DE2313905A1 - PROCESS FOR HYDROGENATION OF AROMATIC HYDROCARBONS - Google Patents

Description

u.z .: K 5O54C (J / WS / gs) March 20, 1973

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ BV
The Hague / Netherlands

"Process for the hydrogenation of aromatic hydrocarbons"
Priority: March 22, 1972 - Great Britain - No. 13 374/72

The invention relates to a process for the hydrogenation of aromatic substances Hydrocarbons over sulfidic catalysts.

The catalytic hydrogenation of aromatic hydrocarbons is a well-known process. It is used, inter alia, for the production of cyclohexane from crude benzene to improve the
Smoke point of kerosene and used to increase the heat of combustion of jet fuels. Precious metals of Group VIII of the Periodic Table of the Elements as well as catalysts containing sulfides of nickel, cobalt, molybdenum and tungsten have already been proposed for these processes. The sulfidic catalysts have the advantage over the noble metal catalysts of group VIII that they are considerably less sensitive to sulfur, so that they can be used to process feeds with

309844/1029

relatively high sulfur content can be used. A However, the disadvantage of sulfidic catalysts is that they are lower in the hydrogenation of aromatic hydrocarbons Have activity. Compared to Group VIII noble metal catalysts of the Periodic Table of the Elements require the sulfidic catalysts to achieve the same Degree of conversion of aromatics a higher reaction temperature. However, cleavage reactions play with increasing reaction temperatures play a greater role, leading to a decreasing yield of the desired product and an increasing hydrogen consumption leads.

It has now been found that the activity of nickel sulfide and / or cobalt sulfide and also molybdenum sulfide and / or tungsten sulfide on catalysts containing a carrier material in the hydrogenation of aromatic hydrocarbons can be increased by incorporating fluorine into these catalysts.

The incorporation of fluorine into the aforementioned catalysts can

some cases
although inyflazu lead that in a process of hydrogenation

aromatic hydrocarbons undesirable cleavage activity- ■■■ "

however, these catalysts are increasing. It was found that the increase the cleavage activity can be suppressed by incorporating nitrogen into the above-mentioned fluorine-containing catalysts can.

8 ^ 4/1029

The invention accordingly relates to a process for hydrogenation aromatic hydrocarbons, which is characterized in that the hydrogenation takes place over a nickel sulfide and / or cobalt sulfide and molybdenum sulfide and / or tungsten sulfide on a support material and also a fluorine-containing catalyst is carried out.

The incorporation of fluorine into the catalysts can in principle can be done in two ways. Fluorine can be introduced into the catalyst by impregnating the latter with a suitable fluorine compound

or

dung, such as ammonium fluoride, incorporated during its manufacture will.

However, it is also possible to use fluorine in the hydrogenation process in which the catalyst is used, by adding a suitable To incorporate fluorine compound into the gas and / or liquid stream passed over the catalyst into the catalyst. Possibly can do the latter, usually called in situ fluorination designated fluorination process, with the former Impregnation processes are combined. For example, a part the required amount of fluorine by impregnating the catalyst during its preparation and the remaining part of the required Fluorine by in situ fluorination in the hydrogenation process, in which the catalyst is used, are incorporated into the catalyst.

It has also been found that catalysts of the present type in which fluorine has been incorporated by in situ fluorination- ·

309844/1029

is, a better activity in the hydrogenation of aromatic hydrocarbons as catalysts with the same metal loading and the same fluorine content as the fluorine through Impregnation has been incorporated. In contrast, in-situ fluorinated catalysts of the present type show the same thing Activity in the hydrogenation of aromatic hydrocarbons as catalysts with the same metal loading as fluorine has been incorporated by impregnation, but with a lower fluorine content. For the hydrogenation according to the invention preferably suitable catalysts are accordingly prepared by the fluorine at least partially and preferably to more than 50 percent by weight is incorporated into the catalyst by in situ fluorination. In particular, such catalysts prepared by incorporating virtually all of the fluorine into the catalyst by in situ fluorination.

Unlike in situ fluorination, which is very easy during of the hydrogenation process, fluorination by impregnation requires special facilities that are in usually in a. Dearomatization system are not available. Since feeds of different compositions hydrogenation catalysts with different fluorine contents for the best possible To make hydrogenation necessary, it was previously necessary to use a number of catalysts with different fluorine contents for the hydrogenation of the aromatics contained in these feeds available. The use of in situ fluorination for incorporation of fluorine in the present catalysts is'from economical Reasons are very important as it offers the possibility of

309 8 UUI 10 29

in feeds with considerably different compositions present aromatic hydrocarbons / inter use of only one basic catalyst that does not contain fluorine contains or has only a low fluorine content to hydrogenate. The in-situ-Pluorierung allows not only the adjustment of the fluorine content of the catalyst to the composition of the Feed, but also offers the possibility of decreasing the fluorine content of the catalyst in the course of the hydrogenation process Increase the activity of the catalyst.

As mentioned above, the in-situ fluorination of des Catalyst by adding a suitable fluorine compound to the gas and / or liquid flow passed over the catalyst carried out .. The in-situ fluorination of the catalyst is preferably carried out in such a way that practically the entire fluorine added to the gas and / or liquid stream into the catalyst is incorporated and the product flowing out of the reactor has practically no fluorine content. The fluorine compound is preferably added to the liquid feed. The fluorine compound can be fed as such or in liquid form In the form of a concentrate, e.g. in a light hydrocarbon fraction, can be added. Since the fluorine compound must be soluble in the feed to be hydrogenated, one is preferred organic fluorine compound is used. Suitable organic fluorine compounds are o-fluorotoluene and difluoroethane.

The total amount of fluorine to be added to the feed depends on the amount of catalyst to be fluorinated and the catalyst required Fluorine content of the catalyst. For the hydrogenation of aromatic

See hydrocarbons, catalysts with a fluorine content of 1 to 15 percent by weight and in particular 2 to 10 percent by weight are preferably used. If it is assumed that practically all of the fluorine added for the feed is taken up by the solvent analyzer, the total amount of the fluorine added for the feed can be calculated in a simple manner. The in-situ fluorination is preferably carried out by continuously adding a certain amount of a fluorine compound per kg of feed until the entire calculated amount has been taken up. At a given space velocity, the time required to incorporate a given amount of fluorine into the catalyst depends on the concentration of the fluorine compound in the feed. If the feed has a higher fluorine content, the time required for the in-situ fluorination is shortened. In the course of the ih-situ fluorination, the properties of the catalyst and accordingly also the composition of the product flowing out of the reactor change. In order to be able to achieve stable operation with the catalyst as quickly as possible, the in-situ fluorination must be carried out within a short time. This can be achieved by using a high concentration of the fluorine compound in the in situ fluorination. However, the concentration of the fluorine compound in the feed must not be too high, since otherwise some of the fluorine added for the feed may possibly get into the product withdrawn from the reactor and not be incorporated into the catalyst. In the case of the in-situ fluorination of the catalyst, an amount of from 0.01 to 0 ^ 5 and in particular from 0.05 to 0.25 percent by weight of fluorine in

309844/10 29

The form of a fluorine compound is continuously added to the feed.

The in-situ fluorination of the catalyst is preferably carried out in an initial stage of the hydrogenation process, e.g., during or after start-up. Optionally, the in-situ fluorination can also be carried out at a later stage in the hydrogenation process.

Although the present fluorine-containing catalysts

according to the invention

already a high degree of stability in the / aromatic hydrogenation Have hydrocarbons, the stability of these catalysts can be further increased by continuously adding a small amount Amount of a fluorine compound to be fed during the process after incorporating the required amount of fluorine into the catalyst, e.g. by in-situ fluorination. Amounts from 0.0002 to 0.005 and in particular from 0.0005 to 0.002 percent by weight Fluorine in the form of a fluorine compound work well for this purpose. It can use the same or a different fluorine compound as used in in situ fluorination.

The incorporation of fluorine in sulfidic catalysts of the present Type significantly increases their activity in the hydrogenation of aromatic hydrocarbons, especially when fluorine is through in situ fluorination has been incorporated. Because of the already described, possibly occurring, in a method for Hydrogenation of aromatic hydrocarbons undesirable increase in the cleavage activity of the fluorine-containing

309 8A4 / 1029

Catalysts, nitrogen can additionally be incorporated into the catalysts to suppress this cleavage activity. The incorporation of nitrogen into the present catalysts is preferably carried out in the course of the hydrogenation process in which the catalyst is used by adding a suitable one Nitrogen connection to the gas and / or liquid stream which is passed over the fluorine-containing catalyst carried out. The ones to be incorporated into the fluorine-containing catalyst The amount of nitrogen is usually 0.05 to 2.0 percent by weight, preferably 0.1 to 1.0 percent by weight, and it becomes accordingly the more nitrogen is incorporated into the catalyst, the higher the fluorine content of the catalyst and the lower the nitrogen content the feed is. The exact amount of nitrogen to be incorporated into the catalyst in each individual case can be determined by means of less Attempts in which increasing amounts of a nitrogen compound to the feed concerned during the hydrogenation of this Feed added over the fluorine-containing catalyst can be easily determined.

Suitable nitrogen compounds added for feed are e.g. ammonia, ammonium hydroxide, alkylamines such as mono-, di- and trimethylamine and mono-, di- and triethylamine, Alkanolamines, such as mono-, di- and triethanolamine, arylamines, such as. Mono-, di- and triphenylamine, mixed alkylarylamines, such as Phenylethylamine, alkyl diamines, such as ethylenediamine, and aryl diamines, like phenylenediamine. Though only the low molecular weight amines have been enumerated, the various homologues of higher molecular weight can also be used. It is

3098 A4 / 1029

also possible other nitrogen compounds, such as organic Nitrates, nitrites, nitriles, nitroso compounds, amides, imides, ammonium salts (such as ammonium acetate), urea and its derivatives, Cyanates, isocyanates, isocyanides, quaternary ammonium compounds, nitro compounds, pyridine and its derivatives, such as quinoln and Piperidines, oximes, hydroxylamine and azo compounds, too.

As already mentioned, the incorporation of nitrogen into the fluorine-containing catalyst can be achieved by adding a suitable Nitrogen connection to the gas and / or liquid stream passed over the catalyst are carried out. The training of nitrogen in the fluorine-containing catalyst is preferably carried out in such a way that virtually all of it the gas and / or liquid stream added nitrogen is absorbed by the catalyst. The nitrogen compound is preferably for liquid feed either as such or in the form of a concentrate, e.g. in a light hydrocarbon fraction, added.

The total amount of nitrogen to be added for feed depends on the amount of fluorine-containing catalyst in the the nitrogen must be incorporated and the nitrogen content required for the catalyst. If it is assumed that all of the nitrogen added to the feed is absorbed by the catalyst, the total amount of nitrogen used for Feed must be added can be calculated in a simple manner. The incorporation of nitrogen into the fluorine-containing one Catalyst is preferably added by continuous addition

309844/1029

a certain amount of nitrogen compound per kg of feed carried out until the calculated amount for feed is reached. When incorporating nitrogen into the catalyst, from 0.0005 to 0.1 and in particular from 0.0025 to 0.025 percent by weight of nitrogen in the form of a _; Nitrogen compound added for feed. :

The incorporation of nitrogen into the fluorine containing catalyst is preferably in an initial stage of the hydrogenation ■ driving, e.g. during start-up.

For the inventive hydrogenation of aromatic hydrocarbons suitable catalysts consist of nickel sulfide and / or cobalt sulfide, molybdenum sulfide and / or tungsten sulfide and fluorine a carrier material. Preferably these catalysts contain from 0.02.5 to 0.5 gram atoms and especially from 0.08 to 0.4 gram atoms of nickel and / or cobalt and from 0.02 to 0.3 gram atoms and especially from 0.04 to 0.25 gram atoms Molybdenum and / or tungsten per 100 g of carrier material. In addition, the atomic ratio between nickel and / or cobalt is on the one hand and molybdenum and / or tungsten, on the other hand, preferably of 0.1: 1 to 1: 1 and in particular from 0.15 ί 1 to 0.6: 1.

· _ Are preferably used for the hydrogenation of aromatic hydrocarbons Nickel, in particular catalysts containing nickel and tungsten, are used,

Suitable support materials for the present catalysts

309844/1029

e.g.

are / amorphous oxides of the elements of groups II, III and IV des Periodic table of the elements, such as silicon oxide, aluminum oxide, magnesium oxide, boron and thorium, as well as mixtures of these Oxides such as silica-alumina and silica-magnesia. Preference is given to containing aluminum oxide as the support material Catalysts used.

The metals can be prepared on a support material by any known method for the preparation of multicomponent catalysts be incorporated into the catalyst. The metals are

one

preferably by mixing impregnation taking place in / or several stages a carrier material with an aqueous one or more nickel and / or cobalt compounds and one or more Solution containing molybdenum and / or tungsten compounds and

dry
subsequent / and calcining produced. If the impregnation is carried out in several stages, the material can be dried and calcined between the successive impregnation stages. The drying and calcining are preferably carried out at temperatures of 50 to 150 ^° C. or 450 and 550 ^° C. Water-soluble nickel and cobalt compounds suitable for producing the present catalysts are nitrates and formates of these metals. Water-soluble molybdenum and tungsten precursors are the molybdates, such as ammonium molybdate, and the tungstates, such as ammonium tungstate. However, heteropoly compounds of molybdenum and tungsten can also be used. To increase the solubility of these compounds and to stabilize the solutions, certain compounds, such as ammonium hydroxide, monoethanolamine and sorbitol, can be added to the solution.

30984A / 1029

The metals must be present as metal sulfides on the carrier material. The sulfidation of the catalysts can be carried out by any known sulfidation process. The sulfidation can z, B. by contacting the catalyst with a sulfur-containing gas such as a mixture of hydrogen and hydrogen sulfide, a mixture of hydrogen and carbon disulfide, or a mixture of hydrogen and one Mercaptan, such as butylmereaptane, can be carried out. The sulphiding however, it can also be carried out by contacting the catalyst with hydrogen and a sulfur-containing hydrocarbon oil will.

The present fluorine-containing sulfidic catalysts show in the hydrogenation of aromatic hydrocarbons, in particular when the fluorine has been incorporated into the catalysts by in situ fluorination, high activity. they are completely or almost insensitive to sulfur / why their activity does not decrease in the presence of sulfur compounds in the hydrocarbon feed. Using this Catalysts offers the option of containing sulfur Aromatic hydrocarbons present in hydrocarbon fractions to hydrogenate in a single reaction stage without prior desulfurization of the feed »

The present catalysts are excellent for. .

of hydrocarbon oil fractions containing hydrogenation of aromatic hydrocarbons and / or aromatics from the petroleum and tar industry, such as crude benzene and petroleum distillates with a final boiling point below 375 ° C.

303844/1029

Examples of petroleum distillates containing aromatics are fractions after hydrogenation of the aromatics contained in them as an aromatic-free solvent, as a Leuchtpetroleunt with improved Smoke point, as fuels for jet engines with increased combustion heat and improved Raudpunkt and as fuels for Diesel engines with increased cetane number can be used. ■

If only a slight improvement, e.g. the smoke point or the cetane number is sought, it is of course not necessary to hydrogenate the entire feed. In this case it is sufficient to hydrogenate only part of the feed and the hydrogenated part with the untreated part of the feed to blend.

The inventive use of the present fluorine and optionally Nitrogen-containing catalysts for the hydrogenation of aromatic hydrocarbons is fed by contacting the feed carried out at elevated temperatures and pressures in the presence of hydrogen with the catalyst. Suitable hydrogenation conditions are temperatures from 200 to 400 ° C, pressures from 25 to 150 kg / cm, Raura flow velocities of 0.4 up to 8 kg feed per liter of catalyst per hour and a water

309844/1029

. - 14 -

material / feed ratio of 100 to 3000 Nl hydrogen each kg feed. Temperatures of 250 to 350 ° C are preferred,

ο
Pressures of 40 to 100 kg / cm, room flow rates of 0.5 to 4 \ zg of feed per liter of catalyst per hour and a hydrogen / feed ratio of 250 to 2000 Nl of hydrogen per kg of feed are used. The inventive method for the hydrogenation of aromatic hydrocarbons ser materials over the present

Catalysts can be in the gas phase, in the liquid phase or partly in the gas phase and partly in the liquid phase take place. The catalyst is preferably present in one or more plague beds with a particle size of 0.5 to 3 mm.

The examples illustrate the invention.

Manufacture of the catalyst -

There are 22 catalysts containing nickel and molybdenum or nickel and tungsten on a carrier material (A - K and I - XII) by impregnating aluminum oxide with a solution of nickel formate and ammonium molybdate or with a solution of nickel formate and ammonium grinder in one or more stages Ramat made in a mixture of monoethanolamine and water. After each impregnation, the material is dried and then caleiniert 3 hours at ⁰ C 5'00. The catalysts Γ to XII represent fluorine-containing catalysts according to the invention, while the catalysts A to K contain no fluorine. The latter catalysts are produced for reasons of comparison. Fluorine is used in the catalysts I and II during their production by impregnation with one other than the metal

30984 4/1029

compounds ammonium fluoride-containing solution incorporated. The catalysts I and II contain 10 parts by weight of fluorine each 100 parts by weight of aluminum oxide. The catalysts III to X are from the. Catalysts A to H, by in-situ-Pluorierung by Addition of o-fluorotoluene to the feed during the initial stage the hydrogenation process using these catalysts in an amount equivalent to 0.15 percent by weight of fluorine over a period of time sufficient to incorporate 10 parts by weight of fluorine per 100 parts by weight of alumina into the present Sufficient catalysts are produced. Catalyst XI is made from catalyst III by adding 0.005 percent by weight of nitrogen in the form of pyridine for feed during the initial stage of the hydrogenation process using the catalyst, over a period of time sufficient to incorporate 0.5 weight percent nitrogen into the catalyst. The catalysts K and XII are made from the catalyst J by in-situ chlorination and or fluorination in the initial stage of the Hydrogenation process using the catalyst. The in-situ chlorination of catalyst J is accomplished by Addition of 0.03 percent by weight of chlorine as tert-butyl chloride to Feeding carried out over the course of 6 hours.

more After this time, the catalyst does not absorb any more chlorine /.

The in-situ fluorination of the catalyst J is carried out by adding 0.03 percent by weight of fluorine as o-fluorotoluene for feed in the course of ² K) hours.

Those used to make the present catalysts

309844/1029

Aluminum oxide support materials have the following composition tongue on:

Aluminum oxide I: 1.5 mm extrudates, density: 0.5 ^ g / ml. Upper

area: 283 m / g, pore volume: 0.63 ml / gi

Alumina II: beads with a particle size of 2.0 mm _f

Density: 0.43 g / ml, surface area:, 185 m ⁸ / g. Pore volume: 0.75 ml / g;

Alumina III: extrudates with a particle size of 1.5 irra

Density: 0.60 g / ml, surface area: 226 m ² / g, pore volume: 0.65 ml / g.

The catalysts are used in their sulfidic form. The catalysts are grounded by dissolving contact with a Mixture of hydrogen and hydrogen sulfide in a volume ratio of? : 1 at a temperature of 4-fjO C and one Pressure of 10 kg / cm sulphided. The catalyst components are given in Table I.

3 0S8Λ 4/10 29

Tabel

Kataly
sator
No. Alumina
Carrier material
No. A. I. B. I. C. I. D. I. E. I. F. I. G I. H II J III I. I. II II

Nickel content in tungsten content in parts by weight per parts by weight each Weight point 100 parts by weight alumina alumina

2.5

7.5
10

'"

2
13.2

3.3

50 50 50 50

.25 ⁺ 20

48.9 ⁺ 50

12.7 ⁺ 50 50

Molybdenum content of the catalyst

Catalyst tests

The catalysts A to H and I to X are used for the hydrogenation of aromatics contained in kerosene. The trials are

carried out under the following conditions:

Feed: kerosene with a boiling range from 150 to 250 ^° C., aromatic content: 15.5 percent by volume, sulfur content: 0.2 percent by weight

Temperature: 240 to 325 ° Cj Pressure:

75 kg / cm;

-1

Hour "¹;

Liquid space flow velocity: 1 liter ♦ liter Gas velocity: 1500 Nl «liter"¹;

Recycle ratio (liquid product / fresh product): 25: 1

3 0 9844/1029

The results of the experiments are summarized in Table II.

Tables

Catalyst, Hydrogenation tem Aromatic content of the Attempt, No. temperature, ⁰ C Hydrogenation product, No. A. Vol-56 1 A. 325 3.3 2 I. 300 4.8 3 I. 325 2 * 2 4th Γ 300 3.6 5 III 275 6.9 6th III 300 1.2 7th III 275 1.9 8th B. 250 5.2 9 IV 325 6.4 10 IV 300 2.2 11 IV 275 . 5.3 12th C. 250 8.5 13th V 325 4.2 14th V 275 2.9. 15th . - D 250 8.0 16 VI 325 • 4.6 17th VI 275 3.9 18th .E 250 8.9 19th E. 325 ' 5.8 20th VII 300 8.1 21 · VII 300 1.6 22nd P. 275 4.1 23 VIII 325 5.1 24 G 275 3.2 25th G 325 4.5 26th IX 300 6.0 27 IX 275 2.2 28 H 240 8.4 ■ . 29 II 325 5.2 30th II 325 2.9 31 X 300 4.4 32 X 300 1.6 33 X 275 2.5 34 250 5.2

From the values of Table II, what is explained below can be seen:

1. The activity of the catalysts for the hydrogenation of aromatics

309844/1029

is increased by incorporating fluorine into these catalysts.

2. Catalysts in which fluorine is incorporated by in situ fluorination show a higher activity in the hydrogenation of aromatics than catalysts containing the same metals have the same loads and the same fluorine content, however, in which fluorine has been incorporated by impregnation.

3. A comparison of the performances of the catalysts III (Ni / W / F / Al ₂ O ₃ ) and VII (Ni / fao / F / AlgO,), which have approximately the same metal loading in gram atoms per 100 grams of aluminum oxide and. have approximately the same ratio of nickel: tungsten or molybdenum, shows that the combination Ni / W / F has a higher activity in the hydrogenation of aromatics than the combination Ni / Mo / F.

en
H-. A comparison of the performance / the catalysts III (Ni / W / F / AlgO.) And IX (Ni / Mo / F / AlgQ *) shows that the catalyst IX, despite a metal loading that is twice as large as the metal loading of the catalyst III, has a lower activity in the hydrogenation of aromatics.

5. A comparison of the performances of the catalysts III, IV, V and VI, which have a tungsten content of 50 parts by weight per 100 parts by weight of aluminum oxide and nickel contents of 5 × 2.5 » 1, 5 or 10 parts by weight per 100 parts by weight of aluminum oxide shows, that the catalyst III with a nickel / WolP-ram weight ratio of 1 i 10 has the highest activity in the hydrogenation of aromatics.

6, A comparison of the performances of catalysts III and VIII, the

3ÜSn /, 4/102 9

having the same nickel / tungsten weight ratio of 1:10 but different metal loadings shows that the activity the number of catalysts in the hydrogenation of aromatics increases with increasing metal loading.

Catalyst XI is used for the hydrogenation of aromatics. It the same kerosene and the same conditions as in experiments 1 to 34 are used. The results of the experiments with catalyst XI are summarized in Table III. The results of experiments 1 and 2 with catalyst A are for comparison and Experiments 6 to 8 with Catalyst III are also listed in Table III.

Table III

Attempt,
No. Kataly
sator,
No. Hydrie
tion s-
tempera-
tur, ⁰ C Aromatic content
of the hydrogenated
Product, VoL- $ Columns in under
half 150 ^X) C them
end products,
Weight % 1 A. 325 3.3 J, 5 2 A. 300 4.8 1.0 6th III 300 1.2 10.2 7th III 275 1.9 3.1 8th III 250 5.2 1.1 35 XI 300 1.3 2.3 36 XI 275 2.5 1.3

From the data in Table III it can be seen that the cleavage activity the catalytic converter increases due to the addition of fluorine. By adding nitrogen, the cleavage activity of the fluorine-containing Catalyst significantly reduced. As a result of the addition of nitrogen, the hydrogenation activity of the fluorine-containing one increases Catalyst only slightly reduced. Because of the strong

3 0 98 kUi 10 29

going back to the incorporation of fluorine into the catalyst Hydrogenation activity, this slight decrease in hydrogenation activity is of no concern.

The activity of the catalysts J , K and XII in the hydrogenation of benzene is tested by means of a benzene hydrogenation test carried out under the following conditions:

Temperature: 400 ° C;

Pressure: 48 kg / cm;

Liquid space flow rate: 5 liter-liter "-hour"; H ₂ / benzene mole ratio: 20: 1;

Hydrogen sulfide partial pressure: 0.33 kg / cm.

The activity of the catalyst is expressed as the constant of the rate of the first order reaction for benzene hydrogenation Expressed in ml benzene (ml catalyst) "» hours ~. The results these experiments are summarized in Table IV.

Table IV

Attempt,
No. Catalyst,
No. Benzene hydrogenation
activity,
ml · ml "^ -" h "^ 37 J 0.37 38 K 0.55 39 XII 1.07

From the values of Table IV it is apparent that the in-situ Pluorierung of the catalyst to a significantly larger increase in activity in the hydrogenation of aromatics than the in situ chlorination

30 9 8 44/1029

ration of the catalyst leads.

309844/1029

Claims (3)

Claims Process for the hydrogenation of aromatic hydrocarbons, characterized in that the hydrogenation takes place over a nickel sulfide and / or cobalt sulfide and molybdenum sulfide und / oder'Wungframsulfid on a carrier material and also Fluorine-containing catalyst is carried out. 2. The method according to claim 1, characterized in that the hydrogenation is carried out over a catalyst in the at least a part and preferably more than 50 percent by weight of the fluorine content has been incorporated by in-situ fluorination are. 3. The method according to claim 2, characterized in that the Hydrogenation is carried out over a catalyst into which practically the entire fluorine content is incorporated by in-situ fluorination has been. 4. The method according to claim 2 or 3, characterized in that the hydrogenation is carried out over a catalyst which by continuous addition of 0.01 to 0.5 percent by weight and preferably 0.05 to 0.25 percent by weight of fluorine in the form a Fluörverbindung for feeding in for the hydrogenation process to reach the necessary fluorine content of the catalytic converters has been j tors in situ fluorinated. 5. The method according to claim 2 to 4, characterized in that the hydrogenation is carried out over a catalyst which 3 0 S fU Λ / 1 0 2 9 fluorinated in situ at an initial stage of the hydrogenation process has been. 6. The method according to claim 1 to 5 »characterized in that that the feed to the process after reaching the required The fluorine content of the catalyst over which the hydrogenation is carried out is further continuously from 0.0002 to 0.005, and preferably 0.0005 to 0.002 percent by weight of fluorine can be added in the form of a fluorine compound. 7. The method according to claim 1 to 6, characterized in that that the hydrogenation is carried out over a catalyst with a fluorine content of 1 to 15 and preferably from 2 to 10 percent by weight will. 8. The method according to claim 1 to 7 *, characterized in that that the hydrogenation is carried out over a catalyst additionally containing nitrogen. 9. The method according to claim 8, characterized gekennzeiehne'c that the hydrogenation is carried out over a catalyst, in the the nitrogen has been incorporated by adding a suitable nitrogen compound to the gas or liquid stream passed over the fluorine-containing catalyst. 10. The method according to claim 9 *, characterized in that the hydrogenation is carried out over a catalyst in which the Nitrogen by continuously adding from 0.0005 to 0.1 and 3 0 9 8 4 4/1029 preferably from 0.0025 to 0.025 percent by weight nitrogen in. Form a nitrogen compound until the required level is achieved Nitrogen content of the fluorine-containing catalyst for feed to the hydrogenation process has been incorporated. 11. The method according to claim 9 or 10, characterized in that that the hydrogenation is carried out over a fluorine-containing catalyst in which the nitrogen in an initial stage of the Hydrogenation process has been incorporated. 12. The method according to claim 8 to 11, characterized in that that the hydrogenation is carried out over a catalyst with a nitrogen content of 0.05 to 2 and preferably 0.1 to 1 percent by weight is carried out. 15. The method according to claim 1 to 12, characterized in that that the hydrogenation is carried out over a catalyst containing 0.025 to 0.5 and preferably 0.08 to 0.4 gram atoms of nickel and / or cobalt and 0.02 to 0.3 and preferably 0.04 to 0.25 Gram atoms of molybdenum and / or tungsten per 100 grams of carrier material contains. l4. Method according to Claims 1 to 13 *, characterized in that that the hydrogenation is carried out over a catalyst which has an atomic ratio of nickel and / or cobalt: molybdenum and / or Tungsten from 0.1: 1 to 1: 1 and preferably from 0.15: 1 to 0.6: 1. 3098 4 4/1029 15. "The method according to claim 1 to l4, characterized in that the hydrogenation is carried out over a nickel, preferably in combination with a tungsten _/ containing catalyst. 16. The method according to claim 1 to 15, characterized in that that the hydrogenation is carried out over a catalyst containing aluminum oxide as a support material. 17. The method according to claim 1 to 16, characterized in that that the hydrogenation is carried out over a catalyst which, by mixing impregnation of the support material with an aqueous, containing one or more nickel and / or cobalt compounds and one or more molybdenum and / or tungsten compounds Solution, which can be done in one or more stages, and subsequent
by drying and calcining the thus obtained Material has been produced. l8. Method according to claims 1 to 17, characterized in that one that. aromatic hydrocarbons in / petroleum distillate with .be hydrogenated at an end boiling point below 375 ° C. 19 «Method according to claim 1 to 18, characterized in that that the hydrogenation at temperatures of 200 to 400 ° C, pressures from 25 to 150 kg / cm, room flow velocities, from 0.4 to 8 kg feed per liter of catalyst per hour and a hydrogen / feed ratio from 100 to 3000 Nl of hydrogen per kg of feed is carried out. "3O9" P4A / 1Q2 9 20. The method according to claim 19, characterized in that the hydrogenation at temperatures of 250 to 35O ° C, pressures of 40 to 100 kg / cm, room flow rates of 0.5 to 4 kg feed per liter of catalyst per hour and hydrogen / feed ratios of 250 to 2000 Nl of hydrogen per kg of feed is carried out. 3 U 3. ' A Λ / 1 0 2 9