DE1542559A1 - Process for the production of catalysts for the hydrocatalytic processing of hydrocarbon fractions - Google Patents

Description

Process for the production of catalysts for hydrocatalytic Processing of hydrocarbon fractions The invention relates to a method for the production of highly active catalysts, did from Blementen VI. and / or VIII. Group of the periodic table or their oxides or sulfides and a carrier Aluminum oxide and silicic acid or aluminum silicate exist, f @ the hydrocatalytic Processing of hydrocarbon fractions, especially for hydro refining of carburetor and diesel fuels as well as lubricating oil fractions for hydro splitting of vacuum distillates, for the isomerization of xylene mixtures and for reforming of heavy gasoline.

It is known to use hydrocarbon fractions hydrocatalytically in the presence to process such catalysts, which are made from Blementen VI. and / or VIII. group of the periodic table or their oxides or sulfides are made on supports Aluminum oxide or aluminum silicates with a silica content suitable for the reaction are upset. Various processes are used to manufacture the catalyst carrier known.

So it is known to use aluminum oxide carriers through the precipitation of aluminum hydroxides or oxide hydrates through the reaction of alkali metal aluminate solutions with acids, of aluminum salt solutions with alkyl hydroxide solutions or aqueous solutions of ammonia or by hydrolysis of aluminum alcoholates or by reacting alkali aluminate with aluminum alkoxide solutions to win. As a result of its high economic efficiency, the latter production method has particular technical interest.

In all cases, changing the pelling conditions at the production of Aluy'niumhydroxida resp.

Oxide hydrate or due to the further aging of the precipitation product and also by the manner in which the aluminum hydroxide or oxide modifications obtained are dried and calcined the properties of this active alumina changed over a wide range and were intended for this purpose Purpose to be adapted.

The catalysts made using alumina however, they have the naah part that sis only a low thermal and low aging resistance show and their acidity is not sufficient to produce isomerization on an industrial scale. and to accelerate hydrocracking reactions with sufficient speed.

These disadvantages are largely avoided by using a catalyst support uses made of aluminum silicates or

Mixtures of aluminum oxide and silica exist. For the production There are three known methods of t'rager alone.

It is known, for example, to fill aluminum parts by means of a multi-stage filling to win. It is based on a pre-precipitated and almost a certain aging period Silica gel soaked in aluminum salt solutions using alkali hydroxide solutions or aqueous solutions of ammonia precipitated aluminum hydroxide. The disadvantage this process consists in each stage of the preparation of the catalyst support must be specially regulated, d. H. The temperature, residence time and pH value must be taken into account are kept constant for each process stage.

It is also known to combine alkali and aluminum silicates Manufacture alkali aluminate solutions. After this process, however, aluminum silicates are used obtained whose catalytic properties are not completely satisfactory.

Both the multi-stage precipitation of the aluminum alicate tea as well as the common fall through double implementation have the other big one Disadvantage that they are used for the production of aluminum silicates with relatively little Silica content are not suitable. For the production of catalysts for Hydro refining of hydrocarbon fractions for the hydro-splitting of vacuum distillates and for reforming heavy gasoline, however, aluminum salts with the high are Silica content, as it is present in Crackkatalyeatoren, unsuitable because they result Their high aoidity has a very high tendency to split in hydrorefining and show deformation, or in the hydrocracking of vacuum distillates under one Allow a pressure of 70 to 120 atm only for a short working period due to rapid coking.

Finally, it is known to separate aluminum hydroxide and silica to precipitate, and in the moist or dried state in the desired proportions to mix with each other. A1B starting components can also include aluminum oxide, Silicasduresol, KieselsQuregel, dried silica and natural or synthetic Aluminum @ silicates can be used.

The disadvantage of this process is that it is not continuous Precipitation of the catalyst support enables and precise compliance with the mixing ratio of aluminum oxide and silica due to the fluctuating water content of the precipitation products is difficult to achieve in technology. Furthermore, the manufacturing is very nu cumbersome, since two different starting solutions have to be dealt with and two similar products are each to be filtered and washed. Also can Simply mixing silica and aluminum oxide does not produce the desired result can be achieved in any case.

This is the case with the addition of natural silicates to an aluminum oxide not possible, the hydrogap performance of the aluminum? xj. dträgers significantly to improve, or z. B. for the isomerization of xylenes, if the aluminum silicate carrier is produced by mixing aluminum oxide and silica, very high operating temperatures, the increased formation of by-products lead to the isomerization.

The purpose of the invention is to avoid the disadvantages outlined above.

. There was thus the task of a continuous and simple Process for the preparation of catalysts supported on alumina and Silicic acid or aluminum silicate for the hydrocatalytic processing of hydrocarbon fractions to develop with which it is possible to use aluminum silicate carriers over a large area the molar ratio of alumina to silica. to get sour, so dab that Method of making more specific.

Catalysts for the hydrocatalytic processing of the most diverse Allows hydrocarbon fractions.

This object is achieved in that. one in the production of Catalysts made from elements of VI. and / or VIII. Grappe of the periodic table or their oxides. or sulfides and a tramer of aluminum oxide and silica or aluminum silicate, aluminum hydroxide and the silicic acid or aluminum silicate according to the invention from a common solution of alkali silicates and aluminum salts, which may optionally contain fluorine compounds, by precipitation with solutions of ammonia, ammonium carbonate, alkali hydroxides or carbonates or alkali aluminates produces and the active components on the carrier material obtained in this way applies in a known manner.

The common aqueous solution of alkali silicates and aluminum salts is expediently prepared in such a way that aqueous solutions of both substances are obtained in the desired Quantity ratio mixed together. The common oil is said to be faintly sour be, with expedient a pH-Berei. h from 0 to 1 is adhered to. The relationship from silica to alumina in the solution can vary according to the respective Purpose of the catalysts between. si. hen 1: 100 to 3: 1 can be varied .-- The Concentration of the solution is dated Silica content dependent and is expediently in total 5 to 10% by weight, based on silica and aluminum oxide.

The common solutions are for further technical processing sufficiently stable and can be stored for long periods of time before flocculation starts from silica.

Water glass is particularly suitable as the alkali silicate. That has the advantage, that a technically easily available and cheap starting product is used comes.

Aluminum sulfate or chloride is preferably used as the aluminum salt or nitrate.

The filling products obtained according to the invention are per se in a known manner with water, optionally with the addition of acids or ammonium salts, Washed alkali-free, dried and ground. The ground aluminum silicate carrier Depending on the aluminum oxide / silica ratio, 1. after peptization with dilute Acid to balls 2 to 4 mm in diameter, 2. in a kneader with t aqueous or ammoniacal Solutions of the catalysts are kneaded and the kneaded product su strands of the desired Grain size or 1. after mixing with the active components to make pills of the desired Size to be deformed. The deformation into spheres is particularly suitable for aluminum silicates With a silica content up to 15%, the deformation into strands for aluminum silicates With a silica content up to 40% and the deformation to'Pills for aluminum silicates with a silica content over 40%.

The aluminum silicate spheres can be impregnated with the active components in the column used to produce the spheres or after the spheres obtained have been calcined with an aqueous or ammoniacal solution of the active components, possibly with the addition of complexing agents An important advantage of the new process is that it allows the aluminum silicate to be continuously precipitated in a simple manner in a wide range of the aluminum oxide / silica ratio and, compared with the known processes, requires particularly little chemicals. The main advantage of the process is that through the appropriate choice of precipitants and the aluminum oxide / silica ratio in the same device and using the same technology, different types of aluminum silicates can be obtained, which are necessary for the individual processes of the hydrocatalytic Processing of hydrocarbon fractions are particularly suitable as catalyst carriers.

As already mentioned, they are suitable as catalyst carriers for hydro refining of hydrocarbon fractions and the reforming of heavy gasoline aluminum silicates with low silica content. It has been found that when using the invention In the process, the silica content of the carrier is expediently between 1 and 5%.

It has also been found that vacuum distillates can be used for hydrocracking at a working pressure of 70 to 120 at catalyst support are suitable, their silica content 3 to 15%.

PUr the hydroforming of vacuum distillates under high pressure of 120 up to 300 at, the silica content of the carrier should expediently be between 10 and 30 %, the cleavage activity of this Travers dureh a content of 0.5 to 2.5% fluorine, in bound form, is favorably influenced. This is where the fluorine is used expediently in the form of hydrofluoric acid or sodium or ammonium fluoride of the common Solution of alkali silicates and aluminum salts too.

A fluorine-activated one produced in this way proves to be far superior Aluminum silicate catalyst in the hydrocracking of vacuum distillates under one Pressure from 120 to 300 at compared to known fluorine-activated catalysts. Under same working conditions he achieves a greater splitting capacity, whereby the fission products one higher degree of refining and a better degree of isomerization exhibit.

For the production of catalysts for the isomerization of xylene special carriers with a silica content of 30 to 70% are suitable. In the It is special to manufacture the catalyst supports with these high silica contents advantageous if aqueous solutions of ammonium carbonate or as the precipitant Ammonia can be used, for example the ammonium salts formed during the precipitation Facilitate washing out the alkali ions from the filter cake.

Furthermore, the catalysts have compared to known catalysts the advantage that in most cases they carry out the reactions enable lower working temperatures with longer running times. So allow one catalyst prepared according to the invention, the isomerization of xylenes in a Pressure from 5 to 100 at and a catalyst space velocity between 0.5 and 4 v / vh berelts in the temperature range between 370 and 440 ° C. In contrast, one requires mixing Catalyst obtained from aluminum oxide and silica has a working temperature that is 70 ° C higher, This results in faster coking of the catalyst and thus shorter operating periods and result in poorer yields.

The catalysts according to the invention are produced by burning off the coking products with air or gases containing oxygen, possibly also with steam Temperatures. between 300 and 600 ° C, preferably at 450 ° C, regenerable in situ.

Example 1: Following the process of the invention, a catalyst became a catalyst (A) prepared as follows: To 3150 l of an aqueous solution of aluminum nitrate with a content of 100 g Al2O3 / l and 25 g HNO3 / l were stirred at room temperature 760 1 aqueous water glass solution with a content of 50 g SiO2 / l given and out the combined solutions with a sodium aluminate solution, the 247 g Al 2 O 3 / l and 246 g NaOH / l, with the addition of water, aluminum hydroxide and silica respectively.

Like aluminum silicate. The precipitation temperature was 40 ° C, the pH value during precipitation 7 and the content of aluminiumailicate in the precipitation suspension 10.7% * The suspension obtained was printed on a filter press, with 200 m3 of water washed and dried at 150 ° C.

Analysis of the dried product showed 69, 73% Al2O3, 2.37 % SiO2, remainder H2O. Based on the anhydrous substance, the SiO2 content was 3.3 %.

125 kg of the dried and ground product were in one Kneader with 70 l of an ammoniacal solution of nickel sulfate, amnionium tungstate and ammonium molybdate with a content of 50.9 g / l Ni, 219.0 g / l WO3 and 154 g / l MoO3 kneaded. The kneaded product was extruded into strands of Deformed 4 mm in diameter and 4 bLa 6 mm in length. The strands were dried and annealed at 550 ° C.

The catalyst obtained had the following composition: 3.15% Ni 11.5% WO3 7.8% MoO3 2.2% SiO2 remainder Al2O3 The bulk weight was 0.75 kp / 1.

A similarly composed catalyst (B) was the difference for the catalyst (A) ethalten that with otherwise the same method of preparation SiO2-containing alumina carriers had been obtained by mixing the components.

The bulk weight of the identically shaped catalyst was 0.82 kgf / l.

Both catalysts were in part under different conditions for the hydrogenative refining of a petroleum vacuum distillate with the following result used: Characteristic data crude raffinate product catalyst-A BB temperature ° C-405 405 430 hydrogen pressure, at-100 100 100 load, v / vh-1 1 1 gas-product ratio Nm3 / m3 - 500: 1 500: 1 500: 1 Density (40 ° C) 0.866 0, 856 0, 859 0, 843 onset of boiling, ° C 260 185 192 141 to 400 ° C sd.,% By volume 30,544,544,154.3 to 450 ° C sd.,% By volume 67, 3 73, 8 69, 8 84 8 to 500 ° C sd.,% By volume 98, 5 98, 9 98, 9 99, 1% by weight 360 ° C 9.6 17.0 15.9 26.8 sulfur, ppm 18 900 400 953 395 'bas. Nitrogen mg NH3 / l 220 35 120 75 Absorbance at 480 m 1, 85 0, 186 0, 310 0, 260 The better performance of the catalyst A is evident.

The refining and hydrogenating effects are at the same operating conditions of the catalyst B substantially below that produced according to the invention Catalyst A.

At a higher working temperature, the degree of refinement of the catalyst increases B improves, but at the same time the fission and thus the hydrogen consumption increase clearly.

Example 2: Using the catalysts prepared according to Example 1 A and B became the hydrorefining of straight-run diesel oil with the following result carried out : Characteristic data crude product raffinate catalyst-A B temperature, ° C-360 360 hydrogen pressure, at-20 20 load, v / vh - 5 5 gas-product ratio Nm3 / m3 - 250: 1 250: 1 Density (20 ° C) 0 836 0, 827 0, 828 Beginning of boiling, ° C 229 203 210 End of boiling, oc 323 323 323 sulfur, ppm 9 100 430 1 230 bas. Nitrogen mg NH3 / 1 12 10 11 example 3: According to the invention, another catalyst (C) was prepared as follows : To 3000 l of an aqueous aluminum sulphate solution with a content of 105 g Al2O3 / l 2400 l of a Wasaerglaaläsung with 50 g SiO2 / l were added with stirring. From the combined solution were with a solution of sodium aluminate with 310 g Al2O3 / l with the addition of water, aluminum hydroxide and silica or aluminum silicate pleases. The temperature during the precipitation was 60 ° C., the pH value 8 and the content of aluminum silicate in the precipitation suspension 9.4%. The dried product had the following composition: 63.9% Al2O3. 7.1% SiO2, remainder H2O. On anhydrous Based on the substance, the SiO2 content was 10%.

150 kg of the dried and ground product were charged with 7, 0 l 50% nitric acid and 120 l of water are peptized. The obtained peptized Solution was dropped into a column filled with ammonia water. The received Balls were dried and calcined and treated with 1000 liters of an ammoniacal solution of nickel nitrate and ammonium molybdate, whose nickel content is 54 g / l and @d MoO3- salary 215 g / l, soaked. After drying again and firing at 550 ° C, the Catalyst with the following composition: 3.0% Ni 16, 0% MoO3 8, 0% SiO2 remainder A1203.

The debris weight was 0.73 kgf / l.

A similarly composed catalyst (D) in which the carrier produced in a known way by mixing Al2O3 and kaolin, had at the same shape has a bulk density of 0.80 kp / 1.

The activity of catalysts C and D was determined for hydrocracking of a vacuum distiller checked. The result of the hydrotreating processing is listed below for comparison: - Characteristic data of crude reaction product produit Catalyst-C D temperature, ° C - 430 430 hydrogen pressure, at 0 100 100 load, v / vh-1 1 Gas-product ratio Nm3 / m3-1000: 1 1 Density (40 ° C) Q, 886 0, 823 0, 827 C1-C2 hydrocarbon, wt% -3.2 4.1 C3 hydrocarbon, wt% -2.3 3.5 C4 hydrocarbon, wt% - 3.1 7.9 fraction C5-180 ° C, wt% - 15.9 27.8 Fraction 180-350 ° C, weight 5 7.8 53.8 43.2 sulfur, ppm 18 900 218 485 basic nitrogen compounds, mg NH3 / l 220 2 17 The catalyst prepared according to the invention As the table shows, C is particularly suitable for hydrocracking vacuum distillates in preferably middle distillates. The medium oil to gasoline ratio is 3.85 compared to 1.55 for catalyst D, which also has more gaseous hydrocarbons and shows inferior refining performance.

Example 4: To 2100 l of an aqueous solution of aluminum nitrate with a content of 100 g Al2O3 / l, 2 g Hf / l and 55 g NH03 / l, were stirred with stirring 3700 1 aqueous water glass solution with a content of 50 g SiO2 / l at room temperature given, and from the combined solutions with a sodium aluminate solution, the 200 g / l A1203 and 200 g / l NDOH, with the addition of water, aluminum hydroxide and silica or aluminum silicate like. The precipitation temperature was 90 ° C. and the tH value in the precipitation 8, 0, and the content of aluminum silicate in the precipitation suspension i, 6%.

The suspension obtained was pressed onto a filter press, with Washed 200 m3 of water and dried at 150 ° C. Analysis of the dried Product resulted in 58.8% Al2O3, 16.7% SiO2, 1.0% F, remainder H2O. On anhydrous substance related, the SiO2 content was 22.1%.

The following amounts of substance were mixed with stirring and added up to Evaporated dry: 40 1 water 40 1 24% ammonia water 2, 46 kg tungstic acid hydrate 1.00 kg molybdic acid 3, 5 1 nickel nitrate solution with 214 g / l Ni 32, 1 kg aluminum silicate.

The dried mass became tablets of 5 mm in diameter and Deformed to a length of 5 mm and then annealed at 550 ° C. The pills received had the following composition: 7 7% WO 295 5% MoO3 3.3% NiO 18.8% SiO2 1.5% F remainder Al2O3 The one produced according to the invention in the above manner Catalyst (E) was used for the two-stage hydrocracking of a petroleum vacuum distillate tested under high pressure in a small-scale experimental apparatus. To one To obtain an exact comparison of activity, were carried out in parallel among the equations Call conditions three catalysts are used in which using the the same type and concentration of heavy metal components as the following carrier materials the following were used: 1. γ-aluminum oxide (catalyst F); 2. fluorine activated γ-aluminum oxide (catalyst G) and 3. fluorine-activated aluminum silicate (catalyst H) by mixing Al2O3, SiO2 and hydrofluoric acid and then deforming it (together with the heavy metal additives).

Working conditions during testing: pressure 280 at (fresh hydrogen, 98.5%) space velocity over the catalyst 1.0 v / vh gas-product ratio 1000: 1 Nm3 / m3 reaction temperature 436 oC ascending direction of flow A vacuum distillate with a Boiling range from 350 to 500 ° C, one. Sulfur content of 2.0%, a nitrogen content of 0.15% and a base number of 370 mg NH3 / l.

A Test results: Catalyst: E P G H WO3 WO3 WO3 WO3 Mo ° 3 MoO3 MoO3 MoO3 and NiO and Nit and Ni0 and NiO on on on on fluor- γ-Al2O3 fluorine fluoradivating activating activated Alu- tem tem minium- # -Al2oe Al2L3 / silicate SiO2 (according to the invention) carrier reaction product: yield% by weight 92, 0. 91, 7 91.7 94.0 Density at 20 ° C g / cm3 0.792 0.823 / 50 ° 0.816 / 50 ° 0.815 / 505 Proportions 350 ° C, wt .-% 88.5 55, 3 60.4 55.0 350 ° C, Geai.-. -% 11, 5 44, 7 39, 6 45.0 base number mg NH3 / l 0 6.2 1.7 11.6 sulfur wt .-% 0, 011 0, 032 0, 020 0, 06 Ratio of iso to normal C6 in light petrol 1.50 1.08 1.13 1.02 pour point im DK ° C-20-13-12-113 From further studies it emerged that to achieve a approximately the same cracking performance for the catalysts with conventional carriers a temperature that was at least 15 to 20 ° higher had to be used.

The catalyst E was taking over 1350 hours. the stated conditions operated without a decrease in activity.

Example 5: A catalyst prepared according to Example 4 E was to determine its applicability in large-scale operations in a Pilot plant tested under operational conditions. The plant had its own gas circuit. The heat management was adiabatic, i. H. the heating the recycle gas / feedstock mixture was set up separately from the reactor Preheating carried out. The heat of reaction was dissipated by feeding in cold gas directly into the catalyst layer.

The catalyst volume was 400 times the volume of the example 4 used small-scale equipment.

Working conditions: pressure 300 at catalyst space velocity 1.33 v / vh circle Running gas / product ratio 1000: 1 Nm3 / m3 reactor inlet temperature 407 ° C reacfor outlet temperature 456 ° C mean Reactor temperature 428 ° C flow reversal, descending feed product : Vacuum distillate according to example 4 reaction product: yield% by weight 92, 3 Density at 20 ° C g / cm3 0.810 Antele up to 350 ° C% by weight 70 parts above 350 ° C wt .-% 30 base number mg NH3 / 1 1, 0 sulfur wt .-% 0.030 Y iso-to normal-06 at 1.50 light petrol pour point at DK ° C-21 Thus it turned out the catalyst E even under the more stringent conditions of a heavier load and the heat management controlled by cold gas as fully functional, example 6: Bine mother liquor obtained by freezing out the p-xylene from a coal tar with about 10% p-xylene, 2% o-xylene, 85% m-xylene and 3% ethylbenzene was with two various catalysts under the conditions given in the table below isomerized.

The large-scale production of the catalyst I with the carrier composition of 50% SiO2 and 50% Al2O3 was carried out according to the invention as follows: 2136 kg of water glass with 24.4% SiO2 and a density of 1.354 g / cm3 were mixed with water diluted to 10 400 1. Dilute waterglass solution containing 50 g SiO 2/1 was with vigorous stirring to 5200 1 aluminum nitrate solution with the composition of 100 g Al2O3 / l and about 90 g free HNO / l are given.

With a simultaneous feed of 220. 1 28% item ammonia water / h and 960 liters of condensed water were made from 1560 liters of the combined waterglass-aluminum nitrate solution / h while maintaining pH 8.0 and a temperature of 20 to 25 ° C continuously Aluminum hydroxide and silica or aluminum silicate are precipitated.

The suspension was pressed onto a filter press and zanachet with Condensation water, then with a 1% ammonium sulfate solution and calculates again washed with condensation. The filter cake was dried at 120 ° C.

The composition of the carrier after drying was: residue on ignition = 77.7%, of which SiO2 = 39.0 Al2O3 = about 38.7% Na2O = below 0.05%.

10 kg of this carrier were with the addition of 30 1 24% ammonia water, 820 g of tungstic acid hydrate (92% VIO 3 and 750 g of molybdic acid trioxide in a stirring pan evaporated to dryness with stirring. The dry mass was ground and with the addition of a lubricant to form cylindrical tablets, each 5 mm high and diameter deformed. The moldings were calcined at 450 ° C. for 5 hours.

The composition of the catalyst was: 7. 5% WO 7, 5% MbO3, and the remainder consisted of equal parts SiO2 and Al2O3. The catalyst K was in a known way by intimate mixing of precipitated and washed, but not dried aluminum hydroxide and separately precipitated and washed Silica hydrogel has been prepared, with molybdic acid during mixing and tungstic acid in ammoniacal solution were added. After drying and pelletizing, the catalyst contained 50% SiO2, 35% Al2O3, 7% MoO3 and 8% WO3.

It can be seen from the table that the catalyst used in the inventive Way was prepared (catalyst I), isomerized at much lower temperatures than the one whose support was made by mixing the components (catalyst K). Due to the lower operating temperature, the operating periods were inevitably much longer Catalysts of type I were regenerated after times of 1000 to 1200 hours and had a total life of about 8000 hours. The invention Catalysts were active and showed up to the first regeneration 2500 to 3000 hours after ten regeneration there is still no reduction in activity.

Table Ka cor temperature ° C 390 470 pressure at 40 40 stressful v / vh 11 m-xylene% 60-64 50-58 o-xylene% 9-13 11-13 p-xylene% 19-21 18-20% of the thermodynamic Equilibrium> 93> 93 ethylbenzene% 2-3 3-4 toluene% 2-3 5-9 by-products %> - 1j-3 Example 7s According to the process of the invention, the catalyst was (L) for the reforming of sulfur made by the following process: To 3150 l of an aqueous solution of aluminum nitrate with a content of 100 g Al2O3 / l and 25 g HNO3 / l were stirred at room temperature 760 l of an aqueous waterglass solution with a content of 50 g 3iO2 / l and from the combined solutions with a 28% aqueous solution of ammonia. Aluminum hydroxide and kielazure or aluminum silicate pleases. The precipitation temperature was 60.degree. C. and the pH was 8. The received sumponsion was gowaechon with water and dried at 150,000.

150 kg of the dried and ground product were charged with 7.0 l 50% nitric acid and 120 1 tasser peptized and the resulting solution in a Dripped column filled with ammonia water. was. The balls obtained were. dried, then calcined and treated with hexachloroplatinic acid using the usual method soaked.

After drying and calcining, the composition of the catalyst was as follows : Residue on ignition 94.5%, of which SiO2 3% γ-Al2O3 92% Pt 0.54%.

A further catalyst (M) was made in a known manner without the addition of SiO2 made from alumina containing fluorine. It had the following composition: GlUhrUckstand 95.5%, consisting of γ-Al2O3 with F 0.55% Pt 0.59%.

Both catalysts were reformed after being regenerated three times of heavy gasoline with the following result: Characteristic data crude catalyst L Catalyst M product temperature ° 0 490 510 490 510 pressure at 35 35 35 35 load v / vh 2 2 2 2 gas prod. Ratio 1000: 1 1000: 1 1000: 1 1000 # 1 density gcm-3 0.758 0.776 0.779 0.7775 0.777 aniline point ° C 55.2 14.7 0.3 18.2 6.4 aromatics% by volume 13, 0-57-53 mean octane number clear 38.0 76 81 75 79 to 100 ° C sd.Vol .-% 1, 0 17 21 15 20 to 150 ° C sd.Vol .-% 58, 0 59 63 58 61 -. Yield, vol .-% 0--83-83 Der Halogen loss in the regenerated catalyst M was about 40%, based on the starting amount of fluorine.

From the table it can be seen that the catalyst according to the invention L superior to a conventional reforming catalyst after a few regenerations is. It gave a reformate with a higher aromatic content and with the same yield higher octane number.

Claims (6)

Claims:. 1. Process for the production of catalysts from elements the VI. and / or VIII. Grappe of the periodic table or their oxides or sulfides and a carrier made of silica and aluminum silicate, respectively, for the hydrocatalytic Processing of hydrocarbon fractions, characterized in that aluminum hydroxide and the silicic acid or the aluminum silicates from a common acidic solution of alkali silicates and aluminum salts, which may contain fluorine compounds can, with solutions of ammonia, ammonium carbonate, alkali hydroxides or carbonates or alkali aluminates precipitates and the active components on the so obtained Applies carrier in a known manner. 2. The method according to claim 1, characterized in that as Alkali silicate water glass and aluminum sulfate, chloride or nitrate as aluminum salts used. 3. Process for the production of catalysts for liydroraffination of hydrocarbon fractions and the reforming of heavy gasoline according to claim 1 and 2, characterized in that in the common acidic solution and in the precipitated aluminum silicates of the silica content 1 to 5%, based on the total weight of silica and alumina. 4. Process for the preparation of catalysts for hydrocracking of vacuum distillates at pressures of 70 to 120 at according to claim 1 and 2, characterized marked that in the common. acidic solution and in the precipitated aluminum silicates the silica content 3 to 15%, based on the total weight of silica and alumina. 5. Process for the preparation of catalysts for hydrocracking of vacuum distillates at pressures of 120 to 300 at according to claim. 1 and 2, thereby characterized in that in common acidic solution and in precipitated aluminum silicates the silica content 10 to 30%, based on the total weight of silica and alumina, and from 0.5 to 2.5% fluorine in bound form delialed therein are. 6. Process for the preparation of catalysts for di. e isomerization of hydrocarbons, in particular xylene mixtures, according to claims 1 and 2, thereby characterized in that in common acidic solution and in precipitated aluminum silicates the silica content is 30 to 70%, based on the total weight of silica and aluminum oxide, and as precipitating agents, aqueous solutions of ammonium carbonate or ammonia can be used.