DE2548697A1 - NEW ZEOLITE, PROCESS FOR MANUFACTURING THE SAME AND ITS CATION-EXCHANGED SHAPES - Google Patents

Description

The invention relates to new zeolites and a process for the production of synthetic crystalline ones Zeolites. Crystalline zeolites with molecular sieve properties can be produced by the joint reaction of silica, Aluminum oxide and suitable alkali hydroxides in certain proportions in an aqueous medium with the following Crystallization of the desired zeolite can be produced from the reaction mixture. Here, however, is the Selection of the reactants and the conditions used are extremely important for the production of special Types of zeolite.

609822/06 3 8

Deutsche Bank (Munich) Account 51/61070 Dresdner Bank (Munich) Account 3939844 Postscheck (Munich) Account 670-43-804

ι '' Τ ¹ · "ι V <; - ί I .λ *

Such zeolites consist of a very large anionic network of AlO ^ and SiO ^ tetrahedra, which have their Oxygen atoms are linked together. The resulting honeycomb-like network contains voids and connecting Channels that contain water or other molecules of suitable size and shape in the interstices can. The negative charge of the network is neutralized by appropriate cations. These cations are mobile and can easily be replaced by other cations, for example exchanged by simple contact with aqueous solutions of salts containing appropriate cations will.

According to GB-PS 1 161 974 a zeolite ZSM5 is prepared, the silicon source to be used not being clear defined, but only given as solid silica; the cations required for the synthesis of the ZSM5 are sodium and tetrapropylammonium ions. In an experimental check it is found that ZSM5 is obtained when the applied solid silica is formed by freshly produced sillcagel. .

Surprisingly, it has now been found that a new zeolite related to zeolite ZSM5, namely zeolite Zeta 1, is obtained, especially if the silicon ^{source is a highly disperse, solid silica (eg W} KS300 "from Hoechst) or a silica formed from the vapor phase

609822/0636 ORIGINAL INSPECTED

or a strongly silicic acid water glass with Si0 ₂ / Na ₂ 0> 3.2, which together with a quaternary ammonium or phosphonium compound (except tetramethylammonium and tetramethylphosphonium compounds) of the formula R ^ gR ^ R ^ .NX or R ^ gR ^ R ^ .PX is used, where:

R ₁ = C ₁ - to C ₂₀ -alkyl, phenyl, benzyl, alkyl-

substituted phenyl or alkyl substituted it is benzyl and

R ₂ , R, and R ^ = C ₁ - to C ₂₀ -alkyl and can be identical or different and

X = »be an acid residue, OH or a halogen

can.

In the following, the groups R ,, R «R, R. .N and ^R 1 ^R 2 ^R 3 ^R 4 * ^{P mi} * ^Q "denotes, which is expediently formed by tetrapropylammonium or cetyltrimethylammonium. In the following it should be understood that degradation products can be used in place of QX or mixtures of compounds that are used in Form common reaction Q in situ, such as a mixture of trialkylamine with a C ₁ - to C _2Q alcohol or a mixture of dialkylarylamine with a C .. to C ₂ Q alcohol.

Zeolite Zeta 1 can be produced at temperatures in the range of G

609822/0616

80 to 25O ⁰ C can be produced. Appropriate proportions

from reaction mixture volume to autoclave volume are used at temperatures above about 104 ⁰ C; excessive evaporation can be prevented by applying pressure with the aid of a permanent gas such as nitrogen,

609822/0636

6,99822 / hkl there
determined Zeoliüi zeta 1 X-ray gun g · si verte (from Tab. 1
974) 11.62 and drawing the 1
vn
I. CD
σ> 200 11.12 there
calculated Zeolite ZSM5
GB-PS 1 I6l d A d A
calculates 10.39
10.04
9.95 Intensity intensity
(Tab. 1) (approx.; From
Character) 120 9.97 11.12 'Ί x 100
0 hkl 11.36 ^p 95 104 9.72. 9.97 30th 200 10.20
9.90 9.15 MS 86
43 9.64 23 210
201
002 OR (GJ 122 8.94 3 9, H. 7.56 'w 15 NAL 9.02 102 co
Tt 2.5 7.54 V 8 S- 202 S.

300 7.44

7.42

130 066 7.07 7.13

132 6.69 6 _; 69 224 6.35 6.34 304 6.04 6.09

212 7.17 7 · /]

311 6.79 6.89

W.

16

302 6.06 6 ₇ 11

Table 1 (cont.)

CD CX)

there
determined Zeolite zeta I \ χ 100 Zeolite ZSM5 (from Tab.
GB-PS 1 l6l 974) 1 and Drawing of the 20th
30th 5.70 there
calculated 6th hkl d A d A
determined calc Intensity intensity
. (Tab. 1). (approx
Sign.) hkl 5.70 · 410 5.77 -5.76
203 5.63 5.64 W.
V 117

σ> 400

ίο 234

506

246

309

5.56

5.36

5.13

316 4,997 137 4.601 342 4.355 138 4.258

4.077

3,999

5.56

5.34

5.13

5.008 4.615 5.364 4.258

4.080 4.003

4 6

7 8

5.42 5 _T 42

5.19 5.20

303 5, 4, 4, 05 5.04 421 - 4, 5.03 500 430 314 4.65 4.65 403 40. 4.37 413 30th 4.30 440 4.12 4.12 441 , 04 4.02

VW

VW

VW

VW

VW

10

16 16

.14 32

8 12

Table- 1 (cont.)

Zeolite zeta I Zeolite ZSM5 (from Table 1 and drawing of GB-PS ι 161 974)

hkl d A

determined

d A calculated

'I χ 100 ο

hkl d A d A intensity intensity

determined calc. ^(Tab - ¹ > ^ ^a : v? ^US s drawing)

408 5.857 5.845 530 5.816 3.818 co
ο 358 3.749 3.745 Ί & * i 516 3.715 5.7.22 ro
ro
• * s » 428 3,646 5.646 O
σ> 429 3.437 5.457 rf » 624 3,552 5,542 454 5.505 5.506 271 5.049 5.050 559 2,978 2.976 274 2.944 2.959 575 2.865 2.865 569 2.728 2.758 380
385
672
695 2.605
2,489
. 2.402
2.005 2.605
2,492
2,598
2.001

100

77

58 44 51

7 5 5

10 2 2 2

'3 4 5 8

115 5.87 5.87 610 5.84 5.82 205 5.77 5.76 611 5.74 5.75 540 5.62 5.65 515 3.50 5.50 650 3.46 5.46 605 5.55 5.54 700 - 5.52 652 5.27 3.27 642 5.07 3.07 515 5.00 5.00

VS

VS

S. W. V W.

VW

94 94

. 50

41 15 15

17 11 16 21

JC - OO CD

V ¥ = very weak, W = weak, M = medium, S = strong, VS = very strong

Table 1 (cont.)

X-ray diffraction values

σ? . ■ ■

ο Unit cell: tetragonal Unit cell: tetragonal

co

OO '

^ V- 22.3 ^a P ⁼ * ³ ' ²

2 ■ c _o - 42.4 C ₀ - 19.9

Formula (dried at 120 ⁰ C) O, OO 7NA _2, 3Q ₂ O · Al ₂ O ₃ .5H ₂ O ₂ .23,8SlO

ro

OG CO CC

_ 9 -

Table 1 compares the X-ray diffraction values for zeolite Zeta 1 with the values for ZSM5. These values were recorded with copper radiation and the d-spacings and intensities were obtained from a strip chart recorder. In order to achieve more precise d-spacings, test series with an internal standard with known d-spacings were recorded and appropriate corrections were made. The values in Table 1 for Zeolite Zeta apply to the product of Example 1 below and are typical for the zeolite, regardless of the Si0 ₂ / Al ₂ 0, ratio and cation content, since variations in the composition lead to only minor changes in the result.

The product from Example 1 had the ^{following composition (dried at 120 °} C.):

0.4Q ₂ O.0.7Na ₂ O.Al ₂ O ₃ .23.8SiO ₂ .5H ₂ O with Q m tetrapropylammonium

and was classified as tetragonal with a = 22.3 and C ₀ »42.4. As Table 1 shows, there is a good agreement between the observed d-spacings for zeolite Zeta 1 and the d-spacings calculated for the proposed unit cell. Although zeolite Zeta 1 is related to ZSM5, it differs significantly from it in terms of its X-ray diffraction values and dimensions of the unit or unit cell.

6 0 9822/0836

Zeollth Zeta 1 also differs from the ZSM5 by a clear difference in the sieve properties. While ZSM5 is unsuitable for a differentiation between the xylene isomers due to the size ratios and all three isomers are abundantly adsorbed, only considerable amounts of p-xylene are adsorbed by zeolite Zeta 1, while the m- and o-isomers are rejected and the zeolite Zeta 1 for ethylbenzene as a border damper (marginal) works. These results suggest that the "inputs" of Zeolite Zeta 1 are only accessible to molecules with a kinetic diameter of 4 6.0 Å, while the inlets of ZSM5 for molecules with a kinetic diameter of up to at least 6.2 i are accessible.

Table 2 shows comparative sorption values for zeolite Zeta 1 and the ZSM5 series of zeolites such as ZSM5, 8, 11 and 12 (those in UK Patents 1,161,974 and 1,334,243, U.S. Pat 3 709 979 and DT-PS 2 213 109).

60 9822/0636

Table 2

Sorption values
Adsorption capacity after 2 hours at 25 ⁰ Cj p / po = »0.5 (wt. #)

OJ
O
CD

•
Zeolite water
(2.8) * n-hexane
(4.2) * Cyclohexane
(6.0) * p-xylene
(6.0) * Ethylbenzene
(6.0) * m-xylene
(6.2) * Zeta 1 (29) ^ 5.7 11.1 8.2 9.9 <1.0 <0.2 ZSM5 (30) ^xx 6.8 9.6 9.5 9.3 9.5 9.1 ZSM8 3.8 9.0 0.9 8.5 ZSM11 7.8 9.7 9.8 ZSM12 7.9 10.1 9.3

(* kinetic diameter) ( ^XX 29 and 30 % Na and 71 and 70 % H ⁺ in the zeolite)

CJl OO

cn cc-

Another unusual feature of zeolite Zeta 1 is the ratio of the adsorption capacity for η-hexane to that for water larger n-paraffin molecules such as n-hexane (4.2 Å diameter) cannot be achieved. The n-hexane / water ratio, for example in the case of zeolite X, is typically around 0.6. In the case of zeolite Zeta 1, this ratio is actually 2, which suggests that parts of the structure are either hydrophobic or, alternatively, have no affinity for water, but a high affinity for hydrocarbons.

According to the invention, a solid, crystalline sodium aluminosilicate, zeolite Zeta 1, is thus provided with the following expressed in molar ratios of the oxides Composition:

0.2 to 0.7Na ₂ 0.0.3 to 0.9Q ₂ O-Al ₂ O ₃ .10 to 150 SiO ₂ .0 to

30 H ₂ O.

where Q is a quaternary ammonium or phosphonium group the formula

R ₁ R ₂ FUR ^ N or R ^ R ₃ R ₃ R ^ P

means with:

609822/0636

R ₁ -C ₁ - to C ₂₀ -alkyl, phenyl, benzyl, alkyl-

substituted phenyl or alkyl-substituted. tuated benzyl and

R ₂ , R, and R ^ «C ₁ - to C ₂₀ -alkyl,

where R ₂ , R, and R ^ can be the same or different, and the crystals are classified as tetragonal with a unit cell with a · 22.3 Å and c «42.4 S. The aluminosilicate according to the invention has essentially an X-ray diffraction pattern, such as it is represented by Table 1.

The invention also includes a process for the preparation of zeolite Zeta 1 of the type just described, which comprises the following steps: reacting together sodium aluminate, at least one silicon compound and at least one compound of the formula QX, where Q of the preceding Meaning and X is an acid residue, OH or a halogen and the reaction mixture is an in Molar ratios has the expressed composition, which falls into the following areas:

O ₃ = 25 to 100

₂₂ O ₃ «1.0

Q ₂ X _{2 / n} / Si0 ₂ = 0.15 to 1, o)

L where η is the Wer-H ₂ 0 / Na ₂ 0 + Q ₂ X _{2 / n} = 5 to 100 J "" β ¹ ^ * of X

609822/0636

The silicon compound is or is principally preferably either a Aerosil or vapor phase silicic acid or highly disperse silica, such as ¹¹ KS300 "from Hoechst, or a strongly kieseisäurehaltiges water glass with a ratio SiOgZNa ₂ O 3 _t2 to 4.0 or a mixture of such silicon sources Alternatively. Silica gel dissolved in quaternary ammonium or phosphonium hydroxide to obtain a silicate.

The reactions can be carried out at temperatures in the range of 80 to 250 ⁰ C. If temperatures beyond the boiling point of the mixture (ie above about 104 ^° C.) are used, an autoclave is used and the ratio of the volume of the reactants to the volume of the autoclave is selected in the range from 0.1 to 0.7. The ratio used can influence the reaction time and also the products actually obtained.

The following 5 examples serve to explain the Method according to the invention, which is accessible to various modifications.

example 1

21.2 g of solid silica ( ⁿ KS300 ⁿ ) were in 100 ml of 50 tetrapropylammonium hydroxide for 2 hours

609822/0636

Dissolved boiling treatment at 10O ⁰ C under reflux. Then 2.4 g of sodium aluminate (1.25 Na ₂ O Al ₂ O,) were dissolved in 50.5 g of water and this liquid was mixed with the silicate liquid with stirring; the stirring treatment was continued for about 15 minutes and the mixture is then transferred into a 1 1 autoclave equipped with "Pyrex" -Auskleidung, in which the reaction mixture was left at 150 ⁰ C a quiet reaction 6 days. The autoclave was then cooled to room temperature and the slurry filtered and the solid washed with 2 1 hot water washed ■ and then at 120 ⁰ C dried. The product obtained had the composition 0.7Na ₂ O.0.4Q ₂ O.Al ₂ O, 23.8 SiO ₂ .5H ₂ O and its X-ray diffraction values corresponded to the data in Table 1. Table 3 shows the sorption values of this Zeta 1 sample for η-hexane and xylenes, namely with sample A a ^{material activated to a sorption equilibrium at 320 °} C. for 2 hours and sample B a ^{material that has been calcined for 24 hours at 550 °} C. (to burn out tetrapropylammonium) was long then for 1 hour exchanged at 95 ⁰ C with an excess of 10% ammonium chloride solution and then again calcined at 55O ⁰ C for 6 hours. The composition of sample B corresponded to:

0.29 Na ₂ O.Al ₂ O ₃ .25SiO ₂

609822/0636

Table 3

Zeolite Sorption capacity p / po = 0.5j 25 ⁰ C; 1 H p-Xylo1 o-xylene m-xylene Sample A
Sample B n-hexane 1 ■
9.5 1
1 1
1 3.6
11.1

Example 2 .

12 g of solid silica were dispersed in 14.6 g of 50% tetrapropylammonium hydroxide and 0.36 g of sodium aluminate were dispersed in 3? ml of water dissolved. The "aluminate liquor" was vigorously stirred into the slurry. The mixture was reacted for 7 days with stirring (50 rpm) in a 1–1 autoclave with a "Pyrex" liner. The autoclave was cooled and the contents filtered and the solid with 2 l of hot water The ^{product, dried at 120 °} C., was a zeolite Zeta 1 with the following composition:.

0.3Na ₂ O 0.75 Q ₂ O.Al ₂ O ₃ .88SiO ₂ .18HO 609822/0636

Example 3

50 g of cetyltrimethylammonium bromide were dissolved in 50 ml of water together with 0.85 g of sodium hydroxide and 1.1 g of solid sodium aluminate. Then 10.6 g of solid silica were stirred in. The mixture was reacted for 5 days at 175 ^° C. and the dried product obtained as in example 2 was again an excellent sample of zeolite Zeta 1 with the following analytical composition:

0.5Na ₂ O. 0.35 Q ₂ O.Al ₂ O ₃ .28SiO ₂ .9H ₂ O where Q = cetyltrimethylammonium.

Example 4

19 »1 g of solid silica were dispersed in 35 g of tripropylamine and 2.2 g of solid aluminate were dissolved in 14.8 g of n-propyl alcohol + 54 ml of water. The aluminate liquid was mixed into the slurry and the mixture ^{reacted at 200 °} C. for 12 days. The dried product contained about 80 % Zeta 1 along with amorphous material.

Example 5

636 g of solid silica were dissolved in 3 # 50% tetra-

6098 2 2/06 3 6

propylammonium hydroxld dispersed. Then 72 g of solid sodium aluminate were dissolved in 1.5 l of water. The aluminate solution was then slurried into the silicic acid. stirred and the mixture was then transferred to a 10 1 autoclave made of stainless steel, in which it was ^{reacted for 5 days at 150 °} C. with vigorous stirring. The autoclave was cooled and the contents filtered and the solid washed with 20 l of hot water. The product dried at 80 ^° C. had the following composition:

0,2Na ₂ O.0,9Q ₂ O.Al ₂ O ₃ .32,5Si0 ₂ 24H ₂ 0th

Acid forms of zeolite Zeta 1 show an excellent. low behavior in the elimination of water from alcohols. For example, Tables 4 and 5 show values obtained during the dehydration of methanol by the hydrogrowth mold from Zeta 1 as well as from acid-leached mordenite and ultra-stable rare earth Y type zeolite. As can be seen, the zeolite Zeta 1 has an exceptional activity with regard to the conversion of methanol in aromatics and it is more effective than mordenite in this regard. The rare earth Y type has no significant Effectiveness in relation to the formation of aromatics.

The hydrogen form of zeolite Zeta 1 was replaced by 2.4-609822 / 0S36

hours burning of the zeolite of Example 1 at 550 ⁰ C and 1 hour at 10 & exchange lgen ammonium chloride solution at 95 ⁰ C (double theoretical amount for the complete exchange) was prepared. This exchange stage was repeated until three exchanges were made. The product was dried, compressed into tablets and broken into 1.6 mm pieces. This material was calcined at 55O ⁰ C for 18 hours and had the following analytical composition: 0,1Na ₂ O.Al ₂ O, .24,7

SiO ₂ .

The X-ray diffraction pattern did not differ appreciably from the freshly prepared sample of zeolite Zeta 1.

The acid-leached mordenite with large inlets corresponded to the composition 0.02Na ₂ O.Al ₂ O ^ I3SiO ₂ and this was pressed into tablets and burned as above.

The rare earth Y type zeolite had a composition of 0.04Na ₂ O.1,39SE ₂ O ^ .Al ₂ O ^ .4,9SiO _2, and this material was pressed into tablets and burned as above. Details of the catalyst experiments are given in the table. The products were analyzed as gas, water-miscible phase and water-immiscible phase. The product analysis of Table 4 clearly shows that

609822/0636

254869?

Zeolite Zeta 1 is a far more active catalyst with regard to the formation of aromatics than acid-leached mordenite. The aromatics formed with zeolite Zeta 1 show much better product yields with regard to the important BTX aromatics (Benzene, toluene, xylene). While Zeta 1 provided 100% conversion in these experiments, showed In the acid-leached mordenite there are very substantial "methanol leakages". These were also found in the case of zeolite of the rare earth Y type, with which only paraffins and olefins were obtained.

In general, the cations or the cation ' from zeolite Zeta 1 by any cations of metals of groups IA, IB, II, III (including rare earths), VIIA (including manganese), VIII (including precious metals) and be replaced by lead and bismuth. The exchange takes place preferably by simple contact in aqueous solution. The acid or hydrogen form of zeolite Zeta can be obtained by reacting the alkali form with a wide range of acidic compounds (i.e. any source of Hydrogen ions) or by first passing through an ammonium or alkyl or aryl ammonium zeolite Ion exchange produces with subsequent decomposition, preferably in air, by heating to achieve the hydro, Gene form of zeolite Zeta 1. If desired, can be made of zeolite Zeta 1 produced catalysts in an inorganic matrix

609822/06 3 6

be incorporated along with other materials that can be either inert or catalytically active. The matrix or base material can be present simply as a binder to hold together small zeolite particles (0.05 to 10 "μ) or it can be added as a diluent to control the extent of conversion in a process that occurs when zeolites are used The base of Zeta 1 would otherwise run at too high a speed, with contamination of the catalyst due to excessive coking or carbon formation.Typical inorganic diluents include kaolin clays, bentonites, montmorillonites, Sepio-11t, attapulgite, Fuller's earths, synthetic porous Materials like SiO ₂ -Al ₂ O ₃ , SiO ₂ -ZrO ₂ , SiO ₂ -ThO ₂ , SiO ₂ -BeO, SiO ₂ -TiO ₂ , highly dispersed silica, or any combination of these oxides. An effective way to mix zeolite Zeta 1 with such diluents consists of mixing appropriate aqueous slurries in a mixing nozzle and then spray drying the slurry lamination. Other types of mixing can be used.

Alkaline earth, rare earth and acidic forms of zeolite Zeta 1 can be further interchanged or with hydrogenation / dehydrogenation components such as Ni, Co, Pt, Pd, Re, Rh are impregnated. Good hydrocracking and reforming catalysts

609822/0636

can be produced in this way from zeolite Zeta 1, provided that its Na20 content is less is reduced than 1% by weight. .

609822/0636

Tab:

catalytic dehydration of methanol

ν. Zeolite
X H-zeta 1
Na ₂ O = 0.4 wt.%
SiO ₂ ZAl ₂ O ₅ = 24.7 6 0 9 8 7 7/0 acid leached fc
H-mordenite
Na ₂ O = 0.1 wt.%
SiO VaI 0 = 18 uitrastable
SEY zeolite
Na _g 0 = 0.5 wt.%
SiO ₂ ZAl ₂ O ₅ = 4.9 * 30th 6 36 Product N _n . ·
Gew.So ■ 'X VersJ7 AfeiB.79 \ fers.76 0 V • -3.2 7.3 1.2 0 ^CH 4 5.5 8.3 " 12.4 - 0.1 0.3 CH-OH .0 0.9 2.3 ^C 2 ^H 4 5.3 0.3 9.4 ^C 2 ^H 6. 2.1 2.6 1.2 5.9 0.5 6.0 ^C 3 ^H 8 36.9 0.4 2.2 Dimethyl ether .0.1 77.5 • 53.1 ^C 4 ^H 8 2.1 0.3 3.1. .6.1 0.1 0.4 ^isoC 4 ^H l0 24.4 0.5 4.4 C5 + paraffin 5.6 0.4 3.8 ^C 6 ^H 6 1.4 0.1 C ₆ H ₅ CH ₅ 13-4. 2.9 C ₆ H ₅ C ₂ H ₅
p- and m- Xj) ^- IoI 1.75
2.2 0.2
25.9 o-xylene 5.7 6.2 Pseudocum oil 7.5 . 2.9 mop-ethyl-t olUO.1 4.7 0.4 NILE 0-ethyl toluene 1.0 0.1 Summa c aromatics 2.8 5.6 Durol ■ 1.9 2.1 Isodurol 0.2 2.9 BTX aromatics: * » ^C 6- ^C 10 ' 71.4 29.0 in C ₆ -C ₉ , in C ₆ -C ₁₀ 95.3 63.2 what s. phase
% CH ₅ OH 0 46 % BTX in aromat oil 49 50 Aromatic yield e
% Vol / vol 32 17th

Table 5 Details of the methanol dehydration attempts

cn
ο
co

Verse.
No. catalyst LHSV
to " ¹ Reactor-
temp,
° C Verse.-
Time
(Hours) Total-
Methanol
in ml 01-
phase
from ml what s.
Pase
from ml gas
away
1 % Methanol
in water. .
Phase (wt.%) ' ? ^6th 10 ml (8.5 g)
SEY type ■ ' 1 370 2 20.05 0 8.6 2.55 ■ 30 77 5.5 ml (3.3 g)
Hydrogen zeta I 1 373 4th 17.9 3.2 7.6 1.27 0 79 ίο mi .. (6.3. he)
acid exhaust
Mo'rdenit. 1 373 2 20.8 9.3 1.72 8.5

Claims (10)

Claims 1. Solid, crystalline sodium aluminosilicate, zeolite Zeta 1, characterized by the the following composition (expressed in molar ratios of the oxides): 0.2 to 0.7 Na ₂ O. 0.3 to 0.9 Q ₂ O.Al ₂ O ₅ .10 to 150 SiO ₂ . 0 to 30 H ₂ O where the Q is a quaternary ammonium or phosphonium group of the formula ^R 1 ^R 2 ^R 3 ^R 4 ^{N or} is, where R ₁ - C ₁ - to C ₂₀ -alkyl, phenyl, benzyl, alkyl substituted phenyl or alkyl substituted Benzyl is and R ₂ , R, and R ^ ■ C ₁ - to C ₂₀ -alkyl may be the mean or different and are equal, and the crystals are classified as tetragonal with a unit Szelle with a _{0 to} 22.3 Å and c = 42.4 _Q Ä. 2. aluminosilicate according to claim 1, characterized by a X-ray diffraction diagram which essentially corresponds to the specifications of 609822/0 63 6 Table 1 corresponds. . 3. aluminosilicate according to claim 1 or 2, thereby, marked. indicates that Q is tetrapropylammonium or cetyltrimethylammonium is.. 4. Process for the preparation of zeolite Zeta 1 according to a of the preceding claims, characterized by a joint implementation of sodium aluminate, at least one Silicon compound and at least one compound of the formula QX, where Q has the meaning already given and X is an acid residue, OH or a halogen, at a temperature in the range of 80 to 25O ⁰ C, wherein the reaction mixture has a composition - in terms of mole ratios - falling within the following ranges: Si0 ₂ / Al ₂ 0 ₃ = 25 until 100 Na ₂ 0 / Al ₂ 0 ₃ 1.0 Q ₂ X _{2 / n} / Si0 ₂ = O , 15 to 1.0 H ₂ 0 / Na ₂ 0 + Q ₂ X ₂ / η - ⁵ until 100 where η is the valence of X. 5. The method according to claim 4, characterized in that a degradation product of QX is used in place of QX. 6. The method according to claim 4, characterized in that 609822/0 636 a mixture of compounds is used which can form in situ during the reaction Q, such as, for example, a mixture of trialkylamine with a CL to CgQ alcohol or a mixture of dialkylarylamine with a Cj to C ₂₀ alcohol. 7. The method according to any one of claims 4 to 6, characterized in that the silicon compound or the main Silicon compound through an aerosil, vapor phase silica, highly disperse silica or a highly silica-containing one Water glass with a SiOg / Na ^ O ratio from 3.2 to 4.0. 8. The method according to any one of claims 4 to 6, characterized in that the silicon compound or the main Silicon compound by dissolving it in quaternary ammonium or phosphonium hydroxide to obtain a silicate Silica gel is formed. 9. A method according to any one of claims 4 to 8, .dadurch in that the reaction is carried out over 104 ⁰ C in an autoclave, wherein the ratio of Reaktantenvolumen is to autoclave volume in the range of 0.1 to 0.7. 10. Ion-exchanged forms of zeolite Zeta 1, thereby 609822/0636 characterized in that the sodium cations of zeolite Zeta 1 according to any one of claims 1 to 3, by hydrogen or
any cations of metals of groups IA, IB, II, III (including rare earths), VIIA (including manganese), VIII (including precious metals), as well as lead and bismuth have been replaced. 609822/0638