JP2016502487A5 - - Google Patents

Claims (48)

A method for producing a zeolitic material having MFI, MEL and / or NWW-type framework structure containing YO ₂ and X ₂ O ₃ , comprising:
(1) Step of preparing a mixture containing one or more YO ₂ sources, one or more X ₂ O ₃ sources, and one or more solvents (2) Crystallizing the mixture obtained in step (1) , A step of obtaining a zeolitic material having an MFI, MEL and / or NWW-type framework structure, and (3) one or more elements selected from alkaline earth metals in the zeolitic material obtained in step (2). Impregnating, and
Y is a tetravalent element, X is a trivalent element, and the mixture crystallized in step (2) is one or more elements of 3% by mass or less with respect to 100% by mass of YO ₂ A production method comprising M (M represents sodium). Crystallized mixture in step (2) The production method of claim 1 comprising one or more elements M of 1 mass% or less with respect to 100 wt% of YO _2.   The production method according to claim 1 or 2, wherein the element M represents sodium and potassium.   The process according to any one of claims 1 to 3, wherein in the step (3), the zeolite material is impregnated with one or more elements selected from Mg, Ca, Ba, Sr and a mixture of two or more thereof. Production method. The process according to the molar ratio of X 2 _{O 3} is any one of claims 1 to 4 in the range of 10 to _{1500: YO} 2 of the mixture prepared in step (1).   The manufacturing method according to any one of claims 1 to 5, wherein Y is selected from Si, Sn, Ti, Zr, Ge, and a mixture of two or more thereof.   The production method according to any one of claims 1 to 6, wherein X is selected from Al, B, In, Ga, and a mixture of two or more thereof.   The manufacturing method according to claim 1, wherein the one or more solvents include one or more polar solvents.   The manufacturing method of any one of Claims 1-8 in which the mixture of a process (1) contains 1 or more types of organic templates.   One or more organic templates are selected from tetraethylammonium compounds, triethylpropylammonium compounds, diethyldipropylammonium compounds, ethyltripropylammonium compounds, tetrapropylammonium compounds, and mixtures of two or more thereof. The manufacturing method of Claim 9 containing a tetraalkylammonium compound. One or more organic _{template, N- (C 2 -C 5)} - alkenyl - tri - _{(C 1} -C ₅₎ according to claim 9 comprising one or more alkenyl selected from alkyl ammonium compound trialkylammonium compound Or the manufacturing method of 10. The total amount molar ratio of the one or more organic template of the mixture obtained in step (1) with respect to YO ₂ is 1: any one of claims 9-11 in the range of (0.1 to 30) The manufacturing method as described in. The manufacturing method of any one of Claims 1-12 in which the mixture of a process (1) contains 1 or more types of OH ^- source further. The manufacturing method according to claim 13, wherein the mixture obtained in step (1) has a molar ratio of OH ⁻ : YO ₂ in the range of 0.01 to 5.   The manufacturing method according to claim 1, wherein the crystallization in the step (2) includes heating of the mixture.   The method according to any one of claims 1 to 15, wherein the crystallization in the step (2) is performed under solvothermal conditions.   The method according to any one of claims 1 to 16, wherein the crystallization in step (2) comprises heating the mixture for at least 3 hours. After step (2) and before (3), further (2a) adjusting the pH of the mixed product obtained in step (2) to a pH in the range of 5-9; and / or (2b) step Isolating the zeolitic material from the mixed product obtained in (2); and / or (2c) washing the zeolitic material; and / or (2d) drying and / or calcining the zeolitic material; And / or (2e) hydrothermally treating the zeolitic material;
The manufacturing method of any one of Claims 1-17 containing these. The method according to claim 18 , wherein the calcination of (2d) is performed at a temperature in the range of 300 to 850 ° C.   The method according to claim 18 or 19, wherein the hydrothermal treatment of (2e) is performed under a self-generated pressure. Method of producing a water-heat treatment (2e) is according to any one of claims 18 to 20 which is performed using an aqueous solvent system. The process according to any one of claims 18 to 21 hydrothermal treatment is carried out under heating (2e). The production method according to any one of claims 18 to 22, wherein the hydrothermal treatment of (2e) is performed in a period of 2 to 72 hours. The manufacturing method according to any one of claims 18 to 23, wherein the hydrothermally treated zeolite material obtained in (2e) exhibits a water absorption of 10.0% by mass or less.   The process according to any one of claims 1 to 24, wherein in the step (3), the zeolitic material is impregnated with one or more elements selected from alkaline earth metals in an amount of 0.1 to 15% by mass relative to the total mass of the zeolitic material. The production method according to claim 1. A zeolitic material having MFI, MEL and / or NWW-type framework structure containing YO ₂ and X ₂ O ₃ ,
Y is a tetravalent element, X is a trivalent element, and the zeolitic material contains 3% by mass or less of one or more elements M with respect to 100% by mass of YO ₂ , Sodium
The zeolitic material further comprises one or more elements selected from alkaline earth metals;
A zeolite material, wherein 95% by mass or more of the primary particles of the zeolite material have a diameter of 1 μm or less.   The zeolitic material according to claim 26, which can be obtained and / or obtained by the production method according to any one of claims 1 to 25.   The zeolitic material according to claim 26 or 27, wherein 90% by mass or more of the primary particles are spherical.   The zeolitic material according to any one of claims 26 to 28, wherein 95% by mass or more of the primary particles have a diameter of 5 to 800 nm. 30. The zeolitic material according to any one of claims 26 to 29, comprising 1% by mass or less of one or more elements M with respect to 100% by mass of YO ₂ .   The zeolitic material according to any one of claims 26 to 30, wherein M represents sodium and potassium.   One or more elements selected from alkaline earth metals further contained in the zeolitic material are contained in the zeolitic material in an amount ranging from 0.1 to 15% by mass relative to the total mass of the zeolitic material. Item 32. The zeolitic material according to any one of Items 26 to 31.   The one or more elements selected from alkaline earth metals further contained in the zeolitic material are selected from Mg, Ca, Ba, Sr, and a mixture of two or more thereof. The zeolitic material described in 1. The zeolitic material according to any one of claims 26 to 33, wherein the YO ₂ : X ₂ O ₃ atomic ratio of the zeolitic material is in the range of 10 to 1500.   The zeolitic material according to any one of claims 26 to 34, wherein Y is selected from Si, Sn, Ti, Zr, Ge, and a mixture of two or more thereof.   36. The zeolitic material according to any one of claims 26 to 35, wherein X is selected from Al, B, In, Ga, and a mixture of two or more thereof.   The zeolitic material according to any one of claims 26 to 36, wherein the zeolitic material contains ZSM-5. The zeolite material, zeolite material according to any one of claims 26 to 37 in the range BET surface area of 200~900m ² / g determined according to DIN 66131. The zeolitic material according to any one of claims 26 to 38, wherein the zeolitic material exhibits a water absorption of 10.0% by mass or less. (I) supplying a gas stream containing one or more oxygen-containing materials;
(II) contacting the gas stream with a catalyst comprising the zeolitic material according to any one of claims 26 to 39;
A method for converting an oxygen-containing substance containing olefin into an olefin.   41. The method of claim 40, wherein the gas stream supplied in step (I) comprises one or more oxygen-containing materials selected from aliphatic alcohols, ethers, carbonyl compounds, and mixtures of two or more thereof.   42. The method according to claim 40 or 41, wherein the gas stream supplied in step (I) comprises from 30 to 100% by volume of oxygen-containing material relative to the total gas stream volume.   43. The method according to any one of claims 40 to 42, wherein the gas stream supplied in step (I) comprises 60% or less water by volume relative to the total gas stream volume.   44. The method according to any one of claims 40 to 43, wherein the contact between the gas stream and the catalyst in step (II) is performed at a temperature of 200 to 700C.   45. A process according to any one of claims 40 to 44, wherein the contact between the gas stream and the catalyst in step (II) is carried out at a pressure of 0.1 to 10 bar.   The method according to any one of claims 40 to 45, wherein at least a part of the method is performed in a continuous mode. The process according to claim 46, wherein the weight hourly space velocity (WHSV) of the gas stream in step (II) is in the range of 0.5 to 50 hours- ¹ .   40. A method of using the zeolitic material according to any one of claims 26 to 39 as a molecular sieve, a catalyst, a catalyst support and / or an adsorbent.