DE2249052A1 - HYDROCARBON CRACKING CATALYST - Google Patents

Description

The invention relates to zeolites for use as a cracking catalyst for the conversion of hydrocarbons with a relatively high molecular weight in derivatives with low molecular weight.

The invention is based on the object of cracking catalysts with particular suitability for use in the fluidized bed process and with particularly low deposition of To develop coke.

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" ² " 22Λ9052

To solve the problem, zeolite catalysts for cracking hydrocarbons in a fluidized bed from abrasion-resistant particles with a particle size of about 50 to 200 / .mu.m, which consist of crystallized aluminosilicates with a silicon dioxide-aluminum oxide ratio of over 3.0: 1, are proposed are characterized in that hydrogen and rare earth metals are present as cations of the zeolite in amounts of 0.3 to I ¹ % trioxides of rare earth metals, based on the weight of the zeolite, and that alkali cations in amounts of less than 1 % alkali oxide, based on the weight of the zeolite.

The invention also relates to catalyst mixtures containing zeolites according to the invention together with an inorganic oxide gel in a fluidizable form and a process for cracking hydrocarbons under Use of the zeolites according to the invention as cracking catalysts, with only a minimal deposit of coke entry.

The crystalline aluminosilicates, usually referred to as synthetic zeolites or molecular sieves, are well-known Cracking catalysts; synthetic faujasites are preferably used as cracking catalysts, mostly in the modified form of the Y zeolites, used. Y zeolites

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correspond, based on oxides, to the gross formula Na ₃ O: Al ₃ O 3.0 - 7 SiO ₂ , i.e. the ratio of sodium cations and silicon dioxide to aluminum oxide is above 3 The relatively high ratio of silicon dioxide to aluminum trioxide gives the Y Zeolites have a relatively good stability against thermal decomposition during the removal of coke deposits. During the cracking of hydrocarbons, a deposit of coke particles forms on the zeolite cracking catalysts, which may deactivate the catalyst, so that this coke deposit has to be burned off to regenerate the catalyst. However, the temperatures required for regeneration can already lead to a breakdown of the zeolite structure, as can be determined from the loss of total surface area, and the thermally decomposed zeolites are only of low catalytic effectiveness. It is common practice to improve the thermal stability of a zeolite by replacing the sodium cation with other ions using the ion exchange process. These other cations can be, for example, hydrogen, the presence of which is generally due to the exchange of sodium with ions such as, for example, ananonium ions, which decompose when heated to form hydrogen like ammonium ion to form ammonia and hydrogen cations; if necessary, others can also

5 non-alkali metals such as the particularly preferred rare ones

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Earth metals are present. When the sodium content of a Y zeolite is carried out as far as practically feasible Rare earth metals is replaced, the content of rare earth metals carries about 30 wt. Rare earth metals.

about making various the ion exchange Faujasites subjected to the improvement of their properties as cracking catalysts are already numerous patents before; In this context, reference is made in particular to the following patents owned by the applicant: US patent 3,595,611, in which those designated by the applicant as "PCI" are partially loaded with rare earths and calcined Y zeolites; U.S. Patent 3,676,368, which is named "REHY" by the applicant Rare earth and hydrogen containing Y zeolites are given and US Patent 3 * 102996, in which by the applicant Y zeolites fully loaded with rare earths and calcium are described as "CRSY".

Synthetic zeolites are mostly small particles with an average size of about 5 / µm, which are therefore for the Use in fluidized beds are too finely divided. It is therefore common to use from the zeolitic catalysts to produce molded bodies of suitable size in the fluidized bed, which the zeolite particles together with a matrix or contain a binder. Generally used as a matrix

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a silica-alumina gel for this use used. However, such composite shaped articles containing zeolite tend to break down during the cracking process to be rubbed together when used in the fluidized bed process. From Applicant's U.S. Patent No. 3 ^ 72,617 however, they are already filler-free, abrasion-resistant zeolite aggregations with the desired particle size from about 50 - 200. um known, which consist of porous bodies a silicon dioxide-containing reactant for synthesis of a zeolite and subsequent conversion of these shaped bodies into zeolites by hydrothermal crystallization in Sodium hydroxide can be produced.

The faujasites according to the invention are microspherical, abrasion-resistant Y zeolites with a particle size of approximately 50 - 200 yum, corresponding to U.S. Patent 3 ^ 72 617, which are partially loaded with rare earth metals, as described in US Pat. No. 3,595,611 for the manufacture of PCY or in iJS patent specification 3,676,368 for manufacture is specified by REHY. Surprisingly, it was

made that such microspherical zeolites des. PCY and REHI types are much more effective at suppressing them of coke formation compared to microspherical zeolites which are prepared according to US Pat

/ are completely loaded with rare earths by CREY.

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The zeolites according to the invention therefore have the particular advantage, when used as hydrocarbon cracking catalysts in a fluidized bed, that they lead to significantly less coke formation compared to the previously used zeolites. The zeolites to be used according to the invention as cracking catalysts for hydrocarbons in a fluidized bed are therefore abrasion-resistant particles about 50-200 μm in size, which consist of crystalline aluminosilicates with a silicon dioxide ¹¹ : aluminum oxide ratio of over 3 * 0: 1, the cations being hydrogen , rare earth metals in amounts of 0.3 to 1 * 1 % trioxides of the rare earths, based on the weight of the zeolite, and alkali metals in amounts of less than 1 % alkali oxide, based on the weight of the zeolite.

According to the invention, a process for the production of PCY or REHY zeolites in microsphere-like form is used Proposed use as a cracking catalyst for hydrocarbons in the fluidized bed by adding (a) microsphere-like Particles with a size of about 50 to 200 .mu.m and a content of silicon dioxide and aluminum trioxide which can then be converted into zeolites, (b) these particles by hydrothermal conversion with sodium hydroxide and optionally for the production of zeolites with the desired silicon dioxide to aluminum

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trioxide ratio of at least 3jO: 1 necessary Silicon dioxide be treated, and then (c) the microspherical zeolites produced in this way are treated with a solution in the ion exchange process, the ions of which lead to the formation of hydrogen cations in the zeolite upon thermal decomposition, whereupon subsequently further treatment with a solution containing sufficient rare earth metal ions Amounts to achieve a content of oxides of the rare earth metals up to about 14 wt. 55, based on the zeolite, and finally calcination takes place.

From US Pat. No. 3,472,617 it is known that as Starting materials for silicon dioxide and aluminum trioxide calcined clays such as metakaolin or silicon dioxide-aluminum trioxide gels can be used as these are essential for the synthesis of the zeolitic sodium älumosilicate the required starting materials, silicon dioxide and aluminum trioxide. More silica can for example in the form of sodium silicate; the starting materials ^ for silicon dioxide and aluminum trioxide ' are shaped so that microspherical particles with a size of about 50 to 200 µm result. A suitable one The production process for these particles is, for example, spray-drying an aqueous slurry. The particles are then converted into zeolitic particles.

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A particularly effective method of converting amorphous

Microspheres of silica-alumina hydrogel in sodium faujäsite consists of forming a mixture of sodium hydroxide, sodium aluminate, 13 % of a mixture of alumina-silica and an alumina hydrogel cracking catalyst, water and zeolitic seed crystals, and then heating the mixture to about 100 ° for 8 to 10 hours C. The mixture used as the seed crystals consists of finely divided amorphous silica-alumina particles which have been found to be particularly effective in the formation of crystalline zeolites. The preparation and use of these vaccine preparations is detailed in US Pat. No. 3,567-1,538. The amounts of sodium, silicon dioxide and aluminum trioxide present in the particles and in the reaction medium are adjusted in such a way that a Y zeolite with the desired silicon dioxide / aluminum trioxide ratio of more than 30: 1 results.

The process described leads to the formation of microspheres Y zeolites. These are according to the invention for the production of microspherical PCY zeolites or REHY zeolites further treated.

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The preparation of microspheric PCY by microspheres of a synthetic Natriumfaujasit having a silica: aluminum trioxide ratio of about 3 _a 2: 7 first with a solution of an ammonium salt such as ammonium chloride or ammonium sulfate for reducing the content of _Na? O to about 1.5 to 4 weight per cent. The ammonium-laden faujasite is then treated with a solution of rare earths such as, for example, a corresponding chloride solution, so that a content of rare earths, calculated as SE _? O, from about 0.3 to 10 wt .: results. The rare earth loaded faujasite is then dried and calcined for about 0.1 to 3 hours at temperatures of about 371 to 871 ° C. After calcination, the thus-treated faujasite is again subjected with ammonium salts to ion exchange to reduce the content of Na ₂ O to reduce to below 1 wt.%.

Microspherical REHY is made by treating suitable microspheres of a sodium faujasite having a silica to alumina ratio greater than 3 with a solution of rare earth ions at a pH of about 3.0 to 3.5, with the alkali oxide content of the faujasite being less than about ¹ J wt. % is reduced. During the exchange treatment, about 6 to 1 * 1 percent by weight of rare earth ions, calculated as RE ₂ O, are taken up by the microspheres of the sodium zeolite. The laden faujasite

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is then calcined for about one to three hours at temperatures of about -25 to 760 ° C. The calcined paujasite is then subjected to a further exchange with a solution of ammonium ions so that the alkali oxide content is reduced to less than about 0.5 % by weight.

The loaded microspherical zeolites according to the invention are preferably physically mixed with an amorphous inorganic gel and / or clay component which has essentially the same physical properties and particle sizes as the zeolite component. The amorphous inorganic gel component mostly consists of amorphous silicon dioxide-aluminum trioxide cracking catalysts such as those commonly used in the petroleum industry. However, the zeolites can also be mixed with thermally or acid-treated microspherical clays such as those used in the refineries in the form of fluidized bed catalysts. In addition to the hydrogels of silicon dioxide and aluminum trioxide, the zeolites according to the invention can also preferably be mixed with other amorphous hydrogels such as silicon dioxide, aluminum trioxide or silicon dioxide-magnesium oxide - if necessary, the amorphous hydrogel component can contain different amounts of clay such as kaolin. A preferably used amorphous gel component contains 60 wt. % Of a silicon dioxide-aluminum

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-Xt-

* A4 -

trioxide hydrogel containing 25 Gevt. Aluminiumtripxid% and about ¹ IO wt.? Kaolin clay.

The zeolites according to the invention can as such as Catalyst can be used, but they are preferably used in admixture with the amorphous gel component namely in amounts of about 1 to 25 Gew.JS, based on the total catalyst mixture. Mixing can be carried out in a conventional manner before the catalyst added to the inventory of a catalytic cracking reactor will. In a preferred embodiment, the zeolitic component of the catalyst is separated from the already existing catalyst belt of a catalytic Crack reactor added, if this already with a batch of an amorphous or a spent zeolite containing catalyst is loaded.

In certain cases it is advantageous to use the zeolitic component according to the invention in catalytic Pretreat conversion processes with steam. The steam treatment is generally about five to fifteen hours in a 20JSigen steam atmosphere at temperatures of about 815 to 8H5 ° C.

The catalyst mixtures according to the invention are particularly suitable for Use in catalytic cracking processes of coal

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Suitable for hydrogen, in which the catalyst is treated with a HC feed stream with a contact time of 1 to 180 seconds and temperatures of about Ί25 to 5 ^ 0 ° C. The use of the catalyst mixture according to the invention in industrial use depends on the equipment available in each case. As already indicated, the catalyst can be pre-mixed with a desired amorphous component or added to the existing inventory in a catalytic cracking reactor. The manufacturers of catalyst mixtures can therefore offer mixtures of the highly active zeolitic component with the less active component, which can contain between 1 to about 100% zeolitic component. Mixtures of virtually 100 % of the zeolite can also be used with certain types of equipment.

The microspherical zeolites according to the invention have excellent abrasion resistance because they have a Roller abrasion index of 5 to 35.

The excellent results obtainable using the zeolites of the present invention can be seen from the enclosed Drawings are taken.

Fig. 1 shows a graph of the data that can be obtained when the activity of the invention

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Catalysts and for comparison of a catalyst the state of the art as a function of the respective time can be applied in oil.

Fig. 2 shows in a graphical representation the data, the coke yields when using the invention Catalysts and for comparison of a catalyst from the prior art as a function of the respective time in oil.

Soil necessary for the production of the catalyst _{mixtures according to the invention}} zeolites which lead only to low coke deposits are used in the form of highly modified synthetic faujasites, which are referred to as PCY and EEHY.

The invention is illustrated in the following by means of the examples explained in more detail.

example 1 Cash splitting of FCY and REHY as well as CREY for comparison

A microspherical M & triumfaujäslt that can be used in a fluidized bed with a silica: alumina trioxide ratio of about 5, S was made from clay as follows: -

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A.

(i) A sample of a commercially available kaolin clay was calcined sixteen "■ hours at 705 ° C and then classified, so that a fraction was obtained which consisted of 50 Gew.I of particles having a size of 50 to 200 to. 660 g 2.130 g of a sodium silicate solution containing 8.1% by weight of Na ₂ O and 28.5 % by weight of SiO ₂ were then added to this calcined kaolin.

(ii) From 200 g NaOH, 3,500 g water and 3,500 g of the above described sodium silicate was a second Mixture made.

(iii) From a first solution containing 116 g sodium aluminate χ 3HpO in 800 g water and a second solution containing% 48 g NaOH ₉ 1,680 g sodium silicate (8.7 % Na ₃ O: 28.5 % SiO ₂ ) and 1.072 g of H ₂ O, a zeolite pot mixture was prepared by cooling the two solutions separately to 20 ° C. and then mixing them with vigorous stirring for 5 minutes. The mixture was then aged for 12 hours at room temperature.

The clay mixture (i), the sodium hydroxide-sodium silicate mixture (ii) and 500 ml of the inoculum mixture (iii) were then combined with stirring and heating to reflux (105 ° C) for 36 hours, using as 309815/1134

End product a synthetic faujasite with a

Total surface area of 935 m / g was obtained.

This faujasite was classified to obtain a fraction with a particle size of over 325 mesh, so that finally a sample of this composite material weighing M50 g on a dry basis.

To transform the microspherical so produced The following procedure was used for sodium faeces in PCY :

⁴¹⁵⁰ g of the microspheric Natriumfäüjasiten were washed twice an hour to exchange with an ammonium sulfate solution using a weight ratio of faujasite. (NH ₁ , KSO ₁ J: H ₂ O of 1: 1.5: 15. The product was then washed free of sulfate with water and then with a solution of rare earth metal chlorides with a weight ratio of zeolite: H ₃ O: SE ₂ O ₃ of 31 * 1: 3110: 22. The product was then washed free of chloride with water and calcined for three hours at 50 ° C. The calcined product was treated twice with an ammonium sulfate solution in a ratio

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of zeolite: (NHh) ₂ SOiIiH ₂ O of 1: 3: 6O, then washed free of sulfate with water and calcined at a temperature of 705 ° C. for two hours. (The rare earth chloride solution consisted of a commercially available mixture of the rare earth metals, mainly cerium and lanthanum).

B. A sample of fluidized bed sodium faujasite was prepared from a commercially available hydrogel catalyst containing 13% alumina / amorphous silica / alumina as follows:

«III ,,

(i) A sodium aluminate solution was prepared from 2,786 g of NaOH in 1,250 g of H ₃ O while stirring and adding 272 g of a commercially available Al ₂ O and heating the mixture to reflux until the AlpO dissolved. The sodium aluminate solution was then cooled to 20 ° C.

(ii) A silica-aluminum trioxide slurry was prepared from a commercial amorphous 8.229 6 SiIiciumdioxid-aluminum trioxide produced with a particle size of 50-20 _/ um and a content of 13 wt.% aluminum trioxide in 9.9OO g water.

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(iii) A zeolite seed solution was prepared as follows:

(a) 101 g of a C-31 aluminum oxide (AlpO,)
were dissolved in a solution containing 595 g of NaOH in 1,072 g of water,

(b) then 1,200 g of water became 2.M00 g of one Sodium silicate solution containing

27.7 wt.% And 8.60 wt siop.% Na ₂ O added

(c) the two solutions were mixed by adding the silicate solution with vigorous stirring was added to the aluminate solution,

(d) this solution was after aging 2 * 1 hour suitable for use as an inoculation solution at room temperature.

The sodium aluminate solution (i), the silica-alumina catalyst slurry (ii) and 3790 ml of the inoculation solution (iii) were then mixed and heated to 100 ° C for 8 to 10 hours. The resulting sodium faujasite in microsphere form was then cooled to room temperature.

To transfer the thus produced microspherical Sodium faujasite in REHY was made using the following procedure applied:

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A solution of rare earth chlorides (mixture of rare earth metals and chloride as under A) was made by diluting Ί0 ml of a 28.5Jfigen SE “O, solution prepared with 225 ml of water; the end 100 g of the sodium faujasite obtained by the specified method in microsphere form and 250 ml of water a slurry was prepared, which was mixed with the solution of the rare earth chlorides with stirring the pH of the slurry was adjusted to 3 »3 to 3.5 by adding hydrochloric acid became. The slurry was then one hour heated to 60 to 70 ° C, the pH was kept at 3 »3 to 3.5 by adding hydrochloric acid.

The loaded with rare earth microspheres were then washed with water until chloride-free, dried and calcined for two hours at 5 ^ 0 ° C. The calcined zeolite was then exchanged at 60 to 70 ° C. with an ammonium sulfate solution using a weight ratio of zeolite: (NH ^) ₂ SO ₁ , 1H ₃ O of 100: 1000: 500.

C. To the inventive coke-selective PCY and REHY zeolites to be able to compare with the zeolites of the state of the art loaded with rare earths, according to the US Pat. No. 3,375 Ο65

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very flat process a sample of a calcined rait rare earth loaded Y (CREY) zeolites.

The chemical and physical properties of the PCY, REHY and CREY components produced in this way are compiled in Table 1:

Table 1

REHY PCJ CREY zeolite

Si / Al ratio SE ₂ O, % by weight

Na ₉ O wt. %

Surface in m / g particle size (mesh)

Example 2

Mixture containing microspherical zeolites and

an amorphous oxide gel

To prepare mixtures of the zeolites with amorphous gel matrices, two samples of a semisynthetic amorphous inorganic hydrogel containing 30 parts of spruce kaolin clay in a mixture with 60 parts by weight of a silicon dioxide-aluminum trioxide hydrogel were prepared. These matrix components were produced by mixing the kaolin clay with dilute sodium silicate solution (5 % ₃ 3.2 SiO ^ Na ₂ O) and then gelling the mixture by adding CO ₂ . To make the silica-alumina-trioxide hydrogel

5.8 5.8 11.90 5.73 13.80 0.22 0 * 08 0.13 774 860 865 60-200 60-200 60-200

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component has a content of Al ₂ O to give 25 Gew.Ji was, the mixture was then treated with a solution of alum (10% AIPO,) and adjusted by adding ammonia to a neutral pH. The mixture was then spray dried to give microspheres on the order of 60 to 200 µm. The microspheres were then washed with ammonium sulfate solution and water, the Na ₂ O and sulfate content being reduced to the values given in Table 2:

Table I I.

Matrix ^ 1 2

AIpO, wt. ^ Na ₂ O wt.?

SO ₁ J wt JS Davison abrasion index

Jersey abrasion index surface in m ² / g *

Pore volume in cnr / g

30, H. 308 29.8 0.009 0.62 O ₁ OIl 0.28 0.06 20.5 13th - 1.9 269 0.51

after three hours of heating at 5 ¹ IO C

Example 3

Regeneration of mixtures of zeolites and amorphous

Hydrogels

To investigate the properties of catalyst mixtures from zeolites with an essentially from amorphous silicon dioxide-aluminum trioxide-clay hydrate existing component

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were mixed the inorganic hydrogel prepared in Example 2 11 Gew.JS, based on the content of silicon dioxide and aluminum trioxide of the zeolite 'with 89 wt.%. Physical mixtures with the CREY, PCY and REHY zeolites prepared according to Example 1 were prepared and investigated. The physical and chemical properties of these mixtures are summarized in Table III:

Table III

Mix no. 1 2 3 Zeolite from Example 1 CREY PCY REHY Zeolite content (wt. % On Si / Al base) ii, 0 11.0 11.0 Matrix no. (From example 2) 1 2 2 SE ₂ O, wt. 1.82 0.55 1.50 After 3 h at 50 ° C: Surface in m ² / g 126 360 329 Pore volume in cm / g 0.59 "0.16 0.15

After S-20 steam treatment: surface area in m ² / g pore volume in cnr / g

181 163 121 0.41 0.39 0.29

'' Steam treatment 12 h, 825 ° C, mixture of 20 % steam and 80 % air

Example 1 '

Investigation of the catalytic effectiveness of mixtures of zeolites and amorphous hydrogels n

In order to investigate the catalytic properties of the catalyst mixtures prepared in Example 3, a

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Process carried out in which the catalyst mixtures were brought into contact with oil in a pilot plant under the conditions of catalytic cracking. The tests were carried out at a temperature of 493 ° C, a ratio of catalyst to oil (C / 0) of Ί, Ο, an hourly weight throughput (WHSV) of about * IO and a contact time or oil time per cycle of 0.375 minutes. A typical test procedure in the test facility was that the catalyst was brought into contact with the oil for about 0.375 minutes, then stripped with 100% steam for 3 minutes and then regenerated for 30 minutes in air at a temperature of 620 ° C and 15 before the next test procedure Was purged with nitrogen for minutes. For each sample, the data were recorded in the oil during a test period of up to about 160 minutes. The data obtained in this way relate to the conversion properties and coke yields of the respective catalysts and are shown in Tables IV, V and VI and in FIGS. 1 shows that the conversion, plotted against the time in oil, for PCY and REHY becomes constant after approximately 100 minutes in the oil. The conversion for the corresponding CREY fluidized bed component is between the values for PCY and REHY after approximately 80 minutes. From Fig. 1 it can thus be seen that the conversion for both zeolites prepared according to the invention and for the known CREY zeolite

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is roughly the same. From Fig. 2, however, it can be seen that that the coke yield for both PCY and REHY to a value of less than about 3> 5 wt.?, based on fresh Use after about 85 minutes for fluidized bed REHY catalysts and drops from the start for fluidized bed PCY catalysts. The well-known fluidized bed CREY catalyst does not sink on any Place under 4 wt. 56, based on the volume of the fresh Use, from. This clearly shows that the inventive PCY and REHY zeolites when used in catalytic processes a previously unattainable low Condition coke production.

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Table IV

Catalyst: catalyst mixture no. 1 (from Table III)

Pretreatment: S-20

M activity: V% conversion 88.4

Batch no.

Conversion: Y% 8l, 28l, 8 76.8 75.8 74.4 73.6 73.9

_M H ₂ : wt% FP 0.023 0.020 0.019 0.025 0.024 0.029 0.023 ο.

<o C _r petrol: V55FF 72.2 72.1 66.2 66.9 65.2 63.9 62.6

"* C ⁺ gasoline / conversion 0.89 0.88 0.86 0.88 0.88 0.87 0.85 cn 0

IT Slight return »1: V $ FF 8.3 8.0 8.1 8.9 9.4 9.4 8.9

co coke: weight 55 FF 3.9 4, ¹ »4.6 4.7 4.5 4.1 4.2

C ⁺ gasoline / coke 18.5 16.4 14.4 14.2 14.5 15.5 14.9

Conversion / coke 20.8 18.6 16.7 16.1 16.5 17.8 17.5

^ Longer one-hour regeneration (normally only I6-I8 min. With heating) for a cycle between batch 5 and 6

■ fr-CD O

Table V.

Catalyst: catalyst mixture no. 2 (from Table III) - ι

Pretreatment: S-20

Batch No. 1 2. 3 4 5 '6' f 8 * 9 10 11 12 13 1 * 1 Conversion: V * 71.2 70.1 67.9 67.4 67.6 66.6. 65.3 66.3 66.1 73.0 72.9 71.0 72.6 73.4 H ₂ : wt. $ FP 0.019 0.028 0.028 0.019 0.022 0.028 0.024 0.025 0.028 0.0.17 0.020 0.024 0.024 0.015 C ^ gasoline ; V * PP 62.2 55.9 58.2 56.8 58.5 56.7 55.8 56.5 57.4 64.9 63.4 63.0 64.1 64.6 C * gasoline / conversion 0.87 0.85 0. -86 0.84 0.87 0.85 0.86 0.85 0.87 0.89 0.87 0.89 0.88 0.88 Light return81:

~ VfPF 10.1 10.5 10.0 9.5 9.1 10.2 10.1 11.5 10.2 10.1 11.1 11.3 10.7 10.6

Coke: - Weight SS FF 2.7 2.6 2.3 2.3 2.4 2.5 .2.1 2.4 1.7 2.1 1.9 1.7 1.8 1.7

C * gasoline / coke 2.50 2.50 25.3 24.7 24.4 22.7 26.6 23.5 33.8 30.9 33.3 37.0 35.6 38.0

^p "■ ■.

Conversion / coke 26.4 27.0 29.5 29.3 28.2 26.6 31.1 27.6 38.9 34.7 38.4 .41.8. 40.3 43.2

Longer one-hour regeneration (usually only 16-18 min. With heating) for a cycle between batch 9 and 10,

to β »

cn

fa"

NJ • tr-CO O Cn NJ

Table VI

Catalyst: Kat aly sat orinis chung No. 3 (from Table IH)

Batch no. 1 2 3 78.1
0.019
69.9 5 "6 7th 8th 9 10 11 Conversion: V%
H ": Gew.se PP
C ^ ⁺ gasoline: V? FF 74.5
0.028
66.7 74.5
0.026
66.4 75.6
0.026
68.5 0.89 76.3
0.025
68.9 77.3
0.027
69.6 76.3
0.028
67.0 73.9
0.023
65.0 73.9
0.028
65.8 77.1
0.023
68.5 77.3
0.031
70.3 j
C ^ 3 gasoline / conversion
Light return oil: 0.90 0.89 0.90 10.9
4.4 0.90 0.90 0.88 0.88 0.89 0.89 0.91 VJR PF
Coke: wt % FF 12.9
3.9 11.1
4.0 3 11.5
,8th 15.9
17.8 11.4
3.9 10.7
4.2 10.6
4.0 12.0
3.6 12.5
3.5 10.3
3.4 9.8
3.4 C- gasoline / coke
Conversion / coke 17.1
19.1 16.6
18.6 18.0
19.9 17.7
19.5 16.6
18.4 16.7
19.1 18.0
20.5 18.8
21.1 20.1
22.7 20.6
22.7

Longer one-hour regeneration (usually only 16-18 min. With heating)
for a cycle between batch 6 and 7

It can be seen from these results that the coke-selective zeolites according to the invention are catalytic cracking catalysts result in an effective conversion of high molecular weight hydrocarbons into valuable low molecular weight Lead derivatives. The coke selectivity of the PCY and REHY zeolite components according to the invention is im Unique compared to the previously known rare earth loaded faujasites. Of particular advantage is furthermore, that the zeolites result in easily utilizable and usable physical mixtures with amorphous matrix components let process.

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The abrasion indices mentioned in the description, namely the roller abrasion index, also known as the Davison abrasion index and the Jersey Abrasion Index are calculated as follows:

1 Davison index (roller index)

A 7 g sample of the catalyst mixture to be examined is sieved to remove particles on the order of 0 to 20 μm. The fraction having a size more than 20, then to five hours of treatment in a standard Roller-Korngrössenanalysator the pinboard Instrument Corporation, Silver Spring, using a nozzle having a 0.1778 cm and IDU tube with 2.5 ¹ J cm subject. The air flow rate is 9 l / min. The Davison Index Value is calculated as follows:

Weight of the

Davison index - formed material with 0-20 , around size »100

Weight of the original fraction with a size over 20 μm

2 Jersey index

The Jersey Index is obtained using the same apparatus and conditions as the Davison Index, but the proportion with a size of 0 to 20 μm during the last four hours of the experiment, i.e. in the second to fifth hour instead of the entire five hours of the experiment is collected, with the

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Material formed during the first hour with a size of 0 to 20 »m is discarded. The Jersey Index is calculated as follows:

Weight of the material obtained during the 2nd to 5th hour of the test with a size

Jersey index = =

4th

Weight of the original fraction with a size of more than 20 um

Claims (6)

PATENT CLAIMS 1. Zeolite catalysts for cracking hydrocarbons in the fluidized bed process from abrasion-resistant particles with a size of about 50-200, which consist of crystalline aluminosilicates with a silicon dioxide: aluminum trioxide ratio of over 3.0: 1, characterized in that the cations Zeolites hydrogen and rare earth metals are present in amounts of 0.3-1 ¹ % of rare earth oxides, based on the weight of the zeolite, and that alkali cations are present in amounts of less than 1 % alkali oxide, based on the weight of the zeolite. 2. Process for the production of a zeolite catalyst for cracking hydrocarbons, characterized in that that (a) microspherical particles with a size of about 50-200 µm and with a content of silicon dioxide and aluminum trioxide which are convertible to zeolites, (b) that these particles in a hydrothermal reaction with sodium hydroxide and with optionally for the production of zeolites with a Silica-alumina ratio of at least 3.0: 1 necessary silicon dioxide are converted, and that (c) the microspherical zeolites an ionic 309815/1134 -If- exchange with solutions are subjected to “the ions of which leave hydrogen cations in the zeolite during thermal decomposition and that loading with rare earth metal ions to achieve a content of rare earth metal oxides of up to 14 % _s based on the weight of the zeolite takes place and that the zeolites are calcined. 3. The method according to claim 2, characterized in that in method step (c) the microspherical zeolites are subjected to the ion exchange and the Caleinierung by (i) reduction of the NapO content of the zeolite to about 1.5 - ^ wt. % By Ion Aus- Exchange with cations that form hydrogen cations in the zeolite during thermal decomposition _s (ii) by ion exchange of the zeolite with a solution of rare earth metal salts with a concentration to achieve a rare earth content of about 0.3-10% by weight, based on the zeolite , (iii) drying and calcining the loaded zeolites at temperatures of about 370 - 87O ⁰ C for 0.1-3 hours, and (iv) by loading the calcined Zeo-.lithen with an ammonium salt solution to reduce the content of sodium oxide to less than 1 weight 55. 30981-5 / 1134 4. The method according to claim 2, characterized in that in process step (c) the microspherical zeolites are subjected to ion exchange and calcination by (i) reducing the Na ₂ O content of the zeolite to less than 4 Gew.JE by ion exchange at a pH value of 3 »0-3» 5 with a solution with a rare earth content to achieve a rare earth content of 6-14 wt.?, based on the zeolite, (ii) by calcining the loaded zeolite at a Temperature of 425 - 760 ° C for 1-3 hours and (iii) by loading the calcined zeolite with a solution containing ions that re-form hydrogen ions in the zeolite after thermal decomposition in sufficient quantities to reduce the alkali oxide content of the zeolite to less than 0, 5 wt / ?. 5. Catalyst mixture for cracking hydrocarbons, characterized in that it is a zeolite Claims 1-4 together with a microspherical inorganic oxide gel contains 6. Use of the zeolite according to claims 1-4 or a mixture according to claim 5 for cracking hydrocarbons without substantial formation of coke. ^{si: g0} 309815/1134 Blank page