DE1221389B - Process for the conversion of high-boiling hydrocarbons into lower-boiling hydrocarbons - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Clog

German class: 23 b -1/04

Number: 1221389

File number: Stl9127IVd / 23b

Filing date: April 19, 1962

Opening day: July 21, 1966

The invention relates to a process for the conversion of relatively high-boiling hydrocarbons to lower boiling hydrocarbons, especially of petroleum distillates to products that predominantly gasoline boiling range, ie up to about 205 ⁰ C, boiling between the boiling points of the butanes.

The process according to the invention for converting higher-boiling hydrocarbons into lower-boiling ones Hydrocarbons on one consisting of a cracking component and a hydrogenation component Catalyst in the presence of a hydrogen-containing gas is that as a catalyst of a metallic hydrogenation component, a solid acidic cracking component and one of the elements Phosphorus, arsenic, antimony or bismuth, optionally containing 0.5 to 6 percent by weight of fluorine, Catalyst is used.

In the case of hydrocarbon mixtures containing polynuclear aromatic compounds, the Process variants are regulated so that a product rich in alkylbenzenes and isoparaffins is obtained results, both of which are valuable components of high octane gasolines. Continue to be normal paraffins in products with a higher content of isoparaffins than they are normally present are convicted. An advantage of the method according to the invention is that the Gas generation is low, d. that is, only a very small proportion of the feed mass is converted into undesirable light gases is transferred, and that the product boils predominantly in the gasoline boiling range.

According to preferred embodiments of the invention, the conversion process is carried out by adding a hydrocarbon distillate boiling between about 150 and 450 ° C, in the presence of hydrogen at a temperature between 260 and about 371 ⁰ C, a pressure of between 13.1 kg / cm ² and 141 kg / cm ² and an hourly liquid space velocity between 0.1 and 10 volumes of oil per hour per volume catalyst with a catalyst consisting of a hydrogenation component, namely metals from group VIII of the periodic table, in particular nickel, platinum, cobalt or palladium, a solid acidic Crack constituent, in particular silicon dioxide-aluminum oxide and arsenic, is brought into contact. Preferably, fluorine is included in the catalyst in order to give an exceptionally high catalyst activity.

In carrying out the process, the selected feed mass is transferred to a reaction zone initiated that the catalyst together with a hydrogen-containing gas, ζ. B. hydrogen gas, catalytic

Procedure for the transfer of
higher boiling hydrocarbons
in lower boiling hydrocarbons

Applicant:

Standard Oil Company, Chicago, JU. (V. St. A.)

Representative:

Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. Assmann

and Dipl.-Chem. Dr. R. Koenigsberger,

Patent Attorneys, Munich 2, Bräuhausstr. 4th

Named as inventor:

Louis Charles Gutberiet, Cedar Lake, Ind .;

Harry Michael Brennan,

Hammond, Ind. (V. St. A.)

Claimed priority:

V. St. v. America April 19, 1961 (104 014),
dated April 13, 1962 (187186)

table reforming gas or a circulated hydrogen-rich gas, from the invention Procedure contains. The process can be in the liquid phase, the vapor phase or in mixed Vapor-liquid phase can be carried out. The catalyst system can be of the fixed bed type as well as a fluidized bed or other suitable system. The loading masses used can come from petroleum, shale oil, gilsonite or other such sources. It may also be desirable to recycle some of the effluent to the reaction zone.

The feed stocks which are satisfactorily hydrocracked by the process Compositions can be practically completely saturated to completely have aromatic compositions. Saturated compounds become paraffins in the gasoline boiling range with a greater concentration of isoparaffins than the equilibrium concentration of the

609 590/353

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3 4

Product cracked with hydrogen, while remaining effective in the case of the desired product,

of multi-grain aromatic compounds to maintain them. At higher nitrogen contents

are partially hydrogenated and the hydrogenated ring portion in the feed mass is more frequent regeneration

Hydrocracking requires an alkyl-substituted benzene and / or higher temperatures,

and forms an isoparaffin. 5 µm a suitable cycle life _; to achieve.

High boiling fractions of crude oil are beneficial- typically the feed can be less than

adhesive charge masses for the inventive nitrogen contain about 0.01 percent by weight and,

Process. In general, the Beschik- falls at a temperature of about 370 ⁰ C or

Kung masses in the range of heavy gasoline and lower is worked, it is desirable that the

Luminous oil to light and heavy gas oils. to keep the amount of nitrogen at around 0.001 to 0.0015%,

The feed stocks will normally, and most advantageously, boil at about 0.0001%.

half about 150 ° C and can boil up to about 540 ° C. The method used according to the invention

Advantageously, the boiling range of the conditions can be within a fairly wide range

Send masses between 150 and 450 ⁰ C. Examples range can be chosen and are accordingly

preferred batches are lightweight 15, batch type and special

catalytic cycle oil with a boiling range applied catalyst adjusted to the fact that

between 150 and 340 ⁰ C, heavy catalytic neither a desired conversion, 'ie the

Circulation oil with a boiling point in the range of the percentage of the load transferred into the product

260 to 450 ° C, crude gas oil with a boiling point in the charge mass, or a product with a

Range between 204 and 450 ⁰ C and coke gas oil with 20 desired octane number is obtained. The formation of

a boiling point in the range from 150 to 430 ⁰ C. Alkylbenzenes from polynuclear, aromatic compounds

The product yields are particularly dependent on the higher pressures and moderate bonds

Type of feed mass favoring process condition temperatures and an increase in this

The two variables used and the two variables used over the procedure have an influence on the increase

Catalyst dependent. In any case, it is necessary to 25 of the degree of conversion. Satisfactory environment

the above-listed factors corresponding to conversions are similar to those described above

set the desired product. Charging masses at pressures in the range of

Conversion of hydrocarbons at about 13.1 to 141 kg / cm ² and temperatures in the range of hydrocracking catalysts is known; similarly, from about 204 to 540 ^° C. are achieved, although pressures are also known as catalysts which contain arsenic. However, and temperatures outside these ranges, a basic basic use of certain feed masses is used in these catalysts. A catalyst modified with a special high refractive load of silver acts in a similar way, while after the can be turned. Advantageously, USA. Patent 2,944,006 be used a a sulfonic pressures in the range of about 52.7 to 105 kg / cm ² and fidierten hydrogenation component on a crack 35 temperatures between about 260 to 371 ° C, existing catalyst catalyst pad Ver - It may be desirable to take a turn during the course. The inventive catalyst of a batch allows the temperature inside the Reaker to work at a much lower temperature zone when the catalyst is heated and has been found to be 200 to 400% more active than deactivated, in order to reduce the catalyst activity of the known catalysts. In addition, give 40 balance. So it can be desirable with a fresh or even with its regeneration no difficulties - just regenerated catalyst. at a temperature of about 260 C in the stream

The previous hydrocracking process was working and the operating temperature was gradually increased

Sulfur in the system is viewed as a catalyst poison, increasing to about 371 ⁰ C during the course of the approach

d. that is, it undesirably increases the catalyst level. In most cases it is desirable

activity decreased. Furthermore, the deposit provided to maintain a low operating temperature,

of sulfur deposits on the catalytic converter, as the higher temperatures increase

Problems with the regeneration of a deactivated coke and an increased gas formation set.

Catalyst because it contains sulfates on the The space flow velocity can between

Form catalyst, whereby the catalyst activity 50 is about 0.1 to 10, usually between about 0.2 to 5

continues to be humiliated. It has been found that the and preferably between about 0.25 to 2 vol / vol / hr.

normal amounts of sulfur that occurs in the above- At lower space air velocities

guided charging masses are included, an increase in the degree of conversion.

according to the invention applied catalyst During the process, hydrogen is consumed

does not adversely affect neither during 55 needs, and it is necessary to use an excess

the time it is under the oil, while still maintaining the hydrogen in the reaction zone,

Time when the catalyst is regenerated. Although that, however, the procedure is relatively little through

Catalysts used in accordance with the invention changes in the hydrogen to oil ratio

have a suitable cycle life, can affect within the general operating conditions

it flows to 60 after an extended period of use. The applied ratio of hydrogen to oil

The reason for the deposition of carbonaceous deposits is in the range of 28.3 to 283 m ^{3 of} hydrogen gas

beat are deactivated, and they can easily be charged per 0.1635 m ³ , advantageously between

be regenerated. 56.6 and 142 m ³ .

Conveniently, nitrogen and oxygen are found to be within wide ranges as constituents of the compounds in the feed 65 of the operating conditions are the products of the hydromass kept as low as possible in order to achieve a cracking process predominantly within the range of desirably long cycle life, i.e. H. the interest boiling range. The dry gas generation, Period during which the catalytic converter is used to d. H. from methane to propane is generally

5 6

less than about 5 weight percent and is more typically Group VIII of the Periodic Table, which is known

wise in the order of about 2 to 3 Ge have a satisfactory hydrogenation activity,

weight percent. The butane-pentane fraction of the pro - in particular nickel, platinum, cobalt and palladium,

The hydrogenation constituent of the catalyst can also be produced

Amount of the operating conditions and the type of 5 advantageously in the catalyst by im-

Charging mass is dependent. If using, impregnation of the porous acidic cracking component

a feed mass, such as light catalytic with a compound which decomposes under heat

Cycle oil, the pentane up to 204 ° C fraction of the hydrogenation metal is incorporated and

of the product generally more than about 70 finally calcined to make the mass

weight percentage of the total converted product. be io. Typically a silicon dioxide

The aluminum oxide cracking catalyst used in the process according to the invention or an acid catalyst consists of a hydrogenation component, treated aluminum oxide base with a solution of a solid acid component and a normal nickel acetate, chloroplatinic acid or the like then dried; then it is pelletized systems (College Chemistry, 2nd Edition by Paul i5 and ^{calcined at elevated temperature (about 54O 0} C). R. Frey, Prentice-Hall, Inc., 1958), ie phosphorus, however, it is also possible to that the finished-arsenic, antimony and bismuth. So far, employed catalyst has been used according to various processes that elements such as arsenic, antimony and the like can be produced, e.g. B. by mixed gel formation with a view to the destruction of the effectiveness of the various constituents or other catalysts used in petroleum processes, in particular known variations of the catalyst production techniques, especially those containing platinum or nickel, so that a finished catalyst interacts with the would. However, it has been found that through gives desirable properties.
Incorporation of These Elements in the Invention The amount of catalyst employed incorporated in the catalyst, the improved resultant hydrogenation component achieved in the process described herein, may vary widely, the amount being left as it is. In addition to the favorable effects which are chosen when the desired use of these catalysts as catalysts results in the activity of the invention. For example, large quantities can be obtained in accordance with methods including those of nickel, e.g. B, up to about 30 weight percent, increased production of branched-chain paraf- can be applied, and relatively small amounts of fine, the more favorable control of the catalyst- 3 ° nickel, z. B. down to about 0.1 weight percent, activity and simplification of the catalyst are also effective, with 0.5 to 10 weight reactivation technique, whereby a slightly regenerative percent nickel is preferred. About 0.1 to 2 percent by weight of platinum catalyst used in the process are effective in the catalyst. and about 0.1 to 1 percent by weight is preferred

The acidic cracking component of the catalyst can be used 35 platinum. The amount of one or more solid, acidic ingredients used, such as. B. hydrogenation constituent in the catalyst depends on silicon dioxide-aluminum oxide (either naturally, consequently, of the catalytic properties and occurring and / or synthetic) silicon dioxide from economic factors.
oxide-magnesium oxide, silicon dioxide-aluminum- The component from the group VA of the Kataoxyd-Zirkonoxyd and similar contain. Also 40 lysatorverbindungen z. B. during the acid treated alumina with or catalyst preparation can be incorporated by using a without halogens, e.g. B. fluorine-treated aluminum-nickel-silicon dioxide-aluminum oxide mass dervoroxide, boron oxide-aluminum oxide and the type described with hetero standing with a solution of a polyacid treated aluminum oxides, ie the organic compound of the element of group VA, with phosphotungstic acid, phosphorus vanadic acid, 45 as z. B. aryl- or alkyl-substituted organo-silicotungstic acid, Silicomolybdenvanadinsäure and metal compounds such as triphenylarsine, triphenyl-like, can be used. However, the crystalline substance and the like are impregnated, and then it is of great value that these materials have a substantial amount of solvent evaporated, with some cracking activity remaining in the completed catalyst storage on the base material. Also have composition. A preferred acidic 50 can be the catalyst bulk with inorganic constituents of the present catalyst compositions such as acids, ammonium salts, composition consists of one of the commercially available nitrates, halides and the like. The normally synthetic silicon dioxide-aluminum oxide crack-solid elements of group VA impregnated are, catalysts containing about 4 to 40 percent by weight z. B. with arsenic trioxide in ammoniacal solution, contain aluminum oxide. Preferably the 55 and then will be dried. Before the acidic component of the catalyst is used as a substrate, the catalyst is used with hydrogen and is highly porous with an elevated surface temperature (about 450 ^° C.). However, in the range between about 100 and 500 m ² per gram, it is also possible that these elements are involved in the preparation and properties of the acidic cracking reaction zone, e.g. B. during the period when the constituents are known and do not need further 60 catalyst is on the oil, or during the re-explained. For this purpose, the publication will be introduced so that the Catalysis "Catalysis" from Emmett (Reinhold Publilysatorgrundmasse comes into contact in situ, Shing Corporation), in particular Vol. VII pp. 1 to 91, whereby these elements are incorporated into the catalyst entrusted. become alive. For example, an organic

Any of the known metallic hydration of arsenic in the reaction zone with the

Ration catalysts can be incorporated into the catalyst, hydrocracking feed, so

but preferably the metallic one is that the catalyst is supplied with arsenic in situ.

Component of this compound from the metals of the For the production of the used according to the invention

7 8

In the context of the invention, the catalyst will not work at an increased temperature, Protection claimed. - to maintain the desired product quality

Usually only small amounts of the egg holdings are held. When the catalyst activity has dropped to a point of group VA in the catalyst required point where it is no longer satisfactory. The total amount applied will often be sufficient, the catalyst can be reactivated to a degree satisfactory by the amount of the catalyst,
The following examples are intended to provide further information, ie, arsenic can either be used as a refinement of the invention without limiting it,
senide or sub-arsenide may be present. Generally

expressed is no more than l'Atom des normaler- io B e i s ρ i e 1 I

wise solid element of group VA per atom of hydrogenation metal in the catalyst required, whether a catalyst was prepared from 5 weight or larger amounts can be used, percent nickel and 2.5 weight percent arsenic to the extent that the desired catalyst activity maintains- a silicon dioxide-alumumum oxide underlay which is preserved. For example, arsenic can contain up to about 2 atoms per atom of hydrogenation metal in the ratio of 15 to about 25 percent by weight of aluminum oxide. A was used in the catalyst to produce the catalyst. Advantageously commercially available silicon dioxide-aluminum oxide is used, however, 0.01 to 1 atom of these elements per cracking catalyst with a high aluminum content with atom of hydrogenation metal, with an aqueous solution of nickel acetate impregnated, ratios between about 0.1 to 0.5 being preferred. 20 The impregnated mass was at about 204 ⁰ C

The preferred catalyst, which dries exceptionally, has high activity mixed with 4% hydrogenated coconut oil, consists essentially of pelletizing to 0.32 cm and calcining a Group VIII hydrogenation metal component at 538 ° C for 6 hours. The calcined catalyst of the periodic table, in particular nickel, a then ^{normally solid element of group VA to a mesh number / cm 2} between 49 to 400, was ground and treated with a solution of triphenylarsine, special arsenic, fluorine, and a catalyst base in n -Heptane impregnated. The heptane was evaporated from silicon dioxide-aluminum oxide. The silicon and arsenic-treated catalyst is then placed in a silicon dioxide-aluminum oxide, preferably a silicon reaction vessel, in which it has been treated with strözium dioxide-aluminum oxide cracking catalyst and using hydrogen at atmospheric pressure and 454 ° C to decompose the arsenic, whereby (about 20 to 30% Al ₂ O ₃ ) or the "low aluminum - an arsenated nickel on a silicon dioxide" (about 10 to 15% Al ₂ O ₃ ) are used. Alumina catalyst yielded.
The amount of Hy applied in the catalyst during the first period of operation

drierungsmetalls varied according to the desired, about 90 cm ^{3 of} the catalyst in the presence of activity. For example, about 0.5 to 5 percent by weight of hydrogen with a slight catalytic weight percent nickel is applied to the catalyst base, cycle oil with a boiling point in the range of, although up to 10 weight percent nickel is brought into contact with about 204 to 316 ° C.
can be used in some cases. For example, the slightly catalytic cycle oil, which is

0.5 to 6 weight percent, and preferably about charge weight, was previously 2 to 4 weight percent halide is incorporated into the catalyst over a cobalt-molybdenum catalyst hydrodelyizer by sulfurizing the catalyst base. The aromatic content of the hydrated organic or inorganic halide compound, either with or without hydrogenation metal, with a desulfurized light catalytic cycle oil had previously been reduced to an amount that will react with it. This was lower than that normally found with a preferred halide, fluorine, since it was found to be the amount found of the stream so refined but gave the catalyst an exceptionally high activity but the aromatics content of the feed. The various ingredients can use up considerably. The feed mass contained about 0.002% catalyst base either concurrently or sulfur, 0.0012% nitrogen and had a specific stage combined, then dried and fish weight of 0.8304. The catalyst was being calcined. In the latter case, apart from the charging mass at 141 kg / cm ² , one usually achieved good results by using a nickel-hourly liquid space velocity of 0.25 containing silicon dioxide-aluminum oxide with a volume of oil per hour per volume catalyst and inorganic fluoride solution, - z. B. Hydrofluoric acid, Am- a ratio of hydrogen to oil of about 85 m ^{3 of} monium fluoride and the like, is impregnated, but 0.1635 m ³ can be brought into contact. The temperature of the catalyst base with a single solution, 55 of the catalyst bed was impregnated during the various times a nickel compound, an arsenic compound and periods of the approach, such as from which the halogenide contains, and e.g. B. in the table below, varies,
Nickel fluoride can be used to advantage. Subsequently, during the second time

After the catalyst described here a space of the approach the feed mass to a has been in operation for a certain period of time, a so crude, light, catalytic cycle oil can be mixed with a Decrease in activity occur, with carbonaceous specific gravity of 0.8805 and with a content Deposits have accumulated on the catalytic converter. of 1.23 percent by weight sulfur and 0.024% The decrease in activity is changed by a lower nitrogen. The results of this approach The conversion rates in the effluent from the reaction zone are shown in the table below. From the or by a decrease in the octane number of the converted values from the table and from the above Product displayed. As noted above, the cycle life carried out, the catalyst activity drop due to the catalyst used according to the invention Increase in working conditions, e.g. B. by Ar- is, with a charge mass with high stick-

ίο

substance content, ζ. Β. the above raw, light catalytic cycle oil, but it is obvious that the catalyst is capable of such Hydrocracking feed masses for considerable periods of time.

Subsequent to the aforementioned second period, the flow of the feed and of the hydrogen to the reaction vessel is terminated and the catalyst bed and reaction vessel are filled with nitrogen flushed out at atmospheric pressure and then regenerated with oxygen while burning off.

During the third period of the run, the reactivated catalyst was contacted with the same feed that had been used during the first run period. The results from this third period are shown in the following table, from which it can be seen that the reactivated catalyst exhibits a high level of activity after prior exposure to a sulfur and nitrogen-rich feed.
During the fourth period of the run the feed was again switched to the light, crude catalytic cycle oil previously used. The results of this fourth preparation period are also listed in the following table.

The octane values of the resulting hydrocracked material in the gasoline range from C ₆ to 180 ^0C, which was prepared with fresh catalyst were in the range of 98 to 100 F-I + 3 cc TEL, and reactivated catalyst were the octane values in the same range as for fresh catalyst.

Hydrocracking batch catalyst: 5 ° / ₀ Ni + 2.5% As on silicon dioxide-aluminum oxide with a high aluminum oxide content

Conditions: 71 kg / cm ² hours ; 0 , 25 vol _{/ hour / vol / H 2} / oil C ₁ to C ₃ = 85m ³ 3weight statement
gas to 204 3.7
2.0
3.0 16.3
6.2
0.5 37.2
9.9
3.1 35.2
40.3
16.2 ⁰ C conversion period temperature 4.8
4.2
1.3
0.3
1.0 Normalized < C ₆ to 204 ⁰ CI 82 43.0
41.3
29.3
41.8
10.2 Weight percent 4 to 18
112 to 136
208 to 232
328 to 352
452 to 476 ⁰ C C ₄ and C ₆ 31.0
30.2
6.9
20.6
0.7 regenerates at 454 ° C and 1 atmosphere 0.4 m ³ 2 ° / ₀ O ₂ in N ₂ ,
hydrotreated at 316 ^° C. and 0.15 atmosphere 99.0
92.5
43.4
69.5
12.4 I *
II ** catalyst
catalyst
turn 312
314
292
309
334 20.2
16.8
5.8
6.9
0.5 then 0.51 m ^{3 of} air;
m ³ Hz before ver 476 to 500
528 to 552
672 to 696 310
309
362 III *
IV ** 92.4
58.4
22.8

* Hydrodesulfurized feed - specific gravity 0.8304; 0.002% S; 0.0012% N. ** Raw feed - specific gravity 0.8805; 1.23 weight percent S; 0.024% N.

Example II

25 grams of a high aluminum silica-alumina cracking catalyst (about 25 weight percent alumina) was impregnated with an ammoniacal solution of nickel acetate tetrahydrate (10 grams) and the catalyst was soaked therein for one hour. It was dried calcined at 204 ⁰ C and 4 hours at 538 ° C. The nickel-containing mass was then treated with a mixture of As ₂ O ₃ (0.8 g) in 3O ^o / pc alcohol H ₂ O ₂ and NH ₄ F impregnated (1.5 g) in water, then dried and calcined as described above. The finished catalyst contained about 9.4 weight percent nickel, 2.4 weight percent arsenic, and 3.0 weight percent fluorine. Prior to contact with the hydrocarbon feed, the catalyst was pretreated with flowing hydrogen for one hour at 399 ° C and one atmosphere pressure.

A light, catalytic cycle oil which had been hydrogenated over a cobalt-molybdenum oxide catalyst was used as the feedstock. The feed composition contained about 0.0003 ° / ₀ sulfur, 0.0013 ° / ₀ nitrogen and showed a specific gravity of 0.8644. In the feed analysis (simulated distillation) to an initial boiling point of 205 ⁰ C, 50 ° / ₀ at 280 ° C and 100% at 396 ° C showed

The catalyst prepared above was placed in a reaction vessel and charged with the above-described charge mass at a temperature of 311 ° C., a pressure of 141 kg / cm ^a , an hourly space velocity of 2.6 and a hydrogen to oil ratio of 198 m ^{3 of} hydrogen brought 0.1635 m ^{3 of} oil into contact. The liquid product from the reaction vessel was analyzed by gas chromatography using the simulated distillation technique and the gas analyzed by mass spectrometry. The product distribution was as follows:

Product distribution percent by weight
C ₁ IC _2-69 ° CIC _2-196 ° CIC _2-217 ° C

0.1

41.0

92.9

94.5

The ratio of Q isoparaffin to normal paraffin was 5.3.

The arsenic nickel-fluoro-catalyst described above on silica-alumina catalyst proved to be about 200 to 235 ° / ₀ active than a

609 590/353

Silica-alumina based catalyst containing 7.2 percent by weight Ni, 2.4 percent by weight As, and 0 percent by weight F on silica-alumina and it was about 300 to 400%. effectively contained as a catalyst on silica-alumina basis of about 5 ° / ₀ Ni, 0 ° / 0% As and F on Süiziumdioxyd-alumina. From the above description it can be seen that the inventive method for hydrocracking a higher boiling hydrocarbon distillate, such as. B. light catalytic cycle oil, is suitable for lower-boiling hydrocarbons. It can also be seen that the products of the process boil predominantly within the gasoline boiling range and have very satisfactory octane values. It can also be seen that the process uses an easily regenerable catalyst which can be reactivated by a simple technique to restore its catalytic properties.

Claims (6)

Patent claims: 1. Process for converting higher-boiling hydrocarbons into lower-boiling ones Hydrocarbons on one consisting of a cracking component and a hydrogenation component Catalyst in the presence of a hydrogen-containing gas, characterized in that that as a catalyst from a metallic hydrogenation component, a solid acidic crack constituent and one of the elements, phosphorus, arsenic, antimony or bismuth, existing, optionally 0.5 to 6 weight percent fire-containing catalyst is used. 2. The method according to claim 1, characterized in that a catalyst with a metal of group VIII of the periodic table is used as a metallic hydrogenation component. 3. The method according to claim 1 or 2, characterized in that a catalyst with 0.01 to 1 atom of one of the elements phosphorus, arsenic, antimony or bismuth per atom of the metal Group VIII is used. 4. The method according to claim 1, characterized in that a Sihziumdioxyd-alumina crack support containing catalyst is used. 5. The method according to claim 1 to 4, characterized in that a catalyst with about 0.5 to 10 percent by weight nickel, about 0.1 to 0.5 atoms of arsenic per atom of nickel, about 0.5 to 6 percent by weight fluoride and a silica-alumina gray base used will. 6. The method according to claim 1 to 5, characterized in that at one temperature between 260 and 371 ° C is worked. Considered publications:
U.S. Patents Nos. 2 911 356, 2 112 387,
926 130;
Chemisches Zentralblatt, 1943/1, pp. 356/357. 609 590/353 7.66 © Bundesdruckerei Berlin