be equipped with packing, wire mesh, column tray, on the head of the scrubber z. B. raffinate, a raffinate fraction or raw gasoline or another suitable washing liquid is abandoned. The scrubbing liquid is expediently heated approximately to the temperature of the gas-vapor stream or a temperature a few degrees above it before it enters the scrubber. The washing is followed by a treatment with fabrics with a large surface. Here, as in the previous scrubber, it is advisable to maintain low flow velocities in order to improve the separation effect.

This deposition of the droplets on substances with a large surface area can become more reactive with hydrogenation Components of the gas-vapors mixture are combined. The gas-vapors mixture becomes in this case passed through a catalyst in the direction from bottom to top. If necessary, can with the addition of a partial flow of the cycle gas or fresh gas or the mixture of both Gases that can be heated to a higher reaction temperature than the gas-vapors stream, the reaction temperature can be set, the z. B. 180 to 250 ° C should be. They then divorce the fine liquid particles as they pass through the catalyst and collect in the sump of the contact container, from which they can be withdrawn. At the same time, be the most responsive Ingredients converted.

The flow rate should in this prehydrogenation catalyst, based on the free cross-section, are below 0.2 m / sec, expediently below 0.1 m / sec. The specific catalyst loading is advantageously chosen between about 0.5 and 4 t of feed per cubic meter of catalyst and hour. The reactions taking place on the hydrogenation catalyst cause an increase in temperature of several degrees, e.g. B. 8 to 20 ° C,

on. The increase in temperature causes the gas-vapor mixture to dry out.

In many cases it is sufficient to use natural or synthetic fillers instead of the hydrogenation catalyst a large specific surface area, which then agglomerates due to its large surface area of the fine liquid droplets and a simultaneous separation of the liquid particles. As natural fillers such. B. bauxite, clay, montmorillonite, silica gel in question, which can also be activated in a known manner with acids.

The gas-vapors mixture is now heated to the reaction temperature in a Knanter type of heat exchanger that can be installed vertically or horizontally. It turns out to be expediently, the gas-vapors mixture to be heated from top to bottom through the tubes of the To lead the heat exchanger, since then still precipitating liquid droplets from the gas flow from the heat exchanger can be discharged and separated in a downstream separator. If several tube bundles are required to accommodate the required heating surface, these will be expediently arranged lying one above the other. The gas-vapors mixture thus reaches the top one first Tube bundle, then into the next lower and emerges from the lowest one, which is followed by a separator, the end. Then the mixture is fed to the reactor.

In the reactor, the catalyst is, for example, in two or more layers one on top of the other arranged. Through these layers, the gas-vapors mixture is successively in ascending order Electricity passed. Liquid that is deposited on the catalyst from the gas-vapors mixture can be drain from the catalyst layers and below the bottom layer from the reactor be derived. To prevent the catalytic converter from becoming unusable prematurely, especially in the lowest or the lower catalyst layers, to avoid these catalyst layers at intervals from about 2 to 7 weeks for a short time with raw gasoline, raffinate, a raffinate fraction or others suitable organic liquids. This washing can also be carried out continuously be performed. The washing prevents an increase in the reaction temperature, which would otherwise be necessary in many cases to maintain the performance of the system. In longer It is advisable to also use the uppermost or upper catalyst layers with washing liquid at intervals to treat.

To maintain a desired temperature gradient in the reactor, between the catalyst layers Hydrogen or hydrogen containing gas, e.g. B. cycle gas or fresh gas or mixtures of both, at the required low temperature and in the amounts desired in each case, such as known per se, can be initiated.

For operational reasons, it is recommended that the catalyst layers, which are frequently or constantly with the Washing liquid are sprinkled in one or more special containers. Two or more parallel containers are expediently arranged. The gas-vapors mixture becomes then alternately passed through one of the two containers. The one switched off from the gas-vapors flow The container can then be treated with the washing liquid alone. It is in all cases possible to carry out the washing of the catalyst layers continuously.

For the layers that are treated with washing liquids, it is not necessary to use the actual one To use hydrogenation catalyst. Instead of the catalyst, you can also use material with a large specific surface, e.g. B. bauxite, clay, silica gel, activated charcoal or the like. Use.

ίο The aim of the extraction of the catalyst is that To remove polymers that are on the way from the prereactor via the heating zone to the reactor form and which reach the catalyst with the gas-vapors stream and are precipitated there.

The method according to the invention ensures trouble-free operation even with the most difficult Raw materials.

By special selection of the evaporator and / or the conditions under which the evaporation

so takes place, e.g. B. according to the German patent 1105 546 from January 8, 1960, significant other advantages can be achieved, e.g. B. can be the downstream of the evaporator Apparatus with smaller dimensions can be used or even individual apparatuses

a5 fall. For example, the pre-hydrogenation or Washing of the gas-vapor stream coming from the evaporator is completely or partially unnecessary. A particular advantage of a conveniently designed evaporation is that the extraction of the Catalyst can take place at much longer intervals, as can the regeneration of the catalyst by burning down.

It has thus proven to be advantageous for the method according to the invention to have flow velocities in the evaporator of the gas-vapors mixture must be kept below 0.1 m / sec, expediently below 0.05 m / sec.

The heat of the reaction mixture flowing out of the reactor can be used in a known manner for the Heating of the substances introduced into the process to the required temperature in each case is used will.

For the process according to the invention, known catalysts which contain one or more oxides or metals of subgroup V to VIII of the Periodic Table, z. B. iron, nickel, Tungsten, molybdenum or cobalt oxide, sulfide or metal catalysts can be used. Catalyst loading, Working pressure and reaction temperatures can be the usual ones.

The invention is explained in more detail with reference to the drawing. In the picture is one for that Process according to the invention suitable plant shown schematically and for example.

The starting material, e.g. B. cracked gasoline, is by the pump 1 on the for the method according to the invention required pressure. It passes through line 2 to heat exchanger 3, where it is on Temperatures of about 90 to 200 ° C is heated, which is necessary for the precipitation of solid polymers are. It is freed from these polymers in the filters 4. Line 5 will do this The filtrate is passed on into the circulation device 6 of the evaporator 7. You can also use the filtered, heated one Raw gasoline or part of it through line 64 into the evaporation chamber 9 of the evaporator 7, z. B. on the second bell bottom, give up. To enable cleaning of the filter device,

7 8

are heat exchangers and filters in duplicate - on a low pressure in one not shown

supply and in parallel connection. Thereof stripping column from hydrogen sulfide and others

one strand can be filtered, the other freed on gases.

Cleaning can be switched. 3 a, 3 b, 4 a and 4 b are that separated from the raffinate in the separator 54

the switching devices. The evaporator 7 consists of 5 gas is fed through 56 to the circulating gas pump 57

out of a heater 8, an evaporation chamber 9, which it via the heat exchanger 48 and the

and a lower part 10. Line 12 of the circulation device 6 of the evaporator

Through line 11, raw gasoline, raffinate 7 can give up.

and / or another washing liquid at the top of the water evaporation chamber freshly introduced into the process are distributed, the appropriate io substance is reactivated with the compressor 58 Internals, such as the column tray, sieves or filling pressure, and brought through the lines 59, 60 and body, is equipped. The circulation device 6, 61 as a cooling medium between the catalyst layers which, for example, designed in the manner of a mammoth pump, is fed into the main reactor 31. If required, and a conveying medium, e.g. hydrogen or water, a part through line 62 in line 30 can contain substances Gas in the form of cycle gas or 15 leads. When larger amounts of cooling gas are required Fresh gas or a mixture of both, from the line, can be part of the circuit-12 through line 63 receives, the liquid in the evaporator conveys from the running gas to the fresh gas. Advantages Space 10 below the heater 8 in the arrest prevails in the refining apparatus up to Steaming space 9, expediently in the lower part of the expansion of the raffinate after separator 54 same. From the evaporator the generated 20 reaches the same pressure, which only differs from apparatus to apparatus Gas-vapors mixture through line 13 changes into that due to the flow resistance. Separator 14. The evaporation residue is

via the line 15 from 10 also in the example 1

Scheider 14 led. In 14 separated liquid 21 per hour gasoline, which at the thermal

will occur together with the evaporation residue 25 splitting of petroleum and petroleum fractions and

taken from the separator through line 16, which has the properties given below,

while the gas-vapors mixture flows through the pipe, the heat exchanger 3 is heated to 150.degree.

17 of the device 18 flows. Through the filling. Solid polymers are formed during this heating process,

this device 18 goes from the bottom to the top in the downstream of the heat exchanger

through and continues through the line 19 in 30 filters 4 are separated. Heat exchanger and

the heater 20. 21 is a hood for in the Vorrich- Filters are provided in duplicate. is

device 18 separated liquid. a filter after 10 to 14 days of running time

The heater 20 consists of three inter-loaded polymer, which is attributed to the pressure loss, lying tube bundles 22, 23 and 24, it is switched to the second line, which, on the other hand, empties the gas-vapors mixture on the pipe side and, if so, the loaded filter stream flows through one after the other to the heating means. required, the heat exchanger is cleaned. in the From the last bundle 24 it goes through the filter line, 0.023% polymer is calculated 25 first in the separator 26 and then occurs on the amount of raw gasoline, retained, through line 27 into the lower part of the reactor from the polytor formed during heating 28 a. In the reactor 28, the catalyst layer is 4 ° merisate freed and heated to 150 ° C crude product 29 housed. The reactor 28 leaving now enters the circulation evaporator 7, in which The gas-vapors mixture passes through the line 30 upper part 9 to the second bubble-cap base from above in the sump of the main reactor 31. In 31, three are abandoned. The cycle gas, that, too Catalyst layers 32, 33 and 34 arranged. Which was heated to 250 ° C by heat exchange occurs liquid 45 separated in 14, 18, 26, 28 and 31 into the circulation device 6 of the evaporator 7 is through lines 16, 21, 35 and 36 and 37 and once causes the gasoline to circulate in the Erin the residue manifold 38 discharged through the heater 8 of the evaporator and the evaporation of the they a not shown residue container of gasoline up to a residue amount of 6%. on and from this to the further processing or further the uppermost bubble cap in the evaporation part 9 use flows. 50 are 100 l / h of a raffinate die boiling above 180 ° C Catalyst layers 32, 33, 34 of the reactor fraction abandoned to the gas-vapors-31 and the layer 29 of the container 28 can be extruded by means of a mixture of entrained liquid particles Wash pump 39 via lines 40, 41, 42 and 43. The circle with gasoline vapor saturated a washing liquid, e.g. B. raffinate, a running gas leaves the evaporator at 210 ° C, through-raffinate fraction or raw product, can be sprinkled. 55 runs a separator 14 in which about before-Das Refined gas-vapors mixture flows above liquid separated from the gas stream from reactor 31 through line 44; it will serve. The gas arrives from this separator the heat exchangers 24, 23 and 22, which through the vapors mixture to the prereactor 18, in which it is with Lines 45 and 46 are connected, as heating means, 210 ° C below the catalyst layer and enters in order to then flow through the line 47 via the heat outlet 60 from bottom to top. In the pre-reactor 48, the heat exchanger 3 and the line tor are about the same flow velocity-49 to be supplied to the condenser 50. In speed of about 0.02 m / sec as in the upper part 9 of Verdiesen the coolant passes through line 51, steam. When passing through the catalytic converter it leaves him through line 52. The most reactive comet in 50 he of the prereactor are produced Condensate flows through line 53 in the 65 components mostly converted into olefins, Separator 54, in which the cycle gas is separated from the raffinate with a temperature increase of about 12 ° C will. The raffinate leaves the separator and enters. In addition, the gas-54 produces very fine nebulae through line 55 and, after expansion, the vapors mixture is largely separated out. Under-

half of the catalyst layer of the prereactor is provided a separation space from the catalyst absorbs dripping liquid, which is then discharged from here, z. B. 0.2 to 0.3 l / h are removed. Due to the partial saturation of the diolefins, the bromine number of the gasoline in the prereactor is reduced 7 g per 100 ml reduced. In addition, the specified increase in temperature causes the gas-vapors mixture dried.

The pre-hydrogenated gasoline with the cycle gas then passes into a heat exchanger in which it is used for heating to the reaction temperature in countercurrent to the mixture coming from the reactor flows through three tube bundles arranged one above the other from top to bottom. At 260 to At 270 ° C it now enters into the hydrogenation. The catalyst is in two reactors of different sizes housed. In the first connected there is only a 2 m high catalyst layer, while In the larger, downstream main reactor, three layers, each 2 m high, are arranged. Flows through both reactors from bottom to top. In the separation room, the lower part of the small one Reactor, as well as at times in the sump of the main reactor, small amounts of liquid are still produced, which are discharged. The division of the catalyst layer into two separate reactors 28 and 31 is useful because the catalyst of the smaller reactor with increasing running time with polymer loaded every 8 days by rinsing with a high, z. B. above 180 ° C, removed boiling raffinate fraction will. This washing can easily be carried out continuously if larger amounts of polymer are used be deposited on the catalyst. To maintain continuous operation are the main reactor is preceded by two parallel reactors, so that the catalyst is flushed once to remove the polymers without interrupting operation by switching to the second Reactor take place and above all a regeneration of this catalyst layer required after about 4 to 5 months can be carried out by burning off without interrupting operation. Through the from Washes of the catalyst carried out from time to time are over 80%, e.g. B. 99% of the seasoned Polymers removed. It succeeds all the more completely, the shorter the time intervals the washing takes place.

The hydrogenation raffinate discharged from the process hardly contains any unsaturated compounds; Sulfur compounds can only be detected as traces. It is suitable for the extraction of pure Aromatics. The table below shows the properties of the crude product and the raffinate specified.

Raw gasoline Raffinate Density at 15 ° C ... 0.7909 0.781 Total sulfur, Weight percent .. 0.02 <0.001 Bromine number, g per 100 ml 92.0 0.1 Beginning of boiling, ⁰ C ... 31 35 5 percent by volume 43 ° C 46 ⁰ C 15 percent by volume 53 ° C 54 ° C 25 percent by volume 64 ⁰ C 62 ° C

continuation Raffinate ⁰ C 70 ° C 35 percent by volume 79 ° c 45 percent by volume 88 ⁰ C 55 percent by volume 100 ⁰ C ₁₀ 65 percent by volume 112 ° c 75 percent by volume 138 ⁰ C 85 percent by volume 163 95 percent by volume 167 Volume ¹ S end of boiling point, ⁰ C (97 percent) Raw gasoline 75 ⁰ C 86 ° C 98 ° C 112 ° C 132 ° C 152 ° C 172 ⁰ C 173 (97 vol percent)

Example 2

If substances with a large surface are used instead of the catalyst in the prereactor, then after Prereactor in gasoline no significant reduction in bromine number and no increase in temperature. That The end product can, however, have the same properties as indicated in the table for example 1, be won. It is only necessary to flush the catalyst in 28 more often, than when working with a pre-hydrogenation catalyst.

Example 3

The method according to the invention is designed in a similar manner when other starting materials are processed. For example, according to the method according to the invention, high-quality Obtain products from mineral spirits of the following composition:

colour

Density, 15 ° C

Bromine number, g per 100 ml of sulfur, percent by weight

Phenol, g / l

Naphthalene,
Weight percent ..

Carbon disulfide, percent by weight. Basic nitrogen, mg / kg

Boiling analysis
Beginning of boiling, ⁰ C ..

up to 60 ° C,
Volume percentage .. up to 70 ° C,

Volume percentage .. up to 80 ° C,
Volume percentage .. up to 90 ° C,

Volume percent .. up to 100 ° C, volume percent ..

Cracking gasoline A

Yellow 0.841

52.5

0.022

Split petrol B

Light brown 0.8330 48.8

0.037

0.06 0.05 309 597/295 0 2.5 O 0.01 5 0 69 47 - 3 - 13th 2 29 9 49 20th 64

continuation

Cracking gasoline A Split petrol B 30th 72.5 40 78 51 83.5 62 86 73 90 84 92 92 93.5 96 95 - (Boil
end)
(98)
1
1.5 96.5
97.0 (boiling point
end)
1.5 0.6 0.5

up to 110 ° C,
Volume percentage ..

up to 120 ° C,
Volume percentage ..

up to 130 ° C,

Volume percentage ..
up to 140 ° C,

Volume percentage ..

up to 150 ° C,
Volume percentage ..

up to 160 ° C,
Volume percentage ..

up to 170 ° C,

Volume percentage ..
up to 180 ° C,

Volume percentage ..

up to 190 ° C,

Volume percentage ..
up to 193 ° C,

Volume percentage ..

Residue,

Weight percent ..
Loss,

Weight percent ..

Since the hydrocarbons listed in the table are relatively benign It is possible to reduce the working temperatures by around 10 to 15 ° C and the space velocity over the catalyst can be increased by 10 to 30%. The end products only contain traces of sulfur compounds, they are completely light and stable in storage and have a bromine number that is less than mg per 100 ml. These substances are particularly suitable good for the production of pure aromatics.

Claims (5)

PATENT CLAIMS: 1. Process for the catalytic hydrogenating refining of hydrocarbon mixtures with substantial contents of aliphatic and cyclic diolefins and acetylene derivatives, in particular of those involved in the cleavage of liquid hydrocarbons are formed, to hydrogenation under elevated pressure and at elevated temperature with removal of higher boiling hydrocarbons, characterized in that the hydrocarbon mixtures to temperatures of between about 80 and 200 ⁰ C, suitably about 90 and 160 ° C is heated, and the resulting solid precipitates be freed that liquid particles are separated from the gas-vapors mixture generated by evaporation with the addition of hydrogen or hydrogen-containing gases, that the gas-vapors mixture is heated to the reaction temperature in a heat exchanger, advantageously flowing downwards, and from bottom to top through the Catalyst is passed, wherein the lowest or the lower catalyst layers are treated with raffinate, a raffinate fraction, the starting material or other washing liquids. 2. The method according to claim 1, characterized in that the gas-vapors mixture according to Deposition of the liquid particles contained therein is subjected to a pre-hydrogenation. 3. Process according to Claims 1 and 2, characterized in that one is used for the deposition of the liquid particles, the gas-vapors mixture from bottom to top through a bed conducts solid substances with a large surface. 4. The method according to any one of claims 1 to 3, characterized in that the gas-vapors mixture by means of a sieve wire pack filled with washing liquid or a packing bed directs. 5. The method according to any one of claims 1 to 4, characterized in that the lowermost catalyst layer or two or more lower catalyst layers in a particular device be arranged in which the catalyst is extracted continuously or discontinuously can be. Considered publications: German Patent Nos. 933 648, 956 539; Patent specification No. 12 392 of the Office for Invention and Patents in the Soviet Zone of Occupation Germany; German Auslegeschriften Nos. 1036 436, 1042 803; French Patent No. 1134 183; U.S. Patent No. 2,707,700. 1 sheet of drawings