DE1269111B - Process for the production of crystalline synthetic zeolites - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

COIb

German KL: 12 i- 33/26

P 12 69 111.1-41
May 19, 1965
May 30, 1968

Crystalline synthetic zeolites with molecular sieve Ion exchange properties are already known. You can by bringing in appropriate amounts Silica, aluminum oxide and alkali metal in a suitable aqueous medium and subsequent crystallization of the desired zeolite can be prepared from the mixture. If you do that during alkali metal usually chosen for manufacture, ζ. B. sodium, by another element, e.g. B. Lithium, Magnesium, calcium, strontium, nickel, zinc, ίο If one wishes to exchange silver or ammonium, this can usually be done easily by ion exchange between the originally obtained zeolite and a solution of the element in question.

In the known processes for producing crystalline synthetic zeolites, aqueous sodium aluminate and sodium silicate solutions (in the form of water glass Na ₂ O · «SiO ₂ , where η is about 2 to 4, or in the form of colloidal silica or silica gel) are combined with one another. In a known production process, the ratio of Na ₂ O: SiO ₂ in the reaction mixture is 1.2 to 1.5, of SiO ₂ : Al ₂ O ₃ is 2.5 to 5.0 and of H ₂ O: Na ₂ O at 35 to 60.

It has now been found that by carefully selecting the silica component used as the starting material significantly affect the outcome and effectiveness of implementation and lead to a can reach particularly effective and economically advantageous production method. The type of silicate solution is of vital importance for economic working conditions.

Method of manufacture

of crystalline synthetic zeolites

Applicant:

Peter Spence & Sons Limited,
Widnes, Lancashire (UK)

Representative:

Dr. rer. nat. J.-D. Mr. v. Uexkull

and Dipl.-Chem. Dr. rer. nat. V. Graf zu Stolberg, patent attorneys,

2000 Hamburg 52, KÖniggrätzstr. 8th

Named as inventor:

Edwin Bolwell Andrews, Widnes, Lancashire;

John Kerr, Warrington, Lancashire;

Thomas Vincent Whittam,

Warrington, Lancashire (UK)

Claimed priority:

Great Britain May 20, 1964 (20 769) - -

According to the invention, a method for production of crystalline synthetic zeolites with molecular sieve and ion exchange properties Combine aqueous sodium aluminate and sodium silicate solutions to form a reaction mixture with a Molar ratio in one of the areas a), b) or c)

a)

b)

c)

SiO ₂ : Al ₂ O ₃
Na ₂ O: SiO ₂
H ₂ O: Na ₂ O

0.06 to 4.0

0.7 to 20.0

15.0 to 200.0 2.0 to 30.0

0.4 to 6.5

10.0 to 150.0

8.0 to 30.0

1.0 to 3.0

10.0 to 120.0

proposed, which is characterized in that the silicate component is at least partially sodium metasilicate pentahydrate Na ₂ O · SiO ₂ · 5H ₂ O special activity in a ratio to other silicate components, expressed as

Na ₂ O-SiO ₂ -5H ₂ O: SiO ₂

1.0: 0 to 1.0: 76.0 is used, and brings the reaction mixture without aging below the crystallization temperature at temperatures between 30 and 120 ° C, preferably between 50 and 100 ⁰ C for crystallization.

The active sodium metasilicate pentahydrate is thereby defines that it is under the conditions of a laboratory test within a reaction time of 3 hours gives zeolite X. The work is carried out under the following conditions:

8 g of sodium metasilicate pentahydrate are obtained at room temperature dissolved in 20 g of water and in this solution g of aqueous sodium aluminate with a content of

809 557/437

0.75 g Na ₂ O and 1.0 g Al ₂ O ₃ mixed in. The mixture is maintained under stirring at 90 to 100 ⁰ C for 3 hours under reflux, filtered, washed and dried the precipitate at 80 to 140 ⁰ C. A measurement of the X-ray diffraction of the powder shows that it is an essentially pure ZeoliteX.

The active sodium metasilicate pentahydrate is commercially available and has the X-ray diffraction pattern described below. The more important diffraction lines are listed in the following table 1, but the diffraction image can contain numerous other lines with lower intensity. The intensity of the lines can vary depending on the type of manufacture. In Table 1 and the following Tables 3 to 5, d denotes the distance in Angstroms and / the visually determined relative line intensity, the / value of the strongest line being set at 10.

Table 1

X-ray diffraction pattern of Na ₂ O · SiO ₂ · 5H ₂ O

d (fo / 6.15 8th 4.0 6th 3.35 9 3.3 9 3.15 10 2.75 8th 1.9 6th

This diffraction pattern is consistent with the ASTM index for sodium metasilicate pentahydrate. It will assumed that in the zeolite synthesis by the inventive choice of the silicate component The advantages achieved are due to the fact that the selected silicate becomes a real one in water Solution of a highly reactive metasilication dissolves, which quickly increases with the aluminum oxide component a homogeneous aluminum silicate gel reacts. It is further believed that the pentahydrations cause the reaction to proceed in the direction desired according to the invention in the reaction solution. From the standpoint of reactivity, the use of micellar silicate solutions, soft require aging prior to the reaction to form the aluminum silicate gel, are considered undesirable.

If the metasilicate hydrate is the only silicate constituent of the reaction mixture, it must be

Molar ratio

Na ₂ O

the same as the reaction mixture

SiO ₂ - ° °

or greater than 1. However, this can be varied by using the preferred highly reactive metasilicate pentahydrate to steer the implementation in the desired direction together with silica in Another form, for example water glass or even free silica, is used.

If there is an adequate amount of the sodium metasilicate pentahydrate in the reaction mixture, will also take advantage of this material, such as increased reaction speed and Selectivity achieved.

The molar ratio of sodium metasilicate pentahydrate to silica of other origin is said to be in the range from 1.0 to 0 to 1.0 to 76.0. To produce zeolite X, a ratio is used

Na ₂ O-SiO ₃ -5H ₂ OrSiO ₂

from 1.0 to 0 to 1.0 to 0.7 preferred.

From the following tables 5 to 13 it can be seen that the advantages according to the invention are only using the material referred to above as active sodium metasilicate pentahydrate can and surprisingly neither anhydrous sodium metasilicate nor Natriummetasüicatnonahydrat are suitable for the task according to the invention. The latter metasilicates behave exactly like the water glasses and disilicates and do not show the increased reaction speed and selectivity of the active metasilicate pentahydrate.

Compared to known methods, the selection of the silicate component according to the invention leads to a) significantly increased reaction rates at all given temperatures, b) usability significantly lower reaction temperatures, c) products with greater purity and d) avoidance long aging stages.

The advantages achieved by the method according to the invention can be seen in particular on the basis of Production of those used as molecular sieves and known as Zeolite A, Zeolite X and Zeolite Y is known from British Patents 777 232 and 973 933 and U.S. Patent 3,130,007 crystalline synthetic zeolites are explained.

Zeolite A was developed by L. Broussard and D. P. Shoemaker in J. Am. Chem. Soc, 82 (1960), p. 1041. Its chemical composition corresponds to the general formula

1.0 ± 0.2M ₂ O: Al ₈ O ₃ : 1.85 ± 0.5 SiO ₈ : FH ₂ O

when Y = 0 to 5 and η is the valence of the cation M, for example sodium, potassium, calcium, magnesium, silver, lithium, ammonium, strontium or thallium. The material is best characterized by its X-ray diffraction pattern. The more important diffraction lines are summarized in Table 2:

Table 2
X-ray diffraction pattern of zeolite A.

/ 12.3 10.0 8.71 6.9 7.11 3.5 5.51 2.5 4.11 3.6 3.71 5.3 3.42 1.6 3.30 4.7 2.99 5.5 2.75 1.2 2.63 2.2 2.14 1.0 1.74 1.3

Zeolite X is very similar to the mineral faujasite (cf. AF We 11 s, "Structural Inorganic Chemistry", Third Edition, 1962, p. 813), but has a lower SiO ₂ : Al ₂ O ₃ ratio than this mineral. Its chemical composition corresponds to the general formula

0.9 ± 0.2 M ₁ O: Al ₃ O ₃ : 2.5 ± 0.5 SiO ₂ : 7H ₂ O

where η is the valence of the cation M and Y = 0 to 8. The cation can be sodium or almost any cation-forming element such as ammonium, quaternary ammonium or any basic amine cation that can be built into the lattice. The material is again best characterized by its X-ray diffraction pattern, the most important diffraction lines of which are summarized in Table 3 below. In addition, there may be lines of lesser intensity and the intensity may be different in different specimens:

Table 3
X-ray diffraction pattern of zeolite X

/ 14.4 10.0 8.85 1.6 7.53 1.0 5.73 1.5 4.42 1.4 3.81 1.9 3.41 1.7 2.948 1.0 2,889 1.9 2.797 1.1

Zeolite Y was described by JA R ab ο et al in Actes du Deuxieme Congres Int. de Catalyse, Paris, 2, 1960, p. 2055. It is isostructural with the mineral faujasite and zeolite X, but has a higher SiO ₂ : Al ₂ O ₃ ratio than zeolite X. Its chemical composition corresponds to the general formula

0.9 ± 0.2M ₁ O: Al ₂ O ₃ : 4.5 ± 1.5 SiO ₈ : 5 ± 5H ₂ O

where η represents the valence of the cation M, all of the cations mentioned above with reference to zeolite X being suitable. The X-ray diffraction pattern is shown in Table 4 below:

Table 4
X-ray diffraction pattern of zeolite Y

d (A)

14.15 to 14.37
8.67 to 8.80
7.39 to 7.50
5.62 to 5.71

10.0
1.6
1.0

For the production of zeolite A, zeolite X or zeolite Y according to the invention, the silicic acid and Alumina constituents to form a mixture within the above as a), b) or c) wide range for the molar ratios of the oxides mixed.

Within the ranges for the molar ratios of the oxides proposed for use according to the invention, certain combinations of the ratios of the reactants yield zeolite A, X or Y mixed with appreciable amounts of crystalline or amorphous impurities. With the broad ranges for X or Y, certain combinations of the ratios yield zeolite Y in the X range and zeolite X in the Y range. This is inevitable, since these materials are isostructural with each other and with natural faujasite and, through an arbitrary subdivision in the previous literature, synthetic faujasites with an SiO ₂ : Al _a O ₃ ratio of 2 to 3 as zeolite X and those with an SiO ₂ : Al ₂ O ₃ ratio above 3 can be referred to as zeolite Y. The following ranges for the molar ratios of the oxides are preferred:

To make Zeolite A:

a)

Al ₂ O ₃
Na ₂ O

SiO ₂
H ₂ O
Well «O

- = 0.19 to 2.7, = 0.85 to 9.7,

= 30.00 to 200.00.

To make Zeolite X: b)

- ^ = 2.8 to 8.0, ALO,

Na ₂ O
SiO ₂
H ₂ O
Na ₂ O

= 0.7 to 5.0,

= 35.0 to 120.0.

To make zeolite Y:

Al ₂ O ₃
Na ₂ O
SiO ₂

H ₂ O
Al ₂ O ₃

8.0 to 20.0, 1.0 to 3.0, 35.0 to 90.0.

During manufacture, the sodium aluminum silicate reaction mixture is held at temperatures in the range from 20 to 120 ^° C., preferably 50 to 100 ^° C., for a sufficient time to form crystals with the above-mentioned chemical composition and X-ray diffraction.

In the conventional methods of preparing zeolite A, water glass or sodium disilicate is usually used as the silicate component. With these components, the reaction proceeds at a reaction temperature of 50 ⁰ C very slowly, and with a disilicate are needed to form zeolite A 120 hours. In contrast, the production according to the invention using metasilicate pentahydrate only requires a reaction time of 24 hours. When using the disilicate, the reaction time was 24 hours

7 8

only get an amorphous product. The lent in this regard, and within a reaction time of 2 hours The results are shown in Table 5. becomes a very profitable product with or without stirring Further attempts to produce zeolites with received, as the stated isobutane capacity shows, various metasilicates are listed in Table 6- This represents a measure of the purity, since the iso and show the reactivity of the metasilicate-5 butane capacity is higher, the more complete the hydrate solution in reactive form. Formation of the crystalline zeolite X takes place. The ones in the

The results shown in Table 7 explain the isobutane capacity given in tables was at measured by using the preferred sodium an isobutane pressure of 770 mm at 25 ° C, metasüicat-pentahydrates as the basis of rapid It was also found that when using Formation of zeolite A achieved significant advantages. io of metasilicate pentahydrate, as is probably the case with others The preferred pentahydrate or silicate constituents, both optimal and the preferred pentahydrate-containing mixtures have a minimal reaction time. This arises compared to other silicates. The table shows from Experiment 38 in Table 9, in which after furthermore, the wide range of usable reac- a reaction time of 2 to 7 hours of pure zeoliteX tion relationships, which, however, in no way to the an- 15 received and after a continuation of the implementation examples are limited. except for 21 hours most of the time X in

Experiments 8 and 9 in particular show that the zeolite B, a material close to Philhpsite, was converted back using metasilicate pentahydrate (cf. British patent 777233, leading advantageous high reaction rate, in which reference is also made to zeolite C). Given the high reaction rates of 20 This result is also confirmed by the experiments 45, for example, 5 to 20 minutes, it is according to the invention 'and confirmed 46th With the systematic re-possible, zeolite A in a continuously working collection of experiments 39 and 46 has been shown to produce the reactor. This can be done by converting the zeolite X to zeolite B at a z. B. the reactive sodium sodium solution and the sodium reaction time between 16 and 48 hours start trium aluminate solution preheated in a heated 25 can.

Mixing pump rapidly and intimately mixed and in one It was also found that for the production of

continuously operating reactor tower sufficient ZeoliteX with optimal quality (measured by keeping the required reaction temperature for a long time. the isobutane capacity) mixing the reaction-The continuous implementation of the inventive partner in a certain way, namely the mixing in according to implementation can, however, also be applied to any other 3 ο the sodium aluminate solution can be carried out in a manner known to those skilled in the art. silicate solution at temperatures below 50 ⁰ C to

In the known processes for the preparation of is preferred. Once the Natriumaluminiumsüicat zeolite X can this is not formed on the industrial scale reaction mixture, the temperature no longer, up to 9tägiges aging the aluminum mini environmentally is increased to the desired operating temperature. In the silicate gels obtained in pure form at room temperature, the test shown in Table 9 was 38 (cf. German Patent 1138 383). Even after the reaction time for the optimal formation of zeolite X of such an aging stage, it is necessary for the optimal quality to be about 2 hours. The corresponding mixture with slight stirring, an additional 3 to 6 STUN the experiments are zusammengeden in Table 10 to be heated to about 100 ⁰ C. With the one in the poses.

Table 9 below, using 4 ° Compliance with the above of disilicate as a silicate component and a technical mixing condition is not decisive Ruch reactions corresponding stirring by- however, contamination of the zeolite X can be Runs 28 to 36 were conducted without any other products occurring when these preferred 24 hour aging of the aluminosilicate gel under conditions not to be used. Room temperature (10 to 35 ° C) either no 45 When using preferably for Zer zeolite Xor another Zeohthenoderamorphic disorder of micelles heated to boiling beforehand Products contain heavily contaminated material. Sodium metasilicate pentahydrate or nonahydrate

On the other hand, on a laboratory scale, zeolite X can also be obtained at 50 ° C without using the known process, zeolite X, within a reaction time of 24 hours if neither thermal 50 denier can be obtained at the reaction temperature. However, it has been done just as after mechanical agitation. In the case of zeolite A, this is shown by the fact that the nonahydrate, unlike the results listed in Table 8, clearly provides moderate results and therefore shows for the invention. Thereafter, any suitable form of hydrati-zeolite X is obtained at 9O ⁰ C with no stirring process according but is already moving at low overbased metasilicate. Using agitation, products other than ZeoliteX 55 sodium disilicate or anhydrous sodium metasilicate are obtained. The method according to the British patent failed to obtain X zeolite. The entschrift 777 233 is not suitable for the semi-technical or speaking experiments are listed in Table 11 for the joint technical production of ZeoliteX. This posed.

is charged by the German patent specification 1138 383. Furthermore, it has been found that when verified, in which the only satisfactory use of nonahydrate instead of sodium for the production of zeolite X in technical metasilicate pentahydrate with or without prior Scale a two-stage process with an old heating to boiling in the process of mastering stage at room temperature, subsequent setting of ZeoliteX at 90 to 100 ° C none rapid heating to reaction temperature and um- zeolite X is obtained as soon as it is stirred. The nonahydrate Settlement without stirring at temperatures of 93 to 65 behaves in exactly the same way under these conditions 100 ° C is suggested. same way as water glass, disilicates or water-

In the inventive use of meta-free metasilicate, and these products are without the Silicate pentahydrate is not an aging level required - aging level according to the German patent specification

383 unsuitable for the industrial production of zeolite X. The conversion of the three types of metasilicate at 90 ° C is explained in Table 12. With regard to the conventional processes for producing zeolite Y, it is stated in US Pat. No. 3,130,007 that it is essential to age the aluminum silicate gel for up to 48 hours and then to react at temperatures of about 100 ^° C. for up to hours. When implementing the implementation with

With the silicate constituents selected according to the invention, the aging stage can be avoided and the reaction can be carried out in a considerably shorter time. When using colloidal silica, zeolite Y could only be obtained after extensive aging or, on a laboratory scale, after long reaction times at 90 to 100 ^° C., avoiding any stirring. The results of these tests are shown in Table 13.

Table 5 Preparation of zeolite A from various silicates

Attempt 2

Raw materials
Sodium aluminate

(1.21 Na ₂ O • Al ₂ O ₃ • 12.2 H ₂ O), g sodium disilicate

(Na ₂ O · 2 SiO ₂ · 14.22 H ₂ O), g .. sodium metasilicate pentahydrate, g

Sodium hydroxide, g

Water, g

Molar ratio

SiO ₂ : Al ₂ O ₃

Na ₂ O: SiO ₂

H ₂ O: Na ₂ O

Reaction temperature ^{, 0 C}

Response time, hours -

Product received

Zeolite A

amorphous product

39.6

24.3

83.1

1.2

1.5

36.0

50
120

39.7

16.9
377.0

0.8
2.95
95.7

19.7 17.5

3.8 357.8

0.8 2.95 95.7

50

24

Table 6 Preparation of zeolite A from various metasilicates

attempt

Raw materials

Sodium aluminate
(1.21 Na ₂ O • Al ₂ O ₃ • 12.2 H ₂ O), g

Sodium metasilicate pentahydrate, g,

Sodium metasilicate nonahydrate, g,

Sodium metasilicate nonahydrate (10 minutes heated to boiling and cooled to 50 ⁰ C), g

Sodium metasilicate (anhydrous), g,

Sodium hydroxide, g

Water, g

Molar ratio

SiO ₂ : Al ₂ O ₃

Na ₂ O: SiO ₂

H ₂ O: Na ₂ O

Reaction temperature ^{, 0 C}

Response time, hours

Product received

Zeolite A

amorphous product

*) Partly with considerable amorphous proportions.

39.7
16.9

377.0

0.8
2.95
95.7

39.7
22.7

2.8
371.0

0.8
2.95
95.7

50
24

39.7

22.7

2 Q

371.0

0.8 2.95 95.7

50

24

397.6

97.6

28.0

3842.0

0.8 2.95 95.7

50 24

809 557/437

Table 7 Preparation of Zeolite A.

12th

10

attempt
I 12

13th

14th

Raw materials
Sodium aluminate

(1.21 Na ₂ O • Al ₂ O ₃ • 12.2 H ₂ O), g

(1.26 Na ₂ O • Al ₂ O ₃ • 12.2 H ₂ O), g

(1.3 Na ₂ O • Al ₂ O ₃ • 12 H ₂ O), g

Sodium metasilicate pentahydrate, g

Sodium metasilicate nonahydrate, g

Sodium metasilicate (anhydrous), g

Sodium disilicate, g,

Water glass (Na ₂ O · 4 SiO ₂ · 43 H ₂ O), g

Sodium hydroxide, g

Water, g

Molar ratio

SiO ₂ : Al ₂ O ₃

Na ₂ O: SiO ₂

H ₂ O: Na ₂ O

Reaction temperature ^{, 0 C}

Response time, hours

Product received

ZeoIithA

amorphous product

Adsorption capacity for n-butane at 25 ° C and 770 mm Hg (target value for zeolite A 13 ° / o), g / 100g

40.2 40.2 57.3 57.3 40.2 40.2 38.9 310 310 25.4 25.4 415 41.5 39.4 30.4
347.0 3.0
347.0 4.3
514 4.3
514 3.0
336.5 3.0
336.5 1.68
551.3 1.46
4.46
33.2 1.46
2.12
68.7 1.46
2.12
68.7 1.46
2.12
68.7 1.46
2.12
68.7 1.46
2.12
68.7 1.77
1.86
65 90 90 90 90 90 90 90 5 min. 10 to 20
Min. 2.0 2.5 2.0 2.5 4th 13.9 14.2 13.0 13.2 14.0

- - 34.0

Table 7 (continued)

17th

18th

attempt
I 20

21

22nd

Raw materials

Sodium aluminate

(1.21 Na ₂ O • Al ₂ O ₃ • 12.2 H ₂ O), g

(1.26 Na ₂ O • Al ₂ O ₃ • 12.2 H ₂ O), g

(1.3 Na ₂ O • Al ₂ O ₃ • 12H ₂ O), g

Sodium metasilicate pentahydrate, g

Sodium metasilicate nonahydrate, g

Sodium metasilicate (anhydrous), g

Sodium disilicate, g

Water glass (Na ₂ O · 4 SiO ₂ · 43 H ₂ O), g

Sodium hydroxide, g

Water, g

Molar ratio

SiO ₂ : Al ₂ O ₃

Na ₂ O: SiO ₂

H ₂ O-Na ₂ O

Reaction temperature ^{, 0 C}

Response time, hours

Product received

Zeolite A

amorphous product

Adsorption capacity for n-butane at 25 ° C and 770 mm Hg (target value for zeolite A 13%), g / 100 g

80.0 80.0 38.9 77.8 - 39.7 54.8 - - - - 39.8 - - - - 10.6 - 275.6 - - 8.06 4.25 34.0 82.0 82.0 27.2 - - - - - - - - - 19.0 19.0 6.92 - 10.4 53.6 2.5 700.0 700.0 325 5.12 401.7 - 828.0 1.77 1.77 1.77 594 1.3 57.2 1.77 1.86 1.86 "1.86 0.19 2.1 2.2 1.86 65 65 65 9.7 15th 0.86 65 90 90 90 97.4 50 35 90 4/6 8th 4th 90 8th 90 8th 13.0 13.9 8th 13.5 12th 13.0 13.8

2.6 292.0

Table 8

14th

Comparative tests according to Table 1 of British patent specification 777 233

attempt

24 I 25 I 26 I.

Corresponding to the example in British patent specification 777

Raw materials
Sodium aluminate

(1.21 Na ₂ O • Al ₂ O ₃ • 12.2 H ₂ O), g sodium disilicate

(Na ₂ O · 2 SiO ₂ · 14.22 H ₈ O), g .. water glass

(Na ₂ O • 3.55 SiO ₂ • 25.8 H ₂ O), g

Sodium hydroxide, g

Water, g

Molar ratio

SiO ₂ : Al ₂ O ₃

Na ₂ O: SiO ₂

H ₂ O: Na ₈ O

Stirring effect

Response time, hours

Product received

Zeolite B

Zeolite C

Zeolite X

100.4
160.5

23.5
520.0

3.0

1.3
38

small amount
47

little

100.4
160.5

23.5
520.0

3.0

1.3
38

80.3

472.0

59.6

740.0

11.4 0.72 18

low 6

+ Tracks

80.3

472.0

59.6

740.0

11.4 0.72 18

Table 9 Production of zeolite X at 90 to 100 ^° C.

28

29

30th

attempt
32 33

34

35

36

Raw materials

Sodium aluminate

(1.21Na ₂ O .Al ₂ O ₃ -12.2H ₂ O), g sodium aluminate

(1.3 Na ₂ O Al ₂ O ₃ 12 H ₂ O), g sodium metasilicate

pentahydrate, g

Sodium disilicate, g

Water glass

(Na ₂ O · 3.55 SiO ₈ · 25.8 H ₂ O), g water glass

(Na ₂ O · 4 SiO ₂ · 43 H ₂ O), g

Sodium hydroxide, g

Water, g

Molar ratio

SiO ₂ : Al ₂ O ₃

Na ₂ O: SiO ₂

H ₂ O: Na ₂ O

Aging time at 20 ^° C., hours

Response time, hours

Product received

Zeolite B

Zeolite C

Zeolite X

amorphous product

Isobutane adsorption capacity, g / 100 g

39.7

82.6

16.1 394

3.85 1.34 47

39.7

82.6

16.1 394

3.85 1.34 47

39.7

82.6

16.1 394

3.85 1.34 47

24

3.85
1.34
47

3O ° / o

39.7

82.6

16.1
394

3.85
1.34
47

24

39.7

96.8

19.1
445

4.5
1.3
50

0
16

17.4

80.3

472.0

59.6 740

11.4 0.72 18

0 6

traces

39.7

134.0 0.32 89.5

0.7 30

39.7

134.0 0.32 89.5

0.7 30

8/16

Table 9 (continued)

16

38 I 39 I 40 I 41

attempt
I 43

45

Raw materials

Sodium aluminate

(1.21Na ₂ O-Al ₂ O ₃ -12.2H ₂ O), g sodium aluminate

(1.3 Na ₂ O-Al ₂ O ₃ -12 H ₂ O) ₅ g sodium metasilicate

pentahydrate, g

Sodium disilicate, g

Water glass

(Na ₂ O · 3.55 SiO ₂ · 25.8 H ₂ O), g water glass

(Na ₂ O · 4 SiO ₂ · 43 H ₂ O), g

Sodium hydroxide, g

Water, g

Molar ratio

SiO ₂ : Al ₂ O ₃

Na ₂ O: SiO ₂

H ₂ O: Na ₂ O

Aging time at 20 ° C, hours reaction time, hours

Product received

Zeolite B

Zeolite C

ZeoliteX

amorphous product

Adsorption capacity for
Isobutane, g / 100 g

49.7

102.0

475

3.85 1.34 47

2/7 *)

18.7

19.2

49.7

102.0

475

3.85 1.34 47

16/48

15.2

18.0

39.8

10.6 71.6

75.4 367

3.85 1.06 60

4.5

18.8

39.8

1.06 81.5

7.2 367

3.85 1.06 60

20 ° / "80%

15.2 39.8
82.8

7.36
368

3.85
1.06
60

4.5

traces

39.8
84.8

117.6
4235

120

0
10

19.0

39.8 169.6

117.6 5060

3 120

18.8

33.1

77.0

33.1

77.0

742

4.35

1.28

96

742

4.35 1.28 96

0 16/48

18.7

9.0 16.0

*) At 90 to 95 ° C on an industrial scale 2 to 3 hours, on a laboratory scale in 5 to 7 hours.

Table 10 Production of zeolite X with different ways of mixing the starting materials

attempt
I 49

50

Raw materials
Sodium aluminate

(1.21 Na ₂ O • Al ₂ O ₃ • 12.2 H ₂ O), g

Sodium metasilicate pentahydrate, g

Water, g

Molar ratio

SiO ₂ : Al ₂ O ₃

Na ₂ O: SiO ₂

H ₂ O: Na ₂ O

Mixed way

Metasilicate solution mixed into the aluminate solution. Aluminate solution mixed into the metasilicate solution

Mixing temperature, ° C

Reaction temperature, ° C

Product received

Zeolite B

Zeolite C

ZeoliteX

Isobutane adsorption capacity, g / 100 g

49.7
102.0
475.0

3.85
1.34
47

20th
90

+
19.0

49.7 102.0 475.0

3.85 1.34 47

50 90

+ 18.7

49.7 102.0 475.0

3.85 1.34 47

50 90

+ 3.0

17th 18th

Table 11 Production of zeolite X in 24 hours at 5O ⁰ C

51 52 attempt
53 54 39.7 39.7
92.1 33
103 33
103 82.6
16.1
394 730 730 730 3.85
1.34
47 4.35
1.28
96.6 4.35
1.28
96.6 4.35
1.28
96.6 O 0 0 0 50 50 50 50 24 24 24 24 * \,

55

Raw materials

Sodium aluminate, g

Sodium metasilicate pentahydrate, g

Sodium metasilicate nonahydrate, g

Sodium metasilicate nonahydrate (heated to boiling), g

Sodium metasilicate anhydrous, g

Sodium disilicate, g

Sodium hydroxide, g

Water, g

Molar ratio

SiO ₂ : Al ₂ O ₃

Na ₂ O: SiO ₂

H ₂ O: Na ₂ O

Aging time, hours .. reaction temperature, ° C reaction time, hours ..

Product received

Zeolite X

amorphous product

*) Significant amounts of amorphous product were also often obtained.

39.7

53.1 944.6

4.35 1.28 96.6

0 50 24

Table 12 Preparation of zeolite X with various metasilicates

57 58 59 attempt 61 62 63 56 33.1 33.1 33.1 60 17.7 17.7 17.7 33.1 - - - 33.1 - - - 103 103 103 77.0 - - - 103 - - - - 26.4 26.4 26.4 - 730 730 730 - 463 463 463 730 4.35 4.35 4.35 742 4.35 4.35 4.35 4.35 1.28 1.28 1.28 4.35 1.28 1.28 1.28 1.28 96.6 96.6 96.6 1.28 96.6 96.6 96.6 96.6 0 12th 12th 96.6 0 0 12th 0 90 90 90 0 90 90 90 90 24 12th 24 90 4th 12th 12th 9 - ΐ 17.5 7th - i 18.7

Raw materials
Sodium aluminate
(ql, 1.21 Na ₂ O • Al ₂ O ₃ • 12.2 H ₂ O), sodium metasilicate pentahydrate, g. Sodium metasilicate nonahydrate, g. Sodium metasilicate anhydrous, g .. water, g

Molar ratio

SiO ₂ : Al ₂ O ₃

Na ₂ O: SiO ₂

H ₂ O: Na ₂ O

Aging time, hours

Reaction temperature, ^{0 C,}

Response time, hours

emotion

Product received

Zeolite B

Zeolite C

Zeolite X

amorphous product

Isobutane adsorption capacity, g / 100 g

17.7

26.4 463

4.35 1.28 96.6

12 90 16

557/437

19th

Table 13 Preparation of Zeolite Y

65

67

attempt
68 I 69

71 j 72

Raw materials
Sodium aluminate

(1.21 Na ₂ O • Al ₂ O ₃ • 12.2 H ₂ O), g sodium aluminate

(1.3 Na ₂ O · Al ₂ O ₃ · 12 H ₂ O), g .. sodium metasilicate pentahydrate, g. Colloidal silica

(SiO ₂ · 7.7 H ₂ O), g

Sodium hydroxide, g

Water, g

Molar ratio

SiO ₂ : Al ₂ O ₃

Na ₂ O: SiO ₂

H ₂ O: Na ₂ O

Aging time, hours

Reaction temperature, ° C

Response time, hours

Product received

Zeolite B

Zeolite C

Zeolite Y

amorphous product

38.9 96.7 96.7 96.7 39.8 39.8 424 49.6 - - - - , . ". 265 540 400 400 400 169.6 149.6 80.7 31.4 31.4 31.4 6250 - 256.5 228 228 228 - 20th 602 27 8th 8th 8th 1412 2.0 10 0.42 0.35 0.35 0.35 8th 90 1.12 33 45 45 45 1.16 0 30th 17th 17th 0 0 90 90 O 90 90 90 90 0 8th 90 48; 72 16 72 90 5 4th

39.8 636

3110.4

Claims (2)

Patent claims: 1. Process for the production of crystalline synthetic zeolites with molecular sieve and Ion exchange properties by combining aqueous sodium aluminate and sodium silicate solutions to a reaction mixture with a molar ratio in one of the ranges a), b) or c) a) b) c) SiO ₂ : Al ₂ O ₃ Na ₂ O: SiO ₂ H ₂ O: Na ₂ O characterized in that sodium metasilicate pentahydrate Na ₂ O · SiO ₂ · 5H ₂ O of particular activity in a ratio to other silicate components, expressed as Na ₂ O · SiO ₂ · 5H ₈ O: SiO ₂ , of 1 is used as the silicate component , 0: 0 to 1.0: 76.0 used and the reaction mixture without aging below -0.06 to 4.0 0.7 to 20.0 15.0 to 200.0 2.0 to 30.0 0.4 to 6.5 10.0 to 150.0 8.0 to 30.0 1.0 to 3.0 10.0 to 120.0 half of the crystallization temperature at temperatures between 30 and 120 ° C, in particular between 50 and 100 ° C, brings to crystallization. 2. The method according to claim 1, characterized in that that the reaction mixture is brought to a molar ratio in one of the ranges a), b) or c) a) b) c) SiO ₂ : Al ₂ O ₃
Na ₂ O: SiO ₂
H ₂ O: Na ₂ O 0.19 to 2.7 0.85 to 9.7 30.0 to 200.0 2.8 to 8.0 0.7 to 5.0 35.0 to 120.0 8.0 to 20.0 1.0 to 3.0 35.0 to 90.0 adjusts. 3. The method according to claim 1 and 2, characterized in that the ratio of Na ₂ O ■ SiO ₂ · 5H ₂ O: SiO _{2 is set} to 1: 0 to 1: 0.7. 4. The method according to claim 1 to 3, characterized in that only sodium metasilicate pentahydrate is used as the silicate component and the Na ₂ O: SiO ₂ ratio in the reaction mixture is equal to or greater than 1. Documents considered: German Auslegeschrift No. 1138 383. 809 557/437 5.68 © Bundesdruckerei Berlin