FR2663920A1 - Zeolites based on silica and tin oxide and process for their synthesis - Google Patents

Abstract

The present invention relates to zeolites based on silica and tin oxide and to a process for their synthesis. The subject of the invention is a zeolite of general formula: in which x is between 0.1 and 3.0. This zeolite has a structure of MFI type and can be used especially in the field of catalysis.

Description

ZEOLITES BASED ON SILICA AND TIN OXIDE
AND THEIR SYNTHESIS METHOD
The present invention relates to zeolites based on silica and tin oxide.

 It relates more particularly to zeolites of MFI structure, and their method of synthesis.

 Zeolites are crystallized tectosilicates. The structures consist of assemblies of TO4 tetrahedra forming a three-dimensional framework by the pooling of oxygen. In zeolites of the aluminosilicate type which are the most common, T represents tetravalent silicon as well as trivalent aluminum. The cavities and channels of molecular size of this framework accommodate cations offsetting the charge deficit related to the presence of trivalent aluminum in tetrahedra. Trivalent elements such as gallium and more rarely boron or beryllium can substitute for aluminum.

 In general, the composition of the zeolites can be represented by the empirical formula M2 / nO; Y203; xZO2 in the dehydrated and calcined state. Z and Y respectively represent the tetravalent and trivalent elements of the TO4 tetrahedra; M represents an electropositive element of valence n, such as an alkaline or alkaline-earth metal, constituting the compensation cations; x can vary from 2 to theoretically the infinite in which case the zeolite is a silica.

 Each type of zeolite has a distinct porous structure. Variation in pore size and shape from one type to another causes changes in adsorbent properties. Only molecules with certain dimensions and shapes are able to enter the pores of a particular zeolite. Because of these remarkable characteristics, zeolites are particularly suitable for purifying or separating gaseous or liquid mixtures, such as, for example, the separation of hydrocarbons by selective adsorption.

 The chemical composition with, in particular, the nature of the elements present in the TO4 tetrahedra and the nature of the exchangeable compensation cations, is also an important factor intervening in the selectivity of the adsorption and especially in the catalytic properties of these products. They are used as catalysts or catalyst supports in the cracking, reforming and modification of hydrocarbons as well as in the preparation of many molecules.

 Many zeolites exist in nature: they are aluminosilicates whose availability and properties do not always meet the requirements of industrial applications. As a result, the search for products with novel properties has led to the synthesis of a large variety of zeolites essentially of the aluminosilicate type. Among the numerous examples of this type, mention may be made of: zeolite A (US-A 2882243), zeolite X (US-A 2882244), zeolite Y (US-A 3130007), zeolite L (FR-A 1224154) , zeolite T (FR-A 1223775), zeolite ZSM5 (US-A 3702886), zeolite ZSM12 (US-A 3832449), zeolite ZSM48 (EP-A 0015132).

 The zeolites are generally obtained from a reaction mixture which is converted, in a hydrothermal medium, by a dissolution-recrystallization process, the crystalline precipitate being, after separation and drying, calcined to give an active zeolite.

 The reaction mixture contains reagents capable of supplying the elements T to be incorporated in the framework of the zeolite, these reagents are generally aqueous gels containing oxides or hydroxides of the elements T.

 It also contains one or more mobilizers favoring the dissolution of these reagents and the transfer from the aqueous phase to the crystals of zeolites in formation, and a structuring agent allowing, by its incorporation, the formation of microporous spaces as well as a stabilization of the zeolite.

 As mobilizers, the OH anions are used. Thus, the reaction media are then characterized by a basic pH generally greater than 10. These media are well suited for the dissolution of the sources containing the silicon and aluminum elements, and generally all the elements giving soluble oxygen anions in a basic medium .

 When strong bases such as alkali metal hydroxides are used, very supersaturated media are obtained which allow rapid crystallization of the zeolites. But it is often difficult to control the formation of the desired crystallized phase which is, in many cases, metastable. On the other hand, a high crystallization rate can lead to the formation of defects in the framework of T04 tetrahedra, such as - T-O instead of T-O-T - bridges.

Finally, the presence of alkaline compensation cations in the channels and cavities is often troublesome in certain applications and it may then be necessary to exchange with other cations. This last disadvantage can be avoided by replacing these bases by other strong bases such as alkylammonium hydroxides which can play a structuring role at the same time. But the high price of these products limits their industrial use. The implementation of weaker bases such as amines which also have structuring properties, largely eliminates the disadvantages mentioned. But in this case, the concentration of OH-mobilizing anions may become too low, which leads to reaction rates that are too low.

 In addition, it is not always easy to incorporate certain metal species into the TO4 tetrahedra of the zeolite framework when the reaction medium is basic.

 An object of the present invention is to provide a novel zeolite based on silica and tin oxide.

 Another objective of the invention is to synthesize it according to a process avoiding the aforementioned drawbacks, from neutral or acidic reaction mixtures permitting the incorporation of tin into the framework of the zeolite and leading to totally dimensioned zeolite crystals. controlled.

The subject of the invention is zeolites based on silica and tin oxide having, after calcination, the following formula (I)
(sig6-x SnX) 0192 (I) wherein x is from about 0.1 to 3.0, preferably from 0.1 to 2.0.

 According to a new characteristic of the invention, zeolites belong to the family of pentasils and are similar to zeolites of structural type MFI. They are called stannozeosilites.

 According to another characteristic of the invention, the zeolites contain fluorine. The concentration of fluorine is generally between 0.01 and 1.3 by weight, before calcination. This fluorine can, however, be removed by hydrothermal treatment at pH> 7 without modifying the structure of the zeolite of the invention.

The invention also relates to a process for synthesizing zeolites according to the invention; this process comprises
(i) the preparation of a reaction mixture in aqueous media
containing a silicon source with oxidation state + 4,
a source of tin with the degree of oxidation + 4, fluorescent ions
rure and a structuring agent; the pH of this reaction mixture
nel being between about 1.5 and about 12.0,
(ii) crystallization of this reaction mixture by heating and
recovery of the crystallized precipitate,
(iii) calcining it at a higher temperature
at 4500C for the removal of the structuring agent occluded in
canals.

 Advantageously, the pH of the reaction mixture is between 6.0 and 11.0.

 The use of fluoride ions in the reaction medium, which act as a mobilizing agent, makes it possible to obtain a solubilization of the T (Si and Sn) species in a synthesis medium having a pH of less than 10. Thus, it It is possible to use NH4 + ions as compensation cations, which can be completely removed, if desired, during calcination. On the other hand, it is advisable to avoid the presence in the reaction medium of alkaline cations.

 In addition, the crystallization taking place in a medium at pH below 11, the nucleation rate is slower. Thus, it is possible to obtain zeolite crystals controlled by controlling the nucleation rate.

Many sources of the +4 oxidation state silicon element can be used. By way of example, mention may be made of silicas in the form of hydrogels, aerogels, xerogels, colloidal suspensions, silicas resulting from precipitation from solutions of soluble silicates or hydrolysis of silicic esters. as
If (OCH3) 4, Si (OC2H5) 4, the silicas prepared by extraction and activation treatments of crystallized or natural or synthetic amorphous compounds such as aluminum silicates, aluminosilicates, clays. It is also possible to use hydrolyzable tetravalent silicon compounds such as silicon halides or the like.

 Among the sources of tin oxide, there may be mentioned, by way of example, crystallized or amorphous tin oxides and hydroxides, the tetravalent tin compounds being able to be hydrolysed, such as halides (SnCl4), alcoholates, soluble salts of tin such as tin nitrate Sn (N03) 4.

 It is also possible to use as sources of silica or tin oxide, compounds comprising the elements Si and Sn such as, for example, glasses or gels based on the oxides of these two elements.

 The sources of silica and tin oxide may be engaged in soluble form or in pulverulent solids but also in the form of agglomerates such as, for example, pellets, extruded which can be converted into zeolite of desired structure without modification of form.

 The mobilizing agent F- is introduced in the form of acid and / or salt (s), not containing alkaline cations, and / or compounds releasing F- by hydrolysis. By way of example, mention may be made of hydrofluoric acid; hydrofluorines of amines; quaternary ammonium fluorides, for example NH (C 3 H 7) 3 F, N (C 3 H 7) 4 F; SiF4; SnF4; (NH4) 2SiF6.

 Ammonium fluoride or acidic ammonium fluoride are preferred salts. Indeed, these salts are very soluble and do not provide any undesirable element and, moreover, they are easily removed at the end of crystallization.

The structuring agents that are suitable for implementing the invention are
tertiary amines of formula (II):

in which
R 1, R 2, R 3, which are identical or different, represent a group
alkyl, linear or branched having 1 to 6 carbon atoms,
preferably a propyl or butyl group.

the quaternary ammonium salts of formula (III)

in which
R1, R2, R3, R4 identical or different represent a group
alkyl, linear or branched having 1 to 6 carbon atoms,
preferably propyl or butyl groups.

compounds of formulas (II) and (III) in which the nitrogen has
been replaced by a phosphorus atom.

 According to a preferred characteristic of the invention, the structuring agents are the compounds which can provide tetrapropylammonium or tripropylammonium cations.

 Advantageously, the structuring agent is introduced into the reaction mixture in the form of a quaternary ammonium salt of formula (III) or of the amine of formula (II); the pH being optionally adjusted using a base. Preferably, this base will have weak structuring agent properties so as not to compete with the added structuring agent.

Thus, the bases suitable for the invention are, by way of example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine.

The reaction mixture has the following composition, expressed in molar ratio
Sn / (Si + Sn) between 0.001 and 0.20, preferably between 0.005 and 0.1.

 Structuring agent / (Si + Sn) between 0.002 and 4, preferably between 0.04 and 1.

 F / (Si + Sn) between 0.02 and 6, preferably between 0.06 and 2.

H2O / (Si + Sn) between 4 and 400, preferably 10 and 200
When a base is used to adjust the pH, the molar ratio of base to (Sn + Si) is preferably less than 12, and preferably 0.1 to 8.

 The addition to this reaction mixture of crystalline seeds of determined structure, MFI, in a proportion that does not exceed a few percent by weight relative to the weight of SiO 2 + SnO 2 engaged, facilitates the crystallization of the zeolite. As crystallization seeds, it is possible to use any zeolite having the MFI structure, irrespective of its chemical composition.

It is preferable to use a zeosilite which is a zeolite equivalent to stannozéosilite, but containing only silicon in its framework. It is also possible to use stannozeosilite seeds originating from a previous manufacture.

 The crystallization of the zeolite can be obtained by heating the reaction mixture at a temperature between about 400C and about 2400C, preferably between 600C and 2200C for the time required for crystallization, according to a standard procedure of zeolite synthesis and known to the skilled person. As an indication, the heating time can be between 6 hours and 500 hours.

 This heating and crystallization are preferably carried out in a vessel or autoclave coated with a layer such as, for example, polytetrafluoroethane.

 The reaction mixture can be stirred or not.

 After crystallization, the precipitate obtained is collected, for example, by filtration.

 This precipitate is then heated after a possible drying, at a temperature above 4500C, preferably above 5000C, in order to decompose by calcination or thermal decomposition organic species contained in the precipitate, such as, for example, the structuring agent.

The stannozeosilite of the structural invention is thus obtained.
MFI.

The subject of the invention is also the zeolite obtained before calcination, hereinafter referred to as "zeolite precursor", which is a crystalline product of the zeolite type based on silica and tin oxide, corresponding to the following formula (IV)
(Sig6 ~ xSnx) O1g2t4 + 1 (S + F-) (IV) in said formula
x is between 0.1 and 3.0, preferably between 0.1 and 2.0.

 S + symbolizes the cation coming from the structuring agent.

 It more particularly represents a cation resulting from the amine of formula (II), a cation of quaternary ammonium type of formula (III), or these same compounds in which the nitrogen is replaced by a phosphorus atom.

 The identification of the zeolite NFI structure can be achieved in particular by the establishment of the diffraction pattern of the precursor which gives rise to it.

 The zeolite precursor of the invention has an orthorhombic crystalline system and an X-ray diffraction pattern defined in Table I.

 In this table, the extreme values of the different lattice equidistances dhkl are given and correspond to the limit concentrations of tin incorporated in the framework of the zeolite before calcination, or more precisely to the ratio Sn / (Si + Sn).

 This diffraction pattern can be obtained using a diffractometer using the conventional powder method with copper Ka radiation. From the position of the diffraction peaks represented by the angle 26 the Bragg relation is used to calculate the characteristic dhkl reticular equidistances of the sample.

The estimation of the measurement error (dhkl) on dhkl is calculated as a function of the absolute error A (28) assigned to the measurement of 26 by the Bragg relation. An absolute error A (20) equal to t 0.20 is currently accepted. The relative intensity I / Io assigned to each value of dhk is estimated from the height of the corresponding diffraction peak.

A scale of symbols is often used to characterize this intensity: FF = very strong, F = strong, mF = medium to strong, m = average, mf = medium to low, f = low, ff = very weak.

 The volume value VO of the crystallographic mesh of the zeolite before calcination is a function of the substitution of silicon by tin.

TABLE I
X-ray diffraction pattern

<tb> Extreme <SEP> values <SEP> I / Io <SEP> Extreme <SEP> values <SEP> I / Io
<tb><SEP> dhkl <SEP> (nm) <SEP><SEP> dhkl <SEP> (nm) <SEP>
<tb><SEP> 1,114-1,133 <SEP> F <SEP> 0,368-0,374 <SEP> mF
<tb><SEP> 0.988-1.008 <SE> F <SEP> 0.361-0.367 <SEP> mF
<tb><SEP> 0.969-0.983 <SEP> mF <SEP> 0.340-0.346 <SEP> m
<tb><SEP> 0.886-0.897 <SEP> f <SEP> 0.330-0.336 <SEP> m
<tb><SEP> 0.734-0.744 <SEP> m <SEP> 0.327-0.332 <SEP> m
<tb><SEP> 0.699-0.709 <SEP> f <SEP> 0.321-0.327 <SEP> mf <SEP>
<tb><SEP> 0.660-0.670 <SEP> f <SEP> 0.314-0.319 <SEP> ff
<tb><SEP> 0.627-0.637 <SEP> m <SEP> 0.310-0.315 <SEP> ff
<tb><SEP> 0.597-0.607 <SEP> m <SEP> 0.300-0.305 <SEP> m
<tb><SEP> 0.591-0.601 <SEP> m <SEP> 0.294-0.299 <SEP> m
<tb><SEP> 0.564-0.574 <SEP> m <SEP> 0.291-0.296 <SEP> mf
<tb> 0.548-0.557 <SEP> m <SEP> 0.282-0.287 <SEP> ff
<tb><SEP> 0.530-0.539 <SEP> ff <SEP> 0.276-0.280 <SEP> ff
<tb> 0.510-0.519 <SEP> ff <SEP> 0.270-0.274 <SEP> ff
<tb><SEP> 0.492-0.301 <SEP> mf <SEP> 0.257-0.261 <SEP> f
<tb><SEP> 0.454-0.462 <SEP> mf <SEP> 0.253-0.257 <SEP> f
<tb><SEP> 0.438-0.446 <SEP> ff <SEP> 0.248-0.252 <SEP> f
<tb><SEP> 0.432-0.440 <SEP> mf <SEP> 0.247-0.251 <SEP> f
<tb><SEP> 0.420-0.427 <SEP> m <SEP> 0.238-0.242 <SEP> f
<tb><SEP> 0.394-0.401 <SEP> mf <SEP> 0.203-0.206 <SEP> ff
<tb><SEP> 0.379-0.386 <SEP> FF <SEP> 0.198-0.202 <SEP> mf <SEP>
<tb> 0.372-0.379 <SEP> mF <SEP> 0.197-0.201 <SEP> m <SEP>
<Tb>
Said zeolite precursor can be obtained by the process comprising
(i) preparing a reaction mixture in an aqueous medium
containing at least one source of silicon with an oxidation degree
+ 4, a source of tin with oxidation + 4,
fluoride ions, a structuring agent; the pH of the mixture
the reaction is between 1.5 and 12.0, preferably
between 6.0 and 11.0.

(ii) crystallization of the reaction mixture and recovery
crystalline precipitate.

 The molar ratios of the different species in the reaction medium are those indicated above.

 The crystalline precipitate is advantageously washed to remove impurities and especially cations or anions not hooked or incorporated into the structure.

 This manipulable product is in particular and mainly used for the production of zeolite by calcination under appropriate conditions and determined according to the desired use of the zeolite.

 The zeolites of the invention can be used in the catalysis of numerous reactions such as, for example, disproportionation or alkylation reactions, hydrogenolysis and hydrogenation of petroleum fractions or in reforming processes.

 Other objects, features and details of the invention will appear more clearly in view of the following examples given solely for information and illustrative purposes.

Example 1
This example describes a synthesis of an acidic zeolite using F- ions as a mobilizing agent.

0.26 g of SnCl4 tin chloride is added dropwise with vigorous stirring to a solution containing
13.2 g of tetrapropylammonium bromide (TPA-Br),
11 g of ammonium fluoride NH4F,
- 120 g of water,
- 6 g of silica AEROSIL 130 sold by DEGUSSA.

 After homogenization of the gel, 0.12 g of a zeolite with structure NFI, namely a zeosilite, are added as crystallization seeds.

 The pH of the reaction mixture is 8.5.

The molar ratios in the reaction mixture are as follows
Sn / Si = 0.01; F / Si = 3.0; TPA + / Si = 0.5; H2O / Si = 70.

 The reaction mixture is transferred to an autoclave whose walls are sheathed with polytetrafluoroethane.

 It is heated for 1 day at 2000C.

 The pH of the medium at the opening of the autoclave is 9.0.

 After filtration, washing with water and drying at 800 ° C., 6.6 g of stannozéosilite precursor of pure MFI type are obtained, the X-ray diffraction pattern of which is in accordance with that given in Table I.

 The crystals obtained are rods of dimensions 5 x 1 pin.

 The chemical analysis of the product gives a fluorine content of 1.0%.

 The previously obtained precursor is calcined at 5500C for 6 hours, which makes it possible to eliminate the structuring agent and to restore the porosity of the stannozéosilite obtained.

EXAMPLE 2
A mixed gel containing the elements Si and Sn is prepared. For this purpose, 2.6 g tin chloride SnCl 4 in 20 g anhydrous methanol and then 15.2 g of Si (OCH 3) 4 silicon tetramethylate are slowly added with stirring. After homogenization, a solution containing 15 g of a 25% aqueous ammonia solution, 6 g of methanol and 10 g of water is added to this mixture. The caking of the gel is instantaneous. It is then redispersed in water and then evaporated and dried at 1200C. The powder obtained is rewashed with water to remove any ammonium chloride that may be formed. About 10 g of a mixed gel (SiO 2, SnO 2) with a Sn / Si molar ratio of 0.1 are thus obtained.

 This gel is dispersed in a solution containing 1.85 g of ammonium fluoride of NH4F, 3.32 g of TPABr, 36 g of water and 0.12 g of a zeosilite, zeolite with MFI structure as crystallization seeds. .

 The pH of the reaction medium is 7.

The molar ratios in the reaction mixture are
Sn / Si = 0.1; F / Si = 0.5; TPA + / Si = 0.125; H2O / Si = 20.

 This gel is heated for 6 days at 200 ° C.

 The pH of the medium at the opening of the autoclave is 9.5.

 After filtration, washing with water and drying, one obtains 8.6 g of solid whose analysis by X-ray diffraction reveals that it is a precursor of zeolite of the MFI type whose diagram complies with that given in Table I and that there is presence of crystalline impurity type SnO2 cassiterite (less than 10%).

 The crystals obtained are rods of dimension 8 x 2 pin.

 A point analysis performed by electron microprobe gives Si / Sn ratios inside the crystals between 20 and 60.

The chemical analysis of the product gives a fluorine content of 0.91%.

After calcination at 5500C for 6 hours, a stannozeosilite is obtained
Example 3
A mixed gel containing the elements Si and Sn is prepared as described in Example 2. This gel is dispersed in a solution containing 1.85 g of NH4F, 6.65 g of TPABr and 72 g of water.

 The pH is 7.5.

The molar ratios in the reaction mixture are
Sn / Si = 0.1; F / Si = 0.5; TPA + / Si = 0.25; H20 / Si = 40.

 This gel is heated for 6 days at 2000C in an oven equipped with a stirring system.

 The pH of the medium at the opening of the autoclave is 9.

 After filtration, washing and drying, 8.9 g of solid are obtained, the X-ray diffraction analysis of which reveals that it is an MFI-type zeolite precursor having a diagram according to that shown in the Table. And that there is a crystalline impurity of the type SnO2 cassiterite.

 The crystals obtained have a length of 1 to 10 μm for a width of 0.5 to 2 μm.

 After calcination at 5500C for 6 hours, stannozeosilite is obtained.

Claims (22)

1. A zeolite characterized in that it has the following general formula, after calcination  (Sig6-x Snx) 0192 wherein x is from 0.1 to 3.0, preferably from 0.1 to 2.0. 2. Zeolite according to claim 1, characterized in that the structure of the zeolite is of the MFI structure type. 3. Zeolite according to claim 1 or 2, characterized in that it contains between 0.01 and 1.3% by weight of fluorine, before calcination. 4. A method of manufacturing a zeolite according to one of the preceding claims, characterized in that it comprises the following steps  (i) the preparation of a reaction mixture in aqueous media  containing a silicon source with oxidation state + 4,  a source of tin at the oxidation state + 4, ions  fluoride and a structuring agent with molar ratios  Sn / (Si + Sn) between 0.001 and 0.20, F / (Si + Sn) between  0.02 and 6, structuring agent / (Si + Sn) between 0.002 and 4; the  pH of this reaction mixture being between 1.5  about 12.0, preferably between 6.0 and 11.0,  (ii) crystallization of the reaction mixture,  (iii) Recovery and calcination of the crystalline precipitate at a  temperature above 4500C. 5. Method according to claim 4, characterized in that the molar ratio Sn / (Si + Sn) is between 0.005 and 0.1. 6. Method according to one of claims 4 and 5 characterized in that the molar ratio F / (Si + Sn) is between 0.06 and 2. 7. Method according to one of claims 4 to 6, characterized in that the molar ratio structuring agent / (Si + Sn) is between 0.04 and 1. 8. Method according to one of claims 4 to 7, characterized in that the molar ratio H2O / (Si + Sn)) in the reaction medium is between 4 and 400, preferably between 10 and 200. 9. Method according to one of claims 4 to 8, characterized in that the pH of the reaction medium is controlled by the addition of a base containing no alkaline ions. 10. The method of claim 9, characterized in that the base is selected from the group comprising methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine. 11. The method of claim 9 or 10, characterized in that the molar ratio base / (Sn + Si) in the reaction medium is less than 12, preferably between 0.1 and 8. 12. Method according to one of claims 4 to 11, characterized in that the silicon oxide and tin oxide have a common source. 13. Process according to one of Claims 4 to 12, characterized in that the structuring agent mentioned above is chosen from the group comprising  tertiary amines of formula (II):

 a propyl or butyl group.  linear or branched having from 1 to 6 carbon atoms, preferably  R1, R2, R3, which may be identical or different, represent an alkyl group  in which

the quaternary ammonium salts of formula (III)  preferably propyl or butyl groups.  alkyl, linear or branched having 1 to 6 carbon atoms,  R5, R2, R3, R4 identical or different represent a group  in which  been replaced by a phosphorus atom.  compounds of formulas (II) and (III) in which the nitrogen has 14. Process according to one of Claims 4 to 11 and 13, characterized in that the source of silicon oxide is chosen from the group comprising hydrogels, aerogels or xerogels, colloidal silica suspensions, silicic esters, silicates soluble in water, silicas extracted from natural or synthetic crystalline compounds, hydrolyzable tetravalent silicon compounds such as silicon halides. 15. Method according to one of claims 4 to 11, 13 and 14, characterized in that the source of tin is selected from the group consisting of crystalline or amorphous tin oxides and hydroxides, halogens, alcoholates soluble salts of tin. 16. The method of claim 12, characterized in that the common source of tin oxide and silica oxide is selected from silica-based glasses and tin and mixed gels. 17. Method according to one of claims 4 to 16, characterized in that the fluoride ions are added to the reaction mixture in the form of hydrofluoric acid, amine hydrofluoride or quaternary ammonium, hydrolysable compounds releasing fluoride anions. 18. The method of claim 17, characterized in that the hydrolyzable compounds are fluorinated salts containing silicon or tin selected from the group consisting of tin fluorides and silicon fluorides. 19. Crystalline compound containing silica and tin oxide, characterized in that it corresponds to the following formula (IV)  (Si96xSnx) O192.4 + 1 (S + F-) (IV) in said formula  x is between 0.1 and 3.0, preferably between 0.1 and 2.0.  S + symbolizes the cation coming from the structuring agent. 20. Crystalline compound according to claim 19, characterized in that S + symbolizes a cation resulting from the amine of formula (II), a quaternary ammonium cation of formula (III), or those same compounds in which nitrogen is replaced by a phosphorus atom. 21. Crystalline compound according to one of claims 19 and 20 characterized in that it has an X-ray diffraction pattern defined in Table I. 22. Process for the preparation of the crystalline compound containing silica and tin oxide described in one of Claims 19 to 21, characterized in that it is obtained by a process comprising the following steps:  (i) Preparation of a reaction mixture in an aqueous medium  containing at least one source of silicon with an oxidation degree  + 4, a source of tin with oxidation + 4,  fluoride ions and a structuring agent with reports  Sn / (Si + Sn) molars between 0.001 and 0.20, F / (Si + Sn)  between 0.02 and 6, structuring agent / (Si + Sn) between 0.002 and  4; the pH of the reaction mixture being between 1.5 and  12.0, preferably between 6.0 and 11.0.  (ii) Crystallization of the reaction mixture (iii) Recovery of the crystalline precipitate.