Continuous synthesis of titanosilicate zeolite materials.

Abstract

The present invention relates to a specific continuous process for preparing a zeolitic material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, preferably having an MFI and / or MEL type framework structure, and containing Si, Ti, and O, and to a zeolitic material obtainable and / or obtainable according to said process. Furthermore, the present invention relates to a process for preparing a shaped article, and to a shaped article obtainable and / or obtainable according to said process. Furthermore, the present invention relates to methods for using said zeolitic material and shaped article.

Description

[Technical Field]

[0001] The present invention relates to a specific continuous process for the preparation of zeolitic materials having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, wherein the framework structure comprises Si, Ti, and O. Furthermore, the present invention relates to zeolitic materials obtainable and / or obtainable according to the process of the present invention, as well as to zeolitic materials having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, wherein the framework structure comprises Si, Ti, and O. In addition, the present invention relates to molded articles comprising the zeolitic materials of the present invention, and to the preparation thereof. Furthermore, the present invention relates to methods of using the zeolitic materials of the present invention and the molded articles of the present invention. [Background technology]

[0002] Titanium-containing zeolitic materials of structure type MFI are known to be efficient catalysts for, for example, epoxidation reactions. In such industrial-scale processes, which are typically carried out in a continuous mode, these zeolitic materials are used in the form of shaped articles that contain a suitable binder in addition to the catalytically active zeolitic material.

[0003] Y. Hu et al. have reported on the ultrafast synthesis of TS-1 without excess framework titanium species in a continuous-flow system. Furthermore, they have reported on the rapid, continuous hydrothermal synthesis of TS-1 nanoparticles using a tubular reactor, using a synthesis gel with molar ratios ranging from 1:1 SiO2:0.02:1 TiO2:0.35:1 TPAOH:(16-35):1 HO.

[0004] CN110028078 A relates to a method for preparing titanium silicon molecular sieves. The method includes mixing a silicon source, a template agent, an alkali source, and a titanium source. It is disclosed that the reactor may be tubular, and that at least a portion of the mother liquor may be recycled in the method.

[0005] DE 3029787 A1 relates to a continuous process for preparing zeolites. EP 0402801 A2 relates to a process for preparing crystalline and zeolitic aluminosilicates. Furthermore, US 4374093 discloses a continuous-flow zeolite crystallizer, in particular a combination of a tubular reactor, a central stirring element, an inlet / outlet means, and a collection vessel. Furthermore, US 6656447 B1 discloses a continuous process for preparing molecular sieves.

[0006] CN110078091 A discloses a method for continuously synthesizing titanium silicalite molecular sieves, which includes the following steps: preparing a continuous microdispersion system; preparing a dealcoholized precursor through a continuous aging dealcoholization system; and realizing rapid crystallization through a continuous crystallization system. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] CN110028078 A [Patent Document 2] DE 3029787 A1 [Patent Document 3] EP 0402801 A2 [Patent Document 4] US 4374093 [Patent Document 5] US 6656447 B1 [Patent Document 6] CN110078091 A [Non-patent literature]

[0008] [Non-Patent Document 1] Y. Hu, Ultrafast synthesis of TS-1 without extra framework titanium species in a continuous flow system Summary of the Invention [Problem to be solved by the invention]

[0009] The object of the present invention is to provide a novel process for preparing zeolitic materials having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more of these, wherein the process is carried out continuously. In particular, it was an object of the present invention to provide a process that is particularly improved in terms of procedural economy and resource efficiency.

[0010] A further object of the present invention was to provide novel zeolitic materials having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, as well as novel molded articles comprising said zeolitic materials, which have advantageous properties, in particular improved propylene oxide selectivity, when used as a catalyst or catalyst component, particularly in the epoxidation reaction of propene to propylene oxide. A further object of the present invention was to provide a process for the preparation of such molded articles, in particular a process which results in molded articles having advantageous properties when used, preferably as a catalyst or catalyst component, specifically in oxidation or epoxidation reactions. A further object of the present invention was to provide an improved process for the epoxidation of propene using hydrogen peroxide as an oxidizing agent, which process exhibits very low selectivity with respect to by-products and by-products of the epoxidation reaction, while at the same time allowing very high propylene selectivity. [Means for solving the problem]

[0011] Surprisingly, it has been found that a method for preparing a zeolite material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and two or more intergrowth structures thereof can be carried out continuously, and this method is particularly characterized by the use of a specific molar ratio of water to one or more silica sources in the synthesis gel. Surprisingly, it has therefore been found that the synthesis gel can be used in a continuous process at a relatively higher concentration than prior art synthesis gels. This results in the surprising advantage that the preparation of a zeolite material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and two or more intergrowth structures thereof can be carried out continuously, avoiding the drawbacks of typical batch processes, such as time interruptions between batch processes, thereby enabling higher throughput.

[0012] Furthermore, it has surprisingly been found that zeolitic materials prepared according to the method of the present invention exhibit certain properties that make them powerful materials for use in catalytic reactions. In particular, it has been found that zeolitic materials exhibiting certain absorbances in the UV-VIS spectrum exhibit improved catalytic activity, particularly in the conversion of propylene to propylene oxide. It is therefore believed that the method of the present invention results in a relatively high content of pentavalent titanium in zeolitic materials known to have relatively high catalytic activity.

[0013] According to the present invention, a molded article is to be understood as a three-dimensional entity resulting from a molding process; the term "molded article" is therefore used synonymously with the term "molded body".

[0014] The present invention therefore relates to a method for continuously preparing a zeolitic material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR and intergrowth structures of two or more thereof, preferably having an MFI and / or MEL type framework structure, more preferably having an MFI type framework structure, and containing Si, Ti and O, said method comprising: (i) one or more Si sources, one or more Ti sources, one or more tetraalkylammonium cations R as structure directing agents 1 R 2 R 3 R 4 N + preparing a mixture comprising the compound to be incorporated and water; (ii) continuously feeding the mixture prepared in step (i) into a continuous flow reactor; and (iii) crystallizing from the mixture in a continuous flow reactor a zeolitic material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, preferably having an MFI and / or MEL type framework structure, more preferably having an MFI type framework structure, wherein the mixture is heated to a temperature in the range of 70 to 300°C. Including, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group; In the mixture prepared in step (i), the H2O:Si molar ratio of water to one or more Si sources, calculated as SiO2, is in the range of 1-15.

[0015] Furthermore, the present invention relates to a zeolitic material obtainable and / or obtained according to the method according to any one of the embodiments disclosed herein.

[0016] Furthermore, the present invention relates to a zeolitic material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, preferably having an MFI and / or MEL type framework structure, more preferably having an MFI type framework structure, and comprising Si, Ti, and O, preferably a zeolitic material obtainable and / or obtainable according to the method according to any one of the embodiments disclosed herein, wherein: in the wavelength range of 200 to 800 nm, the zeolitic material exhibits a UV-visible (ultraviolet-visible) spectrum having a first maximum in the range of 200 to 230 nm, preferably 202 to 225 nm, more preferably 204 to 220 nm, more preferably 206 to 215 nm, more preferably 208 to 210 nm, and a second maximum in the range of 235 to 320 nm, preferably 240 to 300 nm, more preferably 245 to 270 nm, more preferably 250 to 265 nm, more preferably 258 to 262 nm; The ratio of the absorbance of the first maximum value to the absorbance of the second maximum value is in the range of 0.5 to 2.5, preferably 0.7 to 2, more preferably 0.9 to 1.8, more preferably 1 to 1.5, more preferably 1.1 to 1.3, more preferably 1.15 to 1.25.

[0017] Furthermore, the present invention provides (A) providing a zeolitic material according to any one of the embodiments disclosed herein; (B) mixing the zeolite material provided in step (A) with one or more binders; (C) optionally kneading the mixture obtained in step (B); (D) molding the mixture obtained in step (B) or (C) to obtain one or more molded articles; (E) drying the one or more molded articles obtained in step (D); and (F) A step of firing the dried molded product obtained in step (E). The present invention relates to a method for preparing a molded article, comprising:

[0018] Furthermore, the present invention relates to a molded article obtained or obtainable according to the method according to any one of the embodiments disclosed herein.

[0019] Furthermore, the present invention relates to the use of the zeolitic material according to any one of the embodiments disclosed herein, or the shaped article disclosed herein, as a catalyst, catalyst support, adsorbent, or for ion exchange, wherein the shaped article is preferably used as a catalyst and / or catalyst support, more preferably as a catalyst and / or catalyst support in reactions involving the formation and / or conversion of C-C bonds, preferably in isomerization reactions, ammoxidation reactions, amination reactions, hydrocracking reactions, alkylation reactions, acylation reactions, reactions for the conversion of alkanes to olefins, conversion of one or more oxygenates to olefins and / or aromatics. the synthesis of hydrogen peroxide, the aldol condensation reaction, the isomerization of epoxides, the transesterification reaction or the epoxidation reaction, preferably as a catalyst and / or catalyst support in the reaction for the epoxidation of olefins, more preferably in the reaction for the epoxidation of C2 to C5 alkenes, more preferably in the reaction for the epoxidation of C2 to C4 alkenes, more preferably in the reaction for the epoxidation of C2 or C3 alkenes, more preferably in the reaction for the epoxidation of C3 alkenes, and more preferably as a catalyst for the conversion of propylene to propylene oxide. [Brief explanation of the drawings]

[0020] [Figure 1] 1 shows the catalytic performance of the zeolitic material according to Example 1, in particular the selectivity of propylene oxide to hydrogen peroxide (dashed triangle line). The solid black line shows the conversion of hydrogen peroxide, and the dashed circle line shows the temperature of the cooling medium flowing through the reactor jacket. [Figure 2] 2 is a graph showing the catalytic performance of the zeolitic materials according to Examples 2 and 3, in particular the conversion of hydrogen peroxide as a function of temperature. The dashed line with squares shows the conversion of hydrogen peroxide using the zeolitic material from Example 2, the dashed line with diamonds shows the conversion of hydrogen peroxide using the zeolitic material from Example 2, the dotted line with squares shows the temperature of the cooling medium flowing through the reactor jacket when using the zeolitic material from Example 2, and the dotted line with diamonds shows the corresponding temperature of the cooling medium when using the zeolitic material from Example 3. [Figure 3] 3 is a graph showing the catalytic performance, in particular the propylene oxide selectivity relative to hydrogen peroxide, of the zeolitic materials according to Examples 2 and 3. The line with squares shows the propylene oxide selectivity using the zeolitic material from Example 2, and the line with diamonds shows the propylene oxide selectivity using the zeolitic material from Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0021] In the process for the continuous preparation of a zeolitic material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, preferably having an MFI and / or MEL type framework structure, the H2O:Si molar ratio of water to one or more Si sources, calculated as SiO2, in the mixture prepared in step (i) is preferably in the range of 2 to 13, more preferably 3 to 11, more preferably 4 to 10, more preferably 4.5 to 9.5, more preferably 5 to 9, more preferably 5.5 to 8.5, more preferably 6 to 8, more preferably 6.5 to 7.5.

[0022] The continuous supply in step (ii) is preferably carried out for 0.05 to 5 hours. -1 , more preferably 0.1 to 3 hours -1 , more preferably 0.3 to 2 hours -1 , more preferably 0.5 to 1.5 hours -1 , more preferably 0.7 to 1.3 hours -1 , more preferably 0.8 to 1.2 hours -1 , more preferably 0.9 to 1.1 h -1 The liquid hourly space velocity is in the range of

[0023] The volume of the continuous flow reactor is preferably 50 cm 3 ~75m 3 , more preferably 55 cm 3 ~3m 3 , more preferably 60 cm 3 ~1m 3 , more preferably 65 cm 3 ~0.7m 3, more preferably 70 cm 3 ~0.3m 3 , more preferably 75 cm 3 ~0.1m 3 , more preferably 80 to 70,000 cm 3 , more preferably 85 to 50,000 cm 3 , more preferably 90 to 30,000 cm 3 , more preferably 95 to 10,000 cm 3 , more preferably 100 to 7,000 cm 3 , more preferably 105 to 5,000 cm 3 , more preferably 110 to 3,000 cm 3 , more preferably 115 to 1,000 cm 3 , more preferably 120 to 700 cm 3 , more preferably 125 to 500 cm 3 , more preferably 130 to 350 cm 3 , more preferably 135 to 250 cm 3 , more preferably 140 to 200 cm 3 , more preferably 145 to 180 cm 3 , more preferably 150 to 170 cm 3 , more preferably 155 to 165 cm 3 The range is.

[0024] The continuous flow reactor is preferably selected from among tubular reactors, ring reactors, and continuous oscillatory reactors, more preferably from among plain tubular reactors, tubular membrane reactors, tubular reactors with Coanda effect, ring reactors, continuously oscillatory baffle reactors, Taylor-Couette reactors, and combinations thereof. More preferably, the continuous flow reactor is a plain tubular reactor and / or a ring reactor. It is particularly preferred that the continuous flow reactor is a plain tubular reactor.

[0025] The continuous flow reactor is preferably a tubular reactor. When the continuous flow reactor is a tubular reactor, it is preferable that at least a portion of the tubular reactor has a regular cylindrical shape having a constant inner diameter perpendicular to the flow direction, and this inner diameter is preferably in the range of 2 to 1200 mm, more preferably 3 to 800 mm, more preferably 4 to 500 mm, more preferably 4.5 to 200 mm, more preferably 4.5 to 100 mm, more preferably 5 to 50 mm, more preferably 5 to 30 mm, more preferably 5.5 to 15 mm, more preferably 5.5 to 10 mm, more preferably 6 to 8 mm, and more preferably 6 to 6.5 mm.

[0026] The continuous flow reactor preferably has a length in the range of 0.2 to 5,000 m, preferably 0.5 to 3,000 m, more preferably 1 to 1,000 m, more preferably 2 to 500 m, more preferably 3 to 200 m, more preferably 4 to 100 m, more preferably 4.5 to 50 m, more preferably 4.5 to 30 m, more preferably 4 to 20 m, more preferably 4 to 15 m, more preferably 4.5 to 10 m, more preferably 4.5 to 5.5 m.

[0027] The walls of the continuous flow reactor are preferably made of a metallic material. When the walls of the continuous flow reactor are made of a metallic material, the metallic material comprises one or more metals selected from the group consisting of Ta, Cr, Fe, Ni, Cu, Al, Mo, Ti, Zr, and combinations and / or alloys of two or more thereof, more preferably from the group consisting of Ta, Cr, Fe, Ni, Mo, and combinations and / or alloys of two or more thereof, preferably from the group consisting of Cr, Fe, Ni, Mo, and combinations and / or alloys of two or more thereof. Particularly preferably, the metallic material comprises a nickel alloy, a nickel-molybdenum alloy, more preferably a nickel-molybdenum-chromium alloy.

[0028] It is preferred that the surface of the inner wall of the continuous-flow reactor is lined with an organic polymer material, wherein the organic polymer material preferably comprises one or more polymers selected from the group consisting of fluorinated polyalkylenes and mixtures of two or more thereof, preferably (C2-C3) polyalkylenes and mixtures of two or more thereof, preferably fluorinated polyethylene and mixtures of two or more thereof, more preferably the polymer material comprises poly(tetrafluoroethylene), and more preferably the inner wall of the continuous-flow reactor is lined with poly(tetrafluoroethylene).

[0029] Alternatively, the surface of the inner wall of the continuous flow reactor is coated with a polysiloxane, preferably of the formula [R2SiO] n The polymer is backed with a polysiloxane comprising building blocks having the formula: where R is preferably an organic group, more preferably an alkyl group and / or a phenyl group.

[0030] Alternatively, the wall of the continuous flow reactor comprises, and preferably consists of, an organic polymer material, wherein the organic polymer material preferably comprises one or more polymers selected from the group consisting of fluorinated polyalkylenes and mixtures of two or more thereof, preferably from the group consisting of (C2-C3) polyalkylenes and mixtures of two or more thereof, preferably from the group consisting of fluorinated polyethylene and mixtures of two or more thereof, more preferably the polymer material comprises poly(tetrafluoroethylene), and more preferably the interior wall of the continuous flow reactor is lined with poly(tetrafluoroethylene).

[0031] Preferably, the continuous flow reactor is straight and / or comprises one or more curves relative to the flow direction, more preferably the continuous flow reactor is straight and / or has a coiled shape relative to the flow direction.

[0032] Preferably, the continuous flow reactor consists of a single stage.

[0033] It is preferred that no material is added to and / or removed from the reaction mixture during passage through the continuous flow reactor in step (iii), where preferably no material is added, more preferably no material is added and no material is removed from the reaction mixture during passage through the continuous flow reactor in step (iii).

[0034] The flow regime in the reactor is preferably at least partially laminar. If the reaction mixture exhibits shear-thinning rheology (pseudoplastic rheology), the velocity profile v(r) of the reaction mixture in the flow direction satisfies the condition according to (I): v(r) ≦ ((v(r1) - v min ) · (r / r1)) + v min (I) In step (iii), if the reaction mixture exhibits shear thinning rheology (pseudoplastic rheology), the velocity profile v(r) of the reaction mixture in the flow direction satisfies the condition according to (II). v(r) ≧ ((v(r1) - v min ) · (r / r1)) + v min (II) (where r defines the length of a line on a cross section of the reactor space perpendicular to the direction of flow of the reaction mixture in the reactor, said line extending from a first point to a second point on the inner surface of the reactor wall in contact with the mixture, at said first point r0 is defined as 0 and v is its minimum value (v min =v(r0)), and at the second point, r is r max and v is its maximum value (v max =v(r max )) and r1=r max / x, where x=5).

[0035] Preferably, R 1 , R 2 , R 3 and R 4are each independently an optionally branched (C1-C6) alkyl, preferably a (C1-C5) alkyl, more preferably a (C2-C4) alkyl, more preferably an optionally branched (C2-C3) alkyl, and more preferably R 1 , R 2 , R 3 and R 4 are each independently ethyl or propyl, more preferably R 1 , R 2 , R 3 and R 4 represents propyl, preferably n-propyl.

[0036] Preferably, independently of one another, one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The containing compound is a salt, more preferably one or more salts selected from the group consisting of halides, preferably chlorides and / or bromides, more preferably chlorides, hydroxides, sulfates, nitrates, phosphates, acetates and mixtures of two or more thereof, more preferably chlorides, hydroxides, sulfates and mixtures of two or more thereof, and more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The containing compound is a tetraalkylammonium hydroxide and / or chloride, more preferably a tetraalkylammonium hydroxide.

[0037] The mixture prepared in step (i) and crystallized in step (iii) preferably contains one or more tetraalkylammonium cations R in the range of 0.001 to 1.5, more preferably 0.005 to 1, more preferably 0.01 to 0.7, more preferably 0.05 to 0.5, more preferably 0.07 to 0.4, more preferably 0.1 to 0.3, more preferably 0.13 to 0.25, more preferably 0.15 to 0.22, and even more preferably 0.17 to 0.19. 1 R2 R 3 R 4 N + The molar ratio of the contained compound to one or more Si sources calculated as SiO2 is given.

[0038] Preferably, the one or more Si sources comprise one or more compounds selected from the group consisting of silica, silicates, and mixtures thereof, preferably from the group consisting of fumed silica, silica hydrosol, reactive amorphous solid silica, silica gel, silicic acid, water glass, sodium metasilicate hydrate, sesquisilicates, disilicates, colloidal silica, pyrogenic silica, silicate esters, tetraalkoxysilanes, and mixtures of two or more thereof, more preferably from the group consisting of silica hydrosol, silica gel, silicic acid, water glass, sodium metasilicate hydrate, colloidal silica, silicate esters, tetraalkoxysilanes, and mixtures of two or more thereof, more preferably from the group consisting of silica hydrosol, silicic acid, colloidal silica, silicate esters, tetraalkoxysilanes, and mixtures of two or more thereof, Here, more preferably, the one or more Si sources comprise one or more tetraalkoxysilanes selected from the group consisting of (C1-C6) tetraalkoxysilanes and mixtures of two or more thereof, preferably (C1-C5) tetraalkoxysilanes and mixtures of two or more thereof, more preferably (C1-C4) tetraalkoxysilanes and mixtures of two or more thereof, and more preferably (C1-C3) tetraalkoxysilanes and mixtures of two or more thereof; more preferably, the one or more Si sources comprise tetramethoxysilane and / or tetraethoxysilane, preferably tetraethoxysilane; and more preferably, the one or more Si sources are tetramethoxysilane and / or tetraethoxysilane, preferably tetraethoxysilane.

[0039] The one or more Ti sources preferably comprise one or more compounds selected from the group consisting of titanium oxide, titanium salts, titanyl compounds, titanic acids, titanate esters, and mixtures of two or more thereof, preferably tetrabutyl orthotitanate, tetraisopropyl orthotitanate, tetraethyl orthotitanate, titanium dioxide, titanium tetrachloride, titanium tert-butoxide, TiOSO4 and / or KTiOPO4, and mixtures of two or more thereof, more preferably tetrabutyl orthotitanate, tetraisopropyl orthotitanate, tetraethyl orthotitanate, titanium dioxide, titanium tetrachloride, titanium tert-butoxide, and mixtures of two or more thereof, and the titanium source is preferably tetramethyl orthotitanate and / or tetraethyl orthotitanate, more preferably tetraethyl orthotitanate.

[0040] Preferably, the mixture prepared in step (i) is substantially free of phosphorus and / or phosphorus-containing compounds.

[0041] It is preferred that the framework of the zeolitic material obtained in step (iii) is substantially free of phosphorus, whereby preferably the zeolitic material obtained in step (iii) is substantially free of phosphorus and / or phosphorus-containing compounds.

[0042] The Si:Ti molar ratio of the one or more Si sources calculated as SiO2 to the one or more Ti sources calculated as TiO2 in the mixture prepared in step (i) is preferably in the range of 1 to 500, more preferably 2 to 200, more preferably 5 to 150, more preferably 10 to 100, more preferably 20 to 70, more preferably 25 to 50, more preferably 30 to 45, more preferably 35 to 40.

[0043] In step (ii), the mixture prepared in step (i) is continuously fed to a continuous flow reactor for a duration ranging preferably from 3 hours to 360 days, more preferably from 6 hours to 120 days, more preferably from 12 hours to 90 days, more preferably from 18 hours to 60 days, more preferably from 1 to 30 days, more preferably from 1.5 to 25 days, more preferably from 2 to 20 days, more preferably from 2.5 to 15 days, more preferably from 3 to 12 days, more preferably from 3.5 to 8 days, more preferably from 4 to 6 days.

[0044] In step (iii), the mixture is heated to a temperature in the range of preferably 90 to 280°C, more preferably 110 to 250°C, more preferably 130 to 220°C, more preferably 150 to 200°C, more preferably 160 to 190°C, more preferably 170 to 180°C.

[0045] In step (iii), the mixture is preferably heated under autogenous pressure, wherein this pressure is preferably in the range of 0.5 to 15 MPa, more preferably 1 to 10 MPa, more preferably 1.5 to 8 MPa, more preferably 2 to 6 MPa, more preferably 2.5 to 5.5 MPa, more preferably 3 to 5 MPa, more preferably 3.5 to 4.5 MPa, more preferably 3.8 to 4.2 MPa.

[0046] Prior to step (ii), the mixture prepared in step (i) is aged at a temperature in the range of preferably 40 to 120°C, more preferably 50 to 115°C, more preferably 60 to 110°C, more preferably 70 to 105°C, more preferably 80 to 100°C, more preferably 85 to 95°C.

[0047] Prior to step (ii), the mixture prepared in step (i) is preferably aged for a duration ranging from 0.05 to 48 hours, more preferably from 0.15 to 24 hours, more preferably from 0.25 to 12 hours, more preferably from 0.5 to 6 hours, more preferably from 0.75 to 3 hours, more preferably from 1 to 2 hours, more preferably from 1.25 to 1.75 hours.

[0048] It is preferred that the mixture prepared in step (i) is directly fed to a continuous flow reactor in step (ii), wherein the mixture prepared in step (i) is preheated to a temperature in the range of preferably 90 to 280°C, more preferably 110 to 250°C, more preferably 130 to 220°C, more preferably 150 to 200°C, more preferably 160 to 190°C, more preferably 170 to 180°C while being fed to the continuous flow reactor in step (ii).

[0049] The method of the present invention may comprise further process steps. Preferably, the method of the present invention comprises: (iv) treating the reaction product effluent continuously exiting the reactor in step (iii) with a liquid comprising one or more solvents and / or via expansion of the reaction product effluent, and / or preferably (v) isolating the zeolitic material obtained in step (iii) or (iv); (vi) optionally washing the zeolitic material obtained in step (iii), (iv) or (v); (vii) drying the zeolitic material obtained in step (iii), (iv), (v) or (vi), and / or preferably (viii) calcining the zeolitic material obtained in step (iii), (iv), (v), (vi) or (vii). Further includes:

[0050] If the method further comprises step (iv), in step (iv) the liquid comprises one or more solvents selected from the group consisting of polar protic solvents and mixtures thereof, preferably from the group consisting of n-butanol, isopropanol, propanol, ethanol, methanol, water, and mixtures thereof, more preferably from the group consisting of ethanol, methanol, water, and mixtures thereof; Here, more preferably the liquid comprises water, more preferably water, preferably deionized water, is used as the liquid.

[0051] Furthermore, if the method comprises step (iv), in step (iv) the liquid preferably comprises one or more acids, more preferably one or more organic and / or inorganic acids, more preferably one or more inorganic acids, wherein the one or more inorganic acids are preferably selected from the group consisting of HCl, HBr, HNO3, H2SO4, and mixtures of two or more thereof, more preferably from the group consisting of HCl, HNO3, H2SO4, and mixtures of two or more thereof, more preferably the one or more acids comprise HCl and / or HNO3, preferably HNO3, more preferably the acid is HCl and / or HNO3, preferably HNO3.

[0052] In step (iv), if the liquid comprises one or more acids, then in step (iv), the reaction product effluent is neutralized with one or more acids to a pH preferably in the range of 5 to 9, more preferably 6 to 8, more preferably 6.5 to 7.5. The pH adjustment by neutralization with one or more acids described herein is preferably carried out when a filter press or batch filtration is used for the subsequent isolation of the zeolitic material according to step (v).

[0053] If the method comprises step (vii), the drying in step (vii) is preferably carried out at a temperature in the range of 50 to 220°C, preferably 70 to 190°C, more preferably 80 to 170°C, more preferably 90 to 150°C, more preferably 100 to 140°C, more preferably 110 to 130°C.

[0054] If the method includes step (viii), the calcination in step (viii) is preferably carried out at a temperature in the range of 300 to 700°C, more preferably 375 to 625°C, more preferably 425 to 575°C, more preferably 470 to 530°C, more preferably 490 to 510°C.

[0055] If the process comprises step (v), it is preferred that the supernatant obtained from the isolation of the zeolitic material in step (v), and / or a feed having the same composition as said supernatant, is not recycled to the reaction mixture at any time during its passage through the continuous flow reactor.

[0056] When the method comprises steps (v) and / or (vii), preferably, in step (v), isolating the zeolitic material comprises spray drying and / or microwave drying the zeolitic material obtained in step (iii) or (iv); and / or In step (vii), drying the zeolitic material comprises spray drying and / or microwave drying the zeolitic material obtained in step (iii), (iv), (v) or (vi).

[0057] Preferably, the mixture constituting the crystallized feed in step (iii) consists of two liquid phases, where the first liquid phase is an aqueous phase comprising water and the second liquid phase comprises the lubricant.

[0058] When the mixture constituting the crystallized feed in step (iii) consists of two liquid phases, the first liquid phase being an aqueous phase comprising water and the second liquid phase comprising a lubricant, the lubricant preferably comprises one or more fluorinated compounds, more preferably one or more fluorinated polymers, more preferably one or more fluorinated polyethers, more preferably one or more perfluorinated polyethers.

[0059] Furthermore, when the mixture constituting the crystallized feed in step (iii) consists of two liquid phases, the first liquid phase being an aqueous phase comprising water and the second liquid phase comprising a lubricant, the lubricant preferably comprises one or more fluorinated compounds, more preferably one or more fluorocarbons, more preferably one or more perfluorocarbons, more preferably the lubricant comprises perfluorodecalin. Additionally or alternatively, the lubricant may comprise liquid paraffin.

[0060] It is preferred that the mixture crystallized in step (iii) in the continuous-flow reactor is mechanically agitated, wherein preferably the mechanical agitation is achieved by moving parts comprised in the continuous-flow reactor, more preferably the moving parts are arranged to continuously or periodically, preferably to continuously clean the walls of the continuous-flow reactor from zeolitic material and / or solid residues adhering thereto, more preferably the moving parts comprise scrapers, more preferably screws, more preferably rotating screws.

[0061] As mentioned above, the method of the present invention may comprise further process steps, and preferably further comprises (ix) subjecting the zeolitic material obtained in step (v), (vi), (vii) or (viii) to an impregnation procedure, in which the zeolitic material is impregnated with a compound containing one or more metal ions.

[0062] When the method further comprises step (ix), the one or more metal ions are preferably selected from the group consisting of ions of alkaline earth metal elements and / or transition metal elements, more preferably from the group of Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Pt, Pd, Ag, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Cr, Mo, Fe, Ni, Cu, Zn, Pt, Pd, Ag, and mixtures of two or more thereof, even more preferably from the group consisting of Zn, Pd, Pt, and mixtures of two or more thereof.

[0063] Furthermore, the present invention relates to a zeolitic material obtainable and / or obtained according to the method according to any one of the embodiments disclosed herein.

[0064] Furthermore, the present invention relates to a zeolitic material, preferably a zeolitic material obtainable and / or obtainable according to the method according to any one of the embodiments disclosed herein, said zeolitic material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, preferably having an MFI and / or MEL type framework structure, more preferably having an MFI type framework structure, and containing Si, Ti, and O, wherein in the wavelength range of 200 to 800 nm, the zeolitic material has a wavelength of 200 to 230 nm, preferably 202 to 225 nm, more preferably and a second maximum in the range of 235 to 320 nm, preferably 240 to 300 nm, more preferably 245 to 270 nm, more preferably 250 to 265 nm, more preferably 258 to 262 nm, and the ratio of the absorbance of the first maximum to the absorbance of the second maximum is in the range of 0.5 to 2.5, preferably 0.7 to 2, more preferably 0.9 to 1.8, more preferably 1 to 1.5, more preferably 1.1 to 1.3, more preferably 1.15 to 1.25.

[0065] Preferably, the UV-vis spectrum does not exhibit any further maxima between the first and second maxima.

[0066] Preferably, the first maximum and the second maximum have the highest absorbance in the 200-800 nm range of the UV-vis spectrum, and more preferably, the second maximum has the highest absorbance below 330 nm.

[0067] Preferably, the deconvoluted zeolite material 29The Si MAS NMR comprises a first peak (P''1) having a maximum in the range of -111.5 to -114.5 ppm, preferably -112 to -114 ppm, even more preferably -112.5 to -113.5 ppm, and a second peak (P''2) having a maximum in the range of -101 to -105 ppm, preferably -102 to -104 ppm, even more preferably -102.5 to -103.5 ppm, wherein preferably the deconvoluted zeolitic material 29 Si MAS NMR is determined according to Reference Example 1.

[0068] Deconvoluted zeolite materials 29 If the Si MAS NMR contains a first peak (P''1) with a maximum in the range of -111.5 to -114.5 ppm and a second peak (P''2) with a maximum in the range of -101 to -105 ppm, the deconvoluted 29 The Si MAS NMR spectrum preferably comprises one additional peak with a maximum in the range of -114.6 to -118 ppm, more preferably -115 to -117 ppm, even more preferably -115.5 to -116.5 ppm.

[0069] The zeolite material is preferably 300 to 700 m 2 / g, more preferably 350 to 600m 2 / g, more preferably 400 to 550 m 2 / g range, more preferably 450-500m 2 The BET specific surface area, determined according to ISO 9277:2010, in the range of 1 / g is shown.

[0070] The zeolite material preferably exhibits a water absorption in the range of 8 to 15% by mass when exposed to a relative humidity of 85%, preferably the water absorption is in the range of 9 to 14% by mass, more preferably 10 to 13.5% by mass, more preferably 11 to 13% by mass, more preferably 11.0 to 13.0% by mass, wherein the water absorption is preferably determined according to Reference Example 2.

[0071] The Si:Ti molar ratio of the zeolite material is preferably in the range of 1 to 500, more preferably 2 to 200, more preferably 5 to 150, more preferably 10 to 100, more preferably 20 to 70, more preferably 25 to 50, more preferably 30 to 45, and more preferably 35 to 40.

[0072] Preferably, the zeolitic material having an MFI-type framework structure comprises TS-1, more preferably the zeolitic material is TS-1.

[0073] Preferably, the zeolitic material is impregnated with a compound containing one or more metal ions, wherein the one or more metal ions are selected from the group consisting of ions of metals selected from the group consisting of ions of alkaline earth metal elements and / or transition metal elements, more preferably from the group consisting of Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, even more preferably from the group consisting of Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof.

[0074] It is preferred that the framework of the zeolitic material is substantially free of phosphorus, where preferably the zeolitic material is substantially free of phosphorus and / or phosphorus-containing compounds.

[0075] Furthermore, the present invention provides (A) providing a zeolitic material according to any one of the embodiments disclosed herein; (B) mixing the zeolite material provided in step (A) with one or more binders; (C) optionally kneading the mixture obtained in step (B); (D) molding the mixture obtained in step (B) or (C) to obtain one or more molded articles; (E) drying the one or more molded articles obtained in step (D); and (F) A step of firing the dried molded product obtained in step (E). The present invention relates to a method for preparing a molded article, comprising:

[0076] Preferably, the one or more binders are selected from the group consisting of inorganic binders, wherein the one or more binders are preferably selected from the group consisting of one or more sources of metal oxides and / or metalloid oxides, more preferably silica, alumina, titania, zirconia, lanthana, magnesia, and mixtures and / or mixed oxides of two or more thereof, more preferably silica, alumina, titania, zirconia, magnesia, silica-alumina mixed oxides, silica-titania mixed oxides, silica-zirconia mixed oxides, silica-lanthana mixed oxides, silica-zirconia-lanthana mixed oxides, alumina-titania mixed oxides, alumina-zirconia mixed oxides, alumina-lanthana mixed oxides, alumina-zirconia-lanthana mixed oxides, titania-zirconia mixed oxides, and mixtures of two or more thereof. More preferably, the one or more binders comprise one or more silica sources, and more preferably, the one or more binders consist of one or more silica sources, and the one or more silica sources preferably comprise one or more compounds selected from the group consisting of fumed silica, colloidal silica, silica-alumina, colloidal silica-alumina, and mixtures of two or more thereof, more preferably one or more compounds selected from the group consisting of fumed silica, colloidal silica, and mixtures thereof, and more preferably, the one or more binders consist of colloidal silica.

[0077] Preferably, step (B) further comprises mixing the zeolitic material and one or more binders with a solvent system, wherein the solvent system comprises one or more solvents, preferably the solvent system comprises one or more hydrophilic solvents, the hydrophilic solvents preferably selected from the group consisting of polar solvents, more preferably from the group consisting of polar protic solvents, more preferably from the group consisting of water, alcohols, carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C1-C5 alcohols, C1-C5 carboxylic acids, and mixtures of two or more thereof, more preferably water, C1-C4 alcohols. , C1-C4 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C1-C3 alcohols, C1-C3 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, methanol, ethanol, propanol, formic acid, acetic acid, and mixtures of two or more thereof, more preferably from the group consisting of water, ethanol, acetic acid, and mixtures of two or more thereof, more preferably the solvent system comprises water and / or ethanol, more preferably the solvent system comprises water, and even more preferably the solvent system consists of water.

[0078] Preferably, step (B) further comprises mixing the zeolitic material and the one or more binders with one or more pore formers and / or lubricants and / or plasticizers, wherein the one or more pore formers and / or lubricants and / or plasticizers are preferably selected from the group consisting of polymers, carbohydrates, graphite, botanical additives and mixtures of two or more thereof, more preferably polymers vinyl compounds, polyalkylene oxides, polyacrylates, polyolefins, polyamides, polyesters, cellulose and cellulose derivatives, sugars, sesbania cannabina (sesbania cannabina), and mixtures of two or more thereof, more preferably polystyrene, C2-C3 polyalkylene oxide, cellulose derivatives, sugars, and mixtures of two or more thereof, more preferably polystyrene, polyethylene oxide, C1-C2 hydroxyalkylated and / or C1-C2 alkylated cellulose derivatives, sugars, and mixtures of two or more thereof, more preferably polystyrene, polyethylene oxide, hydroxyethyl methylcellulose, and mixtures of two or more thereof; more preferably, the one or more pore-forming agents and / or lubricants and / or plasticizers are one or more selected from the group consisting of polystyrene, polyethylene oxide, hydroxyethyl methylcellulose, and mixtures of two or more thereof, more preferably, the one or more pore-forming agents and / or lubricants and / or plasticizers are a mixture of polystyrene, polyethylene oxide, and hydroxyethyl methylcellulose. In this regard, the botanical additive is typically dried and / or ground so that the botanical additive is preferably provided in powder form. For example, the reference to Sesbania cannabina can be understood to mean a pore-forming agent, lubricant or plasticizer based on said plant and provided in a suitable form, in particular in the form of a powder.

[0079] The dried molded product obtained in step (E) is fired at a temperature in the range of preferably 350 to 850°C, more preferably 400 to 700°C, more preferably 450 to 650°C, more preferably 475 to 600°C.

[0080] The method for preparing a molded article may include further process steps. The method for preparing a molded article preferably further includes (G) subjecting the calcined molded article obtained in step (F) to a hydrothermal treatment, wherein the hydrothermal treatment is preferably carried out under autogenous pressure, more preferably at a temperature in the range of 80 to 200°C, preferably 90 to 180°C, more preferably 100 to 170°C, more preferably 110 to 160°C, more preferably 120 to 150°C.

[0081] If the method for preparing the molded article further comprises step (G), the hydrothermal treatment is preferably carried out in a water-containing solvent system and / or an aqueous solution, wherein the hydrothermal treatment is carried out in distilled water or an acidic solution having a pH preferably in the range of 3 to 6.5, more preferably 4 to 5.5.

[0082] Furthermore, when the method for preparing the molded article further comprises step (G), the hydrothermal treatment is preferably carried out for a duration in the range of 1 to 48 hours, more preferably 2 to 36 hours, more preferably 4 to 24 hours, more preferably 5 to 12 hours, more preferably 2 to 9 hours.

[0083] Furthermore, the present invention relates to a molded article obtained or obtainable according to the method according to any one of the embodiments disclosed herein.

[0084] Furthermore, the present invention relates to the use of the zeolitic material according to any one of the embodiments disclosed herein, or the shaped article disclosed herein, as a catalyst, catalyst support, adsorbent, or for ion exchange, wherein the shaped article is preferably used as a catalyst and / or catalyst support, more preferably as a catalyst and / or catalyst support in reactions involving the formation and / or conversion of C-C bonds, preferably in isomerization reactions, ammoxidation reactions, amination reactions, hydrocracking reactions, alkylation reactions, acylation reactions, reactions for the conversion of alkanes to olefins, conversion of one or more oxygenates to olefins and / or aromatics. the synthesis of hydrogen peroxide, the aldol condensation reaction, the isomerization of epoxides, the transesterification reaction or the epoxidation reaction, preferably as a catalyst and / or catalyst support in the reaction for the epoxidation of olefins, more preferably in the reaction for the epoxidation of C2 to C5 alkenes, more preferably in the reaction for the epoxidation of C2 to C4 alkenes, more preferably in the reaction for the epoxidation of C2 or C3 alkenes, more preferably in the reaction for the epoxidation of C3 alkenes, and more preferably as a catalyst for the conversion of propylene to propylene oxide.

[0085] The unit bar (abs) is 10 5 Refers to absolute pressure in Pa.

[0086] The present invention is further described by the following series of embodiments and combinations of embodiments resulting from the indicated dependencies and backward references. In particular, it should be noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "a continuous process according to any one of embodiments 1 to 4," all embodiments within this range are meant to be expressly disclosed to those skilled in the art, i.e., the wording of this term should be understood by those skilled in the art to be synonymous with "a continuous process according to any one of embodiments 1, 2, 3, and 4." Furthermore, it should be explicitly noted that the following series of embodiments is not a set of claims determining the scope of protection, but represents a conveniently organized part of the description directed to general and preferred aspects of the present invention.

[0087] 1. A method for continuously preparing a zeolitic material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, preferably having an MFI and / or MEL type framework structure, more preferably having an MFI type framework structure, and containing Si, Ti, and O, said method comprising: (i) one or more Si sources, one or more Ti sources, one or more tetraalkylammonium cations R as structure directing agents 1 R 2 R 3 R 4 N + preparing a mixture comprising the compound to be incorporated and water; (ii) continuously feeding the mixture prepared in step (i) into a continuous flow reactor; and (iii) crystallizing from the mixture in a continuous flow reactor a zeolitic material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, preferably having an MFI and / or MEL type framework structure, more preferably having an MFI type framework structure, wherein the mixture is heated to a temperature in the range of 70 to 300°C. Including, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group; The method, wherein in the mixture prepared in step (i), the H2O:Si molar ratio of water to one or more Si sources, calculated as SiO2, is in the range of 1 to 15.

[0088] 2. The method of embodiment 1, wherein the H2O:Si molar ratio of the water to the one or more Si sources, calculated as SiO2, is in the range of 2 to 13, preferably 3 to 11, more preferably 4 to 10, more preferably 4.5 to 9.5, more preferably 5 to 9, more preferably 5.5 to 8.5, more preferably 6 to 8, more preferably 6.5 to 7.5.

[0089] 3. The continuous supply in step (ii) is 0.05 to 5 hours. -1 , more preferably 0.1 to 3 hours -1 , more preferably 0.3 to 2 hours -1 , more preferably 0.5 to 1.5 hours -1 , more preferably 0.7 to 1.3 hours -1 , more preferably 0.8 to 1.2 hours -1 , more preferably 0.9 to 1.1 h -1 3. The method of claim 1 or 2, wherein the liquid hourly space velocity is in the range of

[0090] 4. The volume of the continuous flow reactor is 50 cm 3 ~75m 3 , preferably 55cm 3 ~3m 3 , more preferably 60 cm 3 ~1m 3 , more preferably 65 cm 3 ~0.7m 3 , more preferably 70 cm 3 ~0.3m 3 , more preferably 75 cm 3 ~0.1m 3 , more preferably 80 to 70,000 cm 3 , more preferably 85 to 50,000 cm 3 , more preferably 90 to 30,000 cm 3 , more preferably 95 to 10,000 cm 3 , more preferably 100 to 7,000 cm 3 , more preferably 105 to 5,000 cm 3 , more preferably 110 to 3,000 cm 3 , more preferably 115 to 1,000 cm 3 , more preferably 120 to 700 cm 3 , more preferably 125 to 500 cm 3 , more preferably 130 to 350 cm 3 , more preferably 135 to 250 cm 3 , more preferably 140 to 200 cm 3 , more preferably 145 to 180 cm 3 , more preferably 150 to 170 cm 3, more preferably 155 to 165 cm 3 4. The method of any one of embodiments 1 to 3, wherein the

[0091] 5. The process according to any one of the preceding claims, wherein the continuous flow reactor is selected from among a tubular reactor, a ring reactor, and a continuous oscillatory reactor, preferably from among a plain tubular reactor, a tubular membrane reactor, a tubular reactor with Coanda effect, a ring reactor, a continuously oscillatory baffle reactor, a Taylor-Couette reactor, and combinations thereof; more preferably, the continuous flow reactor is a plain tubular reactor and / or a ring reactor; more preferably, the continuous flow reactor is a plain tubular reactor.

[0092] 6. The process according to any one of embodiments 1 to 5, wherein the continuous flow reactor is a tubular reactor, at least a portion of which is a regular cylinder having a constant inner diameter perpendicular to the flow direction, and the inner diameter is preferably in the range of 2 to 1200 mm, more preferably 3 to 800 mm, more preferably 4 to 500 mm, more preferably 4.5 to 200 mm, more preferably 4.5 to 100 mm, more preferably 5 to 50 mm, more preferably 5 to 30 mm, more preferably 5.5 to 15 mm, more preferably 5.5 to 10 mm, more preferably 6 to 8 mm, more preferably 6 to 6.5 mm.

[0093] 7. The process of any one of embodiments 1 to 6, wherein the continuous flow reactor has a length in the range of 0.2 to 5,000 m, preferably 0.5 to 3,000 m, more preferably 1 to 1,000 m, more preferably 2 to 500 m, more preferably 3 to 200 m, more preferably 4 to 100 m, more preferably 4.5 to 50 m, more preferably 4.5 to 30 m, more preferably 4 to 20 m, more preferably 4 to 15 m, more preferably 4.5 to 10 m, more preferably 4.5 to 5.5 m.

[0094] 8. The method of any one of the preceding claims, wherein the wall of the continuous flow reactor is made of a metallic material, and the metallic material comprises one or more metals selected from the group consisting of Ta, Cr, Fe, Ni, Cu, Al, Mo, Ti, Zr, and combinations and / or alloys of two or more thereof, preferably Ta, Cr, Fe, Ni, Mo, and combinations and / or alloys of two or more thereof, preferably Cr, Fe, Ni, Mo, and combinations and / or alloys of two or more thereof; preferably the metallic material comprises a nickel alloy, a nickel-molybdenum alloy, more preferably a nickel-molybdenum-chromium alloy.

[0095] 9. The method of any one of embodiments 1 to 8, wherein the surface of the inner wall of the continuous-flow reactor is lined with an organic polymer material, and the organic polymer material preferably comprises one or more polymers selected from the group consisting of fluorinated polyalkylenes and mixtures of two or more thereof, preferably from the group consisting of (C2-C3)polyalkylenes and mixtures of two or more thereof, preferably from the group consisting of fluorinated polyethylene and mixtures of two or more thereof; more preferably, the polymer material comprises poly(tetrafluoroethylene); more preferably, the inner wall of the continuous-flow reactor is lined with poly(tetrafluoroethylene).

[0096] 10. The surface of the inner wall of the continuous flow reactor is a polysiloxane, preferably of the formula [R2SiO] n wherein R is preferably an organic group, more preferably an alkyl group and / or a phenyl group.

[0097] 11. The method of any one of the preceding claims, wherein the continuous flow reactor is straight and / or comprises one or more curves relative to the flow direction, preferably wherein the continuous flow reactor is straight and / or has a coiled shape relative to the flow direction.

[0098] 12. The process of any one of the preceding claims, wherein the continuous flow reactor consists of a single stage.

[0099] 13. The method of any one of the preceding embodiments, wherein in step (iii), no substances are added to and / or removed from the reaction mixture during its passage through the continuous flow reactor, preferably no substances are added, more preferably no substances are added or removed from the reaction mixture during its passage through the continuous flow reactor in step (iii).

[0100] 14.R 1 , R 2 , R 3 and R 4 are each independently an optionally branched (C1-C6) alkyl, preferably a (C1-C5) alkyl, more preferably a (C2-C4) alkyl, more preferably an optionally branched (C2-C3) alkyl, and more preferably R 1 , R 2 , R 3 and R 4 are each independently ethyl or propyl, more preferably R 1 , R 2 , R 3 and R 4 represents propyl, preferably n-propyl.

[0101] 15. Independently of each other, said one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The containing compound is preferably one or more salts selected from the group consisting of salts, preferably halides, preferably chlorides and / or bromides, more preferably chlorides, hydroxides, sulfates, nitrates, phosphates, acetates and mixtures of two or more thereof, more preferably chlorides, hydroxides, sulfates and mixtures of two or more thereof, and more preferably one or more tetraalkylammonium cations R 1 R2 R 3 R 4 N + 15. The method of any one of the preceding embodiments, wherein the containing compound is a tetraalkylammonium hydroxide and / or chloride, more preferably a tetraalkylammonium hydroxide.

[0102] 16. The mixture prepared in step (i) and crystallized in step (iii) is a tetraalkylammonium cation R in a range of 0.001 to 1.5, preferably 0.005 to 1, more preferably 0.01 to 0.7, more preferably 0.05 to 0.5, more preferably 0.07 to 0.4, more preferably 0.1 to 0.3, more preferably 0.13 to 0.25, more preferably 0.15 to 0.22, and even more preferably 0.17 to 0.19. 1 R 2 R 3 R 4 N + 16. The method of any one of the preceding claims, wherein the molar ratio of containing compound to the one or more Si sources is shown, calculated as SiO.

[0103] 17. The one or more Si sources comprise one or more compounds selected from the group consisting of silica, silicates, and mixtures thereof, preferably from the group consisting of fumed silica, silica hydrosol, reactive amorphous solid silica, silica gel, silicic acid, water glass, sodium metasilicate hydrate, sesquisilicates, disilicates, colloidal silica, pyrogenic silica, silicate esters, tetraalkoxysilanes, and mixtures of two or more thereof, more preferably from the group consisting of silica hydrosol, silica gel, silicic acid, water glass, sodium metasilicate hydrate, colloidal silica, silicate esters, tetraalkoxysilanes, and mixtures of two or more thereof, more preferably from the group consisting of silica hydrosol, silicic acid, colloidal silica, silicate esters, tetraalkoxysilanes, and mixtures of two or more thereof; 17. The method of any one of embodiments 1 to 16, wherein the one or more Si sources comprise one or more tetraalkoxysilanes selected from the group consisting of (C1-C6)tetraalkoxysilanes and mixtures of two or more thereof, preferably (C1-C5)tetraalkoxysilanes and mixtures of two or more thereof, more preferably (C1-C4)tetraalkoxysilanes and mixtures of two or more thereof, more preferably (C1-C3)tetraalkoxysilanes and mixtures of two or more thereof; more preferably the one or more Si sources comprise tetramethoxysilane and / or tetraethoxysilane, preferably tetraethoxysilane; more preferably the one or more Si sources are tetramethoxysilane and / or tetraethoxysilane, preferably tetraethoxysilane.

[0104] 18. The method of any one of embodiments 1 to 17, wherein the one or more Ti sources comprise one or more compounds selected from the group consisting of titanium oxide, titanium salts, titanyl compounds, titanic acids, titanate esters, and mixtures of two or more thereof, preferably one or more compounds selected from the group consisting of tetrabutyl orthotitanate, tetraisopropyl orthotitanate, tetraethyl orthotitanate, titanium dioxide, titanium tetrachloride, titanium tert-butoxide, TiOSO4 and / or KTiOPO4, and mixtures of two or more thereof, more preferably one or more compounds selected from the group consisting of tetrabutyl orthotitanate, tetraisopropyl orthotitanate, tetraethyl orthotitanate, titanium dioxide, titanium tetrachloride, titanium tert-butoxide, and mixtures of two or more thereof; and the titanium source is preferably tetramethyl orthotitanate and / or tetraethyl orthotitanate, more preferably tetraethyl orthotitanate.

[0105] 19. The method of any one of the preceding embodiments, wherein the mixture prepared in step (i) is substantially free of phosphorus and / or phosphorus-containing compounds.

[0106] 20. The process of any one of the preceding embodiments, wherein the framework of the zeolitic material obtained in step (iii) is substantially free of phosphorus, preferably the zeolitic material obtained in step (iii) is substantially free of phosphorus and / or phosphorus-containing compounds.

[0107] 21. The method of any one of embodiments 1 to 20, wherein the mixture prepared in step (i) has a Si:Ti molar ratio of the one or more Si sources, calculated as SiO2, to the one or more Ti sources, calculated as TiO2, in the range of 1 to 500, preferably 2 to 200, more preferably 5 to 150, more preferably 10 to 100, more preferably 20 to 70, more preferably 25 to 50, more preferably 30 to 45, more preferably 35 to 40.

[0108] 22. The method of any one of the preceding embodiments, wherein in step (ii), the mixture prepared in step (i) is continuously fed to the continuous flow reactor for a duration ranging from 3 hours to 360 days, more preferably from 6 hours to 120 days, more preferably from 12 hours to 90 days, more preferably from 18 hours to 60 days, more preferably from 1 to 30 days, more preferably from 1.5 to 25 days, more preferably from 2 to 20 days, more preferably from 2.5 to 15 days, more preferably from 3 to 12 days, more preferably from 3.5 to 8 days, more preferably from 4 to 6 days.

[0109] 23. The method of any one of embodiments 1 to 22, wherein in step (iii), the mixture is heated to a temperature in the range of 90 to 280°C, preferably 110 to 250°C, more preferably 130 to 220°C, more preferably 150 to 200°C, more preferably 160 to 190°C, more preferably 170 to 180°C.

[0110] 24. The method of any one of embodiments 1 to 23, wherein in step (iii), the mixture is heated under autogenous pressure, which is preferably in the range of 0.5 to 15 MPa, more preferably 1 to 10 MPa, more preferably 1.5 to 8 MPa, more preferably 2 to 6 MPa, more preferably 2.5 to 5.5 MPa, more preferably 3 to 5 MPa, more preferably 3.5 to 4.5 MPa, more preferably 3.8 to 4.2 MPa.

[0111] 25. The method of any one of embodiments 1 to 24, wherein prior to step (ii), the mixture prepared in step (i) is aged at a temperature in the range of 40 to 120°C, preferably 50 to 115°C, more preferably 60 to 110°C, more preferably 70 to 105°C, more preferably 80 to 100°C, more preferably 85 to 95°C.

[0112] 26. The method of any one of the preceding embodiments, wherein prior to step (ii), the mixture prepared in step (i) is aged for a duration ranging from 0.05 to 48 hours, more preferably from 0.15 to 24 hours, more preferably from 0.25 to 12 hours, more preferably from 0.5 to 6 hours, more preferably from 0.75 to 3 hours, more preferably from 1 to 2 hours, more preferably from 1.25 to 1.75 hours.

[0113] 27. The process of any one of embodiments 1 to 26, wherein the mixture prepared in step (i) is fed directly to the continuous-flow reactor in step (ii), and while feeding to the continuous-flow reactor in step (ii), the mixture prepared in step (i) is preferably preheated to a temperature in the range of 90 to 280°C, preferably 110 to 250°C, more preferably 130 to 220°C, more preferably 150 to 200°C, more preferably 160 to 190°C, more preferably 170 to 180°C.

[0114] 28. (iv) treating the reaction product effluent continuously leaving the reactor in step (iii) with a liquid comprising one or more solvents and / or via expansion of said reaction product effluent, and / or preferably (v) isolating the zeolitic material obtained in step (iii) or (iv); (vi) optionally washing the zeolitic material obtained in step (iii), (iv) or (v); (vii) drying the zeolitic material obtained in step (iii), (iv), (v) or (vi), and / or preferably (viii) calcining the zeolitic material obtained in step (iii), (iv), (v), (vi) or (vii). 28. The method of any one of embodiments 1 to 27, further comprising:

[0115] 29. The method according to embodiment 28, wherein in step (iv), the liquid comprises one or more solvents selected from the group consisting of polar protic solvents and mixtures thereof, preferably from the group consisting of n-butanol, isopropanol, propanol, ethanol, methanol, water, and mixtures thereof, more preferably from the group consisting of ethanol, methanol, water, and mixtures thereof; more preferably, the liquid comprises water; more preferably, water, preferably deionized water, is used as the liquid.

[0116] 30. The method of embodiment 28 or 29, wherein in step (iv), the liquid comprises one or more acids, preferably one or more organic and / or inorganic acids, more preferably one or more inorganic acids, wherein the one or more inorganic acids are preferably selected from the group consisting of HCl, HBr, HNO3, H2SO4, and mixtures of two or more thereof, more preferably from the group consisting of HCl, HNO3, H2SO4, and mixtures of two or more thereof, more preferably the one or more acids comprise HCl and / or HNO3, preferably HNO3, more preferably the acid is HCl and / or HNO3, preferably HNO3.

[0117] 31. The process of embodiment 30, wherein in step (iv), the reaction product effluent is neutralized with one or more acids to a pH in the range of 5 to 9, more preferably 6 to 8, more preferably 6.5 to 7.5.

[0118] 32. The method of any one of embodiments 28 to 31, wherein the drying in step (vii) is carried out at a temperature in the range of 50 to 220°C, preferably 70 to 190°C, more preferably 80 to 170°C, more preferably 90 to 150°C, more preferably 100 to 140°C, more preferably 110 to 130°C.

[0119] 33. The method of any one of embodiments 28 to 32, wherein the calcination in step (viii) is carried out at a temperature in the range of 300 to 700°C, preferably 400 to 625°C, more preferably 500 to 600°C, more preferably 525 to 575°C, more preferably 540 to 560°C.

[0120] 34. The method of any one of embodiments 28 to 33, wherein the supernatant obtained from the isolation of the zeolitic material in step (v) and / or a feed having the same composition as the supernatant is not recycled to the reaction mixture at any time during passage through the continuous-flow reactor.

[0121] 35. In step (v), isolating the zeolitic material comprises spray drying and / or microwave drying the zeolitic material obtained in step (iii) or (iv); and / or 35. The method of any one of embodiments 28 to 34, wherein in step (vii), drying the zeolitic material comprises spray drying and / or microwave drying the zeolitic material obtained in step (iii), (iv), (v), or (vi).

[0122] 36. The method of any one of the preceding claims, wherein the mixture constituting the crystallized feed in step (iii) consists of two liquid phases, the first liquid phase being an aqueous phase comprising water, and the second liquid phase comprising a lubricant.

[0123] 37. The method of embodiment 36, wherein the lubricant comprises one or more fluorinated compounds, preferably one or more fluorinated polymers, more preferably one or more fluorinated polyethers, more preferably one or more perfluorinated polyethers.

[0124] 38. The method of embodiment 36 or 37, wherein the lubricant comprises one or more fluorinated compounds, preferably one or more fluorocarbons, more preferably one or more perfluorocarbons, more preferably the lubricant comprises perfluorodecalin.

[0125] 39. The method of any one of embodiments 36 to 38, wherein the lubricant comprises liquid paraffin.

[0126] 40. The method of any one of the preceding claims, wherein the mixture crystallized in step (iii) in the continuous-flow reactor is mechanically agitated, preferably achieved by moving parts comprised in the continuous-flow reactor, more preferably arranged to continuously clean the walls of the continuous-flow reactor from zeolitic material and / or solid residues adhering thereto, more preferably wherein the moving parts comprise a scraper, more preferably a screw, more preferably a rotating screw.

[0127] 41. (ix) subjecting the zeolitic material obtained in step (v), (vi), (vii), or (viii) to an impregnation procedure, wherein the zeolitic material is impregnated with a compound containing one or more metal ions. 41. The method of any one of embodiments 1 to 40, further comprising:

[0128] 42. The method of embodiment 41, wherein the one or more metal ions are selected from the group consisting of ions of alkaline earth metal elements and / or transition metal elements, preferably selected from the group of Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably selected from the group of Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Pt, Pd, Ag, and mixtures of two or more thereof, more preferably selected from the group of Mg, Cr, Mo, Fe, Ni, Cu, Zn, Pt, Pd, Ag, and mixtures of two or more thereof, even more preferably selected from the group of Zn, Pd, Pt, and mixtures of two or more thereof.

[0129] 43. A zeolitic material obtainable and / or obtainable according to the method of any one of embodiments 1 to 42.

[0130] 44. The zeolite material has an MFI and / or MEL-type framework structure, preferably an MFI-type framework structure, and contains Si, Ti, and O; and in the wavelength range of 200 to 800 nm, the zeolite material has a first maximum in the range of 200 to 230 nm, preferably 202 to 225 nm, more preferably 204 to 220 nm, more preferably 206 to 215 nm, more preferably 208 to 210 nm, and a second maximum in the range of 235 to 320 nm, preferably 240 to 300 nm, more preferably 250 to 325 nm. 43. The zeolitic material according to embodiment 42, exhibiting a UV-vis spectrum having a second maximum in the range of preferably 245 to 270 nm, more preferably 250 to 265 nm, more preferably 258 to 262 nm, and wherein the ratio of the absorbance of the first maximum to the absorbance of the second maximum is in the range of 0.5 to 2.5, preferably 0.7 to 2, more preferably 0.9 to 1.8, more preferably 1 to 1.5, more preferably 1.1 to 1.3, more preferably 1.15 to 1.25.

[0131] 45. The zeolitic material of embodiment 44, wherein the UV-vis spectrum does not exhibit any additional maxima between the first maximum and the second maximum.

[0132] 46. ​​The zeolitic material of embodiment 44 or 45, wherein the first maximum and the second maximum have the highest absorbance in the 200 to 800 nm range of the UV-vis spectrum.

[0133] 47. The deconvoluted zeolite material 29 Preferably, the deconvoluted Si MAS NMR comprises a first peak (P''1) having a maximum in the range of -111.5 to -114.5 ppm, preferably -112 to -114 ppm, even more preferably -112.5 to -113.5 ppm, and a second peak (P''2) having a maximum in the range of -101 to -105 ppm, preferably -102 to -104 ppm, even more preferably -102.5 to -103.5 ppm. 29 47. The zeolitic material of any one of embodiments 44 to 46, wherein Si MAS NMR is determined according to Reference Example 1.

[0134] 48. The deconvoluted 29 Preferably, the deconvoluted Si MAS NMR spectrum comprises one further peak having a maximum in the range of -114.6 to -118 ppm, more preferably -115 to -117 ppm, even more preferably -115.5 to -116.5 ppm. 29 48. The zeolitic material of embodiment 47, wherein the Si MAS NMR is determined according to Reference Example 1.

[0135] 49. The zeolite material is 300 to 700 m 2 / g, preferably 350 to 600m 2 / g, more preferably 400 to 550 m 2 / g range, more preferably 450-500m 2 49. The zeolitic material according to any one of embodiments 44 to 48, exhibiting a BET specific surface area, determined in accordance with ISO 9277:2010, in the range of 1 / g.

[0136] 50. The zeolitic material of any one of embodiments 44 to 49, wherein the zeolitic material exhibits a water absorption in the range of 8 to 15% by weight when exposed to 85% relative humidity, preferably, the water absorption is in the range of 9 to 14% by weight, more preferably 10 to 13.5% by weight, more preferably 11 to 13% by weight, more preferably 11.0 to 13.0% by weight.

[0137] 51. The zeolitic material according to any one of embodiments 44 to 50, wherein the Si:Ti molar ratio of the zeolitic material is in the range of 1 to 500, preferably 2 to 200, more preferably 5 to 150, more preferably 10 to 100, more preferably 20 to 70, more preferably 25 to 50, more preferably 30 to 45, more preferably 35 to 40.

[0138] 52. The zeolitic material according to any one of embodiments 44 to 51, wherein the zeolitic material having an MFI-type framework structure comprises TS-1, more preferably the zeolitic material is TS-1.

[0139] 53. The zeolitic material of any one of embodiments 44 to 52, wherein the zeolitic material is impregnated with a compound containing one or more metal ions, and the one or more metal ions are selected from the group consisting of ions of metals selected from the group consisting of ions of alkaline earth metal elements and / or transition metal elements, preferably selected from the group consisting of Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably selected from the group consisting of Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably selected from the group consisting of Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, even more preferably selected from the group consisting of Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof.

[0140] 54. The zeolitic material of any one of embodiments 44 to 53, wherein the framework of the zeolitic material is substantially free of phosphorus, preferably the zeolitic material is substantially free of phosphorus and / or phosphorus-containing compounds.

[0141] 55. (A) Providing a zeolitic material according to any one of embodiments 44 to 54; (B) mixing the zeolitic material provided in step (A) with one or more binders; (C) optionally kneading the mixture obtained in step (B); (D) molding the mixture obtained in step (B) or (C) to obtain one or more molded articles; (E) drying the one or more molded articles obtained in step (D); and (F) A step of firing the dried molded product obtained in step (E). A method for preparing a molded article, comprising:

[0142] 56. The one or more binders are selected from the group consisting of inorganic binders, and the one or more binders are preferably one or more sources of metal oxides and / or metalloid oxides, more preferably from the group consisting of silica, alumina, titania, zirconia, lanthana, magnesia, and mixtures and / or mixed oxides of two or more thereof, more preferably silica, alumina, titania, zirconia, magnesia, silica-alumina mixed oxides, silica-titania mixed oxides, silica-zirconia mixed oxides, silica-lanthana mixed oxides, silica-zirconia-lanthana mixed oxides, alumina-titania mixed oxides, alumina-zirconia mixed oxides, alumina-lanthana mixed oxides, alumina-zirconia-lanthana mixed oxides, titania-zirconia mixed oxides, and mixtures and / or mixed oxides of two or more thereof. comprises one or more sources of metal oxides and / or metalloid oxides selected from the group consisting of mixed oxides, more preferably selected from the group consisting of silica, alumina, silica-alumina mixed oxides, and mixtures of two or more thereof; more preferably the one or more binders comprise one or more silica sources; more preferably the binder consists of one or more silica sources; the one or more silica sources preferably comprise one or more compounds selected from the group consisting of fumed silica, colloidal silica, silica-alumina, colloidal silica-alumina, and mixtures of two or more thereof, more preferably one or more compounds selected from the group consisting of fumed silica, colloidal silica, and mixtures thereof; more preferably the one or more binders consist of colloidal silica.

[0143] 57. The step (B) further comprises mixing the zeolite material and one or more binders with a solvent system, wherein the solvent system comprises one or more solvents, preferably the solvent system comprises one or more hydrophilic solvents, wherein the hydrophilic solvent is preferably selected from the group consisting of polar solvents, more preferably from the group consisting of polar protic solvents, more preferably from the group consisting of water, alcohols, carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C1-C5 alcohols, C1-C5 carboxylic acids, and mixtures of two or more thereof, more preferably water, C1-C4 alcohols, C1-C4 carboxylic acids. 57. The method of embodiment 55 or 56, wherein the solvent system comprises one or more polar protic solvents selected from the group consisting of water, C1-C3 alcohols, C1-C3 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, methanol, ethanol, propanol, formic acid, acetic acid, and mixtures of two or more thereof, more preferably from the group consisting of water, ethanol, acetic acid, and mixtures of two or more thereof; more preferably, the solvent system comprises water and / or ethanol; more preferably, the solvent system comprises water; even more preferably, the solvent system consists of water.

[0144] 58. The step (B) further comprises mixing the zeolite material and one or more binders with one or more pore formers and / or lubricants and / or plasticizers, wherein the one or more pore formers and / or lubricants and / or plasticizers are preferably selected from the group consisting of polymers, carbohydrates, graphite, botanical additives, and mixtures of two or more thereof, more preferably from the group consisting of polymeric vinyl compounds, polyalkylene oxides, polyacrylates, polyolefins, polyamides, polyesters, cellulose and cellulose derivatives, sugars, sesbania cannabina, and mixtures of two or more thereof, more preferably from the group consisting of polystyrene, C2-C3 polyalkylene oxides, cellulose derivatives, sugars, and mixtures of two or more thereof, more preferably polystyrene, polyethylene oxide 58. The method of any one of embodiments 55 to 57, wherein the one or more pore-forming agents and / or lubricants and / or plasticizers are selected from the group consisting of polystyrene, polyethylene oxide, hydroxyethyl methylcellulose, and mixtures of two or more thereof, more preferably from the group consisting of polystyrene, polyethylene oxide, hydroxyethyl methylcellulose, and mixtures of two or more thereof, more preferably wherein the one or more pore-forming agents and / or lubricants and / or plasticizers consist of a mixture of polystyrene, polyethylene oxide and hydroxyethyl methylcellulose.

[0145] 59. The method according to any one of embodiments 55 to 58, wherein the calcination of the dried shaped article obtained in step (E) is carried out at a temperature in the range of 350 to 850°C, preferably 400 to 700°C, more preferably 450 to 650°C, more preferably 475 to 600°C.

[0146] 60. (G) The method further comprises a step of subjecting the calcined molded article obtained in step (F) to a hydrothermal treatment; 60. The method according to any one of embodiments 55 to 59, wherein the hydrothermal treatment is preferably carried out under autogenous pressure, more preferably at a temperature in the range of 80 to 200°C, preferably 90 to 180°C, more preferably 100 to 170°C, more preferably 110 to 160°C, more preferably 120 to 150°C.

[0147] 61. The method of embodiment 60, wherein the hydrothermal treatment is carried out in a water-containing solvent system and / or an aqueous solution, preferably the hydrothermal treatment is carried out in distilled water or an acidic solution having a pH in the range of 3 to 6.5, preferably 4 to 5.5.

[0148] 62. The method of embodiment 60 or 61, wherein the hydrothermal treatment is carried out for a duration in the range of 1 to 48 hours, preferably 2 to 36 hours, more preferably 4 to 24 hours, more preferably 5 to 12 hours, more preferably 2 to 9 hours.

[0149] 63. A shaped article obtained or obtainable according to the method of any one of embodiments 55 to 62.

[0150] 64. Use of the zeolitic material according to any one of embodiments 43 to 54 or the shaped article according to embodiment 63 as a catalyst, catalyst support, adsorbent or for ion exchange, wherein the shaped article is preferably used as a catalyst and / or catalyst support, more preferably as a catalyst and / or catalyst support in reactions involving the formation and / or transformation of C—C bonds, preferably in isomerization reactions, ammoxidation reactions, amination reactions, hydrocracking reactions, alkylation reactions, acylation reactions, reactions for the conversion of alkanes to olefins, reactions for the conversion of one or more oxygenates to olefins and / or aromatics, peroxidation reactions, Use as a catalyst and / or catalyst support in reactions for the synthesis of hydrogen, aldol condensation reactions, reactions for the isomerization of epoxides, transesterification reactions or epoxidation reactions, preferably as a catalyst and / or catalyst support in reactions for the epoxidation of olefins, more preferably as a catalyst and / or catalyst support in reactions for the epoxidation of C2 to C5 alkenes, more preferably as a catalyst and / or catalyst support in reactions for the epoxidation of C2 to C4 alkenes, more preferably as a catalyst and / or catalyst support in reactions for the epoxidation of C2 or C3 alkenes, more preferably as a catalyst for the conversion of propylene to propylene oxide.

[0151] The present invention will be further illustrated by the following examples and reference examples. [Example]

[0152] Reference Example 1: Determination of NMR Resonances For solid-state nuclear magnetic resonance (NMR) spectroscopy, samples were prepared by packing them into a 7 mm ZrO rotor with a Kel-F cap. A 7.05 Tesla magnet (300 MHz) was used. 1 Measurements were carried out using a Bruker Avance spectrometer equipped with a 1H resonance frequency (H resonance frequency) under magic angle sample spinning at 5.0 kHz. Spectra were recorded as follows: 29Directly polarized Si 5 μs 90° pulse, 30 ms acquisition of free induction decay with 50 kHz heteronuclear proton decoupling, averaged over at least 156 transients with a 120 s recycle delay, and Fourier transformed with 20 Hz exponential line broadening. The resonance is at 37.77 ppm according to Pure Appl. Chem., 80(1):59 (2008). 13 The C methylene resonances were indirectly referenced to pure tetramethylsilane, with the absolute chemical shift scale related via adamantane as a secondary standard. Linear resolution was performed with DMFit (Magn. Res. Chem. 40:70 (2002)). For resonances near -103, -113, and -116 ppm, the parameter x in the sum x*Gaussian + (1-x)*Lorentzian was limited to 0.5, 0.7, and 0.8, respectively.

[0153] Reference Example 2: Determination of water adsorption / desorption isotherms The calculation of water adsorption properties of the examples in the experimental section was carried out on a TA Instruments VTI SA instrument according to a step isotherm program. The experiment consisted of one or a series of runs performed on sample material placed on a microbalance pan inside the instrument. Before the start of the measurement, the sample was heated to 100 °C (heat ramp 5 °C / min) and N 2Residual moisture was removed from the sample by holding it under flow for 6 hours. After the drying program, the temperature inside the cell was lowered to 25 °C and maintained isothermal throughout the measurement. The microbalance was calibrated and the mass of the dried sample was measured (maximum mass deviation: 0.01% by mass). The amount of water adsorbed by the sample was measured as the mass increase relative to the dry sample. First, the relative humidity (RH) (expressed as the moisture content in the atmosphere inside the cell in mass%) to which the sample was exposed was increased and the amount of water adsorbed by the sample at equilibrium was measured. The RH was increased from 5 to 85% in 10% by mass steps, and the system controlled the RH at each step. The sample mass was monitored and the amount of water adsorbed was recorded until equilibrium was reached. After exposing the sample to 85% by mass, the total amount of water adsorbed by the sample was measured. During the desorption measurement, the RH was decreased from 85% by mass to 5% by mass in 10% by mass steps, and the change in the sample mass (water adsorption) was monitored and recorded.

[0154] Reference example 3: UV-VIS measurement UV-VIS measurements were performed using a PerkinElmer Lambda 950 equipped with a Labsphere 150 mm integrating sphere for diffuse reflectance measurements (gloss trap closed). The powder cuvette used for solid samples was filled with the solid sample so that the measurement area was completely covered by the sample. A Spectralon standard sample was used as a reference. Measurements were performed at room temperature with an integration time of 0.2 seconds, a scan speed of 267 nm / min, and a spectral range of 200–800 nm. The resulting spectrum was converted to a Kubelka-Munk spectrum.

[0155] Reference Example 4: Determination of total pore volume The determination of the total pore volume was determined by intrusion mercury porosimetry in accordance with DIN 66133.

[0156] Reference Example 5: X-ray powder diffraction and crystallinity determination Powder X-ray diffraction (PXRD) data were collected using a diffractometer (D8 Advance Series II, Bruker AXS GmbH) equipped with a LYNXEYE detector operated with a copper anode X-ray tube at 40 kV and 40 mA, Bragg-Brentano geometry, and an air scattering shield was used to reduce air scattering.

[0157] Crystallinity calculation: The crystallinity of the samples was determined using the software DIFFRAC.EVA from Bruker AXS GmbH, Karlsruhe. The method is described in the user manual on page 153. The default parameters for the calculation were used.

[0158] Calculation of phase composition: The phase composition was calculated for the raw data using the modeling software DIFFRAC.TOPAS from Bruker AXS GmbH, Karlsruhe. The identified crystal structures of the phases, the instrumental parameters, and the crystal sizes of the individual phases were used to simulate diffraction patterns, which were then fitted to the data with a function that modeled the background intensity.

[0159] Data Collection: For Bragg-Brentano geometry data collection, samples were homogenized in a mortar and then pressed into a standard flat sample holder provided by Bruker AXS GmbH. A flat surface was achieved by pressing and flattening the sample powder using a glass plate. Data were collected over an angular range of 2 to 70° 2θ with a step size of 0.02° 2θ, and the variable divergence slit was set at a fixed angle of 0.1°. The crystalline content represents the intensity of the crystalline signal relative to the total scattered intensity. (DIF-FRAC.EVA V5.1 (2019) User Manual, Bruker AXS GmbH, Karlsruhe.)

[0160] Reference Example 6: Provision of synthetic gel To prepare the gel, 500 g of tetraethyl orthosilicate (TEOS) and 15 g of tetraethyl orthotitanate (TEOTi) were placed in a beaker. Next, 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 13.50. The mixture was hydrolyzed at room temperature for 60 minutes, during which the temperature was raised to 60°C. At this time, the pH of the mixture was 12.18. Ethanol was then distilled off for approximately 130 minutes until the sump reached a temperature of 95°C, thus obtaining a synthesis gel with a molar ratio of Si:0.027 Ti:0.18 TPAOH:6.9 HO. During the distillation, 548 g of distillate was obtained, due to the theoretical distillation of 454.4 g of ethanol.

[0161] Example 1: Continuous synthesis of TS-1 zeolite For the continuous synthesis of TS-1 zeolite, a Teflon tube with a volume of 160 ml and an inner diameter of 6.4 mm was used as the reactor. The reactor was 6 m long and could be heated over a length of approximately 5 m. The reactor and its lining were filled with approximately 200 ml of perfluorinated decalin, and the receiver tank was filled with approximately 470 ml of the synthesis gel prepared in Example 6. To start the reaction, the synthesis gel prepared in Example 6 was introduced into the reactor, the pressure was set to 5 bar using nitrogen gas, and the reactor was heated to a temperature of 175 °C. To monitor the progress of the reaction, the reactor temperature was recorded using four thermocouples fixed on the outside of the reactor tube. The temperature measured at the reactor inlet was 150 °C, the temperature measured at the middle section was 175.4 °C, the temperature measured at the reactor outlet was 176.2 °C, and the temperature of the heat exchanger downstream of the reactor was 24 °C. Additionally, pressure gauges were used to record the pressure at the top of the receiver tank and downstream of the reactor outlet. After reaching the desired temperature, the pressure was increased to 40 bar. A 1.3 mL tube was placed downstream of the heat exchanger located downstream of the reactor. A first ball valve was placed at the intersection of the reactor and the tube, and a second ball valve was placed at the end of the tube. During the reaction process, the first ball valve briefly opened once every 36 seconds, releasing 1.3 mL of zeolite product suspension from the reactor. When the first ball valve was closed, the second ball valve opened, releasing this 1.3 mL of product suspension from the reactor setup into a separate container, where it was collected. This resulted in a semi-continuous flow of 1.3 mL / 36 seconds, resulting in a semi-continuous flow of 302 g of starting gel through the reactor setup. After approximately 60 minutes of reaction time, the decalin was removed from the reactor. In total, approximately 290 g of zeolite product-containing suspension was obtained. For workup, the product suspension was acidified with aqueous nitric acid (10 wt. % HNO3 in water) until a pH of approximately 7 was reached. The suspension was then filtered, and the resulting solid was washed with deionized water, dried at 120 °C for 4 h, and then calcined at 490 °C for 5 h. XRD measurements showed that the reaction yielded 85 wt. % TS-1 zeolite as the product, which contained no crystalline anatase and only crystalline TS-1.

[0162] The resulting product had a Si content of 43 g / 100 g, a Ti content of 1.9 g / 100 g, a sodium content of less than 0.01 g / 100 g, and a TOC of less than 0.03 g / 100 g, yielding 478 m 2 / g BET specific surface area, and 635 m 2 / g. UV-VIS showed a first maximum at 209 nm with a relative intensity of 1.76 and a second maximum at 260 nm with a relative intensity of 1.47. 29 Si MAS NMR showed a first peak with a maximum at -103.1 ppm, a second peak with a maximum at 113.0 ppm, and a third peak with a maximum at 116.0 ppm. When exposed to 85% relative humidity, the zeolite absorbed 11.9% water by mass.

[0163] Examples 2 and 3: Continuous synthesis of TS-1 zeolite The same procedure as in Example 1 was carried out, but with the following longer run times:

[0164] [Table 1]

[0165] Furthermore, compared to Example 1, liquid paraffin was used as the lubricant instead of perfluorinated decalin.

[0166] In Examples 2 and 3, respectively, the reaction yielded 84% and 87% by weight of TS-1 zeolite as products containing only crystalline TS-1, with no crystalline anatase, according to XRD measurements.

[0167] In Example 2, where the run time was 6 hours, the product had a Si content of 42 g / 100 g, a Ti content of 1.9 g / 100 g, and a sodium content of less than 0.01 g / 100 g, yielding 462 m 2 / g BET specific surface area, and 633 m 2 / g Langmuir specific surface area.

[0168] In Example 3, where the run time was 22 hours, the product had a Si content of 44 g / 100 g, a Ti content of 2.0 g / 100 g, a sodium content of less than 0.01 g / 100 g, and a TOC of 0.03 g / 100 g, yielding 455 m 2 / g BET specific surface area, and 616 m 2 / g Langmuir specific surface area.

[0169] Example 4: Preparation of molded articles 80 g of TS-1 zeolite from Example 1 was mixed with 3.0 g of Walocel™ (Walocel MW 15000 GB, Wolff Cellulosics GmbH & Co. KG, Germany) and kneaded in a kneader for 5 minutes. Then, 75 g of a polystyrene aqueous dispersion (25.1 g of polystyrene dissolved in water) was added, and the mixture was kneaded for another 10 minutes, followed by the addition of 1 g of polyethylene alkoxide (PEO Alkox E160; Meisei Chemical Works). After another 10 minutes of kneading, 50 g of an aqueous silica dispersion (colloidal Ludox® AS 40) was added, followed by the addition of 30 ml of deionized water. The total kneading time was 50 minutes. The kneaded mixture was then subjected to molding. For molding, the kneaded mixture was extruded at a pressure of 50 bar (abs) to obtain strands with a circular cross section and a diameter of 1.9 mm. The strands were then dried in air and calcined according to the following program: 1. Heat to a temperature of 120°C at a heating rate of 2°C / min. 2. Maintain the temperature at 120°C for 4 hours. 3. Heat at a heating rate of 1°C / min to a temperature of 490°C. 4. Maintain the temperature at 490°C for 5 hours.

[0170] The yield was 86.6 g and the bulk density of the product was 390 g / ml.

[0171] The same procedure was repeated for TS-1 zeolites from Examples 2 and 3, and strands were obtained in the same manner.

[0172] Example 5: Water treatment of molded body 27 g of the material prepared according to Example 4 was divided into three 9 g portions and mixed with 180 ml of deionized water per portion. The resulting mixture was heated in an autoclave at 145° C. for 8 hours. The water-treated strands were then dried and calcined according to the following program: 1. Heat to a temperature of 120°C at a heating rate of 5°C / min. 2. Maintain the temperature at 120°C for 5 hours. 3. Heat to a temperature of 450°C at a heating rate of 2°C / min. 4. Maintain the temperature at 450°C for 2 hours.

[0173] The yield was 26.8 g, and the bulk density of the product was 440 g / ml. The resulting product had a Si content of 44 g / 100 g, a Ti content of 1.5 g / 100 g, and a TOC of less than 0.1 g / 100 g, and a mass of 344 ml. 2 / g BET specific surface area, and 455 m 2 The product exhibited a Langmuir specific surface area of ​​0.95 ml / g. The total pore volume according to Reference Example 4 was 0.95 ml / g. The product contained 68% by mass of TS-1 zeolite as determined according to Reference Example 5, where the TS-1 zeolite contained 0.7% by mass of crystalline anatase and 99.3% by mass of crystalline TS-1 zeolite.

[0174] The same procedure was repeated for further extrusions of Example 4 (TS-1 zeolite from Examples 2 and 3 was used) to similarly obtain strands.

[0175] Example 6: Catalyst Testing - Determination of Propylene Epoxidation Catalyst Performance In a continuous epoxidation reaction setup, 15 g of the strand-form moldings described in each of the above examples was placed in a vertically arranged tubular reactor (length: 1.4 m, outer diameter: 10 mm, inner diameter: 7 mm) equipped with a thermostatting jacket. The remaining reactor volume was filled with an inert material (steatite spheres, 2 mm diameter) to a height of approximately 5 cm at the bottom of the reactor and the remainder at the top. The following starting materials were passed through the reactor at their respective flow rates: methanol (49 g / h); hydrogen peroxide (9 g / h; used as an aqueous hydrogen peroxide solution with a hydrogen peroxide content of 40% by weight); and propylene (7 g / h; polymer grade). The temperature of the reaction mixture was regulated via a cooling medium passing through the cooling jacket so that the hydrogen peroxide conversion, determined based on the reaction mixture leaving the reactor, was essentially constant at 90%. The pressure inside the reactor was kept constant at 20 bar (abs), and in addition to the fixed-bed catalyst, the reaction mixture consisted of a single liquid phase.

[0176] The effluent stream from the reactor downstream of the pressure control valve was collected, weighed, and analyzed. It was analyzed for organic components by two gas chromatographs. Hydrogen peroxide content was determined colorimetrically using the titanyl sulfate method. A given propylene oxide selectivity was determined relative to propene and hydrogen peroxide and calculated as 100 times the ratio of the number of moles of propylene oxide in the effluent stream divided by the number of moles of propene or hydrogen peroxide in the feed stream.

[0177] The results of the catalytic test of the TS-1 zeolite according to Example 1 are shown in Figure 1, and the results of the catalytic test of the TS-1 zeolites obtained according to Examples 2 and 3 are shown in Figures 2 and 3, respectively.

[0178] Clearly, the zeolitic material according to the present invention exhibits good selectivity values.

[0179] As can be seen from Figure 1, the average hydrogen conversion was about 85%, the average propylene oxide selectivity based on hydrogen peroxide was 91%, and the calculated propylene oxide yield was 77%. Furthermore, the zeolitic material of the present invention was found to exhibit excellent stability with respect to propylene oxide selectivity relative to hydrogen peroxide over the entire test period.

[0180] As can be seen from Figure 2, the temperature at which 90% hydrogen peroxide conversion was achieved only increased slightly with increasing run time. Therefore, the zeolitic material of the present invention was found to exhibit excellent stability over the entire test period. Furthermore, as can be seen from Figure 3, selectivity to propylene oxide of over 90% was maintained even when the run time was doubled, compared to the results shown in Figure 1.

[0181] References - Y. Hu et al., Microporous and Mesoporous Materials 2018, 270, 149 - CN 110028078 A - DE 3029787 A1 - EP 0402801 A2 - US 4374093 - US 6656447 B1 - CN110078091 A

Claims

1. 1. A process for continuously preparing a zeolitic material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, and containing Si, Ti, and O, said process comprising: (i) one or more Si sources, one or more Ti sources, one or more tetraalkylammonium cations R as structure directing agents １ R ２ R ３ R ４ N ＋ preparing a mixture comprising the compound to be incorporated and water; (ii) continuously feeding the mixture prepared in step (i) into a continuous flow reactor; and (iii) crystallizing a zeolitic material having a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, by heating the mixture to a temperature in the range of 70 to 300°C. Including, R １ , R ２ , R ３ and R ４ are each independently an alkyl group; In the mixture prepared in step (i), water and SiO ２ H with the one or more Si sources calculated as ２ The O:Si molar ratio is in the range of 1 to 15.

2. In the mixture prepared in step (i), water and SiO ２ The H with the one or more Si sources is calculated as ２ 2. The method of claim 1, wherein the O:Si molar ratio is in the range of 2 to 13.

3. 3. The method according to claim 1 or 2, wherein the continuous flow reactor is selected from the group consisting of a tubular reactor, a ring reactor, and a continuous oscillatory reactor.

4. The mixture prepared in step (i) and crystallized in step (iii) contains the one or more tetraalkylammonium cations R １ R ２ R ３ R ４ N ＋ Compounds containing SiO ２ The method according to claim 1 , wherein the molar ratio of the one or more Si sources is calculated as:

5. 5. The method of any one of claims 1 to 4, wherein the Si:Ti molar ratio of the mixture prepared in step (i) is in the range of 1 to 500.

6. 6. The method of any one of claims 1 to 5, wherein in step (iii), the mixture is heated to a temperature in the range of from 90 to 280°C.

7. 7. The method of claim 1, wherein in step (iii) the mixture is heated under autogenous pressure.

8. 8. The method of any one of claims 1 to 7, wherein the mixture prepared in step (i) is fed directly to the continuous flow reactor in step (ii), and the mixture prepared in step (i) is preheated while being fed to the continuous flow reactor in step (ii).

9. (iv) treating the reaction product effluent continuously exiting the reactor in step (iii) with a liquid comprising one or more solvents and / or via expansion of said reaction product effluent; and / or (v) isolating the zeolitic material obtained in step (iii) or (iv); (vi) optionally washing the zeolitic material obtained in step (iii), (iv) or (v); (vii) drying the zeolitic material obtained in step (iii), (iv), (v) or (vi); and / or (viii) calcining the zeolitic material obtained in step (iii), (iv), (v), (vi) or (vii).

9. The method of claim 1, further comprising:

10. 10. A zeolitic material obtained according to the method of any one of claims 1 to 9.

11. 11. The zeolite material according to claim 10, wherein the zeolite material has a framework structure type selected from the group consisting of MFI, MEL, IMF, SVY, FER, SVR, and intergrowth structures of two or more thereof, and contains Si, Ti, and O; and in the wavelength range of 200 to 800 nm, the zeolite material exhibits a UV-vis spectrum having a first maximum in the range of 200 to 230 nm and a second maximum in the range of 235 to 320 nm, and a ratio of the absorbance of the first maximum to the absorbance of the second maximum is in the range of 0.5 to 2.

5.

12. (A) providing a zeolitic material according to claim 10 or 11, (B) mixing the zeolitic material provided in step (A) with one or more binders; (D) molding the mixture obtained in step (B) to obtain one or more molded articles; (E) drying the one or more molded articles obtained in step (D); and (F) A step of firing the dried molded product obtained in step (E). A method for preparing a molded article, comprising:

13. The method of claim 12, further comprising kneading the mixture obtained in step (B).

14. (G) A step of subjecting the calcined molded product obtained in step (F) to hydrothermal treatment.

14. The method of claim 12 or 13, further comprising:

15. A molded article obtained according to the method of any one of claims 12 to 14.

16. Use of the zeolitic material according to claim 10 or 11 or the shaped article according to claim 15 as a catalyst, catalyst support, adsorbent or for ion exchange.

Images