DE2058871A1 - Process for producing a zeolite - Google Patents

Description

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ U.V., The Hague, Netherlands

"Process for the preparation of a zeolite"

Priority: December 2, 1969, the Netherlands, No. 691806o 22nd September 1970, the Netherlands, no 7014021

The invention relates to a process for the production of a zeolite, which is used as a catalyst, in particular for the conversion of hydrocarbons, can be used.

The term "zeolite" generally refers to a Class of naturally occurring metal aluminosilicates containing hydrated water with crystalline structure. However, numerous zeolites have also been produced synthetically. The zeolites differ from one another in terms of crystal structure, composition and adsorption properties. A suitable one Method for elucidating the structure of both naturally occurring and synthetic zeolites is based on powder X-ray diffraction analysis.

With regard to their structure, the zeolites are made of a three-dimensional

ßional lattice of SiO ₄ - and ΑΙΟ, tetrahedra ·, which over

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-2- 2053871

like oxygen atoms are in connection with each other. The negative electron valence of the aluminum containing tetrahedra is due to the incorporation of cations, such as alkali or Alkaline earth ions, compensated in the crystal. These cations can be replaced by other cations after suitable dipping processes will. The zeolites are therefore often used as ion exchangers.

The zeolite crystals have cavities of molecular dimensions which are usually filled with water of hydration. After at least partial dehydration, ^ i., - per zeolite as effective adsorbent used v / earth, the adsorbed molecules retained in the aforementioned cavities

will. The cavities are located about in the crystal structure

borrowed openings accessible. Depending on the cross-section / these openings the dimensions and shape of the molecules that can be adsorbed are limited. This makes it possible to determine certain Separate molecules from mixtures on the basis of the dimensions of these molecules by removing only very specific molecules from the Zeolite are adsorbed. In reference to this property, many zeolites are referred to as "molecular sieves". These The property of the zeolites is made usable in particular when the zeolites are used as catalysts or catalyst supports in such processes are used in which only those are converted from a mixture of different compounds, their .Molecules have the appropriate shape and dimensions to penetrate the molecular sieve.

There is extensive literature on both naturally occurring and synthetic zeolites (see, for example, "Revue de

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1 «Institut Francais du Petrol, 26 (1969), pages 657 to 677).

The object of the invention was to provide a new method for production To provide a zeolite of the molecular sieve type with certain adsorption properties, which zeolite turns out to be Adsorption, extraction or drying agents or as ion exchangers and above all as catalysts or catalyst carriers, especially for the catalytic conversion of hydrocarbons, suitable. ' This object is achieved by the invention.

The subject of the invention is thus a process for the production ' of a zeolite with

a) a powder X-ray diffraction diagram with the in Table A indicated reflection lines

2 = Cu Tabel A. 15th Θ -K ^ ₁ ; Wavelength = 1.5405 A radiation 80 - 7, relative intensity 70 - '9, 95 M. 7, 00 - 13, 80 NS 8th, 55 - 17, 10 ST 12, 60 -17, 00 M. ■ 15, 40 - 20, 95 SST 17, 15th - 21, 20th M. 19 80 - 22, 60 SST 20, 20th - 26, 75 M. 22 90
00
25th
30th - 28, 20th ST 25, 40 - 30,
- 30,
- 31,
- 31, 80 SST 27 35 - 34, ⁵⁰ )
80 <
05
90 ^; SST 29
30,
30,
31, - 50, 80 .M 34, 95 M. 50,

1 OSR? W 1 7 50

in which θ ^{see the Bragg 1} V / inkel, SST mean "very strong", ST "strong", M "medium" and SCH mean "weak",

b) a composition of the formula

0.7-1.2 Na ₂ O ₄ Al ₂ O ₃ . 4.7-5.3 SiO ₂ . χ H ₂ O where χ has at most the value 12, preferably 3 to 9, and

c) an ^{adsorption of η-hexane measured at 10O 0} C and a hydrocarbon pressure of 40 Torr after that carried out at 240 C and reduced pressure. Dehydration of the zeolite of at least 0.25 mmol / g and a ratio of the value 'BiMol / g adsorbed η-hexane to the value mmol / g adsorbed 2,3-dimethylbutane of at least 8: 1,

which method is characterized in that an aqueous Mixture of sodium hydroxide and a cogel of aluminum hydroxide on silica hydrogel, which is the mixture in mol Composition expressed in terms of oxides

.3,5 - 4.5 Na ₂ O _{5 £} 0.Al .9,5 - 13.0 SiO _2. 100-400 H ₂ O, under.; Keeping things moving, preferably stirring or shaking, heated to temperatures of 70 to 160 ° C. and that the crystals of the zeolite formed are separated from the mother liquor.

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& ■ 205887V

The access of molecules to the zeolite produced according to the invention lith is determined by its openings, which have a

• ο. ·

5A. The manufactured according to the invention Zeolite is hereinafter referred to as "Zeolite KSO1".

With regard to, for example, that for analyzing the structure of the present invention X-ray diffraction methods used to produce zeolites or the corresponding apparatus, the moisture content, the temperature and the orientation of the powder crystals the intensity and position of the X-ray reflection lines vary to a certain extent. Through the structure on- clarification of the zeolite KSO1 produced according to the invention indicated X-ray diffraction spectrum should therefore not exclude those materials which, on the basis of one of the aforementioned Variables or in some other known way a slight change in intensity or a Shifting the position of one or more

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the X-ray reflection lines listed in Table A zeir.on.

The full X-ray diffraction diagram of a typical example of a zeolite KSO1 is shown in Table B, where a.-K # radiation of a wavelength of 1. £> 4Q5 ^ - used vmrdi

Table B.
2 θ

7.55

9.30 12.90 16.00 17.75 19.90 21.00 22.45 26.00 28.00 30.20 30.40 30.65 31.60 34.60 38.30 39.20 39.40 * 42.70

^w 43.50

47.80

50.65 53.40

54.35 54.98 56.00 61.40

* I s intensity of the strongest, occurring separately in the diagram Reflection line. "'"

The lines used in Table B to describe the reflection lines Letters have the following meanings:

d, 4 relative in- ■ Description of the - intensity, Reflection lines (100. 1 / I ₀ ) 11.7 50 B. 9.5 26th B ₁ D 6.86 69 . S. 48 EB, D 4 ^ 99 100 * S. 4.45 46 S '' 4.23 250 SB 3.96 42 S. 3.42 62 " S. 3.18 88 EB, D 2.96 S. 2.94 464 SB, D 2.91 D. 2.83 S. 2.59 36 S. 2.35 2 S. 2.30 ■ 4 " S. 2.29 4th S. 2.12 .6 S. 2.08 31 S. 1.90 11 S. 1.80 43 1.71 "31 S. 1.69 8th S. 1.67 16 S. 1.64 13th .. B 1.51 11 B.

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S = sharp, D = diffuse, B = broad, S3 = very broad, EB = extreme

wide; θ = Bragg's l / inch, d = distance between the lattice levels. · · -

The ZedLith KSOl is not only characterized by the powder X-ray diffraction diagram described above, but also by the following, approximate composition expressed in terms of the oxides marked:

0.7-1.2 Na _{2 O.Al 2} O ₃ . 4.7-5.3 SiO ₂ . χ H ₂ O;

χ has at most the value 12, preferably "one" value from 3 to 9. ■ -. - - "-'- —-

Finally, the iZeolite KSOl has a very special adsorption behavior towards η-hexane and 2,3-dimethylbutane. after dehydration at 240 C and reduced pressure
the adsorption of η-hexane measured at 100 ° C and a hydrocarbon pressure of 40 Torr at least 0.25 mmol / g and that
The ratio of the fourth mmol adsorbed n-hexane / g to the fourth mmol adsorbed 2,3-dimethylbutane / g at least 8: 1.

According to the powder X-ray diffraction diagram described above, the composition and adsorption behavior are
Zeolite KSOl fully characterized and can be used by the
Characteristics of other known zeolites can be distinguished.

With regard to the proportion of adsorbed by the zeolite KSOl

"_". ,. ^ _. at least , " ,

η-hexane, which under the aforementioned conditions / 0.25 ml'iOl / g

it should be added that it depends on the manufacturing method Zeolites KSOL can be obtained which have a considerably higher ability to adsorb n-kexane, for example an adsorption value of at least 0.40 inl-Iol / g

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or even at least 0.75 ml / g. When using a zeolite KSOL where a material is often preferred, its ability for adsorption of η-hexane is as high as possible.

Zeolites of the aluminosilicate type are generally produced by that you have an aqueous, alkaline, certain amounts of at least one aluminum compound and at least one silicon compound containing mixture holds for some time at elevated temperatures and then the formed, crystalline Separating zeolite from the mother liquor. Specific examples of known suitable aluminum compounds are aluminum hydroxide, Uatrium aluminate and activated alumina grades, v / ie, / '- aluminum oxide. Suitable silicon compounds are ITodium silicate, Silica gels, silicic acid, aqueous colloidal silicic acid sols and amorphous, solid silicon dioxide types, v / ie airgel silicon dioxide types, chemically precipitated silicas

and precipitated silica sols. ...

It was found that the type of aluminum and silicon compounds used in the manufacture of the KSOl zeolite The initial device should be of particular importance

while is different. Aqueous, alkaline mixtures in which / aluminum and / or silicon compounds are contained, which, however, are expressed in moles of the oxides (NagO / AlgO ^ / SiO ^ I ^ O) have the same composition, do not always provide the right

in addition
desired zeolite KSOL, which / optionally mixed with amorphous material and / or other zeolites. Sometimes will

even
/ receive a completely amorphous material or a zeolitic material mixed with amorphous material,

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which, however, does not contain any zeolite KSO1. Even if aqueous., alkaline mixtures are used, which in the main contain the same aluminum and silicon compounds and also the same expressed in moles of oxides Have composition, very different results are achieved in many cases. For these differences are possibly minor deviations in the structure of the starting materials. It does, however now the process of the invention is available, which not only enables the producibility of a high-crystalline zeolite KSO1 guaranteed, at most to a very small extent by crystalline material of a different crystal structure or composition is contaminated, but also provides completely reproducible results.

In the production of zeolite KSO1 according to the invention, one proceeds preferably from a mixture of the following composition, expressed in moles of the oxides:

3.8-4.2 Ka _{2 O.Al 2} O ₅ . 9.8-12.0 SiO ₂ . 125 - 375 H ₂ O.

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As used herein, the term "cogel" refers to a silica / alumina mixture obtained by precipitating an aluminum hydroxide gel onto a silica hydrogel. Such a cogel is therefore not a "joint precipitation", since silicon dioxide hydrogel and alurainium hydroxide gel are precipitated out of the solution at least approximately simultaneously to produce such a joint precipitation. It is assumed that the silica spheres in the cogel are coated with a layer of aluminum oxide P.

With regard to · the in the for the preparation of the zeolite KSOl Serving starting mixture required pick-up ratio 5102 / AIgO ^ should this ratio in the amorphous silicon dioxide / aluminum oxide Cogel9i5: 1 to 15: 1, preferably 9 * 8: 1 to 12: 1.

A silicon dioxide / aluminum oxide cogel can conveniently through Precipitation of an aluminum hydroxide gel on a silica hydrogel in an aqueous medium can be prepared by | an aluminum compound and an alkaline reacting solution clogs. Any known method can be used to obtain a silica hydrogel, e.g. hydrolysis of orthosilicic acid esters using mineral acids or of silicon tetrachloride with cold methanol and water. However, alkali metal silicates are preferably used to produce the silicon dioxide hydrogel. Very functional Process for making a silica / alumina cogel is that a silicon dioxide hydrogel is first made from a solution containing silicate ions by adding mineral acid fails, then the solution is an aluminum

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nium salt is added and finally the aluminum hydroxide gel by adding an alkaline solution to the precipitation As an aqueous solution containing silicate ions, water glass can be used to serve. The mineral acid is preferably that acid from which the aluminum salt to be subsequently added is derived derives. V / water soluble aluminum salts are preferred. One A very suitable alkaline solution is aqueous ammonia. It is sometimes advisable to go before the actual Preparation of the Cogel First, the obtained silica hydrogel either at room temperature or for some time at elevated temperatures, such as [temperatures from 25 to 40 C to age. ! laughing at the formation of the Cogel will be the The precipitate formed is separated from the liquid -. with.

Washed in water and dried at at least 100 ° C. The production of a Cogel suitable as a starting material for the production of the zeolite KSO1 according to the invention is explained in greater detail in British patent specification 181 188.

Instead of one obtained by the method described above Cogels can, with great advantage, be a commercially available low-cost silica / alumina cracking catalyst Alumina content can be used as a cogel. Such Kxack catalysts generally have an aluminum oxide content from about 10 to 16 percent by weight and are also won in the form of a cogel. Using such commercially available silica / alumina cracking catalysts Outstanding results are achieved as the starting material for the production of the zeolite KSOl according to the invention.

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The preparation of the zeolite Ksol of a silica / alumina cogel is carried out, v / ie mentioned, characterized in that holds nan an aqueous alkaline mixture of sodium hydroxide and the cogel under stirring at temperatures of 70 to 16O ⁰ C ..

1 "

The production of the zeolite KSOL according to the Cogel process can be carried out both at atmospheric pressure and at elevated pressures. If higher reaction temperatures are used than the boiling point of the mixture, the process is preferably carried out in an autoclave at autogenous pressure. The zeolite KSOL is preferably prepared by adding the mixture, for example with stirring or shaking, for at least 4 hours

Holds temperatures of 90 to 110 C. In order to ensure the achievement of a high yield of crystalline product, it is important that the mixture from which the zeolite is produced, during the recovery of the zeolite KSOL according to the Cogel process. is kept in motion. For this purpose, the mixture can be stirred or shaken, for example. After the formation of the zeolite, the crystals are separated from the mother liquor, for example by filtering, decanting or centrifuging. The crystal mass is then washed with water and finally dried at temperatures of 100 to 200.degree.

l) he zeolite KSOL is very suitable as a catalyst or catalyst carrier for a wide variety of catalytic processes. With regard to its uniform pore diameter, the Zeolite KSOl is of particular importance for selective methods for carrying out catalytic processes in which due to the The fact that only compounds with a linear structure can enter or leave the zeolite from a mixture

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of compounds with a linear or branched structure only those with linear structure converted to ground or being a compound is only converted to compounds with a linear structure. Examples of such catalytic processes are the selective (Hydro) cracking and the dehydrogenation of η-paraffin hydrocarbons, the selective hydrogenation, hydration and amination

U.N-

unbranched alkenes and the selective dehydration of branched ones Alcohols in mixtures, which.These compounds together with corresponding compounds with branched and / or cyclic Structure included. -. "-" ■ "- -" '~

As mentioned, the zeolites contain exchangeable cations. In the case of zeolite KSOL, these exchangeable cations are urodium ions. To obtain active, stable and selective catalysts or catalyst supports, it is advisable to use at least one Part of these sodium ions by other cations, such as hydrogen, Ammonium or calcium ions or ions of the rare earth metals, too substitute.

If the zeolite KSOL is used as a catalyst or catalyst carrier, a material is preferred whose ilodium content has been reduced to a value below 1 percent by weight, in particular below 0.05 percent by weight of the zeolite are obtained with a solution containing exchangeable cations. For example, the solution containing the Öa can ²⁺ zeolite Ksol or 1T} L ⁺ zeolite by treating the zeolite Ksol Ksol with a calcium or Aranoniuinionen be prepared. by calcination of the 1TH, * - Zeolite KSOl, the H ⁺ zeolite KSOl can be obtained «

10982 A / 17-50. -. ·

A very useful method for separating sodium ions from the zeolite KSOL is described below. Of the Zeolite is subjected to a treatment comprising the following stages:

a) heating the zeolite at least once with an aqueous, Solution containing ammonium ions;

b) calcining the ITH obtained according to a). -Zeolite at temperatures below 55O ⁰ C; and

c) treating the calcined zeolite with an aqueous solution containing ammonium ions.

During stage a) the zeolite is preferably heated several times, each time with a fresh solution containing ammonium ions. The treatment stages a) "'" and b) can be repeated several times, repeatedly grounding before step c) is carried out, but this is often not necessary. One treatment stage each a) or b) and a subsequent treatment of the calcined material with an aqueous solution containing ammonium ions is often sufficient to reduce the sodium content to what is desired Value. Treatment of the calcined material with aqueous aqueous solution containing ammonium ions is preferred carried out by heating the calcined material with the solution at least once. During this treatment, ground The sodium ions dissolved out of the crystal lattice by the calcination are removed by the ion exchange. During execution of the process described above, an aqueous ammonium nitrate solution can expediently be used as the solution containing ammonium ions can be used. Before the combined treatment described above, the zeolite can first be precalcined

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2Q58871

the. Sine such method, which in general is for removal of alkali ions from zeolites with a SiOg / A ^ O, molar ratio from 3il to 7: 1 can be used is in "British Patent 1 162 969 explained in more detail.

With regard to the calcination temperature, it should be noted that, according to the method described in British Patent 1,162,969 for the separation of sodium ions Zeolite calcination temperatures of up to 700 ° C can be used can. When this method is applied to the KSOl zeolite, the aforementioned calcination temperature should be used in view of the danger of crystallinity occurring at high temperatures

less than ₀₊

loss / 550 C. The. Calcination of the IiH ^ zeolite ----- KSOl is preferably carried out at (temperatures of 450 to 500 C. ·

Although the zeolite KSOL as such - regardless of whether at least some of the sodium ions are replaced by other cations has a catalytic activity or not, it is preferably used as a catalyst carrier when used for catalytic purposes used for one or more active metal components. Depending on the intended use of the catalyst the metals which can be applied to the zeolite KSOL, the metals of the I., II., V., VI «, VII.-lifting and / or VIII »Group of the Periodic Table, examples of these metals are-copper, silver, zinc, 'cadmium, vanadium, chromium, Molybdenum, tungsten, manganese, rhenium, the "metals of the iron group And the metals of the platinum and palladium groups. The abovementioned metals can be applied to the zeolite KSOL according to the

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v / grounding methods carried out, for example by impregnation » Percolating, impregnating with the help of a slurry formation or ion exchange. One can use the active lietallko:; - components also through a "competitive ion exchange"

ι _r

bring Under such a method is ¹ understand zn an exchange method in v; hich the applied metal ion with other ions present in the solution of the exchangeable sites on or in the zeolite must compete for. Generally, the ammonium ion is used as a competitive ion ψ verwen- det. The metals are preferably grounded to those specified in the IiH. -Form applied zeolite, i. E. on a zeolite KSOl,

i ■ ·

in which at least some of the sodium ions are replaced by amraonium

■ ι

ions has been replaced. "If-to lower the" latrium content of the zeolite KSOl, the combined process described above was used, which includes the treatment stages a), b) and c), it is advisable that the zeolite obtained in this way is first neutralized before the metals be applied to it. In the case of the | ten calcination is formed from the NHi zeolite H zeolite and in the subsequent treatment with an aqueous ammonium ion containing solution, the zeolite is not completely converted into the UH, form. The neutralization can very conveniently be carried out using a nitrogenous base such as ammonia.

The zeolite KSOl can be used with great advantage as a catalyst carrier in hydrocarbon conversion processes, such as cracking, isomerization, Alkylation, dealkylation or hydro-cracking can be used. For this purpose one brings on the zeolite

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Air

at least one active metal component, which the finished Catalyst gives hydricrend-dehydrogenating properties. One or more metals are very suitable for this purpose the VI., YII. love and / or VIII. group of the periodic Systems. The catalysts based on the zeolite KSOL are of particular importance for the conversion of hydrocarbons by hydro cracking. Catalysts can be used for this purpose

either whose catalytically active Hetallkcmponente / a noble metal of the platinum group or a non-noble metal or /. is a combination of light precious metals. Catalysts with a noble metal as active metal components generally contain 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, of the metal per 100 parts by weight of the support. Very suitable noble metals are palladium and platinum. Catalysts with a light noble metal or a combination of non-noble metals as active metal component generally contain 0.1 to 35 parts by weight of the metal or metal combination per 100 parts by weight of the support. A suitable metal combination is established composed of (a) metal (s) of the VI and / or VII subgroup of the periodic table and a metal of the iron group. Suitable hydro-Kraok catalysts contain 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight * of the non-noble metal of Group VIII of the Periodic Table (iron group) and 0.1 to 50 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of the support , (a) metal (es) of the VI «and / or VII. life group of the Periodic Table. Combinations of nickel and / or cobalt with tungsten and / or colybdenum and / or rhenium are suitable as metal combinations.

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After the application of the catalytically active metal components The catalyst is generally applied to the support "at temperatures dried from 100 to 200 C and then calcined. The Caüoinierung can in the conventional way in an oxydie

The atmosphere can be carried out at temperatures below 550 C. Preferably, .the calcination is performed stepwise, whereby the material first to a first calcination temperature of 200 to 250 C, is then heated to a second calcium W nierungstemperatur of 250 to 35O ⁰ C and finally to a third calcination temperature of 350 to 550 C. The material is kept at both the first and the second calcination temperature for at least 15 minutes, preferably for at least 1 hour, while the temperature of the material is carefully adjusted by adjusting the feed rate of the oxygen or free oxygen required for the calcination Gas, such as air or a mixture of oxygen and nitrogen, is regulated. During the calcination, the ketal components applied to the zeolite are converted into the corresponding oxides. The calcination described above, carried out in stages, is optionally also used to convert the NIL · zeolite KSOL into its * H form.

Catalysts for hydrocarbon conversion processes are generally used in the form of particles with a diameter of 0.5 to 5 mm. The zeolite KSOL obtained by the Cogel process has a very fine crystalline structure and "has the appearance of a fine powder. The zeolite can, for example by pressing, form particles with large dimensions

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be shaped. Shaping is preferably done after application of the metal components carried out »but before the calcination, in which the metals are converted into the corresponding oxides. During the formation, the zeolite can with a

inorganic
inorganic matrix or a / binder can be combined.

Examples of suitable matrices or binders are of course occurring clays such as attapulgite, kaolin, kaolinite, bentonite, Montmorillonite, chlorite or halloysite. More suitable Matrices or binders are synthetic inorganic oxides such as aluminum oxide, silicon dioxide, magnesium oxide, boron trioxide or zirconium dioxide, as well as corresponding combinations, such as silicon dioxide / aluminum oxide, Silicon dioxide / zirconium dioxide, silicon

—Dioxide / boron trioxide or — silicon dioxide / magnesium oxide, before — the ~ - ~

To form the shaped particles, the zeolite and the matrix or the binder should first be homogeneously mixed with one another. The homogeneous mixing can be carried out in various ways, for example by mixing the as dry powders. present complexes "in a suitable mixing device and subsequent processing of the mixture in a kneading device with water to form a plastic mass, or by mixing the dry powder with water in a homogenizer, whereby a slurry is formed. It is also very advantageous _{for the} zeolite with an inorganic oxide, such as silicon dioxide or aluminum oxide in hydrated form, for example in the form of a hydrosol, hydrogel or a water-containing gelatinous precipitate, to form a slurry. The homogenized slurry can then be processed into shaped particles by known methods,

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for example by granulation, pelletization, tablet production, extrusion, trickling or pouring or circulating in drums. The shaped particles can be of any shape or size and are, for example, in the form of beads, spheres, pellets, tablets, briquettes or granules. \! hen the zeolite Ksol with a matrix or binder is combined, can be applied in principle any mixing ratio, preferably v / but shaped particles prepared ground comprising 10 to 90 weight percent of the matrix or

- 'Contains binder. A matrix or a binding agent is preferred, whether it contains any alkali metals or their alkali metal content is very low. Such a material can be made, for example, by using an alkali metal containing material at least once with an aqueous solution containing ammonium ions, such as an ammonium nitrate solution, heated. When used as a catalyst carrier, the zeolite KSOl is optionally mixed with other zeolites, such as zeolite X, Y or £ i used. Such a zeolite

W \ misch can also be used in combination with an inorganic matrix or a binder.

For many hydrocarbon conversion processes, the

Zeolites prepared according to the invention based on / preferably in their sulfidic catalysts Form used. This applies in particular to those catalysts whose catalytically active metal component is a non-precious metal or a combination of non-precious metals, e.g. a coordination made of nickel and / or cobalt with tungsten and / or molybdenum. The catalysts with a noble metal as an active metal component are often used in their reduced form.

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The conversion of catalysts based on zeolite KSOl into the sulphidic form can be very useful by treating the catalysts with a mixture of hydrogen and hydrogen sulphide (volume ratio H_ / H _O S = 5: 1 to 15: 1) at temperatures below 500.degree The conversion of the catalysts can also be carried out by adding sulfur compounds in a proportion of 0.001 to 5 percent by weight, preferably 0.01 to 2.5 percent by weight, to the starting material under the reaction conditions. ·

Although the catalysts based on the KSOL zeolite have a very long service life, it is advisable to regenerate them from time to time. The regeneration can be carried out in a simple manner by burning off the catalyst. Care must be taken to ensure that the catalyst temperature does not exceed 55O ⁰ C during burning. Very zweekmässig is a regeneration using an oxygen substoichiometric at temperatures below 500 ⁰ C,

The catalysts based on zeolite KSOL are very active Hydro cracking catalysts, due to the uniform pore diameter of the zeolite KSOl, these catalysts are particularly suitable for the selective hydro-octopus of n-paraffin carbons, which in from n-paraffin hydrocarbons and others. Hydrocarbon fractions composed of hydrocarbons are included. The hydrocarbon fractions,

Zeolites KSOl soft with the help of catalysts based on / hydrogenating

can be-cracked, can be mild to severe gasolines

Zeolites can be KSOl distillates. The catalysts based on / are "both suitable

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Playfully very good for the one-step hydra cracking of hydrocarbons substance fractions, which are essentially below Boil 350 C, such as heavy gasoline, kerosene, light gas oils or heavy gas oils, boiling at temperatures of 65 to 180 G " Gasoline fractions and the low-boiling hydrocarbons known under the name "LPG" are obtained.

• Zeolite KSOl As the catalysts are based on / in counterv / type of nitrogen

at least partially retain their activity, they are also very suitable for single-stage hydro-cracking processes in which Beds made of various catalysts are used and are used for where hydrocarbon fractions are cracked by hydrogenation,

ι ·

which substantially above 35O ⁰ C boil, such heavy "Plash" ~ DestillateuJid deasphalted resid KöhTenwasser- 'fabric oils. -

Very good results can be obtained using the hydro cracking catalysts based on "Zeolith'KSOl for hydro-cracking"

of products obtained by isomerization or catalytic reforming of light hydrocarbon fractions with a boiling point below 200 G, such as gasoline or heavy gasoline. The octane number of the hydrocarbon fraction should be increased both by isomerization, in which n-paraffin hydrocarbons are converted to isoparaffin hydrocarbons, and by catalytic reforming, in which, among other things, paraffin hydrocarbons are converted into aromatics. Depending on the conditions under which these processes are carried out, the reaction products also contain a certain amount of n-paraffin hydrocarbons, which have a low octane number. If . 10982A / 17B0

anachliessend these products by means of the ~ - '~ Hydro-Kraekkatalysators be cracked hydrogenating based on zeolite Ksol, a large part is still "contained therein n-paraffin hydrocarbons ^ selectively converted. If those-

selective hydrocracking of n-paraffin hydrocarbons with

Zeolitic KSOl using a catalyst based on / on an isomer is applied, this should be. Isomerizate preferably originates from an isomerization process in which a solid platinum / Mordenite catalyst or a liquid HP / SbPe catalyst was used. An isomerization process in which a solid platinum / cordenite catalyst is used is in US Pat British patent specification 1 151 653 * and an isomerization process' in which a liquid EF / SbFc-Katälysator v / ends is described in British Patent Specification 981,311.

In the selective hydrocracking of n-paraffin hydrocarbons to light hydrocarbon fractions, such as C _c -Ben-

i Ρ "

Zinc fractions, to improve their Oetsn number one receives

+
In addition to the desired Cc -gasoline fraction with increased octane number, a C. "" fraction, which "is more valuable due to its higher .O ^ / C weight ratio." It was found that during selective hydrocracking of n ~ paraffin hydrocarbons to light hydrocarbon fractions with

"according to the invention

, With the help of catalysts based on the / nergesfcelifcen eeolite KSOl, which different Ifetall © the VI ,, YII "JTeben" ^ nd / or . VIII «group of the periodic table contain the highest CWC. Weight ratio at (^ "Product obtained when a 'Nickel-containing catalyst is used. The nickel can on zeolite KSOL either in the sulphidic or oxidic

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or reduced form. The proportion of the i-nickel present on the carrier is preferably 0.1 to 35 parts by weight, in particular 1 to 15 parts by weight, per 100 parts by weight of the carrier, "

The selective hydro-cracking of n-Paraffinkohlenwa- jerstoffen to Cc fractions, the conversion of n-paraffin hydrocarbons can ^, v / elk to an increase in the octane number leads, be accompanied by a conversion of the "aromatic compounds, for example, h from a dealkylation or Hydrogenation to ITaphthenes, after which these naphthenes, if appropriate, to lighter products

be cracked. Since the aromatics are generally very high

!
_ Have an octane rating, the

n-paraffin hydrocarbons achieved an increase in the octane number in Follow these 'side reactions completely or partially to-

dip

not done. It is therefore important for that to be selective Hydro-cracking of ji-paraff ^ hydrocarbons in aro-

used catalysts light hydrocarbon fractions containing mates / the aroma

^ convert mates as little as possible. The degree of aromatic conversion is expressed, among other things, in the loss of the yield of 0 _r products per unit of the increase in the octane number (RCZ-O). The lower the degree of conversion of the aromatics, the lower this loss of yield. It has been found that in the selective hydrocracking of paraffinic hydrocarbons in aromatics containing light

. Hydrocarbon fractions using eggs according to the invention

manufactured

according to / catalysts based on zeolite KSOl, -which different Metals of the VI., VII. Minor and / or VIII. Group of the periodic Systems contain the lowest loss of yield

1 0982 A / 1 75-0 "

of C _r ⁺ products per unit of increase in the cetane number (ROZ-O) is achieved if a catalyst is used, which contains nickel in the sulfidic form. The favorable effect of the cWC. weight ratio on the (^ "" Fraction of catalysts based on zeolite KSOl containing Tücke 1 compared to catalysts based on zeolite KSOl containing other metals of the VI., VII. Love and / or VIII group of the Periodic Table in the present case , in which nickel is present in the sulphidic form on the zeolite, does not affect "In the case of selective hydrocracking of n-paraffin hydrocarbons, it is advisable that, in addition to the low degree of aromatic conversion, the lowest possible degree of conversion of the isoparaffin hydrocarbons occurs." found that with catalysts based on zeolite KSOl, which contain nickel in the sulphidic form, a very low degree of isoparaffinic hydrocarbon conversion is achieved will. . * .- ■ ·

The use of catalysts containing Kicke1 based on Zeolite KSOl, in which the hickel is present in the sulphidic form on the zeolite, is of particular importance, when the hydrocarbon fraction to be converted is a catalytic reformate with a chromate content of 20 to 80 percent by weight and an octane number (HOZ-O) of over 85 is «

That Hydro-cracking by means of a hydro-cracking catalyst based on zeolite ICSOl can be very conveniently at temperatures of 250 to 55Q ⁰ C and V / on Hydrogen partial pressures of 5 to 200 kg / ora performed. The space velocity can

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0.2 to 20 kg hydrocarbon feed / kg catalyst. H and the amount of hydrogen supplied is 250 to 5000 normal liters / kg Loading amount. The hydrocracking is preferably carried out at temperatures from 275 to 450 ° C. and hydrogen partial pressures carried out from 10 to 100 kg / cm «,

The zeolite KSOL is not only suitable as a catalyst or as a catalyst carrier, but can also be used for numerous others Purposes are used, for example as adsorption, ^ extraction or drying agent or ion exchanger.

Except for the use of the zeolite KSOL as a catalyst for catalysts For the conversion of hydrocarbons, an important application of this zeolite is as a molecular sieve for the separation of compounds with an unbranched structure from a mixture of these compounds with corresponding compounds with a branched structure. For this purpose the zeolite is to be at least partially dehydrated. Both the zeolite KSOL as such and that from it Replacement of at least part of the sodium ions dunh other cations produced product are suitable for the aforementioned Intended use.

The examples illustrate the invention.

example 1

A commercially available silicon dioxide / aluminum oxide cracking catalyst with a water content of 23.8 percent by weight, an aluminum oxide content of 13.1 percent by weight (based on the trookene. Material), a sodium content of below 1 is used as the starting material for the production of a zeolite KSOl Ge

1 0 9 8 2 A / 1 7 5 0

Weight percentage (based on the dry material) and a specific surface or pore volume after calcination at 600 C of 668 m / g and 0.69 cm / g, respectively.

A mixture of the molar composition 4 ITa ₂ O. ₂ 11.2 SiO _{2 is obtained} . 150 H ₂ O prepared by gradually introducing a solution of 32 g of sodium hydroxide in 75 ml of v / water into a mixture of 102.2 g of the aforementioned cracking catalyst and 163.5 ml of Vfesser with stirring. The total mixture is then boiled under reflux for 12 hours with stirring. After the reaction mixture has cooled, the zeolite is filtered off and washed with water until the piltrate has a ρττ value. below 10, and finally dried at 120.degree.

The zeolite ESOl (zeolite I) obtained in this way has the following properties:

Powder X-ray diffraction pattern: essentially as shown in Table B.

Chemical composition: 1.05 ITa ₂ O.Al ₂ O ,. 4.85 SiO ₂ . 5.15 H ₂ ^O ; Adsorption behavior at 100 C and a hydrocarbon pressure of 40 Torr (after dex dehydration at 240 C and reduced pressure; adsorption of n-hexane = 0.8 mmol / g; adsorption of 2,3-dimethylbutane = 0.055 mmol / g.
'mKol adsorbed n ~ hexane / g

raKol adsorbed 2,3-dimethylbutane / g

= 14.5

The specific surface or the pore volume after drying at 225 C is 42 m / g or 0.13 cm / g *

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Example 2

A commercially available silicon dioxide / aluminum oxide cracking catalyst with a water content of 15.3 percent by weight, an aluminum content or sodium content ("based on the dry material) of 12.8 or below is used as the starting material for the production of a zeolite KSOL 0.5 percent by weight, and a specific surface or a pore volume after calcination at 60O ⁰ C of 658 m / g or 0.75 cm / g verv / ends.

Ec becomes a mixture of the molar composition 4! Νε ^, Ο. AIpO-. 11.2 SiOp. 150 HpO prepared by introducing a solution of 8 kg of sodium hydroxide in 18.75 liters of water with stirring into a mixture of 24.82 kg of the aforementioned cracking catalyst and 41.6 liters of water. The total mixture is refluxed for 12 hours with stirring. After the reaction mixture has cooled, the zeolite is filtered off, washed with water until the p n value of the piltrate is below 10 t, and finally dried at 120.degree.

The zeolite KSOL (Zeolite II) produced in this way has the following properties:

Powder X-ray diffraction pattern: essentially as in Table B shown;

Chemical composition: 1.12 NagO. AIpO ₇ .. 5.03 SiOg. 4.70 HpOi

Adsorption behavior at 100 ° C. and a hydrocarbon pressure of 40 torr (after dehydration at 240 ° C. and reduced pressure): adsorption of n-kexane = 0.84 mHol / g; Adsorption of 2,3-dimethylbutane = 0.06 mmol / g.

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ml-Iol adsorbed n-hexane / e

:: mi-ίο I adsorbed 2,3 ~ dimethylbutane / g

= -1-4 »

The specific surface and the pore volume after drying at 225 ° C are 286 m / g and 0.24 cm '/ g, respectively.

' Example 3

A mixture of the molar composition 4 ITa ₂ O.AIpQ *. ^ O SiOp. 320 HpO prepared by mixing a solution of 32.4 g of aluminum in sodium hydroxide solution (192 g of sodium hydroxide in 600 ml of v / water) within 10 minutes with stirring in a mixture of 456 g of a commercially available silicon dioxide and 2749.2 ml of water enters. The total mixture is refluxed for 41 hours with stirring. After the reaction mixture has cooled, the solid substances are filtered off, washed with water until the piltrate has a Pg value below 10, and finally dried at 120.degree.

With the help of the powder X-ray diffraction diagram and with the help of the chemical Composition and adsorption behavior is shown that the product produced in the aforementioned way is a pure zeolite KSOL.

The same result can be achieved if the mixture is stirred and stirred for 12 hours instead of 41 hours is refluxed.

Comparative example A ''

A mixture of the molar composition 4 ITa ₂ O.Al ₂ O ,. 10 SiO ₂ . 320 H ₂ O prepared by adding a solution of 2.7 g of aluminum in sodium hydroxide solution (16 g of sodium hydroxide, in 50 ml of v / water)

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with stirring into a mixture of 31.5 g of a commercially available " Chen silica and 235 ml v / ater enters. The overall mix It is refluxed with stirring for 41 hours. After the reaction mixture has cooled down, the solid ones become grounded Substances are filtered off, washed with water until the filtrate has a value below 9 and finally with 120 g dried.

The X-ray diffraction analysis shows that the obtained in this way The product consists of 93 percent by weight of amorphous substance and 7 percent by weight of zeolite A.

Comparative example B

A mixture of the molar composition 4 ITa ₂ O.A1 ₂ O ~. 10 SiO ₂ . 320 H ₂ O prepared by adding a solution of 2.7 g of aluminum in sodium hydroxide solution (16 g of sodium hydroxide in 50 ml of v / ater) with stirring to a mixture of 34.1 g of silicon dioxide and 232.9 ml of v / ater « The total mixture is koclat for 41 hours with stirring and under reflux. After cooling the reaction mixture, the solid substances are filtered off, washed with water up to a _pH value of below 10 PiItrats and finally dried at 120 ⁰ C. The X-ray diffraction analysis shows that the product produced in the aforementioned manner contains 25 percent by weight of amorphous substance, 65 percent by weight of faujasite, 7 percent by weight of zeolite P and 3 percent by weight of zeolite KSOL.

Comparative Example C

A mixture of the molar composition 4 Na ^ O.AIoO *.

10 S102 · 320 H2O prepared by adding a device of 7.8 g

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Aluminum hydroxide (in the form of bayarite), 16 g I sodium hydroxide and 47.3 ml v / water with stirring in a mixture of 38 g of an im Commercially available silicon diocide and 229 ml of water is introduced. The total mixture is heated to 100 ° C. in a closed vessel for 41 hours with stirring, after which the reaction mixture has cooled the solid substances are filtered off and washed with water until the ρ ,, - value of the piltrate is below 10 and finally dried at 120 C

The X-ray diffraction analysis shows that the product obtained does not contain any zeolite material,

Comparative Example D.

A mixture of the molar composition 4 ITa ₂ O. Al ₂ O.,. 10 SiO ₂ . 320 H ₂ O prepared by adding a mixture of 7.12 g of a commercially available aluminum oxide, 16 g of sodium hydroxide and 48 ml of water to a mixture of 38 g of a commercially available silicon dioxide and 229 ml of v / ater with stirring. ^{The total mixture is heated to 100 °} C. for 41 hours with stirring in a closed vessel. Ilach cooling the reaction mixture, the solid substances are filtered off, washed with water up to a p ~ value of the _H Piltrats below 10 and finally dried at 120 C.

The X-ray diffraction analysis shows that the produced in this way The product consists entirely of amorphous substance.

Comparative example OJel E ·.

The experiment of Comparative Example A is repeated, but a different commercial silicon dioxide product is used.

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. The X-ray diffraction analysis shows that the

Weight per cent

Asked product to 60 / zeolite KSOL and 40 percent by weight Zeolite P is

■ Comparative example F

The experiment of Comparative Example A is repeated, but again another commercial silicon dioxide product is used.

The X-ray diffraction analysis shows that the produced in this way The product consists of 50 percent by weight of KSOL zeolite and 50 percent by weight of zeolite P.

Comparative example G

The experiment from Example 1 is repeated, but the total mixture is ^{heated to 100 °} C. for 24 hours in a closed vessel while stirring.

The X-ray diffraction analysis shows that the produced in this way The product consists entirely of amorphous substance.

A comparison of those achieved using Examples 1 to 3 and those achieved Results of the same examples A to F / veranscnaulicht the high influence of the Type of silicon and aluminum compounds used on the product obtained. That used in Examples 1 and 2 Cogel process delivers a completely reproducible result,

A comparison of the result of Example 1 with each of the comparative example G also shows that in the production of the zeolite KSOl by the Cogel process, it is important that the

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mix is constantly stirred during the process.

Example 1 4

(see example 2)

250 g of zeolite II / are "for 1 hour with 2 liters of 1 M ammonium nitrate solution cooked. After filtering and viewing the

this*
Zeolite with water is boiled for another hour with 2 liters of 1 M ammonium nitrate solution. After filtering off again and washing with water, the zeolite is dried at 120.degree.

The IIH4 zeolite KSOl (zeolite III) essentially has the i Powder X-ray diffraction diagram described in Table A, a liatrium content of 0.91 percent by weight and a specific one Surface or pore volume after drying at 225 ° C. of 67 m / g and 0.12 cnr / g, respectively.

A portion of the zeolite III is calcined for 3 hours at 45O ⁰ C and then for 1 hour long cooked with 1 M ammonium nitrate solution. After filtering off the zeolite and washing it with water, it is boiled for another hour with 1M ammonium nitrate solution. The zeolite at 120 ° C iTach the renewed filtration and V, ^r v ash with water {/ ird dried.

The 1JH ₄ ⁺ / H ⁺ zeolite KSOL (zeolite IY) essentially has the powder X-ray diffraction diagram shown in Table A, a liatrium content of 0.021 percent by weight and a specific surface area or /. a pore volume after drying at 225 ° 0 of 476 m ² / g or 0.33 cm ⁵ / g. '

A portion of the zeolite IV is calcined for 3 hours at 45O ⁰ C and then for 1 hour long cooked with 1 m Amraoniumnitratlösung. After filtering off and washing the zeolite with water

10 9 8 2 4/1750

if it is boiled for another hour with 1 ra ammonium nitrate solution, laugh at the renewed filtering and washing with water the zeolite is dried at 120.degree.

The UH. ^ / H ^ Zeolite KSOl (Zeolite V) essentially has that X-ray powder diffraction pattern shown in Table A, however all lines show a reduced intensity, v / as indicates a certain loss of crystallinity. The liatrium content of zeolite V is 0.0013 percent by weight and its specific surface or its pore volume after drying 225 C / 363ra / g and 0.3 cm / g, respectively. It is now producing Catalysts from zeolites obtained according to the invention and the Use of these catalysts for hydro cracking described. On the zeolites III, I? and V becomes platinum in proportions of each 0.2 g / 100 g applied as follows. Earth corresponding proportions of zeolites III, IV and V for each 14 g of dry substance mixed with 70 ml v / ater each. Each of these mixtures is within 15 minutes with stirring with a solution of 0.05 g Pt (NIk) ^ CIp added to 10 ml V / water. The resulting mixtures are then stirred for a further 2 hours. After filtering off the zeolites and washing them with water, they become dried at 120 C. The powders obtained in this way are pressed into tablets and then down to a particle size crushed from 0.177 to 0.595 mm (30 to 80 mesh). The products obtained in this way are finally kept at 450 ° C. for 3 hours calcined. In this way, the catalysts A or B or C are obtained from the zeolites III or IV or V.

The aforementioned catalysts are used for the selective hydrocracking of η-hexane in a device consisting essentially of η-hexane and isohexane . At the beginning of every attempt

1 0982W 1 750

the catalyst is first for 1 hour "at 400 C and one Pressure of 30 kg / cm reduced with hydrogen.

The conditions under which the hydrocracking tests are carried out are listed below. Composition of the starting material; isohexane, percent by weight 49.0

η-hexane, weight percent- 49.5

Methylcyclopentane, weight percent 1.5

Temperature, ⁰ C 350

Pressure, kg / cm - 30 ■ -

Weight space velocity, "'" .._. "' ..-,. -. .... kg of starting material l / l: g Kata- 2.5 lyser. H

Molar ratio V hydrogen / 2 5 "'starting material * ■>

The results of the aforementioned tests are shown in Table C.

Table C.

Product composition,
Weight percent A. catalyst
13th C. C _{1 +} σ ₂ 1.9 5.2 6.3 ^C 3 5.4 20.2 21.0 C _4. + C ₅ . 4.1 10.8 11.4 Isohexane 53.2 55.5 56.3 n-hexane 33.7 7.0. 3.4 Methylcyclopentane ' 1.5 1.5 1.4

Degree of conversion of n-hexane, $

(based on the initial 31.9 85.9 93.2 material contained n-Kexan) '

From the results shown in Table C, it can be seen that the catalysts A, B and C for the selective hydrocracking of in mixtures of n-paraffin hydrocarbons and isoparaffin

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n-paraffin hydrocarbons containing hydrocarbons
suitable. Table C also shows that the activity of catalysts A or 3 or C (sodium content = 0.91 or 0.021 or
0.0031 percent by weight) increases sharply with a decrease in the sodium content.

iL_! LjL play 5

First a zeolite VI is produced with the following properties:

X-ray powder diffraction pattern: essentially as shown in Table B;

Chemical composition: 1.09 Na ₂ O-Al ₂ O ^. 4.91 SiO ₂ . 4.83 HgO; Adsorption at 100 ⁰ C and a Kohlenwassersotffdruck of 40 Torr (after dehydration at 240 ° C and reduced pressure): adsorption of n-hexane = 0.78 mmol / g; Adsorption of 2,3-dimethylbutane = 0.05 mmol / g.

W mmol adsorbed n-hexane / g _Λί - c

mmoles of 2,3-dimethylbutane adsorbed / g

By percolating with 1 M ammonium nitrate solution, the
Sodium ions in zeolite VI replaced by ammonium ions. The percolation is continued until no more sodium ions can be detected in the drain. After washing with water, the zeolite at 120 ⁰ C is dried.

The NH ^ zeolite KSOl (zeolite VII) produced in this way

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- '. / Ρ-; ^ν *;,: »" Cl: ■: 'J! rl] * iji

has essentially the powder X-ray diffraction diagram shown in Table A, a specific surface area or a pore volume after drying at 225 ° C. of 526 m ^ / g and 0.27 cnr / g, respectively a sodium content below 0.2 percent by weight.

Example 6

The sodium ions in zeolite VI are replaced by calcium ions by percolating with a 0.5 m Ca (NO, J ^ HpO solution. Percolating is continued until no more sodium ions can be detected in the drain washing with water, the zeolite at 120 ⁰ C is dried. the sodium content is then below 0.2 weight percent. the Ca-zeolite prepared in this manner Ksol has substantially the X-ray powder diffraction pattern shown in Table A.

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Claims (10)

Claims 1, method of making a zeolite using a) a powder X-ray diffraction diagram with the in Table A indicated reflection lines Tabel A. Radiation = Cu-KpC ₁ ; Wavelength = 1.5405 A 2 θ relative intensity 7.15-7.95 M. 8.80-9.80 NS ί2.7Ο - 13.10 ST 15.00-17.00 M. 17.55-17.95 SST 19.60-20.20 M. 20.40-21.60 SST 22.15-22.75 M. 25.80-26.20 ST 27.20-28.80 SST 29.90-30.5Ov
30.00 - 30.80 <
30.25-31.05 <
31.30 - 31.90 ' SST 34.40-34.80 M. 50.35-50.95 M. in which θ the Bragg's angle, SST "very strong", ST "strong", M means "medium" and SCH "weak", b) a composition of the formula 0.7-1.2 Na _{2 O.Al 2} O ₅ . 4.7-5.3 SiO ₂ . χ H ₂ O where χ is at most 12, preferably 3 to 9, has and 0) one at 100 ⁰ C and a hydrocarbon pressure of 40 torr 1098 24/17 50 measured adsorption of η-hexane after the dehydration of the carried out at 240 C and reduced pressure Zeolite of at least 0.25 mmol / g and a ratio of the value of mmol / g adsorbed η-hexane to V / ert mmol / g adsorbed 2,3-dimethylbutane is at least 8: 1, characterized in that an aqueous mixture of sodium hydroxide and a cogel of aluminum hydroxide on silicon. dloxidhydrogel, which mixture has the composition expressed in moles of oxides 3.5-4.5 Na ₂ CAl ₂ O ₅ . 9.5-13.0 SiO ₂ . 100 - 400 H ₂ O, keep moving,. preferably stirring or shaking, heated to temperatures of 70 to 160 ° C. and that the crystals of the zeolite formed are separated off from the mother liquor. 2. The method according to claim 1, characterized in that the Mixture of sodium hydroxide and the cogel of aluminum hydroxide on silica hydrogel, the composition expressed in moles of the oxides 3.8-4.2 Na ₂ O-Al ₂ O ₅ . 9.8-12.0 SiO ₂ . 125 - 375 H ₂ O. 3. The method according to claim 1 or 2, characterized in that the mixture is held at temperatures of 90 to 110 ° C for at least 4 hours. '' ■ 4. The method according to claim 1 to 3, characterized in that that the cogel is a commercially available silicon dioxide / aluminum low alumina oxide cracking catalyst. ψ 109 8 2A./17 50 5. The method according to claim 1 to 4, characterized in that the zeolite is then at least once with an exchangeable Bringing solution containing cations into contact. 6.. Process according to claim 5> characterized in that one a) the zeolite at least once with an aqueous ammonium ion containing solution heated, ^ b) the NH, zeolite obtained according to a) at temperatures below 550 g calcined and c) treating the calcined zeolite with an aqueous solution containing ammonium ions. 7. The method according to claim 6, characterized in that • the calcination (b) at temperatures of 450 to 500 ⁰ C is carried out. _ 8th. Method according to Claim 6 or 7, characterized in that that the zeolite is then neutralized with a nitrogenous base, preferably ammonia. 10.9 8 2 4/17 50