Process for the synthesis of izm-10 aei zeolite with very high purity in the presence of a nitrogen-containing organic structuring agent

Abstract

This invention relates to a method for preparing AEI-based IZM-10 zeolite, the method comprising at least mixing the following substances in an aqueous medium: FAU-based zeolite, whose SiO2... 2(FAU) / Al2O 3(FAU) The precursor gel obtained at the end of step i) is then subjected to hydrothermal treatment, comprising a molar ratio of 10 to 60 (inclusive of endpoints) and less than 0.005% by mass of sodium in cationic form, a nitrogen-containing organic compound R, wherein R is (6R,10S)-6,10-dimethyl-5-aza-onium spiro[4.5]decane in hydroxide form, and optionally sodium hydroxide. The invention also relates to AEI-based zeolites having a SiO2 / Al2O3 molar ratio of 10 to 60 (inclusive of endpoints) and a purity greater than or equal to 98% by weight, preferably greater than or equal to 99% by weight, wherein the zeolite is in a partially or fully protonated form and is obtained by the method described.

Description

Technical Field

[0001] This invention relates to a novel method for preparing AEI-based IZM-10 zeolite. This novel method enables the synthesis of AEI-based IZM-10 zeolite under hydrothermal conditions by converting / transforming FAU-based zeolite. Specifically, the novel method uses FAU-based zeolite as a source of silicon and aluminum, and organic molecules or specific structural reagents ((6R,10S)-6,10-dimethyl-5-azaspiro[4.5]decane in hydroxide form) as raw materials to achieve the synthesis of AEI-based IZM-10 zeolite. The AEI-based IZM-10 zeolite obtained according to the method of this invention can advantageously be used as a catalyst, adsorbent, or separating agent.

[0002] Existing technology

[0003] Crystalline microporous materials, such as zeolites or aluminosilicates, are solids widely used in the petroleum industry as catalysts, catalyst supports, adsorbents, or separating agents. Although many microporous crystal structures have been discovered, the refining and petrochemical industries are constantly searching for new zeolite structures with special properties for applications such as gas purification or separation and the conversion of carbon-based materials.

[0004] AEI-based zeolites, particularly zeolite SSZ-39 (Wagner, P et al.), J. Am. Chem. Soc. ,122, 263-273 (2000)), and zeolite-type material ALPO-18 (Simmen, A. et al., Zeolites , 11, 654-661 (1991)) and SAPO-18 (Chen, JS et al., Catalysis Letters , 28, 241-248 (1994)). The “AEI” framework type is defined by the “Structure Committee” of the International Zeolite Association (IZA).

[0005] AEI-framework type zeolites possess a three-dimensional porous system defined by eight tetrahedral TO4 atoms, obtained through three-dimensional linkages of bicyclic (D6R) atoms of T (where T can be silicon, aluminum, or phosphorus). Many methods for synthesizing AEI-framework type zeolites are known. They require the simultaneous use of an organic structuring agent and an inorganic base (sodium hydroxide or potassium hydroxide). To obtain the protonated form of the zeolite, an ion exchange step with an aqueous solution of NH4NO3, NH4Cl, ammonium acetate, or any other ammonium cation is necessary.

[0006] Patent application CN112758954 discloses the synthesis of a core-shell SSZ-39 zeolite, wherein the core contains copper. The synthesis is carried out in the presence of sodium hydroxide or potassium hydroxide, in the presence of an organic structuring agent selected from the following ions: N,N-diethyl-2,6-dimethylpiperidinium, 1,1,3,5-tetramethylpiperidinium, 2,6-dimethyl-5-azapyron[4.5]decane, N,N-diethyl-2-ethylpiperidinium, N-ethyl-N-propyl-2,6-dimethylpiperidinium, N-methyl-N-ethyl-2,6-dimethylpiperidinium, N-methyl-N-ethyl-2-ethylpiperidinium, 2,5-dimethyl-N,N-diethylpyridinium, and 2,5-dimethyl-N,N-diethylpyridinium. The reagents used are: pyruvate, 2,6-dimethyl-N,N-dimethylpiperidinium, 3,5-dimethyl-N,N-dimethylpiperidinium, 2-ethyl-N,N-dimethylpiperidinium, 2,2,6,6-tetramethyl-N-methyl-N-ethylpiperidinium, N-cyclooctylpyridinium, 2,2,6,6-tetramethyl-N,N-dimethylpiperidinium, and N,N-dimethyl-N,N-bicyclononane; preferably, the organic structuring agent is selected from: N,N-diethyl-2,6-dimethylpiperidinium and / or 3,5-dimethyl-N,N-dimethylpiperidinium. Na₂O is present in the synthesis mixture. (NaOH) The SiO2 molar ratio is 0.05 to 0.25. To obtain the protonated form of zeolite, an ion exchange step with NH4NO3 is necessary.

[0007] Patent application US2022106192 discloses the synthesis of AEI-type zeolites in the presence of N,N-dialkyldialkylpiperidinium cationic and N,N-(C1-C3)dialkyl-(C1-C3)dialkylpiperidinium cationic (preferably N,N-(C1-C2)dialkyl-(C1-C3)dialkylpiperidinium cationic, more preferably N,N-diethyl-2,6-dimethylpiperidinium cationic, and even more preferably N,N-diethyl-cis-2,6-dimethylpiperidinium cationic) organic structuring agents. The zeolite synthesis is carried out in the presence of sodium hydroxide and any other Na cation source. Na₂O in the synthesis mixture... (NaOH) The SiO2 molar ratio is 0.25 to 1. Preferably, the synthesized gel does not contain FAU-based zeolites. To obtain the protonated form of the zeolite, an ion exchange step with NH4NO3 is necessary.

[0008] The article, "Hydrothermal Conversion of Titanated FAU to AEI Zeolite and Its Enhanced Catalytic Performance for NOx Reduction," Adv. Porous Mater.(2016, Vol. 4, No. 1, 62) A method for synthesizing AEI zeolite using [Al,Ti]-FAU zeolite as the silicon and aluminum source in the presence of sodium hydroxide and the organic structuring agent 1,1-diethyl-2,6-dimethylpiperidinium hydroxide (DEDMPOH) was proposed. The Na₂O in the synthesis mixture... (NaOH) The molar ratio of SiO2 is 0.1. To obtain the protonated form of zeolite, an ion exchange step with NH4NO3 is necessary.

[0009] Patent application CN105314646A discloses the synthesis of AEI-based zeolites in the presence of organic structuring agents selected from the following cations: 1-methyl-2,6-dimethylpiperidinium, 1-ethyl-2,6-dimethylpiperidinium, 1-methyl-3,5-dimethylpiperidinium, 1-ethyl-3,5-dimethylpiperidinium, 1,1-dimethyl-2,6-dimethylpiperidinium, 1,1-diethyl-2,6-dimethylpiperidinium, 1,1-dimethyl-3,5-dimethylpiperidinium, 1-ethyl-3,5-dimethylpiperidinium, 1,1-diethyl-2,6-dimethylpiperidinium, and 1,1-diethyl-3,5-dimethylpiperidinium. The synthesis of AEI-based zeolites is carried out in the presence of sodium hydroxide or potassium hydroxide. Na₂O in the synthesis mixture... (NaOH) The SiO2 molar ratio is 0.1 to 0.5. To obtain the protonated form of zeolite, an ion exchange step with NH4NO3 is necessary.

[0010] Patent application CN107285333A discloses the synthesis of AEI-type zeolites using microwaves in the presence of organic structuring agents selected from the following cations: 1,1,2,2,6,6-hexamethylpiperidinium, 1,1,2,2,6,6-hexamethyl-4-oxopiperidinium, 1,1,3,5-tetramethyl-4-oxopiperidinium, 1-hydroxy-1,1,2,2,6,6-hexamethylpiperidinium. The synthesis of AEI-based zeolites, including methylpiperidinium, 1,1-dimethyl-4,4-propoxypiperidinium, 3,5-dimethoxy-1,1-dimethylpiperidinium, 3,5-dihydroxy-1,1-dimethylpiperidinium, 4-ethyl-1,1-dimethyl-3,5-dioxopyridinium, 1-ethyl-1-methyl-2,2,6-methylpiperidinium, and 1-epoxypropyl-1-methyl-2,2,6,6-hexamethylpiperidinium, was carried out in the presence of sodium hydroxide or potassium hydroxide. Na₂O was added to the synthesis mixture. (NaOH) The molar ratio of SiO2 is 0.1 to 0.5.

[0011] Patent application CN107308980A proposes the use of copper-containing AEI framework type zeolites in NH3-SCR. The synthesis of AEI-based zeolites was carried out in the presence of sodium hydroxide and an organic structuring agent selected from the following cations: 1,1,2,2,6,6-hexamethylpiperidinium, 1,1,2,2,6,6-hexamethyl-4-oxoperidinium, 1,1,3,5-tetramethyl-4-oxoperidinium, 1-hydroxy-1,1,2,2,6,6-hexamethylpiperidinium, 1,1-dimethyl-4,4-propoxypiperidinium, 3,5-dimethoxy-1,1-dimethylpiperidinium, 3,5-dihydroxy-1,1-dimethylpiperidinium, 4-ethyl-1,1-dimethyl-3,5-dioxoperidinium, 1-ethyl-1-methyl-2,2,6-methylpiperidinium, and 1-epoxypropyl-1-methyl-2,2,6,6-hexamethylpiperidinium. Na2O in the synthesis mixture (NaOH) The molar ratio of SiO2 is 0.1 to 0.5.

[0012] Patent application US5958370 discloses the synthesis of AEI-type SSZ-39 zeolite in the presence of sodium hydroxide and an organic structuring agent selected from the following cations: N,N-diethyl-2,6-dimethylpiperidinium, N,N-dimethyl-9-azabicyclo[3.3.1]nonane, N,N-dimethyl-2,6-dimethylpiperidinium, N-ethyl-N-methyl-2,6-dimethylpiperidinium, N,N-diethyl-2-ethylpiperidinium, N,N-dimethyl-2-ethylpiperidinium, N,N-dimethyl-2-ethylpiperidinium, N,N-dimethyl-2-ethylpiperidinium, N,N-dimethyl-2-ethylpiperidinium, N,N-dimethyl-2-ethylpiperidinium, N,N-dimethyl-2-ethylpiperidinium, N,N-dimethyl-2-methyl ... N,N-dimethyl-2-ethylpiperidinium, N,N-dimethyl-3,5-dimethylpiperidinium, N-ethyl-N-methyl-2-ethylpiperidinium, 2,6-dimethyl-1-azainium[5.4]decane, N-ethyl-N-propyl-2,6-dimethylpiperidinium, 2,2,4,6,6-pentamethyl-2-azainium bicyclo[3.2.1]octane, N,N-diethyl-2,5-dimethyl-2,5-dihydropyrroleium. The Na2O in the synthesis mixture... (NaOH) The / SiO2 molar ratio is 0.3 to 1. The synthesis time is greater than 6 days. According to the patent, the structuring reagents N,N-dimethyl-2-ethylpiperidinium, N-ethyl-N-methyl-2-ethylpiperidinium, 2,6-dimethyl-1-azainium[5.4]decane and N-ethyl-N-propyl-2,6-dimethylpiperidinium cannot yield pure AEI framework type SSZ-39 zeolite, as analcime impurities are present. In order to obtain the protonated form of the zeolite, an ion exchange step with NH4NO3 is necessary.

[0013] Patent application US2017128921 discloses the synthesis of AEI-type zeolites in the presence of sodium hydroxide and organic structuring agents selected from the following cations: N,N-dimethyl-3,5-dimethylpiperidinium, N,N-dimethyl-2-(2-hydroxyethyl)piperidinium, N,N-dimethyl-2-ethylpiperidinium, and 2,2,4,6,6-pentamethyl-2-aza-onium bicyclo[3.2.1]octane. The synthesis mixture contains Na₂O. (NaOH) The SiO2 molar ratio is 0.2 to 1. To obtain the protonated form of zeolite, an ion exchange step with ammonium acetate is necessary.

[0014] The article "Transformation synthesis of aluminosilicate SSZ-39 zeolite from ZSM-5 and beta zeolite" J. Mater. Chem. A (2019, 7, 4420) A method for synthesizing AEI-framework type SSZ-39 zeolite via inter-zeolite conversion in the presence of the organic structuring reagent N,N-diethyl-cis-2,6-dimethylpiperidinium hydroxide and sodium hydroxide was proposed. Na₂O in the synthesis mixture... (NaOH) The molar ratio of SiO2 is 0.17. To obtain the protonated form of zeolite, an ion exchange step with NH4NO3 is necessary.

[0015] The article, "Synthesis of high-silica AEI zeolites with enhanced thermal stability by hydrothermal conversion of FAU zeolites, and their activity in the selective catalytic reduction of NOx with NH3," J. Mater. Chem. A (2015, 3, 857) proposed the synthesis of AEI-framework zeolites via interconversion in a fluoride medium in the presence of the organic structuring agent tetraethylphosphine. This synthesis yields AEI-framework zeolites that are more stable at high temperatures than those obtained in an alkaline medium using the organic structuring agent N,N-diethyl-2,6-dimethylpiperidinium. Na₂O in the synthesis mixture... (NaOH)The molar ratio of SiO2 is 0.05. To obtain the protonated form of zeolite, an ion exchange step with NH4Cl is necessary.

[0016] Patent application US2018093257 discloses the synthesis of JMZ-8 zeolite of the AEI framework type in the presence of sodium hydroxide and an organic structuring agent R selected from N,N-diethyl-cis-2,6-dimethylpiperidinium or N,N-dimethyl-3,5-dimethylpiperidinium. The synthesis mixture contains Na₂O. (NaOH) The molar ratio of Al2O3 is 0.5 to 2. The purity of the obtained AEI zeolite is greater than 90%. To obtain the protonated form of the zeolite, an ion exchange step with NH4NO3 is necessary.

[0017] US Patent 2018093256 discloses the synthesis of JMZ-9 zeolite of the AEI framework type in the presence of an organic structuring agent R selected from N,N-diethyl-cis-2,6-dimethylpiperidinium or N,N-dimethyl-3,5-dimethylpiperidinium or mixtures thereof. The claimed molar ratios are: (SiO2) / (Al2O3) 20 to 50, H2O / SiO2 10 to 40, R / SiO2 0.25 to 1, and H2O... - / SiO2 is 0.25 to 1.

[0018] Patent application US2020-0360906A1 discloses the synthesis of JMZ-8 zeolite of the AEI framework type in the presence of sodium hydroxide and an organic structuring agent R selected from N,N-diethyl-cis-2,6-dimethylpiperidinium or N,N-dimethyl-3,5-dimethylpiperidinium. The synthesis mixture contains Na₂O. (NaOH) The molar ratio of Al2O3 is 0.5 to 2. The purity of the obtained AEI zeolite is greater than 90%. To obtain the protonated form of the zeolite, an ion exchange step with NH4NO3 is necessary.

[0019] Patent application WO2016 / 166245 discloses the synthesis of AEI-type zeolites in the presence of sodium hydroxide and organic structuring agents selected from the following: N,N-dimethyl-3,5-dimethylpiperidinium, N,N-diethyl-2,6-dimethylpiperidinium (DEDMP), N,N-dimethyl-2,6-dimethylpiperidinium, and N-ethyl-N-methyl-2,6-dimethylpiperidinium, used alone or as a mixture. The Na₂O in the synthesis mixture... (NaOH) The molar ratio of Al2O3 is 0.001 to 2. To obtain the protonated form of zeolite, an ion exchange step with NH4NO3 is necessary. Summary of the Invention

[0020] Surprisingly, the applicant discovered that AEI-type zeolites can be obtained in the synthesis with little or no sodium hydroxide (NaOH) in the presence of an organic structuring agent ((6R,10S)-6,10-dimethyl-5-aza-onium spiro[4.5]decane in hydroxide form). Furthermore, the partially or fully protonated form of the zeolite can be obtained by direct calcination after synthesis without prior exchange with a soluble ammonium cation source. For the purposes of this invention, the term "partially protonated" should be understood to mean that the AEI zeolite contains an Al₂O₃ / Na₂O molar ratio of 100 to 400, while "fully protonated" should be understood to mean that the AEI zeolite contains an Al₂O₃ / Na₂O molar ratio greater than 400.

[0021] This invention relates to a method for preparing AEI framework type zeolites (which may be referred to by the term "IZM-10"), comprising at least the following steps: i) Mix the following substances in an aqueous medium: FAU framework type zeolite with SiO₂ 2(FAU) / Al2O 3(FAU) The reaction mixture has a molar composition of 10 to 60, including endpoint values, and less than 0.005% by mass of sodium in cationic form, containing a nitrogen-containing organic compound R, wherein R is (6R,10S)-6,10-dimethyl-5-aza-onium-spiro[4.5]decane in hydroxide form, and optionally sodium hydroxide. (SiO 2(FAU) ) / (Al2O 3(FAU) The value is 10 to 60, preferably 30 to 50. H2O / (SiO 2(FAU) The value is 20 to 60, preferably 30 to 50. R / (SiO 2(FAU) The value is 0.05 to 0.70, preferably 0.15 to 0.60. Na2O (NaOH) / (SiO 2(FAU) The value is 0 to 0.20, preferably 0 to 0.15. Na2O (FAU) / (SiO 2(FAU) ) is 3.5×10 -5 Up to 7×10 -5 4×10 is preferred -5 Up to 6×10 -5 Na2O (FAU) This indicates the amount of Na2O contributed by FAU zeolite. (NaOH) This indicates the amount of Na₂O contributed by sodium hydroxide, SiO₂ 2(FAU)This represents the amount of SiO2 contributed by FAU zeolite, and Al2O 3(FAU) This indicates the amount of Al2O3 contributed by FAU zeolite until a homogeneous precursor gel is obtained; ii) The precursor gel obtained at the end of step i) is subjected to hydrothermal treatment at a temperature of 120°C to 220°C for 12 hours to 7 days.

[0022] The term "IZM-10" is the name used by the inventors to refer to a novel zeolite specifically obtained through this method.

[0023] The SiO2 / Al2O3 molar ratio of the obtained AEI zeolite can advantageously be 10 to 60, preferably 12 to 50 (including endpoint values), and the Al2O3 / Na2O molar ratio of the obtained AEI zeolite is advantageously greater than 100, preferably greater than 400.

[0024] The SiO2 / Al2O3 molar ratio of FAU framework type zeolites can advantageously be 20 to 50 (including endpoint values), and the mass percentage of sodium in cationic form is less than 0.0048%.

[0025] Advantageously, no sodium hydroxide is added to the synthetic gel (Na2O). (NaOH) / (SiO 2(FAU) ) = 0), and directly obtain IZM-10 zeolite of the AEI framework type in protonated form.

[0026] Seed crystals of AEI framework type zeolite can be added to the reaction mixture of step i), preferably in an amount of 0.01% to 10% by weight relative to the total mass of tetravalent and trivalent elements present in anhydrous form in the mixture, excluding the total mass of SiO2 and Al2O3.

[0027] Step i) may include aging the reaction mixture for 30 minutes to 48 hours at a temperature of 20 to 100°C, with or without stirring.

[0028] The hydrothermal treatment in step ii) can be carried out under autogenous pressure at a temperature of 120°C to 220°C, preferably 150°C to 200°C, more preferably 160°C to 195°C, for 12 hours to 7 days, preferably 12 hours to 6 days.

[0029] The solid phase obtained at the end of step ii) can be filtered, washed, and dried at a temperature of 20 to 150°C, preferably 60 to 100°C, for 5 to 24 hours to obtain dried zeolite.

[0030] The dried zeolite can then be calcined at 450 to 700°C for 2 to 20 hours, with the temperature gradually increased before calcination.

[0031] The present invention also relates to an AEI framework type zeolite having a SiO2 / Al2O3 molar ratio of 10 to 60 (inclusive), a purity greater than or equal to 98% by weight, preferably greater than or equal to 99% by weight, very preferably greater than or equal to 99.8% by weight, being in a partially or fully protonated form, particularly obtained by the above method, and containing the following significant X-ray diffraction lines:

[0032] Where VS = extremely strong; S = strong; m = moderate; mw = moderately weak; w = weak; vw = extremely weak, relative strength I rel The relative intensity scale is given, where the value of the strongest line in the X-ray diffraction pattern is set to 100: vw<15; 15≤w<30; 30≤mw<50; 50≤m<65; 65≤S<85; VS≥85.

[0033] Preferably, the SiO2 / Al2O3 molar ratio of the zeolite is 10 to 60, more preferably 12 to 50 (including endpoint values), and the Al2O3 / Na2O molar ratio is greater than 100, more preferably greater than 400. Attached Figure Description

[0034] Figure 1 The chemical formula represents the nitrogen-containing organic compound ((6R,10S)-6,10-dimethyl-5-aza-onnaft[4.5]decane in hydroxide form) used in the synthesis method of the present invention.

[0035] Figure 2 The image shows the X-ray diffraction pattern of IZM-10 zeolite of the AEI framework type obtained according to Example 2.

[0036] Figure 3 This represents a scanning electron microscope (SEM) image of IZM-10 zeolite of the AEI skeleton type obtained according to Example 2.

[0037] Figure 4 The X-ray diffraction pattern of the mixture of AEI and MOR framework-type zeolites obtained according to Comparative Example 5 is shown.

[0038] Other features and advantages of the synthesis method of the present invention will become apparent after reading the following non-limiting exemplary embodiments described with reference to the accompanying drawings. Detailed Implementation

[0039] One subject of this invention is a novel method for preparing AEI framework type IZM-10 zeolite by converting / transforming FAU framework type zeolite with less than 0.005% by mass of sodium in cationic form under hydrothermal conditions in the presence of a nitrogen-containing organic compound or a specific structuring agent ((6R,10S)-6,10-dimethyl-5-aza-onium[4.5]decane in hydroxide form).

[0040] More specifically, one subject of the present invention is a novel method for preparing IZM-10 zeolite of the AEI framework type, comprising at least the following steps: i) Mix the following substances in an aqueous medium: FAU framework type zeolite with SiO₂ 2(FAU) / Al2O 3(FAU) The reaction mixture has a molar composition of 10 to 60, including endpoint values, and less than 0.005% by mass of sodium in cationic form, containing a nitrogen-containing organic compound R, wherein R is (6R,10S)-6,10-dimethyl-5-aza-onium-spiro[4.5]decane in hydroxide form, and optionally sodium hydroxide. (SiO 2(FAU) ) / (Al2O 3(FAU) The value is 10 to 60, preferably 30 to 50. H2O / (SiO 2(FAU) The value is 20 to 60, preferably 30 to 50. R / (SiO 2(FAU) The value is 0.05 to 0.70, preferably 0.15 to 0.60. Na2O (NaOH) / (SiO 2(FAU) The value is 0 to 0.20, preferably 0 to 0.15. Na2O (FAU) / (SiO 2(FAU) ) is 3.5×10 -5 Up to 7×10 -5 4×10 is preferred -5 Up to 6×10 -5 Na2O (FAU) This indicates the amount of Na2O contributed by FAU zeolite. (NaOH) This indicates the amount of Na₂O contributed by sodium hydroxide, SiO₂ 2(FAU) This represents the amount of SiO2 contributed by FAU zeolite, and Al2O 3(FAU) This indicates the amount of Al2O3 contributed by FAU zeolite until a homogeneous precursor gel is obtained; ii) The precursor gel obtained at the end of step i) is subjected to hydrothermal treatment at a temperature of 120°C to 220°C for 12 hours to 7 days.

[0041] The SiO2 / Al2O3 molar ratio of the obtained AEI zeolite can advantageously be 10 to 60, preferably 12 to 50 (including endpoint values).

[0042] Advantageously, the SiO2 / Al2O3 molar ratio of the FAU framework type zeolite can be 10 to 60, preferably 20 to 50 (including endpoint values), and the mass percentage of sodium in cationic form is less than 0.005%, preferably less than 0.0048%, in order to minimize the sodium content in the synthesis reaction medium while promoting zeolization to the AEI framework type zeolite.

[0043] Na2O (NaOH) / (SiO 2(FAU) A ratio of 0 means that no sodium hydroxide was added to the synthetic gel. In this case, the sodium content in the reaction mixture is solely attributed to the inherent sodium contribution from the starting FAU zeolite.

[0044] During step i) of the method of the present invention, it may be advantageous to add seed crystals of AEI framework type zeolite to the reaction mixture to reduce the time required for the formation of AEI framework type IZM-10 zeolite crystals and / or the total crystallization time. The seed crystals also promote the formation of the AEI framework type IZM-10 zeolite and reduce impurities. Such seed crystals comprise crystalline solids, particularly crystals of AEI framework type zeolite. Typically, the seed crystals are added in proportions of 0.01% to 10% of the total anhydrous mass of FAU zeolite used in the reaction mixture, excluding the total mass of SiO2 and Al2O3 sources. The seed crystals are also not considered when determining the composition of the above reaction mixture and / or gel, i.e., when determining the various molar ratios of the reaction mixture composition.

[0045] Perform mixing step i) until a homogeneous mixture is obtained, preferably for more than or equal to 15 minutes, preferably by stirring using any system known to those skilled in the art, at low or high shear rates.

[0046] Once step i) is completed, a uniform precursor gel will be obtained.

[0047] During step i) of the method of the present invention, aging of the reaction mixture prior to hydrothermal crystallization can be advantageous in order to control the size of the IZM-10 zeolite crystals. The aging also promotes the formation of the IZM-10 zeolite and reduces impurities. During step i) of the method of the present invention, the aging of the reaction mixture can be carried out at ambient temperature or at a temperature of 20 to 100°C, advantageously for 30 minutes to 48 hours with or without stirring.

[0048] According to step (ii) of the method of the present invention, the precursor gel obtained at the end of step (i) is subjected to hydrothermal treatment, preferably at a temperature of 120°C to 220°C for 12 hours to 7 days, until the IZM-10 zeolite of the AEI framework type is formed.

[0049] The precursor gel is advantageously placed under hydrothermal conditions under autogenous reaction pressure, optionally by adding a gas (e.g., nitrogen), at a temperature preferably 120°C to 220°C, more preferably 150°C to 200°C, and even more preferably 160°C to 195°C, until the AEI framework type zeolite is completely crystallized.

[0050] The time required for crystallization is 12 hours to 7 days, preferably 12 days to 6 days.

[0051] The reaction is typically carried out with or without stirring, but preferably with stirring. Any system known to those skilled in the art can be used as the stirring system, such as inclined blades with baffles, a stirred turbine mixer, or an Archimedes screw.

[0052] At the end of the reaction, after carrying out step ii) of the preparation method of the present invention, the formed IZM-10 zeolite is preferably subjected to solid-phase filtration, washing, and then drying. Drying is typically carried out at a temperature of 20 to 150°C, preferably 60 to 100°C, for 5 to 24 hours.

[0053] The dried zeolite can then be advantageously calcined. Calcinated AEI framework type IZM-10 zeolite is typically analyzed by X-ray diffraction, a technique that can also be used to determine the purity of the zeolite obtained by the method of the present invention.

[0054] Advantageously, the method of the present invention can form AEI-framework type IZM-10 zeolite, free from any other crystalline or amorphous phases. The AEI-framework type IZM-10 zeolite after the drying step can then be used in subsequent steps, such as calcination. For this step, all conventional methods known to those skilled in the art can be employed.

[0055] The present invention also relates to an AEI framework type zeolite having a SiO2 / Al2O3 molar ratio of 10 to 60 (inclusive of endpoint values), and being at least partially protonated, i.e., containing an Al2O3 / Na2O molar ratio of 100 to 400, preferably greater than 400, which can be obtained by the above preparation method.

[0056] Zeolites of the starting FAU framework type with a SiO2 / Al2O3 molar ratio of 10 to 60 (inclusive) and a sodium mass percentage in cationic form of less than 0.005% can be obtained by any method known to those skilled in the art, such as by steam treatment (steaming) and acid washing of FAU framework type zeolites with a SiO2 / Al2O3 molar ratio of less than 6.00. Among FAU sources with a SiO2 / Al2O3 molar ratio of 10 to 60 (inclusive) and a sodium mass percentage in cationic form of less than 0.005%, commercial zeolites CBV712, CBV720, and CBV760 from Zeolyst and commercial zeolites HSZ-350HUA, HSZ-360HUA, and HSZ-385HUA from Tosoh can be mentioned.

[0057] According to the present invention, SiO 2(FAU) / Al2O 3(FAU) FAU framework-type zeolite with a molar ratio of 10 to 60 (inclusive) and a sodium mass percentage of less than 0.005% in cationic form is added to the reaction mixture to carry out step (i) as a source of silicon and aluminum.

[0058] According to the present invention, R is a nitrogen-containing organic compound in the form of hydroxide (6R,10S)-6,10-dimethyl-5-aza-onium-spiro[4.5]decane.

[0059] According to the present invention, Na2O (NaOH) This indicates the amount of Na₂O contributed by sodium hydroxide. When Na₂O (NaOH) When the amount is zero, it means that no sodium hydroxide source is introduced into the reaction mixture of step i).

[0060] The loss on ignition (LOI) of the AEI-type IZM-10 zeolite obtained after drying and before calcination is typically from 5% to 25% by weight. According to the invention, LOI refers to the percentage of mass loss experienced by a solid compound, mixture of solid compounds, or paste (preferably the prepared IZM-10 zeolite in this invention) during heat treatment at 1000°C for 2 hours in a static furnace (muffle furnace type), relative to the initial mass of the solid compound, mixture of solid compounds, or paste, and preferably relative to the mass of the dried IZM-10 zeolite tested in this invention. LOI typically corresponds to the loss of solvents (such as water) contained in the solid, but also to the removal of organic compounds contained in the mineral solid components.

[0061] The calcination step of the AEI framework type IZM-10 zeolite obtained by the method of the present invention is preferably carried out at a temperature of 450°C to 700°C for 2 to 20 hours.

[0062] The AEI-frame type IZM-10 zeolite obtained at the end of the calcination step contains no organic matter, especially no organic structuring agent R.

[0063] At the end of the calcination step, X-ray diffraction can confirm that the solid obtained by the method of the present invention is indeed an AEI framework type zeolite. The resulting purity is advantageously greater than 98% by weight, preferably greater than or equal to 99% by weight, and very preferably greater than or equal to 99.8% by weight. The resulting solid (IZM-10) has at least... Figure 2 The X-ray diffraction pattern includes lines present in the background. Preferably, the X-ray diffraction pattern does not contain lines with significantly different intensities (i.e., intensities greater than approximately three times the background noise) compared to the background noise. Figure 2 Other diffraction lines present in the sample.

[0064] The diffraction pattern was obtained by radiographic crystallography using a conventional powder diffractometer with copper Kα1 irradiation (λ = 1.5406 Å). The interplanar spacing d of the sample was calculated using Bragg's law based on the positions of the diffraction peaks, expressed in terms of angle 2θ. hkl Features. Regarding d hkl Measurement error Δ(d) hkl The absolute error Δ(2θ) is calculated according to Bragg's law and is given as a function of the absolute error Δ(2θ) assigned to the 2θ measurement. An absolute error Δ(2θ) of ±0.02° is typically accepted, in angstroms (Å). Each of these values ​​must be within the range of ±0.6 Å to ±0.01 Å of the measurement error Δ(d). hkl )Inside.

[0065] The X-ray diffraction pattern of the AEI framework type IZM-10 zeolite according to the present invention includes at least the d values ​​given in Table 1 above. hkl The values ​​at the specified points are given in Table 1, which presents the d values ​​measured on the X-ray diffraction patterns of the calcined AEI framework type IZM-10 zeolite according to the present invention. hkl And the average value of relative intensity. In d hkl In the value series, the average lattice spacing is expressed in angstroms (Å). Each of these values ​​must be within a measurement error Δ(d) of ±0.6 Å to ±0.01 Å. hkl )Inside.

[0066] Table 1

[0067] Where VS = Very strong; S = Strong; m = Moderate; mw = Moderately weak; w = Weak; vw = Very weak. Relative Intensity I relIt is given relative to the relative intensity scale, where the value of the line with the highest intensity in the X-ray diffraction pattern is 100: vw<15; 15≤w<30; 30≤mw<50; 50≤m<65; 65≤S<85; VS≥85.

[0068] X-ray fluorescence (XRF) spectroscopy is a chemical analysis technique that utilizes the physical properties (X-ray fluorescence) of materials. It can analyze most chemical elements, starting with beryllium (Be), at concentrations ranging from a few ppm to 100%, with accurate and reproducible results. X-rays are used to excite atoms in the sample, causing them to emit X-rays with the characteristic energies of each present element. The intensity and energy of these X-rays are then measured to determine the concentration of the element in the material.

[0069] The method according to the invention can directly obtain the AEI zeolite in its protonated form (partially protonated or fully protonated). This is possible if sodium hydroxide (Na₂O) is not added during synthesis. (NaOH) / (SiO 2(FAU) If the ratio is 0), then the method according to the present invention can directly obtain the fully protonated form of IZM-10 zeolite of the AEI framework type without ion exchange with a solution containing ammonium cations and then calcination.

[0070] For the purposes of this invention, the term "partially protonated" should be understood as meaning that the Al2O3 / Na2O molar ratio contained in AEI zeolite is 100 to 400, while "fully protonated" should be understood as meaning that the Al2O3 / Na2O molar ratio contained in AEI zeolite is greater than 400.

[0071] The AEI-framework type IZM-10 zeolite obtained by the method of this invention can be used directly or, after calcination, as an acidic solid for catalysis in refining and petrochemical fields. It can also be used as an adsorbent or molecular sieve.

[0072] Example

[0073] The present invention is illustrated by the following examples, which are not intended to be limiting.

[0074] Example 1: Preparation of (6R,10S)-6,10-dimethyl-5-aza-onium-spiro[4.5]decane in hydroxide form (structuring agent R).

[0075] To a 500 mL two-necked round-bottom flask containing 140 mL of water, add 5.68 g (0.142 mol) of sodium hydroxide and 30.66 g (0.142 mol, 16.82 mL) of 1,4-dibromobutane with stirring. Heat the mixture under reflux, and add 16.07 g (0.142 mol, 19.13 mL) of (2R,6S)-2,6-dimethylpiperidine dropwise over half an hour using a dropping funnel. After reflux for twelve hours, cool the mixture to 0 °C and add 70 mL of cold 40% NaOH solution. Extract the formed precipitate three times with 200 mL of chloroform. Evaporate the extracted organic fraction to a volume of 100 mL and precipitate the bromide form of the amine with diethyl ether. The reaction yield is approximately 80-85%.

[0076] Empirical: C 11 H 22 NBr

[0077] Molar mass: 248 g / mol

[0078] (6R,10S)-6,10-dimethyl-5-azapyronspiro[4.5]decane (cis-trans mixture) 1 H NMR (D2O,400MHz, 25℃, δ ppm): 1.30 (d, 6H, CH3); 1.55 (m, 4H, CH2); 1.70 (m, 2H, CH2); 2.10 (m, 4H, CH2); 3.28 (t, 2H, CH2-N); 3.50 (t, 2H, CH2-N); 3.64 (m, 2H, CH-N).

[0079] 18.9 g of Ag₂O (0.08 mol, 99%, Aldrich) was added to a 250 mL Teflon beaker containing 20 g of (6R,10S)-6,10-dimethyl-5-aza-spiro[4.5]decane bromide (0.08 mol) and 100 mL of deionized water. The reaction medium was stirred for 12 hours in the dark. The mixture was then filtered, and a portion of the water was evaporated using a rotary evaporator. The resulting filtrate consisted of an aqueous solution (29.06 wt%) of (6R,10S)-6,10-dimethyl-5-aza-spiro[4.5]decane in hydroxide form. The determination of this substance was performed by proton NMR using formic acid as an internal standard.

[0080] Example 2: Preparation of IZM-10 zeolite of AEI framework type according to the present invention.

[0081] 1.25 g of FAU framework type zeolite (CBV720, SiO2 / Al2O3 = 33.34, Zeolister, LOI = 14.34%, sodium percentage in cationic form = 0.0045%) was mixed with 6.22 g of an aqueous solution (29.06 wt%) of (6R,10S)-6,10-dimethyl-5-aza-onium spiro[4.5]decane in hydroxide form prepared according to Example 1. 7.54 g of deionized water was added to the previous mixture, and the resulting preparation was stirred for 10 minutes. The molar composition of the precursor gel was as follows: 1 SiO2 : 0.03 Al2O3 : 0.58 R : 40 H2O, i.e., a SiO2 / Al2O3 ratio of 33.3. The precursor gel was then transferred to an autoclave after homogenization. The autoclave was shut off, and the mixture was heated at 180°C for 140 hours while being stirred at 35 rpm using a rotary spit system. The resulting solid was filtered, washed with deionized water, and then dried overnight at 100°C. The loss on ignition of the dried solid was 10%. The solid was then introduced into a muffle furnace for calcination: the calcination cycle consisted of increasing the temperature to 200°C at 1.5°C / min, maintaining a stabilization period at 200°C for 2 hours, increasing the temperature to 550°C at 1°C / min, maintaining a stabilization period at 550°C for 8 hours, and then returning to ambient temperature.

[0082] X-ray diffraction analysis of the calcined solid product confirmed that it consisted of IZM-10 zeolite with an AEI framework purity greater than 99% by weight. X-ray fluorescence analysis showed that the SiO2 / Al2O3 molar ratio was 30.00 and the Al2O3 / Na2O molar ratio was 450.

[0083] Example 3: Preparation of IZM-10 zeolite (containing seed crystals) of AEI framework type according to the present invention.

[0084] 1.25 g of FAU framework-type zeolite (CBV720, SiO2 / Al2O3 = 33.34, Zeolister, LOI = 14.34%, sodium percentage in cationic form = 0.0045%) was mixed with 6.22 g of an aqueous solution (29.06 wt%) of (6R,10S)-6,10-dimethyl-5-aza-onium spiro[4.5]decane in hydroxide form prepared according to Example 1. 7.54 g of deionized water was added to the previous mixture, and the resulting preparation was stirred for 10 minutes. To promote the formation of AEI framework-type IZM-10 zeolite, 54 mg of AEI framework-type IZM-10 zeolite seed crystals (5% relative to the mass of zeolite CBV720) prepared according to Example 2 was added to the synthetic mixture and stirred for 5 minutes. The molar composition of the precursor gel was as follows: 1 SiO2 : 0.03 Al2O3 : 0.58 R : 40 H2O, i.e., the SiO2 / Al2O3 ratio was 33.3. The precursor gel was then homogenized and transferred to an autoclave. The autoclave was closed, and the mixture was heated at 180°C for 140 hours while stirring at 35 rpm using a rotary jet system. The resulting solid was filtered, washed with deionized water, and then dried overnight at 100°C. The loss on ignition of the dried solid was 10%. The solid was then introduced into a muffle furnace for calcination: the calcination cycle consisted of heating to 200°C at 1.5°C / min, maintaining a stabilization period at 200°C for 2 hours, heating to 550°C at 1°C / min, maintaining a stabilization period at 550°C for 8 hours, and then returning to ambient temperature.

[0085] X-ray diffraction analysis of the calcined solid product confirmed that it consisted of IZM-10 zeolite with an AEI framework purity greater than 99% by weight. X-ray fluorescence analysis showed that the SiO2 / Al2O3 molar ratio was 29.20 and the Al2O3 / Na2O molar ratio was 460.

[0086] Example 4: Preparation of Na2O (NaOH) / (SiO 2(FAU) IZM-10 zeolite of the AEI skeleton type with a ratio of 0.15.

[0087] 1.33 g of FAU framework-type zeolite (CBV720, SiO2 / Al2O3 = 33.34, Zeolister, LOI = 14.34%, sodium percentage in cationic form = 0.0045%) was mixed with 2.304 g of an aqueous solution (29.06 wt%) of (6R,10S)-6,10-dimethyl-5-aza-onium-spiro[4.5]decane in hydroxide form prepared according to Example 1. 11.15 g of deionized water and 0.212 g of NaOH were added to the previous mixture, and the resulting preparation was stirred for 10 minutes. The molar composition of the precursor gel was as follows: 1 SiO2 : 0.03 Al2O3 : 0.15 Na2O (NaOH) The SiO2 / Al2O3 ratio was 33.3, with a ratio of 0.20 R to 40 H2O. The precursor gel was then homogenized and transferred to an autoclave. The autoclave was closed, and the mixture was heated at 180°C for 48 hours while stirring at 35 rpm using a rotary jet system. The resulting solid was filtered, washed with deionized water, and then dried overnight at 100°C. The loss on ignition of the dried solid was 12%. The solid was then introduced into a muffle furnace for calcination: the calcination cycle consisted of increasing the temperature to 200°C at 1.5°C / min, maintaining a stabilization period at 200°C for 2 hours, increasing the temperature to 550°C at 1°C / min, maintaining a stabilization period at 550°C for 8 hours, and then returning to ambient temperature.

[0088] X-ray diffraction analysis of the calcined solid product confirmed that it consisted of IZM-10 zeolite with an AEI framework purity greater than 99% by weight. X-ray fluorescence analysis showed that the SiO2 / Al2O3 molar ratio was 20.10 and the Al2O3 / Na2O molar ratio was 150.

[0089] Example 5: Comparative example, preparation of Na2O (NaOH) / (SiO 2(FAU) Zeolite with a ratio of 0.35.

[0090] 1.32 g of FAU framework-type zeolite (CBV720, SiO2 / Al2O3 = 33.34, Zeolister, LOI = 14.34%, sodium percentage in cationic form = 0.0045%) was mixed with 2.30 g of an aqueous solution (29.06 wt%) of (6R,10S)-6,10-dimethyl-5-aza-onium-spiro[4.5]decane in hydroxide form prepared according to Example 1. 11.16 g of deionized water and 0.493 g of NaOH were added to the previous mixture, and the resulting preparation was stirred for 10 minutes. The molar composition of the precursor gel was as follows: 1 SiO2 : 0.03 Al2O3 : 0.35 Na2O : 0.20 R : 40 H2O, i.e., a SiO2 / Al2O3 ratio of 33.3. The precursor gel was then transferred to an autoclave after homogenization. The autoclave was shut off, and the mixture was heated at 180°C for 48 hours while being stirred at 35 rpm using a rotary jet system. The resulting solid was filtered, washed with deionized water, and then dried overnight at 100°C. The loss on ignition of the dried solid was 12%. The solid was then introduced into a muffle furnace for calcination: the calcination cycle consisted of increasing the temperature to 200°C at 1.5°C / min, maintaining a stabilization period at 200°C for 2 hours, increasing the temperature to 550°C at 1°C / min, maintaining a stabilization period at 550°C for 8 hours, and then returning to ambient temperature.

[0091] X-ray diffraction analysis of the calcined solid product determined that it was composed of a mixture of zeolites with an AEI and MOR (mordenite) framework.

Claims

1. A method for preparing a zeolite, specifically designated ZM-10 and having an AEI framework, the method comprising at least the following steps: i) Mix the following substances in an aqueous medium: FAU framework type zeolite with SiO₂ 2(FAU) / Al2O 3(FAU) The reaction mixture has a molar composition of 10 to 60, including endpoint values, and less than 0.005% by mass of sodium in cationic form, containing a nitrogen-containing organic compound R, wherein R is (6R,10S)-6,10-dimethyl-5-aza-onium-spiro[4.5]decane in hydroxide form, and optionally sodium hydroxide. (SiO 2(FAU) ) / (Al2O 3(FAU) The value is 10 to 60, preferably 30 to 50. H2O / (SiO 2(FAU) The value is 20 to 60, preferably 30 to 50. R / (SiO 2(FAU) The value is 0.05 to 0.70, preferably 0.15 to 0.

60. Na2O (NaOH) / (SiO 2(FAU) The value is 0 to 0.20, preferably 0 to 0.

15. Na2O (FAU) / (SiO 2(FAU) ) is 3.5×10 -5 Up to 7×10 -5 4×10 is preferred -5 Up to 6×10 -5 Na2O (FAU) This indicates the amount of Na2O contributed by FAU zeolite. (NaOH) This indicates the amount of Na₂O contributed by sodium hydroxide, SiO₂ 2(FAU) This represents the amount of SiO2 contributed by FAU zeolite, and Al2O 3(FAU) This indicates the amount of Al2O3 contributed by FAU zeolite until a homogeneous precursor gel is obtained; ii) The precursor gel obtained at the end of step i) is subjected to hydrothermal treatment at a temperature of 120°C to 220°C for 12 hours to 7 days.

2. The preparation method according to claim 1, wherein the SiO2 / Al2O3 molar ratio of the obtained AEI zeolite is 10 to 60, preferably 12 to 50, including endpoint values, and the Al2O3 / Na2O molar ratio of the obtained AEI zeolite is greater than 100, preferably greater than 400.

3. The preparation method according to claim 1 or 2, wherein the SiO2 / Al2O3 molar ratio of the FAU framework type zeolite is 20 to 50, including endpoint values, and the mass percentage of sodium in cationic form is less than 0.0048%.

4. The method as described in any of the preceding claims, wherein no sodium hydroxide (Na₂O) is added to the reaction mixture in step i). (NaOH) / (SiO 2(FAU) ) = 0), and directly obtain IZM-10 zeolite of the AEI framework type in its fully protonated form.

5. The method according to any one of claims 1 to 4, wherein the seed crystals of the AEI framework type zeolite are added to the reaction mixture of step i), preferably in an amount of 0.01% to 10% by weight relative to the total mass of the tetravalent and trivalent elements present in anhydrous form in the mixture, wherein the seed crystals are not included in the total mass of the SiO2 and Al2O3 sources.

6. The method according to any one of claims 1 to 5, comprising aging the reaction mixture at a temperature of 20 to 100°C for 30 minutes to 48 hours with or without stirring.

7. The method according to any one of claims 1 to 6, wherein the hydrothermal treatment in step ii) is carried out under autogenous pressure at a temperature of 120°C to 220°C, preferably 150°C to 200°C, more preferably 160°C to 195°C, for 12 hours to 7 days, preferably 12 hours to 6 days.

8. The method according to any one of claims 1 to 7, wherein the solid phase obtained at the end of step ii) is filtered, washed, and dried at a temperature of 20 to 150°C, preferably 60 to 100°C, for 5 to 24 hours to obtain dried zeolite.

9. The method of claim 8, wherein the dried zeolite is then calcined at a temperature of 450 to 700°C for 2 to 20 hours, with the temperature gradually increased before calcination.

10. An AEI framework type zeolite having a SiO2 / Al2O3 molar ratio of 10 to 60, including endpoint values, a purity greater than or equal to 98% by weight, preferably greater than or equal to 99% by weight, very preferably greater than or equal to 99.8% by weight, said zeolite being in a partially or fully protonated form, particularly obtained by the method according to any one of claims 1 to 9, and containing the following significant X-ray diffraction lines: Table 1 Where VS = extremely strong; S = strong; m = moderate; mw = moderately weak; w = weak; vw = extremely weak; relative strength I rel The relative intensity scale is given, where the value of the strongest line in the X-ray diffraction pattern is set to 100: vw<15; 15≤w<30; 30≤mw<50; 50≤m<65; 65≤S<85; VS≥85.

11. The AEI framework type zeolite as described in claim 10, wherein the SiO2 / Al2O3 molar ratio is 10 to 60, preferably 12 to 50, including endpoint values, and the Al2O3 / Na2O molar ratio is greater than 100, preferably greater than 400.

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