DE1256824B - Process for the hydrocracking of hydrocarbons - Google Patents

Description

GERMAN W9TW> PATENT OFFICE DeutscheKl .: 23 b -1/04

EDITORIAL _NUMBER

File number: U8503IVd / 23b J 256 824 Filing date: November 28, 1961

Opened on: December 21, 1967

The invention relates to a process for hydrocracking hydrocarbons for production lower boiling hydrocarbons, in which the hydrocarbons are in the presence of added hydrogen under hydrocracking temperature and pressure conditions with a tablet or pill-shaped catalyst are brought into contact.

For the hydrocracking of hydrocarbons, catalysts with a gel-like amorphous silica-alumina cracking base have generally been used up to now. Since these catalysts are not very selective in terms of their activity and, moreover, the process has to be carried out at relatively high temperatures, undesirably high levels of coke and methane formation occur. For this reason, the hydrocracking processes carried out using the known catalysts suffer from certain serious shortcomings. In general, the processes are carried out at relatively high temperatures, above about 455 ^: C. However, these temperatures favor dehydration and coking. To achieve a significant hydrogenation effect through the added hydrogen and to reduce the coking rate. it is necessary to use relatively high pressures of 210 to 560 at. A catalyst which is already active at low temperatures is therefore very desirable both from the standpoint of reducing the rate of coke deposition and from the standpoint of using low pressures.

The deficiencies occurring when using the known catalysts are particularly noticeable in working processes with a fixed bed. The main problem with these processes is the extension of the operating time between the individual catalyst regenerations. If regeneration is required every few days, it is generally necessary to have two catalysts, which doubles the amount of catalysts required per reactor. Only one reactor is then always in operation while the other is being regenerated. If a catalyst maintains its activity for several weeks, it is generally more economical to regenerate and shut down the plant than to provide an additional reactor. In any case, however, regeneration is an expensive process and, moreover, leads to irreversible damage to the catalysts. In order to obtain maximum overall catalyst life and to keep operating costs to a minimum, it is therefore necessary to use maximum loading processes for hydrocracking
Hydrocarbons

Applicant:

Union Oil Company of California,
Los Angeles, Calif. (V. St. A.)

Representative:

Dipl.-Ing. F. Weickmann,

Dr.-Ing. A. Weickmann,

Dipl.-Ing. H. Weickmann

and Dipl.-Phys. Dr. K. Fincke, patent attorneys,

Munich 27, Möhlstr. 22nd

Named as inventor:

Rowland Curtis Hansford, FuUerton, Calif.

(V. St. A.)

Claimed priority:
V. St. ν. America November 29, 1960
(72 325)

drive times between regenerations.

Since a fresh catalyst generally shows maximum activity and since it is relatively constant Conversion and throughput rates are desired in large-scale operations, it is common to use the Start operation at a relatively low temperature. If then the catalyst becomes less active the temperature is raised periodically to maintain the desired rate of conversion. This process continues until a final temperature is reached at which the deactivation rate of the catalyst because of the accelerated precipitation of coal products increases exponentially. The difference between the start and end temperatures can be about between 14 and 165 ° C or in an even larger range.

In the case of hydrocracking processes that are carried out below 175 at, the final temperature is at

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light feed hydrocarbon mixtures with a final boiling point of about 315 C as a rule at 415 to 455 C. For heavy feed hydrocarbon mixtures with a final boiling point of 485 C, the final temperature is around 400 to 415 C. Proportional ratios result for other feed hydrocarbon mixtures depending on their final boiling points and their general flammability. It is therefore clear that under given working conditions and given hydrocarbon mixture the duration of operation is determined by the permissible initial temperature. When a predetermined rate of conversion with a rise in temperature of 0.28 C per day and if the final temperature is 440 "C so an operating time of 300 days can be achieved if the desired conversion is carried out with the fresh catalyst is triggered at 345 C. However, the operating time is reduced to 100 days if the initial temperature has to be 400 ° C.

This shows the importance of the catalyst activity at low temperatures.

Hydrocracking is preferably started at space velocities of about 0.5-5.0 and at temperatures between 235-315C. This then results in conversion rates in mineral spirits to 30 to 80 ⁰ / rt per pass. This conversion continues to a final temperature of about 400 to 455 C, with about half of the operation being carried out ^{below about 400: C.} So pressures from 56 to 210 at can be used. Operating times of at least 60 days are easy to achieve and can be increased to about 6 months if necessary.

The catalysts can be used under the following conditions when carrying out hydrocracking processes can be used.

Brewing bar

Temperature, C

Pressure, at

Room air flow velocity
Η -, - ΌΊ ratios m ³ hl

to 455
up to 350
0.2 to 6.0
17.5 to 350

Preferred

260 to 400
56 to 140
0.5 to 5.0
52.5 to 175

The object of the invention is therefore this when using the known hydrocracking catalysts to remedy deficiencies and more effective and selective hydrocracking catalysts indicate the maximum conversion of a hydrocarbon mixture to hydrocarbons in the gasoline boiling range with a minimum of destructive degradation these products to substances such as cause methane or coke, for example.

Another object of the invention is. Catalysts indicate that their activity over a long period of time Retain the duration of use between the necessary regenerations. In doing so, it is considered particularly important to see that catalysts are used that allow only a small amount of coke formation and with the aid of which the hydrocracking can be carried out under relatively low hydrogen pressures can, while at the same time reducing the operating and plant costs and the risk of explosions and chain reactions should be kept to a minimum.

It is a further object of the invention to provide catalysts for the hydrocracking of high Coatings which require hydrocracking temperatures are suitable, such as cyclic oils from conventional ones catalytic or thermal cracking process, with an additional conversion can be made to gasoline. In addition, it is an object of the invention to provide catalysts indicate that are active at low temperatures, which further reduces coke formation and the operating life of the catalysts between successive regenerations is extended.

To solve these problems, it is proposed according to the invention to use a catalyst, the at least partially decationized zeolitic alumina silicate molecular sieve having a relative uniform crystal pore diameter between about 6 and 14 Å and a SiCVAliQi molar ratio greater than about 3, which contains a small amount of a hydrogenating transition metal and intimately mixed with a relatively inert powdery, refractory aggregate material which has an average grain size which is substantially larger than the average crystal size of the molecular sieve.

It is particularly advantageous to use a catalyst whose molecular sieve is used is of crystal type Y and is at least about 40% decationized and a Group VIII noble metal of the periodic table.

In a special embodiment it is provided that a catalyst is used in that in the manufacture of the water content of the molecular sieve before mixing with the aggregate material has been adjusted to about 10 to 25 percent by weight and the solidification of the Tablets or pills was carried out with a pressure that was sufficient on the one hand to keep the tablets or to give pills a sufficient hardness, but on the other hand was not so high that the volume of the macropores from about 20 to about 10,000 Å in diameter to less than about 5% of the volume of the tablets or pills has been reduced, and in which the tablets or pills in a known manner have been dried and activated.

As studies have shown, the catalysts processed into pills or tablets which contain aggregates show a significantly higher effective activity than equal volumes of the metal zeolite component processed into tablets or pills alone.
It is to be regarded as a particularly surprising result when proceeding according to the invention that extremely high ratios of iso-normal paraffin amounts were found in the CaCe fractions. The catalysts, as they are according to the invention

are used, have extremely favorable isomerization activities for lower paraffins. The isomerization activity in the presence of hydrocracking feed hydrocarbon mixtures was partially suppressed to such an extent that they are far higher than the thermodynamic equilibrium conditions from iso- to normal paraffins.

It is to be regarded as particularly advantageous that hydrocracking temperatures are to be used which are essential lower than with the usual methods, namely between about 235 and 440 C, preferably between about 260 and 400 C. The effectiveness at lower temperatures is above all attributable to the improved activity of the catalysts. The selectivity of the conversion is to be regarded as an accompanying result of the lower temperatures and the intrinsic selectivity of the catalysts.

The advantages of the procedure according to the teaching of the invention occur in particular with working methods with a fixed bed in appearance, because of the reduction in the coking rate due to the selectivity the catalyst activity and the lower temperatures used the operating time between the necessary catalyst regenerations can be significantly extended can.

The scope of the method according to the invention is relatively broad. So in the As a rule, any mineral oil fractions that boil higher than the usual gasoline are treated, d. H. above about 150 C and usually above about 205 C, and the one final boiling point of up to have about 555 C. These include gas oils and heavy oils obtained through crude oil distillation. Coke distillate gas oils and heavy oils, deasphalted crude oils, from catalytic or thermal cracking processes resulting cyclic oils and the like. These fractions can be obtained from crude petroleum oils, shale oils, tar sand oils. Carbohydrate products and the like. Entries that are between approximately Boil 205 and 345 C, have a specific gravity of 0.9340 to 0.8498 and at least about 30 percent by volume Contain acid-soluble components (aromatics and olefins).

Difficulties sometimes arise in the direct hydrocracking of oils with final boiling points above about 345 ° C. These oils sometimes cause a faster rate of coking of the catalyst, resulting in a rapid drop in catalyst activity. To overcome this problem, feed hydrocarbon mixtures boiling above about 345 C can be subjected to a prehydrogenation treatment to at least partially saturate the heavy polycyclic aromatic hydrocarbons containing three or more condensed rings. The prehydrogenation can be carried out under conventional hydrogenation conditions by using a hydrogenation catalyst which contains any oxides and / or sulfides of the transition metals, in particular an oxide or sulfide of a metal from group VIII (preferably iron, cobalt or nickel), mixed with an oxide or sulfide a Group VI B metal (preferably molybdenum or tungsten). These catalysts are usually applied to an absorbent support in quantities between about 2 and 25 percent by weight. The preferred hydrogenation catalyst consists of cobalt oxide and / or sulfide plus molybdenum oxide and / or sulfide on a carrier of activated alumina or an alumina stabilized with silica which contains about 3 to 15 percent by weight of co-precipitated silica gel. The hydrogenation is normally carried out at temperatures from 290 to 440 C. Pressures from 35 to 210 at, space velocities from 0.5 to 10 with hydrogen rates from 8.75 to 210 m ³ hl of the hydrocarbon mixture.

The low-boiling hydrocarbon mixtures, i.e. those that boil below 345 C, can can also be subjected to hydrogenation in order to reduce their nitrogen and sulfur content and also to increase their sensitivity to subsequent hydrocracking treatment.

The special properties of the catalysts used according to the teaching of the invention should in the following as well as their representation are described and explained for the sake of completeness but only their use for hydrocracking hydrocarbons and their production is not regarded as essential to the invention.

These properties are likely due primarily to the physical and / or chemical properties of the silica-rich zeolitic molecular sieve cracking carriers in their "decationized" or hydrogenated form. These crystalline zeolites consist almost entirely of silica and alumina. The SiO 2 -Al 2 O : s molar ratio is at least 3 and preferably about 3 to 6. This distinguishes them from the molecular sieve zeolites of the "X" type, as described, for example, in US Pat. No. 2,882,244 that the X-zeolites have a SiOo-AloO :; ratio of only about 2.5 and cannot be decationized to a high degree without their crystal structure being destroyed. The highly silica-containing zeolites, as they are used according to the teaching of the invention, are described in more detail in the documents laid out in Belgian patent 589582. The most common zeolites are those of the "Y" crystal type. The "L" crystal type is also suitable within the scope of the invention.

The Y zeolites can be obtained in their sodium form by heating an aqueous sodium-aluminum-silicate mixture at temperatures between about 25 and 125 C (preferably 80 to 125 C) until crystals form and the subsequent separation of the Crystals are produced from the mother liquor. Used as the source of the colloidal silica sol If silica is used, the aqueous sodium-aluminum-silicate mixture can have the following composition. expressed in molar ratios, have:

Na ₂ O SiO ₂ 0.2 to 0.8

SiO ₂ Al ₂ O ₃ 10 to 30

H ₂ Oz Na ₂ O 25 to 60

If sodium silicate is used as the starting material for the silica, the optimal molar ratios are as follows:

Na ₂ O SiO ₂ 0.6 to 2.0

SiO ₂ Al ₂ O «10 to 30

H ₂ OZNa ₂ O 30 to 90

1

The resulting Y zeolites conform to the general formula

0.9- 0.2 Na ₂ O to Al ₂ O, to «SiO ₂ to λΉ ₂ 0,

in the /; is a number between 3 to about 6 and χ is any number up to about 10.

The decationized or hydrogenated form of the Y-zeolite can be driven off by ion exchange of the alkali metal cations for ammonium ions or other easily decomposable cations, such as methyl- ίο substituted quaternary ammonium ions, with subsequent heating up to, for example, 300 to 400 C of ammonia can be obtained. This process is further described in the laid-open documents of Belgian patent 598,683. The degree of decationization or hydrogen exchange should be at least about 20 "·", preferably at least about 40 " _{(1 of} the maximum theoretically possible. The final composition should preferably have less than about 6 percent by weight Na ₂ O.

Mixed hydrogen, polyvalent metal forms of the Y zeolite are also contemplated. In general, such mixed forms are produced by subjecting a zeolite which has already been subjected to an exchange process and which contains polyvalent metals to a further ion exchange with ammonium cations which are later decomposed with loss of ammonia in a thermal activation treatment. Here, too, it is preferred that at least about 40 " 0 of the monovalent metal cations are replaced by hydrogen ions.

As used here, the term "decationized" refers to the elimination of zeolite sodium or other monovalent lattice metal ions from the zeolite and / or their Replacement by hydrogen ions. It is still questionable whether the final activated form of the zeolite actually occurs is "decationized" in the sense. that a cation deficiency has been reached or whether those initially generated Hydrogen ions have remained in it. It is believed, however, that a substantial proportion of hydrogen ions remains in the decationized zeolite.

The hydrogenation component can be introduced into the zeolite in any way that results in a leads to substantially intimate mixing. Useful methods include

50

1. Cation exchange using an aqueous solution of a suitable metal salt, where the metal itself forms the cation,

2. Cation exchange using an aqueous solution of a suitable metal compound, in which the metal in the form of a complex cation with complex-forming coordination agents, such as ammonia, with subsequent thermal decomposition of the cationic complex.

3. Customary impregnation with an aqueous solution of a suitable metal salt followed of drying and thermal decomposition of the metal compound.

Ion exchange methods 1 and 2 are preferred because a more uniform and complete

824

more division of the metal on the zeolite is obtained.

Method 1 is generally used to introduce iron group metals, while Method 2 is generally best for introducing Group VIII precious metals is used. If Method 1 is used to introduce an iron group metal, it is desirable, the subsequent thermal activation in a non-oxidizing or reducing Atmosphere to avoid oxidation of the metal and exposure to avoid the metal from the zeolite lattice. For Group VIII precious metals are such precautionary measures are usually not necessary. The thermal decomposition of the cationic In these cases, the complex can, if desired, be carried out in air.

The ion exchange of the hydrogenation metal on the zeolite can be carried out using the usual method such as those described in the laid-open documents of Belgian patent 598,686 Methods. The metal compound is dissolved in an excess of water, namely in an amount calculated to provide the desired amount of metal in the finished catalyst results. This solution is then added to a zeolite that has previously been exchanged with ammonia ions, with stirring, and then, when the ion exchange has occurred, that of the exchange treatment subjected zeolite separated by filtration. The filtered zeolite can then to the extent that it is necessary to remove any remaining trapped Remove salts. This is followed by drying, which turns into tablets or Pills yields workable powder.

For impregnation purposes, a suitable salt solution of the desired hydrogenation metal is first used manufactured. The powdered or pelletized zeolite is then introduced into the solution. It remains immersed in this solution for a few minutes, is then drained, dried and finally calcined, at about 260 to 670 ° C. Preferred metal salts for the impregnation are including nitrates, acetates, formates and sulfates.

As in the case of the X zeolite, the Y zeolites also contain pores of relatively uniform diameter in the individual crystals. In the case of the X zeolites, the diameter of the pores in Range from about 6 to 14 Å, depending on which metal ions are present. This is alike the case with Y zeolites, although these usually have crystal pores with diameters of about 9 to 10 Å.

The table shows the X-ray powder diagram of the Y zeolite. Common techniques were used to obtain this diagram. The Kri doublet of cobalt (/. = 1.7889 Å) served as the radiation source. A Geiger counter spectrometer with a tape recorder was used for recording. The peak heights / and the values of the respective Bragg angles were read from the spectrometer tape. From this, the relative intensities Uli were estimated, the highest peak being set = 100, and the plane distances i / ( λ) from the equation ?. = 2d sin (-),

(/ -: wavelength of the X-rays, (-) the Bragg angle and d the plane spacing in angstroms).

Tabel

cl (A)

lh

14.6

8.85
7.50
5.69
4.75
4.37
3.50
3.76
3.46
3.30
3.32
3.02
2.91
2.85
2.76
2.70
2.63
2.59
2.37

100 15 10 25 15 17 <10 30 <10 20 <10 <10 <10 14 <10 <10 <10 <10 <10

25th

30th

The metals platinum, rhodium and palladium serve as hydrogenation components. Chromium, molybdenum, tungsten, Iron, cobalt, and nickel, and the oxides and sulfides of these. Mixtures of any two ors more of these substances can be used. In particular, Group VIII precious metals are used and of these, in turn, palladium is preferred.

The hydrogenation metals are preferably used in amounts that are between about 0.1 to 20 percent by weight of the end product, calculated on free metal. For most purposes, the optimal proportion between about 0.5 and 10%. Are precious metals used, such as palladium or Platinum, the optimal proportions are generally in the range between 0.05 and 2 percent by weight.

Since the zeolite catalysts are usually microcrystalline (cubic lattice) and one crystal size of about 1 to 5 microns will result in pelletizing or agglomeration of such crystals to large grains, tablets or pills, often to a relatively impenetrable mass that can be by packing the crystals. The result is that the outer surface of the grains is relatively one forms impenetrable limit for the diffusion of gases. This will become the active posts in the micropores inside the tablets and the like are only insufficiently exploited. From these and For other reasons it has been found that increased activity can be achieved when using the powdered Mixes catalyst with a relatively inert, powdery refractory aggregate material that among other things causes the distance between the zeolite crystals and the formation relative causes large pores which lead into the interior of the catalyst grains. The mean grain size of the aggregate material is preferably larger than the crystal size of the zeolite. The mix of powdered catalyst and the aggregate is compressed into tablets, pills or granules. she can also be moistened first and then pressed through a nozzle that delivers pellets. These can then be dried, calcined and, if desired, calcined, to be used if necessary Remove lubricants or binders.

Suitable refractory materials that can be used as catalyst additives include inorganic oxides and halides. Sulphates, phosphates, sulphides and silicates, which are stable at temperatures above 485 C and which are inert towards the zeolite catalyst components. Compounds of monovalent metals, in particular those with alkali metals, should not be used, nor should compounds of vaporizable metals or those that contain catalyst poisons, such as PH? or M0O3. Low-melting compounds such as V ₂ Os, B2O3, ZnClo and the like, which melt easily or melt the zeolite component, should also not be used. Amorphous, non-crystalline materials are preferred, although not critical.

As a rule, the aggregate material should be relatively inert in terms of its hydrocracking activity Compared to the molecular sieve catalyst. However, it is not intended to use such materials which themselves have some desirable catalytic activity. Preferably the aggregate material is one mesh size (Tyler) coarser than about 325 and finer than about 50 mesh (coarser than the clear mesh size 0.044 mm, finer than the clear mesh size 0.25 mm) and used in proportions comprised between about 10 and 80 percent by weight of the final catalyst product preferably between 30 and 75%. Examples of suitable aggregates are as follows :

Oxides Halides Sulfates Clay (gamma, eta or kappa) Magnesium fluoride Magnesium sulfate Silica gel Aluminum fluoride Calcium sulfate Magnesium oxide Calcium fluoride Strontium sulfate Titanium oxide Magnesium chloride Barium sulfate Chromium oxide Calcium chloride Zinc oxide rare earth oxides Beryllium oxide

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Phosphates

Sulphides Silicates

Boron phosphate

Magnesium pyrophosphate

Aluminum phosphate

Calcium phosphate

Calcium pyrophosphate

Zinc pyrophosphate

Zirconium phosphate

Iron sulfide Cobalt sulfide Nickel sulfide Manganese sulfide clays (low Na20 content)

Aluminum silicate

Magnesium silicate

Calcium silicate

Titanium silicate

In addition, other materials can include animal charcoal, activated carbon, and silicon carbide to be used.

The pressure with which the zeolite catalyst powder increases with the powder of the aggregate material Tablets and the like is pressed, on the one hand should be low enough that a considerable volume of Interstitial pores remain on so-called macropores that have a diameter greater than have about 20 Å. In particular, it is preferred that the final catalyst pellets etc. have at least about 5 percent by volume macropores with diameters of 20 to 1000 Å (measured with the mercury porosimeter method, as described in the journal Industrial and Engineering Chemistry, Volume 41, p. 780 [1949], or with the desorption isotherm method. like them in that Journal of the American Chemical Society, vol. 73, p. 373 [1951]). To such porous To obtain pellets and at the same time to ensure adequate cohesion of the microparticles achieve, so that pellets with sufficient mechanical strength result, it is special inconvenient to pelletize the completely dry powders. The cohesive forces between the dry powder particles are so low that very high pressing pressures are required, which the volume of macropores can decrease. However, if the moisture content of the zeolite (preferably also of the aggregate material) set to about 10 to 25% (measured by weight loss or firing at temperatures of about 485 C). so it has been found that pellets are sufficiently mechanical Strength can be obtained at pelletizing pressures low enough to be at least about To allow 5 volume percent of the macropores in the diameter range from 20 to 1000 Å to exist.

However, care must be taken in adjusting the moisture content of the zeolites. If the zeolite crystals have been previously dehydrated, a considerable loss in crystallinity can be obtained upon rapid rehydration with liquid water. The desired water content is therefore achieved either by careful monitoring of the initial dehydration of the zeolite or by rehydration at medium temperatures of, for example, 24 to 95 ^: C in the presence of water vapor at atmospheric pressure or lower.

The catalysts are made by extrusion of moistened plastic mixtures of the powder components produced, a water content greater than 25% is required for mechanical reasons. This water content can be achieved without

50

55 reduce crystallinity either by using the wet zeolite as it results from the hydrogenation metal ion exchange or impregnation step or by careful hydration with steam at low pressure as described above and subsequent addition of liquid water.

In a modified embodiment, the powdered aggregate material can be modified by incorporating a hydrogenation component. This hydrogenation component can be the same as or different from the hydrogenation component used for the zeolitic component. This modification is particularly useful tend in the treatment of hydrocarbon blends with high final boiling points above about 345 ⁰ C and up to severe to about 555 C. polycyclic materials in the hydrocarbon mixtures with a high final boiling point to clog the pores of the ZeoIithkristalle. However, they can be effectively hydrogenated or - if desired - hydrocracked by bringing them into contact with the active surface area of the aggregate material, if this is modified by the incorporation of a hydrogenation component. This can be achieved in view of the large mean pore diameter of the aggregate material, which is generally in the range between approximately 50 and 150 Å. The hydrogenation component is preferably added to the aggregate material before the zeolitic component is incorporated into it.

Suitable examples of particular catalysts which are useful for the purposes of the invention are compiled in the following table. The percentages given relate to that dry weight. In all cases the cracking carrier is a 90 to 95% decationized Y molecular sieve zeolite with a pore diameter of 9 to 10 Å, containing about 75 percent by weight of silica, Contains 25 percent by weight of aluminum oxide and about 1 percent by weight of sodium and accordingly has an X-ray diagram as shown in Table 1.

Examples of catalysts

1. Decationized zeolite Y, ion-exchanged with an aqueous solution of tetrammine palladium chloride [Pd (NHj ) J] Cl »; dried and calcined. End product contains 0.5% Pd.

2. Decationized Y zeolite, impregnated with cobalt nitrate, calcined and sulfidized. End product contains 10% Co as CoS.

3. Decationized zeolite Y, ion-exchanged with an aqueous solution of nickel nitrate, calci-

1

nates and reduces in hydrogen. End product contains 10% Ni.

4. Decationized zeolite Y, impregnated with ammonium molybdate, dried and calcined. End product contains 10% Mo as MoO ₃ .

5. Composition 1 (50 parts ground [0.048 mm mesh size] and rehydration with water vapor up to a water content of about 20%), mixed pelletized with 50 parts of activated Alumina with a grain size corresponding to 0.15 to 0.044 mm clear mesh size.

6. Composition 1, as stated above (50 parts ground to a mesh size of 0.04 mm and rehydration with steam to about 20% water content), mixed pelletized with 50 parts of activated alumina, corresponding to a grain size of 0.15 to 0.048 mm clear mesh size , impregnated with IO ⁰ Zct Ni.

7. Composition 1, as stated above (50 parts of ground, clear mesh size 0.04 mm and rehydration with steam to a water content of about 20%), mixed pelletized with 50 parts of silica-alumina gel (85% SiO ₂ to 15% Al ₂ O :!) with a grain size corresponding to 0.15 to 0.048 mm clear mesh size impregnated with 10% Ni.

Further details of the invention are given with reference to the following examples, which are in particular refer to the pretreatment of the catalyst material used, explained.

Example I.

In this embodiment, an unconverted cyclic oil is obtained with the following Features

Specific gravity 0.8333

Boiling point, Engler 230 to 295 C

Acid-soluble components .. 18.5 volume percent sulfur, weight percent 0.1 (added) Nitrogen, weight percent 0.0007

Aniline point, C 66.2

subjected to a hydrocracking process carried out as a test. This cyclic oil had been subjected to a preliminary hydrogenation and hydrocracking treatment in which a coke gas oil was first subjected to hydrogenation over a cobalt-molybdate-alumina type catalyst and then immediately passed into a hydrocracking zone via a hydrocracking catalyst co-precipitated a presulphided mixture of nickel hydroxide, silica, zirconium and titanium. The hydrocracked products were then fractionated to remove gasoline and minor bottoms. The remaining gas oil then formed the starting material used for the example. For the hydrocracking of this gas oil according to the teaching of the invention, a catalyst was then used which was prepared by mixing together 43 parts by weight of presulphided isomerization catalyst in the form of pills or tablets of size 4.76-3.18 mm. which had been produced by ion exchange on a 90% decationized Y zeolite with palladium and contained 5 percent by weight palladium 75 ^ 0.5% SiO ₂ , 25-0.5% Al ₂ O ₃ and 1.5% Na ₂ O (his X-ray powder diagram can be seen from the table), with 75 parts by weight of activated alumina. The catalyst

824

was ground before mixing (clear mesh size 0.048 mm), while the grain size of the activated alumina was clear mesh size 0.15 to 0.044 mm. The mixture was then compressed into pills or tablets with a diameter of 3.17 mm. The catalyst prepared in this way was then ^{reduced in hydrogen for 1 hour at 370 °} C. for 1 hour and then at 345 ° C. for 2 hours under a pressure of 70 atm before being used for hydrocracking. It was then sulfidized with luminous oil containing 10% sulfur (as thiophene). The sulfidation took place over a period of 2 hours at 345 ° C. 70 at and with a space flow rate of 175 m ³ / hl of hydrogen. The temperature was then reduced to 315 ° C. and the luminescent oil was replaced by the cyclic oil. The other conditions remained the same while the hydrocracking process was carried out. Despite the high space velocity, low temperature and low pressure, the conversion to gasoline with a final boiling point of 205 ⁰ C was 81.4 volume percent of the entry compared with 61.5 percent by volume with the use of the neat, that is used without additional material catalyst, as determined by parallel experiments could be. The activity of the catalyst did not decrease significantly within 16 hours. A visual inspection of the catalyst at the end of the process showed that it had practically no coke deposited on it.

Example II

In this exemplary embodiment, part of the catalyst produced by pressing together the catalyst and aggregate material (alumina) was reduced in hydrogen at 485 ° C. in order to remove the sulphide sulfur. The catalyst was then used to hydrocrack the cyclic oil used in the previous example. The oil contained less than 0.05% sulfur. Under the same hydrocracking conditions as in the preceding example, the rate of conversion to gasoline was 97.1% with a final boiling point of 205 ^C C. It can be seen from this that the catalyst in the end-sulfided form is even more active than in the sulfided form. The conversion rate of 97.1% at 315 ° C and an effective space velocity of more than 4 (calculated with respect to the pure catalyst) indicates that the catalyst had a greater activity than other known hydrocracking catalysts.

Example III

Add to the activated clay that has been ground to a mesh size of 0.15 to 0.048 mm, such as it is used as an aggregate material according to Example I, 10% NiS and presses this with 50 parts of the aforementioned isomerization catalyst, which grind to a grain size had been (clear mesh size 0.048 mm) into pills or tablets, a catalyst is obtained, how the comparative implementation of the hydrocracking process according to the previous one Examples shows, in its sulfidized form, is still significantly more active than the catalyst according to Example I.

Claims (3)

15 16 The comparative investigations with other hydrocarbons, in which the hydrocarbons - hydrocarbon mixtures showed, substances in the presence of added water, that this catalyst is particularly suitable for hydrocrackers under hydrocracking temperature and pressure hydrocarbon mixtures, which a conditions with one tablet - or have the final boiling point of the pill above 345 c. The 5-shaped catalyst brought into contact with the upper limit of the final boiling point is characterized in that 555 C. A catalyst is used which at least As these examples show, the partially decationized zeolitic clay mixing of granular aggregate materials results in a substantial silicate -Molecular sieve achieved with a relatively equal increase in yield. This moderate crystal pore diameter between approximately an increase in the yield succeeds without impairment 6 and 14- and a SiCVAl-aCV molar ratio impairment of the catalyst effectiveness, as it contains greater than about 3, in which a small one is then given, for example. when the catalyst quantity of a hydrogenating transition metal is found to be small grains or a powder and this is intimately ground with a relatively inert one. If, for example, the catalyst 15 pulverulent, refractory aggregate material is ground ver-Zii grains with a grain size (1.6 to mixed, which has a mean grain size, the 0.84 mm clear mesh size), one obtains, although much larger than that mean crystal size an increase in the yield of gasoline with one of the molecular sieves. Final boiling point of 205 c from 61.5% to 73.4%. 2. The method according to claim 1, characterized in this, however, it is noticeable disturbing, 20 is characterized in that a catalyst is used that the fine catalyst grains in fixed bed operation whose molecular sieve is of the crystal type Y and form a tightly packed bed, whereby in all- is at least about 40% decationized and generally a high pressure drop is caused. a noble metal of group VIII of the periodic An analysis of the gasoline products obtained contains, with regard to their iso-normal paraffin ratios 25 3. The method according to one of claims 1 showed the following results: and 2, characterized in that a catalyst fraction ^ "' ί-Γ11? 1 "sator is used in which the water content of the molecular sieve p" j before mixing with the aggregate material has been set to P ° j ^ 'q 30 about 10 to 25 percent by weight in the production ratio 6' and the solidification to tablets or pills As can be seen from these values, the pressure has been carried out, the values obtained are substantially higher than the thermo sufficient on the one hand to give the tablets or dynamic equilibrium ratio, to give pills a sufficient hardness, on the other hand corresponding results are obtained if, on the other hand, it was not so high that the volume in the Y-type molecular sieve instead of that of the macropore n from about 20 to about 1000 Å palladium, other diameters which favor hydrogenation, can be used to less than about 5% of the Vo substances. In addition, the lumens of the tablets or pills can be reduced as granular aggregate materials, and in which the tablets or materials are dried in a known manner as the clay or 40 pills mentioned in the example and activated nickel sulfide clay is used. have been fourth. Claims: ~ 1. Process for Hydrocracking Coals- Older Patents Considered: Hydrogen for the production of lower boiling 45 German patents No. 1 136 990, 1 162 332. 709 709/415 12.67 Q Bundesdruckerei Berlin