Zeolite synthesis in a continuous-flow reactor using a pulsating flow regime.

Abstract

The present invention relates to a continuous process for producing a zeolitic material containing SiO2 in its framework structure, said process comprising the steps of: (i) sequentially preparing a mixture comprising one or more solvents, one or more structure directing agents, and one or more sources of SiO; (ii) continuously feeding the mixture prepared in step (i) into one or more continuous flow reactors; and (iii) heating the mixture in one or more continuous flow reactors to continuously obtain a zeolitic material comprising SiO2 in its framework structure. Including, The mixture contained in the one or more continuous flow reactors is subjected to a pulsating flow regime.The invention also relates to a zeolitic material obtainable and / or obtained by said process, and to the use of said zeolitic material as a molecular sieve, as an adsorbent, for ion exchange, or as a catalyst and / or as a catalyst support.

Description

[Technical field]

[0001] The present invention relates to a process for the preparation of a zeolitic material and to a catalyst as such which is obtainable or obtainable by said process.Furthermore, the present invention relates to the use of a zeolitic material, in particular as a catalyst. [Background technology]

[0002] The synthesis of zeolitic materials from simple starting compounds often involves complex self-assembly processes that require special conditions such as high temperature and / or pressure, and such reactions generally require heating of the starting materials under autogenous pressure, resulting in zeolitic materials after long reaction times ranging from days to weeks. Thus, due to the often harsh reaction conditions and long reaction times, batch synthesis has long been the method of choice for the synthesis of zeolitic materials. However, batch reactions have a number of limitations, particularly with regard to the level of space-time yield that can be achieved.

[0003] Thus, efforts have been made to find improved batch reaction procedures and alternative methods that offer advantages over the classical batch synthesis procedures utilized for the synthesis of zeolitic materials. One method that has been investigated in this regard involves the use of a continuous stirred tank reactor, in which fluid reagents are continuously introduced at the top of the tank reactor and an effluent containing solid reaction products is continuously removed from the bottom of the tank reactor. Although said method eliminates the need to empty the reaction vessel during batch operation under discontinuous conditions, the reaction time required for crystallization remains long.

[0004] In view of that, reactor geometries have been devised that allow for the rapid synthesis of zeolitic materials. Hence, US2016 / 0115039A1 relates to a method for the continuous production of zeolites in a tubular reactor exhibiting a low ratio of volume to external area. Similarly, Liu et al., Angew.Chem.Int.Ed. 2015, 54, 5683-5687, disclose the continuous synthesis of high-silica zeolite SSZ-13 using very short reaction times. On the other hand, Ju, J. et al., Chemical Engineering Journal, 2006, 116, 115-121 and Vandermeersch, T. et al., Microporous and Mesoporous Materials, 2016, 226, 133-139, respectively, disclose the rapid synthesis of micron-sized NaA zeolite in a continuous flow reactor configuration. Liu, Z. et al., Chemistry of Materials, 2014, 26, 2327-2331, relates to ultra-fast continuous flow synthesis of crystalline microporous aluminophosphate AlPO4-5. Slangen et al., "Continuous Synthesis of Zeolites using a Tubular Reactor", 12th International Zeolite Conference, Materials Research Society, 1999, relates to the continuous synthesis of NaA zeolite, NaY zeolite, and silicalite-1 in a tubular reactor of 6 mm OD (~3 mm ID) and variable length. Bebon, C. et al., Microporous and Mesoporous Materials, 2002, 53, 13-20, relates to a method for the synthesis of zeolites using a guide tube contained in an autoclave, where the reaction mixture is conveyed through the guide tube with the aid of an Archimedes screw positioned within the guide tube along its axis.

[0005] For reactions not requiring high pressure, microwave-assisted procedures have been investigated, such as Bonaccorsi, L. et al., Microporous and Mesoporous Materials, 2008, 112, 481-493, for the continuous synthesis of zeolite LTA. Similarly, US2001 / 0054549A1 relates to a continuous method and apparatus for the preparation of inorganic materials using microwaves.

[0006] WO2020 / 109292A1 relates to a method for continuous inter-zeolite conversion, and WO2020 / 025799A relates to the continuous synthesis of titanol silicate materials.

[0007] Considerable progress has been made in terms of reaction efficiency considering the use of continuous stirred tank and multi-stage reactors, but the progress made in terms of reducing reaction times has been limited to reactor geometries applied at laboratory scale levels. Moreover, the efforts made in terms of reducing reaction times remain extremely limited in terms of economically viable run times due to reactor clogging, especially due to pronounced changes in the rheology of the reaction mixture that occur during zeolite synthesis. More specifically, when heated in a laminar flow tubular reactor, the synthesis gel usually exhibits high shear rates in the near-wall regions, but almost no shear rate in the center due to the slow rate of heat transfer toward the center, in part due to the insulating effect of the synthesis gel in the near-wall regions. As a result, the synthesis gel exhibits large temperature gradients from the wall regions toward the center, and large residence distribution times are observed. Considering the severe non-uniform processing of the synthesis gel that occurs in this situation, it is necessary to use very long reactors to obtain a satisfactory crystallinity.

[0008] In this regard, WO2019 / 101854A relates to a method for the synthesis of zeolites in a reactor with controlled velocity profile.

[0009] Despite the advances made with respect to the continuous synthesis of zeolitic materials, there remains a need for methods that avoid the problems of poor heat transfer and subsequent non-uniform reaction conditions experienced by synthesis gels in continuous flow reactors.

Prior technical literature

[0010]

Patent Document 1

Patent document 2

Patent document 3

Patent document 4

Patent document 5

Non-licensed literature

[0011]

Non-licensed literature 1

Non-licensed Document 2

Non-licensed Document 4

Non-licensed Document 5

Non-licensed Document 6

[0012] It is therefore an object of the present invention to provide an improved method for producing zeolitic materials which prevents clogging of continuous flow reactors during the formation of the zeolitic material due to the sudden increase in viscosity during the crystallization process, whereby it has surprisingly been found that clogging can be prevented by using a pulsatile flow regime having a defined shear rate.

[0013] The present invention therefore relates to a continuous process for the production of a zeolitic material containing SiO2 in its framework structure, said process comprising the steps of: (i) sequentially preparing a mixture comprising one or more solvents, one or more structure directing agents, and one or more sources of SiO; (ii) continuously feeding the mixture prepared in step (i) into one or more continuous flow reactors; and (iii) heating the mixture in one or more continuous flow reactors to continuously obtain a zeolitic material comprising SiO2 in its framework structure. Including, The mixture contained within one or more continuous flow reactors is subjected to a pulsating flow regime. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 shows the results of viscosity measurement of the synthetic gel of Reference Example 2 at room temperature. [Diagram 2] Figure 2 shows the simulation results of the "Piff-paff" mode in the flow regime, plotting the mass fraction of zeolite and the corresponding viscosity. [Diagram 3] Figure 3 shows the simulation results for the "Piff-paff" mode without applied flow, plotting the mass fraction of zeolite and the corresponding viscosity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] In the sense of the present invention, pulsating flow preferably refers to a harmonic variation of the pressure gradient along a tube or pipe, i.e. a sinusoidal wave, but in general the flow pulsation does not have to be caused by a harmonic motion, i.e. a square, sawtooth or other profile would also represent a pulsating flow in the sense of the present invention.

[0016] The maximum shear rate achieved by the pulsatile flow regime is 0 to 2,500 s -1 , preferably 0 to 1,500 seconds -1 , more preferably 0 to 1000 seconds -1 , more preferably 0 to 700 seconds -1 , more preferably 0 to 500 seconds -1 , more preferably 0 to 400 seconds -1 , more preferably 0 to 300 seconds -1 , more preferably 0 to 250 seconds -1 , more preferably 0 to 200 seconds -1 , more preferably 0 to 150 seconds -1 , more preferably 0 to 100 seconds -1 , and more preferably 0 to 50 seconds -1According to the invention, the maximum shear rate in the continuous flow reactor is preferably determined based on the volumetric or mass flow rate. More specifically, starting from the measured mass flow rate, previously measured material laws are applied in an iterative mathematical model to calculate the velocity profile and the final shear rate. In particular, the maximum shear rate is determined by a process of determining a non-Newtonian shear thinning law by measurements in a small-scale laboratory device, preferably using a Schubspannungskontrolliertes Rotationsviskosimeter Physika MCR301. By applying a force to the fluid, a certain flow profile is formed. The obtained law, i.e. mu=f (shear rate, temperature, composition), together with information on the volumetric flow rate Q due to the operating conditions (e.g. from the use of displacement pumps and displacement pulsators) and the geometry of the reactor, is implemented in a fluid dynamics simulation tool, preferably using the state-of-the-art Ansys® Fluent CFD code. The shear rate is then calculated by the velocity gradient.

[0017] After step (i) and before (ii), the mixture prepared in step (i) is preferably homogenized, which is preferably achieved by stirring the mixture. Furthermore, the homogenization is preferably carried out in two continuous stirred tank reactors (CSTRs), the first CSTR being located upstream of the second CSTR in a continuous process, and the mixture obtained in the first CSTR being continuously fed to the second CSTR.

[0018] When homogenization is carried out in two continuous stirred tank reactors (CSTRs), with the first CSTR located upstream of the second CSTR in a continuous manner, and the mixture obtained in the first CSTR being continuously fed to the second CSTR, it is preferred that the first CSTR employs one or more stirred shafts, each equipped with one or more baffles. Additionally, and independently, it is preferred that the first CSTR is operated at a temperature in the range of 20-120°C, preferably 21-80°C, more preferably 22-40°C, more preferably 23-30°C, and more preferably 24-26°C.

[0019] It is preferred that the first CSTR is operated at a pressure in the range of 1 to 3 bar, preferably 1 to 2.5 bar, more preferably 1 to 2 bar, more preferably 1 to 1.5 bar, and more preferably 1 to 1.2 bar.

[0020] The first CSTR preferably has a capacity in the range of 10 to 1,000L, preferably 100 to 800L, more preferably 150 to 600L, more preferably 200 to 400L, and more preferably 240 to 260L.

[0021] The second CSTR preferably employs one or more stirring shafts each equipped with one or more spiral stirrers.

[0022] It is preferred that the second CSTR is operated at a temperature in the range of 20 to 120°C, preferably 21 to 80°C, more preferably 22 to 40°C, more preferably 23 to 30°C, and more preferably 24 to 26°C.

[0023] It is preferred that the second CSTR is operated at a pressure in the range of 1 to 3 bar, preferably 1 to 2.5 bar, more preferably 1 to 2 bar, more preferably 1 to 1.5 bar, and more preferably 1 to 1.2 bar.

[0024] The second CSTR preferably has a capacity in the range of 20 to 2,000L, preferably 200 to 1,200L, more preferably 300 to 800L, more preferably 450 to 550L, and more preferably 490 to 510L.

[0025] In step (ii), it is preferred that the mixture continuously prepared in step (i) is continuously fed to one or more continuous flow reactors at a rate in the range of 10 to 2,000 kg / h, preferably 50 to 1200 kg / h, more preferably 100 to 800 kg / h, more preferably 150 to 400 kg / h, more preferably 250 to 350 kg / h, and preferably 290 to 310 kg / h.

[0026] In step (ii), it is preferred that the mixture continuously prepared in step (i) is continuously supplied to 1 to 10 continuous flow reactors, preferably 1 to 8 continuous flow reactors, more preferably 1 to 6 continuous flow reactors, more preferably 1 to 4 continuous flow reactors, and more preferably 2 to 3 continuous flow reactors.

[0027] In step (ii), the continuous feeding is preferably achieved by pumping with one or more dosing pumps, preferably one dosing pump per continuous flow reactor.

[0028] In step (ii), if the continuous feed is achieved by pumping with one or more dosing pumps, the one or more dosing pumps are preferably selected from dosing pumps capable of building up above the vapor pressure of the reaction mixture at the reaction temperature, preferably the one or more dosing pumps are piston diaphragm pumps, and more preferably piston diaphragm pumps with a pulsation damper.

[0029] In step (ii), when the continuous feed is achieved by pumping with one or more dosing pumps, it is preferred that each of the one or more dosing pumps is operated at a speed in the range of from 5 to 500 kg / h, preferably from 20 to 400 kg / h, more preferably from 40 to 300 kg / h, more preferably from 80 to 150 kg / h, and more preferably from 90 to 110 kg / h.

[0030] It is preferred that each of the one or more dosing pumps is operated at a pressure in the range of 0.5 to 15 MPa, 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, and more preferably 3.8 to 4.2 MPa, this pressure referring to the pressure occurring at the outlet of the one or more dosing pumps.

[0031] When each of the one or more dosing pumps is operated at a pressure in the range of 0.5-15 MPa, this pressure referring to the pressure occurring at the outlet of the one or more dosing pumps, the pulsating flow regime is preferably achieved by a semi-continuous flow regime in the general direction of flow or in the general direction of flow and counter-direction, the general direction of flow being defined by the inlet end of each of the one or more continuous flow reactors to which the mixture prepared in step (i) is continuously fed and the outlet end of each of the one or more continuous flow reactors to which the zeolitic material obtained in step (iii) is continuously withdrawn.

[0032] When the pulsating flow regime is achieved by a semi-continuous flow regime in the general direction of flow or in the general direction of flow and counter-direction, the general direction of flow being defined by the inlet end of each of one or more continuous flow reactors to which the mixture prepared in step (i) is continuously fed and the outlet end of each of one or more continuous flow reactors to which the zeolitic material obtained in step (iii) is continuously withdrawn, the pulsating flow regime is preferably achieved by a pulsating motion in the general direction of flow or in the general direction of flow and counter-direction.

[0033] When the pulsating flow regime is achieved by pulsating motion in the general direction of flow or in both the general direction of flow and the opposite direction, the frequency of pulsation is between 0.001 and 1 second. -1 , preferably 0.003 to 0.7 seconds -1 , more preferably 0.005 to 0.4 seconds -1 , more preferably 0.008 to 0.2 seconds -1, more preferably 0.01 to 0.15 seconds -1 , more preferably 0.04 to 0.1 seconds -1 , and more preferably 0.05 to 0.07 seconds -1 It is preferable that the range is 100%.

[0034] The pulsating flow regime is preferably achieved by periodically alternating the direction of flow between the general direction of flow and the opposite direction.

[0035] When the pulsating flow regime is achieved by periodically alternating the flow direction between the general direction of flow and the opposite direction, the frequency of the flow direction alternation is between 0.01 and 3 seconds. -1 , preferably 0.03 to 2 seconds -1 , more preferably 0.05 to 1.5 seconds -1 , more preferably 0.08 to 1.2 seconds -1 , more preferably 0.1 to 1 second -1 , more preferably 0.15 to 0.8 seconds -1 , and more preferably 0.2 to 0.5 seconds -1 It is preferable that the range is 100%.

[0036] The continuous supply in step (ii) is carried out for 0.1 to 10 h. -1 range, preferably 0.5 to 8 h -1 , more preferably 1 to 6 hours -1 , more preferably 1.25 to 4 h -1 And more preferably 1.5 to 2 hours -1 It is preferred that the liquid hourly space velocity is in the range of 100-200 / s.

[0037] In step (iii), the mixture is preferably heated to a temperature in the range of 90 to 280°C, preferably 100 to 270°C, more preferably 150 to 260°C, more preferably 200 to 265°C, and more preferably 248 to 252°C.

[0038] In step (iii), the mixture is preferably heated under autogenous pressure, preferably the pressure is 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, and more preferably 3.8 to 4.2 MPa.

[0039] In step (ii), it is preferred to continuously supply the mixture prepared in step (i) to one or more continuous flow reactors for a period in the range of 5 to 365 days, preferably 10 to 300 days, more preferably 15 to 240 days, more preferably 30 to 180 days, more preferably 50 to 120 days, and more preferably 80 to 100 days.

[0040] The mixture constituting the feed to be crystallized in step (iii) preferably 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 comprising one or more fluorine compounds.

[0041] When the mixture constituting the feed to be crystallized in step (iii) consists of two liquid phases, the first liquid phase being an aqueous phase containing water, and the second liquid phase containing a lubricant, the lubricant preferably containing one or more fluorine compounds, it is preferred that the lubricant contains one or more fluorinated polymers, preferably one or more fluorinated polyethers, and more preferably one or more perfluoropolyethers. Additionally and independently, it is preferred that the lubricant contains one or more fluorocarbons, preferably one or more perfluorocarbons, and more preferably the lubricant contains perfluorodecalin.

[0042] Preferably, the lubricant comprises liquid paraffin.

[0043] The volume of each of the one or more continuous flow reactors is preferably in the range of 0.5 to 1,000 L, preferably 20 to 750 L, more preferably 30 to 250 L, more preferably 40 to 90 L, and more preferably 49 to 51 L.

[0044] Each of the one or more continuous flow reactors is preferably selected from among tubular reactors, ring reactors and continuous oscillatory reactors, preferably from among flat tube reactors, tubular membrane reactors, ring reactors, continuously oscillatory baffle reactors and combinations thereof, more preferably each of the one or more continuous flow reactors is a flat tube reactor and / or a ring reactor, more preferably each of the one or more continuous flow reactors is a flat tube reactor.

[0045] It is preferred that each of the one or more continuous flow reactors is straight in the direction of flow and / or comprises one or more curves, preferably each of the one or more continuous flow reactors is straight in the direction of flow and / or has a coiled configuration, more preferably each of the one or more continuous flow reactors has a coiled configuration in the direction of flow.

[0046] When each of the one or more continuous flow reactors is linear with respect to the direction of flow and / or includes one or more curves, it is preferred that the inner diameter of the coil configuration is in the range of 6 to 100 mm, preferably 7 to 80 mm, more preferably 8 to 60 mm, more preferably 9 to 40 mm, more preferably 10 to 25 mm, and more preferably 15 to 10 mm.

[0047] Each of the one or more continuous flow reactors is preferably a tubular reactor, and at least a part of the tubular reactor is a right cylinder having a certain inner diameter perpendicular to the flow direction, and this inner diameter is preferably in the range of 5 to 250 mm, more preferably in the range of 10 to 200 mm, more preferably in the range of 15 to 150 mm, more preferably in the range of 20 to 75 mm, and more preferably in the range of 23 to 27 mm.

[0048] It is preferred that each of the one or more continuous flow reactors has a length in the range of 1 to 500 m, preferably 30 to 400 m, more preferably 50 to 300 m, more preferably 85 to 150 m, and more preferably 98 to 102 m.

[0049] Preferably, the wall of each of the one or more continuous flow reactors is made of a metallic material, the metallic material comprising one or more metals selected from the group consisting of Ta, Cr, Fe, Ni, Cu, Al, Mo, and combinations and / or alloys of two or more thereof, 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, preferably the metallic material comprises stainless steel, more preferably the metallic material consists of stainless steel.

[0050] It is preferred that the surface of the inner wall of each of the one or more continuous flow reactors 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), and more preferably the inner wall of each of the one or more continuous flow reactors is lined with poly(tetrafluoroethylene).

[0051] The surface of the interior wall of each of the one or more continuous flow reactors is a polysiloxane, preferably a polysiloxane having the formula [RSiO] n wherein R is preferably an organic group, more preferably an alkyl group and / or a phenyl group.

[0052] Each of the one or more continuous flow reactors preferably consists of a single stage.

[0053] The reaction mixture continuously exiting the one or more continuous flow reactors preferably exhibits a solids content in the range of 2 to 50% by weight relative to 100% by weight of the reaction mixture, preferably 4 to 40% by weight relative to 100% by weight of the reaction mixture, more preferably 6 to 30% by weight, more preferably 10 to 20% by weight, and more preferably 13 to 15% by weight.

[0054] It is preferred that the zeolitic material further comprises X2O3 in its framework structure, where X represents a trivalent element, and the mixture in step (i) further comprises one or more sources of X2O3.

[0055] When the zeolitic material further comprises X2O3 in its framework structure, where X represents a trivalent element, and the mixture in step (i) further comprises one or more sources of X2O3, it is preferred that X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, X is preferably Al and / or B, and more preferably Al.

[0056] Preferably, the one or more sources of SiO2 and X2O3 include a first zeolitic material comprising SiO2 and X2O3 in its framework structure; and In step (iii), the mixture is heated in one or more continuous flow reactors to obtain a second zeolitic material comprising SiO2 and X2O3 in its framework structure, the second zeolitic material obtained in step (iii) having a different type of framework structure than the first zeolitic material contained in the mixture prepared in step (i).

[0057] The one or more sources of SiO2 and X2O3 include a first zeolitic material comprising SiO2 and X2O3 in a framework structure; and In step (iii), the mixture is heated in one or more continuous flow reactors to obtain a second zeolitic material comprising SiO2 and X2O3 in its framework structure, and when the second zeolitic material obtained in step (iii) has a different type of framework structure from the first zeolitic material contained in the mixture prepared in step (i), it is preferred that the first zeolitic material has a FAU-, GIS-, MOR-, LTA-, FER-, TON-, MTT-, BEA-, MEL-, MWW-, MFS-, and / or MFI-type framework structure, preferably a FAU-, GIS-, BEA-, and / or MFI-type framework structure, more preferably a FAU- and / or BEA-type framework structure, and more preferably a FAU-type framework structure.

[0058] The first zeolite material having an FAU-type framework structure is preferably selected from the group consisting of ZSM-3, faujasite, [Al-Ge-O]-FAU, CSZ-1, ECR-30, zeolite X, zeolite Y, LZ-210, SAPO-37, ZSM-20, Na-X, US-Y, Na-Y, [Ga-Ge-O]-FAU, Li-LSX, [Ga-Al-Si-O]-FAU, and [Ga-Si-O]-FAU, and mixtures of two or more thereof, and more preferably selected from the group consisting of ZSM-3, faujasite, CSZ-1, ECR-30, zeolite X, zeolite Y, LZ-210, ZSM-20, Na-X, US-Y, Na-Y, and Li-LSX, and mixtures of two or more thereof. more preferably from the group consisting of faujasite, zeolite X, zeolite Y, Na-X, US-Y, and Na-Y, and mixtures of two or more thereof, more preferably from the group consisting of faujasite, zeolite X, and zeolite Y, and mixtures of two or more thereof; more preferably the first zeolitic material having an FAU-type framework structure comprises zeolite X and / or zeolite Y, preferably zeolite Y; more preferably the first zeolitic material having an FAU-type framework structure is zeolite X and / or zeolite Y, preferably zeolite Y.

[0059] The second zeolitic material preferably has a CHA-, AEI-, GME- and / or MFI-type framework structure, preferably a CHA- and / or AEI-type framework structure, and more preferably a CHA-type framework structure.

[0060] It is preferred that the second zeolitic material obtained in step (iii) has a CHA-type framework structure, and preferably the zeolitic material having a CHA-type framework structure is selected from the group consisting of Wilhendersonite, ZYT-6, SAPO-47, Na-chabazite, chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-chabazite, MeAPSO-47, Phi, DAF-5, UiO-21, |Li-Na|[Al-Si-O]-CHA, (Ni(deta)2)-UT-6, SSZ-13, and SSZ-62, and mixtures of two or more thereof, more preferably ZYT-6, SAPO-47, Na-chabazite, chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14 , K-chabazite, Phi, DAF-5, UiO-21, SSZ-13 and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, Linde D, Linde R, SAPO-34, SSZ-13 and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, SSZ-13 and SSZ-62, and mixtures of two or three thereof, more preferably the second zeolitic material obtained in step (iii) comprises chabazite and / or SSZ-13, preferably SSZ-13, and more preferably the second zeolitic material obtained in step (iii) is chabazite and / or SSZ-13, preferably SSZ-13.

[0061] It is preferred that the framework structures of the first zeolitic material, independently of one another, exhibit a YO2:X2O3 molar ratio in the range of 5-120, preferably 8-80, more preferably 10-50, more preferably 15-40, more preferably 20-30, more preferably 22-28, and more preferably 24-26.

[0062] The mixture prepared in step (i) and heated in step (iii) is treated with OH - Preferably, the mixture further comprises at least one source for hydroxide in the framework structure of the first zeolite material versus OH of SiO2. - The SiO2 molar ratio is in the range of 0.05 to 1, preferably 0.1 to 0.7, more preferably 0.3 to 0.6, more preferably 0.4 to 0.55, more preferably 0.45 to 0.5, more preferably 0.46 to 0.49, and more preferably 0.47 to 0.48.

[0063] It is preferred that the one or more solvents in the mixture prepared in step (i) comprise water, preferably distilled water, and more preferably, water, preferably distilled water, is included as the one or more solvents in the mixture prepared in step (i).

[0064] When one or more of the solvents in the mixture prepared in step (i) comprises water, it is preferred that the H2O:SiO2 molar ratio of SiO2, calculated as hydroxide to oxide, in the mixture prepared in step (i) is in the range of 3-50, preferably 7-40, more preferably 9-30, more preferably 11-25, more preferably 13-22, more preferably 15-20, more preferably 16-19, and more preferably 17-18.

[0065] The mixture prepared in step (i) and heated in step (iii) is treated with OH - Preferably, the catalyst further comprises at least one source for said OH - Preferably, the at least one source for comprises a metal hydroxide, more preferably a hydroxide of an alkali metal M, more preferably sodium hydroxide and / or potassium hydroxide, and more preferably sodium hydroxide, more preferably OH - At least one source for is sodium hydroxide.

[0066] It is preferred that the mixture prepared in step (i) further comprises seed crystals, preferably the seed crystals comprise a zeolitic material having a CHA-, AEI-, GME- and / or MFI-type framework structure, more preferably the seed crystals comprise a zeolitic material having a CHA-type and / or AEI-type framework structure, more preferably the zeolitic material of the seed crystals is obtainable and / or obtained by any one of the particular and preferred embodiments of the present invention.

[0067] When the mixture prepared in step (i) further comprises seed crystals, preferably the seed crystals comprise a zeolitic material having a CHA-, AEI-, GME-, and / or MFI-type framework structure, and the zeolitic material having a CHA-type framework structure contained in the seed crystals is selected from the group consisting of Wilhendersonite, ZYT-6, SAPO-47, Na-chabazite, chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-chabazite, MeAPSO-47, Phi, DAF-5, UiO-21, |Li-Na|[Al-Si-O]-CHA, (Ni(deta)2)-UT-6, SSZ-13, and SSZ-62, and mixtures of two or more thereof, preferably ZYT-6, SAPO-47, Na -chabazite, chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-chabazite, Phi, DAF-5, UiO-21, SSZ-13 and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, Linde D, Linde R, SAPO-34, SSZ-13 and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, SSZ-13 and SSZ-62, and mixtures of two or three thereof, more preferably the zeolitic material having a CHA-type framework structure contained in the seed crystal is chabazite and / or SSZ-13, preferably SSZ-13. Additionally and independently, it is preferred that the amount of seed crystals in the mixture prepared in step (i) and heated in step (iii) is in the range of 0.1-25% by weight relative to 100% by weight of SiO2 in the framework structure of the first zeolitic material, preferably 0.5-15% by weight relative to 100% by weight of SiO2 in the framework structure of the first zeolitic material, more preferably 1-10% by weight, more preferably 2-7% by weight, more preferably 3-6% by weight, and more preferably 4-5% by weight.

[0068] The one or more structure directing agents are selected from the group consisting of one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N +-containing compounds, preferably 1 , R 2 , R 3 and R 4 each independently represents alkyl.

[0069] The one or more structure directing agents are one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + -containing compounds, 1 , R 2 , R 3 and R 4 are each independently an alkyl group, R 4 Preferably, represents adamantyl and / or benzyl, preferably 1-adamantyl.

[0070] R 4 represents adamantyl and / or benzyl, preferably 1-adamantyl, R 1 , R 2 , and R 3 preferably, independently of each other, optionally substituted and / or optionally branched (C1-C6) alkyl, preferably (C1-C5) alkyl, more preferably (C1-C4) alkyl, more preferably (C1-C3) alkyl, and more preferably optionally substituted methyl or ethyl, more preferably R 1 , R 2 , and R 3 are each independently an optionally substituted methyl or ethyl, preferably an unsubstituted methyl or ethyl, more preferably R 1 , R 2 , and R 3 each independently represents an optionally substituted methyl, preferably an unsubstituted methyl. 4preferably represents optionally heterocyclic and / or optionally substituted adamantyl and / or benzyl, preferably optionally heterocyclic and / or optionally substituted 1-adamantyl, more preferably optionally substituted adamantyl and / or benzyl, more preferably optionally substituted 1-adamantyl, more preferably unsubstituted adamantyl and / or benzyl, and more preferably unsubstituted 1-adamantyl.

[0071] one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The -containing compound is one or more N,N,N-tri(C1-C4)alkyl-1-adamantanemonium compounds, preferably one or more N,N,N-tri(C1-C3)alkyl-1-adamantanemonium compounds, more preferably one or more N,N,N-tri(C1-C2)alkyl-1-adamantanemonium compounds, more preferably one or more N,N,N-tri(C1-C2)alkyl-1-adamantanemonium and / or one or more N,N,N-tri(C1-C 2) alkyl-1-adamantane monium compounds, more preferably one or more compounds selected from N,N,N-triethyl-1-adamantane monium, N,N-diethyl-N-methyl-1-adamantane monium, N,N-dimethyl-N-ethyl-1-adamantane monium, N,N,N-trimethyl-1-adamantane monium compounds, and mixtures of two or more thereof, more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The -containing compound includes one or more N,N,N-trimethyl-1-adamantanmonium compounds.

[0072] one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N +It is preferred that the -containing compound is a salt, preferably one or more salts selected from the group consisting of halides, sulfates, nitrates, phosphates, acetates, and mixtures of two or more thereof, more preferably from the group consisting of bromides, chlorides, hydroxides, sulfates, and mixtures of two or more thereof, more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The -containing compounds are tetraalkylammonium hydroxides and / or sulfates, and more preferably tetraalkylammonium hydroxides.

[0073] The one or more structure directing agents are one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + -containing compounds, 1 , R 2 , R 3 and R 4 are each independently an alkyl group, R 4 Preferably represents cycloalkyl.

[0074] R 4 When represents cycloalkyl, R 1 and R 2 preferably, independently of each other, optionally substituted and / or optionally branched (C1-C6) alkyl, preferably (C1-C5) alkyl, more preferably (C1-C4) alkyl, more preferably (C1-C3) alkyl, and more preferably optionally substituted methyl or ethyl, more preferably R 1 and R 2 are each independently an optionally substituted methyl or ethyl, preferably an unsubstituted methyl or ethyl, more preferably R 1 and R 2 represent, independently of one another, optionally substituted methyl, preferably unsubstituted methyl.

[0075] R 3 represents optionally substituted and / or optionally branched (C1-C6) alkyl, preferably (C1-C5) alkyl, more preferably (C1-C4) alkyl, more preferably (C1-C3) alkyl, and more preferably optionally substituted methyl or ethyl, more preferably R 3 represents optionally substituted ethyl, preferably unsubstituted ethyl.

[0076] R 4 preferably represents an optionally heterocyclic and / or optionally substituted 5- to 8-membered cycloalkyl, preferably a 5- to 7-membered cycloalkyl, more preferably a 5- or 6-membered cycloalkyl, more preferably R 4 represents optionally heterocyclic and / or optionally substituted 6-membered cycloalkyl, preferably optionally substituted cyclohexyl, and more preferably unsubstituted cyclohexyl.

[0077] one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N +It is preferred that the --containing compound comprises one or more compounds selected from one or more N,N,N-tri(C1-C4)alkyl-(C5-C7)cycloalkylammonium compounds, preferably one or more N,N,N-tri(C1-C3)alkyl-(C5-C6)cycloalkylammonium compounds, more preferably one or more N,N,N-tri(C1-C2)alkyl-(C5-C6)cycloalkylammonium compounds, more preferably one or more N,N,N-tri(C1-C2)alkyl-cyclopentylammonium and / or one or more N,N,N-tri(C1-C2)alkyl-cyclohexylammonium compounds, more preferably N,N,N-triethyl-cyclohexylammonium, N,N-diethyl-N-methyl-cyclohexylammonium, N,N-dimethyl-N-ethyl-cyclohexylammonium, N,N,N-trimethyl-cyclohexylammonium compounds, and mixtures of two or more thereof, more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The -containing compound includes one or more N,N-dimethyl-N-ethyl-cyclohexylammonium compounds.

[0078] one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + It is preferred that the -containing compound is a salt, preferably one or more salts selected from the group consisting of halides, sulfates, nitrates, phosphates, acetates, and mixtures of two or more thereof, more preferably from the group consisting of bromides, chlorides, hydroxides, sulfates, and mixtures of two or more thereof, more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N +The -containing compounds are tetraalkylammonium hydroxides and / or sulfates, and more preferably tetraalkylammonium hydroxides.

[0079] The one or more structure directing agents are selected from the group consisting of one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + Preferably, the mixture prepared in step (i) and heated in step (iii) comprises an R-containing compound, wherein the R-containing compound is one or more tetraalkylammonium cations in the framework structure of the first zeolitic material versus the R of SiO. 1 R 2 R 3 R 4 N + The molar ratio of SiO2 is in the range of 0.05 to 1.5, preferably 0.1 to 0.8, more preferably 0.3 to 0.5, more preferably 0.5 to 0.3, more preferably 0.7 to 0.2, more preferably 0.8 to 0.15, more preferably 0.85 to 0.12, more preferably 0.9 to 0.11, and more preferably 0.95 to 0.1.

[0080] In step (iii), it is preferable to heat the mixture to a temperature in the range of 70 to 300°C, preferably 90 to 280°C, more preferably 120 to 250°C, more preferably 140 to 230°C, more preferably 160 to 220°C, more preferably 180 to 210°C, and more preferably 190 to 200°C.

[0081] It is preferred that the zeolitic material further comprises TiO2 in its framework structure, the mixture in step (i) further comprising one or more sources of TiO2, and the one or more structure directing agents are preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + -containing compounds, 1 , R 2 , R 3 and R 4each independently represents alkyl.

[0082] When the zeolitic material further comprises TiO2 in its framework structure and the mixture in step (i) further comprises one or more sources of TiO2, it is preferred that the zeolitic material obtained in step (iii) 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, preferably the zeolitic material obtained in step (iii) has an MFI- and / or MEL-type framework structure, preferably an MFI-type framework structure.

[0083] It is preferred that one or more solvents in the mixture prepared in step (i) comprise water, preferably distilled water, and more preferably, water, preferably distilled water, is included as one or more solvents in the mixture prepared in step (i).

[0084] When the one or more solvents in the mixture prepared in step (i) comprise water, it is preferred that the H2O:SiO2 molar ratio of the one or more Si sources, calculated as water to SiO2 in the mixture prepared in step (i), is in the range of 2-13, preferably 3-11, more preferably 4-10, more preferably 4.5-9.5, more preferably 5-9, more preferably 5.5-8.5, more preferably 6-8, and more preferably 6.5-7.5.

[0085] 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, and more preferably an optionally branched (C2-C3) alkyl, 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 4represents propyl, preferably n-propyl.

[0086] one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + It is preferred that the -containing compounds are, independently of one another, salts, preferably 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 salts selected from the group consisting of chlorides, hydroxides, sulfates and mixtures of two or more thereof, 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, and more preferably a tetraalkylammonium hydroxide.

[0087] The mixture prepared in step (i) and crystallized in step (iii) is preferably a tetraalkylammonium cation R 1 R 2 R 3 R 4 N + It is preferred that the molar ratio of the --containing compound to the one or more sources of Si, calculated as SiO2, is in the 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.

[0088] The one or more sources of SiO2 are selected from the group consisting of SiO2, 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, the silica gel may be selected 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, the composition contains one or more compounds selected from the group consisting of silica hydrosol, silicic acid, colloidal silica, silicic acid ester, tetraalkoxysilane, and a mixture of two or more thereof; More preferably, the one or more sources of SiO2 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 sources of SiO2 comprise tetramethoxysilane and / or tetraethoxysilane, preferably tetraethoxysilane; and more preferably, the one or more sources of Si are tetramethoxysilane and / or tetraethoxysilane, preferably tetraethoxysilane.

[0089] Preferably, the one or more sources of Ti comprise one or more compounds selected from the group consisting of titanium oxide, titanium salts, titanyl compounds, titanic acids, titanic acid 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 and / or tetraethyl orthotitanate, more preferably tetraethyl orthotitanate.

[0090] It is preferred that the SiO2:TiO2 molar ratio of the one or more sources of SiO2, calculated as SiO2, to the one or more sources of TiO2, calculated as TiO2, of the mixture prepared in step (i) is in the range of 1-500, preferably 2-200, more preferably 5-150, more preferably 10-100, more preferably 20-70, more preferably 25-50, more preferably 30-45, and more preferably 35-40.

[0091] In step (iii), it is preferred to heat the mixture 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, and more preferably 170 to 180°C.

[0092] Prior to step (ii), it is preferable to age the mixture prepared in step (i) 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, and more preferably 85 to 95°C.

[0093] Prior to step (ii), it is preferred to age the mixture prepared in step (i) for a period in the range of 0.05 to 48 hours, more preferably 0.15 to 24 hours, more preferably 0.25 to 12 hours, more preferably 0.5 to 6 hours, more preferably 0.75 to 3 hours, more preferably 1 to 2 hours, and more preferably 1.25 to 1.75 hours.

[0094] The method is (iv) concentrating the zeolitic material obtained in step (iii), preferably by filtration, more preferably by membrane filtration, and more preferably by cross-flow filtration; and / or, preferably, and (v) washing the zeolitic material obtained in step (iii) or (iv) with a liquid comprising one or more solvents; and / or, preferably, and (vi) drying the zeolitic material obtained in step (iii), (iv) or (v); and / or, preferably, and (vii) calcining the zeolitic material obtained in step (iii), (iv), (v) or (vi). It is preferred that the composition further comprises:

[0095] The method is (iv) concentrating the zeolitic material obtained in step (iii), preferably by filtration, more preferably by membrane filtration, and more preferably by cross-flow filtration; and / or, preferably, and (v) washing the zeolitic material obtained in step (iii) or (iv) with a liquid comprising one or more solvents; and / or, preferably, and (vi) drying the zeolitic material obtained in step (iii), (iv) or (v); and / or, preferably, and (vii) calcining the zeolitic material obtained in step (iii), (iv), (v) or (vi). In the case where the method further comprises the steps of: concentrating in step (iv) and washing in step (v) are preferably carried out simultaneously in two or more successive stages of membrane filtration, preferably 2 to 10 stages, more preferably 3 to 8 stages, more preferably 3 to 7 stages, more preferably 4 to 6 stages, and more preferably 4 to 5 stages, wherein the retentate of one stage of membrane filtration is diluted with a liquid containing one or more solvents when it is fed to the subsequent stage.

[0096] When the concentration in step (iv) and the washing in step (v) are carried out simultaneously in two or more successive stages of membrane filtration, and the retentate of one stage of membrane filtration is diluted with a liquid containing one or more solvents when fed to the subsequent stage, it is preferred to continuously recycle the permeate of one stage of membrane filtration, containing a portion of the one or more structure-directing agents from the mixture continuously prepared in step (i), to step (i).

[0097] The membrane filtration is preferably carried out at a pressure in the range of 0.2 to 60 bar, preferably 0.5 to 20 bar, more preferably 1 to 15 bar, more preferably 3 to 12 bar, and more preferably 5 to 8 bar.

[0098] The membrane filtration is preferably carried out at a temperature in the range of 20 to 200°C, preferably 50 to 150°C, more preferably 80 to 120°C, more preferably 90 to 110°C, and more preferably 97 to 103°C.

[0099] Preferably the membrane filtration is cross-flow filtration.

[0100] When the membrane filtration is cross-flow filtration, the cross-flow filtration is preferably carried out in one or more consecutive cross-flow filtration units, preferably 1 to 10 consecutive cross-flow filtration units, more preferably 2 to 9 consecutive cross-flow filtration units, more preferably 3 to 8 consecutive cross-flow filtration units, more preferably 4 to 6 consecutive cross-flow filtration units, and more preferably 4 to 5 consecutive cross-flow filtration units.

[0101] When cross-flow filtration is performed in one or more sequential cross-flow filtration units, each of the one or more sequential cross-flow filtration units preferably comprises 10 to 10,000 tubes, preferably 250 to 7,500 tubes, more preferably 500 to 5,000 tubes, more preferably 750 to 2,500 tubes, and more preferably 975 to 1025 tubes.

[0102] When one or more successive cross-flow filtration units each contain 10-10,000 tubes, it is preferred that the inner diameter of the tubes is in the range of 2-25 mm, preferably 3-20 mm, more preferably 4-15 mm, more preferably 5-10 mm, and more preferably 5.5-6.5 mm.

[0103] In step (v), it is preferred that 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, and more preferably water, preferably deionized water, is used as liquid.

[0104] The drying in step (vi) 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, and more preferably 110 to 130°C.

[0105] Preferably, drying the zeolitic material in step (vi) comprises spray drying the zeolitic material obtained in step (iii), (iv) or (v).

[0106] When drying the zeolitic material in step (vi) comprises spray drying the zeolitic material obtained in step (iii), (iv) or (v), the spray drying is preferably carried out using a drying gas having a temperature in the range of 100 to 500°C, preferably 150 to 450°C, more preferably 200 to 400°C, more preferably 250 to 350°C, and more preferably 275 to 325°C.

[0107] The present invention also relates to a zeolitic material obtainable and / or obtained by the process of any one of the particular and preferred embodiments of the present invention.

[0108] It is preferred that the zeolitic material has a CHA-framework structure, and preferably the zeolitic material is selected from the group consisting of Wilhendersonite, ZYT-6, SAPO-47, Na-chabazite, chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-chabazite, MeAPSO-47, Phi, DAF-5, UiO-21, |Li-Na|[Al-Si-O]-CHA, (Ni(deta)2)-UT-6, SSZ-13, and SSZ-62, and mixtures of two or more thereof, more preferably ZYT-6, SAPO-47, Na-chabazite, chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-chabazite, MeAPSO-47, Phi, DAF-5, UiO-21, |Li-Na|[Al-Si-O]-CHA, (Ni(deta)2)-UT-6, SSZ-13, and SSZ-62, and mixtures of two or more thereof. 4, K-chabazite, Phi, DAF-5, UiO-21, SSZ-13, and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, Linde D, Linde R, SAPO-34, SSZ-13, and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, SSZ-13, and SSZ-62, and mixtures of two or three thereof, more preferably the zeolitic material comprises chabazite and / or SSZ-13, preferably SSZ-13, and more preferably the zeolitic material is chabazite and / or SSZ-13, preferably SSZ-13.

[0109] The present invention also relates to the use of a zeolitic material according to any of the particular and preferred embodiments of the present invention as a molecular sieve, as an adsorbent, for ion exchange, or as a catalyst and / or catalyst support, preferably as a catalyst and / or catalyst support, for the production of nitrogen oxides NO x for selective catalytic reduction (SCR) of CO2, for storage and / or adsorption of CO2, for oxidation of NH3, in particular for oxidation of NH3 slip in diesel systems, for decomposition of N2O, as additives in fluid catalytic cracking (FCC) processes and / or as catalysts and / or catalyst supports, in organic conversion reactions, preferably in the conversion of alcohols to olefins and more preferably in methanol to olefins (MTO) catalysis, more preferably in the decomposition of nitrogen oxides NO x and more preferably for selective catalytic reduction (SCR) of nitrogen oxides NO in exhaust gases from combustion engines, preferably diesel engines or lean-burn gasoline engines. x The present invention relates to a method for selective catalytic reduction (SCR) of a fuel cell.

[0110] In the case of the zeolitic material obtainable and / or obtained by the process of any one of the particular and preferred embodiments of the present invention, it is preferred that the zeolitic material has an MFI-type framework structure, the zeolitic material having an MFI-type framework structure comprises TS-1, more preferably the zeolitic material is TS-1.

[0111] The present invention also relates to the use of a zeolitic material according to any of the particular and preferred embodiments of the present invention as a molecular sieve, as an adsorbent, for ion exchange, or as a catalyst and / or catalyst support, preferably as a catalyst and / or catalyst support, in reactions involving C-C bond formation and / or conversion, and preferably as a catalyst and / or catalyst support, in isomerization reactions, in ammoxidation reactions, in amination reactions, in hydrocracking reactions, in alkylation reactions, in acylation reactions, in reactions for the conversion of alkanes to olefins or in reactions for the conversion of one or more oxygenates to olefins and / or aromatics, The present invention relates to the use of a catalyst in reactions for the synthesis of hydrogen peroxide, in aldol condensation reactions, in reactions for the isomerization of epoxides, in transesterification reactions or in epoxidation reactions, preferably as a catalyst and / or catalyst support in reactions for the epoxidation of olefins, more preferably in reactions for the epoxidation of C2-C5 alkenes, more preferably in reactions for the epoxidation of C2-C4 alkenes, for the epoxidation of C2 or C3 alkenes, more preferably in reactions for the epoxidation of C3 alkenes and more preferably for the conversion of propylene to propylene oxide as a catalyst.

[0112] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependent claims and back references shown. In particular, in each instance where a range of embodiments is mentioned, it should be noted that in the context of terms such as "the method according to any one of embodiments 1 to 4", all embodiments within this range are meant to be explicitly disclosed to those skilled in the art, that is, the expression of this term is understood by those skilled in the art to be synonymous with "the method according to any one of embodiments 1, 2, 3, and 4". Furthermore, it should be explicitly noted that the following set of embodiments represents a suitably constructed part of the description of the general and preferred aspects of the present invention, rather than a set of claims determining the scope of protection.

[0113] 1. A continuous process for producing a zeolitic material containing SiO2 in its framework structure, comprising: (i) sequentially preparing a mixture comprising one or more solvents, one or more structure directing agents, and one or more sources of SiO; (ii) continuously feeding the mixture prepared in step (i) into one or more continuous flow reactors; and (iii) heating the mixture in one or more continuous flow reactors to continuously obtain a zeolitic material comprising SiO2 in its framework structure. Including, A method wherein the mixture contained within one or more continuous flow reactors is subjected to a pulsating flow regime.

[0114] 2. The maximum shear rate achieved by the pulsatile flow regime is between 0 and 2,500 s -1 , preferably 0 to 1,500 seconds -1 , more preferably 0 to 1000 seconds -1 , more preferably 0 to 700 seconds -1 , more preferably 0 to 500 seconds -1 , more preferably 0 to 400 seconds -1 , more preferably 0 to 300 seconds -1 , more preferably 0 to 250 seconds -1 , more preferably 0 to 200 seconds -1 , more preferably 0 to 150 seconds -1 , more preferably 0 to 100 seconds -1 , and more preferably 0 to 50 seconds -1 2. The continuous method of embodiment 1, wherein the

[0115] 3. A continuous process according to embodiment 1 or 2, wherein after step (i) and before (ii), the mixture prepared in step (i) is homogenized, wherein homogenization is preferably achieved by stirring the mixture.

[0116] 4. The continuous process of embodiment 3, wherein the homogenization is carried out in two continuous stirred tank reactors (CSTRs), the first CSTR being located upstream of the second CSTR in the continuous process, and the mixture obtained in the first CSTR being continuously fed to the second CSTR.

[0117] 5. The continuous process of embodiment 4, wherein the first CSTR employs one or more stirred shafts each equipped with one or more baffles.

[0118] 6. The continuous process according to embodiment 4 or 5, wherein the first CSTR is operated at a temperature in the range of 20 to 120°C, preferably 21 to 80°C, more preferably 22 to 40°C, more preferably 23 to 30°C, and more preferably 24 to 26°C.

[0119] 7. The continuous process according to any of embodiments 4 to 6, wherein the first CSTR is operated at a pressure in the range of 1 to 3 bar, preferably 1 to 2.5 bar, more preferably 1 to 2 bar, more preferably 1 to 1.5 bar, and more preferably 1 to 1.2 bar.

[0120] 8. The continuous process according to any of embodiments 4 to 7, wherein the first CSTR has a capacity in the range of 10 to 1,000 L, preferably 100 to 800 L, more preferably 150 to 600 L, more preferably 200 to 400 L, and more preferably 240 to 260 L.

[0121] 9. The continuous process of any of embodiments 4 to 8, wherein the second CSTR employs one or more stirring shafts each equipped with one or more spiral stirrers.

[0122] 10. The continuous process of any of embodiments 4 to 9, wherein the second CSTR is operated at a temperature in the range of 20 to 120°C, preferably 21 to 80°C, more preferably 22 to 40°C, more preferably 23 to 30°C, and more preferably 24 to 26°C.

[0123] 11. The continuous process according to any of embodiments 4 to 10, wherein the second CSTR is operated at a pressure in the range of 1 to 3 bar, preferably 1 to 2.5 bar, more preferably 1 to 2 bar, more preferably 1 to 1.5 bar, and more preferably 1 to 1.2 bar.

[0124] 12. The continuous process according to any of embodiments 4 to 11, wherein the second CSTR has a capacity in the range of 20 to 2,000 L, preferably 200 to 1,200 L, more preferably 300 to 800 L, more preferably 450 to 550 L, and more preferably 490 to 510 L.

[0125] 13. The continuous process according to any of the preceding embodiments, wherein in step (ii), the mixture continuously prepared in step (i) is continuously fed to one or more continuous flow reactors at a rate in the range of 10 to 2,000 kg / h, preferably 50 to 1200 kg / h, more preferably 100 to 800 kg / h, more preferably 150 to 400 kg / h, more preferably 250 to 350 kg / h, and preferably 290 to 310 kg / h.

[0126] 14. The continuous process according to any of the preceding embodiments, wherein in step (ii), the mixture continuously prepared in step (i) is continuously fed to 1 to 10 continuous flow reactors, preferably 1 to 8 continuous flow reactors, more preferably 1 to 6 continuous flow reactors, more preferably 1 to 4 continuous flow reactors, and more preferably 2 to 3 continuous flow reactors.

[0127] 15. A continuous process according to any of the preceding embodiments, wherein in step (ii), the continuous feeding is achieved by pumping with one or more dosing pumps, preferably one dosing pump per continuous flow reactor.

[0128] 16. The continuous process according to embodiment 15, wherein the one or more dosing pumps are selected from dosing pumps capable of building up above the vapor pressure of the reaction mixture at the reaction temperature, preferably the one or more dosing pumps are piston diaphragm pumps, and more preferably piston diaphragm pumps having a pulsation damper.

[0129] 17. A continuous process according to embodiment 15 or 16, wherein each of the one or more dosing pumps is operated at a speed in the range of 5 to 500 kg / h, preferably in the range of 20 to 400 kg / h, more preferably in the range of 40 to 300 kg / h, more preferably in the range of 80 to 150 kg / h, and more preferably in the range of 90 to 110 kg / h.

[0130] 18. The continuous process according to any of embodiments 15 to 17, wherein each of the one or more dosing pumps is operated at a pressure in the range of 0.5 to 15 MPa, 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, and more preferably 3.8 to 4.2 MPa, this pressure referring to the pressure occurring at the outlet of the one or more dosing pumps.

[0131] 19. A continuous process according to any of the preceding embodiments, wherein the pulsating flow regime is achieved by a semi-continuous flow regime in the general direction of flow or against the general direction of flow, the general direction of flow being defined by the inlet end of each of one or more continuous flow reactors to which the mixture prepared in step (i) is continuously fed and the outlet end of each of one or more continuous flow reactors to which the zeolitic material obtained in step (iii) is continuously withdrawn.

[0132] 20. A continuous method as described in embodiment 19, wherein the pulsating flow regime is achieved by pulsating motion in the general direction of flow or in both the general direction of flow and the opposite direction.

[0133] 21. Pulsation frequency is 0.001 to 1 second -1 , preferably 0.003 to 0.7 seconds -1 , more preferably 0.005 to 0.4 seconds -1 , more preferably 0.008 to 0.2 seconds -1 , more preferably 0.01 to 0.15 seconds -1 , more preferably 0.04 to 0.1 seconds -1 , and more preferably 0.05 to 0.07 seconds-1 21. The continuous method of embodiment 20, wherein the

[0134] 22. A continuous method according to any of embodiments 19 to 21, wherein the pulsating flow regime is achieved by periodically alternating the direction of flow between the general direction of flow and the opposite direction.

[0135] 23. The frequency of flow direction alternation is 0.01 to 3 seconds. -1 , preferably 0.03 to 2 seconds -1 , more preferably 0.05 to 1.5 seconds -1 , more preferably 0.08 to 1.2 seconds -1 , more preferably 0.1 to 1 second -1 , more preferably 0.15 to 0.8 seconds -1 , and more preferably 0.2 to 0.5 seconds -1 23. The continuous method of embodiment 22, wherein the

[0136] 24. The continuous supply in step (ii) is 0.1 to 10 h -1 range, preferably 0.5 to 8 h -1 , more preferably 1 to 6 hours -1 , more preferably 1.25 to 4 h -1 And more preferably 1.5 to 2 hours -1 24. The continuous process of any of the preceding embodiments, wherein the process is carried out at a liquid hourly space velocity in the range of

[0137] 25. The continuous process according to any one of the preceding embodiments, wherein in step (iii), the mixture is heated to a temperature in the range of 90 to 280°C, preferably 100 to 270°C, more preferably 150 to 260°C, more preferably 200 to 265°C, and more preferably 248 to 252°C.

[0138] 26. The continuous process according to any one of embodiments 1 to 25, wherein in step (iii), the mixture is heated under autogenous pressure, preferably the pressure is 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, and more preferably 3.8 to 4.2 MPa.

[0139] 27. The continuous process according to any of the preceding embodiments, wherein in step (ii), the mixture prepared in step (i) is continuously fed to one or more continuous flow reactors for a period in the range of 5 to 365 days, preferably 10 to 300 days, more preferably 15 to 240 days, more preferably 30 to 180 days, more preferably 50 to 120 days, and more preferably 80 to 100 days.

[0140] 28. A continuous process according to any of the preceding embodiments, wherein the mixture constituting the feed to be crystallized 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 comprising one or more fluorine compounds.

[0141] 29. The continuous process of embodiment 28, wherein the lubricant comprises one or more fluorinated polymers, preferably one or more fluorinated polyethers, and more preferably one or more perfluoropolyethers.

[0142] 30. The continuous process of embodiment 28 or 29, wherein the lubricant comprises one or more fluorocarbons, preferably one or more perfluorocarbons, more preferably the lubricant comprises perfluorodecalin.

[0143] 31. The continuous process of any of embodiments 28 to 30, wherein the lubricant comprises liquid paraffin.

[0144] 32. The continuous process according to any of the preceding embodiments, wherein the volume of each of the one or more continuous flow reactors is in the range of 0.5 to 1,000 L, preferably 20 to 750 L, more preferably 30 to 250 L, more preferably 40 to 90 L, and more preferably 49 to 51 L.

[0145] 33. The continuous process according to any of the preceding embodiments, wherein each of the one or more continuous flow reactors is selected from among tubular reactors, ring reactors, and continuous oscillatory reactors, preferably from among flat tube reactors, tubular membrane reactors, ring reactors, continuous oscillatory baffle reactors, and combinations thereof, more preferably each of the one or more continuous flow reactors is a flat tube reactor and / or a ring reactor, more preferably each of the one or more continuous flow reactors is a flat tube reactor.

[0146] 34. A continuous process according to any of the preceding embodiments, wherein each of the one or more continuous flow reactors is linear with respect to the direction of flow and / or comprises one or more curves, preferably each of the one or more continuous flow reactors is linear with respect to the direction of flow and / or has a coiled configuration, more preferably each of the one or more continuous flow reactors has a coiled configuration with respect to the direction of flow.

[0147] 35. The continuous process according to embodiment 34, wherein the inner diameter of the coil form is in the range of 6 to 100 mm, preferably 7 to 80 mm, more preferably 8 to 60 mm, more preferably 9 to 40 mm, more preferably 10 to 25 mm, and more preferably 15 to 10 mm.

[0148] 36. The continuous process according to any one of the preceding embodiments, wherein each of the one or more continuous flow reactors is a tubular reactor, at least a portion of the tubular reactors being right cylindrical with a constant inner diameter perpendicular to the direction of flow, the inner diameter being preferably in the range of 5 to 250 mm, more preferably in the range of 10 to 200 mm, more preferably in the range of 15 to 150 mm, more preferably in the range of 20 to 75 mm, and more preferably in the range of 23 to 27 mm.

[0149] 37. The continuous process according to any of the preceding embodiments, wherein each of the one or more continuous flow reactors has a length in the range of 1 to 500 m, preferably 30 to 400 m, more preferably 50 to 300 m, more preferably 85 to 150 m, and more preferably 98 to 102 m.

[0150] 38. The continuous process according to any of the preceding embodiments, wherein the walls of each of the one or more continuous flow reactors are made of a metallic material, the metallic material comprising one or more metals selected from the group consisting of Ta, Cr, Fe, Ni, Cu, Al, Mo, and combinations and / or alloys of two or more thereof, 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, preferably wherein the metallic material comprises stainless steel, more preferably wherein the metallic material consists of stainless steel.

[0151] 39. The continuous process according to any of the preceding embodiments, wherein the surface of the inner wall of each of the one or more continuous flow reactors is lined with an organic polymeric material, the organic polymeric material preferably comprising 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 polymeric material comprises poly(tetrafluoroethylene), more preferably the inner wall of each of the one or more continuous flow reactors is lined with poly(tetrafluoroethylene).

[0152] 40. The surface of the inner wall of each of the one or more continuous flow reactors is a polysiloxane, preferably a polysiloxane of the formula [R2SiO] nwherein R is preferably an organic group, more preferably an alkyl group and / or a phenyl group.

[0153] 41. The continuous process of any of the preceding embodiments, wherein each of the one or more continuous flow reactors consists of a single stage.

[0154] 42. The continuous process according to any of the preceding embodiments, wherein the reaction mixture continuously exiting the one or more continuous flow reactors exhibits a solids content in the range of 2 to 50% by weight relative to 100% by weight of the reaction mixture, preferably 4 to 40% by weight relative to 100% by weight of the reaction mixture, more preferably 6 to 30% by weight, more preferably 10 to 20% by weight, and more preferably 13 to 15% by weight.

[0155] 43. The continuous process according to any of the preceding embodiments, wherein the zeolitic material further comprises X2O3 in its framework structure, where X represents a trivalent element, and the mixture in step (i) further comprises one or more sources of X2O3.

[0156] 44. The continuous process of embodiment 43, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, and X is preferably Al and / or B, and more preferably Al.

[0157] 45. The one or more sources of SiO2 and X2O3 include a first zeolite material comprising SiO2 and X2O3 in a framework structure; and 45. The continuous process according to embodiment 43 or 44, wherein in step (iii), the mixture is heated in one or more continuous flow reactors to obtain a second zeolitic material comprising SiO2 and X2O3 in its framework structure, the second zeolitic material obtained in step (iii) having a different type of framework structure than the first zeolitic material contained in the mixture prepared in step (i).

[0158] 46. ​​The continuous process according to embodiment 45, wherein the first zeolitic material has a FAU-, GIS-, MOR-, LTA-, FER-, TON-, MTT-, BEA-, MEL-, MWW-, MFS-, and / or MFI-type framework structure, preferably a FAU-, GIS-, BEA-, and / or MFI-type framework structure, more preferably a FAU- and / or BEA-type framework structure, and more preferably a FAU-type framework structure.

[0159] 47. The first zeolitic material having an FAU-type framework structure is selected from the group consisting of ZSM-3, faujasite, [Al-Ge-O]-FAU, CSZ-1, ECR-30, zeolite X, zeolite Y, LZ-210, SAPO-37, ZSM-20, Na-X, US-Y, Na-Y, [Ga-Ge-O]-FAU, Li-LSX, [Ga-Al-Si-O]-FAU, and [Ga-Si-O]-FAU, and mixtures of two or more thereof, preferably ZSM-3, faujasite, CSZ-1, ECR-30, zeolite X, zeolite Y, LZ-210, ZSM-20, Na-X, US-Y, Na-Y, and Li-LSX, and mixtures of two or more thereof. 47. A continuous process according to embodiment 45 or 46, wherein the first zeolitic material having an FAU-type framework structure is selected from the group consisting of zeolite X, zeolite Y, Na-X, US-Y, and Na-Y, and mixtures of two or more thereof, more preferably from the group consisting of faujasite, zeolite X, and zeolite Y, and mixtures of two or more thereof, more preferably from the group consisting of faujasite, zeolite X, and zeolite Y, and mixtures of two or more thereof; more preferably the first zeolitic material having an FAU-type framework structure comprises zeolite X and / or zeolite Y, preferably zeolite Y; more preferably the first zeolitic material having an FAU-type framework structure is zeolite X and / or zeolite Y, preferably zeolite Y.

[0160] 48. The continuous process according to any of embodiments 45 to 47, wherein the second zeolitic material has a CHA-, AEI-, GME-, and / or MFI-type framework structure, preferably a CHA- and / or AEI-type framework structure, and more preferably a CHA-type framework structure.

[0161] 49. The second zeolitic material obtained in step (iii) has a CHA-type framework structure, preferably the zeolitic material having a CHA-type framework structure is selected from the group consisting of Wilhendersonite, ZYT-6, SAPO-47, Na-chabazite, chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-chabazite, MeAPSO-47, Phi, DAF-5, UiO-21, |Li-Na|[Al-Si-O]-CHA, (Ni(deta)2)-UT-6, SSZ-13, and SSZ-62, and mixtures of two or more thereof, more preferably ZYT-6, SAPO-47, Na-chabazite, chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-chabazite, Phi, DAF 49. A continuous process according to any of embodiments 45 to 48, wherein the second zeolitic material obtained in step (iii) is selected from the group consisting of: UiO-21, SSZ-13 and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, Linde D, Linde R, SAPO-34, SSZ-13 and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, SSZ-13 and SSZ-62, and mixtures of two or three thereof; more preferably the second zeolitic material obtained in step (iii) comprises chabazite and / or SSZ-13, preferably SSZ-13; and more preferably the second zeolitic material obtained in step (iii) is chabazite and / or SSZ-13, preferably SSZ-13.

[0162] 50. The continuous process according to any of embodiments 45 to 49, wherein the framework structures of the first zeolitic material exhibit, independently of one another, a YO2:X2O3 molar ratio in the range of from 5 to 120, preferably from 8 to 80, more preferably from 10 to 50, more preferably from 15 to 40, more preferably from 20 to 30, more preferably from 22 to 28, and more preferably from 24 to 26.

[0163] 51. The mixture prepared in step (i) and heated in step (iii) is OH -and the mixture further comprises at least one source for hydroxide in the framework structure of the first zeolite material versus OH of SiO2. - 51. The continuous process according to any one of embodiments 45 to 50, wherein the molar ratio of SiO2 to SiO2 is in the range of 0.05 to 1, preferably 0.1 to 0.7, more preferably 0.3 to 0.6, more preferably 0.4 to 0.55, more preferably 0.45 to 0.5, more preferably 0.46 to 0.49, and more preferably 0.47 to 0.48.

[0164] 52. A continuous process according to any one of the preceding embodiments, wherein the one or more solvents in the mixture prepared in step (i) comprise water, preferably distilled water, and more preferably, water, preferably distilled water, is contained as the one or more solvents in the mixture prepared in step (i).

[0165] 53. The continuous process according to embodiment 52, wherein the H2O:SiO2 molar ratio of SiO2, calculated as hydroxide to oxide, in the mixture prepared in step (i) is in the range of 3 to 50, preferably 7 to 40, more preferably 9 to 30, more preferably 11 to 25, more preferably 13 to 22, more preferably 15 to 20, more preferably 16 to 19, and more preferably 17 to 18.

[0166] 54. The mixture prepared in step (i) and heated in step (iii) is treated with OH - wherein said OH - Preferably, the at least one source for comprises a metal hydroxide, more preferably a hydroxide of an alkali metal M, more preferably sodium hydroxide and / or potassium hydroxide, and more preferably sodium hydroxide, more preferably OH - 54. The continuous process of any of the preceding embodiments, wherein at least one source for is sodium hydroxide.

[0167] 55. The continuous process according to any of the preceding embodiments, wherein the mixture prepared in step (i) further comprises seed crystals, preferably the seed crystals comprise a zeolitic material having a CHA-, AEI-, GME-, and / or MFI-type framework structure, more preferably the seed crystals comprise a zeolitic material having a CHA-type and / or AEI-type framework structure, more preferably the zeolitic material of the seed crystals is obtainable and / or obtained by any one of the preceding embodiments.

[0168] 56. The zeolite material having a CHA-type framework structure contained in the seed crystals is preferably selected from the group consisting of Wilhendersonite, ZYT-6, SAPO-47, Na-chabazite, chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-chabazite, MeAPSO-47, Phi, DAF-5, UiO-21, |Li-Na|[Al-Si-O]-CHA, (Ni(deta)2)-UT-6, SSZ-13, and SSZ-62, and mixtures of two or more thereof. 56. A continuous process according to embodiment 55, wherein the zeolitic material having a CHA-type framework structure contained in the seed crystals is selected from the group consisting of: 4, K-chabazite, Phi, DAF-5, UiO-21, SSZ-13, and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, Linde D, Linde R, SAPO-34, SSZ-13, and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, SSZ-13, and SSZ-62, and mixtures of two or three thereof, more preferably the zeolitic material having a CHA-type framework structure contained in the seed crystals is chabazite and / or SSZ-13, preferably SSZ-13.

[0169] 57. The continuous process according to embodiment 55 or 56, wherein the amount of seed crystals in the mixture prepared in step (i) and heated in step (iii) is in the range of 0.1-25% by weight relative to 100% by weight of SiO2 in the framework structure of the first zeolitic material, preferably 0.5-15% by weight relative to 100% by weight of SiO2 in the framework structure of the first zeolitic material, more preferably 1-10% by weight, more preferably 2-7% by weight, more preferably 3-6% by weight, and more preferably 4-5% by weight.

[0170] 58. One or more structure directing agents are selected from the group consisting of one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + -containing compounds, wherein R 1 , R 2 , R 3 and R 4 58. The continuous process of any of the preceding embodiments, wherein each independently represents alkyl.

[0171] 59. R 4 59. The continuous process according to embodiment 58, wherein represents adamantyl and / or benzyl, preferably 1-adamantyl.

[0172] 60. R 1 , R 2 , and R 3 are each independently an optionally substituted and / or optionally branched (C1-C6) alkyl, preferably a (C1-C5) alkyl, more preferably a (C1-C4) alkyl, more preferably a (C1-C3) alkyl, and more preferably an optionally substituted methyl or ethyl, more preferably R 1 , R 2 , and R 3 are each independently an optionally substituted methyl or ethyl, preferably an unsubstituted methyl or ethyl, more preferably R 1 , R 2 , and R 3and R 1 and R 2 each independently represent optionally substituted methyl, preferably unsubstituted methyl.

[0173] 61. R 4 represents optionally heterocyclic and / or optionally substituted adamantyl and / or benzyl, preferably optionally heterocyclic and / or optionally substituted 1-adamantyl, more preferably optionally substituted adamantyl and / or benzyl, more preferably optionally substituted 1-adamantyl, more preferably unsubstituted adamantyl and / or benzyl, and more preferably unsubstituted 1-adamantyl.

[0174] 62. One or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The -containing compound is one or more N,N,N-tri(C1-C4)alkyl-1-adamantanemonium compounds, preferably one or more N,N,N-tri(C1-C3)alkyl-1-adamantanemonium compounds, more preferably one or more N,N,N-tri(C1-C2)alkyl-1-adamantanemonium compounds, more preferably one or more N,N,N-tri(C1-C2)alkyl-1-adamantanemonium and / or one or more N,N,N-tri(C 1 to C2) alkyl-1-adamantanemonium compounds, more preferably one or more compounds selected from N,N,N-triethyl-1-adamantanemonium, N,N-diethyl-N-methyl-1-adamantanemonium, N,N-dimethyl-N-ethyl-1-adamantanemonium, N,N,N-trimethyl-1-adamantanemonium compounds, and mixtures of two or more thereof, more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The continuous process of any of embodiments 59 to 61, wherein the containing compound comprises one or more N,N,N-trimethyl-1-adamantanmonium compounds.

[0175] 63. One or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + -containing compound is preferably one or more salts selected from the group consisting of halides, sulfates, nitrates, phosphates, acetates, and mixtures of two or more thereof, more preferably from the group consisting of bromides, chlorides, hydroxides, sulfates, and mixtures of two or more thereof, more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The continuous process according to any of embodiments 59 to 62, wherein the -containing compound is a tetraalkylammonium hydroxide and / or sulfate, and more preferably a tetraalkylammonium hydroxide.

[0176] 64. R 4 59. The continuous process of embodiment 58, wherein represents cycloalkyl.

[0177] 65. R 1 and R 2 are each independently an optionally substituted and / or optionally branched (C1-C6) alkyl, preferably a (C1-C5) alkyl, more preferably a (C1-C4) alkyl, more preferably a (C1-C3) alkyl, and more preferably an optionally substituted methyl or ethyl, more preferably R 1 and R 2 are each independently an optionally substituted methyl or ethyl, preferably an unsubstituted methyl or ethyl, more preferably R 1 and R 2 and R 1 and R 2 each independently represent optionally substituted methyl, preferably unsubstituted methyl.

[0178] 66. R 3represents optionally substituted and / or optionally branched (C1-C6) alkyl, preferably (C1-C5) alkyl, more preferably (C1-C4) alkyl, more preferably (C1-C3) alkyl, and more preferably optionally substituted methyl or ethyl, more preferably R 3 66. The continuous process according to embodiment 64 or 65, wherein R represents optionally substituted ethyl, preferably unsubstituted ethyl.

[0179] 67. R 4 represents an optionally heterocyclic and / or optionally substituted 5- to 8-membered cycloalkyl, preferably a 5- to 7-membered cycloalkyl, more preferably a 5- or 6-membered cycloalkyl, more preferably R 4 67. The continuous process according to any of embodiments 64 to 66, wherein R represents optionally heterocyclic and / or optionally substituted 6-membered cycloalkyl, preferably optionally substituted cyclohexyl, and more preferably unsubstituted cyclohexyl.

[0180] 68. One or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N +the -containing compound comprises one or more compounds selected from one or more N,N,N-tri(C1-C4)alkyl-(C5-C7)cycloalkylammonium compounds, preferably one or more N,N,N-tri(C1-C3)alkyl-(C5-C6)cycloalkylammonium compounds, more preferably one or more N,N,N-tri(C1-C2)alkyl-(C5-C6)cycloalkylammonium compounds, more preferably one or more N,N,N-tri(C1-C2)alkyl-cyclopentylammonium and / or one or more N,N,N-tri(C1-C2)alkyl-cyclohexylammonium compounds, more preferably N,N,N-triethyl-cyclohexylammonium, N,N-diethyl-N-methyl-cyclohexylammonium, N,N-dimethyl-N-ethyl-cyclohexylammonium, N,N,N-trimethyl-cyclohexylammonium compounds, and mixtures of two or more thereof, more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The continuous process of any of embodiments 64 to 67, wherein the containing compound comprises one or more N,N-dimethyl-N-ethyl-cyclohexylammonium compounds.

[0181] 69. One or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + -containing compound is preferably one or more salts selected from the group consisting of halides, sulfates, nitrates, phosphates, acetates, and mixtures of two or more thereof, more preferably from the group consisting of bromides, chlorides, hydroxides, sulfates, and mixtures of two or more thereof, more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N +The continuous process according to any of embodiments 64 to 68, wherein the -containing compound is a tetraalkylammonium hydroxide and / or sulfate, and more preferably a tetraalkylammonium hydroxide.

[0182] 70. One or more structure directing agents are selected from the group consisting of one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The mixture containing the SiO2-containing compound prepared in step (i) and heated in step (iii) is a mixture of one or more tetraalkylammonium cations in the framework structure of the first zeolitic material versus the R of SiO2. 1 R 2 R 3 R 4 N + 70. The continuous process according to any one of embodiments 64 to 69, wherein the molar ratio of SiO2 to SiO2 is in the range of 0.05 to 1.5, preferably 0.1 to 0.8, more preferably 0.3 to 0.5, more preferably 0.5 to 0.3, more preferably 0.7 to 0.2, more preferably 0.8 to 0.15, more preferably 0.85 to 0.12, more preferably 0.9 to 0.11, and more preferably 0.95 to 0.1.

[0183] 71. The continuous process according to any of the preceding embodiments, wherein in step (iii), the mixture is heated to a temperature in the range of 70-300°C, preferably 90-280°C, more preferably 120-250°C, more preferably 140-230°C, more preferably 160-220°C, more preferably 180-210°C, and more preferably 190-200°C.

[0184] 72. The zeolitic material further comprises TiO2 in its framework structure, the mixture in step (i) further comprises one or more sources of TiO2, and the one or more structure directing agents are preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + -containing compounds,1 , R 2 , R 3 and R 4 43. The continuous process of any of the preceding embodiments, wherein each independently represents alkyl.

[0185] 73. The continuous process according to embodiment 72, wherein the zeolitic material obtained in step (iii) 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, preferably the zeolitic material obtained in step (iii) has an MFI- and / or MEL-type framework structure, preferably an MFI-type framework structure.

[0186] 74. The continuous process according to embodiment 72 or 73, wherein the one or more solvents in the mixture prepared in step (i) comprise water, preferably distilled water, more preferably the one or more solvents in the mixture prepared in step (i) comprise water, preferably distilled water.

[0187] 75. The continuous process of embodiment 74, wherein the H2O:SiO2 molar ratio of the one or more Si sources, calculated as water to SiO2 in the mixture prepared in step (i), 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, and more preferably 6.5 to 7.5.

[0188] 76. 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, and 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 , R3 and R 4 76. The continuous process according to any of embodiments 72 to 75, wherein R represents propyl, preferably n-propyl.

[0189] 77. One or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + -containing compounds are, independently of one another, salts, preferably halides, preferably chlorides and / or bromides, more preferably salts selected from the group consisting of chlorides, hydroxides, sulfates, nitrates, phosphates, acetates and mixtures of two or more thereof, more preferably salts selected from the group consisting of chlorides, hydroxides, sulfates and mixtures of two or more thereof, more preferably one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + The continuous process according to any of embodiments 72 to 76, wherein the containing compound is a tetraalkylammonium hydroxide and / or chloride, and more preferably a tetraalkylammonium hydroxide.

[0190] 78. The mixture prepared in step (i) and crystallized in step (iii) contains one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + 78. The continuous process according to any of embodiments 72 to 77, wherein the molar ratio of the -containing compound to the one or more sources of Si, calculated as SiO2, is in the 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.

[0191] 79. The one or more sources of SiO2 are selected from the group consisting of SiO2, 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, the silica gel may be selected 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, the composition comprises one or more compounds selected from the group consisting of silica hydrosol, silicic acid, colloidal silica, silicic acid esters, tetraalkoxysilanes, and mixtures of two or more thereof; More preferably, the one or more sources of SiO2 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 sources of SiO2 comprise tetramethoxysilane and / or tetraethoxysilane, preferably tetraethoxysilane; and more preferably, the one or more sources of Si are tetramethoxysilane and / or tetraethoxysilane, preferably tetraethoxysilane.

[0192] 80. The continuous process according to any of embodiments 72 to 79, wherein the one or more sources of Ti comprise one or more compounds selected from the group consisting of titanium oxide, titanium salts, titanyl compounds, titanic acids, titanic acid 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 and / or tetraethyl orthotitanate, more preferably tetraethyl orthotitanate.

[0193] 81. The continuous process according to any of embodiments 72 to 80, wherein the SiO2:TiO2 molar ratio of the one or more sources of SiO2, calculated as SiO2, to the one or more sources of TiO2, calculated as TiO2, of the mixture prepared in step (i) 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, and more preferably 35 to 40.

[0194] 82. The continuous process according to any of embodiments 72 to 81, 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, and more preferably 170 to 180°C.

[0195] 83. The continuous process according to any of embodiments 72 to 82, 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, and more preferably 85 to 95°C.

[0196] 84. The continuous process according to any of embodiments 72 to 83, wherein prior to step (ii), the mixture prepared in step (i) is aged for a period 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, and more preferably from 1.25 to 1.75 hours.

[0197] 85. The following steps: (iv) concentrating the zeolitic material obtained in step (iii), preferably by filtration, more preferably by membrane filtration, and more preferably by cross-flow filtration; and / or, preferably, and (v) washing the zeolitic material obtained in step (iii) or (iv) with a liquid comprising one or more solvents; and / or, preferably, and (vi) drying the zeolitic material obtained in step (iii), (iv) or (v); and / or, preferably, and (vii) calcining the zeolitic material obtained in step (iii), (iv), (v) or (vi). 85. The continuous method of any of the preceding embodiments, further comprising:

[0198] 86. The continuous process according to embodiment 85, wherein the concentration in step (iv) and the washing in step (v) are carried out simultaneously in two or more successive stages of membrane filtration, preferably 2 to 10 stages, more preferably 3 to 8 stages, more preferably 3 to 7 stages, more preferably 4 to 6 stages, and more preferably 4 to 5 stages, and the retentate of one stage of membrane filtration is diluted with a liquid comprising one or more solvents when fed to the subsequent stage.

[0199] 87. The continuous process according to embodiment 86, in which the permeate of one stage of membrane filtration, comprising a portion of the one or more structure-directing agents from the mixture continuously prepared in step (i), is continuously recycled to step (i).

[0200] 88. The continuous process according to any of embodiments 85 to 87, wherein the membrane filtration is carried out at a pressure in the range of 0.2 to 60 bar, preferably 0.5 to 20 bar, more preferably 1 to 15 bar, more preferably 3 to 12 bar, and more preferably 5 to 8 bar.

[0201] 89. The continuous process according to any of embodiments 85 to 88, wherein the membrane filtration is carried out at a temperature in the range of 20 to 200°C, preferably 50 to 150°C, more preferably 80 to 120°C, more preferably 90 to 110°C, and more preferably 97 to 103°C.

[0202] 90. A continuous process according to any of embodiments 85 to 89, wherein the membrane filtration is cross-flow filtration.

[0203] 91. The continuous process according to embodiment 90, wherein the cross-flow filtration is carried out in one or more sequential cross-flow filtration units, preferably in 1 to 10 sequential cross-flow filtration units, more preferably in 2 to 9 sequential cross-flow filtration units, more preferably in 3 to 8 sequential cross-flow filtration units, more preferably in 4 to 6 sequential cross-flow filtration units, and more preferably in 4 to 5 sequential cross-flow filtration units.

[0204] 92. The continuous process according to embodiment 91, wherein each of the one or more sequentially consecutive cross-flow filtration units comprises 10 to 10,000 tubes, preferably 250 to 7,500 tubes, more preferably 500 to 5,000 tubes, more preferably 750 to 2,500 tubes, and more preferably 975 to 1025 tubes.

[0205] 93. The continuous process according to embodiment 92, wherein the inner diameter of the tube is in the range of 2 to 25 mm, preferably 3 to 20 mm, more preferably 4 to 15 mm, more preferably 5 to 10 mm, and more preferably 5.5 to 6.5 mm.

[0206] 94. The continuous process according to any of embodiments 85 to 93, wherein in step (v) 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, and more preferably water, preferably deionized water, is used as the liquid.

[0207] 95. The continuous process according to any of embodiments 85 to 94, wherein the drying in step (vi) 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, and more preferably 110 to 130°C.

[0208] 96. The continuous process according to any of embodiments 85 to 95, wherein drying the zeolitic material in step (vi) comprises spray drying the zeolitic material obtained in step (iii), (iv) or (v).

[0209] 97. The continuous process according to embodiment 96, wherein the spray drying is carried out using a drying gas having a temperature in the range of 100 to 500°C, preferably 150 to 450°C, more preferably 200 to 400°C, more preferably 250 to 350°C, and more preferably 275 to 325°C.

[0210] 98. A zeolitic material obtainable and / or obtained by the method according to any one of embodiments 1 to 97.

[0211] 99. The zeolitic material has a CHA-framework structure, preferably the zeolitic material is selected from the group consisting of Wilhendersonite, ZYT-6, SAPO-47, Na-chabazite, chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-chabazite, MeAPSO-47, Phi, DAF-5, UiO-21, |Li-Na|[Al-Si-O]-CHA, (Ni(deta)2)-UT-6, SSZ-13, and SSZ-62, and mixtures of two or more thereof, more preferably ZYT-6, SAPO-47, Na-chabazite, chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-chabazite, Ph 99. The zeolitic material according to embodiment 98, wherein the zeolitic material is selected from the group consisting of chabazite, Linde D, Linde R, SAPO-34, SSZ-13, and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, SSZ-13, and SSZ-62, and mixtures of two or more thereof, more preferably from the group consisting of chabazite, SSZ-13, and SSZ-62, and mixtures of two or three thereof; more preferably the zeolitic material comprises chabazite and / or SSZ-13, preferably SSZ-13, and more preferably the zeolitic material is chabazite and / or SSZ-13, preferably SSZ-13.

[0212] 100. The zeolitic material according to embodiment 98 or 99 is used as a molecular sieve, as an adsorbent, for ion exchange or as a catalyst and / or catalyst support, preferably as a catalyst and / or catalyst support, to remove nitrogen oxides NOx for selective catalytic reduction (SCR) of CO2, for storage and / or adsorption of CO2, for oxidation of NH3, in particular for oxidation of NH3 slip in diesel systems, for decomposition of N2O, as additives in fluid catalytic cracking (FCC) processes and / or as catalysts and / or catalyst supports, in organic conversion reactions, preferably in the conversion of alcohols to olefins and more preferably in methanol to olefins (MTO) catalysis, more preferably in the decomposition of nitrogen oxides NO x and more preferably for selective catalytic reduction (SCR) of nitrogen oxides NO in exhaust gases from combustion engines, preferably diesel engines or lean-burn gasoline engines. x A method for selective catalytic reduction (SCR) of

[0213] 101. The zeolitic material of embodiment 98, wherein the zeolitic material has an MFI-type framework structure, and the zeolitic material having an MFI-type framework structure comprises TS-1, more preferably the zeolitic material is TS-1.

[0214] 102. The zeolitic material according to embodiment 98 or 101 is used as a molecular sieve, as an adsorbent, for ion exchange, or as a catalyst and / or catalyst support, preferably as a catalyst and / or catalyst support, in reactions involving C-C bond formation and / or conversion, and preferably as a catalyst and / or catalyst support, in isomerization reactions, in ammoxidation reactions, in amination reactions, in hydrocracking reactions, in alkylation reactions, in acylation reactions, in reactions for the conversion of alkanes to olefins or in reactions for the conversion of one or more oxygenates to olefins and / or aromatics, of hydrogen peroxide. in reactions for the synthesis of, in aldol condensation reactions, in reactions for the isomerization of epoxides, in transesterification reactions or in epoxidation reactions, preferably as a catalyst and / or catalyst support in reactions for the epoxidation of olefins, more preferably in reactions for the epoxidation of C2-C5 alkenes, more preferably in reactions for the epoxidation of C2-C4 alkenes, for the epoxidation of C2 or C3 alkenes, more preferably in reactions for the epoxidation of C3 alkenes and more preferably for the conversion of propylene to propylene oxide as a catalyst. EXAMPLES

[0215] The present invention will be further illustrated by the following examples and reference examples.

[0216] Reference Example 1: Preparation of seed crystals having a CHA-skeleton structure 194.5 g of deionized water and 943.1 g of 1-adamantyltrimethylammonium hydroxide (AdaTMAOH) solution (20.17 wt.% aqueous solution obtained from BASF) were placed in a flask and treated with 86.4 g of sodium hydroxide solution (50 wt.% aqueous solution) to obtain a clear solution. 28.1 g of aluminum hydroxide (obtained from Sigma Aldrich) were then added stepwise and the resulting mixture was stirred at room temperature for 30 minutes to obtain a milky solution. 901.3 g of Ludox SM30 (30 wt.% SiO2 suspension in water obtained from Sigma Aldrich) were then added with stirring, during which the viscosity of the mixture increased. The suspension, showing a molar ratio of SiO2:Al(OH)3:NaOH:AdaTMAOH of 1:0.04:0.24:0.20, was stirred at room temperature for another 30 minutes.

[0217] The reaction mixture was then placed in a 2.5 L autoclave and heated to 160° C. with stirring (200 rpm) over 45 minutes and then held at that temperature for 120 minutes. The maximum pressure measured inside the autoclave during the reaction was 0.5 MPa (5 bar). After synthesis, the suspension was filtered and the solid product was washed with distilled water. The filter cake (214.8 g) was dried overnight in a circulating air oven at 120° C. to give a crystalline product.

[0218] The framework structure was determined to be CHA-type by X-ray diffraction pattern. The crystallinity was calculated to be 52% based on the X-ray diffraction diagram of the sample. The volume average particle size D50 determined by ISO13320:2009 was 150 μm, and the particle sizes D10 and D90 were 12 μm and 504 μm, respectively.

[0219] Elemental analysis of the product gave C: 15.7%, Al: 2.3%, Na: 0.37%, and Si: 34%.

[0220] Reference Example 2: Preparation of synthesis gel for the continuous synthesis of zeolite materials with CHA-type framework structure 423.3 g of an aqueous solution of cyclohexyltrimethylammonium hydroxide (CHTMAOH) (20 wt.% aqueous solution from BASF) and 123.7 g of an aqueous solution of tetramethylammonium hydroxide (TMAOH) (25 wt.% aqueous solution obtained from Sachem) were placed in a 2 L four-neck round-bottom flask. 16.9 g of aluminum hydroxide (obtained from Wako) was then added stepwise and the resulting mixture was stirred at room temperature for 45 minutes to obtain a white suspension. 450.0 g of Ludox AS40 (40 wt.% SiO2 suspension in water obtained from Grace) was then added with stirring and the resulting mixture was stirred for another 15 minutes. Then 18.0 g of the crystalline product from Reference Example 1 was added and the resulting mixture, having a molar ratio of SiO2:Al(OH)3:CHTMAOH:TMAOH:HO=1:0.072:0.177:0.113:13, was heated to 85°C and stirred (270 rpm) at that temperature overnight to give an aged gel.

[0221] Example 1: Simulation of a continuously operated reactor The preparation of zeolitic materials with CHA framework structure was simulated by computational fluid dynamics (CFD) using Fluent®.

[0222] The synthetic gel according to Reference Example 2 was considered in the simulation.

[0223] Generally, the formation of chabazite starts from an aqueous mixture whose viscosity decreases during heating. Further heating induces a transition to a gel phase that exhibits non-Newtonian behavior. Viscosity was therefore assumed as an indicator of reaction progress. As the zeolite formation progresses, the rheology changes back to Newtonian and the viscosity drops significantly. Previous experiments have shown this to occur a few hours after start-up. The results of the experiment are shown in Figure 1.

[0224] The linear increase on the semi-logarithmic chart was assumed to be a first-order simple reaction of the type r=-k*[gel].

[0225] Table 1 lists the parameters set for the simulation.

[0226] [Table 1]

[0227] A CFD simulation was set up to determine the actual shear rate in the tubular reactor in pulsating mode (also called "Piff-Paff" mode, after the sound of the flow control valve) to understand the shear rate required for stable operation. The reactor setup is described in detail in Example 1b) of WO2021 / 122533A1. The feed is modeled as an aqueous fluid. This fluid is converted to a gel via the reaction kinetics shown above. In the CFD simulation tool, the aqueous feed is modeled as water. The gel is defined with the same material properties as water, except for the non-Newtonian rheology.

[0228] As an experimental setup, the reactor was simulated to be filled with an inert oil filling. The pressurized tank, which is usually installed upstream of the heated reactor, can be omitted in the simulation and the feed is applied directly to the inlet of the tubular reactor. The "Piff-Paff" mode is modeled as an alternating flowing and no-flowing inlet boundary condition.

[0229] The flow rate in open valve (flow) mode was based on an average flow rate of 300 mL / h. In actual operation, flow was only applied for 0.5 seconds, and for 39.5 seconds the inlet and outlet were blocked and no flow passed through the system. This means that the actual flow rate during the short open flow period was 80 times the time averaged flow rate. For the given system, this results in an actual flow rate of 0.11 m / s.

[0230] In the first section, the boundary conditions for the feed flow were set. The inlet had a constant inlet velocity, here 0.11 m / s (set directly in Fluent®), and the outlet was a pressure outlet. This condition was held for 0.5 seconds while running the simulation with a time step of 0.05 seconds. Then, a no-flow condition was set with walls at both the inlet and outlet. This condition was held for 39.5 seconds with a simulation time step of 0.5 seconds.

[0231] The key results of the simulation are shown in Figure 2-3. The flowing condition (open valve) is shown in Figure 2, and the no-flow condition (closed valve) is shown in Figure 3. For each situation, the gel mass fraction and the corresponding viscosity are shown. As can be seen in Figure 2-3, the transition from the feed to the gel phase already occurs at the 90° bend in the feed pipe. Shear rate 220 s -1 was found to be preferred.

[0232] When the mixture is moving, the viscosity is moderate, but when the valve is closed and the mixture is at rest, the viscosity increases significantly, due to the non-Newtonian nature of the gel (here shear thinning).

[0233] An option to overcome this challenge is the application of a pulsator device. The pulsator does not affect the mass flow but keeps the liquid moving back and forth inside the tubular reactor. Due to non-Newtonian rheology, CFD methods were used to design such pulsators. In one study, it was investigated whether the modeled system could be simplified. It was then tested whether the shear rates obtained in the simulation of the complete tubular reactor could be reproduced in a model of a short tube. This test was successful and some results are summarized in Table 2.

[0234] [Table 2]

[0235] By including non-Newtonian rheology in the simplified tube test, the optimum shear rate can be obtained. The pulsator simulation allows the required pulsation rate profile to be identified. This information can be used in the design of the pulsator and its operation, e.g. size, pass and frequency. Shear rate 220 sec -1 is the reactor tube diameter of 6.2 mm and the gel flow rate of 3.3 × 10 -6 m 3 / s. A pulsator is required to provide this velocity. For a given pipe diameter, the pulsator size, path length and frequency can be determined. Two pulsator systems are considered and their calculated frequencies are shown in Table 3.

[0236] [Table 3]

[0237] In summary, it was found that the preparation of zeolitic materials in a tubular reactor operated semi-continuously with an alternating flow pattern ("Piff-Paff" mode) allows for stable zeolite conversion, while a slow constant flow rate seems to cause problems such as blocking of the reactor.

[0238] Prior art cited: - US2016 / 0115039A1 - Liu et al., Angew. Chem. Int. Ed. 2015, 54, 5683-5687 - Ju, J. et al., Chemical Engineering Journal, 2006, 116, pp. 115-121 - Vandermeersch, T. et al., Microporous and Mesoporous Materials, 2016, 226, 133-139 - Liu, Z. et al., Chemistry of Materials, 2014, 26, pp. 2327-2331 - Slangen et al., "Continuous Synthesis of Zeolites using a Tubular Reactor", 12th International Zeolite Conference, Materials Research Society, 1999 - Bonaccorsi, L. et al., Microporous and Mesoporous Materials, 2008, 112, 481-493 - US2001 / 0054549A1 - WO2020 / 109292A1 - WO2020 / 025799A - WO2019 / 101854A

Claims

1. A continuous method for producing a zeolite material containing SiO ２ in a skeletal structure, comprising: (i) A step of continuously preparing a mixture containing one or more solvents, one or more structure-directing agents, and one or more sources of SiO ２ ; (ii) continuously feeding the mixture prepared in step (i) into one or more continuous flow reactors, and (iii) heating the mixture in the one or more continuous flow reactors to continuously obtain a zeolite material containing SiO ２ in its framework structure comprising a method wherein the mixture contained in the one or more continuous flow reactors is subjected to a pulsating flow regime.

2. The continuous method according to claim 1, wherein in step (ii), the mixture continuously prepared in step (i) is continuously fed into the one or more continuous flow reactors at a rate of 10 to 2,000 kg / h.

3. The continuous method according to claim 1 or 2, wherein in step (ii), the mixture continuously prepared in step (i) is continuously fed into 1 to 10 continuous flow reactors.

4. The continuous method according to claim 1 or 2, wherein the pulsating flow regime is achieved by a semi-continuous flow regime in the general direction of the flow or in the general direction of the flow and the opposite direction thereof, and the general direction of the flow is defined by the inlet end of each of the one or more continuous flow reactors into which the mixture prepared in step (i) is continuously fed and the outlet end of each of the one or more continuous flow reactors from which the zeolite material obtained in step (iii) is continuously recovered.

5. The continuous method according to claim 4, wherein the pulsating flow regime is achieved by a pulsating motion in the general direction of the flow or in the general direction of the flow and the opposite direction thereof.

6. The frequency of the pulse is in the range of 0.001 to 1 second －１ The continuous method according to claim 5, wherein the range is as defined above.

7. The continuous method according to claim 1 or 2, wherein in step (iii), the mixture is heated to a temperature in the range of 90 to 280 °C.

8. The continuous method according to claim 1 or 2, wherein in step (iii), the mixture is heated under autogenous pressure.

9. The continuous method according to claim 1 or 2, wherein in step (ii), the mixture prepared in step (i) is continuously fed into the one or more continuous flow reactors for a period in the range of 5 to 365 days.

10. The continuous method according to claim 1 or 2, wherein each of the one or more continuous flow reactors is selected from a tubular reactor, a ring reactor, and a continuous vibration reactor.

11. The zeolite material further contains X in its framework structure ２ O ３ wherein X represents a trivalent element, and the mixture in step (i) further contains one or more sources of X ２ O ３ The continuous process according to claim 1 or 2.

12. The continuous method according to claim 11, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof.

13. The zeolite material further contains TiO in its framework structure ２ and the mixture in step (i) further contains one or more sources of TiO ２ The continuous process according to claim 1 or 2

14. A zeolite material obtainable and / or obtained by the method according to claim 1 or 2.

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

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