DE3521675A1 - SYNTHESIS AND USE OF PREFORMED ZEOLITHS - Google Patents

Description

Zeolites are crystalline aluminosilicates that correspond to the following general formula: - M AlO ₂ (SiO ₂ ) χ H ₀ O) I, where M is an alkali or alkaline earth element of valence η and r represents the atomic ratio Si / Al. The structure consists of tetrahedra AlO, and SiO ₇₁ , which are connected to each other

4 4

Oxygen peaks are connected. The arrangement of the tetrahedra in space forms polyhedra that delimit a network of channels, cages or cavities. The cations M place themselves at the points of the structure where they can balance the negative charges that the AlO.-tetrahedra have. The arrangements of the tetrahedra AlO. and SiO ₄ may be different and thus there are a large number of

15 different zeolite structures.

This family of products gives rise to numerous industrial ones Applications mainly in two general domains, adsorption and dor catalysis.

Due to their increased microporosity, the zeolites are used as adsorbents, for drying, for separation of gaseous mixtures and the like.

The cations can easily be exchanged, which offers the possibility of producing solid acids, a Form under which the zeolites are most often used as catalysts or catalyst carriers.

The zeolites are generally obtained by one or mixing multiple sources of silicon and aluminum with one or more inorganic or organic bases.

They are obtained in the form of powder most frequently, the average diameter of the particles is generally below 100 microns (100 x 10 ^-6 m).

It can be seen that for large scale use,

—R—

as in adsorption or catalysis, it is advantageous to use molded products because of the problems the loss of batches caused by fine powders. The methods of agglomeration of zeolite powders are in State of the art well known. They generally require the addition of a binder that allows them to be formed and gives the product sufficient mechanical strength. The consequence is that the purity of the products reduced by the addition of this binder, which does not have the special properties of zeolites, and that the effectiveness of the molded product is so deteriorated.

US Pat. No. 3,119,660 describes the preparation of zeolites starting from already formed kaolin to obtain preformed zeolites.

The present invention permits the production of extrudates containing 100% zeolite. Besides, the mechanical strength of these products improved. Classic products made by molding zeolite with the addition of Binders are obtained, contain the minimum amount of binder so as not to deteriorate their activity too much, however, this is detrimental to mechanical strength.

So a compromise has to be found between the degree of purity and mechanical strength. The mechanical Strength is also an essential parameter for an industrial product if this product, be it an adsorbent or a catalyst is to be filled into a fixed bed or even more so into a circulation bed. the Circulation bed or fluidized bed processes have become more and more important for refining and are very demanding wear-resistant catalysts. But even in the fixed bed process, the mechanical strength is sufficient to make it too great To avoid loss of filling of the unit. In addition, the catalyst is regenerated more and more outside the unit, with the result that the catalyst is subjected to numerous manipulations, what

-9- 352167b

1 requires good mechanical strengths.

The zeolites of the present invention have, although they contain no binder, excellent mechanical properties, especially due to the degree of resistance against crushing and the amount of abrasion (the method will be described later) are evaluated are difficult to obtain using traditional molding techniques.

Another aspect of the invention relates to obtaining zeolites of small crystallite size. It can actually be advantageous to use a zeolite for a catalytic application, which consists of very fine There are crystals whose mean size is e.g. 0.1 to 0.3 μΐη (0.1 to 0.3 χ 10 ~ m). Such a product does not present the serious problems of crystallization, however the separation of the crystals from the mother liquors is extremely difficult to synthesize. Very long times of filtration or centrifugation are an obstacle to the industrial production of this type of product.

A method described in the present invention allows these problems to be avoided and directly Obtaining zeolites, the crystallites of which are very small and incompatible, with a synthesis in the form of powder.

The invention allows large shapes to be obtained Strength, which consist of 100% pure zeolite, a zeolite whose crystallite sizes are generally below 1 μπι lie.

The zeolites can be characterized using various methods be identified which chemical analysis, X-ray diffraction, adsorption various Molecules ^ such as η-hexane and cyclohexane ^ include and the sizes the crystallites can be determined by scanning electron microscopy and the mechanical strength by measuring the abrasion

1 and the compressive or crush strength can be determined.

Chemical analysis enables the content of silicon and aluminum as well as the proportion of cations to be determined. 5

X-ray diffraction determines the distances "d" that exist between the lattice planes of the crystals exist, as well as the relative intensities that correspond to each distance, being these relative intensities are expressed based on the most intense radiation in the diagram. The pair distance / Intensity is characteristic of every zeolite, although it changes small as a function of its structure can show cations present.

The adsorption capacities are determined in a conventional Mac Bain type apparatus. The zeolites are activated under a pressure of 5 Torr at about 400 ⁰ C. Then the sample is at the desired temperature, often at 20 ⁰ C, with a known partial pressure of the to be adsorbed

20 product brought into contact.

The crystallite sizes can be assessed by scanning electron microscopy using the following method. After crushing of the grain, the powder is placed on a sample carrier and then metallized with gold and passed into a microscope Camebax type introduced by CAMECA.

Two tests are carried out for mechanical strength: a measurement of the crushing of grain with grain and a measurement of abrasion.

The crush (compressive) strength is determined by progressive concern a growing load on the grain. The apparatus used is a press with a moving piston of the ERWEKA brand. The measurement is carried out on 30 grains and the arithmetic mean of the values is calculated. For extrudates, the index is expressed as the ratio between the compressive force required for breaking

in kilograms (or in Newtons) and the length of the extrudate expressed in millimeters.

A second method of evaluating the mechanical properties of the product is to measure the abrasion of a bed of grains as a function of the pressure exerted on that bed. The measuring method is as follows: 20 cm ^{3 of} grains are placed in a cylinder 50 mm high and 27.6 mm inside diameter. The grains are covered with 5 cm ³ steel balls 4.5 mm thick. An increasing pressure is applied gradually to these pieces of steel by means of a piston. The fines obtained from different prints are separated by sieving and weighed. The fines are those particles that pass through the mesh of a sieve with openings equal to 2/3 of the characteristic smaller dimension of the initial grain. The pressure resistance is represented by the value of the pressure, expressed in megapascals, at which 0.5% fines are obtained, a value obtained by interpolation on a diagram based on the content of fines obtained at different pressures, is created.

The present invention relates to preformed synthetic zeolites from the group zeolite Y, zeolite omega, offretite, Erionite, Zeolite L and Ferrierite, these zeolites being produced starting from a first starting material based on at least one product that contains at least aluminum or silicon. This starting product can 3Q be crystalline or amorphous. It can be through a previous Treatment of crystallized or amorphous zeolite, the zeolite used being natural or synthetic and can be of any crystallite size.

Natural zeolites include analcime, chabazite, clinoptilolite, ferionite,, faujasite, ferrierite and mordenite to name. These zeolites rarely have a high degree of purity and can be mixed and accompanied by

find amorphous products. It may be of interest to use them directly in the state of pounded grains that have passed through Grinding of the mineral are obtained.

5 Among the synthetic zeolites one can find zeolite A,

the zeolites X and Y and call mordenite for those who are actually on the. Market are available. One can possibly use other zeolites, provided that their Si / Al atomic ratio is lower than that of the product to be obtained. The X-ray diffraction spectra of the faujasites X and Y are given in French patents 1,117,756 and 1,231,239, respectively.

The diffraction spectrum of mordenite is in an article by SAND et al in Adv. Chem. Ser. ACS. WASHINGTON DC (1971) 101 page 12 stated. The diffraction spectrum of zeolite A. is shown in U.S. Patent 2,882,243.

All of these zeolites can, at least in part, be exchanged with cations other than their original cations, like K, Li; NH. , H, where the degree of exchange between 0 and 100%.

The zeolites can also be subjected to a treatment for the depletion of aluminum according to conventional methods the technology can be modified.

It is also possible to use extrudates or granules or spheres or other forms of amorphous material as the first starting material synthetic silica or alumina. These products can be synthesized for this purpose and are also available in stores.

It is also possible to use a clay of the kaolin or metakaolin type.

It is also possible to use a mixture of the aforementioned products. In particular, the zeolites can easily with the help of a binder, e.g. an aluminum oxide or

1 tone can be / be shaped.

According to the invention and with a view to obtaining a preformed synthetic zeolite, the preformed Product brought into contact with at least one liquid organic or inorganic base selected from the group Lithium hydroxide, potassium hydroxide, sodium hydroxide, ammonia and the hydroxides of tetraalkylammonium, 2 B. the hydroxides of tetramethyl-, or -ethyl

10 or -propyl- or -butylammonium is selected.

In this reaction medium containing the preformed material, the Si / Al atomic ratio of which is r. is , and at least one liquid base, one adds at least one product based on silicon dioxide, which can be, for example, an amorphous silicon dioxide or a colloidal silicon dioxide, around a preformed zeolite with the ratio Si / Al, r,., of more than r. to obtain, and this preformed zeolite obtained in this way an excellent mechanical strength

20 has speed.

The more specific synthetic conditions for these preformed zeolites are as follows: the atomic ratio Si / Al, r ,, of the preformed starting material should be between 0.5 and 90; the concentration of anions (OH) ~ der Base should be between 0.01 and 10 mol / l of the solution used, the molar ratio of the tetraalkylammonium cations to (OH) anions is between 0 and 0.5. The amount of silicon dioxide used should be between 0.1 and 30 g per gram of the anhydrous aluminosilicate material used. The weight ratio of the liquid phase . the preformed aluminum silicate starting material should be between 2 and 30, the treatment temperature between and 200 ° C and the treatment time between about 2 hours

35 and 200 days.

The atomic ratio Si / Al, r _f , of the zeolite obtained should be greater than the ratio r. and range from 1.5 to 100.

The products that can be prepared according to the invention include, in particular, the zeolites Y, Omega, Offretit, Erionite, L and Ferrierite.

The zeolite Y is characterized by a network of three-dimensional channels with openings of about 8 A (χ 8 ~ 10 m). It is generally obtained in sodium form with an Si / Al atomic ratio which, according to the invention, is between 1.5 and 3 and preferably between 2.0 and 2.7. Its X-ray diffraction diagram is given in Table 1 (extract from US Pat. No. 3,130,007); d is the space between two network levels, expressed in meters, and I / I _Q (or I / I) is the ratio, expressed in percent,

III Cl Λ

between the intensity of any radiation I and the intensity of the most intense radiation I _n or I. Man

U max

holds only the radiations that correspond to the circumstances

I / I or 1 / I _{n are greater} than 10. It is well known to max υ

that there are slight deviations in the distances α and in the ratios I / I _Q between one product and another. These deviations do not lead to a change in the structure, but are due to the replacement of certain cations by others or a deviation in the Si / Al ratio.

-15 table

d ⁹ (S) (in meters) 100 14.29 x ^{10 "10} 24 7.46 x ^{10 "10} 44
23
35
12th 5.68 x ^{10 "10}
4.76 x ^{10 "10}
4.38 x ^{10 "10}
3.9IxIO " ¹⁰ 47
37 3.77 x ^{10 "10}
3.3IxIO " ¹⁰ 16 3, O2x10 " ¹⁰ 21
48
20th 2.92xl0 " ¹⁰
2.86 x ^{10 "10}
2.77 x ^{10 "10} 19th 2.64 x ^{10 "10} 11th 2.59xl0 " ¹⁰

The zeolite Omega has a network of monodimensional channels ²⁵ with openings of about 8 Å (8 × 10 ~ m). It contains im

generally at least sodium ions and has an atomic ratio Si / Al which is generally between 2 and 6 for the present invention. His diffraction diagram showing the distances corresponding to the most intense radiations _; ³⁰ is given in Table 2 (extract from US-PS 3,578,723).

-16-Table 2

d 20th (in meters) 100 16.0 x10 " ¹⁰ 20th 9.18 x ^{10 "10} 30th 7.96 x ^{10 "10} 33 6.94 x ^{10 "10} 31 6.0IxIO " ¹⁰ 11th 4.73 x ^{10 '10} 69 3.97 x ^{10 "10} 28 3.82 x ^{10 "10} 26th 3.74 x ^{10 "10} 54 3.64 x ^{10 "10} 14th 3.54x10 " ¹⁰ 48 3.46 x ^{10 "10} 23 3.17 x ^{10 "10} 21 3.1 OxIO " ¹⁰ 13th 3, O5x10 " ¹⁰ 28 2.99 x ¹⁰ "10" 2.93 x ^{10 "10}

The offretite zeolite has a network of monodimensional channels with openings of about 6.5 (6.5 10 ~ ¹ ° m) and a narrower network perpendicular to the first. It is generally synthesized with at least potassium cations under an atomic ratio Si / Al between 2 and 8 for the present invention. Its diffraction diagram, which shows the distances corresponding to the most intense radiations, is given in Table 3.

-17-Table 3

d ¹⁷ I. (in meters) ll, 45 x ^{10 "10} 100 7.54x10 " ¹⁰ 17th 6.63 x ^{10 ~ 10} 55 6.3 OxIO " ¹⁰ 10 5.74xl0 " ¹⁰ 15th 4.57 x ^{10 "10} 27 4.34 x ^{10 '10} 43 3.76 x ^{10 "10} 89 3.59x10 " ¹⁰ 43 3.3IxIO " ¹⁰ 19th 3.15x10 " ¹⁰ 17th 2.93xl0 " ¹⁰ 10 2.35 x ^{10 "10} GO 2.68 x ^{10 "10} 19th 2.5IxIO " ¹⁰ 14th

'Erionite has a structure similar to that of Offretite, but with layers on different levels. The consequences of the layers are regular for pure erionite; if these layer sequences are irregular and the defects in the structure Corresponding to the base of Offretit you are dealing with Erionit T. It has a network of pores with openings of

- 1 0
4 to 5 Å (4 to 5 χ 10 m); the atomic ratio Si / Al can vary between 2 and 6 according to the present invention. Its X-ray diffraction diagram (the most intense radiations) is given in Table 4 (extract from US Pat. No. 2,950,952).

-18 table

d ^{T /} r (in meters) ¹ O (S) ll, 45 x ^{10 "10} 100 7.54x10 " ¹⁰ 13th 6.63 x ^{10 "10} 54 4.34 x ^{10 "10} 45 3.82 x ^{10 "10} 16 3.76 x ^{10 "10} 56 3.59x10 " ¹⁰ 30th 3.3IxIO ^'10 16 3.18 x ^{10 "10} 12th 3.15 x ^{10 '10} 18th 2.93 x ^{10 "10} 11th 2.87 x ^{10 "10} 38 -in
2.85x10 ^iU 45

The zeolite L which is a zeolite having pore openings of about 6.5 to 7 Å (6.5 to 7 m χ 10 ~ ¹⁰⁾ is generally between 2 and 4 from the atomic ratio Si / Al. Its X-ray diffraction spectrum (most intense radiation) is given in Table 5 (extract from US Pat. No. 3,216,789).

-19 table

d I / _T (in meters) I (C '\ 5.59x10 " ¹⁰ 100 11.2 OxIO " ¹⁰ 14th 11.8IxIO " ¹⁰ 15th 14.8 OxIO " ¹⁰ 25th 15.4 OxIO " ¹⁰ 11th 19.41x10 ^l 32 .20,2IxIO " ¹⁰ 13th 20.49xl0 " ¹⁰ 13th 22.72 x ^{10 "10} 30th 23.52xl0 " ¹⁰ 13th 24.3 OxIO * ¹⁰ 19th 25.58 x ^{10 "10} 23 27.33xl0 ~ ¹⁰ 14th 28.13 x ^{10 ~ 10} 34 29.06xl0 " ¹⁰ 22nd 29.55x10 ^iU 15th 30.7 OxIO " ¹⁰ 23 33.8 OxIO " ¹⁰ 19th

Ferrxerite is a zeolite with pore openings of about

5 to 5 ₇ 5 Å from the Si / Al ratio, which is generally between 3 and 100 for the present invention (atomic ratio), its X-ray diffraction spectrum (the most intense radiations) is given in Table 6 (excerpt from US Pat

4,017,590).

-20 table 6

I / ο (* ^J ) (in meters) 75 9.55x10 ~ ¹⁰ 52 7.13 x ^{10 "10} 25th -in
6.65x10 ^iU 20th 5.75 x ^{10 "10} 23 5.69 x ^{10 "10} 43 3.99 x ^{10 "10} 30th 3.93 x ^{10 "10} 54 3.78 x ^{10 "10} 33 3.65 x ^{10 "10} 100 3.55x10 " ¹⁰ 92 3.48 x ^{10 "10} 21 3.32 x ^{10 "10} 42 3.13 x ^{10 "10} 32 3, O3x10 " ¹⁰ 10 -in
2.48x10 ^iU

The parameters of the synthesis are given in Table 7.

Tables 8 to 13 show the necessary procedural, Features for the preparation of the preformed synthetic zeolites according to the invention and the main features of these synthetic zeolites (breadth and preferred ranges). Table 8 relates to the production of faujasite Y, table 9 the production of zeolite omega, table 10 the production of offretite, table 11 the production of erionite, table 12 the production of zeolite L and table 13 the

35 Manufacture of ferrierite.

1 Table 7

r. Atomic ratio Si / Al of the preformed starting aluminum

silikarts. 5 B Base used.

S ₁ weight ratio liquid phase / preformed starting alaminosilicate.

10 S ₂ concentration of (OH) ions (mol / 1).

S_ molar ratio of tetraalkylammonium cations / OH anions.

Q Amount of silica used (in grams of dry silica per gram of dry starting preformed aluminosilicate).

T temperature ( ⁰ C).

t treatment time of the preformed aluminosilicate with the base solution and the silicon dioxide (in days).

d size of the elementary crystals of the zeolite obtained, in micrometers (1 μια = 10 m).

x- atomic ratio Si / Al of the zeolite obtained.

ω ο

to

to

preformed Γ i ^S l before
admitted ^S 2 before
admitted ^S 3 before
admitted Q before
admitted T before
admitted t before
admitted d before
admitted r _f before
admitted B. gang aluminum
minosili-
cat wide before
admitted breil 2 ireit 1 ireit 0 riding 0.5 wide 80 wide 3 wide 0.1 breil 2 0.8 0.9 2 until 0.2 until 0 until 0.1 until 60 until 1 until 0.02 until 1.5 until A. until until until 25th until 8th until 0.05 until 20th until 100 until 10 until 10 until 2.7 1.4 1.2 30th 10 0.1 30th 120 20th 50 3 . NaOH 0.9 1 H ti It dd » M. Il Ii X until until Il H η Il Il Il ■■ " .NaOH + LiC 1.6 1.5 40 0.2 Hydrocide ■
from Tetra
alkyl
Ammonium amorphous
Kieselr 0.5 '0.8 Il ti ti 20th until 0.1 until M. Il acid / alu "until until * · It ti until HO until 40 " oxide 2.7 2.5 140 200 0.9 0.9 Kaolin Il M. Il " until until Il It ti " " 1.1 1.1

TABLE 8

Manufacture of faujasite Y.

10

15 20 25 30 35

k U D. CM Xl X
O _{+ +} SiJ = I. B. _ ο ω O P. until (O OX OO XX X φ
OXO OH I P
rH -rf H ul N ιη
O IS mo (α ■ «- φ ι «; _e cn ο ω
> J- ¹ φ M. • Η - '- = It. 1 > ι 0 norp
reading
Sure ^ I Xl η —— '- • 'E > a X in 4Y CM Xl 1 O in I.
O M. ιη CM _m m O η O * Η Xl OO S. + i O Ul
• Η (- <ul 4-
ί. Λ O O Xl ιη * —I I / I
Location
τ Λ Xl ο * W. / pr- N 140 ^Λ Q) until O CVJ jQ • a Xl _ο ■ Η ug ο Ul br « N Xl U) evor- m ΙΛ S. S. O ■ ° • Η sr O U Λ 4Y O
* - < O I. ο IGO - S. O
CM O a = X O ΙΛ O Φ O • rl O
CM O χι M. £ S. O O 1-4
O S. ω S. n O X) Xl , 01 X I.
U ρ ο Ul
Ή O S. O
P. N Xl ΓΟ φ " Z ο Ul Xl + J O 1 Ui fH S. S. O 'J ω = N O η _ v ο ΙΛ Λ cn ■ rl IA CO • Η r S. Xl 4Y M. I. σ CM O ρ Ul CO ο Xl O ι /> dl cn ι-Ι S. σ> _m * - * Xl ο Ul in U ₁ O _Λ r- * ij Xl ιη φ
You co CM O \ «- · η 3 ο Ul -Q I. N φ ο G Xl ro _ _ -H
r-f ΙΛ ■ Η «C χι CM P I 4Y »—I U ^ Λ υι η
ο> O
C G ■ p- Ο · B m »ιο iX> "CM O ^Λ ι- " t χ: ■ HO SO

M Tue

ω ο

to
ο

CJi

CJt

before hair dryer
end
gangsalu
mincsili wide before
admitted ^S l before
admitted ^S 2 before
admitted ^S 3 before
admitted Q before
admitted T before
admitted t before
admitted d before
admitted ^r f ■■ Il It before
admitted B. A. 0.8
until
1.4 0.9
until
1.2 porridge « 3
until
25th > ride 0.2
until
8th : ride 0.01
until
0.3 quarrel 0.5
until
20th wide 140
until
180 wide 0.8
until
C. wide 0.1
until
10 breil 3
until
7th \
. KOH
. KOH ⁺
KaOH
. KOH +
LiOH ^-
•. KOH +
After τ
I LiOH
pydroxide
iron tetra
klkyl-
(Ammonium X 0.9
¥, ^ε 6 1
^b i. ^S 5 2
until
30th M. 0.1
until·
10 Il 0.01
until
0.5 Il 0 _: l
until
3ü » 100
until
200 Il 0.6
until
10 η 0.02
until
50 H 2
until
8th H Y 1.6
until
3.2 1.7
until
■ 3 U It H Il η 11th · ' Il Il Il Il H Il M. ■ · amorphous
Gravel1-
s5ure / Al
minium
oxide 0.5
,-until
5 0.8
until
4th H H H Il H » ■ · Il 40
until
130 11th 0.2
until
■ 10 Il " Il kaolin 0.9
until
1.1 0.9
until
1.1 ti H H Il Il II ■ · 20th
until
200 It 0.1
until
200 It Il 11th Il Il Il Il Il ·.

TABLE 10 Preparation of Zeolite Offretite.

co
ο

to
cn

to
ο

cn

preformed
te s off Y r i ^S l Il Il Il before ^S 2 before ^S 3 before Q before T before 1 before d before ^r f before B. gangs a Iu- wide before wide admitted wide admitted wide admitted wide admitted wide admitted porridge admitted wide admitted wide admitted minosili-
cat admitted 3 0.2 0 0.5 140 0.8 0.1 3 amorphous 0.8 0.9 2 until ' 0.1 until 0 until· 0.1 until lOO until 0.5 until 0.02 until 2 until A. pebble until until until 2 B until 8th bia 0.008 until 20th until 180 until 5 bie 10 until 5 acid / alt 1.4 1.2 30th 10 0.01 30th 200 8th 50 6th .KOH minium
ovi rl 0.9 1 " H Il .KOH + _f H Il " Il NaOH Λ until until .KOH + kaolin 1.6 1.5 LiOH .KOH + 1.6 1.7 K ' Il Il Il « M. » HaOH + until until H H Il H H ti Il LiOII
• 3.2 . 3 iydroxide 40 0.2 Il Il 0.5 0.8 Il Il Il 20th until 0.1 until It Il ilkyl- until until H Il ti until 100 until 40 unraonium "5 200 200 0.9 0.9 ti " ti Il until until Il H " ti ^11th 1.1 1.1

TABLE 11 Preparation of Zeolite Erionite.

co ο

to ο

cn

preformed ■ riding 1 ^S l before S, before ^S 3 before Q before T before t before Il Il d before jreit before B. \ . KOH before jreit admitted wide admitted wide admitted admitted admitted admitted admitted admitted . KOH + gangsalu- 0.8 admitted 3 0.2 0 wide 0..5 wide 70 wide 0.8 wide 0.05 2 2.5 NaOH minosili-
cat until 0.9 2 until 0.1 bie 0 until until until until until until until . KOH + 1.4 until until 25th bie 8th until 0.01 0 1 2ü 50 180 0.5 8th 0.01 5 4th 3.5 LiOH A. 0 9 1.2 30th 10 0.05 until until until until . KOH +
NaOH + bi" 1 It Il ■ · 30th 200 M. 10 Il IC » Il " LiOH 1.6 until Il M. Il Hydroxide" X 1.5 " - Il Il ran tetr; 1.6 ilkyl- until 1.7 Il II ti " ti Il " " It taaonium 3.2 until H Il Y 0.5 3 " » Il 0.8 It Il Il I. M. Il ■ ι Il amorphous " until Il I. Pebble- 3.5 until Il Il Il Il acid / Alv 0.9 3 miniuro-
ηχΐ, ίΐ 0.9 Il Il Il _M. M. until Il H Il 1.1 until H kaolin 1.1

M (Ti I

TABLE 12

Manufacture of Zeolite L. _t

ω ο

to O

cn

CJi

iorgeforni-
: it out wide before ^S l before ^S 2 • ti before ^S 3 before Q riding before T before t before d before ^r f before B. jangsalu- admitted wide admitted riding admitted wide admitted admitted riding admitted Three admitted Three admitted 3 riding admitted ninosili-
:at 0.8 U, 9 3 0.1 0.01 0.1 0.5 200 0.2 0.05. 4th until until 2 until 0.01 until 0.01 until until until 180 until 0.1 until 0.01 until 3 until Λ 1.4 1.2 until 25th until Il 4th until 0.3 30th 20th until 350 until 2 until 10 until 40 0.9 1 30th 5 0.4 350 5 5U 100 . NaOH until until Il II It " ^11th Il Il " Il . ! IaOH -> ,, 1.6 1.5 Il Il Il " •1 Il Il Il LiOH 1.6 1.7 3 * 2 * until Il Il Il Il 11th Il Il hydroxide Y 4th ³ Il Il Ii " Il Il Il of Tetr; until • 4.5 alkyl amorphous until Il Il ■ I " Aimaoniurr. pebble
acid / alu C. " minium 0.5 until 0.8 UJ 0, 2 90 until Il Il II until until Il Il kaolin 0.9 35 » Il SO 3) ti until 0.9 0.1 0.5 1.1 until Ii until until " 1.1 ^M. .10 20th

TABLE 13 Production of Zeolite Ferrierite.

co FTl

The synthetic zeolites thus obtained can be used in applications such as sorption, heterogeneous Relate to catalysis and cation exchange.

they can be used as they are, but can are generally subject to certain modifications necessary for the application envisaged, e.g. at least one pre-treatment. Among the pretreatments necessary for the preformed synthetic zeolites can be, for example cation exchange, thermal treatment with e.g. different atmospheres in the Call calcination. The zeolite obtained after synthesis and washing can be calcined, especially for disposal possibly used for the synthesis of organic cations that are also present in the structure, e.g. of the tetrapropylammonium type or tetrabutylammonxum. These can be used for sorption, catalysis or ion exchange applications preformed synthetic zeolites can be exchanged with any other possible cation.

In particular for catalytic applications and in particular for acid catalysis, it can be advantageous to remove the alkali cations present in the structure and to replace them with protons, which is usually done by one or more cation exchanges with ionizable ammonium salts such as nitrate, sulfate, chloride, acetate or equivalents he follows. The ammonia is then removed by calcination with or without water vapor and with or without gas purge in a temperature range from 300 to 900 ⁰ C. The treatments can lead to modifications of the zeolite which are known and are called treatments for stabilization or ultra-stabilization. In order to obtain zeolites in protonic form, it is also possible to carry out treatments with organic or inorganic acids, which also partially or completely free the crystal network from aluminum. The depletion of aluminum with gelling agents or by treatments, in the vapor phase, with silicon tetrachloride, hydrochloric acid or other equivalent methods, can also be used.

1 perform bindings.

It can also be interesting to introduce other cations, especially cations of the alkaline earths, the rare earths, 5 or the metals of groups VIB, VIIB, VIII, IB, HB, IHA, IVA, VA, VIA.

For catalytic applications that require bifunctional catalysts, i.e. the association of an acidic Function with a metal function (a phase called active) can be one or more metal compounds or non-metal compounds introduce according to known methods, the ion exchange, impregnation in the dry state, vapor deposition and the like. The metallic or non-metallic precursor compound can optionally at the time the synthesis of the preformed zeolite.

There are numerous uses for this type of shaped zeolite in sorption, ion exchange and in the Catalysis.

The zeolites according to the invention are particularly suitable for catalytic applications. To improve the quality

Because of the cold behavior of gas oil, it can be advantageous to reduce this Sections of a treatment under hydrogen pressure with a To subject the catalyst to the invention produced catalyst consists. The catalyst can be at least one noble metal or non-noble metal of the group

30VIII, and / or a metal of one or more other groups of the periodic table of elements included; the carrier of the catalyst may, for example, be based on Be offretite, ferrierite or erionite, with the preferred zeolites being offretite and ferrierite. Generally suitable These types of catalysts are good for catalytic cracking reactions in the presence or absence of one Matrix or other permanent connection.

Another application concerns the improvement of the octane number of fuels by cracking normal paraffins, contained in the mixture. The quality of a reformate can be improved by catalytic treatment with Zeolites produced according to the invention. The catalyst can consist of offretite, ferrierite or erionite, with the preferred zeolites are ferrierite and erionite and can contain small amounts of at least one Group VIII metal, which can be a precious or non-precious metal.

The aromatic conversion reactions are also carried out with advantage by using zeolites prepared according to the invention. So you can see the disproportionation of toluene, the isomerization of xylenes, the alkylation of toluene-methanol and the alkylation of benzene-ethylene to name.

The hydrocracking of medium to heavy cuts can advantageously be carried out in the presence of zeolites prepared according to the invention. The catalyst may contain a Group VIII metal, optionally accompanied by a Group VIB metal. The process takes place under a hydrogen pressure between 20 and 200 bar and at temperatures between 220 and 450 ^° C.

The conversion of methanol is also a transformation which is possible with a catalyst whose support contains at least one of the zeolites prepared according to the invention. This reaction, which is carried out under pressure below 10 bar and at a temperature between 300 and 550 ^° C., leads to the formation of condensation products of methanol. The process can be optimized to either use light olefins which essentially contain 2 to 4 carbon atoms per molecule or to use one as a fuel base.

to obtain gc bares mixture.

The dehydrocyclization of paraffins is also an application according to the invention. She can with advantage

Zeolite L produced according to the invention are carried out, which mainly contains potassium ions. It is sufficient to introduce at least one Group VIII metal, preferably platinum, possibly accompanied by another metal, e.g. the group

5VIIB. The application takes place under the same conditions as for catalytic reforming and with a load that contains a high proportion of paraffins for processes with a high aromatic content.

10 The following examples illustrate the invention.

Example 1: Production of a zeolite Y (faujasite Y).

Method 1

To 40 g of an extrudate of zeolite A (r. = 0.95) is added 230 g colloidal silica with 40% by weight silica and 670 ml sodium hydroxide solution with a concentration of 2.1 M. The synthesis parameters (see Tables 7 and 8) are the following:

20S ₁ = 21.35; S ₂ = 1.65 mol / l; S ₃ = 0; Q = 2.3. After heating to 100 ^° C. for 7 hours, the extrudates are filtered, washed and dried, which, according to X-ray diffraction, consist of faujasite Y with an atomic ratio Si / Al, r _f of 2.65. The crushing grain on grain gives a value of 18.3 N / mm and

The compressive strength in the bed is 1.3 MPa, compared to 3.3 N / mm and 0.9 MPa for zeolite A. The adsorption capacity for benzene at 30 ^° C. and 35 Torr partial pressure of a sample which had been desorbed ^{up to 300 ° C. under vacuum} , is 20.4% by weight. The BET specific surface area is 880 m ² / g. According to micros-

₃₀ copic examination, the crystallite size is about 0.2 μΐη (0.3 χ 10 ~ ⁶ m).

Method 2

35 to 63 g of amorphous extrudates containing 70% silica and 30% Containing aluminum oxide (r. = 1.98) add 819 g of water, 75 g of sodium hydroxide in biscuits and 227 g of colloidal Silica with 40% by weight silica. The synthesis para-

meters are the following (see Tables 7 and 8): S = 15.16; S ₉ = 1.96; S_ = 0 and Q = 1.44. After 5 days of aging at 4O ⁰ C for 24 hours, the mixture is brought to 100 ⁰ C. The extrudates are then filtered, washed and dried. The diffraction spectrum corresponds to that of faujasite Y (r _f = 2.30).

Method 3

50 g of extrudates of kaolinite (r. = 1) are mixed with 280 g of colloidal silica with 40% by weight of silicon dioxide, 30 g
Caustic soda and 840 ml of water mixed. The synthesis parameters are as follows (see Tables 7 and 8): S ₁ = 20.16;
S ₀ = 1.74; S_ = 0 and Q = 2.24. After i-days of aging

, r 2 3

40 ⁰ C and 5 days of heating at 100 ⁰ C wira filtered, washed and dried. The diffraction spectrum corresponds to
that of zeolite Y (r = 1.245).

Example 2: Preparation of Zeolite Omega. 20th

Method 1

5 g extrudates of zeolite 4 A (r. = 1) are mixed with 105 ml of a solution added to each 6.1% wt .-% in 1.68% * °, and 31.8% of sodium hydroxide, tetramethylammonium hydroxide and silica contains. The synthesis parameters correspond to Table 9 and are as follows: S ₁ = 21.0; S ₂ = 2.38 mol / l; S ₃ = 0.106; Q = 9.32 g / g.

After heating to 170 ^° C. for 24 hours, the extrudates are filtered, washed, dried and calcined ^{at 600 ° C.} 9.4 g of the extrudates of Zeolite Omega vom
Atomic ratio (r) Si / Al = 3.54 according to the X-ray

diffraction is of great purity. 35

The crushing grain on grain is 21.2 N / mm and the
Compressive strength in bed is 1.4 MPa compared to 8.3 N / mm and 0.9 MPa for zeolite 4 A.

The size of the elementary crystals is according to scanning electron microscopy between 0.08 and 0.8 μΐη.

Method 2

3.76 g of amorphous silica, 1.76 of caustic soda in cookies and 32 ml of a 0.13 M solution of tetramethylammonium hydroxide are added to 2.5 g of extrudates of NaY zeolite with a ratio of r. = 2.6. The synthesis parameters are as follows: S ₁ = 12.8; S ₂ = 1.51 mol / l; S ₃ = 0.086; Q = 1.50 g / g.

The mixture thus prepared is heated for 36 hours in an autoclave at 17O ⁰ C. After filtering, washing and drying, 3.7 g of zeolite omega (r _f = 3.7) are obtained.

Method 3

5 g of extrudates of kaolinite (r- = 1) are covered with 95 ml of a 2Q solution which contains 6% by weight, 1.5% by weight and 30% by weight of sodium hydroxide, tetramethylammonium hydroxide and silicon dioxide, respectively. The synthesis parameters are as follows: S ₁ = 19.0; S ₃ = 1.67; S ₃ = 0.099; Q = 7.83. After heating to 170 ^° C. for 24 hours, the extrudates are filtered, washed and dried and calcined ^{at 600 ° C.} The crushing grain on grain is 21.9 N / mm and the compressive strength in the bed is 1.4 MPa compared to 9.9 N / mm and 0.9 MPa for the starting kaolinite (r _f = 3.8).

30 Example 3: Production of Offretit. Method 1

50 g of extrudates of zeolite NaY having an atomic ratio Si / Al of 2.5 is suspended in 200 ml of a molar solution of ammonium nitrate at 8O ⁰ C for 14 hours retained. After filtration and washing, this operation is repeated twice. The solid phase is then separated from the solution

separated, washed with water and ^{dried at 10O 0} C for 4 hours. After calcining at 550 ^° C. for 3 hours, 41 g of extrudates of zeolite HY are obtained.

25 g of a ^ 2 M solution of

Potassium hydroxide, 5 ml of a 20 wt .-% solution of Tetramethylamtnonium- \ hydroxide and 7.5 g of colloidal silica with 40 wt .-% silica.

The synthesis parameters that agree with Table 10 are fol
Q = 1.2 g / g.

are the following: S ₁ = 14.4; S ₂ = 1.69 mol / l; S ₃ = 0.179;

The whole is ^{heated to 170 °} C. in an autoclave for 24 hours. After cooling, the extrudates are filtered, washed with water, ^{dried at 100 °} C. for 3 hours and then calcined ^{at 550 ° C. for 3 hours.} The extrudates produced in this way show a diffraction pattern analogous to that of an offretite with an atomic ratio r _f Si / Al of 4.5. The mean value of the crushing grain on grain is 10.6 N / mm. For the starting zeolite NaY it was 5.3. The compressive strength in the bed is 1.58 MPa compared to 1.05 for the starting material. The adsorption capacity for cyclohexane was 6.5 wt .-% at 2O ⁰ C under a pressure of 65 Torr. After four successive cation exchanges in solutions of ammonium nitrate, followed by calcination at 500 ^° C., the adsorption capacity is 8.9% by weight, which shows the excellent purity of the product. The potassium content is 2.1%.

An examination by scanning electron microscopy shows that the mean size of the elementary crystals of the zeolite is around 0.3 μΐη lies.

35 Method 2

100 g extrudate of zeolite 4 A with an atomic ratio of r. Si / Al = 1 are 3 times with 500 ml of a molar solution of

Ainmoniumacetat exchanged at 60 ⁰ C for 24 hours. After washing with water and drying at 100 ^° C. for 3 hours, the extrudate is ^{calcined at 500 °} C. for 4 hours. 780 g of extrudate are obtained in this way. The synthesis parameters are as follows: S ₁ = 21.5; S ₂ = 3.02; S ₃ = 0.19; Q = 9.75.

40 g of this extrudate are mixed with 860 ml of a solution which contains 9.1% by weight, 3.46% by weight and 31.5% by weight of potassium hydroxide, tetramethylammonium hydroxide and silicon dioxide, respectively. After 24 hours of heating at 17O ⁰ C in an autoclave, the extrudate is filtered, washed and dried and calcined at 550 ⁰ C for 4 hours. Are thus obtained 84 g of offretite 6.8 wt .-% cyclohexane at 2O ⁰ C under 65 mm of mercury absorbed.

15th

The mean value of the crushing grain on grain is 29 N / mm compared to 8.3 N / mm for the zeolite 4 A. The compressive strength in bed is 1.6 MPa versus 0.0 MPa for the Zeolite 4 A (r = 3.85).

20th

Method 3

To 5 g of kaolin (r. = 1) (synthesis parameters: S ₁ = 8; S, = 4.89; S_ = 0.091; Q = 5.8) are added 24 g of potassium hydroxide, 1.95 g of tetramethylammonium chloride, 29 g of amorphous Silica and 40 ml of water and bring the mixture to 170 ^° C. for 24 hours. The extrudate obtained is then filtered, washed and dried. This gives 9.1 g of offretite which absorbs 8.2% of η-hexane at 20 ^° C. below 95 mm Hg (r, = 3.8).

The crushing grain on grain is 23 N / mm and the compressive strength in bed is 1.4 MPa versus 9.9 N / mm and 0.9 MPa for the starting kaolin.

Method 4

35

To 2.5 g extrudate of zeolite NaX with the ratio Si / Al r.

= 1.1 are added 44 g of water, 6.21 g of amorphous silica, 5.23 g of potassium hydroxide and 1.6 g of tetramethylammonium chloride

and heating the mixture for 24 hours at 17O ⁰ C. After filtration, washing and drying, an extrudate of offretite from the Si / Al ratio (r _f) = 3.9. The synthesis parameters were as follows: S ₁ = 17.6; S "= 2.45; S "=

5 0.135; Q = 2.48.

Method 5

3.7 g of sodium hydroxide, 2.15 g of potassium hydroxide, 6 ml of a 10% strength by weight tetramethylammonium hydroxide solution and 16.4 g of colloidal silica with 40% by weight are added to 5 g of amorphous extrudate which contains 75% silicon dioxide and 25% aluminum oxide % Silica. The mixture produced in this way is ^{heated to 140 °} C. for 24 hours. The extrudate is then filtered, washed, dried and ^{calcined at 530 °} C. for 4 hours. Are thus obtained 8.64 g of offretite extrudate of 8.2% cyclohexane at 2O ⁰ C under 65 mm Hg absorbed. The synthesis parameters are as follows: r _i = 2.55; S ₁ = 3.8; S ₃ = 7.18; S ₃ = 0.0048; Q = 1.31;

20 ^(r f ^{= 4} ' ⁷⁾

Example 4: Production of Erionite.

Method 1

10 g of amorphous extrudate containing 80% silica and 20% alumina is mixed with 91 ml of water, 4.75 g Sodium hydroxide, 2.57 g potassium hydroxide and 6.84 g amorphous Silica mixed. The synthesis parameters are the following

₃ Q and correspond to Table 11: S ₁ = 9.1; S "= 1.81 mol / l; S- = 0; Q = 0.68 g / g (r. = 3.4). After heating to 140 ^° C. for 24 hours, 7.6 g of extrudate of erionite with an atomic ratio of Si / Al = 3.95, which is free from zeolite L according to the X-ray diffraction spectrum and electron microscopy, is obtained. To

gg desorption under vacuum at 300 ^° C., the product adsorbs 8.2% η-hexane and 1.3% cyclohexane.

The crushing grain on grain is 12.4 N / mm compared

10.1 for the starting product and the compressive strength 12.5 MPa versus 8.9 MPa.

Method 2 5

Mix 5 g of NaY zeolite extrudate with an atomic ratio of r. = 2.45 with 3.45 g of caustic soda in cookie form, 2.87 g of potassium hydroxide, 6.56 g of amorphous silica and 50 ml of water. The synthesis parameters are: S ₁ = 10; S ₂ = 2.75 mol / l; S ₃ = 0; Q = 1.31 g / g. After 36 hours of heating at 170 ^° C., a zeolite of the erionite type is obtained according to X-ray diffraction (r_ = 3.5).

Method 3

To 2.5 g of zeolite NaX with the ratio r, Si / Al = 1.1 are added 46 g of water, 12.10 g of amorphous silica, 5.42 g of caustic soda and 4.40 g of potassium hydroxide in cookie form. After 48 hours of heating at 170 ⁰ C, the extrudate is filtered, washed and dried for 3 hours at 12O ⁰ C. 4.15 g of erionite, which is free from zeolite L and a ratio τ, are obtained. = 3.2 has. The synthesis parameters are as follows: S ₁ = 16; S ₂ = 4.65; S ₃ = 0; Q = 4.84.

25 Method 4

5 g of kaolin (r. = 1), which was previously formed by tabletting, are mixed with 80 g of water, 22 g of amorphous silica, 10 g of caustic soda and 8 g of potassium hydroxide. After 48 hours of heating at 170 ^° C., the tablets are filtered, washed and dried. They show a diffraction spectrum that agrees with that of erionite, with a ratio r of 3.2. The synthesis parameters are the following:

= 16; S ₂ = 4.91; S ₃ = 0; Q = 4.4.

"JO-

1 Example 5: Preparation of Zeolite L. Method 1

50 g extrudate of zeolite 3 A (r. = 1) are mixed with 1020 ml of a solution which contains 9.8% potassium hydroxide, 0.2% sodium hydroxide and 32% silicon dioxide. The production parameters are according to Table 12: S ₁ = 20.4; S ₂ = 2.48 mol / l; S ₃ = 0; Q = 9.27 g / g. The mixture is left in an autoclave ^{at 160 ° C. for 18 hours.} The extrudate is then filtered, washed and dried. The diffraction spectrum corresponds to that of zeolite L. The adsorption capacity for benzene at a partial pressure of 70 Torr is 16.5%. The ratio r _f Si / Al = 3.05 and the content of

15 potassium is 13.0%.

The crushing grain on grain is 20.9 N / mm and the compressive strength in the bed is 1.2 MPa instead of 8.1 N / mm or 0.9 MPa for the starting material zeolite 3 A. The mean grain size, observed under the electron microscope, is 0.4 μΐη (average).

Method 2

20 g of spherical kaolin are mixed with 52.5 g of potassium hydroxide, 2 g of sodium hydroxide, 110 g of amorphous silica and 150 ml of water. The mixture is ^{heated to 170 °} C. for 24 hours and then the spheres are filtered and washed. The diffraction spectrum corresponds to that of zeolite

30 L (r _f = 3). The synthesis parameters are as follows: r _± = 1; S ₁ = 7.5; S ₃ = 6.25; S ₃ = 0; Q = 5.5.

Method 3

50 g of amorphous extrudate containing 75% silicon dioxide and 25% Containing aluminum oxide are combined with 71 g of potassium hydroxide, 2 g of sodium hydroxide and 230 g of colloidal silica 30 wt% silica mixed. The mixture is 2 hours

heated ^{to 150 °} C. for a long time. The extrudate is filtered, washed and dried. The diffraction spectrum corresponds to that of zeolite L (r _f = 3.2). The synthesis parameters are: x _± = 2.55; S ₁ = 3.68; S ₃ = 7.15; S ₃ = 0; Q = 1.38.

Example 6: Manufacture of Ferrierite.

Method 1

10 g extrudate of mordenite Na with the ratio Si / Al (r.) = 5 are mixed with a solution which contains 23 ml of 1.08 M tetramethylammonium hydroxide, 4 g of caustic soda in the form of cookies and 44 g of colloidal silica with 30% by weight of silicon dioxide . After 16 hours of heating at 250 ^° C., the solid phase is filtered off, washed and dried. This gives an extrudate of zeolite with a Si / Al ratio of 7.5, the diffraction spectrum of which is that of pure ferrierite. The synthesis parameters are as follows: S ₁ = 5.82; S ₂ = 2.21; S ₃ = 0.221; Q = 1.32; χ = 10.2.

Method 2

10 g of an extrudate of NaY zeolite with a Si / Al ratio (r. = 2.4) are mixed with 9 g of amorphous silica, 1/7 g of caustic soda in the form of cookies, 1.91 g of tetramethylammonium hydroxide. Pentahydrate and 45 ml of water. After 16 hours of heating at 25O ⁰ C, the extrudate is filtered, washed and dried for 3 hours at 120 ⁰ C. The ferrierite extrudate obtained has a Si / Al ratio = 5 (r _f ).

QQ The synthesis parameters are as follows: S ₁ = 4.5; S ₉ = 1.17; S ₃ = 0.198; Q = 0.90.

Method 3

4 g of colloidal silica are added to 5 g of amorphous extrudate which contains 75% silicon dioxide and 25% aluminum oxide with 40 wt .-% silicon dioxide, 23 ml of molar sodium hydroxide solution and 1.01 g of tetramethylammonium chloride. The synthesis parameters

are as follows and correspond to those of Table 13: S ₁ = 5.24; S ₂ = 1.0 mol / l; S ₃ = 0.286; Q = 1.0 g / g;

^r i ^{= 2 '55} *

After heating at 235 ^° C. for 22 hours, 10.1 g of ferrierite extrudate with a Si / Al = 7.9 (r) ratio are obtained.

The crushing grain on grain is 24.3 N / mm compared to 12.8 for the preformed starting aluminosilicate and the Compressive strength in bed is 1.6 MPa versus 1.1 MPa.

Example 7; Improving the cold behavior of gas oil with Help from Offretit.

The zeolite prepared according to Example 3, Method 1, is used after replacing it with ammonium nitrate which also contains 2.1% by weight of potassium. 0.4% by weight of palladium is then introduced by exchanging with the cationic precursor Pd (NH ₃ ). (NO,) - or palladium tetrammine nitrate in a solution of

-3
of concentration 5x10 M. The product is then ^{calcined in air at 500 °} C. and then reduced in a catalytic unit at 450 ^° C. under hydrogen.

A batch is then added, the characteristics of which are given in Table 14 below.

TABLE 14

distillation End point : 220 ⁰ C Density (20 °) : 0.876 : 305 ⁰ C Sulfur (wt%) : 1.60 Starting point : 328 ⁰ C 10% : 362 ⁰ C Nitrogen (ppm) : 260 50% : 375 ⁰ C 90% Pour point ( ⁰ C) : 21 (Standard AFNOR N 07 .042) Cloud point (° C): 21

.41- 352Ί675

The test v / ill be at a pressure of 40 bar a Raumgeschwindig- · ness of the feed (WH) in Volumenl ^ .schickung per volume of catalyst per hour of 1, a volume ratio H / gas oil of 500 1/1 and a temperature of 41O ⁰ C carried out. After working for 20 hours, the cloud point and the pour point of the 20O ⁺ fraction are respectively +3 and 0 ⁰ C. (The cloud point corresponds to the temperature at which the first crystals of paraffins appear; the pour point corresponds to the temperature at which the whole mass becomes solid).

Example 8: Improvement of the cold behavior of a gas oil with a ferrierite.

The extrudate of Example 6, Method 3, is ion-exchanged twice in succession with molar solutions of ammonium sulfate in such a way that the sodium content falls to 0.2% by weight, followed by an exchange with a solution of 0.1 M nickel acetate in this way that the content of nickel is 2.1% by weight. After calcination and reduction, the catalyst is subjected to the same test as described in Example 7, wherein the operating conditions are identical in that the temperature is 38O ⁰ C with the exception. After 200 hours, the cloud point is and the

25 Flow point of the cut 20O ⁺ +6 or +3 ⁰ C.

Example 9; Hydrocracking on zeolite Y.

The extrudate of zeolite Y, which was obtained according to Example 1, Method QQ, is subjected to four cation exchanges with 1.5 M solutions of ammonium chloride, so that the sodium content is brought to 1.8% by weight and then becomes Calcined at 600 ^° C. for 3 hours in a static atmosphere and then exchanged twice so that the sodium content is brought to 0.15% and finally it is calcined ^{at 700 ° C. in a static atmosphere.} 0.5% palladium is then introduced by impregnating the precursor palladium chloride. The catalyst is then exposed to dry air

calcined at 500 ^° C. and prereduced in the reactor of a hydrocracking pilot unit.

The characteristics of the batch are given in Table 15.

TABLE 15

Distillation starting point ( ⁰ C) point at 50% ( ⁰ C) end point ( ⁰ C)

210 332 435

S (wt%) 1.2%

N (ppm)

840

This batch is previously hydrotreated to the essential Eliminate some of the nitrogen compounds and sulfur compounds (less than 5 ppm nitrogen in the Outflow); the effluents which the previous one Hydrotreatment formed H_S and NH .. contain are on a zeolite catalyst under the following conditions:

Pressure (bar)

hourly volume velocity

(Liter / liter / hour)

H ₂ / batch (l / glass / l / liquid)

120

1.5 1000

At a temperature of 355 ⁰ C for 2 hours of operation, to obtain a conversion to products having a boiling point below 200 ⁰ C of 69% with a mass selectivity for the cut C _5-180 of 75%.

Example 10; Hydrocracking on Zeolite Omega

The zeolite of Example 2, Method 1, undergoes cation exchanges subjected, which reduce the sodium content to 0.5 wt .-%. 0.3% platinum is introduced by exchange with platinum tetrammine nitrate. The catalyst is at

500 ⁰ C calcined and prereduced under hydrogen at 500 ⁰ C in a test unit.

The catalyst is hydrocracked on the same hydrotreated batch as in Example 8 and subjected under the identical conditions except for the temperature.

At a temperature of 38O ⁰ C are obtained after 200 hours of operation the conversion into products with boiling points below 22O ⁰ C of 60% with a mass selectivity for the cut C ₅ - 18O ⁰ C of 78%.

Example 11; Conversion of methanol with offretite.

The zeolite of Example 1, Method 1 is 4 times successively subjected to cation exchange with 2 M ammonium nitrate and calcined and then dried at 500 ⁰ C. The potassium content is 2.1%.

15 cm ^{3 of} the extrudate is placed in a reactor and tested with a methanol charge. At atmospheric pressure with a space velocity of the feed (WH, in volume of methanol per volume of catalyst per hour) of 2 and a temperature of 400 ^° C., the results given in Table 16 are obtained after 10 minutes.

conversion TABEL 16 30th Weight—
yield: : CH ₃ OH 100% : Ethylene 29% Propylene 25% 35 Butene 11% methane
Ethane 6%
1% propane 16% butane 7% ^C 5 ⁺ 5%

-44-1 Example 12: Flavoring with Zeolite L.

The zeolite of Example 5, Method 1, is placed in a solution of potassium nitrate which contains the ion Pt (NH_). contains in an amount of 0.3 g / l. The product is calcined at 450 ⁰ C and loaded by impregnation with a solution of rhenium Re ₂ (CO) _"Q with rhenium. After filling into a catalytic unit, activation begins under hydrogen at 450 ^° C. and then passivation with a mixture of 1% hydrogen sulfide in hydrogen, followed by flushing at 500 ^° C. under hydrogen for 8 hours at a pressure of 10 bar.

A batch of η-hexane is then added under the following conditions: temperature: 470 ^° C.; Pressure: 3 bar; molar ratio hydrogen / η-hexane = 3; Hourly volume velocity = 3. After 25 hours of operation, the conversion of n-hexane is 93% and the weight selectivity of benzene is 78% and the selectivity of products C ₁ to C ₁ . is 3.1%.

Claims (16)

Claims 1. Preformed synthetic zeolite from the group zeolites Y, Omega, Offretite, Erionite, L and Ferrierite, the atomic ratio r _f Si / Al of which is between 1.5 and 100 and which is obtainable starting from at least one preformed aluminosilicate material from the group of natural or synthetic zeolites, amorphous silica-alumina and clays, this material having an atomic ratio r ^ Si / Al below r _f and between 0.5 and 90, and this preformed synthetic zeolite being obtainable by treating it Material with a product based on silica in the presence of at least
an organic or inorganic base from the group - D-8000 Munich 2 FOB 26 02 47 cable: tv onnn λ / Γί »« / 4 »Λ * ι ο« x * m _A u # « phone Telecopier Xnfotec 6400 B Telex Lithium hydroxide, sodium hydroxide, potassium hydroxide and of the hydroxides of tetraalkylammonium, and the concentration of OH * "anions between 0.01 and 10 mol / 1 solution is the molar ratio the tetraalkylammonium cations to the OH anions is between 0 and 0.5, the amount of silicon dioxide added to this material is between 0.1 and 30 g per g of the anhydrous aluminosilicate material, the weight ratio of liquid phase / anhydrous aluminosilicate material is between 2 and 30 and this treatment is between 50 and 200 ⁰ C is carried out for a period of about 2 hours to 200 days. 2. Process for the preparation of the zeolite according to claim 1, characterized in that starting from at least one preformed aliminosilicate material from the group of natural or synthetic zeolites, amorphous silicon dioxide-aluminum oxides and clays, which has an atomic ratio r _i Si / Al below r _f and this atomic ratio is between 0.5 and 90, treated with a product based on silicon dioxide in the presence of at least one organic or inorganic base from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and tetraalkylammonium hydroxides, the concentration of OH ~ anions _ is between 0.01 and 10 mol / 1 solution, the molar ratio of the tetraalkylammonium cations to the OH ~ anions is between 0 and 0.5, the amount of silicon dioxide added to this material is between 0.1 and 30 g per g of the anhydrous aluminosilicate material the liquid phase / anhydrous aluminosilicate material weight ratio is between en is 2 and 30 and this treatment is carried out between 50 and 200 ⁰ C for a period of about 2 hours to 200 days. 3. The method according to claim 2, characterized in that the natural zeolites from the group Analcin, chabazite, clinoptilolite, erionite, faujasite, Ferrierite and mordenite are chosen. 5 4. The method according to claim 3, characterized in that that the zeolite used is in the broken grain state. 5. The method according to claim 2, characterized in that the synthetic zeolite from the group zeolite A, Zeolites X and Y and mordenite is chosen. 6. The method according to any one of claims 2 to 5, characterized characterized in that the preformed material is a crystallized zeolite in which one Exchanging at least a part of at least one of its cations with at least one other Cation than that originally in this material "* Subjects existing cations, this cation ■ is chosen from the group consisting of K ⁺ , Li ⁺ , NH ₄ , H is chosen, and on this cation exchange thermal treatment can follow. 7. The method according to any one of claims 2 to 6, characterized characterized in that the material is a crystallized zeolite which is at least partially one Subjected to aluminum depletion treatment Has.
30th 8. The method according to any one of claims 2 to 7- for the production of a zeolite of the "faujasite Y" type starting from a material from the group zeolite A, faujasite X, amorphous silicon dioxide Alumina and kaolin by treating this Materials with at least one mineral base from the group of caustic soda, potassium hydroxide, lithium hydroxide, tetraalkylammonium hydroxide and the precursors of these Hydroxides, characterized in that the in Table 5 7 defined values for r ^, S-, S ₂ , S ₃ , Q, T, t, d and r- are within the broad limits shown in Table 8. 9. The method according to any one of claims 2 to 7 for the production of a zeolite "Omega" starting from a material selected from the group consisting of zeolite A, faujasite X and Y, amorphous silica-alumina and Kaolin by treating the material with at least one mineral base from the group of caustic soda, Potash lye, lithium hydroxide, tetraalkylammonium hydroxide 15 and precursors of these hydroxides, characterized in that that the values r., S-, S ₃₇ S ₃ , Q, T, t, d, r _f as defined in Table 7 are within the broad limits. according to Table 9. 10. The method according to any one of claims 2 to 7 for Production of a zeolite "Offretite" starting from a material from the group zeolite A, faujasite X and Y, amorphous silicon dioxide-aluminum oxide and kaolin by treating this material with at least one mineral base from the group of caustic soda, potassium hydroxide, lithium hydroxide, tetraalkylammonium hydroxide and precursors of these hydroxides , characterized in that the values r _if S-, S ₂ , S ₃ , Q, T, t, d, r _f according to Definition of Table 7 within the broad limits 30 according to table 10. 11. The method according to any one of claims 2 to 7 for Production of an "erionite" zeolite starting from a material from the group zeolite A, faujasite X. and Y, amorphous silica-alumina and kaolin by treating this material with at least one mineral base from the group of caustic soda, potash Lye, lithium hydroxide, tetraalkylammonium hydroxide and precursors of these hydroxides, characterized in that the values r ,, S., S_, S ₃ , Q, T, t, d, r _f as defined in Table 7 between the broad limits 5 according to Table 11. 12. The method according to any one of claims 2 to 7 for the production of a zeolite ¹ L "starting from a material from the group zeolite A, faujasite X and Y, amorphous silicon dioxide-aluminum oxide and kaolin by treating this material with at least one mineral base from the group Sodium hydroxide, potassium hydroxide, lithium hydroxide, tetraalakylammonium hydroxide and precursors of these hydroxides, characterized in that the values r., S-, S ^ * S ₃ / Q, T, t, d, r _f according to the definition of Table 7 between the broad limits according to Table 12. 13.Verfahren according to any one of claims 2 to 7 for the production of a zeolite "ferrierite" starting from a material from the group zeolite A, faujasite X and Y, amorphous silicon dioxide-aluminum oxide and kaolin by treating this material with at least one mineral base from the group Sodium hydroxide, potassium hydroxide, lithium hydroxide, tetraalakylammonium hydroxide and precursors of these hydroxides, characterized in that the values r-, S-, S ₂ 1 S ₃ , Q, T, t, d, r _f according to Öefiniton of Table 7 between the broad limits according to Table 12. 14. Use of a preformed zeolite according to claim 1 or prepared according to any one of claims 2 to 13 for sorption or for ion exchange or as a catalyst or catalyst support for the 'heterogeneous Catalysis, wherein the zeolite alone or in a mixture with at least one other component from the Group of carriers or matrices and the metals or non-metals is used. 15. Use according to claim 14, characterized in that that the preformed zeolite is subjected to at least one pretreatment before use, which Pretreatment from the ion exchange group, treatment with at least one organic or inorganic acid or thermal treatment is selected. 16. Use of a preformed zeolite according to claim or prepared according to one of claims 2 to 13, for catalytic cracking or hydrocracking, whereby the zeolite alone or in a mixture with at least one other constituent from the group of carriers or matrices and the metals or non-metals • is used.