DE1442853B2 - Process for the preparation of an aluminosilicate catalyst - Google Patents

Description

The invention relates to a method for producing an improved Aluminosilikatkatalysators, which is useful for the, conversion of organic compounds, and r to the use of the crystalline Aluminosilikatkatalysators prepared for cracking hydrocarbons.

A variety of zeolites, both natural and synthetic, are known, including z. B. chabazite, gmelinite, mesolite, mordenite, natrolite, sodalite, scapolite, lazurite, leucrite and cancrinite. Synthetic zeolites can be of the Α-type, X-type, Y-type or other known molecular sieve forms belong. The preparation of the synthetic zeolites mentioned above is π in the literature has been described, e.g. B. Α-type zeolite in US-PS 28 82 243, X-type zeolite in US-PS 28 82 244 and Y-type zeolite in BE-PS 5 77 642 and 5 98 582. In the originally prepared form the metal of the aluminosilicate is an alkali metal and w usually sodium. This alkali metal can exchange cations with many other metal ions be subjected. The molecular sieve materials obtained in this way are unusually porous.

From DE-PS 11 00 009 a method for τ> Production of crystalline, zeolitic molecular sieves based on metal aluminum silicates containing water of hydration the following compositions:

1.0 ± 0.1

M ₁ O

: Al ₂ Oj: 6.4 ± 0.5 SiO ₂ : y H ₂ O,

W)

in which M is at least one exchangeable cation, η is the valence of M and / any value between 0 and 7, with a certain unit cell and a specific Debye-Scherrer diagram bekanntge- b ^r> been, in which a specific metal aluminum silicate mixture at temperatures of 100 to 120 ° C into crystalline potassium aluminum silicates, which may also contain sodium, is converted, where appropriate, the potassium ion and optionally also the sodium ion with a sodium, lithium, barium, calcium, cerium, magnesium, strontium, zinc, hydrogen or ammonium cation containing solution can be exchanged.

The known crystalline zeolitic molecular sieves are intended as adsorbents.

From US-PS 29 71 903 the production of a hydrocarbon conversion catalyst is known, the uniform pore openings should have between about 6 and 15 Å, wherein a crystalline alkali aluminosilicate zeolite can be subjected to a cation exchange. According to the only example, the crystalline aluminosilicate zeolite an SiO2 / Al2O3 ratio of 2.7.

As tests have shown, the known hydrocarbon conversion catalysts are still sufficient not all requirements.

The object of the invention is to produce a highly active and selective aluminosilicate catalyst, for the conversion of organic compounds, especially the conversion of hydrocarbons, such as hydrocarbon cracking, alkylation, dealkylation, disproportionation, isomerization and polymerization is suitable and has a long useful life and also water vapor resistance having.

This object is achieved by a process for producing an aluminosilicate catalyst, in which a crystalline alkali aluminosilicate zeolite _{with an SiO 2 ZAl 2} Or ratio over 3 is subjected to a cation exchange to replace alkali metal ions, washed, dried and calcined, which is characterized in that one finely divided crystalline aluminosilicate of the Y-type, the alkali metal ions of which are at least 70%, in particular more than 80%, cation-exchanged by ions of rare earths, calcium, ammonium or hydrogen or mixtures thereof, in a carrier made of a hydrous oxide, a dispersed inorganic gel or clay, the product obtained is cation-exchanged to remove alkali metal ions, optionally with ions of rare earths, calcium, ammonium or hydrogen or mixtures thereof, after drying and calcination, optionally a treatment with steam at a temperature temperature of 204 to 815 ° C for at least about 2 hours, with an alkali metal content of less than 3 wt .-%, in particular less than 2 wt .-%, is present after completion.

The catalyst according to the invention is unlike previous conventional cracking catalysts made of a Y-type crystalline aluminosilicate having a structure of rigid has three-dimensional networks made up of uniform pores with a diameter of 6 to 15 angstrom units are characterized and in which preferably substantially all of the original alkali metal cation is exchanged. The obtained uniform pore openings within the above Range occur in all dimensions and allow easy access of all hydrocarbon reactant molecules to the catalyst surface and lead to an easy release of the Product molecules. Surprisingly, the catalyst also has an unusual stability,

when it is in the form of a hydrogen or acidic Y-aluminosilicate, which is in a hydrous Oxide carrier has been replaced. The high stability of such a catalyst is apparently one synergistic effect between the acidic aluminosilicate and the surrounding water-containing oxide carrier attributable to.

According to one embodiment of the process according to the invention, a cracking catalyst is used exceptional activity and selectivity consisting essentially of 1 to 90% by weight of a crystalline Y-aluminosilicate consists, whose original alkali metal ions are essentially completely replaced by the specified ions are exchanged, the aluminosilicate having a mean value determined by weighing Particle diameter of less than 40 μm and preferably less than 15 μm and in one Hydrous oxide carrier made of clay or inorganic oxide gels suspended and whole in it is distributed.

The crystalline aluminosilicates which can be used in the process according to the invention are known as Y zeolites. The latter are particularly described in BE-PS 5 77 642 and 5 98 582 and can are expediently prepared in the procedure described there. The molar composition such zeolites falls into the general formula:

0.9 ± 0.2 Na ₂ O: Al ₂ O ₃ : 3rd - 6.5 SiO ₂ · 9H ₂ O.

The above-mentioned zeolite used in the preparation of the catalyst of the present invention has a uniform pore structure with openings that are defined by an effective pore diameter between 6 and 15 Angstrom units are marked. /

A cation exchange takes place in order to produce the catalysts by the process according to the invention of the alkali metal Y-aluminosilicate with ions of rare earths, calcium, ammonium or of hydrogen or mixtures thereof, by at least 70 and preferably more than 80% of the to replace the original alkali metal ions with ions of the aforementioned group. the According to the invention, catalysts can be prepared by intimately mixing a crystalline alkali metal-Y-alumino- ' silicate with a uniform effective pore diameter between 6 and 15 Å in finely divided form, expediently with a mean particle diameter determined by weighing of less than about 40 μιτι and preferably less than about 15μπι, getting produced.

The maximum alkali metal content in the finished Catalyst compositions that can be tolerated depend in part on the nature of the cation present away. So if the cation is a rare earth metal ion or a combination of metal and Hydrogen ions, amounts up to 3% by weight of exchangeable alkali metal are tolerated. in the In the case of calcium, the residual amount of exchangeable alkali metal is generally below 2 and preferably kept below 1.5 wt .-%.

Intimate mixing of the finely divided aluminosilicate and the binder, e.g. B. of metal powder, clays or inorganic oxide hydrogel, for example, can be prepared by using the two materials are ground together over an extended period of time in a ball mill, preferably in the presence of water under conditions to reduce the particle diameter of the aluminosilicate to one mean particle diameter determined by weighing of less than 40 and preferably less than 15 μπι to reduce. However, this method of blending is less preferred than that in which the Aluminosilicate in finely divided form in a hydrous inorganic oxide, e.g. B. a hydrosol or a hydrogel. When using this working method, the finely divided aluminosili-

K) kat are dispersed in an already prepared hydrogel or hydrosol; when the hydrosol through a short gelation time is characterized, the finely divided aluminosilicate can preferably to one or several of the reactants used in forming the hydrosol can be added or it may be in the form of a separate stream in a mixing nozzle or other device in which the Reactants are brought into intimate contact with one another, with currents of the hydrosol forming reactants are mixed. As noted earlier, it is desirable that this be included in the Hydrosol introduced aluminosilicate has a mean particle diameter determined by weighing of less than about 40 μm and preferably less than 15 μm and, if large particles are desired, has between 2 and 7 μΐη. It was found that the use of aluminosilicate with an average particle diameter determined by weighing of more than 40 μΐη to the occurrence of a physically

ίο gave rise to a weak product, while the use of aluminosilicate with a mean particle diameter determined by weighing of less than 1 μm resulted in a product of low diffusivity.
The powdery hydrosol of the inorganic

] 5 Oxydes solidifies after a suitable one has passed Period to a hydrogel; the resulting hydrogel is cation exchanged when, as a result of the Using an alkali silicate zeolitic alkali metal has been introduced, and then washed, too dried a gel and at a temperature below the melting point of the incorporated aluminosilicate powder thermally activated. It has been found that the resulting product, essentially of aluminosilicate suspended in a carrier of the inorganic oxide gel and completely distributed therein of the Y-type, the cation of which consists of rare earths, calcium, ammonium or hydrogen or mixtures is formed therefrom, particularly advantageous properties as a hydrocarbon conversion catalyst owns.

It has been found desirable, in some cases in addition to that described above Y-type aluminosilicate in the catalyst support together with the finely divided aluminosilicate from Y-type to incorporate a secondary solid excipient, which is also present in finely divided form, in the generally in the particle size range of an average particle diameter determined by weighing from 1 to 40 μπι, and is able to the resulting

w) to give the composition increased diffusivity. Such additive may be inert or it may add to the overall catalytic activity of the final Contribute catalyst composition. The amount of such an additive can be up to 40% by weight

tv5 rich in composition. When the catalyst is in the form of gel beads, the mean particle diameter of the additive material determined by weighing is generally less than 10 μπι. Suitable

Additives for the above purpose include, for example, clay, aluminum oxide, zircon, Barytes, carbon, wood flour, silicon dioxide, recycled catalyst fines, magnesium oxide, fines of spent cracking catalyst and various ores and naturally occurring minerals. These Additives can remain in the final composition or, in the case of combustible ones, they can Substances such as carbon or wood flour due to the effect of elevated temperatures on the catalyst, either through an associated preparatory treatment or during use, beforehand have been removed.

The binder which the carrier forms in the preparation of the catalyst according to the invention should be thermally stable under the conditions at which the conversion reaction is carried out. Accordingly, solid porous adsorbents, carriers and support materials are useful in the heretofore catalytic operations used in conjunction with the crystalline aluminosilicate described above Y-type used. Such materials can be catalytically inert or they can be of their own catalytic activity or an activity that is closely associated or reactive with the crystalline Y-type aluminosilicate is ascribable. Such materials include e.g. B. dried inorganic oxide gels and gelatinous precipitates of aluminum oxide, silicon dioxide, zirconium oxide, magnesium oxide, Hafnium oxide, thorium oxide, titanium dioxide, boron oxide, and combinations of these oxides with one another and with other components. Other suitable binding materials include activated metal powders, Charcoal mullite, kieselguhr, activated carbon, bauxite, silicon carbide, sintered clay and various clays a. Preferably the aluminosilicate is coated with a hydrous oxide material, e.g. B. a hydrogel an inorganic oxide or a clay of the type described above, intimately combined.

While inorganic oxide gels can generally find utility as a suitable carrier, it will preferred that the inorganic oxide gel used is a mixed gel of silicon dioxide and an oxide of at least one metal from groups IIA, IHB and IVA of the periodic table is. Such components include e.g. B .:

Silica-alumina,
Silica-magnesia,
Silica-zirconia,
Silica-hafnium oxide,
Silica-thorium oxide,
Silica beryllium oxide,
Silicon dioxide-titanium dioxide,
and ternary combinations such as B.
Silica-alumina-thorium oxide,
Silica-alumina-zirconia,
Silica-alumina-magnesia and

Silica-Magnesia-Zirconia.
In the above gels, silicon dioxide is generally present as the main component and the metal oxides are contained in a minor proportion. Thus, the silica content of such gels is generally within the range of about 55-100% by weight with a metal oxide content in the range of 0-45% by weight. The hydrosols of inorganic oxides used according to the invention and the hydrogels obtained therefrom can be prepared by any known method, e.g. B. by hydrolysis of ethyl orthosilicate, acidification of an alkali metal silicate, which may contain a compound of a metal, the oxide of which is to form the mixed gel with silicon dioxide, etc. The relative proportions of finely divided crystalline aluminosilicate and carrier can be changed within wide ranges, the content of crystalline aluminosilicate can be in the range of about 1 to 90% by weight and more, and usually, especially when the composition is made in the form of beads, in the range of about 1 to about 50% by weight of the composition, as indicated above , becomes the crystalline

Alkali metal Y-aluminosilicate a cation exchange with ions of rare earths, calcium, ammonium or hydrogen or mixtures subject to it. The cation exchange is carried out by at least 70, and preferably more than 80% of the original alkali metal ions to be exchanged for ions of the above-mentioned group and to reduce the exchangeable alkali metal content of the finished catalyst to below 3%. This in finely divided form and with a suitable binder or carrier material in the form of Aggre- ί Gatpartchen-bound aluminosilicate can either before or after intimate mixing with the binding material can be cation exchanged.

It has also been found that the catalyst selectivity of the composition described above is greatly improved when the same is subjected to a mild steam treatment. The act of exposing the catalyst to the action of water vapor is a very desirable step in obtaining a product capable of providing an increased yield of gasoline. The steam treatment may be carried out at a temperature within the range of about 204-788 ⁰ C for at least about 2 hours. Usually, steam is used at a temperature of about 538-760 ° C, with treatment times ranging from about 2 to about 100 hours. An atmosphere comprising a substantial amount of water vapor, e.g. B. at least about 5% by volume but also contains air or other gas which is substantially inert with respect to the composition being treated; such mixtures may in some cases be desirable in connection with the use of more elevated temperatures in order to avoid possible deactivation of the catalyst. The steam treatment can be effected at pressures from atmospheric pressure up to about 35 kg / cm ^2. The above steam treatment serves to reduce the surface area of the calcined composition. It is particularly preferred to subject the calcined catalytic composition described above to the treatment with steam to reduce its surface area by at least about 20% but not more than about 75%. bo The reactions catalyzed by the crystalline aluminosilicate compositions described herein include the rearrangement or conversion of organic compounds which are catalytically convertible in the presence of acidic catalyst sites. Typical of such reactions are the cracking of paraffinic, olefinic, aromatic and naphthenic hydrocarbons and their mixtures, e.g. B. petroleum fractions, for example

those who boil in the gas oil range; the disproportionation of aromatics; the dehydration of alcohols to olefins and ethers; the hydration of olefins to alcohols, the isomerization and polymerization of olefins, the isomerization of terpenes; the alkylation of isoparaffins and the alkylation and Dealkylation of aromatic hydrocarbons.

The cracking of hydrocarbons is a particularly advantageous application of the aluminosilicate catalysts according to the invention, since the nature of the products can be well controlled. Of the Catalyst can be used in such processes in the form of pellets in a fixed bed mode of operation, or it can work in a compact moving bed mode or in a mode with Find fluidized bed application. The general operating conditions mask as a result of the wide Usability of the catalysts has a wide range. It is generally desirable to have such Process at a temperature within the range of about 260-648 ° C and a pressure in the range from sub-atmospheric pressure up to several hundred atmospheres. the Contact time of the oil within the catalyst is in each case according to the conditions of particular oil charge and the particular desired results adapted to a substantial Amount of cracking to lower boiling products.

The cracking activity of the catalyst is a measure of its ability to catalyze various hydrocarbon conversions and it is expressed here as the percentage conversion of a gas oil with a boiling range of 232-510 ° C to gasoline with an end boiling point of 210 ° C when vapors are passed through it gas oil through the catalyst at 468-482 ⁰ C, about atmospheric pressure and a feed of 0.6 volume -16 liquid oil per volume of catalyst per hour over 10 min continuous operation cycles between regenerations.

When analyzing the results obtained with the catalyst prepared according to the invention, it has It has been found useful to compare this with the results obtained with a conventional one technical silica-alumina gel cracking catalyst, which contains about 10 wt .-% aluminum oxide can be achieved. The extraordinary activity, The stability and selectivity of the catalyst prepared according to the invention can be clearly seen in one Comparison of the various product yields obtained with such a catalyst with the Yields of the same products as the conventional silica-alumina catalyst in the results in the same conversion amount. The differences (4 values) given below represent those of yields given to the catalyst according to the invention minus those of the conventional one Catalyst yields.

example 1

Y-type crystalline sodium aluminosilicate was prepared from the following reactants:

A. Silica solution

1551 ecm (1870 g) colloidal silicon dioxide containing 0.361 gSKVccm

B. Sodium aluminate solution

75 g NaAlO ₂ (41.7% by weight Al ₂ O ₃ ,

30% by weight Na ₂ O)
330 g NaOH (77.5% by weight H ₂ O)
.5 1345 ecm H ₂ O

The above solutions were mixed at a temperature of about 27 ° C by adding the Solution B was poured into solution A. Which

The resulting mixture became vigorous for about 1/2 hour touched. The slurry thus obtained was then heat-treated at a temperature of about 93 ° C for 42 hours The solid material present was then removed from the supernatant liquid by filtration separated. The filter cake obtained was used to remove the free liquor with a volume Washed water per volume of initial slurry.

The composition of this example was prepared by adding 10% by weight of that in the preceding Y-zeolite produced in a carrier made of silica-alumina gel, which about 94 wt .-% silica and 6 wt .-% alumina were dispersed.

It became the reactants indicated below used:

C. Silicate paste solution

1. 4.74 kg of sodium silicate (28.5% by weight SiO ₂ ,

8.9% by weight Na ₂ O,

62.6% by weight of H ₂ O)

2.39 kg of water

2.24 kg of water

0.30 kg sodium Y-aluminosilicate
(54.3 wt. O / o solids)

Solution 2 was added to solution 1 with vigorous stirring and a solution was obtained which had a specific gravity of 1.182 at 16 ° C.

D. Acid solution

25.9 kg of water

1.92 kg Al ₂ (SO ₄ J ₃ - 18H ₂ O

0.90 kg H ₂ SO ₄ (97%)
Specific gravity at 25 ⁰ C = 1.056

The above solutions were passed through a mixing nozzle in amounts of 394 ccm / min of solution D to 374 ccm / min of solution C. The resulting hydrosol, which has a pH of

so 8.5 had, was introduced in the form of droplets into an oil phase in which it was 2.2 seconds at a temperature of 17 ° C solidified to form hydrogel beads.

The pearl hydrogel was base-exchanged with an aqueous solution of 2% by weight rare earth metal chlorides of the following composition: 0.63% cerium chloride, 0.33% lanthanum chloride, 0.06% praseodymium chloride, 0.23% neodymium chloride and traces of samarium chloride, gadolinium chloride and other rare earth metal chlorides. The base exchange was carried out using 12 contacts (9 contacts of 2 hours each and 3 contacts of 20 hours each) with V ₂ volumes of solution per volume of hydrogel beads. The exchanged hydrogel was washed free of soluble anions, dried in air at 132 ° C. for 24 hours, tempered in air at 538 ° C. for 10 hours and at 1.05 kg / cm ² and 648 ° C. for both 30 hours and 60 hours Treated with steam.

909 540/1

The final composition contained 0.21% by weight of sodium and had a rare earth metal oxide content of 10.8% by weight. The surface area of the product treated with steam for 30 hours was 195 m ² / g and that of the product treated with steam for 60 hours was 167 m ² / g.

Table I.

example
1

description

Carrier Si / Al (94/6)

Fine parts

Type Na / Al / Si (13Y)

Concentration 10

Cation exchange

SECl ₃ -OH ₂ O solution

Conc.,% By weight 2

composition

Na, wt% 0.21

(SE) ₂ O ₃ , wt% 10.8

Physical Properties

Surface size, 195 (1) 167 (2)

steam treated, m ² / g

Catalytic investigation

Conversion,% by volume 63.0 60.8 Space velocity 4th 4th Gasoline, vol .-% 55.2 53.7 Excess. C ₄ ,% by volume 10.2 10.8 C ₅ + gasoline, vol .-% 52.5 51.1 Total C ₄ ,% by volume 12.9 13.3 Drying gas, wt .-% 6.4 5.1 Coke, wt% 2.4 2.3 Advantage over standard Cracking catalyst *) Gasoline, vol .-% +8.8 +8.5 Excess. C. ,, vol .-% -4.8 -2.9 C ₅ + gasoline, vol .-% +8.4 +8.5 Total G ,, vol .-% -4.2 -3.2 Drying gas, wt .-% -1.8 -2.6 Coke, wt% -2.7 -2.5 Cs + gasoline yield advantage +2.2 +2.4

via SiO, / Al ₂ O ₃ -SEHX **)

*) Technical silicon dioxide-aluminum oxide catalyst,

containing about 90% SiO ₂ and 10% Al ₂ O _3.
**) IJ X zeolite, cation-exchanged with rare-earth-ammonium chloride and contained in a carrier made of SiO ₂ -AhO ₁ - (JeI.

(1) 30 hours at 648 C carrier and 1.05 kg / cnr with 100% Treated with steam.

(2) W) hours at 648 C and 1.05 kg / cnr with 100% water vapor treated.

10

The values for the catalyst according to Example 1 are for comparison with the results in Use of an industrial silica-alumina cracking catalyst at the same conversion and further with a catalyst composed of 10% by weight of sodium aluminosilicate from X-type dispersed in a gel matrix composed of 94% by weight of silica and 6% by weight of alumina and with combined rare earth metal and ammonium chloride solutions fractions were exchanged up to a low residual sodium content.

The values in Table I show the catalytic benefits of the exchanged contained in a carrier Y-type aluminosilicate over the comparable X-type aluminosilicate as well as the very pronounced one Improvement of the activity and the selectivity compared to the technical standard silicon dioxide / Alumina catalyst.

Examples2-3

The compositions of these examples were prepared in the same manner as those of Example 1, with the exception that the cation exchange of the pearl hydrogel with an ammonium chloride solution was carried out.

In the case of these two examples, the exchange of the pearl hydrogel was effected by contact with an aqueous solution of 1% by weight ammonium chloride, 12 contacts of 2 hours each with ^x 1 volume of solution per volume of hydrogel being used. The exchanged hydrogel was then washed, dried and tempered as in Example 1. The composition of Example 2 was treated for 30 hours at 1.05 kg / cm ² and 648 ⁰ C with water vapor, while the composition of Example 3 was treated for 24 hours under the specified conditions with steam.

Example 4

The composition of this example was made by cation exchange of 200 g of the Y zeolite, prepared as in Example 1, with a 5 weight percent aqueous solution of ammonium chloride. The cation exchange was carried out at 82 ^° C. using 12 contacts of 2 hours each with 1/2 volume of solution per volume of slurry. The exchanged material was washed, dried and tempered as in Example 1 and then treated with steam at atmospheric pressure for 20 hours at 662 ° C.

The composition obtained in this way had a sodium content of 1.19% by weight, an aluminum oxide content of 27.0% by weight and a surface area of 66 m ² / g.

Example 5

The composition of this example was prepared in the same manner as that of example 2 with

ho with the exception that the sodium aluminosilicate for X-type and was present in an amount corresponding to 25% by weight.

The cation exchange of the hydrogel beads was carried out in this example by contact with an aqueous

tv-, solution of 2% by weight ammonium chloride at room temperature carried out, with 8 contacts of 2 hours each with 1/2 volume of solution per volume of hydrogel beads came into use. That exchanged

The hydrogel was then washed free of chloride, dried in air at 110 ° C., tempered in air at 538 ° C. for 10 hours and ^{treated with steam at 1.05 kg / cm 2 for} 24 hours at 648 ° C.

The compositions of Examples 2-5 were in the manner described in their catalytic cracking activity was examined and the results are shown in Table II below:

Table II example 60.3 51.3 3 61.9 4th 5 2 2 3 2 49.4 43.7 50.7 Si / Al description 12.7 10.5 13.1 (94/6) carrier 47.1 41.7 48.5 14.9 12.4 15.4 Na / Al / Si Na / Al / Si Fine parts 7.4 5.7 Si / Al (94/6) 7.4 (13Y) (13X) Type Si / Al (94/6) 1.7 1.1 2.0 100 25th concentration NH ₄ Cl NH ₄ Cl Cation exchange +4.3 +3.4 +4.9 5 2 solution -1.1 -0.5 Na / Al / Si (13 Y) -1.4 Conc.,% By weight Na / Al / Si (13Y) +4.3 +3.7 +4.9 1.19 1.09 composition -1.1 -0.9 10 -1.2 27.0 13.6 Na, wt% 10 -0.4 -0.5 -0.6 Al ₂ O ₃ , wt% -3.0 -2.2 NH ₄ Cl -2.8 0.66 0.81 Physical Properties NH ₄ Cl 1 66 Apparent Density g / ccm 1 Surface area, water vapor 0.3 treated, m ² / g 0.27 53.2 30.0 Catalytic investigation 8.1 4th 4th Conversion,% by volume 0.82 47.2 27.5 Space velocity 0.86 136 9.3 4.2 Gasoline, vol .-% 137 44.7 25.8 Excess. C ₄ ,% by volume 11.8 5.8 C ₅ + gasoline, vol .-% 43.3 5.2. ,, 3.1 Total C ₄ , volume% 43.2 4th 0.99 1.0 Drying gas, wt .-% 4th 37.9 Coke, wt% 38.3 7.5 Advantage over standard crack 7.6 36.0 +5.9 catalyst*) 36.3 9.4 -2.2 Gasoline, vol .-% 9.6 4.4 +5.7 Excess. C ₄ ,% by volume 4.5 1.26 -2.0 C ₅ + gasoline, vol .-% 0.9 -1.3 Total C ₄ ,% by volume -2.4 Drying gas, wt .-% +2.1 Coke, wt% 1-2.5 -1.1 -0.9 +2.5 +2.8 -1.6 -1.4 -0.6 -0.4 -0.7 -1.0

*) Technical silica-aluminum oxide mixed gel analyzer, containing _{about 90% SiO 2} and 10% Al _{2 Oj.}

The catalytic values summarized in the table above show that the acidic Y-aluminosilicates are active cracking catalysts that provide improved selectivity over the standard silica / alumina catalyst demonstrate. To make a direct comparison of the catalysts according to Examples 2 and 3 with the rare earth metal catalyst To employ according to Example 1, it was necessary to use the

former catalysts under conversion conditions at an hourly space velocity the liquid of 2 operate. At an hourly space velocity of 2, the activities for the catalysts according to Examples 2 and J were 60.3 and 61.9% by volume, respectively Conversion increased. These acidic catalysts show good selectivity in this conversion, the

Selectivity is at the expense of the coke and drying gas with little loss of total C4 improved.

The values given in Table II also show the fact that the catalyst according to Example 2, which contained 10% by weight sodium Y-aluminosilicate, almost reached the activity of the pure material, d. H. of the catalyst according to Example 4, although it was treated in a much more severe manner with steam. These data show that the incorporation of Y-type aluminosilicate in a silica-alumina carrier, followed by cation exchange with ammonium chloride solution, for increased stability of the resulting acidic aluminosilicate. Although the reason for such a surprising one increased stability is not known with certainty, it can be assumed that this is a synergism between the Y-type acid aluminosilicate and the carrier containing this silicate is.

From the values in Table II it can also be seen that the catalyst according to Example 5, from X-type crystalline aluminosilicate was much less active than the catalysts according to Examples 2 and 3, both of which contain a smaller amount of crystalline aluminosilicate, however Y-type included.

The following examples show that hydrous alumina and hydrous clay are used as carriers Can be used to make dilute rare earth Y-aluminosilicate catalysts with exceptional catalytic properties.

, B e i s ρ i e 1 6

Crystalline sodium Y-aluminosilicate was prepared as in Example 1. Of the resulting aluminosilicate, 230 g of a combined aqueous solution containing 5% by weight LaCl ₃ · 6 H ₂ O and 2% by weight NH 4 Cl was continuously cation exchanged for 48 hours, the equivalent of 24 two hour exchanges with one Volume of solution per volume of slurry was used. The cation-exchanged material would be washed free of soluble anions and dried.

Thirty grams of the dried Lantham exchanged powder was mixed with 90 grams of hydrous alumina containing 66.5% solids at 538 ° C. The mixing process was carried out in a mixing device with 150 ecm of added water in order to stir the mixture into a paste-like, homogeneous mass. The resulting mixture was ^{dried in air at 110 °} C. for 24 hours, then pelletized and formed into particles with a size of 4 × 10 mesh. The particles thus obtained were calcined at 538 ° C. for 10 hours and then ^{treated with steam at 1.05 kg / cm 2} and 648 ° C. for 24 hours.

The resulting composition had a sodium content of 0.3% by weight, a La2C> 3 content of 4.25% by weight and a surface area of 172 m ² / g after the steam treatment.

Example 7

The composition of this example was prepared in the same manner as that of Example 6 except that the cation exchange _{solution contained 5% by weight rare earth metal chloride (SECl 3} · _{6H 2} O) and 2% by weight ammonium chloride and more hydrous Clay was used as a thinning vehicle.

In this example, 22 grams of the dried rare earth metal exchanged material weighed 76 grams raw clay (88% solids at 538 ° C) mixed. The dry mixed product then became as in that previous example pelletized, calcined and steamed.

The finished composition had a sodium content of 0.44% by weight, a rare earth metal oxide content of 4.0% by weight and a surface area of 105 m ² / g after the steam treatment.

The properties and results obtained when testing the compositions according to the examples 6 and 7 for their catalytic cracking activity are listed in Table III below:

Table III

Example no. 7th 6th description 75% water content. volume carrier 75% water content. Al ₂ O ₃ Fine parts SEHY Type LaHY 25th concentration 25th composition 0.44 Na, wt% 0.3 4.0 (SE) ₂ Oj, wt% 4.25 Physical Properties

Surface size, steam treated, m ² / g

105

16

continuation

Example no.
6th

Catalytic investigation

Conversion,% by volume
Space velocity
Gasoline, vol .-%
Excess. C ₄ ,% by volume
C ₅ + gasoline, vol .-%
Total C ₄ ,% by volume
Drying gas, wt .-%
Coke, wt%

Advantage over standard cracking catalyst *)

Gasoline, vol .-%
Excess. C ₄ ,% by volume
C ₅ + gasoline, vol .-%
Total C ₄ ,% by volume
Drying gas, wt .-%
Coke, wt%

C ₅ + gasoline yield _{advantage over SiO 2} / Al ₂ O ₃ -SEHX **)

*) Technical silica-alumina catalyst, containing _{about 90% SiO 2} and 10% Al ₂ O _3.

**) 13 X zeolite, cation-exchanged with rare earth ammonium chloride and contained in a carrier made of SiO ₂ -Al ₂ O ₃ -GeL

64.5 77.2 66.8 4th 4th 8th 59.2 60.6 58.1 8.9 16.2 11.8 55.9 58.1 55.1 12.2 18.8 14.8 5.6 10.1 6.3 2.0 4.4 2.6 +12.2 +8.6 +10.1 -6.5 -5.4 -4.7 +11.1 +7.7 +9.1 -5.4 -4.4 "3.7 -2.9 -0.9 -2.6 -3.4 -3.6 -3.2 +5.1 - +3.2

'Example 8

This example shows that a catalyst can be made with good activity and selectivity when using pre-exchanged rare earth metal Y-aluminosilicate used together with added powdered material for increased diffusivity. That Fine material consisted of 5 wt% rare earth Y-aluminosilicate and 24% by weight clay with a mean particle diameter determined by weighing from 4-5 μm. The resulting pearl hydrogel was cation exchanged, washed, dried, tempered and treated with steam.

The final composition contained 0.18% by weight sodium, 0.95% by weight rare earth metal oxide and 16.6% by weight aluminum oxide. The surface area of the composition after the steam treatment was 126 m ² / g.

The results obtained in testing the composition of this example for catalytic cracking activity are listed in Table IV below:

Table IV

example
8th

example

Cation exchange

solution
Conc.,% By weight
contacts

composition

Na, wt%

(SE) ₂ O ₃ ,% by weight
Al ₂ O ₃ , wt%

Physical Properties

Apparent Density, g / cc

Surface size,

steam treated,

m ² / g

description
carrier

Fine parts

Type
concentration

Si / Al (94% SiO ₂ -6%
Al ₂ O ₃ )

5% SEY + -24% clay

Catalytic investigation

Conversion,% by volume
Space velocity
Gasoline, vol .-%
Excess. C ₄ ,% by volume
C ₅ + gasoline, vol .-%

NH ₄ Cl

a 24 hour. continuous exchange at room temperature, equivalent to 12 2 hour exchanges

0.18 0.95 16.6

0.78 126

51.6

46.4

7.0

43.6

909 546/1

continuation

example Table V

Example No. 9

IO

15th

20th

Catalytic investigation

Total Q, VoL% 9.9

Dry gas, wt% 5.0

Coke, wt% 1.2

Advantage over standard cracking catalyst *)

Petrol, vol% +5.9

Excess. C ₄ , Vol-% -4.0

C ₅ + petrol, vol-% + 5.4

Total C ₄ , vol% -3.4

Dry gas, wt% -1.2

Coke, wt% -1.9

*) Technical silica-alumina catalyst, containing _{about 90% SiO 2} and 10% Al ₂ O _3.

Example 9

This example shows the use of a pulver- jo shaped metal as a carrier for the catalysts of the above type.

Y zeolite was prepared as in Example 1 and cation exchanged with an aqueous solution containing 2% by weight ammonium chloride and 5% by weight mixed rare earth metal chlorides of the following composition: 1.57% cerium chloride, 0.83 % Lanthanum chloride, 0.17% praseodymium chloride, 0.58% neodymium chloride and traces of samarium chloride, gadolinium chloride and other rare earth metal chlorides. The cation exchange was carried out continuously for 48 hours at 82 ° C. using the equivalent of 24 two hour exchange treatments with one volume of solution per volume of slurry. The cation-exchanged material was then washed free of chloride, ^{dried for 24 hours at HO 0} C, tempered for 10 hours in air at 538 ° C and finally brought into contact with 100% water vapor for ^{20 hours at 662 0 C at atmospheric pressure.} The residual sodium content of the cation-exchanged material was 1.32% by weight. This cation-exchanged aluminosilicate was mixed with aluminum powder by intimately mixing 50 g of the dried rare earth hydrogen Y-aluminosilicate with 150 g of metallic aluminum powder in a ball mill for 4 hours. The mixed material was then pelletized, classified, annealed in air at 538 ° C. for 10 hours and finally treated with steam for ^{24 hours at 648 ° C. and 1.05 kg / cm 2.}

The composition bo obtained in this way had a sodium content of 0.09% by weight and a rare earth metal oxide content of 2.76% by weight. The surface area of the composition after the steam treatment was 76 m ² / g.

The results obtained in testing the composition of this example for catalytic cracking activity are listed in Table V below:

description powdery carrier Aluminum metal Fine parts SEHY Type 25% concentration composition 0.09 Na, wt% 2.76 (SE) ₂ O ₃ ,% by weight

Physical Properties

Apparent Density, g / ccm 0.76

Surface area, steam treated, 76 m ² / g

Catalytic investigation

Conversion,% by volume 71.9

Steam treated 4

Gasoline, vol% 64.3

Excess, C ₄ , vol% 12.0

C ₅ + gasoline,% by volume 61.1

Total C ₄ , vol% 15.3

Dry gas, wt% 5.9

Coke, wt% 2.6

H ₂ , wt% 0.02

Advantage over standard crack + 14.2 catalyst*) -6.9 Gasoline, vol .-% + 12.8 Excess. C ₄ ,% by volume -5.5 C ₅ + gasoline, vol .-% -3.9 Total C ₄ ,% by volume -4.2 Drying gas, wt .-% Coke, wt%

*) Technical silica-alumina catalyst, containing _{about 90% SiO 2} and 10% Al ₂ O _3.

From the above data, it can be seen that the resulting catalyst comprised 25% by weight rare earth hydrogen aluminosilicate contained, had superior catalytic properties. The catalytic values summarized in Table V show that this catalyst was extremely selective by having a C5 + gasoline advantage of about 12.8 vol% over standard silica / alumina cracking catalyst delivered.

Example 10

The composition of this example was prepared by adding a sodium Y-aluminosilicate with a combined solution of 5% by weight CaCl ₂ and 2

19 20

Wt% NH ₄ Cl at 82 ° C for 72 hours continuously

was cation exchanged, the total solution Example 36 two hour exchanges with a 10th Volume of solution per volume of slurry was equivalent.

The cation-exchanged product was weighed 5

see, dried, tempered and then treated with steam for 24 hours at physical properties 648 ° C and a pressure of 1.05 kg / cm ^2.

The properties of the composition and the
Results obtained when tested for catalytic cracking activity in the manner described above
are shown in Table VI below
listed:

15th

20th

25th

Table VI example 10 description Sodium aluminosilicate Type Na / Al / Si (13Y) 100 concentration Cation exchange CaCl ₂ + NH ₄ Cl solution 5 2 Conc.,% By weight 3 24-hour cont contacts personal contacts, equivalent to 36 2h good contacts composition 0.82 Na, wt% 6.8 Ca, wt%

Surface size, 187 steam treated, m ² / g Catalytic investigation Conversion,% by volume 61.8 Space velocity 10 Gasoline, vol .-% 57.0 Excess. C ₄ ,% by volume 9.5 C ₅ + petrol, vol-% 54.0 Total C ₄ ,% by volume 12.5 Drying gas, wt .-% 4.8 Coke, wt% 1.5 Advantage over hour cracking catalyst*) Gasoline, vol .-% +11.2 Excess. C ₄ ,% by volume -4.8 C ₅ + gasoline, vol .-% + 10.4 Total C ₄ ,% by volume -4.1 Drying gas, wt .-% -3.2 Coke, wt% -3.3 C, + gasoline yield +2.4 advantage over SEHX **)

*) Technical silica-alumina catalyst,

containing about 90% SiO ₂ and 10% Al ₂ O _3. **) 13 X zeolite, cation exchanged with rare earth ammonium chloride solution.

Claims (2)

Patent claims: 1. A process for producing an aluminosilicate catalyst comprising a crystalline alkali aluminosilicate zeolite with an S1O2 / AI2O3 ratio above 3 subjected to a cation exchange to replace alkali metal ions, washed, dried and is calcined, characterized in that that a finely divided crystalline aluminosilicate of the Y-type, its alkali metal ions at least 70%, in particular more than 80%, by ions of the rare earths, calcium, des Ammonium or the hydrogen or mixtures thereof are cation exchanged in one Carrier of a hydrous oxide, an inorganic gel or clay dispersed, the obtained product for the removal of alkali metal ions, optionally by rare ions Earth, calcium, ammonium or hydrogen or mixtures thereof cation exchange ^ after drying and calcination, if appropriate, a treatment with steam subjected to a temperature of 204 to 815 ° C for at least about 2 hours, after which Completion an alkali metal content of less than 3 wt .-%, in particular less than 2 wt .-%, is available. 2. Use of a crystalline aluminosilicate catalyst prepared according to claim 1 for Hydrocarbon cracking.