SYNTHESIS OF AN IZM-2 ZEOLITE IN THE PRESENCE OF ETHANOL

Abstract

The present invention relates to a new process for preparing a microporous crystalline solid, called IZM-2 microporous solid or IZM-2 zeolite. This new process makes it possible to synthesize an IZM-2 zeolite from at least one source of silicon, at least one source of aluminum, at least one source of an alkali and / or alkaline earth metal of valence n, in the absence of an organic structurer and in the presence of at least one alcohol and preferably ethanol and calcined IZM-2 zeolite seeds.

Description

Title of the invention: SYNTHESIS OF A ZEOLITHEIZM-2 IN THE PRESENCE OF ETHANOL technical field

[0001] The present invention relates to a new process for preparing a microporous crystalline solid, called IZM-2 microporous solid or IZM-2 zeolite. This new process makes it possible to synthesize an IZM-2 zeolite from at least one silicon source, at least one aluminum source, at least one alkali and / or alkaline earth metal source of n valence, in the absence of an organic structurer and in the presence of at least one alcohol, preferably ethanol, and calcined IZM-2 zeolite seeds. In particular, said new process makes it possible to synthesize an IZM-2 zeolite without a structurer, using calcined IZM-2 zeolite seeds to promote zeolite crystallization and alcohol, preferably ethanol, to fill the pores of the zeolite. The said zeolite IZM-2 obtained according to the process of the invention advantageously finds its application as a catalyst, adsorbent or separating agent. EARLIER ART

[0002] Crystalline microporous materials, such as zeolites or silicoaluminophosphates, are solids widely used in the petroleum industry as catalysts, catalyst supports, adsorbents, or separating agents. Although many microporous crystalline structures have been discovered, the refining and petrochemical industries are still searching for new zeolite structures that exhibit specific properties for applications such as gas purification or separation, carbonaceous species conversion, or other uses.

[0003] The IZM-2 zeolite is a solid with an unknown structure. Model reactions (metaxylene isomerization and dismutation and n-decane isomerization-hydrocracking) were used to predict the topology of the microporous material IZM-2 (Fecant et al. in J. Catal., 20, (2013) 20-29). The results obtained for these reactions suggest that the structure of the IZM-2 material consists of two pore sizes (10-MR and 12-MR).

[0004] Zeolite IZM-2 has been synthesized in its aluminosilicate form (Fecant et al. FR2918050 Al) and in its purely silicic form (Fecant et al. FR2918050 Al and Li et al. in Microporous Mesoporous Mater., 237 (2017) 222-227), using the quaternary ammonium ion 1,6-bis(methylpiperidinium)hexane as a structurer, in its hydroxide or bromide form. In these documents, the synthesis consists of performing a hydrothermal treatment of an aqueous gel containing a silicon source, an agent structuring agent (l,6-bis(methylpiperidinium)hexane), possibly a source of amorphous aluminium, and possibly a source of an alkali and / or alkaline earth metal (NaOH).

[0005] Recent work has made it possible to obtain the desired zeolite in the absence of an organic structurer and using zeolite seeds. In this case, aluminum-rich zeolites are generally obtained. (Tatsumi et al. Angew. Chem. Int. Ed. 2009, 48, 9884-9887; T. Okubo et al. J. Am. Chem. Soc. 2012, 134, 11542-11549). It has recently been reported that pure silica zeolites can also be obtained in the absence of a structurer. Quinming Wu et al. (ANGew. Chem. Int. Ed. 2019, 58, 12138-12142) propose that the absence of organic molecules and the use of zeolite seeds and ethanol as pore-filling agents allow the preparation of pure silica zeolites. To confirm this, a theoretical simulation was conducted using pure silica ZSM-5 as the zeolite and ethanol as the pore-filling agent. More recently, Yuhan Yanhg et al. (Dalton Trans.2022, 51, 12021) studied the preparation of pure silica zeolites with six-membered rings (SOD, MTN and non) using zeolite seeds and ethanol in the absence of organic structurer.

[0006] The present invention relates to a new process for preparing a microporous solid IZM-2 or an IZM-2 zeolite in the absence of an organic structurer. The process involves mixing, using a stirrer, a silicon source, an aluminum source, an alkali and / or alkaline earth metal source M, in the presence of at least one alcohol, preferably ethanol, and calcined IZM-2 zeolite seeds. This reaction mixture is then transferred to an autoclave at a temperature of 120 to 220 °C for a crystallization time of between 1 and 10 days. Summary of the invention

[0007] The present invention relates to a new method for preparing a microporous solid IZM-2 or an IZM-2 zeolite which consists of mixing, using a stirrer, a silicon source, an aluminum source, an alkaline source, in the presence of ethanol and calcined IZM-2 zeolite seeds.

[0008] An advantage of the present invention is therefore to provide a new preparation process allowing the preparation of an IZM-2 zeolite in the absence of an organic structurer, in the presence of at least one alcohol and preferably ethanol and calcined IZM-2 zeolite seeds, the process being carried out under specific operating conditions.

[0009] An advantage of the present invention is that it provides a new preparation method for forming a pure IZM-2 zeolite. Any other crystalline or amorphous phase is generally and very preferentially absent from the solid. crystallized, consisting of the IZM-2 zeolite obtained at the end of the preparation process.

[0010] Another advantage of the present invention is that it allows the preparation of an IZM-2 zeolite having a SiO2 / Al2O3 ratio between 70 and 350, and preferably between 90 and 300, and more preferably between 100 and 260. LIST OF FIGURES [Fig. 1]

[0011] Fig. 1 represents the X-ray diffraction patterns of the IZM-2 zeolite obtained according to Example 4. [Fig. 2]

[0012] Fig. 2 represents the X-ray diffraction diagrams of comparative example 11. Detailed description of the invention

[0013] The present invention relates more specifically to a new process for preparing a microporous solid IZM-2 or a zeolite IZM-2 without a structurer, comprising at least the following steps:

[0014] i) the mixture, in the presence of at least one alcohol and water, of at least one source of at least one tetravalent element X in the form of oxide XO2, of at least one source of at least one trivalent element in the form of oxide Y2O3, of at least one source of at least one alkali and / or alkaline earth metal M of valence n, n being an integer greater than or equal to 1, and of calcined zeolite IZM-2 seeds, the mixture having the following molar composition:

[0015] XO2 / Y2O3 between 70 and 350,

[0016] H2O / XO2 between 1 and 5,

[0017] Alcohol / XO2 between 0.05 and 30,

[0018] M2 / nO / XO2 between 0.05 and 0.45,

[0019] wherein Y is one or more trivalent element(s) chosen from the group formed by the following elements: aluminium, iron, boron, gallium

[0020] X is one or more tetravalent element(s) chosen from the group formed by the following elements: silicon, germanium, titanium,

[0021] M is one or more alkali metal(s) and / or alkaline earth metal(s) selected from lithium, sodium, potassium, calcium, magnesium and mixtures of at least two of these metals,

[0022] the alcohol is chosen from the group formed by primary, secondary and tertiary alcohols,

[0023] until a homogeneous mixture called precursor gel is obtained;

[0024] ii) the hydrothermal treatment of said precursor gel obtained at the end of step i) at a temperature between 120 and 220°C, for a period of between 1 day and 10 days until the said IZM-2 zeolite forms.

[0025] According to the invention, at least one source of at least one tetravalent element X in the form of oxide XO2 is incorporated into the mixture for the implementation of step (i) of the preparation process, X being one or more tetravalent element(s) selected from the group formed by the following elements: silicon, germanium, titanium and preferably X being silicon.

[0026] When X is silicon, the source(s) of said tetravalent element(s) may be any compound comprising element X and capable of releasing this element in aqueous solution in reactive form.

[0027] The silicon source can be any of said sources commonly used for the synthesis of zeolites, preferably chosen from powdered silicas, silicic acid, colloidal silicas, dissolved silica and silicon alkoxides such as tetraethyl orthosilicate (TEOS), alone or in mixture.

[0028] Among powdered silicas, precipitated silicas can be used, in particular those obtained by precipitation from an alkali metal silicate solution, fumed silicas, for example "CAB-O-SIL" and silica gels. Colloidal silicas having different particle sizes, preferably with an average equivalent diameter between 10 and 15 nm or between 40 and 50 nm, such as those marketed under registered trademarks like "LUDOX", can advantageously be used.

[0029] Preferably, the silicon source is tetraethyl orthosilicate or TEOS.

[0030] According to the invention, at least one source of at least one trivalent element in the form of Y2O3 oxide is incorporated into the mixture for carrying out said step (i) of the preparation process according to the invention, Y being one or more trivalent element(s) selected from the group formed by the following elements: aluminum, iron, boron, indium and gallium, and at least one of the trivalent elements Y being aluminum.

[0031] The aluminum source in the form of Al₂O₃ oxide is preferably selected from aluminum hydroxide, aluminum salts, aluminum alkoxides, and alumina itself, preferably in hydrated or hydratable form, preferably selected from colloidal alumina, pseudoboehmite, gamma alumina, or alpha or beta trihydrate. Mixtures of the sources mentioned above may also be used.

[0032] Preferably, the source of aluminium in the form of oxide A12O3 is an aluminium salt selected from aluminium chlorides, aluminium nitrates, aluminium sulfates, sodium aluminates, alone or in mixture.

[0033] Preferably, the source of aluminium in the form of oxide A12O3 is sodium aluminate.

[0034] According to the invention, at least one source of at least one alkali metal and / or Alkaline earth metal M, with valence n, is used in the reaction mixture of step i), n being an integer greater than or equal to 1, M being preferably chosen from lithium, potassium, sodium, magnesium, and calcium, and mixtures of at least two of these metals. Most preferably, M is sodium.

[0035] Preferably, the source of at least one alkali and / or alkaline earth metal M is sodium hydroxide.

[0036] According to the invention, seeds of a calcined IZM-2 zeolite are added to the reaction mixture during said step (i) in order to reduce the time required for the formation of IZM-2 zeolite crystals and / or the total crystallization time. These crystal seeds also promote the formation of said IZM-2 zeolite at the expense of impurities. Such seeds include crystalline solids, in particular crystals of a calcined IZM-2 zeolite.

[0037] Calcined IZM-2 zeolite nuclei are advantageously added to the mixture in step i) in a proportion of between 0.01 and 13%, preferably between 0.01 and 10%, and preferably between 0.01 and 5% of the total mass of the sources of said tetravalent element(s) in their oxide form (SiO2) used in the reaction mixture, said nuclei not being included in the total mass of the sources of the tetravalent elements. Said nuclei are not taken into account in determining the composition of the reaction mixture and / or the gel, defined further below, i.e., in determining the various molar ratios, in particular XO2 / Y2O3, H2O / XiO2, alcohol / XO2, M2 / nO / XO2, of the composition of the reaction mixture.

[0038] It is important that the IZM-2 zeolite seeds added to the mixture in step i) be calcined so that the added IZM-2 zeolite seeds no longer include any organic structurer in the porosity of said IZM-2 zeolite.

[0039] According to the invention, at least one alcohol is added to the mixture in step i). The alcohol is at least one alcohol selected from the group formed by primary, secondary and tertiary alcohols, preferably from primary alcohols and preferably, the alcohol is ethanol.

[0040] Step (i) of the process according to the invention consists of preparing a reaction mixture in the presence of at least one alcohol and water, at least one source of a tetravalent element X in the form of oxide XO2, at least one source of a trivalent element Y in the form of oxide Y2O3, in the presence of at least one source of one or more alkali metal(s) and / or alkaline earth metal(s) M and calcined IZM-2 zeolite seeds, to obtain a precursor gel of an IZM-2 zeolite.

[0041] The quantities of said reagents in the reaction mixture are adjusted so as to give this gel a composition allowing the crystallization of an IZM-2 zeolite.

[0042] In accordance with the invention, the mixture of step i) has the following molar composition:

[0043] XO2 / Y2O3 between 70 and 350, preferably between 95 and 300, and more preferably between 100 and 260

[0044] H2O / XO2 between 1 and 5, preferably between 1 and 3

[0045] Alcohol / XO2 between 0.05 and 30, preferably between 0.065 and 20

[0046] M2 / nO / XO2 between 0.05 and 0.45, preferably between 0.09 and 0.3

[0047] Step i) of mixing is carried out until a homogeneous mixture is obtained, preferably for a period of between 5 and 15 minutes, preferably under agitation by any system known to the person skilled in the art with low or high shear rate.

[0048] At the end of step i) a homogeneous precursor gel is obtained.

[0049] Advantageously, the precursor gel obtained at the end of step i) has a molar ratio of the total amount expressed as tetravalent element oxides to the total amount expressed as trivalent element oxides of between 70 and 350.

[0050] In the case where X=Si and Y=A1, the precursor gel obtained at the end of step i) has a molar ratio SiO2 / Al2O3 between 75 and 350.

[0051] In accordance with step (ii) of the process according to the invention, the precursor gel obtained at the end of step i) is subjected to hydrothermal treatment carried out at a temperature between 120 and 220°C for a period of between 1 day and 10 days, until said zeolite IZM-2 is formed.

[0052] The precursor gel is advantageously subjected to treatment under autogenous reaction pressure, optionally by adding gas, for example nitrogen, at a temperature preferably between 150 and 195°C, until complete crystallization of an IZM-2 zeolite.

[0053] Preferably, the time required to obtain crystallization varies between 1 day and 7 days, and more preferably between 2 days and 5 days.

[0054] Step (ii) is generally carried out under agitation or in the absence of agitation, preferably under agitation. Any agitation system known to those skilled in the art may be used, preferably inclined blades with counter-blades, agitator turbines, or Archimedes screws.

[0055] At the end of the reaction, after implementation of said step ii) of the preparation process according to the invention, the solid phase formed of an IZM-2 zeolite is preferably filtered, washed and then dried.

[0056] Drying is preferably carried out at a temperature between 20 and 120°C, preferably between 25 and 100°C, for a period of between 1 and 24 hours.

[0057] Preferably, said IZM-2 zeolite, possibly dried, does not undergo a calcination step.

[0058] Uncalcined IZM-2 zeolite is generally analyzed by X-ray diffraction, this technique also allowing the purity of said zeolite to be determined obtained by the process of the invention.

[0059] Advantageously, the process of the invention leads to the formation of an IZM-2 zeolite, free from any other crystalline or amorphous phase. After the drying step, said IZM-2 zeolite is then ready for subsequent steps such as ion exchange. For these steps, all conventional methods known to those skilled in the art can be used.

[0060] Following said drying step, X-ray diffraction makes it possible to verify that the solid obtained by the process according to the invention is indeed an IZM-2 zeolite. The purity of the IZM-2 zeolite obtained is thus greater than or equal to 90% by weight, preferably greater than or equal to 95% by weight, most preferably greater than or equal to 97%, more preferably greater than or equal to 98%, and even more preferably greater than or equal to 99%, or even greater than or equal to 99.8% by weight with respect to the total mass of crystallized solid material obtained.

[0061] The resulting solid exhibits the X-ray diffraction pattern including at least the lines listed in Table 1. Preferably, the X-ray diffraction pattern does not contain any other lines of significant intensity (i.e., of intensity greater than about three times the background noise) than those listed in Table 1.

[0062] This diffraction pattern is obtained by X-ray crystallography using a diffractometer with the classical powder method and copper Kai radiation (X = 1.5406 Å). From the position of the diffraction peaks represented by the angle 20°, the characteristic interplanar spacings dhki of the sample are calculated using Bragg's law. The measurement error A(dhki) on dhki is calculated using Bragg's law as a function of the absolute error A(20°) assigned to the measurement of 20°. An absolute error A(20°) of ± 0.02° is commonly accepted. The relative intensity Irei assigned to each value of dhki is measured from the height of the corresponding diffraction peak.The X-ray diffraction pattern of the crystalline solid IZM-2 according to the invention includes at least the lines with the dhki values ​​given in Table 1, which presents the average dhki values ​​and relative intensities measured on an X-ray diffraction pattern of the uncalcined crystalline solid IZM-2. In the dhki column, the average values ​​of the interplanar spacings in Angstroms (Å) are indicated. Each of these values ​​must be adjusted by the measurement error A(dhki) of between ±0.6Å and ±0.01Å.

[0063] ff <15 ; 15 <f <30 ; 30 < mf <50 ; 50 <m < 65 ; 65 <F < 85 ; FF >85

[0064] [Tables 1] 2 theta (°) dhkl (Â) Irel 2 theta (°) dhkl (Â) Irel 7.25 12.18 f 24.36 3.65 f 7.60 11.63 f 26.34 3.38 ff 7.95 11.11 ff 26.41 3.37 ff 8.71 10.14 f 26.61 3.35 f 14.73 6.01 f 30.36 2.94 f 18.83 4.71 ff 32.80 2.73 ff 21.56 4.12 ff 33.26 2.69 ff 21.11 4.21 ff 34.39 2.61 f 22.18 4.00 FF 34.99 2.56 f 22.98 3.87 f 35.80 2.51 f 23.40 3.80 f 44.41 2.04 f

[0065] where FF = very strong; F = strong; m = medium; mf = medium weak; f = weak; ff = very weak. The relative intensity Irei is given in relation to a relative intensity scale where a value of 100 is assigned to the most intense line of the X-ray diffraction pattern: ff < 15; 15 <f <30 ; 30 < mf <50 ; 50 <m < 65 ; 65 <F < 85 ; FF >85.

[0066] It is also advantageous to obtain the protonated form of the IZM-2 zeolite obtained by the process according to the invention. This protonated form can be obtained by performing an ion exchange with an acid, in particular a strong mineral acid such as hydrochloric, sulfuric, or nitric acid, or with a compound such as ammonium chloride, sulfate, or nitrate. The ion exchange can be carried out by suspending said IZM-2 zeolite in one or more stages with the ion exchange solution. Said zeolite can be calcined after the ion exchange, or between two ion exchange stages.

[0067] The IZM-2 zeolite obtained by the process of the invention can be used after ion exchange as an acidic solid for catalysis in the fields of refining and petrochemicals. It can also be used as an adsorbent or as a molecular sieve.

[0068] The process according to the invention allows the obtaining of an IZM-2 zeolite in the absence of an organic structurer by using calcined IZM-2 zeolite seeds in a reaction mixture comprising at least one alcohol, preferably ethanol, and water, having a SiO2 / Al2O3 ratio between 70 and 350, preferably between 90 and 300, and more preferably between 100 and 260 in the case where X = Si, and Y=A1. EXAMPLES

[0069] Comparative Example 1: Preparation of an IZM-2 zeolite in the presence of the organic structuring agent 1,6-bis(methylpiperidinium)hexane dibromide (R(Br)2)

[0070] 49.45 g of an aqueous solution of 1,6-bis(methylpiperidinium)hexane dibromide (20.01 wt.) were mixed with 28.66 g of deionized water and stirred for 10 minutes. 1.63 g of sodium hydroxide (99.5 wt., Aldrich) were added to the previous mixture, and the resulting preparation was stirred for 15 minutes. 0.108 g of sodium aluminate (53 wt., Carlo Erba) were added to the previous mixture, and the resulting preparation was stirred for 15 minutes. Subsequently, 20.15 g of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture, and it was kept under agitation for the time necessary to evaporate the solvent until the desired gel concentration was obtained, i.e. a molar composition of the mixture as follows: 1 SiO2: 0.004 Al2O3: 0.167 R(Br)2: 0.167 Na2O: 33.33 H2O, i.e. a SiO2 / Al2O3 ratio of 120. The mixture was stirred vigorously for half an hour.The mixture is then transferred, after homogenization, to a 160 mL stainless steel reactor equipped with a four-bladed stirring system. The reactor is closed and then heated for 7 days at 170°C with stirring at 250-300 rpm. The resulting crystallized product is filtered, washed with deionized water (to achieve a neutral pH), and then dried overnight at 100°C. The solid is then introduced into a muffle furnace where calcination takes place: the calcination cycle consists of a temperature increase to 200°C, a holding period at 200°C for 2 hours, a temperature increase to 550°C followed by a holding period at 550°C for 8 hours, and then a return to room temperature.

[0071] The calcined solid product was analyzed by X-ray diffraction and identified as being composed of IZM-2 solid.

[0072] Example 2: preparation of an IZM-2 zeolite according to the invention

[0073] 0.17 g of deionized water were mixed with 0.237 g of sodium hydroxide (99.5% by weight, Aldrich). 0.015 g of sodium aluminate (53% by weight, Carlo Erba) is added to the previous mixture, and the resulting preparation is stirred for 15 minutes. 5.22 g of ethanol (98% by weight, Fisher) is added to the synthesis mixture and stirred for 10 minutes. Subsequently, 4.395 g of silicon alkoxide (TEOS, 25% by weight, Fluka) is incorporated into the synthesis mixture and stirred for 5 minutes. To promote the formation of the IZM-2 crystallized solid, 0.109 g of IZM-2 zeolite seeds (10% of the total mass of tetravalent elements as SiO2) prepared according to Example 1 The ingredients are added to the synthesis mixture, which is then stirred for 10 minutes. The resulting precursor gel has the following molar composition: 1 SiO2: 0.004 Al2O3: 10 EtOH: 0.17 Na2O: 1 H2O, for a SiO2 / Al2O3 ratio of 250. After homogenization, the mixture is transferred to an autoclave. The autoclave is closed and heated for 5 days at 170°C with stirring at 35 rpm using a rotisserie system. The crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0074] The solid product was analyzed by X-ray diffraction and identified as being composed of an IZM-2 zeolite.

[0075] Example 3: Preparation of an IZM-2 zeolite according to the invention

[0076] 0.486 g of deionized water were mixed with 0.704 g of sodium hydroxide (99.5% by weight, Aldrich). 0.029 g of sodium aluminate (53% by weight, Carlo Erba) is added to the previous mixture, and the resulting preparation is stirred for 15 minutes. 0.15 g of ethanol (98% by weight, Fisher) is added to the synthesis mixture and stirred for 10 minutes. Subsequently, 8.663 g of silicon alkoxide (TEOS, 25% by weight, Fluka) is incorporated into the synthesis mixture and stirred for 5 minutes. To promote the formation of the IZM-2 crystallized solid, 0.217 g of IZM-2 zeolite seeds (10% of the total mass of tetravalent elements as SiO2) prepared according to Example 1 are added to the synthesis mixture, which is stirred for 10 minutes. The precursor gel obtained has the following molar composition: 1 SiO2: 0.004 Al2O3: 0.09 EtOH: 0.25 Na2O: 1 H2O, i.e. a SiO2 / Al2O3 ratio of 250. The mixture is then transferred, after homogenization, into an autoclave.The autoclave is closed and then heated for 5 days at 170°C with agitation at 35 rpm using a rotisserie system. The resulting crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0077] The solid product was analyzed by X-ray diffraction and identified as being composed of an IZM-2 zeolite.

[0078] Example 4: Preparation of an IZM-2 zeolite according to the invention

[0079] 4.84 g of deionized water were mixed with 7.204 g of sodium hydroxide (99.5% (by weight, Aldrich). 0.28 g of sodium aluminate (53% by weight, Carlo Erba) are added to the previous mixture, and the resulting preparation is stirred for 15 minutes. 1.39 g of ethanol (98% by weight, Fisher) are added to the synthesis mixture and stirred for 10 minutes. Subsequently, 86.49 g of silicon alkoxide (TEOS, 25% by weight, Fluka) are incorporated into the synthesis mixture and stirred for 5 minutes. To promote the formation of the IZM-2 crystallized solid, 2.17 g of IZM-2 zeolite seeds (10% of the total mass of tetravalent elements as SiO2) prepared according to Example 1 are Added to the synthesis mixture, the mixture is stirred for 10 minutes. The resulting precursor gel has the following molar composition: 1 SiO2: 0.004 Al2O3: 0.08 EtOH: 0.26 Na2O: 1 H2O, for a SiO2 / Al2O3 ratio of 250. After homogenization, the mixture is transferred to an autoclave. The precursor gel is then transferred, after homogenization, to a 160 mL stainless steel reactor equipped with a four-bladed stirring system. The reactor is closed and heated for 7 days at 170°C with stirring at 250–300 rpm. The resulting crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0080] The solid product was analyzed by X-ray diffraction and identified as being composed of an IZM-2 zeolite.

[0081] Examples: preparation of an IZM-2 zeolite according to the invention

[0082] 1.7 g of deionized water were mixed with 2.479 g of sodium hydroxide (99.5% (by weight, Aldrich). 0.144 g of sodium aluminate (53% by weight, Carlo Erba) are added to the previous mixture, and the resulting preparation is stirred for 15 minutes. 52.034 g of ethanol (98% by weight, Fisher) are added to the synthesis mixture and stirred for 10 minutes. Subsequently, 43.82 g of silicon alkoxide (TEOS, 25% by weight, Fluka) are incorporated into the synthesis mixture and stirred for 5 minutes. To promote the formation of the IZM-2 crystallized solid, 1.10 g of IZM-2 zeolite seeds (10% of the total mass of tetravalent elements as SiO2) prepared according to Example 1 are added to the synthesis mixture, which is stirred for 10 minutes. The precursor gel obtained has the following molar composition: 1 SiO2: 0.004 Al 2O3: 6.08 EtOH: 0.18 Na2O: 1 H2O, i.e. a SiO2 / Al2O3 ratio of 250. The mixture is then transferred, after homogenization, into an autoclave.The precursor gel is then transferred, after homogenization, into a 160 mL stainless steel reactor equipped with a four-bladed stirring system. The reactor is closed and then heated for 7 days at 170°C with stirring at 250-300 rpm. The resulting crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0083] The solid product was analyzed by X-ray diffraction and identified as being composed of an IZM-2 zeolite.

[0084] Example 6: Preparation of an IZM-2 zeolite according to the invention

[0085] 1.7 g of deionized water were mixed with 2.482 g of sodium hydroxide (99.5% (by weight, Aldrich). 0.142 g of sodium aluminate (53% by weight, Carlo Erba) are added to the previous mixture, and the resulting preparation is stirred for 15 minutes. 52.05 g of ethanol (98% by weight, Fisher) are added to the synthesis mixture and stirred for 10 minutes. Subsequently, 43.82 g of silicon alkoxide (TEOS, 25% by weight, Fluka) are incorporated into the synthesis mixture and stirred for 5 minutes. In order to promote the To form the IZM-2 crystallized solid, 1.10 g of IZM-2 zeolite seeds (10% of the total mass of tetravalent elements in SiO2 form) prepared according to Example 1 are added to the synthesis mixture, which is then stirred for 10 minutes. The resulting precursor gel has the following molar composition: 1 SiO2: 0.004 Al2O3: 6.08 EtOH: 0.18 Na2O: 1 H2O, corresponding to a SiO2 / Al2O3 ratio of 250. After homogenization, the mixture is transferred to an autoclave. The precursor gel is then transferred, after homogenization, to a 160 mL stainless steel reactor equipped with a four-bladed stirring system. The reactor is closed and then heated for 5 days at 190°C with stirring at 250–300 rpm. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100°C.

[0086] The solid product was analyzed by X-ray diffraction and identified as being composed of an IZM-2 zeolite.

[0087] Example 7: Preparation of an IZM-2 zeolite according to the invention

[0088] 4.83 g of deionized water were mixed with 7.2 g of sodium hydroxide (99.5% in weight, Aldrich). 0.28 g of sodium aluminate (53 wt., Carlo Erba) are added to the previous mixture, and the resulting preparation is stirred for 15 minutes. 1.39 g of ethanol (98 wt., Fisher) are added to the synthesis mixture and stirred for 10 minutes. Subsequently, 86.46 g of silicon alkoxide (TEOS, 25 wt., Fluka) are incorporated into the synthesis mixture and stirred for 5 minutes. To promote the formation of the IZM-2 crystallized solid, 1.089 g of IZM-2 zeolite seeds (5 wt. of the total mass of tetravalent elements as SiO2) prepared according to Example 1 are added to the synthesis mixture, which is stirred for 10 minutes. The precursor gel obtained has the following molar composition: 1 SiO2: 0.004 Al 2O3: 0.08 EtOH: 0.26 Na2O: 1 H2O, i.e. a SiO2 / Al2O3 ratio of 250. The mixture is then transferred, after homogenization, into an autoclave.The precursor gel is then transferred, after homogenization, to a 160 mL stainless steel reactor equipped with a four-bladed stirring system. The reactor is closed and then heated for 5 days at 170°C with stirring at 250-300 rpm. The resulting crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0089] The solid product was analyzed by X-ray diffraction and identified as being composed of an IZM-2 zeolite.

[0090] Example 8: Preparation of an IZM-2 zeolite according to the invention

[0091] 1.7 g of deionized water were mixed with 2.48 g of sodium hydroxide (99.5% in weight, Aldrich). 0.148 g of sodium aluminate (53% by weight, Carlo Erba) are added to the previous mixture, and the resulting preparation is stirred for 15 minutes. 52.04 g of ethanol (98% by weight, Fisher) are added to the synthesis mixture and stirred for 10 minutes. Subsequently, 43.78 g of silicon alkoxide (TEOS, 25% by weight, Fluka) are incorporated into the synthesis mixture and stirred for 5 minutes. To promote the formation of the IZM-2 crystallized solid, 0.55 g of IZM-2 zeolite seeds (5% of the total mass of tetravalent elements as SiO2) prepared according to Example 1 are added to the synthesis mixture, which is then stirred for 10 minutes. The resulting precursor gel has the following molar composition: 1 SiO2: 0.004 Al2O3: 6.09 EtOH: 0.18 Na2O: 1 H2O, corresponding to a SiO2 / Al2O3 ratio of 250. The mixture is then transferred, after homogenization, to an autoclave. The precursor gel is then transferred, after homogenization, to a 160 mL stainless steel reactor equipped with a four-bladed stirring system. The reactor is sealed and then heated for 5 days at 190°C with stirring at 250–300 rpm. The resulting crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0092] The solid product was analyzed by X-ray diffraction and identified as consisting of an IZM-2 zeolite.

[0093] Example 9: Preparation of an IZM-2 zeolite according to the invention

[0094] 4.81 g of deionized water were mixed with 7.2 g of sodium hydroxide (99.5% in weight, Aldrich). 0.47 g of sodium aluminate (53 wt., Carlo Erba) are added to the previous mixture, and the resulting preparation is stirred for 15 minutes. 1.39 g of ethanol (98 wt., Fisher) are added to the synthesis mixture and stirred for 10 minutes. Subsequently, 86.38 g of silicon alkoxide (TEOS, 25 wt., Fluka) are incorporated into the synthesis mixture and stirred for 5 minutes. To promote the formation of the IZM-2 crystallized solid, 2.163 g of IZM-2 zeolite seeds (10% of the total mass of tetravalent elements as SiO2) prepared according to Example 1 are added to the synthesis mixture, which is stirred for 10 minutes. The precursor gel obtained has the following molar composition: 1 SiO2: 0.007 Al2O3: 0.08 EtOH: 0.26 Na2O: 1 H2O, i.e. a SiO2 / Al2O3 ratio of 150. The mixture is then transferred, after homogenization, into an autoclave.The precursor gel is then transferred, after homogenization, to a 160 mL stainless steel reactor equipped with a four-bladed stirring system. The reactor is closed and then heated for 5 days at 170°C with stirring at 250-300 rpm. The resulting crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0095] The solid product was analyzed by X-ray diffraction and identified as being composed of an IZM-2 zeolite.

[0096] Example 10: Preparation of an IZM-2 zeolite according to the invention

[0097] 1.7 g of deionized water were mixed with 2.36 g of sodium hydroxide (99.5% in weight, Aldrich). 0.24 g of sodium aluminate (53% by weight, Carlo Erba) are added to the previous mixture, the resulting preparation is kept under stirring for 15 52.00 g of ethanol (98% by weight, Fisher) are added to the synthesis mixture and stirred for 10 minutes. Subsequently, 43.79 g of silicon alkoxide (TEOS, 25% by weight, Fluka) are incorporated into the synthesis mixture and stirred for 5 minutes. To promote the formation of the IZM-2 crystallized solid, 1.1 g of IZM-2 zeolite seeds (10% of the total mass of tetravalent elements as SiO2) prepared according to Example 1 are added to the synthesis mixture, which is then stirred for 10 minutes. The resulting precursor gel has the following molar composition: 1 SiO2: 0.007 Al2O3: 6.09 EtOH: 0.17 Na2O: 1 H2O, for a SiO2 / Al2O3 ratio of 150. After homogenization, the mixture is transferred to an autoclave. Following further homogenization, the precursor gel is transferred to a 160 mL stainless steel reactor equipped with a four-bladed stirring system.The reactor is closed and then heated for 5 days at 190°C with stirring at 250-300 rpm. The resulting crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0098] The solid product was analyzed by X-ray diffraction and identified as being composed of an IZM-2 zeolite.

[0099] Example 11: Synthesis not according to the invention: Synthesis in a more dilute medium

[0100] 3.85 g of deionized water were mixed with 0.147 g of sodium hydroxide (99.5% (by weight, Aldrich). 0.009 g of sodium aluminate (53% by weight, Carlo Erba) are added to the previous mixture, and the resulting preparation is stirred for 15 minutes. 3.22 g of ethanol (98% by weight, Fisher) are added to the synthesis mixture and stirred for 10 minutes. Subsequently, 2.17 g of silicon alkoxide (TEOS, 25% by weight, Fluka) are incorporated into the synthesis mixture and stirred for 5 minutes. To promote the formation of the IZM-2 crystallized solid, 0.067 g of IZM-2 zeolite seeds (10% of the total mass of tetravalent elements as SiO2) prepared according to Example 1 are added to the synthesis mixture, which is stirred for 10 minutes. The precursor gel obtained has the following molar composition: 1 SiO2: 0.005 Al2O3: 7.6 EtOH: 0.21 Na2O: 24.3 H2O, i.e. a SiO2 / Al2O3 ratio of 193. The mixture is then transferred, after homogenization, into an autoclave.The autoclave is closed and then heated for 5 days at 170°C with agitation at 35 rpm using a rotisserie system. The resulting crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0101] The solid product was analyzed by X-ray diffraction and identified as being made of Quartz (ICDD datasheet, PDF 00-011-0252).

[0102] Example 12: Synthesis not according to the invention: Synthesis in a more dilute medium

[0103] 5.63 g of deionized water were mixed with 0.21 g of sodium hydroxide (99.5% (by weight, Aldrich). 0.018 g of sodium aluminate (53% by weight, Carlo Erba) are added to the previous mixture, and the resulting preparation is stirred for 15 minutes. 0.085 g of ethanol (98% by weight, Fisher) are added to the synthesis mixture and stirred for 10 minutes. Subsequently, 3.92 g of silicon alkoxide (TEOS, 25% by weight, Fluka) are incorporated into the synthesis mixture and stirred for 5 minutes. To promote the formation of the IZM-2 crystallized solid, 0.099 g of IZM-2 zeolite seeds (10% of the total mass of tetravalent elements as SiO2) prepared according to Example 1 are added to the synthesis mixture, which is stirred for 10 minutes. The precursor gel obtained has the following molar composition: 1 SiO2: 0.006 Al2O3: 0.11 EtOH: 0.17 Na2O: 19.3 H2O, i.e. a SiO2 / Al2O3 ratio of 174. The mixture is then transferred, after homogenization, into an autoclave.The autoclave is closed and then heated for 5 days at 170°C with agitation at 35 rpm using a rotisserie system. The resulting crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0104] The solid product was analyzed by X-ray diffraction and identified as being made of Quartz (ICDD datasheet, PDF 00-011-0252).

[0105] Example 13: Synthesis not according to the invention: Synthesis without the addition of ethanol

[0106] 5.99 g of sodium hydroxide (99.5% by weight, Aldrich) were mixed with 0.249 g of sodium aluminate (53 wt., Carlo Erba) is stirred for 15 minutes. Subsequently, 47.971 g of colloidal silica (Ludox HS40, 40 wt., Aldrich) is incorporated into the synthesis mixture and stirred for 5 minutes. To promote the formation of the IZM-2 crystallized solid, 1.92 g of IZM-2 zeolite seeds (10% of the total mass of tetravalent elements as SiO2) prepared according to Example 1 are added to the synthesis mixture, which is then stirred for 10 minutes. The resulting precursor gel has the following molar composition: 1 SiO2: 0.004 Al2O3: 0.25 Na2O: 3 H2O. resulting in a SiO2 / Al2O3 ratio of 250. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and heated for 5 days at 170°C with agitation at 35 rpm using a rotisserie system. The resulting crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0107] The solid product was analyzed by X-ray diffraction and identified as being made of Quartz (ICDD datasheet, PDF 00-011-0252).

[0108] Example 14: Synthesis not according to the invention: Synthesis without the addition of ethanol or nucleus of IZM-2 zeolite

[0109] 5.99 g of sodium hydroxide (99.5% by weight, Aldrich) were mixed with 0.245 g of sodium aluminate (53% by weight, Carlo Erba) is maintained under The mixture is stirred for 15 minutes. Subsequently, 47.98 g of colloidal silica (Ludox HS40, 40% by weight, Aldrich) is incorporated into the synthesis mixture and stirred for 5 minutes. The resulting precursor gel has the following molar composition: 1 SiO2: 0.004 Al2O3: 0.25 Na2O: 4 H2O, corresponding to a SiO2 / Al2O3 ratio of 250. After homogenization, the mixture is transferred to an autoclave. The autoclave is closed and heated for 5 days at 170°C with stirring at 35 rpm using a rotary spindle. The resulting crystallized product is filtered, washed with deionized water, and then dried overnight at 100°C.

[0110] The solid product was analyzed by X-ray diffraction and identified as consisting of Kenyaite (ICDD datasheet, PDF 00-020-1157).

Claims

Demands

1. A process for preparing a microporous IZM-2 solid or a structuring-free IZM-2 zeolite comprising at least the following steps: (i) mixing, in the presence of at least one alcohol and water, at least one source of at least one tetravalent element X in the form of oxide XO2, at least one source of at least one trivalent element in the form of oxide Y2O3, at least one source of at least one alkali and / or alkaline earth metal M of valence n, n being an integer greater than or equal to 1, and calcined IZM-2 zeolite seeds, the mixture having the following molar composition: XO2 / Y2O3 from 70 to 350, H2O / XO2 from 1 to 5, Alcohol / XO2 from 0.05 to 30, M2 / nO / XO2 from 0.05 to 0.45, where Y is one or more trivalent element(s) chosen from the group formed by the following elements: aluminum, iron, boron, gallium; X is one or more tetravalent element(s) chosen from the group formed by the following elements: silicon,germanium, titanium, M is one or more alkali and / or alkaline earth metal(s) selected from lithium, sodium, potassium, calcium, magnesium and mixtures of at least two of these metals, the alcohol is selected from the group formed by primary, secondary and tertiary alcohols, until a homogeneous mixture called precursor gel is obtained; ii) hydrothermal treatment of said precursor gel obtained at the end of step i) at a temperature between 120 and 220°C, for a period of between 1 and 10 days until said zeolite IZM-2 is formed.

2.

3. A method according to claim 1 wherein X is silicon. A method according to claim 2 wherein the silicon source is selected from powdered silica, silicic acid, colloidal silica, dissolved silica and silicon alkoxides, alone or in mixture.

4. A method according to claim 3 wherein the silicon source is tetraethyl orthosilicate or TEOS.

5. A method according to any one of claims 1 to 4 wherein Y is aluminum.

6. A process according to claim 5 wherein the aluminum source in the form of A12O3 oxide is an aluminum salt selected from aluminum chlorides, aluminum nitrates, aluminum sulfates, sodium aluminates, alone or in mixture.

7. A method according to claim 6 wherein the source of aluminium in the form of oxide A12O3 is sodium aluminate.

8. A method according to any one of claims 1 to 7 wherein the source of at least one alkali and / or alkaline earth metal M is sodium hydroxide.

9. A process according to any one of claims 1 to 8 wherein the calcined IZM-2 zeolite seeds are added to the mixture of step i) in a proportion of between 0.01 and 13%, preferably between 0.01 and 10% and preferably between 0.01 and 5% of the total mass of the sources of said tetravalent and trivalent element(s) used in the reaction mixture, said seeds not being taken into account in the total mass of the sources of the tetravalent and trivalent elements.

10. A process according to any one of claims 1 to 9 wherein the alcohol added in step i) is ethanol.

11. A process according to any one of claims 1 to 10, wherein the mixture of step i) has the following molar composition: XO2 / Y2O3 from 100 to 260; H2O / XO2 from 1 to 3; Alcohol / XO2 from 0.065 to 20; M2 / nO / XO2 from 0.09 to 0.3

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