FR2785201A1 - Synthesis of a zeolite of structural type EUO, useful for e.g. the preparation of isomerization catalysts for eight carbon aromatic hydrocarbons, with the aid of seeds of another zeolitic material - Google Patents

Abstract

The EUO structure zeolite, comprising zeolites EU1, TPZ-3 and ZSM-50, is synthesized in the presence of seeds of another zeolite of a different structural type and/or different chemical composition of the crystal lattice. The synthesis is also carried out in the presence of a structuring agent. The EUO zeolite comprises an element X (Si or Ge) and an element T, chosen from Fe, Al, Ga, B, Ti, V, Zr, Mo, As, Sb, Cr and Mn. In the synthesis, seeds of a zeolite material comprising an element X<1> (Si or Ge) and T<1> (Fe, Al, Ga, B, Ti, V, Zr, Mo, As, Sb, Cr or Mn) are used, such that X<1> / T<1> is less than 200, this zeolite differing from the EUO zeolite to be prepared. Independent claims are also included for the EUO zeolites prepared by the process and their uses, and preparation of catalysts containing the zeolites and their uses.

Description

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Technical field The present invention relates to a new process for preparing a zeolitic material with structure type EUO. EUO-structural-type zeolites include EU-1 zeolite, TPZ-3 zeolite, and ZSM-50 zeolite and generally have the following formula in anhydrous form: 0 to 20 R20: 0-10 T2O3: 0-100 XO2: where R represents a monovalent cation or 1 / n of a cation of valence n, X represents silicon and / or germanium, T represents at least one element chosen from aluminum, iron, gallium, boron, titanium , vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese.

Zeolites with structure type EUO are generally synthesized by mixing in aqueous medium a source of silica and / or germanium and a source of at least one element chosen from aluminum, iron, gallium, boron , titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese in the presence of at least one nitrogenous organic compound playing the role of structuring agent, or corresponding degradation products or precursors. The mixture is generally maintained at a certain temperature until the zeolite crystallizes.

PRIOR ART The EU-1 zeolite with structure type EUO, already described in the prior art, exhibits a one-dimensional microporous network, the pore diameter of which is 4.1 x 5.7 Å (1 = 1 Angstrom = 1.10-10 m) (Atlas of Zeolites Structure types, WM Meier and DH Oison, 4th Edition, 1996). On the other hand, NA Briscoe et al taught in an article in the journal Zeolites (1988, 8, 74) that these one-dimensional channels have side pockets with a depth of 8.1 A and a diameter of 6.8 x 5.8 A. The method of synthesis of EU-1 zeolite and its physicochemical characteristics have been described in patent EP 42 226. The method of synthesis comprises the mixture of a silicon and / or germanium oxide and of an oxide. of at least one element chosen from aluminum, iron, gallium and boron, in the presence of a structuring agent comprising at least one alkyl derivative of a polymethylene [alpha] - # diammonium, a degradation product of said derivative or precursors of said derivative.

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The synthesis of EU-1 zeolite from silicalite or EU-1 seeds is described in the literature (Casci, JL; Whittam, TV; Lowe, BM, Proc. Int. Zeolite Conf., 6 th (1984) , Meeting Date 1983, 984-904 Editors Oison, David, Bisio, Attilio, Publisher: Butterworth, Guildfold, UK).

US Pat. No. 4,640,829 relates to zeolite ZSM-50, which according to "The Atlas of Zeolites Structure types", W. M. Meier and D.H. Oison, 4th Edition, 1996, has the structure type EUO. Said patent discloses a mode of synthesis of ZSM-50 comprising mixing a source of alkali metal ions, dibenzyldimethylammonium ions or precursors thereof, silicon oxide, aluminum oxide and water.

Patent application EP 51 318 deals with the TPZ-3 zeolite, which has, according to "the Atlas of Zeolites Structure types", WM Meier and DH Oison, 4th Edition, 1996, the same EUO structural type as the EU zeolite. -1. The preparation of the zeolite comprises mixing a soluble alkali metal compound, a compound of 1,6N, N, N, N ', N', N'-hexamethylhexamethylenediammonium, a compound capable of yielding silica and a compound capable of giving alumina, at a temperature above 80 C.

Summary of the invention The present invention relates to a process for preparing a zeolite with structure type EUO comprising at least one element X chosen from silicon and germanium and at least one element T chosen from iron, aluminum, iron. gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, characterized in that seeds of at least one zeolitic material comprising at least an element X 'chosen from silicon and germanium and at least one element T chosen from iron, aluminum, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, l' antimony, chromium and manganese, said seeds being different from the EUO-structural-type zeolite which is prepared. The zeolite seeds used have an X '/ T' ratio of less than 200.

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Interest of the invention The process according to the invention makes it possible to reduce the crystallization time of the EUO zeolite after formation of the mixture and makes it possible to achieve a maximum yield of pure product, which provides a cost saving. The composition of the reaction medium can be wider, which provides a gain in flexibility.

Thus, the Applicant has discovered that the synthesis of a zeolite with structure type EUO characterized by the use of seeds of at least one zeolitic material different from the material which is sought to be synthesized made it possible in particular to obtain the advantages mentioned above. above, that is to say a saving of time, of yield of purer product and of flexibility of the composition of the reaction mixture.

Description of the invention The present invention relates to a process for preparing a zeolitic material with structure type EUO comprising at least one element X chosen from silicon and germanium and at least one element T chosen from iron, aluminum, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, characterized in that seeds of at least one zeolitic material comprising at least one at least one element X 'chosen from silicon and germanium and at least one element T' chosen from iron, aluminum, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, said seeds being different from the EUO-structural-type zeolite which is prepared. The zeolite seeds used have an X '/ T' ratio of less than 200.

The difference between the EUO-structural-type zeolite that it is sought to synthesize and the zeolitic material introduced as seeds lies either in the difference in structural type, or in the difference in chemical composition of the crystalline framework, or in the difference in structural type and difference in chemical composition of the crystal framework.

The preparation process according to the invention comprises the mixing in aqueous medium of at least one source of at least one element X chosen from silicon and

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germanium, of at least one source of at least one element T chosen from aluminum, iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, of at least one nitrogenous organic compound Q chosen from alkyl derivatives of polymethylene [alpha] - # diammonium, dibenzyldimethylammonium salts, an amine degradation product corresponding to said organic compound Q, precursors corresponding to said organic compound Q, and seeds of zeolitic material S. The invention is characterized in that at least one zeolitic material different from the EUO zeolite that it is sought to prepare is used as seeds. The reaction of the mixture is maintained until crystallization of the zeolite.

The alkyl derivative of polymethylene [alpha] - # diammonium, playing the role of organic structuring agent, used more particularly for the synthesis of EU-1 zeolite or of TPZ-3 zeolite, is defined by the formula: R1R2R3 N + (CH2) n N + R4R5R6, n being between 3 and 12 and R1 to R6, identical or different, possibly representing alkyl or hydroxyalkyl radicals having from 1 to 8 carbon atoms, up to five radicals R, to R6 possibly being from hydrogen.

Thus, it is possible to use seeds of at least one solid of structural type LTA such as zeolite A, of structural type LTL, of structural type FAU such as X and Y zeolites, of structural type MOR, of structural type MAZ, of type structural type OFF, structural type FER, structural type ERI, structural type BEA, structural type MFI such as ZSM-5 and silicalite, structural type MTW, structural type MTT, structural type LEV, structural type TON , of structural type NES such as zeolite NU-87, or a zeolite NU-85, NU-86, NU-88, IM-5 or a zeolite of structural type EUO of chemical composition of the crystalline framework different from the chemical composition of the crystalline framework of the EUO zeolite which is prepared, in particular with different X ′ / T ′ ratios, these being less than 200. Preferably, seeds are used for the synthesis of a zeolite of EUO structural type. zeolite seeds with structure type LTA, FAU, MOR, MFI, EUO of X '/ T' ratio less than 200.

The zeolite materials playing the role of seeds can be introduced at any time during the preparation of the zeolite that is to be synthesized. Germs can be introduced at the same time as the sources of the elements X

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and T, that the organic structuring agent Q, or the seeds can be introduced first into the aqueous mixture or else the seeds can be introduced after the introduction of the sources of the elements X and T and of the structuring agent. Preferably, the seeds are introduced after homogenization at least in part of the aqueous mixture containing the sources of the elements X and T and the structuring agent.

The zeolite materials playing the role of seeds can be introduced during the synthesis of the zeolite which it is sought to synthesize in several forms. Thus, the seeds can be introduced, after having undergone at least one of the stages chosen from the following stages: washing, drying, calcination and ion exchange. The seeds can also be introduced in the crude synthetic form.

The size of the seed particles can have an influence on the synthesis process and should preferably have the desired size. The term “zeolite seed particle” is understood to mean either a zeolite crystal or an aggregate of zeolite crystals. Thus, at least most of the seed particles introduced during the preparation of zeolitic material have a size of between 0.001 and 500 m, preferably between 0.005 and 250 m.

In a particular implementation, independent or not of the previous implementation, it may be advantageous to add to the reaction medium at least one alkali metal or ammonium salt P. Mention may be made, for example, of strong acid radicals. such as bromide, chloride, iodide, sulfate, phosphate or nitrate, or weak acid radicals such as organic acid radicals, for example citrate or acetate. This salt can accelerate the crystallization of EUO zeolites from the reaction mixture.

In the process according to the invention, the reaction mixture has the following composition, expressed in the form of oxide:

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X02 / T203 (mol / mol) at least 10 OH- / XO2 (mol / mol) 0.002 to 2.0 Q / XO2 (mol / mol) 0.002 to 2 Q / (M + + Q) (mol / mol) 0, 1 to 1.0 H2O / XO2 (mol / mol) 1 to 500 P / X02 (mol / mol) 0 to 5 S / XO2 (g / g) 0.0001 to 0.1 preferably, the reaction mixture has the following composition, expressed as oxides:
XO2 / T2O3 (mol / mol) at least 12
OH- / XO2 (mol / mol) 0.005 to 1.5 Q / X02 (mol / mol) 0.005 to 1.5
Q / (M + + Q) (mol / mol) 0.1 to 1.0
H2O / XO2 (mol / mol) 3 to 250
P / XO2 (mol / mol) 0 to 1 S / XOz (g / g) 0.0005 to 0.07 and, even more preferably, the reaction mixture has the following composition, expressed as oxides: X02 / T203 (mol / mol) at least 15
OH- / XO2 (mol / mol) 0.01 to 1
Q / XO2 (mol / mol) 0.01 to 1 Q / (M + + Q) (mol / mol) 0.1 to 1.0
H20 / X02 (mol / mol) 5 to 100 P / X02 (mol / mol) 0 to 0.25
S / XO2 (g / g) 0.001 to 0.04

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where X is silicon and / or germanium, T is at least one element selected from aluminum, iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, M + represents an alkali metal or the ammonium ion, Q represents the organic structuring agent, or the decomposition products corresponding to said derivative or the precursors of said derivative, S represents the zeolite seeds present in the raw form , dried, calcined or exchanged, with an X '/ T' ratio of less than 200, P represents the alkali metal or ammonium salt.

M and / or Q can be present in the form of hydroxides or salts of inorganic or organic acids provided that the OH- / XO2 criterion is met.

The quantity of seeds introduced relative to the quantity of oxide X02 is between 0.001 and 10%, and preferably between 0.05 and 7%, and even more preferably between 0.1 and 4%.

The synthesis of the EUO zeolite according to the process of the present invention is carried out using an organic compound Q playing the role of structuring agent.

N,N,N,N,N,N-hexaméthylhexaméthylène #-û) diammonium, par exemple l'halogénure, l'hydroxyde, le sulfate, le silicate, l'aluminate. In the case of the synthesis of EU-1 zeolite, the starting preferred alkyl derivatives of [alpha] - # polymethylenediammonium Q are, inter alia, the alkylated hexamethylene [alpha] - # diammonium derivatives and especially the methylated derivatives of 'hexamethylene a-co diammonium and even more preferably the salts of 1.6

N, N, N, N, N, N-hexamethylhexamethylene # -û) diammonium, eg halide, hydroxide, sulfate, silicate, aluminate.

Alkyl derivatives of polymethylene [alpha] - # diammonium can be obtained from precursors. Suitable precursors of the starting polymethylene α-diammonium alkyl derivatives include the related diamines together with related alcohols, alkyl halides, alkanediols or alkane dihalides together with alkylamines. They can be mixed as is with the other reagents or they can be preheated together in the

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reaction vessel preferably in solution before the addition of the other reagents necessary for the synthesis of the EU-1 zeolite.

In the case of the preparation of the ZSM-50 zeolite, the organic structuring agent Q can be a dibenzyldimethylammonium salt such as the halide, the hydroxide, the sulfate, the silicate or the aluminate.

Dibenzyldimethylammonium salts can be obtained from precursors.

Suitable precursors are benzyldimethylamine and benzyl halide or benzyl alcohol. They can be used as they are in situ or can be preheated together in the reaction vessel, preferably in solution, before the addition of the other reagents necessary for the synthesis of the ZSM-50 zeolite.

The preferred alkali metal (M +) is sodium. The preferred element X is silicon.

The preferred T element is aluminum.

The source of silicon can be any of those whose use is normally envisaged for the synthesis of zeolites, for example solid silica in powder, silicic acid, colloidal silica or silica in solution. Among the powdered silicas which can be used, mention should be made of precipitated silicas, especially those obtained by precipitation from a solution of an alkali metal silicate, such as Zeosil or Tixosil, produced by Rhône-Poulenc, pyrogenic silicas. such as Aerosils produced by Degussa and Cabosils produced by Cabot and silica gels. Colloidal silicas of various particle sizes can be used, such as those sold under the trademarks LUDOX from Dupont, and SYTON from Monsantos.

The dissolved silicas which can be used are in particular the soluble glasses or silicates marketed containing: 0.5 to 6.0 and especially 2.0 to 4.0 moles of SiO 2 per mole of alkali metal oxide and the silicates obtained by dissolving silica in an alkali metal hydroxide, a quaternary ammonium hydroxide or a mixture thereof.

The source of aluminum is most preferably sodium aluminate, but can also be aluminum, an aluminum salt, for example chloride, nitrate or sodium.

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sulfate, an aluminum alkoxide or the alumina itself which should preferably be in a hydrated or hydratable form such as colloidal alumina, pseudoboehmite, boehmite, gamma alumina, or trihydrates.

Mixtures of the sources mentioned above can be used. Combined sources of silicon and aluminum can also be used, such as amorphous silica alumina or certain clays.

The reaction mixture is usually reacted under autogenous pressure, optionally with the addition of a gas, for example nitrogen, at a temperature between 85 and 250 C until crystals of the mixture form. zeolite, which can last from 1 minute to several months depending on the composition of the reagents, the heating and mixing mode, the working temperature and the agitation. Stirring is optional, but preferable because it shortens the reaction time.

At the end of the reaction, the solid phase is collected on a filter and washed and is then ready for the following operations such as drying, calcination and ion exchange.

Thus, in order to obtain the hydrogen form of the zeolite of structure EUO, ion exchange can be carried out with an acid, especially a strong mineral acid such as hydrochloric, sulfuric or nitric acid, or with a compound such as ammonium chloride, sulfate or nitrate. Ion exchange can be accomplished by one or more dilution with the ion exchange solution. The zeolite can be calcined before or after the ion exchange, or between two ion exchange steps, preferably before the ion exchange in order to remove any absorbed organic substance, since the ion exchange is facilitated.

As a general rule, the cation (s) of the zeolite with structure type EUO can be replaced by any cation (s) of metals and in particular those of groups IA, IB, IIA, IIB, IIIA, IIIB (including rare earths ), VIII (including noble metals) as well as by lead, tin and bismuth (The periodic table is as in "Handbook of Physic and Chemistry", 76th edition).

The exchange is carried out using any water soluble salts containing the appropriate cation.

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The present invention also relates to the use of the zeolite as prepared according to the process of the present invention as an adsorbent for the control of pollution, as a molecular sieve for separation and as an acidic solid for catalysis in the fields of refining and processing. petrochemicals.

For example, when it is used as a catalyst, the zeolite of structure EUO can be associated with an inorganic matrix which can be inert or catalytically active and with a metallic phase. The inorganic matrix can be present simply as a binder to hold together the small particles of the zeolite in the various known forms of catalysts (extrudates, beads, powders), or it can be added as a diluent to dictate the degree of conversion in a process which would otherwise progress at too fast a rate leading to fouling of the catalyst as a result of excessive coke formation. Typical inorganic matrices include support materials for catalysts such as silica, various forms of alumina, and kaolin clays, bentonites, montmorillonites, sepiolite, attapulgite, fuller's earth, porous materials. synthetic such as Si02-Al203, SiO2-ZrO2, Si02-Th02, Si02-BeO, Si02-Ti02 or any combination of these compounds.

The EUO-structural-type zeolite can also be combined with at least one other zeolite and act as the main active phase or as an additive.

The inorganic matrix can be a mixture of different compounds, in particular an inert phase and an inorganic phase.

The metallic phase is introduced onto the zeolite alone, the inorganic matrix alone or the inorganic matrix-zeolite assembly by ion exchange or impregnation with cations or oxides chosen from among the following, Cu, Ag,, Ga, Mg, Ca, Sr, Zn, Cd, B, AI, Sn, Pb, V, P, Sb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Pt, Pd, Ru, Rh, Os, Ir and any other element of the periodic table of elements.

The catalytic compositions comprising the zeolite of structural type EUO can find their application in the reactions of isomerization, transalkylation and disproportionation, alkylation and dealkylation, hydration and dehydration, oligomerization and polymerization, cyclization. , flavoring, cracking and

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hydrocracking, reforming, hydrogenation and dehydrogenation, oxidation, halogenation, amine syntheses, hydrodesulfurization and hydrodenitrification, catalytic elimination of nitrogen oxides, formation of ether and the conversion of hydrocarbons and the synthesis of organic compounds in general, said reactions comprising saturated and unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated organic compounds and organic compounds containing nitrogen and / or sulfur, as well as organic compounds containing other functional groups.

The invention is illustrated by the following examples.

EXAMPLES 1 to 16: Synthesis of EU-1 (or TPZ-3) zeolite with an Si / Al ratio equal to 15 with hexamethonium bromide as organic structuring agent and zeolite seeds of different structure and / or Si / Al ratio , having an Si / Al ratio <200.

Examples 1 and 2 correspond to syntheses carried out without adding seeds for comparison. Examples 3 to 16 correspond to syntheses carried out with zeolite seeds, the characteristics of which are given below.

The zeolites added as seeds come in different cationic forms (Na, K, NH4, NH4 + TMA, Na + Hx, H) and in the form of particles of variable size (from 3 to 115 m for the median diameter Dv, 50). These seeds are different from the solid EU-1 synthesized at the level of the structural type and / or of the Si / Al ratio.

The synthesis mixture has the following composition: Si02 (mol) 60 Al203 (mol) 2 Na20 (mol) 10
HxBr2 (mol) 20
H20 (mol) 2800 germs / Si02 (g / g) 0 (ex. 1 and 2) or 0.02 (ex. 3 to 16)
Hx Br2 = hexamethonium bromide = Me3 N (CH2) 6 N Me3 2+ (Br ') 2

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<tb>
<tb> germs
<tb> Examples <SEP> zeolite <SEP> type <SEP> Si / AI <SEP> form <SEP> Dv, 10 <SEP> Dv, 50 <SEP> Dv, 90
<tb>

structural (mol/mol) (cations) (hum) (hum) (hum)

structural (mol / mol) (cations) (hum) (hum) (hum)

<tb>
<tb> 3 <SEP> (invention) <SEP> ZSM-5 <SEP> MFI <SEP> 14.3 <SEP> Na <SEP> 48 <SEP> 115 <SEP> 205
<tb> 4 <SEP> (invention) <SEP> ZSM-5 <SEP> MFI <SEP> 27.7 <SEP> H <SEP> 52 <SEP> 107 <SEP> 173
<tb> 5 <SEP> (invention) <SEP> ZSM-5 <SEP> MFI <SEP> 76.5 <SEP> H <SEP> 2.8 <SEP> 5.8 <SEP> 24
<tb> 6 <SEP> (invention) <SEP> ZSM-5 <SEP> MFI <SEP> 150 <SEP> H <SEP> 1.7 <SEP> 4.8 <SEP> 14
<tb> 7 <SEP> (comparative) <SEP> silicalite <SEP> MFI <SEP>> 500 <SEP> - <SEP> 1.4 <SEP> 2.7 <SEP> 5.2
<tb> 8 <SEP> (invention) <SEP> A <SEP> LTA <SEP> 1.0 <SEP> K <SEP> 1.1 <SEP> 5.3 <SEP> 11 <SEP>
<tb> 9 <SEP> (invention) <SEP> X <SEP> FAU <SEP> 1.3 <SEP> Na <SEP> 1.3 <SEP> 3.4 <SEP> 8.7
<tb> 10 <SEP> (invention) <SEP> Y <SEP> FAU <SEP> 2.8 <SEP> NH4 <SEP> 1.4 <SEP> 3.1 <SEP> 7.0
<tb> 11 <SEP> (invention) <SEP> mordenite <SEP> MOR <SEP> 118 <SEP> H <SEP> 5,1 <SEP> 15 <SEP> 26
<tb> 12 <SEP> (invention) <SEP> mazzite <SEP> MAZ <SEP> 3,6 <SEP> NH4 + TMA <SEP> 7,0 <SEP> 18 <SEP> 25
<tb> 13 <SEP> (invention) <SEP> EU-1 <SEP> EUO <SEP> 25.2 <SEP> NH4 <SEP> 3.0 <SEP> 16 <SEP> 26
<tb> 14 <SEP> (invention) <SEP> EU-1 <SEP> EUO <SEP> 69.7 <SEP> Na + Hx <SEP> 3.0 <SEP> 16 <SEP> 40
<tb> 15 <SEP> (invention) <SEP> EU-1 <SEP> EUO <SEP> 144 <SEP> Na + Hx <SEP> 3.2 <SEP> 17 <SEP> 33
<tb> 16 <SEP> (comparative) <SEP> EU-1 <SEP> EUO <SEP>> 500 <SEP> Na-Hx <SEP> 1.5 <SEP> 2.9 <SEP> 5.8
<tb>
TMA = tetramethylammonium Hx = hexamethonium Dv, X = diameter of the equivalent sphere of the particles such that X% volume of the particles have a size less than said diameter Solution A composed of silicon and structuring agent is prepared by diluting 12.03 g of bromide d hexamethonium (Fluka, 97%) in 57.42 g of water then adding 14.50 g of colloidal silica sol (Ludox HS40, Dupont, 40% Si02). 0.985 g of solid sodium hydroxide (Prolabo, 99%) and 0.715 g of solid sodium aluminate (Prolabo, 46% Al2O3, 33% Na20) are then dissolved in 7.18 g of water to form solution B .

Solution B is added to solution A with stirring and then 7.18 g of water. The mixture is mixed until homogenization and 0.116 g (Examples 3 to 16) of dried zeolite seeds are added (no addition of seeds for Examples 1 and 2). The resulting mixture is reacted in a 125 ml autoclave with stirring at 180 ° C. under the

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autogenous pressure. After cooling, the product is filtered and washed with 0.5 liter of demineralized water and then dried in a ventilated oven at 120 C.

The results of X-ray diffraction and chemical analysis are reported in Table 1 as a function of the addition of seeds or not and of the various zeolites added as seeds. The use of different zeolites with an Si / Al ratio of less than 200 as seeds (examples 3 to 6 and 8 to 15) leads to pure EU-1 zeolite (crystallinity of 100% 3, Si / Al ratio close to 15 ), of maximum yield (approximately 5%) in 96 hours at 180 C. Under identical conditions, the tests with zeolite seeds with an Si / Al ratio greater than 200 give a solid which is not completely crystallized in EU-1 zeolite (examples 7 and 16). Under identical conditions, the experiment without the addition of seeds (Example 2) does not produce the EU-1 zeolite. Thus, in Example 1, it is necessary to go up to 125 hours of synthesis time to allow the formation of the pure EU-1 zeolite and of maximum yield.

EXAMPLES 17 to 32: Synthesis of ZSM-50 zeolite with an Si / Al ratio equal to 125 with the precursors of dibenzyldimethylammonium chloride as organic structuring agent and zeolite seeds of different structure and / or Si / Al ratio, having an Si ratio / AI <200.

Examples 17 and 18 correspond to syntheses carried out without adding seeds for comparison. Examples 19 to 32 correspond to syntheses carried out with the seeds of zeolites identical to those used in the preceding examples.

The synthesis mixture has the following composition: Si02 (mol) 60 Al203 (mol) 0.24 Na20 (mol) 3.6 BDMA (mol) 6 BCI (mol) 6 H20 (mol) 1000 seeds / Si02 (g / g ) 0 (ex. 11 and 12) or 0.02 (ex. 13 to 20)

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BDMA = benzyldimethylamine BCI = benzyl chloride Solution C composed of silicon and structuring precursors is prepared by diluting 3.537 g of benzyldimethylamine (Fluka, 98%) and 3.274 g of benzyl chloride (Fluka, 99%) in 42.72 g of water then adding 38.43 of colloidal silica sol (Ludox HS40, Dupont, 40% Si02). 1.133 g of solid sodium hydroxide (Prolabo, 99%) and 0.227 g of solid sodium aluminate (Prolabo, 46% A1203, 33% Na20) are then dissolved in 5.34 g of water to form solution D Solution D is added to solution C with stirring and then 5.34 g of water. The mixture is mixed until homogenization and 0.307 g (Examples 19 to 32) of dried zeolite seeds are added (no addition of seeds for Examples 17 and 18). The resulting mixture is reacted in a 125 ml autoclave with stirring for 75-98 hours at 160 ° C. under autogenous pressure. After cooling, the product is filtered and washed with 1.5 liters of demineralized water and then dried in a ventilated oven at 120 C.

The results of X-ray diffraction and chemical analysis are reported in Table 2 as a function of the addition of seeds or not and of the various zeolites added as seeds. The use of different zeolites with an Si / Al ratio of less than 200 as seeds (examples 19 to 22 and 24 to 31) leads to pure EU-1, ZSM-50 zeolites (crystallinity of 100% 3, Si / Al ratio around 125), maximum efficiency (about 15%) in 75 hours at 160 C.

Under identical conditions, the tests with zeolite seeds with a high Si / Al ratio give a solid which is not completely crystallized in zeolite EU-1 and ZSM-50 (examples 23 and 32). Under identical conditions, the experiment without the addition of seeds (Examples 2 and 18) does not produce the EU-1 zeolite or the ZSM-50 zeolite. Thus, in Example 1 and Example 17, it is necessary to go up to 125 hours or 98 hours of synthesis time to allow the formation of the EU-1 zeolite and of the pure ZSM-50 zeolite and of maximum yield. .

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L'ç l 'ç 9'Ç Z'ç 9'Ç' ç 17'≈ ['ç L'Ç l' ç 6't Z'ç t'ç ['ç 1'9' ç) U3 iapiiai pu 8, l 1'171 6 '[S'Ì 6'[L'tl6'tlL'Ì pu '171 8'CI Z'tl S'Ì fold t'Çl (X) (VIlS OWV OWV + 1- 11.3 1-11.3 1-11.3 [-ria 1-11.3 1-11.3 1-flu 1-ng 1-11.3 + [- 11.3 (-11.3 [-11.3 1-na l-na [- (la (xa)% 06 % 01 G Z01% 00% 66% 66% IO (% 001 Ob zol / v S8 G 66% L6% R6 '% JI 0 OWV% v 001 3SC

<tb> solid
<tb> 96 <SEP> 125 <SEP> (4) <SEP> time
<tb> tempering <SEP> 180
<tb> (C)
<tb>

ItOI]BSIjIB]SLIJ 9 00S< Vl>'1= L'69= Z'Z= =1V/'S 00< or= Ç'9L= L'ÇZ= ,171= (VflS IVflS IV/TS (VflS ZHW 811 8'c= Ì= 0'1= IV/IS IV/!S Id/S (V/iS IVflS [-11.3 [-11.3 [-11.3 r-na -b'W,I, =IV/!,, (VflS IV/!S (VflS Dill 9 S-W57.

ItOI] BSIjIB] SLIJ 9 00S <Vl>'1 = L'69 = Z'Z = = 1V /' S 00 <or = Ç'9L = L'ÇZ =, 171 = (VflS IVflS IV / TS (VflS ZHW 811 8'c = Ì = 0'1 = IV / IS IV /! S Id / S (V / iS IVflS [-11.3 [-11.3 [-11.3 r-na -b'W, I, = IV / !, , (VflS IV /! S (VflS Dill 9 S-W57.

1 rdUIX,1 3DU3J3J3J mod 33AU 'x suofoj sap UOI]aEl3IQ = X2IQ iunjuouiure|qiaiurji3i = yjAIl X 3DU3DS3Jonu =)8: UIn!u041?UIr.X4 = XH 4dtOUffi = OWV -xH-uN -xH-eN -XII-UN -xH-eN -WIN 2IOW-H À-1711N X-uN V-1 -U.111'S -knsz-ll -WSZ-H -V <JSZ-H -cN sues S; JWJ; J: '! -XH-TN olo Z - O'H 008Z - zl9xH OZ - OluN 01 - [01: [V z - lois 09 "} RlmuJoJ la :) (uosIs (uoslu (uose (uoslu induioa) irdmoa) jedmoa) jedtuoi) 91 SI tl fi n Il 01 6 8 L 9 S t Z 1 aldmaxa or

1 rdUIX, 1 3DU3J3J3J mod 33AU 'x suofoj sap UOI] aEl3IQ = X2IQ iunjuouiure | qiaiurji3i = yjAIl X 3DU3DS3Jonu =) 8: UIn! U041? UIr.X4 = XH 4dtOUffi = OW

<Desc / Clms Page number 16>

IV/!S st-toddtu t9 xnBJiipnjjs s;Jd.\ srantp ap s3qt))<Mz ap sauuaS sap MAe SU ap uisioa IVI!S tJ'oudfj ap os-MSZ 3lU!l<>?z Pol ap sasaqjuAs : j nB3|qBX

Z'g 8'171 0' 9' 6'81 8,ça O'Çl Ç'Çl 9'91 R'Çr Ou91 ZÇi l'Li Ç[ ('K,) :11'110<; ;::'91 8'H O'ÇI 9'ÇI 6-8) 8-0 0S Z'ÇI Ç'ÇI 9'Çl g'çl ('Çl 0'91 Z'Ç( l'LI Ç'ÇI '"3PUÎU Pu Ll 9171 ICI IZI ZÌ ZI ÌI 601 Pu SÌ 811 zzi 61 pu 1 (Xd)It/S

IV /! S st-toddtu t9 xnBJiipnjjs s; Jd. \ Srantp ap s3qt)) <Mz ap sauuaS sap MAe SU ap uisioa IVI! S tJ'oudfj ap os-MSZ 3lU! L <>? Z Pol ap sasaqjuAs: j nB3 | qBX

Z'g 8'171 0 '9'6'81 8, ça O'Çl Ç'Çl 9'91 R'Çr Ou91 ZÇi l'Li Ç [('K,): 11'110 <;; :: '91 8'H O'ÇI 9'ÇI 6-8) 8-0 0S Z'ÇI Ç'ÇI 9'Çl g'çl (' Çl 0'91 Z'Ç (l'LI Ç'ÇI '"3PUÎU Pu Ll 9171 ICI IZI ZÌ ZI ÌI 601 Pu SÌ 811 zzi 61 pu 1 (Xd) It / S

<tb> 50+ <SEP> 50+
<tb> AMO <SEP> AMO
<tb>

-WSZ OS-WSZ OS-WSZ OS-WSZ OS-WSZ OS-WS7. OS-WSZ OS-WS7. OS-WSZ -WSZ o-Ksz OS-WSZ OS-WS'7, OS-WSZ 0-MSZ /v S8 !v 86 % ZOr /n OOf % 86 !n I01 % 86 6 Òf % f0I % SL % 001 % 66 % 66 % L6 OWV % 001 (X21(I) ;)smd

-WSZ OS-WSZ OS-WSZ OS-WSZ OS-WSZ OS-WS7. OS-WSZ OS-WS7. OS-WSZ -WSZ o-Ksz OS-WSZ OS-WS'7, OS-WSZ 0-MSZ / v S8! V 86% ZOr / n OOf% 86! N I01% 86 6 Òf% f0I% SL% 001% 66% 66% L6 OWV% 001 (X21 (I);) smd

<tb> solid
<tb> 75 <SEP> 86 <SEP> (4) <SEP> time
<tb> (C)
<tb>

091 ;)lnll'l?dw;<I1

091;) lnll'l? Dw; <I1

<tb> 3.6
<tb> crystallization
<tb>

0pS< 1717 1 L69= ZSZ= =IV/'S si[ OOS< OSr= S'<>L= L'ÇZ= '171= IV/!S IV/IS IV/!S IV/IS ZVW =IV/'S 8'c= 'I= IV/IS )V/'S IV/TS tV/vs IV/'S 1-ng 1-cig 1-fig [-nu -dws How [VIlS IV/TS [=IV/!S ato 9 ç ç s-wsz -XH-BN -xH-uN -xll-rN -xH-t'N WIN -tHN | A-W1N X-rN V-)I -1);)111<; -kSZ-11 -WSZ-H -WSZ-H -eN sues sucs S"UI.I;} sauuag /, Z - OzH 008Z - 1JOxFl OZ - OzrN 01 - FOZIV '0 - zOS 09 tB)nmjoj

0pS <1717 1 L69 = ZSZ = = IV / 'S if [OOS <OSr = S'<> L = L'ÇZ = '171 = IV /! S IV / IS IV /! S IV / IS ZVW = IV / 'S 8'c =' I = IV / IS) V / 'S IV / TS tV / vs IV /' S 1-ng 1-cig 1-fig [-nu -dws How [VIlS IV / TS [= IV /! S ato 9 ç ç s-wsz -XH-BN -xH-uN -xll-rN -xH-t'N WIN -tHN | A-W1N X-rN V-) I -1);) 111 <; -kSZ-11 -WSZ-H -WSZ-H -eN sues S "UI.I;} sauuag /, Z - OzH 008Z - 1JOxFl OZ - OzrN 01 - FOZIV '0 - zOS 09 tB) nmjoj

<tb> ratif) <SEP> ratif) <SEP> ratif)
<tb> freeze
<tb>

gdmoa) Bduioa) rdmoa) Z Tf Of 6Z 8Z L'l 9 SZ tZ f ZZ TZ OZ: 61 81 l.1 a|dui3x:) u hexaméthomum = xH

X 3ou3os3jon)j =Xd [rCzuaq ap ajnjo[q3 )3g iunruouiun2[i3Uicn3i = VW1 1 1 3|diusx9. [ 3DU3J3j?.i siuuio 03AB 'x suoCel sap uoraar.r;3 - XO 3uiujn|Xqj3Ui(p[Xzu3q = VWO9 ;:1ljdJOWU = OWV

gdmoa) Bduioa) rdmoa) Z Tf Of 6Z 8Z L'l 9 SZ tZ f ZZ TZ OZ: 61 81 l.1 a | dui3x :) u hexamethomum = xH

X 3ou3os3jon) j = Xd [rCzuaq ap ajnjo [q3) 3g iunruouiun2 [i3Uicn3i = VW1 1 1 3 | diusx9. [3DU3J3j? .I siuuio 03AB 'x suoCel sap uoraar.r; 3 - XO 3uiujn | Xqj3Ui (p [Xzu3q = VWO9;: 1ljdJOWU = OWV

Claims (18)

CLAIMS 1. Process for preparing a zeolitic material with structure type EUO comprising at least one element X chosen from silicon and germanium and at least one element T chosen from iron, aluminum, gallium, boron and titanium. , vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, characterized in that seeds of at least one zeolitic material comprising at least one element X 'chosen from silicon are used and germanium and at least one element T 'chosen from iron, aluminum, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese , with an X ′ / T ′ ratio of less than 200, said seeds being different from the zeolite with structure type EUO which is prepared. 2. The method of claim 1 wherein the seeds of zeolitic material have a different structural type from the EUO structural type. 3. Method according to one of claims 1 to 2 such that the seeds have a chemical composition of the crystalline framework different from the chemical composition of the crystalline framework of the EUO-structural-type zeolite which is prepared. 4. Method according to one of claims 1 to 3, such that the zeolite material used as seeds is chosen from zeolites with structure type LTA such as zeolite. A, of structural type LTL, of structural type FAU such as X and Y zeolites, of structural type MOR, of structural type MAZ, of structural type OFF, of structural type FER, structural type ERI, structural type BEA, structural type MFI such as ZSM-5 and silicalite, structural type MTW, structural type MTT, structural type LEV, structural type TON, structural type NES such as zeolite NU- 87, zeolites NU-85, NU-86, NU-88, IM-5, or zeolites of structural type EUO of chemical composition of the crystalline framework different from the zeolite EUO which are prepared such as EU-1, ZSM-50 and TPZ-3 zeolites. 5. Method according to one of claims 1 to 4 such that the seeds used are chosen from seeds of at least one zeolite material of LTA structure type, FAU, MOR, MFI and EUO. <Desc / Clms Page number 18> 6. Method according to one of claims 1 to 5 comprising the synthesis of an aqueous mixture comprising at least one source of at least one element X and at least one source of at least one element T, at least one source of 'an organic structuring agent and seeds of at least one zeolitic material. 7. Method according to one of claims 1 to 6 wherein the seeds of zeolitic material are introduced at any time during the preparation. 8. Method according to one of claims 1 to 7 wherein the seeds of zeolitic material are introduced after the homogenization at least in part of the aqueous mixture containing the source of element X, the source of element T, the source of. organic structuring. 9. Method according to one of claims 1 to 8 such that the element X is silicon and the element T is aluminum. 10. Method according to one of claims 1 to 9 such that the organic structuring agent is an alkyl derivative of polymethylene [alpha] - # diammonium of formula: R1R2R3 N + (CH2) n N + R4R5R6 and / or an amine degradation product corresponding to said derivative and / or a precursor corresponding to said derivative, n being between 3 and 12 and Ri to R6, which may be identical or different, possibly representing alkyl or hydroxyalkyl radicals having from 1 with 8 carbon atoms, up to five of the radicals R1 to R6 can be hydrogen. 11. Method according to one of claims 1 to 9 such that the organic structuring agent is a compound comprising dibenzyldimethylammonium and / or an amine degradation product corresponding to said derivative and / or a precursor corresponding to said derivative. 12. Method according to one of claims 1 to 11 such that at least one salt is introduced. P of alkali metal or ammonium. 13. Method according to one of claims 1 to 10 wherein the reaction mixture has the following composition, expressed in the form of oxides: <Desc / Clms Page number 19> S represents the zeolite seeds present in the crude, dried, calcined or exchanged form, with an X '/ T' ratio of less than 200. Q represents the organic structuring agent, or the decomposition products corresponding to said derivative or the precursors of said derivative, M + represents an alkali metal or the ammonium ion, T is at least one element chosen from aluminum, iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese X is silicon and / or germanium, S / X02 (g / g) 0.0001 to 0.1 where P / XO2 (mol / mol) 0 to 5 OH- / XO2 (mol / mol) 0.002 to 2.0 Q / X02 (mol / mol) 0.002 to 2 Q / (M + + Q) (mol / mol) 0.1 to 1.0 H20 / X02 (mol / mol) 1 to 500 X02 / T203 (mol / mol) at least 10 P represents the alkali metal or ammonium salt. 14. Zeolite of structural type EUO obtained according to the process of one of claims 1 to 13. 15. EU-1 zeolite synthesized according to one of claims 1 to 13. 16. Use of the EUO-structural-type zeolite according to claim 14 as an adsorbent for the control of pollution, as a molecular sieve for the separation. 17. Catalyst comprising a zeolite of EUO structure synthesized according to one of claims 1 to 12 or according to one of claims 14 to 15. 18. A process for converting hydrocarbons in the presence of a catalyst according to claim 17.