Synthesis of IWR framework-type zeolite materials from zeolite precursor materials.

Abstract

The present invention relates to a process for the preparation of a zeolitic material having an IWR framework structure, and to a zeolitic material having an IWR framework structure obtained and / or obtainable by said process, and to a process for the use of said zeolitic material.

Description

[Technical field]

[0001] The present invention relates to a process for the preparation of a zeolitic material having an IWR framework structure, and to a zeolitic material having an IWR framework structure obtained and / or obtainable by said process, and to methods of using said zeolitic material. [Background technology]

[0002] The ITQ-24 zeolite with IWR structure was first synthesized in the presence of germanium species using hexamethonium as an organic template. Thus, EP1609758B1 discloses the zeolite Ge-ITQ-24, obtained by using Ge as a tetravalent element in addition to Si in the zeolite framework.

[0003] ITQ-24 has attracted much attention due to its unique three-dimensional 12×10×10 ring pore structure (opening sizes 5.8×6.8, 4.6×5.3, and 4.6×5.3 Å). However, the presence of a large amount of germanium species in the IWR framework significantly reduces its thermal and hydrothermal stability. Furthermore, the use of germanium species in the synthesis is costly, which strongly impedes the application of IWR zeolites as heterogeneous catalysts. To solve this problem, Cantin, A. et al., J. Am. Chem. Soc. 2006, 128, 4216-4217, described a Ge-free route to synthesize IWR zeolites by introducing boron species instead of germanium, since the Si-O-Ge angle is very close to the Si-OB angle, and here pure silica IWR could also be synthesized with the assistance of the species. However, from the viewpoint of industrial applications, aluminosilicate IWR zeolites would be more attractive due to their strong acidity and excellent thermal and hydrothermal stability. In the absence of a direct synthesis method for aluminosilicate IWR zeolites, Shamzhy, M. et al., Catal.Today 2015, 243, 76-84, describes a post-synthetic treatment to aluminize borogermanosilicate IWR zeolites.

[0004] On the other hand, WO2020 / 244630A discloses a direct synthesis method for aluminosilicates with IWR framework structures, and the resulting material does not contain germanium. The material is designated COE-6, as described in Hong, X. et al., J. Am. Chem. Soc. 2019, 141, 45, 18318-18324.

[0005] In view of the progress in the synthesis of zeolitic materials with IWR framework structure, a method has been developed to obtain zeolitic materials containing additional heteroatoms in the framework structure. Thus, CN111847474A relates to the synthesis of Ti-ITQ-24, a framework containing only Si and Ti as tetravalent elements in its structure. The synthesis of Ti-ITQ-24 is also described in US7344696B2, where B-Ti-ITQ-24 is synthesized in a first step, after which boron is leached from the material by an acidic deboronation treatment.

[0006] Notwithstanding the above results, there remains a need for synthetic procedures to obtain zeolitic materials that exhibit improved physical and chemical properties, especially since they are frequently used in catalytic applications. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] EP1609758B1 [Patent Document 2] WO2020 / 244630A [Patent Document 3] CN111847474A [Patent Document 4] US7344696B2 [Non-patent literature]

[0008] [Non-Patent Document 1] Cantin, A. et al., J. Am. Chem. Soc. 2006, 128, 4216-4217 [Non-Patent Document 2] Shamzhy, M. et al., Catal.Today 2015, 243, 76-84 [Non-Patent Document 3] Hong, X. et al. J. Am. Chem. Soc. 2019, 141, 45, 18318-18324 Summary of the Invention [Problem to be solved by the invention]

[0009] It is therefore an object of the present invention to provide improved zeolitic materials with an IWR-type framework structure and a method for their synthesis.It is further an object of the present invention to provide improved zeolitic materials for catalytic applications, in particular for heterogeneous catalysis, and in particular as catalysts for epoxidation reactions.It has thus surprisingly been found that zeolitic materials with an IWR-type framework structure containing Si and further tetravalent elements in the framework can be synthesised with particularly high purity and high crystallinity. [Means for solving the problem]

[0010] The present invention therefore relates to a method for the preparation of a zeolitic material having an IWR-type framework structure, said method comprising the steps of: (1) One or more organic templates as structure-directing agents and SiO in the framework 2 and YO 2 where Y is a tetravalent element other than Si, and one or more SiO 2 other than the one or more zeolitic materials. 2 preparing a mixture comprising a source and a solvent system; (2) SiO in the framework 2 and YO 2 heating the mixture obtained in (1) to crystallize the zeolitic material having an IWR-type framework structure comprising Including, The one or more organic templates may be of formula (I): R 3 R 5 R 6 N + -R 1-QR 2 -N + R 4 R 7 R 8 (I) (In the formula, R 1 and R 2 are independent of each other (C 1 ~C 3 ) alkylene, preferably C 1 Or C 2 alkylene, more preferably methylene or ethylene, and more preferably methylene, Q is C 6 -Arylene, preferably 1,4-C 6 -arylene, and more preferably benzene-1,4-diyl, R 3 and R 4 are independent of each other, (C 1 ~C 4 ) alkyl, preferably (C 1 ~C 3 ) alkyl, more preferably methyl or ethyl, and more preferably methyl; and R 5 , R 6 , R 7 , and R 8 are independent of each other, (C 1 ~C 6 ) alkyl, preferably (C 1 ~C 5 ) alkyl, more preferably (C 1 ~C 4 ) alkyl, more preferably (C 1 ~C 3 ) alkyl, more preferably ethyl, isopropyl or n-propyl, and more preferably ethyl or n-propyl. The organic dications include: [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 shows the XRD pattern of TS-1 obtained in Comparative Example 1. [Diagram 2] FIG. 2 shows the XRD pattern of the crystalline material obtained according to Comparative Example 1. [Diagram 3] FIG. 3 is an SEM image of the crystalline material obtained according to Comparative Example 1. [Figure 4] FIG. 4 shows the XRD pattern of Ti-COE-6 obtained in Example 1. [Diagram 5] FIG. 5 is a SEM image of Ti-COE-6 obtained in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] It is preferred that the one or more zeolitic materials of (1) exhibit a framework structure type selected from the group consisting of MFI, MWW, MEL, BEA, CHA, MOR, and mixtures of two or more thereof, more preferably from the group consisting of MFI, MWW, BEA, and mixtures of two or more thereof, more preferably the one or more zeolitic materials of (1) exhibit a framework structure of the MFI and / or MWW type.

[0013] The tetravalent element Y is preferably selected from the group consisting of Sn, Ti, Zr, and mixtures of two or more thereof, more preferably Sn and / or Ti, and more preferably Ti. According to a particular preferred embodiment in which Y is Ti, the framework structure does not contain SiO 2 and YO 2 The one or more zeolitic materials of (1) comprising ZMQ-TB and / or TS-1, more preferably TS-1, preferably having no SiO in the framework structure. 2 and YO 2 is ZMQ-TB and / or TS-1, more preferably TS-1. Furthermore, independently of that, according to a particular preferred embodiment where Y is Ti, the zeolitic material having an IWR-type framework structure (2) is preferably Ti-COE-6.

[0014] One or more SiO 2 other than one or more zeolitic materials 2the source being selected from the group consisting of silicates, fumed silica, silica hydrosol, reactive amorphous solid silica, silica gel, silicic acid, colloidal silica, silicic acid esters, and mixtures of two or more thereof; More preferably, silica hydrosol, silica gel, silicic acid, water glass, sodium metasilicate hydrate, sesquisilicate, disilicate, colloidal silica, tetra(C 1 ~C 4 ) alkyl orthosilicates, and mixtures of two or more thereof, More preferably, silica hydrosol, silicic acid, tetra(C 2 ~C 3 ) alkyl orthosilicates, and mixtures of two or more thereof; More preferably, SiO 2 The one or more sources for include tetraethyl orthosilicate, more preferably SiO 2 Tetraethyl orthosilicate is used as one or more sources for.

[0015] Alkyl group R 5 and R 6 are linked together to form a common alkylene chain, more preferably (C 5 ~C 7 ) alkylene chain, more preferably (C 5 ~C 6 ) alkylene chain, more preferably pentylene chain or hexylene chain, and more preferably pentylene chain.

[0016] Alkyl group R 7 and R 8 are linked together to form a common alkylene chain, more preferably (C 5 ~C 7 ) alkylene chain, more preferably (C 5 ~C 6 ) alkylene chain, more preferably pentylene chain or hexylene chain, and more preferably pentylene chain.

[0017] The organic dication of formula (I) is represented by the formula (II) [ka] It is preferred that the compound has the formula:

[0018] It is preferred that the one or more organic templates are provided as a salt, more preferably one or more salts selected from the group consisting of halides, sulfates, nitrates, phosphates, acetates, hydroxides, and mixtures of two or more thereof, more preferably bromides, chlorides, hydroxides, sulfates, and mixtures of two or more thereof, more preferably the one or more organic templates are provided as hydroxides and / or bromides, and more preferably hydroxides.

[0019] It is preferred that the mixture prepared in (1) further comprises seed crystals, the seed crystals preferably comprising one or more zeolitic materials having an IWR type framework structure, more preferably one or more all-silica zeolitic materials having an IWR type framework structure, more preferably the seed crystals comprise all-silica ITQ-24, more preferably one or more zeolitic materials having an IWR type framework structure, more preferably one or more all-silica zeolitic materials having an IWR type framework structure are used as seed crystals, more preferably all-silica ITQ-24 is used as seed crystals.

[0020] When the mixture prepared in (1) further contains seed crystals, the amount of seed crystals contained in the mixture prepared in (1) is SiO 2 One or more SiO 2 other than one or more zeolitic materials calculated as 2 Based on 100% by mass of the source, the content is in the range of 0.1 to 25% by mass, and more preferably 0.5 to 20% by mass, more preferably 1 to 18% by mass, more preferably 3 to 15% by mass, more preferably 5 to 12% by mass, and more preferably 8 to 9% by mass.

[0021] The mixture prepared in (1) and heated in (2) is SiO 2 One or more SiO 2 other than one or more zeolitic materials calculated as2 For 100% by mass of the source, GeO 2 It is preferred that the composition contains less than 5% by weight, more preferably less than 3% by weight, more preferably less than 1% by weight, more preferably less than 0.5% by weight, more preferably less than 0.1% by weight, more preferably less than 0.05% by weight, more preferably less than 0.01% by weight, more preferably less than 0.005% by weight, and more preferably less than 0.001% by weight of Ge.

[0022] It is preferred that the mixture prepared in (1) and heated in (2) contains less than 0.5%, more preferably less than 0.1%, more preferably less than 0.05%, more preferably less than 0.01%, more preferably less than 0.005%, and more preferably less than 0.001%, by weight of the trivalent element X, calculated as the element and relative to 100% by weight of Si contained in the mixture. It is preferred that X is Al and / or B, more preferably X is Al and B, more preferably X is Al, B and Ga, more preferably X is Al, B, In and Ga.

[0023] The mixture prepared in (1) and heated in (2) preferably contains less than 5% by weight P, more preferably less than 3% by weight, more preferably less than 1% by weight, more preferably less than 0.5% by weight, more preferably less than 0.1% by weight, more preferably less than 0.05% by weight, more preferably less than 0.01% by weight, more preferably less than 0.005% by weight, and more preferably less than 0.001% by weight, based on 100% by weight of Si contained in the mixture.

[0024] The SiO contained in the mixture prepared in (1) and heated in (2) 2 and YO 2It is preferred that the one or more zeolitic materials comprising the compound have an atomic ratio of Si:Y, Si to the tetravalent element Y, in the range of 5:1 to 500:1, more preferably 10: to 250:1, more preferably 20:1 to 150:1, more preferably 25:1 to 100:1, more preferably 30:1 to 70:1, more preferably 32:1 to 50:1, more preferably 34:1 to 42:1, and more preferably 36:1 to 39:1.

[0025] It is preferred that the atomic ratio of Si:Y, Si to the tetravalent element Y, in the mixture prepared in (1) and heated in (2) is in the range of 5 to 1,500, more preferably 10 to 1,000, more preferably 20 to 600, more preferably 30 to 400, more preferably 40 to 250, more preferably 50 to 150, more preferably 60 to 100, and more preferably 70 to 80.

[0026] It is preferred that the organic template:Si molar ratio, of one or more organic templates to Si, in the mixture prepared in (1) and heated in (2) is in the range of 0.01 to 1.5, more preferably 0.05 to 1.2, more preferably 0.1 to 0.9, more preferably 0.15 to 0.7, more preferably 0.2 to 0.5, and more preferably 0.25 to 0.3.

[0027] It is preferred that the mixture prepared in (1) further comprises one or more fluoride sources, more preferably the F:Si atomic ratio in the mixture prepared in (1) and heated in (2) is in the range of 0.01-2, preferably 0.05-1.5, more preferably 0.1-1, more preferably 0.3-0.8, and more preferably 0.5-0.6. It is preferred that the one or more fluoride sources are selected from the group consisting of fluoride salts, HF, and mixtures of two or more thereof, more preferably alkali metal fluoride salts, HF, and mixtures of two or more thereof, more preferably the one or more fluoride sources comprise HF, more preferably HF is used as the one or more fluoride sources.

[0028] The heating (2) is preferably carried out for a duration in the range of 10 minutes to 10 days, more preferably 30 minutes to 9 days, more preferably 1 hour to 8 days, more preferably 2 hours to 7 days, and more preferably 3 hours to 6 days, more preferably 6 hours to 5.5 days, more preferably 0.5 to 5 days, more preferably 1 day to 4.5 days, more preferably 2 days to 4 days, and more preferably 2.5 to 3.5 days.

[0029] The heating in (2) is preferably carried out at a temperature in the range of 80 to 220°C, more preferably 110 to 200°C, more preferably 130 to 190°C, more preferably 140 to 180°C, more preferably 150 to 170°C, and more preferably 155 to 165°C.

[0030] The heating in (2) is preferably carried out under autogenous pressure, more preferably under solvothermal conditions, more preferably under hydrothermal conditions, and preferably the heating in (2) is carried out in an airtight vessel, preferably an autoclave.

[0031] The method comprises the steps of: (3) isolating the zeolitic material obtained in (2); and / or (4) washing the zeolitic material obtained in (2) or (3); and / or (5) Calcining the zeolite material obtained in (2), (3) or (4). It is preferred that the composition further comprises Steps (3) and / or (4) and / or (5) may be performed in any order; and One or more of the above steps are preferably repeated one or more times.

[0032] The firing in (5) is preferably carried out for a duration in the range of 0.5 to 15 hours, more preferably 1 to 10 hours, more preferably 2 to 8 hours, more preferably 3 to 7 hours, more preferably 3.5 to 6.5 hours, more preferably 4 to 6 hours, and more preferably 4.5 to 5.5 hours. Furthermore, independently of this, the firing in (5) is preferably carried out at a temperature in the range of 300 to 800°C, more preferably 350 to 700°C, more preferably 400 to 650°C, more preferably 450 to 600°C, and more preferably 500 to 550°C.

[0033] The solvent system was arbitrarily branched (C 1 ~C 4 ) alcohol, distilled water, and mixtures thereof, more preferably optionally branched (C 1 ~C 3 ) is preferably selected from the group consisting of alcohol, distilled water, and mixtures thereof, more preferably from the group consisting of methanol, ethanol, distilled water, and mixtures thereof, more preferably the solvent system comprises distilled water, more preferably the solvent system consists of distilled water. According to a particular preferred embodiment in which the solvent system comprises or consists of distilled water, the H in the mixture prepared in (1) and heated in (2) is 2 O:YO 2 Molar ratio, H 2 O vs. SiO 2 One or more SiO 2 other than one or more zeolitic materials calculated as 2 The number of sources is preferably in the range of 0.5-15, more preferably 1-10, more preferably 1.5-5, and more preferably 2-3.

[0034] The present invention also relates to a zeolitic material having an IWR-type framework structure obtainable and / or obtained by the process of any one of the particular preferred embodiments of the present invention.

[0035] The zeolitic material having an IWR-type framework structure is preferably Ti-COE-6.

[0036] The present invention also relates to the use of a zeolitic material having an IWR type framework structure according to any one of the particular preferred embodiments of the present invention as a molecular sieve, as an adsorbent, for ion exchange or as a catalyst and / or as a catalyst support, more preferably in reactions involving C-C bond formation and / or conversion as a catalyst, and preferably in isomerization reactions, ammoximation reactions as a catalyst. reaction), amination reaction, hydrogenolysis reaction, alkylation reaction, acylation reaction, reaction for conversion of alkanes to olefins or reaction for conversion of one or more oxyacid salts to olefins and / or aromatics, reaction for synthesis of hydrogen peroxide, aldol condensation reaction, reaction for isomerization of epoxides, transesterification reaction, hydroxylation reaction, Baeyer-Villiger type oxidation reaction, Dakin type reaction, synthesis of isoprenol, Prins condensation reaction, or epoxidation reaction, preferably as a catalyst in hydroxylation reaction, Baeyer-Villiger type oxidation reaction, Dakin type reaction, Prins condensation reaction, or reaction for epoxidation of olefins, more preferably in reaction for epoxidation of olefins, more preferably in reaction for epoxidation of C2-C5 alkenes, more preferably in reaction for epoxidation of C2-C4 alkenes, more preferably in reaction for epoxidation of C2 or C3 alkenes, more preferably in reaction for epoxidation of C3 alkenes, and more preferably in the conversion of propylene to propylene oxide as a catalyst.

[0037] It is preferred to use a zeolitic material as a catalyst for the activation of hydrogen peroxide.

[0038] The present invention is further described by the set of embodiments shown below, and the combination of embodiments resulting from the dependent claims and back references. In particular, in each case where a range of embodiments is mentioned, it is to be noted that in the context of terms such as "the method according to any one of the embodiments 1 to 4", each embodiment within this range is meant to be explicitly disclosed to a person skilled in the art. That is, the wording of this term is understood by a person skilled in the art to be equivalent to "the method according to any one of the embodiments 1, 2, 3, and 4". Furthermore, it is to be clearly noted that the set of embodiments below represents a properly structured part of the description directed to the general and preferred aspects of the present invention, rather than a set of claims determining the scope of protection.

[0039] 1. A method for producing a zeolitic material having an IWR-type framework structure, comprising the steps of: (1) One or more organic templates as structure-directing agents and SiO in the framework 2 and YO 2 where Y is a tetravalent element other than Si, and one or more SiO 2 other than the one or more zeolitic materials. 2 preparing a mixture comprising a source and a solvent system; (2) SiO in the framework 2 and YO 2 heating the mixture obtained in (1) to crystallize the zeolitic material having an IWR-type framework structure comprising Including, The one or more organic templates have the formula (I): R 3 R 5 R 6 N + -R 1 -QR 2 -N + R 4 R 7 R 8 (I) (In the formula, R 1 and R 2 are independent of each other (C 1 ~C 3 ) alkylene, preferably C 1 Or C2 alkylene, more preferably methylene or ethylene, and more preferably methylene, Q is C 6 -Arylene, preferably 1,4-C 6 -arylene, and more preferably benzene-1,4-diyl, R 3 and R 4 are independent of each other, (C 1 ~C 4 ) alkyl, preferably (C 1 ~C 3 ) alkyl, more preferably methyl or ethyl, and more preferably methyl; and R 5 , R 6 , R 7 , and R 8 are independent of each other, (C 1 ~C 6 ) alkyl, preferably (C 1 ~C 5 ) alkyl, more preferably (C 1 ~C 4 ) alkyl, more preferably (C 1 ~C 3 ) alkyl, more preferably ethyl, isopropyl or n-propyl, and more preferably ethyl or n-propyl. The method comprises the steps of:

[0040] 2. The method according to embodiment 1, wherein the one or more zeolitic materials in (1) exhibit a framework structure type selected from the group consisting of MFI, MWW, MEL, BEA, CHA, MOR, and mixtures of two or more thereof, preferably from the group consisting of MFI, MWW, BEA, and mixtures of two or more thereof, more preferably the one or more zeolitic materials in (1) exhibit a framework structure of MFI and / or MWW type.

[0041] 3. The method of embodiment 1 or 2, wherein the tetravalent element Y is selected from the group consisting of Sn, Ti, Zr, and mixtures of two or more thereof, preferably Y is Sn and / or Ti, more preferably Y is Ti.

[0042] 4. Y is Ti and the framework contains SiO 2 and YO 2 The one or more zeolitic materials of (1) comprising ZMQ-TB and / or TS-1, preferably TS-1, preferably have no SiO in the framework structure. 2 and YO 2 The method of embodiment 3, wherein the one or more zeolitic materials comprising is ZMQ-TB and / or TS-1, preferably TS-1.

[0043] 5. The method according to embodiment 3 or 4, wherein Y is Ti and the zeolitic material having an IWR-type framework structure is Ti-COE-6.

[0044] 6. One or more SiO 2 particles other than one or more zeolitic materials 2 the source being selected from the group consisting of silicates, fumed silica, silica hydrosol, reactive amorphous solid silica, silica gel, silicic acid, colloidal silica, silicic acid esters, and mixtures of two or more thereof; Preferably, silica hydrosol, silica gel, silicic acid, water glass, sodium metasilicate hydrate, sesquisilicate, disilicate, colloidal silica, tetra(C 1 ~C 4 ) alkyl orthosilicates, and mixtures of two or more thereof, More preferably, silica hydrosol, silicic acid, tetra(C 2 ~C 3 ) alkyl orthosilicates, and mixtures of two or more thereof; More preferably, SiO 2 The one or more sources for include tetraethyl orthosilicate, more preferably SiO 2 6. The method of any of the preceding claims, wherein tetraethyl orthosilicate is used as the one or more sources for.

[0045] 7. Alkyl group R 5 and R 6 are linked together to form a common alkylene chain, preferably (C5 ~C 7 ) alkylene chain, more preferably (C 5 ~C 6 7. The method of any of the preceding claims, wherein the alkylene chain is an alkylene chain, more preferably a pentylene chain or a hexylene chain, and more preferably a pentylene chain.

[0046] 8. Alkyl group R 7 and R 8 are linked together to form a common alkylene chain, preferably (C 5 ~C 7 ) alkylene chain, more preferably (C 5 ~C 6 8. The method of any of the preceding claims, wherein the alkylene chain is an alkylene chain, more preferably a pentylene chain or a hexylene chain, and more preferably a pentylene chain.

[0047] 9. The organic dication of formula (I) is a compound of formula (II) [ka] 9. The method according to any one of the preceding embodiments, comprising:

[0048] 10. The method of any one of the preceding embodiments, wherein the one or more organic templates are provided as a salt, preferably one or more salts selected from the group consisting of halides, sulfates, nitrates, phosphates, acetates, hydroxides, and mixtures of two or more thereof, more preferably bromides, chlorides, hydroxides, sulfates, and mixtures of two or more thereof, more preferably the one or more organic templates are provided as hydroxides and / or bromides, and more preferably hydroxides.

[0049] 11. The method of any one of the preceding embodiments, wherein the mixture prepared in (1) further comprises seed crystals, the seed crystals preferably comprising one or more zeolitic materials having an IWR-type framework structure, preferably one or more all-silica zeolitic materials having an IWR-type framework structure, more preferably the seed crystals comprise all-silica ITQ-24, more preferably one or more zeolitic materials having an IWR-type framework structure, more preferably one or more all-silica zeolitic materials having an IWR-type framework structure are used as seed crystals, more preferably all-silica ITQ-24 is used as seed crystals.

[0050] 12. The amount of seed crystals contained in the mixture prepared in (1) is SiO 2 One or more SiO 2 other than one or more zeolitic materials calculated as 2 The method according to embodiment 11, wherein the amount of the carboxylic acid is in the range of 0.1 to 25% by mass, and preferably 0.5 to 20% by mass, more preferably 1 to 18% by mass, more preferably 3 to 15% by mass, more preferably 5 to 12% by mass, and more preferably 8 to 9% by mass, based on 100% by mass of the source.

[0051] 13. The mixture prepared in (1) and heated in (2) is SiO 2 One or more SiO 2 other than one or more zeolitic materials calculated as 2 For 100% by mass of the source, GeO 2 13. The method of any one of the preceding claims, wherein the composition contains less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight, more preferably less than 0.5% by weight, more preferably less than 0.1% by weight, more preferably less than 0.05% by weight, more preferably less than 0.01% by weight, more preferably less than 0.005% by weight, and more preferably less than 0.001% by weight of Ge, calculated as

[0052] 14. The method according to any one of the preceding claims, wherein the mixture prepared in (1) and heated in (2) contains less than 0.5% by weight, preferably less than 0.1% by weight, more preferably less than 0.05% by weight, more preferably less than 0.01% by weight, more preferably less than 0.005% by weight, and more preferably less than 0.001% by weight of the trivalent element X, calculated as the element and relative to 100% by weight of Si contained in the mixture.

[0053] 15. The method of embodiment 14, wherein X is Al and / or B, preferably X is Al and B, more preferably X is Al, B and Ga, more preferably X is Al, B, In and Ga.

[0054] 16. The method of any one of the preceding embodiments, wherein the mixture prepared in (1) and heated in (2) contains less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight, more preferably less than 0.5% by weight, more preferably less than 0.1% by weight, more preferably less than 0.05% by weight, more preferably less than 0.01% by weight, more preferably less than 0.005% by weight, and more preferably less than 0.001% by weight of P relative to 100% by weight of Si contained in the mixture.

[0055] 17. The SiO contained in the mixture prepared in (1) and heated in (2) 2 and YO 2 17. The method according to any one of the preceding embodiments, wherein the one or more zeolitic materials comprising:

[0056] 18. The method of any one of embodiments 1 to 17, wherein the atomic ratio of Si:Y, Si to the tetravalent element Y, in the mixture prepared in (1) and heated in (2) is in the range of 5 to 1,500, preferably 10 to 1,000, more preferably 20 to 600, more preferably 30 to 400, more preferably 40 to 250, more preferably 50 to 150, more preferably 60 to 100, and more preferably 70 to 80.

[0057] 19. The method of any one of embodiments 1 to 18, wherein the organic template:Si molar ratio of the one or more organic templates to Si in the mixture prepared in (1) and heated in (2) is in the range of 0.01 to 1.5, preferably 0.05 to 1.2, more preferably 0.1 to 0.9, more preferably 0.15 to 0.7, more preferably 0.2 to 0.5, and more preferably 0.25 to 0.3.

[0058] 20. The method of any one of embodiments 1 to 19, wherein the mixture prepared in (1) further comprises one or more fluoride sources, and preferably, the F:Si atomic ratio in the mixture prepared in (1) and heated in (2) is in the range of 0.01 to 2, preferably 0.05 to 1.5, more preferably 0.1 to 1, more preferably 0.3 to 0.8, and more preferably 0.5 to 0.6.

[0059] 21. The method of embodiment 20, wherein the one or more fluoride sources are selected from the group consisting of fluoride salts, HF, and mixtures of two or more thereof, preferably from the group consisting of alkali metal fluoride salts, HF, and mixtures of two or more thereof, more preferably the one or more fluoride sources comprise HF, more preferably HF is used as the one or more fluoride sources.

[0060] 22. The method according to any one of embodiments 1 to 21, wherein the heating in (2) is carried out for a duration in the range of 10 minutes to 10 days, preferably 30 minutes to 9 days, more preferably 1 hour to 8 days, more preferably 2 hours to 7 days, and more preferably 3 hours to 6 days, more preferably 6 hours to 5.5 days, more preferably 0.5 to 5 days, more preferably 1 day to 4.5 days, more preferably 2 days to 4 days, and more preferably 2.5 to 3.5 days.

[0061] 23. The method according to any one of embodiments 1 to 22, wherein the heating in (2) is carried out at a temperature in the range of 80 to 220°C, preferably 110 to 200°C, more preferably 130 to 190°C, more preferably 140 to 180°C, more preferably 150 to 170°C, and more preferably 155 to 165°C.

[0062] 24. The method according to any one of the preceding embodiments, wherein the heating of (2) is carried out under autogenous pressure, preferably under solvothermal conditions, more preferably under hydrothermal conditions, and preferably, the heating of (2) is carried out in an airtight vessel, preferably an autoclave.

[0063] 25. (3) isolating the zeolite material obtained in (2); and / or (4) washing the zeolitic material obtained in (2) or (3); and / or (5) Calcining the zeolite material obtained in (2), (3) or (4). Further comprising: Steps (3) and / or (4) and / or (5) may be performed in any order; and 25. The method according to any one of the preceding embodiments, wherein one or more of the steps are repeated, preferably one or more times.

[0064] 26. The method according to embodiment 25, wherein the calcination in step (5) is carried out for a duration in the range of 0.5 to 15 hours, preferably 1 to 10 hours, more preferably 2 to 8 hours, more preferably 3 to 7 hours, more preferably 3.5 to 6.5 hours, more preferably 4 to 6 hours, and more preferably 4.5 to 5.5 hours.

[0065] 27. The method according to embodiment 25 or 26, wherein the calcination in step (5) is carried out at a temperature in the range of 300 to 800°C, preferably 350 to 700°C, more preferably 400 to 650°C, more preferably 450 to 600°C, and more preferably 500 to 550°C.

[0066] 28. The solvent system is arbitrarily branched (C 1 ~C 4 ) alcohol, distilled water, and mixtures thereof, preferably optionally branched (C 1 ~C 3 28. The method of any one of the preceding claims, wherein the solvent system is selected from the group consisting of alcohol, distilled water, and mixtures thereof, more preferably from the group consisting of methanol, ethanol, distilled water, and mixtures thereof, more preferably the solvent system comprises distilled water, more preferably the solvent system consists of distilled water.

[0067] 29. H in the mixture prepared in (1) and heated in (2) 2 O:YO 2 Molar ratio, H 2 O vs. SiO 2 One or more SiO 2 other than one or more zeolitic materials calculated as 2 The method according to embodiment 28, wherein the source is in the range of 0.5 to 15, preferably 1 to 10, more preferably 1.5 to 5, and more preferably 2 to 3.

[0068] 30. A zeolitic material having an IWR-type framework structure obtainable and / or obtained by the method according to any one of embodiments 1 to 29.

[0069] 31. The zeolitic material of embodiment 30, wherein the zeolitic material having an IWR-type framework structure is Ti-COE-6.

[0070] 32. A process for the use of the zeolitic material according to embodiment 30 or 31 as a molecular sieve, as an adsorbent, for ion exchange or as a catalyst and / or catalyst support, wherein the zeolitic material is preferably used as a catalyst in reactions involving C-C bond formation and / or conversion, and preferably in isomerization reactions, ammoximation reactions, amination reactions, hydrocracking reactions, alkylation reactions, acylation reactions, reactions for the conversion of alkanes to olefins or reactions for the conversion of one or more oxyacid salts to olefins and / or aromatics, reactions for the synthesis of hydrogen peroxide, aldol condensation reactions, reactions for the isomerization of epoxides, transesterification reactions, hydroxylation reactions, Baeyer-Village condensation reactions, hydroxylation ... Preferably, in a hydroxylation reaction, a Baeyer-Villiger type oxidation reaction, a Dakin type reaction, a Prins condensation reaction, or a reaction for the epoxidation of an olefin, more preferably in a reaction for the epoxidation of an olefin, more preferably in a reaction for the epoxidation of a C2-C5 alkene, more preferably in a reaction for the epoxidation of a C2-C4 alkene, more preferably in a reaction for the epoxidation of a C2 or C3 alkene, more preferably in a reaction for the epoxidation of a C3 alkene, and more preferably in a method for the conversion of propylene to propylene oxide as a catalyst.

[0071] 33. The use according to embodiment 32, wherein the zeolitic material is used as a catalyst for the activation of hydrogen peroxide. EXAMPLES

[0072] Experimental Section Characterization by X-ray diffraction analysis X-ray powder diffraction (XRD) patterns were measured using a Rigaku Ultimate VI X-ray diffractometer (40 kV, 40 mA) with CuKα (λ = 1.5406 Å) radiation.

[0073] SEM and TEM characterization Scanning electron microscopy (SEM) experiments were performed on a Hitachi SU-1510 electron microscope. Transmission electron microscopy (TEM) experiments were performed using a JEOL JEM-2100P at 200 kV.

[0074] K-80 Exam Experimental procedure A clean 100 ml flask equipped with a magnetic stir bar and a thermometer was charged with 24 g of deionized water and 5.2 g of 40% by weight aqueous hydrogen peroxide at room temperature. At this point, approximately 0.3 ml of the t=0 probe was pipetted. The flask was loosely stoppered and then immersed in a pre-equilibrated bath set at 80°C. To obtain reproducible results, it is important to always use the same amount of catalyst and to control the temperature to better than ±1°C during the experiment. Once the aqueous hydrogen peroxide solution was in thermal equilibrium with the bath, 400 mg (±1 mg) of catalyst (powder or extrudate) was added. The suspension was stirred and samples of the supernatant were taken at regular intervals. The probe was taken with a 1 ml syringe equipped with a one-way filter Millipore Millex-HV SLHV013NL (order no. 4875 160) or equivalent. First, 0.6 ml of solution was drawn into the syringe through the filter. 0.3 ml of the solution was then refluxed through the filter into the flask. This was necessary to minimize loss of catalyst. The remaining 0.3 ml in the syringe was used to measure peroxide. The probe interval was usually 30-60 min, depending on the catalyst activity.

[0075] The experiment was terminated after 7 hours.

[0076] analysis Probe H 2 O 2The content was analyzed using standard serimetric titration. Probes were preferably analyzed as soon as possible after collection. To ensure good accuracy, at least 5 ml of titrant was used. If necessary, larger probes had to be weighed out.

[0077] Data analysis H 2 O 2 The natural log of concentration was plotted against time. When comparing data, it is important to always use the same units (e.g., H 2 O 2 Concentrations are mass % and time is hours. This plot usually yields a good straight line. The least squares method was used to extract the slope. This slope is the linear relationship between the H 2 O 2 The pseudo-first-order decay rate (unit: h -1 ) and is called the k80 value.

[0078] Materials for analysis p-Xylylene dibromide (C 8 H 8 Br 2 , 97%, Aladdin Chemistry Co., Ltd.), Tetraethyl orthosilicate (C 8 H 20 O 4 Si, TEOS, 99%, Aladdin Chemistry Co., Ltd.), hydrofluoric acid (HF, AR, 40%, Aladdin Chemistry Co., Ltd.), 1-methylpyrrolidine (C 5 H 11 N, 98%, Aladdin Chemistry Co., Ltd.), acetonitrile (C 2 H 3 N, AR, 99%, Sinopharm Chemical Reagent Co., Ltd.), titanium butoxide (C 16 H 36 O 4 Ti, 99%, Aladdin Chemistry Co., Ltd.

[0079] Reference Example 1: Synthesis of TS-1 For the gel preparation, 500 g of tetraethyl orthosilicate (TEOS) and 15 g of tetraethyl orthotitanate (TEOTi, Merck) were placed in a beaker. Then, 300 g of deionized water and 220 g of an aqueous solution of tetrapropylammonium hydroxide (TPAOH, 40% by weight in water) were added under stirring (200 rpm). The pH of the resulting mixture was 13.83. The mixture was hydrolyzed at room temperature for 60 minutes, during which the temperature was increased to 60° C. The pH of the mixture was 12.71. Then, ethanol was distilled off until the temperature of the sump reached 95° C. 558 g of distillate was obtained.

[0080] The synthesis gel was then cooled to 40° C. under stirring and 558 g of deionized water was added, the pH of the resulting mixture was 11.95.

[0081] The synthesis gel was then transferred to an autoclave. The synthesis gel was heated in the autoclave with stirring to a temperature of 175 ° C and stirred at this temperature under autogenous pressure for 16 h. The pressure ranged from 8.4 to 11.4 bar (abs). The suspension obtained was then worked up. For this purpose, the suspension obtained was diluted with deionized water, the mass ratio of suspension to deionized water was 1:1. About 152 g of nitric acid (10% by mass in water) was then added, the pH of the resulting mixture was 7.21. The solid obtained was filtered and washed three times with deionized water (1000 ml of deionized water was used each time). The solid was then dried in an oven in air at 120 ° C for 4 h and then calcined in air at 490 ° C for 5 h (the heating rate for calcination was 2 ° C / min).

[0082] The resulting TS-1 material had a Si content of 43 wt%, a Ti content of 2 wt%, and a total carbon loss of less than 0.1 wt%. The BET specific surface area of ​​the resulting TS-1 material was 447 m 2 The crystallinity was 92%, and about 0.5% anatase was detected by X-ray diffraction.

[0083] Next, 382.0 g of deionized water was provided to the beaker. 150.9 g of tetrapropylammonium hydroxide (as an aqueous solution containing 40% by weight of tetrapropylammonium hydroxide) was added under stirring. Then, 71.0 g of TS-1 feedstock was added. The mixture was homogenized for 30 minutes. The mixture was then transferred to an autoclave. The mixture was hydrothermally treated at 170° C. for 6 hours. The resulting solid was separated by centrifugation and the resulting solid residue was washed with deionized water. The resulting solid was dried in air at 120° C. for 4 hours and calcined in an oven at 490° C. for 5 hours.

[0084] The resulting TS-1 product had a Si content of 44 wt%, a Ti content of 1.9 wt%, and a total carbon loss of less than 0.1 wt%. The BET specific surface area of ​​the resulting TS-1 product was 446 m 2 The crystallinity was 93%, and approximately 0.7% anatase was detected by X-ray diffraction.

[0085] Figure 1 shows the XRD pattern of the TS-1 material.

[0086] Reference Example 2: Synthesis of p-xylylene-bis((N-methyl)N-pyrrolidinium) hydroxide In a typical example of organic template synthesis, 13.2 g of p-xylylene dibromide was dissolved in 250 mL of acetonitrile, followed by the addition of 10.6 g of 1-methylpyrrolidine and stirring under reflux for 48 h. After cooling to room temperature, the mixture was filtered and washed three times with acetonitrile. The solid was dried overnight under vacuum conditions. The bromide cation was converted to the hydroxide form using hydroxide exchange resin in water, and the resulting solution was titrated with 0.1 M HCl as a titration.

[0087] Comparative Example 1: Synthesis of titanium zeolite with IWR-type framework structure 0.5 g of TS-1 obtained from Reference Example 1 was added to a solution of p-xylylene-bis((N-methyl)N-pyrrolidinium)hydroxide (4.25 g, 0.98 mmol / g) obtained from Reference Example 2 in a 25 mL beaker. After stirring for 2 hours, 0.36 mL of hydrofluoric acid (40% aqueous solution) was added to the solution and the beaker was placed in an oven at 80 °C to evaporate excess water. Finally, 0.03 g of pure silica IWR seeds (seeds were synthesized using the same organic template) was added to the mixture before grinding it. The final molar composition of the mixture was SiO 2 1.0:OSDA 0.5:TiO 2 0.0263:HF 1:H 2 O was 2. After grinding, the powder was transferred to a Teflon-lined autoclave, sealed, and crystallized at 160° C. under rotating conditions (50 rpm) for 72 h.

[0088] The XRD pattern of the crystalline material is shown in Figure 2. The TEM image of the crystalline material is shown in Figure 3.

[0089] As can be seen from the XRD patterns in Figure 2, a small amount of TS-1 remained in the final product.

[0090] Example 1: Synthesis of high-purity titanium zeolite with IWR-type framework structure (Ti-COE-6) 0.25 g of TS-1 obtained from Reference Example 1 was added to a solution of p-xylylene-bis((N-methyl)N-pyrrolidinium)hydroxide (3.375 g, 0.75 mmol / g) obtained from Reference Example 2 in a 25 mL beaker, and then 1.274 g of tetraethyl orthosilicate (TEOS) was added to the mixture. After stirring for 12 hours, 0.22 mL of hydrofluoric acid (40% aqueous solution) was added to the solution, and the beaker was placed in an oven at 80 °C to evaporate excess water. Finally, 0.03 g of pure silica IWR seeds (seeds were synthesized using the same organic template) was added to the mixture, and then the mixture was ground. The final molar composition of the mixture was SiO 2 1.0:OSDA 0.25:TiO 2 0.0133:HF 0.5:H2 O was 2. After grinding, the powder was transferred to a Teflon-lined autoclave, sealed, and crystallized at 160° C. for 72 h under rotating conditions (50 rpm).

[0091] Figure 4 shows the XRD pattern of Ti-COE-6 material, and Figure 5 shows the TEM image of Ti-COE-6 material.

[0092] As can be seen from the XRD pattern in Figure 4, compared with the XRD pattern of the crystalline material from Comparative Example 1 (see Figure 2), the TI-COE-6 material obtained from Example 1 was of very high purity, and no trace of the TS-1 starting material was found in the diffraction pattern. Furthermore, as can be seen from the TEM image displayed in Figure 5, compared with the TEM image of the crystalline material from Comparative Example 1 (see Figure 3), the crystals of the Ti-COE-6 material obtained from Example 1 were significantly larger.

[0093] When the Ti-COE-6 material obtained in Example 1 was subjected to the K-80 test, the -1 A K-80 value of 100 was obtained.

[0094] Thus, it has been surprisingly found that the method of the present invention can provide Ti-COE-6 with very high purity and large primary crystal size. Furthermore, as shown by the results of the K-80 test, the Ti-COE-6 material can activate hydrogen peroxide.

[0095] Cited Prior Art - EP1609758B1 - Cantin, A. et al., J. Am. Chem. Soc. 2006, 128, 4216-4217 - Shamzhy, M. et al., Catal.Today 2015, 243, 76-84 - WO2020 / 244630A - Hong, X. et al., J. Am. Chem. Soc. 2019, 141, 45, 18318-18324 - CN111847474A <h2 style=";text-align:left;direction:ltr">- US7344696B2

Claims

1. A method for producing a zeolite material having an IWR-type framework structure, comprising the steps of: (1) One or more organic templates as structure directing agents and SiO in the framework structure ２ and Y.O. ２ wherein Y is a tetravalent element other than Si; and one or more SiO ２ preparing a mixture comprising a source and a solvent system; (2) SiO in the skeleton structure ２ and Y.O. ２ heating the mixture obtained in (1) to crystallize the zeolitic material having an IWR-type framework structure comprising Including, The one or more organic templates have the formula (I): R ３ R ５ R ６ N ＋ -R １ -Q-R ２ -N ＋ R ４ R ７ R ８ (I) (In the formula, R １ and R ２ are independently (C １ ~C ３ ) alkylene; Q is C ６ - represents arylene, R ３ and R ４ are each independently １ ~C ４ ) alkyl, and R ５ , R ６ , R ７ , and R ８ are each independently １ ~C ６ ) represents alkyl The method comprises the steps of:

2. 2. The method of claim 1, wherein the one or more zeolitic materials of (1) exhibit a framework structure type selected from the group consisting of MFI, MWW, MEL, BEA, CHA, MOR, and mixtures of two or more thereof.

3. 3. The method of claim 1 or 2, wherein the tetravalent element Y is selected from the group consisting of Sn, Ti, Zr, and mixtures of two or more thereof.

4. Y is Ti, and the skeleton structure contains SiO ２ and Y.O. ２ 4. The method of claim 3, wherein the one or more zeolitic materials comprise ZMQ-TB and / or TS-1.

5. Alkyl group R ５ and R ６ The method according to claim 1 or 2, wherein are linked together to form a common alkylene chain.

6. Alkyl group R ７ and R ８ The method according to claim 1 or 2, wherein are linked together to form a common alkylene chain.

7. The organic dication of formula (I) is represented by formula (II): 【Chemistry 1】 The method according to claim 1 or 2, comprising:

8. The mixture prepared in (1) and heated in (2) is SiO ２ One or more SiO other than the one or more zeolite materials, calculated as ２ GeO relative to 100% by mass of the source ２ 3. The method of claim 1, wherein the Ge content is less than 5% by weight, calculated as:

9. 3. The method of claim 1 or 2, wherein the mixture prepared in (1) and heated in (2) contains less than 0.5% by weight of a trivalent element X, calculated as the element and relative to 100% by weight of Si contained in the mixture.

10. 10. The method of claim 9, wherein X is Al and / or B.

11. 3. The method of claim 1 or 2, wherein the mixture prepared in (1) further comprises one or more fluoride sources.

12. 12. The method of claim 11, wherein the one or more fluoride sources are selected from fluoride salts, HF, and mixtures of two or more thereof.

13. The method according to claim 1 or 2, wherein the heating in (2) is carried out at a temperature in the range of 80 to 220° C.

14. 3. A zeolitic material with an IWR-type framework structure obtainable and / or obtained from the method according to claim 1 or 2.

15. 15. Use of the zeolitic material according to claim 14 as a molecular sieve, as an adsorbent, for ion exchange or as a catalyst and / or as a catalyst support.

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