FR2785278A1 - Synthesis of EUO zeolites, useful e.g. as catalysts in isomerization reactions of eight carbon aromatic hydrocarbons, uses precursors of structuring agents - Google Patents

Abstract

The synthesis of EUO zeolites is effected in the presence of organic structuring precursors which are less hazardous in use than the structuring agents themselves. The synthetic process involves the mixing, in aqueous solution, of a source of an element X (Si or Ge), a source of an element T, chosen from Al, Fe, Ga, B, Ti, V, Zr, Mo, As, Sb, Cr and Mn, and a monoamine precursor of a structuring agent comprising an alkylated derivative of polymethylene alpha ,w diammonium. Independent claims are also included for the EUO zeolite obtained by the process, and its uses.

Description

Technical Field The present invention relates to a new process for

  preparation of EUO structural type zeolites. EUO structural type zeolites synthesized according to the process of the present invention include EU-1 and TPZ-3 zeolites. These zeolites generally have the following formula in anhydrous form 0 to 20 R20 0-10 T203: 100 XO2 o R represents a monovalent cation or 1 / n of a cation of valence n, T represents at least one element chosen from aluminum , iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony,

  to chromium and manganese, X represents silicon and / or germanium.

  EUO structural type zeolites such as EU-1 and TPZ-3 zeolites are generally synthesized by mixing in an aqueous medium at least one source of silica and / or germanium and at least one 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 an organic compound comprising a derivative alkylated polymethylene CL- (,) diammonium, playing the role of structuring. The mixture is generally kept at a certain

  temperature until the zeolite crystallizes.

  PRIOR ART The EU-1 zeolite of structural type EUO, already described in the prior art, has a one-dimensional microporous network, the pore diameter of which is 4.1 × 5.7 AA 315 (1 A = 1 Angstrom = 1 . 10'1 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 review Zeolites (1988, 8, 74) that these one-dimensional channels have side pockets of depth 8, 1 A and diameter 6.8 x 5.8 A. The mode of synthesis of the EU-1 zeolite and its physicochemical characteristics have been described in the patent EP-42 226. The method of synthesis comprises the mixture of a silicon oxide and / or germanium and an oxide of at least one element chosen from aluminum, iron, gallium and boron, in presence of a structuring agent comprising at least one alkylated derivative of polymethylene cE-o diammonium of formula R1R2R3 N + (CH2) n N * R4R5R6, the products ts of degradation of said derivative or the

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  precursors of said derivative. The precursors of the alkylated derivative are the related diamine

  together with alcohols or alkyl halides.

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

io greater than 80 C.

  Summary of the Invention The present invention relates to a new process for the preparation of a zeolitic material of structural type EUO in the presence of at least one precursor of an alkylated derivative of polymethylene x- c) diammonium playing the role of structuring chosen from

monoamines.

  Advantage of the invention The process according to the invention makes it possible to reduce the crystallization time of the zeolite after formation of the mixture, which provides a cost saving. In addition, the use of precursors of the structuring agent according to the invention makes it possible to increase safety during the synthesis of the zeolite, said precursors being less dangerous than the structuring itself or than the precursors of the prior art, and also reduces the cost of reagents, said precursors being less expensive than the structuring itself

  or that the precursors of the prior art.

  Thus the Applicant has surprisingly discovered that the synthesis of a zeolite characterized by the use of specific precursors of the structuring makes it possible in particular to obtain the advantages mentioned above, that is to say a gain in

  time, safety and cost of reagents.

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Description of the invention

  The invention relates to a process for the synthesis of a zeolitic material of EUO structural type comprising the mixing in aqueous medium of at least one source of at least one element chosen from silicon and germanium and 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, in the presence of 'at least one precursor of an alkylated derivative of polymethylene ca-s diammonium playing the role of structuring. The mixture is generally kept at a certain temperature until the zeolite crystallizes. The invention is characterized in that at least one precursor of the

  alkylated derivative of polymethylene c & -o diammonium chosen from monoamines.

  The alkylated derivative of polymethylene ct- (o diammonium playing the role of structuring has the following formula: R1R2R3 N * (CH2) n N * R4RsR6 n being between 3 and 14 and R1 to R6, identical or different, which may represent radicals alkyls or hydroxyalkyls having from 1 to 8 carbon atoms, up to

  five radicals R1 to R6 which may be hydrogen.

  In addition to the precursor (s) of the structuring agent chosen from the monoamines according to the method of the present invention, the other structuring group (s) is (are) generally introduced using any suitable precursor to obtain a quaternary ammonium. These precursors are of the F-R-F type, where F and F ′ are identical or different leaving groups such as, for example, an alcohol function or a halide. By way of example, we also choose as a precursor to

  at least one compound chosen from alkanediols and alkane dihalides.

  The precursors of the structuring agent according to the invention and the other precursors can be preheated together in the reaction vessel or can be mixed as such with the other reagents. Precursors can be introduced to any

  what time of the preparation of the zeolite.

  Preferably, the precursors of the structuring agent are introduced in solution before the addition.

  other reagents necessary for the synthesis of the zeolite.

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  In a particular implementation, it may be advantageous to add to the reaction medium seeds S of at least one zeolite. It is possible to add seeds having the structural type of the EUO zeolite or the structural type of other accessible and inexpensive zeolites such as for example the zeolites of structural type LTA, FAU, MOR, MFI. These seeds can accelerate the crystallization of the EUO zeolite from the reaction mixture. The germs can be introduced at any time during the synthesis of the zeolite. Preferably, in the eventual case where the EUO zeolite is synthesized using seeds, said seeds are added after

  homogenization at least in part of the mixture containing the other reagents.

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

  EUO from the reaction mixture.

  The aqueous reaction mixture generally has the following molar composition, expressed in the form of oxide: XO2 / T203 (mol / mol) at least 10 OH- / XO2 (mol / mol) 0.002 to 2.0 Q / XO2 (mol / mol) 0.002 to 2.0 Q / (M + + O) (mol / mol) 0.1 to 1.0 H2O / XO2 (mol / mol) 1 to 500 P / XO2 (mol / mol) 0 to 5 S / XO2 (g / g) 0 to 0.1 preferably, the reaction mixture has the following composition, expressed in the form of oxides

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  XO2 / T203 (mol / mol) at least 12 OH- / XO2 (mol / mol) 0.005 to 1.5 Q / XO2 (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 / XO2 (g / g) 0.0005 to 0.07 and, even more preferred, the reaction mixture has the following composition, expressed in the form of oxides: XO2 / 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 H2O / XO2 (mol / mol) 5 to 100 P / XO2 (mol / mol) 0 to 0.25 S / XO2 (g / g) 0.001 to 0.04 o X is silicon and / or germanium, T is at least one element chosen 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 aforementioned alkylated derivative of polymethylene u- co diammonium, introduced using suitable precursors corresponding, containing a monoamine, S represents the germs of z olithe expressed as dried, calcined or exchanged,

  P represents the alkali metal or ammonium salt.

  M and / or Q can be present in the form of hydroxides or acid salts

  inorganic or organic provided that the OH '/ XO2 criterion is satisfied.

  The invention is characterized in that the organic structuring agent comprising an alkylated derivative of polymethylene c-so diammonium is introduced using at least one precursor chosen from monoamines. By monoamine is meant any organic compound having an amine function. Preferably, the precursors according to the invention are chosen from alkylamines having from 1 to 18 carbon atoms per molecule, and preferably having from 1 to 8 carbon atoms per molecule. The alkylamines can be primary, secondary or tertiary. More specifically

  the precursors are chosen from trialkylamines.

  1o The preferred starting precursors are, inter alia, those which lead to the preferred alkylated polymethylene cc-co-diammonium derivatives, preferably to the alkylated derivatives of hexamethylenediammonium and especially the methylated derivatives of hexamethylenediammonium and even more preferably the salts of 1.6 -N, N, N, N ', N', N'-hexamethylhexamethylenediammonium having the formula (CH3) 3 N + (CH2) 6 N * (CH3) 3, for example the halide, the hydroxide, the sulfate, the silicate, aluminate. For example, preferably, the precursor according to the invention chosen from monoamines is trimethylamine and the other precursor is dibromohexane. The preferred alkali metal (M +) is sodium. The preferred T element is aluminum

  The preferred element X is silicon.

  The source of silicon may be any one of those the use of which is normally envisaged for the synthesis of zeolites, for example solid silica powder, silicic acid, colloidal silica or silica in solution. Among the powdered silicas that may 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 than aerosil produced by Degussa and Cabosil produced by Cabot and silica gels. Colloidal silicas of various particle sizes can be used, such as those sold under the registered trademarks, <LUDOX ", from Dupont, and (, SYTON" from Monsantos. The dissolved silicas which can be used are in particular the soluble glasses or silicates sold containing: 0.5 to 6.0 and especially 2.0 to 4.0 moles of SiO2 per mole of alkali metal oxide and the silicates obtained by

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  dissolution of silica in an alkali metal hydroxide, an ammonium hydroxide

  quaternary or a mixture thereof.

  The aluminum source is most advantageously sodium aluminate, but can be aluminum, an aluminum salt, for example chloride, nitrate or sulfate, an aluminum alcoholate or the alumina itself. even which should preferably be in a hydrated or hydratable form such as colloidal alumina, the

  pseudoboehmite, boehmite, gamma alumina, or trihydrates.

  Mixtures of the sources cited above can be used. Combined sources

  silicon and aluminum can also be used such as silica-

  amorphous aluminas 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 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 stirring. Agitation 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 EUO zeolite, an ion exchange can be carried out with an acid, especially a strong mineral acid such as hydrochloric, sulfuric or nitric acid, or with an ammonium compound such as ammonium chloride, sulfate or nitrate. The ion exchange can be carried out by dilution in one or more stages with the ion exchange solution. EUO zeolite can be calcined before or after ion exchange or between two ion exchange stages, preferably before ion exchange in order to remove any organic substance

  absorbed, to the extent that ion exchange is facilitated.

  As a general rule, the cation or cations of the EUO zeolite can be replaced by any cation or cations of metals and in particular those of groups IA, 1B,

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  IIA, IIB, IIIA and IIIB (including rare earths) VIII (including noble metals) as well as lead, tin and bismuth (The periodic table is as in "Handbook of Physic and Chemistry" , 76th edition). The exchange is executed at

  using any water soluble salt containing the appropriate cation.

  The present invention also relates to the use of the EUO zeolite as prepared according to the process of the present invention as an adsorbent for pollution control, as a molecular sieve for separation and as an acid solid

  for catalysis in the fields of refining and petrochemicals.

  For example, when used as a catalyst, the EUO zeolite synthesized according to the process of the present invention can be associated with an inorganic matrix which can be inert or catalytically active and with an active phase. The inorganic matrix can be present simply as a binder to hold i5 together the small particles of the zeolite in the various known forms of catalysts (extrudates, beads, powders), or else can be added as diluent to impose the degree of conversion in a process. which would otherwise progress at an excessively rapid rate leading to fouling of the catalyst as a result of excessive formation of coke. Typical inorganic diluents are, in particular, support materials for catalysts such as silica, different forms of alumina and kaolinic clays, bentonites, montmorillonites, sepiolite, attapulgite, fuller's earth, synthetic porous materials. like SiO2-AI203,

  SiO2-ZrO2, SiO2-ThO2, SiO2-BeO, SiO2-TiO2 or any combination of these compounds.

  The EUO structural type zeolite can also be associated with at least one other

  zeolite and play the role of main active phase or 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 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.

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  The catalytic compositions comprising the zeolite of structural type EUO can find their application in reactions of isomerization, transalkylation and disproportionation, alkylation and dealkylation, hydration and dehydration, oligomerization and polymerization, cyclization , aromatization, cracking and hydrocracking, hydrogenation and dehydrogenation, reforming, oxidation, halogenation, synthesis of amines, hydrodesulfurization and hydrodenitrification, catalytic elimination of oxides nitrogen, ether formation and hydrocarbon conversion and 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 7: (Comparative) Synthesis of EU-1 zeolite (or TPZ-3) with variable Si / AI ratio from 15 to 100 with hexamethonium bromide (1.6 hexamethylhexamethylenediammonium bromide) as organic structuring agent The mixture of synthesis with the following molar composition: example 1 2 3 and 4 5 6 7 Si / AI = 15 Si / AI = 15 Si / AI = 30 Si / AI = 40 Si / AI = 70 Si / AI = 100 SiO2 (mol) 60 60 60 60 60 60 A1203 (mol) 2 2 1 0.75 0.43 0.3 Na2O (mol) 10 10 10 10 5 5 HxBr2 (mol) 20 20 20 20 20 20 H20 (mol) 2800 2800 2800 2800 2800 2800 EU-1 / SiO2 (g / g)) 0 0.04 0.04 0.04 0.04 0.04 Hx Br2 = hexamethonium bromide = Me3 N (CH2) 6 N Me32 + (Br ') 2 Solution A, composed of silicon and structuring agent, is prepared by diluting the hexamethonium bromide (Fluka, 97%) in 80% of the water necessary for the formation of the gel Io0 2785278 and then adding the colloidal silica sol (Ludox HS40 , Dupont, 40% SiO2). The solid sodium hydroxide (Prolabo, 99%) and the solid sodium aluminate (Prolabo, 46% A1203, 33% Na2O) are then dissolved in 10% of the water required to form the gel to form the solution. B. Solution B is added to solution A with stirring and then the remainder of water (10%). Mix until homogenized and add the seeds of dried EU-1 zeolite. The resulting mixture is reacted

  in a 125 ml autoclave with stirring at 180 ° C. under autogenous pressure.

  After cooling, the product is filtered and washed with 0.5 liters of demineralized water and then dried in a ventilated oven at 120 C. The quantities of reagents introduced are given in the following table: example 1 2 3 and 4 5 6 7 Si / AI = 15 Si / AI = 15 Si / AI = 30 Si / AI = 40 Si / AI = 70 Si / AI = 100 colloidal silica 14.50 14.50 14.52 14.53 14.61 14 , 61 (g) 0.715 0.715 aluminate 0.358 0.269 0.155 0.108 sodium (g) sodium hydroxide (g) 0.985 0.985 1, 139 1.177 0.584 0.604 HxBr2 (9) 12.03 12.03 12.05 12.05 12.12 12, 12 water (g) 71.77 71.77 71.93 71.97 72.53 72.55 germs EU-1 (g) 0 0.232 0.232 0.232 0.234 0.234 Hx Br2 = hexamethonium bromide = Me3 N (CH2) 6 N Me32 + (Br ') 2 The results of X-ray diffraction and chemical analysis are reported in Table 1. The syntheses of Examples 2, 3, 5, 6 and 7 carried out at 180 C with the structuring agent of the art previous, with seeds of EU-1, lead to the pure EU-1 zeolite (crystallinity of 100% + 3) of variable Si / AI ratio ent re 15 and 100, maximum yield (about 5%). Example 1 corresponds to a germ-free preparation and requires a longer crystallization time compared to Example 2 to produce the EU-1 zeolite (125 hours versus 96 hours). Example 4 mainly gives the EU-1 zeolite with a little cristobalite due to a too long crystallization time compared with Example 3 (96 hours

72 hours).

  tl 2785278 EXAMPLE 8 to 13: (comparative) Synthesis of EU-1 zeolite (or TPZ-3) with variable Si / AI ratio from 15 to 100 with the precursors of hexamethonium iodide (1.6 iodide hexamethylhexamethylenediammonium) as an organic structuring agent containing a diamine (1-6 tetramethylhexamethylene diamine and methyl iodide) The synthesis mixture has the following molar composition: example 8 9 10 11 12 13 Si / AI = 15 Si / AI = 15 Si / AI = 30 Si / AI = 40 Si / AI = 70 Si / AI = 1 00 SiO2 (mol) 60 60 60 60 60 60 A1203 (mol) 2 2 1 0.75 0.43 0.3 Na2O (mol) 10 10 10 10 5 5 TMHMDA (mol) 20 20 20 20 20 20 CH31 (mol) 40 40 40 40 40 40 H20 (mol) 2800 2800 2800 2800 2800 2800 EU-1 / SiO2 (g / g) 0 0.04 0.04 0, 04 0.04 0.04 TMHMDA = 1-6 tetramethylhexamethylene diamine = Me2 N (CH2) 6 N Me2 The preparation is the same as that described in examples 1 to 7 with, in addition, the mixture of the two precursors at the start, the 1 -6 tetramethylhexamethylene diamine (Acros, 99%) and methyl iodide (Acr bone, 99%), within 80% of the water necessary for gel formation. The quantities of reagents introduced are given in the following table:

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  example 8 9 10 11 12 13 Si / AI = 15 Si / AI = 15 Si / AI = 30 Si / AI = 40 Si / AI = 70 Si / AI = 100 colloidal silica (g) 14.07 14.07 14, 10 14.10 14.18 14.18 0.69 0.694 aluminate 0.347 0.261 0.150 0.105 sodium (g) sodium hydroxide (g) 0.956 0.956 1.105 1.143 0.566 0.586 TMHMDA (g) 5.43 5.43 5.44 5.44 5.45 5.47 CH31 (g) 8.97 8.97 8.99 8.99 9.04 9.04 water (g) 69.87 69.87 70.02 70.06 70.59 70.61 germs EU-1 (g) 0 0.225 0.226 0.226 0.227 0.227 TMHMDA = 1-6 tetramethylhexamethylene diamine = Me2 N (CH2) 6 N Me2 The results of X-ray diffraction and chemical analysis are given in Table 2. The summaries examples 9, 10, 11, 12 and 13 carried out at 180 ° C. with the structuring agent of the prior art, with seeds of EU-1, lead to the pure EU-1 zeolite (crystallinity of 100% + 3) of ratio If / AI variable between 15 and 100, maximum yield (about 5%). Example 8 corresponds to a preparation without germs and requires a longer crystallization time by comparison with

  Example 9 to produce the EU-1 zeolite (122 hours versus 93 hours).

  EXAMPLES 14 to 20: (invention) Synthesis of EU-1 zeolite (or TPZ-3) with variable Si / AI ratio between 15 and 100 with

  specific precursors of hexamethonium bromide (1.6 hexa- bromide

  methylhexamethylenediammonium) as an organic structuring agent containing a monoamine (trimethylamine and dibromohexane) The synthetic mixtures have the following molar composition:

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  example 14 15 16 and 17 18 19 20 Si / AI = 15 Si / Al = 15 Si / AI = 30 Si / AI = 40 Si / AI = 60 Si / AI = 100 SiO2 (mol) 60 60 60 60 60 60 A1203 (mol) 2 2 1 0.75 0.43 0.3 Na2O (mol) 10 10 10 10 5 5 DBH (mol) 20 20 20 20 20 20 TMA (mol) 40 40 40 40 40 40 H20 (mol) 2800 2800 2800 2800 2800 2800 EU-1 / SiO2 (g / g)) 0 0.04 0.04 0.04 0.04 0.04 DBH = dibromohexane TMA = trimethylamine The preparation is the same as that described in examples 1 to 7 with in addition the mixture of the two precursors at the start, the aqueous solution of trimethylamine (Acros, 45%) and the dibromohexane (Acros, 99%), in the 80% of water necessary for the formation of the gel. The quantities of reagents introduced are given in the following table: O10 example 14 15 16 and 17 18 19 20 Si / AI = 15 Si / AI = 1 5 Si / AI = 30 Si / AI = 40 Si / AI = 60 Si / AI = 100 colloidal silica 14.50 14.50 14.52 14.53 14.61 14.61 (g) 0.715 aluminate 0.75 0.758 0.369 0.29 0.180 0.108 sodium (g) sodium hydroxide (g) 0.985 0.985 1.139 1.177 0.573 0.604 DBH (g) 8.02 8.02 8.03 8.04 8.08 8.09 TMA (g) 8.45 8.45 8.46 8.47 8.51 8.52 water (g) 67.3 67.33 67.48 67.52 68.04 68.07 germs EU-1 0 0.232 0.232 0.232 0.234 0.234 (g) DBH = dibromohexane TMA = trimethylamine

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  The results of X-ray diffraction and chemical analysis are reported in Table 3. The syntheses of Examples 15, 16, 18, 19 and 20 carried out at 180 C with

  the specific precursors of the structuring agent according to the invention, with seeds of EU-

  1, lead to the pure EU-1 zeolite (crystallinity of 100% + 3) of Si / AI ratio variable between 15 and 100, of maximum yield (approximately 5%). Example 14 corresponds to a germ-free preparation and requires a longer crystallization time compared to Example 15 to produce the EU-1 zeolite (110 hours versus 85 hours). Example 17 gives mainly the EU-1 zeolite with a little cristoballite due to a longer crystallization time by

  comparison with Example 16 (82 hours versus 65 hours).

Table 1:

  Syntheses of EU-1 zeolites with the organic structuring agent according to the prior art n example i 1 2 3 4 5 6 7 gel formulation 60 SiO2 - a A1203 - b Na2O - 20 HxBr2 - 2800 H20 - 0-4% EU-1 SVAI = 301a 15 15 30 30 40 70 100 (mol / mol) alkalinity b 10 10 10 10 10 5 5 seeds no yes yes yes yes yes yes crystallization temperature 180 úc) time (h) 125 96 72 96 72 72 60 solid phase ( DRX) 100% 101% 100% 90% EU-1 + 98% 99% 102%

  EU-1 EU-1 EU-1 10% CRISTO EU-1 EU-1 EU-1

  Si / AI (FX) 14.2 13.9 26.6 nd 36.9 68.6 90.7 yield in 5.1 5.8 5.2 5.3 5.1 5.6 5.2 solid (%) CRISTO: cristobalite Hx Br2 = hexamethonium bromide = Me3 N (CH2) 6 N Me32, (Br ') 2 DRX: X-ray diffraction with example 1 FX X fluorescence

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Table 2:

  Syntheses of EU-1 zeolites with organic structuring precursors according to the prior art n example 8 9 10 11 12 13 gel formulation 60 SiO2 a A1203 - b Na2O - 20 TMHDA - 40 CH31 - 2800 H2O - 4% EU-1 Si / AI = 30 / a 15 15 30 40 70 100 (mo / mol) alkalinity b (mol) 10 10 10 10 5 5 crystallization temperature (C) I180 time (h) 122 [93 | 70 70 | 70 | 60 solid phase (DRX) 100% EU-1 99% EU-1 98% EU-1 101% EU-1 100% EU-1 98% EU-1 Si / AI (FX) 14.2 13.8 13, 2 13.7 14.3 13.5 solid yield (%) 5.0 5.2 4.8 5.6 5.4 5.1 TMHMDA = 1; 6 tetramethylhexamethylene diamine = Me2 N (CH2) 6 N Me2 XRD: X-ray diffraction with reference to example 8 FX: X-ray fluorescence

Table 3:

  10 Syntheses of EU-1 zeolites with the precursors of the organic structuring agent according to the invention n example gel 4 n example 14 15 16 1 17 18 19 20 gel formulation 60 SiO2 - a A1203 - b Na2O - 20 DBrH - 40 TMA - 2800 H20 - 0-4% EU-1 If / AI = 30 / a 15 15 30 30 40 60 100 alkalinity b (mol) 10 10 10 10 10 5 5 germs no yes yes yes yes yes yes yes crystallization temperature (C) _ 180 time (h) 110 85 65 82 65 65 53 solid phase (DRX) 100% 102% 101% 90% EU-1 + 99% 100% 98%

EU-1 EU-1 EU-1 10% EU-1 EU-1 EU-1

CRISTO

  Si / AI (FX) 14.4 14.2 25.4 nd 34.6 57.6 92.3 solid yield (/ o) 5.5 5.0 5.5 5.2 5, 6 5.7 5.8 CRISTO: cristobalite DBH = dibromohexane TMA = trimethylamine DRX: X-ray diffraction with example 14 as an example FX: X fluorescence

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  Summary of EU-1 zeolite syntheses The data in Tables 1, 2 and 3 show that EU-1 zeolites synthesized using specific precursors of the organic structuring agent containing a monoamine are crystallized in a shorter time than EU-zeolites 1 synthesized by a method according to the prior art, which allows a cost saving. In addition, during the implementation of the addition of zeolite seeds during the preparation, it is further improved.

  performance in terms of crystallization time.

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Claims (18)

  1. Method for synthesizing a zeolitic material of structural type EUO comprising at least one element X chosen from silicon and germanium and at least one element T chosen from aluminum, iron, gallium, boron, titanium , vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, comprising the mixture in aqueous medium of at least one source of at least one element X, of at least one source at least one element T, and at least one precursor of a structuring agent comprising an alkylated derivative of polymethylene (ze)   diammonium chosen from monoamines.   2. Method according to claim 1 such that the alkylated derivative of polymethylene (z-) diammonium has the following formula: RiR2R3 N + (CH2) n Ns R4RsR6 n being between 3 and 12 and R1 to R6, identical or different, which may represent alkyl or hydroxyalkyl radicals having from 1 to 8 carbon atoms, up to five radicals   R1 to R6 can be hydrogen.   3. Method according to one of claims 1 to 2 wherein the alkylated derivative of   polymethylene ca-e) diammonium is a compound of alkylated hexamethylenediammonium.   4. Method according to one of claims 1 to 3, wherein the alkylated derivative of   polymethylene (c-e) diammonium is a 1,6-N, N, N ', N', N'hexamethylhexa- salt methylenediammonium.   5. Method according to one of claims 1 to 4, in which the precursor of the derivative   alkylated polymethylene o-w diammonium chosen from monoamines is a trialkylamine.   6. Method according to one of claims 1 to 5, in which the precursor chosen   among the monoamines is trimethylamine (TMA). 18 2785278   7. Method according to one of claims 1 to 6 wherein at least one precursor of the alkylated derivative of polymethylene ca-co diammonium is used.   among alkane dihalides and alkanediols.   8. The method of claim 7 wherein the precursor is dibromohexane.   9. Method according to one of claims 1 to 8 wherein is added to the mixture   reaction at least one seed of at least one zeolite.   10. Method according to one of claims 1 to 9 wherein is added to the mixture at least one salt P.   11. Method according to one of claims 1 to 10 wherein the reaction mixture   has the following molar composition, expressed in the form of oxides: XO2 / T203 (mol / mol) at least 10 Q / XO2 (mol / mol) 0.002 to 2.0 OH / X02 (mol / mol) 0.002 to 2 , 0 Q / (M ++ Q) (mol / mol) 0.1 to 1 H2O / X02 (mol / mol) 1 to 500 P / X02 (mol / mol) 0 to 5 S / X02 (g / g) 0 to 0.1 o M + represents an alkali metal or ammonium and Q represents the alkylated derivative of polymethylene ao) diammonium, introduced using precursors comprising a monoamine.   12. Method according to one of claims 1 to 1 1 wherein X is silicon and T is aluminum.   13. Method according to one of claims 1 to 12 in which the   precursors of the alkylated derivative of polymethylene c-o) diammonium to any time of synthesis.   14. Method according to one of claims 1 to 13 in which the   precursors in solution before the addition of element T and element X. 19 2785278   15. EUO structural type zeolite synthesized according to one of claims 1 to 14.   16. Use of the EUO structural type zeolite according to claim 15 as an adsorbent for pollution control, as a molecular sieve for separation. 17. Catalyst comprising a zeolite with EUO structure synthesized according to one of the   claims 1 to 14 or according to claim 15.   O10 18. Method for converting a hydrocarbon feedstock in the presence of a catalyst according to claim 17.