Method for producing a molded article containing zinc and titanium-containing zeolite

Abstract

A method for producing a molded product is provided that can be applied to any type of titanium-containing zeolite material having an MWW framework. [Solution] The method includes: (i) preparing a shaped article containing a titanium-containing zeolite material having a framework MWW; (ii) preparing an aqueous suspension containing a zinc source and the shaped article containing the titanium-containing zeolite material having a framework MWW prepared in (i); (iii) heating the aqueous suspension prepared in (ii) under autogenous pressure to a temperature of the liquid phase of the aqueous suspension in the range of 100 to 200°C to obtain an aqueous suspension containing zinc and the shaped article containing the titanium-containing zeolite material having a framework MWW; and (iv) separating the shaped article containing zinc and the titanium-containing zeolite material having a framework MWW from the liquid phase of the suspension obtained in (iii).

Description

[Technical Field]

[0001] The present invention is directed to a process for the preparation of a shaped article comprising a zinc- and titanium-containing zeolitic material, wherein the zeolitic framework structure of the zeolitic material has framework type MWW. Furthermore, the present invention relates to a shaped article obtained or obtained by said process, as well as to the use of said shaped article as a catalyst. [Background technology]

[0002] TiMWW catalysts, e.g., ZnTiMWW catalysts, i.e., catalysts comprising a titanium-containing zeolite material with a framework MWW and further comprising zinc, are known to be excellent catalysts for propene epoxidation. Such catalysts are typically prepared by a synthesis process that includes a shaping step, such as an extrusion process, to produce moldings suitable for use in industrial-scale processes such as the epoxidation process described above. The shaping process typically begins with a zinc-containing zeolite material. Methods for producing such moldings are disclosed, for example, in WO 2013 / 117536A, and have resulted in catalysts exhibiting the best properties for their preferred application, i.e., as epoxidation catalysts. As described in WO 2013 / 117536A, this process is a multi-step process, and the shaping process is based on a powder of the zinc-containing zeolite material. Therefore, the shaping process is preferably designed based on the properties of the powder. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] WO2013 / 117536A [Patent Document 2] WO2015 / 010990A Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, although the catalysts described in WO 2013 / 117536A exhibit excellent properties, there was a need to provide a molding method that can be applied to all types of titanium-containing zeolite materials with framework MWW. Furthermore, there was a certain desire to provide a more economical method than the method described in WO 2013 / 117536A. Surprisingly, it was found that by incorporating zinc into the moldings during the molding process, it was possible to arrive at catalysts that, when used, for example, as epoxidation catalysts, have the same or even improved properties compared to the moldings of WO 2013 / 117536A. Furthermore, it was found that by doing so, it was possible to eliminate one step of the multi-stage method of WO 2013 / 117536A, thus making the overall process more economical. This is a highly advantageous feature, particularly for production methods in technical fields where the respective obtained products are commercial products used in industrial-scale processes, such as, for example, in the case of epoxidation catalysts. [Means for solving the problem]

[0005] The present invention therefore provides a method for producing a molding comprising zinc and a titanium-containing zeolitic material having framework type MWW, comprising the steps of: (i) providing a molded article comprising a titanium-containing zeolite material having a framework type MWW; (ii) preparing an aqueous suspension comprising a zinc source and a molding comprising the titanium-containing zeolite material having framework type MWW prepared in (i); (iii) heating the aqueous suspension prepared in (ii) under autogenous pressure to a liquid phase temperature of the aqueous suspension in the range of 100 to 200°C to obtain an aqueous suspension containing extrudates containing zinc and a titanium-containing zeolite material having a framework type MWW; (iv) separating from the liquid phase of the suspension obtained in (iii) a shaped product comprising zinc and a titanium-containing zeolitic material having a framework type MWW. The present invention relates to a manufacturing method comprising the steps of: DETAILED DESCRIPTION OF THE INVENTION

[0006] Process (i) Generally, the shaped product prepared in (i) can consist of a titanium-containing zeolitic material having a framework type MWW. The shaped product preferably comprises a binder in addition to the titanium-containing zeolitic material having a framework type MWW. In addition to the binder and the titanium-containing zeolitic material having a framework type MWW, the shaped product may also comprise one or more additional components. Preferably, at least 90% by weight, more preferably at least 95% by weight, even more preferably at least 99% by weight, and even more preferably at least 99.9% by weight of the shaped product prepared in (i) consists of the titanium-containing zeolitic material having a framework type MWW and the binder. More preferably, apart from impurities that may be contained in the binder and / or the titanium-containing zeolitic material having a framework type MWW, the shaped product does not contain any additional components, and therefore the shaped product essentially consists of, and more preferably consists of, the binder and the titanium-containing zeolitic material having a framework type MWW. The mass ratio of the titanium-containing zeolite material having a framework type MWW to the binder in the molded article prepared in (i) is not subject to any particular limitation. For example, the mass ratio can be in the range of 0.01:1 to 100:1 or 0.1:1 to 10:1. This mass ratio is preferably in the range of 1:1 to 9:1, more preferably in the range of 2:1 to 7:1, and even more preferably in the range of 3:1 to 5:1. The chemical nature of the binder is not subject to any particular limitation, but the binder preferably comprises a silica binder, and more preferably is a silica binder.

[0007] Therefore, it is preferred that at least 99.9% by mass of the formed article provided in (i) consists of a titanium-containing zeolite material having framework MWW and a silica binder.

[0008] The shape of the molded product provided in (i) is not subject to any particular limitation. Preferably, the molded product provided in (i) is in the form of a tablet, sphere, cylinder, star, strand, or trilob, where the molded product is preferably a strand, more preferably an extruded strand, and preferably has a rectangular, triangular, hexagonal, square, elliptical, or circular cross section. The diameter of the suitable circular cross section is preferably in the range of 0.2 to 5.0 mm, more preferably in the range of 0.5 to 3.5 mm, and even more preferably in the range of 1.0 to 2.0 mm.

[0009] Preferably, the formed product provided in (i) is a calcined formed product, wherein the calcination is preferably carried out at a temperature in a gas atmosphere in the range of 350 to 650° C., more preferably in the range of 400 to 600° C., more preferably in the range of 450 to 550° C. Here, suitable gas atmospheres include air, lean air, or nitrogen such as technical nitrogen, more preferably air.

[0010] Preferably, the molded article provided in (i) exhibits one or more of the following properties (1) to (3), preferably two or more of the following properties (1) to (3), more preferably the following properties (1) to (3): (1) At least 300 m, measured as described in Reference Example 1 of this specification 2 BET specific surface area in / g; (2) a pore volume of at least 0.9 mL / g, measured as described in Reference Example 2 herein; (3) A mechanical strength in the range of 5 to 10 N, preferably in the range of 6 to 9 N, measured as described in Reference Example 3 of the present specification.

[0011] Therefore, it is preferable that at least 99.9% by mass of the molded product prepared in (i) is composed of a titanium-containing zeolite material having a framework MWW and a silica binder, and that the molded product exhibits the above properties (1) to (3).

[0012] The method for preparing the molded product provided in (i) is not particularly limited. A preferred method for producing the molded product is (i.1) preparing a mixture comprising a titanium-containing zeolite material having framework type MWW, a binder or binder source, a pasting agent, and optionally a pore former; (i.2) shaping the mixture prepared in (i.1) to obtain a molding comprising a titanium-containing zeolite material having framework type MWW and a binder or a binder source; (i.3) Drying the extrusions obtained in (i.2); (i.4) Calcining the dried molded product obtained in (i.3) to obtain a molded product containing a titanium-containing zeolite material having an MWW framework and a binder. Includes.

[0013] Preferably, the paste according to (i) comprises water and one or more hydrophilic polymers, more preferably water and one or more carbohydrates, even more preferably water and carbohydrates. The carbohydrate preferably comprises one or more cellulose and cellulose derivatives, more preferably one or more cellulose and cellulose derivatives, more preferably one or more cellulose, cellulose ethers, and cellulose esters, even more preferably one or more cellulose, cellulose ethers, and cellulose esters, more preferably cellulose ethers, more preferably cellulose alkyl ethers, even more preferably methylcellulose, even more preferably cellulose ethers, more preferably cellulose alkyl ethers, and even more preferably methylcellulose. Therefore, the paste according to (i.1) preferably comprises water and methylcellulose, even more preferably water and methylcellulose.

[0014] If the mixture prepared in (i.1) includes a pore-forming agent, it is preferred that the pore-forming agent comprises a mesopore-forming agent, preferably a mesopore-forming agent, which is preferably one or more polyalkylene oxides, such as polyethylene oxide, polystyrene, polyacrylate, polymethacrylate, polyolefin, polyamide, polyester. Polyethylene oxide is preferred, where the average molecular weight MW (g / mol) may be in the range of 100,000 to 6,000,000, for example about 4,000,000.

[0015] The binder or binder precursor of the mixture prepared in (i.1) preferably contains a silica binder or a silica binder precursor, more preferably a silica binder or a silica binder precursor. Regarding the silica binder precursor, it is generally possible to use both colloidal silica and so-called "wet process" silica and so-called "dry process" silica. Particularly preferably, the silica is amorphous silica, with a silica particle size in the range of, for example, 1 to 100 nm and a surface area of ​​50 to 500 m. 2 / g. Colloidal silica, preferably as an alkaline and / or ammoniacal solution, more preferably as an ammoniacal solution, is commercially available, for example, under the trade names Ludox®, Syton®, Nalco®, or Snowtex®, among others. "Wet process" silica is commercially available, for example, under the trade names Hi-Sil®, Ultrasil®, Vulcasil®, Santocel®, Valron-Estersil®, Tokusil®, or Nipsil®, among others. "Dry process" silica is commercially available, for example, under the trade names Aerosil®, Reolosil®, Cab-O-Sil®, Fransil®, or ArcSilica®, among others. Among these, ammoniacal solutions of colloidal silica are preferred in the present invention. Preferably, according to the present invention, the precursor of the silica binder contained in the mixture according to (i.1) comprises one or more of silica gel, precipitated silica, fumed silica, and colloidal silica, more preferably one or more of silica gel, precipitated silica, fumed silica, and colloidal silica. More preferably, the precursor of the silica binder contained in the mixture according to (i.1) comprises colloidal silica, more preferably colloidal silica. More preferably, the precursor of the silica binder contained in the mixture according to (i.1) consists of colloidal silica, where more preferably the silica binder or precursor comprises colloidal silica, preferably colloidal silica.

[0016] In the mixture prepared in (i.1), the mass ratio of the titanium-containing zeolitic material with framework MWW to the silica contained in the binder or binder precursor is preferably in the range of 1:1 to 9:1, more preferably in the range of 2:1 to 7:1, and even more preferably in the range of 3:1 to 5:1.

[0017] The mixture prepared in (i.1) is preferably free of zinc, neither in the binder nor in the titanium-containing zeolitic material having framework type MWW, nor in any other component of the mixture. The term "free of zinc" does not exclude minimal amounts of zinc that may be present in the mixture due to unavoidable impurities in one or more components of the mixture.

[0018] Preferably, at least 99% by weight, preferably at least 99.5% by weight, more preferably at least 99.9% by weight of the mixture prepared in (i.1) consists of titanium-containing zeolitic material with framework type MWW, binder or binder precursor, and pasting agent.

[0019] Preferably, preparing the mixture according to (i.1) includes mechanically stirring, more preferably kneading, the mixture until the individual components of the mixture, which are added in the proper order, come together to form a homogeneous mass.

[0020] The shaping according to (i.2) preferably involves extruding the mixture prepared in (i.1). There are no particular limitations regarding the extrusion according to (i.2). Generally, any method for extruding the mixture obtained from (i.1) can be used. The term "extrusion" as used herein refers to a method for obtaining a molded product having an essentially fixed cross-sectional shape, in which the composition obtained from (iv) is extruded through a suitable die exhibiting the desired cross-section. The molded products obtained from the extrusion device used can be cut downstream of the die, for example, using a suitable air stream and / or a mechanical cutting device such as a suitable wire. If it is not necessary to obtain molded products of essentially the same length, it is also possible to obtain molded products of different lengths by allowing the molded products obtained from the extrusion device to break under their own weight downstream of the die without cutting. The cross-section of the molded product can be, for example, circular, elliptical, star-shaped, etc. According to the present invention, the molded product preferably has a circular cross-section, and its diameter is preferably in the range of 0.2 to 5.0 mm, more preferably 0.5 to 3.5 mm, and even more preferably 1.0 to 2.0 mm.

[0021] Preferably, the extrusion is dried according to (i.3). Drying is preferably carried out in a gas atmosphere at a gas atmosphere temperature in the range of 80 to 200° C., more preferably in the range of 90 to 175° C., more preferably in the range of 100 to 150° C. Any suitable gas atmosphere can be used, with suitable gas atmospheres including air, lean air, or nitrogen, such as technical nitrogen.

[0022] Preferably, according to (i.4), the dried shaped product obtained from (i.3) is calcined. Calcination is preferably carried out in a gas atmosphere, preferably at a gas atmosphere temperature in the range of 350 to 650° C., more preferably in the range of 400 to 600° C., more preferably in the range of 450 to 550° C. Any suitable gas atmosphere can be used, and suitable gas atmospheres include air, diluted air, or nitrogen, such as technical nitrogen.

[0023] There are no specific limitations on the chemical composition of the titanium-containing zeolitic material having a framework MWW contained in the molded article prepared in (i). Thus, in addition to Ti, Si, O, and H, the zeolitic material may contain additional framework and / or extra-framework elements, such as one or more trivalent, one or more tetravalent, and / or one or more pentavalent framework elements, such as Al, In, Ga, B, Ge, and Sn. It is preferred that at least 95% by weight, more preferably at least 98% by weight, and more preferably at least 99% by weight of the titanium-containing zeolitic material having a framework MWW contained in the molded article prepared in (i) be composed of Ti, Si, O, and H. In this case, the framework of the zeolitic material preferably consists essentially of Ti, Si, and O. The titanium content of the titanium-containing zeolitic material having a framework MWW contained in the molded article prepared in (i) is not subject to any specific limitations. Preferably, the titanium-containing zeolitic material having a framework MWW contained in the molded product prepared in (i) has a titanium content, calculated as elemental titanium, in the range of 0.1 to 5 mass %, more preferably 0.5 to 3 mass %, and more preferably 1 to 3 mass %, based on the total mass of the titanium-containing zeolitic material having a framework MWW. A suitable range may be 1.5 to 2 mass %. Preferably, the titanium-containing zeolitic material having a framework MWW contained in the molded product prepared in (i) has a silicon content, calculated as elemental silicon, in the range of 30 to 60 mass %, preferably 35 to 55 mass %, more preferably 40 to 50 mass %, and more preferably 1 to 3 mass %, based on the total mass of the titanium-containing zeolitic material having a framework MWW. A suitable range may be 44 to 48 mass %. Therefore, the titanium-containing zeolite material with framework MWW contained in the formed product prepared in (i) preferably has a titanium content in the range of 1 to 3 mass % and a silicon content in the range of 40 to 50 mass %, and in some cases it may be preferable for the titanium content to be in the range of 1.5 to 2 mass % and the silicon content to be in the range of 44 to 48 mass %.

[0024] Preferably, the titanium-containing zeolitic material with framework MWW contained in the shaped article provided in (i) has a total organic carbon content of at most 0.1% by weight, based on the total weight of the titanium-containing zeolitic material with framework MWW. Preferably, the titanium-containing zeolitic material with framework MWW contained in the shaped article provided in (i) has a boron content, calculated as elemental boron, of at most 0.1% by weight or at most 0.5% by weight, more preferably at most 0.5% by weight, based on the total weight of the titanium-containing zeolitic material with framework MWW. Preferably, the titanium-containing zeolitic material with framework MWW contained in the shaped article provided in (i) has a boron content, calculated as elemental boron, of at least 400m 2 / g, preferably 400 to 600m 2 / g, more preferably 450 to 550 m 2 / g, where the BET specific surface area is measured as described in Reference Example 1 herein. Preferably, the titanium-containing zeolitic material with framework MWW contained in the molded article prepared in (i) has a crystallinity of at least 70%, preferably in the range of 70-90%, more preferably in the range of 70-80%. Here, the crystallinity is measured as described in Reference Example 4 herein. Preferably, the titanium-containing zeolitic material with framework MWW contained in the molded article prepared in (i) is in the form of a powder having a particle size distribution characterized by a Dv10 value in the range of 1 to 10 micrometers, preferably in the range of 1.5 to 10 micrometers, more preferably in the range of 2 to 6 micrometers, a Dv50 value in the range of 5 to 50 micrometers, preferably in the range of 7 to 50 micrometers, even more preferably in the range of 8 to 30 micrometers, and a Dv90 value in the range of 12 to 200 micrometers, preferably in the range of 12 to 90 micrometers, more preferably in the range of 13 to 70 micrometers. The particle size distribution is measured as described in Reference Example 5 of the present specification. The titanium-containing zeolite material having framework type MWW contained in the extruded product prepared in (i) may be a spray powder, i.e., a powder obtained by a spray drying method, or a powder obtained by other methods such as flash drying (which may be microwave drying) that can result in a powder having the above-mentioned suitable particle size distribution.

[0025] According to a preferred embodiment of the present invention, the titanium-containing zeolitic material having framework type MWW contained in the extrusion prepared in (i), for example contained in the mixture prepared in (i.1), is (a) preparing a boron-containing zeolitic material having framework type MWW, wherein at least 99% by weight of the zeolitic framework is composed of B, Si, O, and H; (b) deboronating the boron-containing zeolitic material having framework type MWW prepared in (a) to obtain a deboronated zeolitic material having framework type MWW, wherein at least 99 wt.% of the zeolitic framework of the deboronated zeolitic material consists of B, Si, O, and H, and wherein the zeolitic framework of the deboronated zeolitic material has vacant framework sites; (c) incorporating titanium into the deboronated zeolitic material obtained from (b), which comprises preparing an aqueous synthesis mixture containing the deboronated zeolitic material obtained from (b), a titanium source, and an MWW template compound; and hydrothermally synthesizing a titanium-containing zeolitic material having an MWW framework from the aqueous synthesis mixture prepared in (c), to obtain a mother liquor containing a titanium-containing zeolitic material having an MWW framework; (d) separating the titanium-containing zeolitic material having framework type MWW synthesized in (c) from the mother liquor; (e) treating the separated titanium-containing zeolite material having framework type MWW obtained from (d) with an aqueous solution having a pH of up to 5; (f) separating the titanium-containing zeolitic material having framework MWW obtained from (e) from the aqueous solution, and optionally subsequently washing the separated titanium-containing zeolitic material having framework MWW; (g) preparing a suspension, preferably an aqueous suspension, containing the titanium-containing zeolitic material having framework type MWW obtained from (f) and subjecting the suspension to spray drying; (h) Calcining the titanium-containing zeolite material having framework type MWW obtained from (g). The present invention relates to a method for producing a medicament for the treatment of a medicament comprising the steps of:

[0026] According to a preferred embodiment of the present invention, the step of preparing the titanium-containing zeolitic material having framework MWW contained in the molding prepared in (i) comprises the steps of: (a) preparing a boron-containing zeolitic material having framework type MWW, wherein at least 99% by weight of the zeolitic framework is composed of B, Si, O, and H; (b) deboronating the boron-containing zeolitic material having framework type MWW prepared in (a) to obtain a deboronated zeolitic material having framework type MWW, wherein at least 99 wt.% of the zeolitic framework of the deboronated zeolitic material consists of B, Si, O, and H, and wherein the zeolitic framework of the deboronated zeolitic material has vacant framework sites; (c) incorporating titanium into the deboronated zeolitic material obtained from (b), which comprises preparing an aqueous synthesis mixture containing the deboronated zeolitic material obtained from (b), a titanium source, and an MWW template compound; and hydrothermally synthesizing a titanium-containing zeolitic material having an MWW framework from the aqueous synthesis mixture prepared in (c), to obtain a mother liquor containing a titanium-containing zeolitic material having an MWW framework; (d) separating the titanium-containing zeolitic material having framework type MWW synthesized in (c) from the mother liquor; (e) treating the separated titanium-containing zeolite material having framework type MWW obtained from (d) with an aqueous solution having a pH of up to 5; (f) separating the titanium-containing zeolitic material having framework MWW obtained from (e) from the aqueous solution, and optionally subsequently washing the separated titanium-containing zeolitic material having framework MWW; (g) preparing a suspension, preferably an aqueous suspension, containing the titanium-containing zeolitic material having framework type MWW obtained from (f) and subjecting the suspension to spray drying; (h) Calcining the titanium-containing zeolite material having framework type MWW obtained from (g). Includes.

[0027] According to a preferred embodiment of the present invention, preparing the boron-containing zeolitic material having framework type MWW in (a) comprises: (a.1) preparing an aqueous synthesis mixture comprising a silicon source, a boron source, and a MWW template compound; (a.2) hydrothermally synthesizing a precursor of a boron-containing zeolite material having an MWW framework from the aqueous synthesis mixture prepared in (a.1) to obtain a mother liquor containing a precursor of a boron-containing zeolite material having an MWW framework; (a.3) separating the precursor of the boron-containing zeolitic material having framework MWW from the mother liquor to obtain a separated precursor of the boron-containing zeolitic material having framework MWW; (a.4) Calcining the isolated precursor of the boron-containing zeolitic material having framework MWW to obtain the boron-containing zeolitic material having framework MWW. Includes.

[0028] In the aqueous synthesis mixture prepared in (a.1), the molar ratio of the MWW template compound to Si contained in the silicon source, calculated as elemental silicon, is preferably at least 0.4:1, more preferably in the range of 0.4:1 to 2.0:1, more preferably in the range of 0.6:1 to 1.9:1, and more preferably in the range of 0.9:1 to 1.4:1. In the aqueous synthesis mixture prepared in (a.1), the molar ratio of water to the silicon source, calculated as elemental silicon, is preferably in the range of 1:1 to 30:1, more preferably in the range of 3:1 to 25:1, and more preferably in the range of 6:1 to 20:1. In the aqueous synthesis mixture prepared in (a.1), the molar ratio of the boron source, calculated as elemental boron, to the silicon source, calculated as elemental silicon, is preferably in the range of 0.4:1 to 2.0:1, more preferably in the range of 0.6:1 to 1.9:1, and more preferably in the range of 0.9:1 to 1.4:1. In (a.1), the boron source is preferably one or more of boric acid, borate, and boron oxide, and more preferably boric acid. In (a.1), the silicon source is preferably fumed silica or colloidal silica, more preferably colloidal silica, and even more preferably ammonia-stabilized colloidal silica. In (a.1), the MWW template compound is preferably one or more of piperidine, hexamethyleneimine, N,N,N,N',N',N'-hexamethyl-1,5-pentanediammonium ion, 1,4-bis(N-methylpyrrolidinium)butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, and hexyltrimethylammonium hydroxide, and more preferably piperidine. Preferably, at least 99 wt. %, more preferably at least 99.5 wt. %, and even more preferably at least 99.9 wt. % of the aqueous synthesis mixture prepared in (a.1) consists of water, the boron source, the silicon source, and the MWW template compound.

[0029] In (a.2), the hydrothermal synthesis is preferably carried out at a temperature of the aqueous synthesis mixture in the range of 160 to less than 180°C, more preferably 170 to 177°C. In (a.2), the hydrothermal synthesis is preferably carried out for a time period in the range of 1 to 72 hours, more preferably 6 to 60 hours, and even more preferably 12 to 50 hours. In (a.2), the hydrothermal synthesis is preferably carried out in a closed system under autogenous pressure. The pH of the mother liquor obtained in (a.2) is preferably greater than 10, more preferably at least 10.5, and more preferably at least 11. After (a.2) and before (a.3), the pH of the mother liquor is preferably adjusted to a value in the range of at most 10, more preferably at most 9, more preferably at most 8, and more preferably 7 to 8. The pH of the liquid phase of the mother liquor is preferably adjusted by subjecting the liquid phase of the mother liquor to an acid treatment, where the acid is preferably an inorganic acid, more preferably one or more of phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid, more preferably nitric acid.

[0030] Preferably, the separation according to (a.3) comprises filtering the mother liquor obtained in (a.2), and preferably, the separation according to (a.3) comprises drying, preferably spray drying.

[0031] In (a.4), the isolated precursor of the boron-containing zeolitic material with framework MWW is calcined at a temperature preferably in the range of 400-800°C, more preferably 600-700°C.

[0032] In (b), the boron-containing zeolitic material having framework type MWW prepared in (a) is preferably deboronated by treating the boron-containing zeolitic material having framework type MWW with a liquid solvent system to obtain a deboronated zeolitic material having framework type MWW, wherein preferably at least 99 wt.% of the zeolitic framework of the deboronated zeolitic material consists of B, Si, O, and H, and the zeolitic framework of the deboronated zeolitic material has empty framework sites. Preferably, the molar ratio of boron, calculated as B2O3, to silicon, calculated as SiO2, for the deboronated zeolitic material with framework MWW obtained from (b) is at most 0.02:1, more preferably at most 0.01:1, more preferably in the range of 0.001:1 to 0.01:1, more preferably in the range of 0.001:1 to 0.003:1, wherein preferably at least 99.5% by weight, more preferably at least 99.9% by weight, of the deboronated zeolitic material with framework MWW consists of B, Si, O, and H. In (b), the liquid solvent system is preferably one or more of water, methanol, ethanol, propanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, and propane-1,2,3-triol. Preferably, the liquid solvent system is free of inorganic and organic acids. Prior to (b), the mass ratio of the liquid solvent system to the zeolitic material having a framework MWW is preferably in the range of 5:1 to 40:1, more preferably in the range of 7.5:1 to 30:1, and even more preferably in the range of 10:1 to 20:1. In (b), the treatment with the liquid solvent system is preferably carried out at a liquid solvent system temperature in the range of 50 to 125°C, more preferably in the range of 90 to 115°C, and even more preferably in the range of 95 to 105°C. In (b), the treatment with the liquid solvent system is preferably carried out for a period of 6 to 20 hours, more preferably in the range of 7 to 17 hours, and even more preferably in the range of 8 to 12 hours. In (b), the treatment with the liquid solvent system is preferably carried out in an open system under reflux or in a closed system without reflux. Preferably, (b) includes drying the deboronated zeolitic material having a framework MWW, more preferably by spray drying.Also, the deboronated zeolitic material with framework MWW obtained from (b) is preferably not calcined prior to (c).

[0033] In (c), the MWW template compound is preferably one or more of piperidine, hexamethyleneimine, N,N,N,N',N',N'-hexamethyl-1,5-pentanediammonium ion, 1,4-bis(N-methylpyrrolidinium)butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, and hexyltrimethylammonium hydroxide, more preferably piperidine. In (c), the titanium source is preferably one or more of tetra-n-butyl orthotitanate, tetraisopropyl orthotitanate, tetraethyl orthotitanate, titanium dioxide, titanium tetrachloride, and titanium tert-butoxide, more preferably tetra-n-butyl orthotitanate. In the aqueous synthesis mixture (c), the molar ratio of Ti contained in the titanium source, calculated as TiO, to Si contained in the deboronated zeolitic material having a framework MWW, calculated as SiO, is preferably in the range of 0.005:1 to 0.1:1, more preferably 0.01:1 to 0.08:1, and even more preferably 0.02:1 to 0.06:1. The molar ratio of HO to Si contained in the deboronated zeolitic material having a framework MWW, calculated as SiO, is preferably in the range of 8:1 to 20:1, more preferably 10:1 to 18:1, and even more preferably 12:1 to 16:1. The molar ratio of the MWW template compound to Si contained in the deboronated zeolitic material having a framework MWW, calculated as SiO, is preferably in the range of 0.5:1 to 1.7:1, more preferably 0.8:1 to 1.5:1, and even more preferably 1.0:1 to 1.3:1. In (c), the hydrothermal synthesis is preferably carried out at a temperature in the range of 80 to 250° C., more preferably in the range of 120 to 200° C., more preferably in the range of 160 to 180° C., preferably in a closed system under autogenous pressure. Preferably, the titanium-containing zeolitic material having framework MWW is not separated from its mother liquor during, after, or before (d).

[0034] Preferably, the mother liquor containing the titanium-containing zeolitic material having an MWW framework and subjected to (d) has, after concentration or dilution as necessary, a solids content in the range of 5 to 25 mass %, more preferably in the range of 10 to 20 mass %, based on the total mass of the mother liquor containing the titanium-containing zeolitic material having an MWW framework. Preferably, the separation in (d) comprises spray drying, wherein during the spray drying in (d), the drying gas inlet temperature is preferably in the range of 200 to 700°C, preferably in the range of 200 to 350°C, and the drying gas outlet temperature is preferably in the range of 70 to 190°C.

[0035] In (e), the mass ratio of the aqueous solution to the titanium-containing zeolitic material having a framework MWW is preferably in the range of 10:1 to 30:1, more preferably 15:1 to 25:1, and even more preferably 18:1 to 22:1. The aqueous solution preferably contains an inorganic acid, more preferably one or more of phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid, and even more preferably nitric acid. After (d) and before (e), the separated titanium-containing zeolitic material having a framework MWW obtained from (d) is preferably not calcined. In (e), the aqueous solution preferably has a pH in the range of 0 to 5, more preferably 0 to 3, and even more preferably 0 to 2. In (e), the titanium-containing zeolitic material having a framework MWW is treated with the aqueous solution at a temperature of the aqueous solution preferably in the range of 50 to 175°C, more preferably 70 to 125°C, and even more preferably 95 to 105°C, preferably in a closed system under autogenous pressure.

[0036] The separation of the titanium-containing zeolitic material having a framework MWW according to (f) preferably comprises washing the titanium-containing zeolitic material having a framework MWW. The separation of the titanium-containing zeolitic material having a framework MWW according to (f) preferably comprises drying the titanium-containing zeolitic material having a framework MWW. The separation of the titanium-containing zeolitic material having a framework MWW according to (f) preferably comprises preparing a suspension, preferably an aqueous suspension, containing the titanium-containing zeolitic material having a framework MWW obtained from (e), wherein the suspension has a solids content of preferably 5 to 25% by mass, more preferably 10 to 20% by mass, based on the total mass of the suspension, and subjecting the suspension to spray drying. During spray drying, the drying gas inlet temperature is preferably in the range of 200 to 700°C, more preferably 200 to 330°C, and the drying gas outlet temperature is preferably in the range of 100 to 180°C, more preferably 120 to 180°C.

[0037] The firing in (h) is preferably carried out at a temperature in the range of 400 to 800°C, more preferably in the range of 600 to 700°C.

[0038] Process (ii) In general, there is no particular limitation on the chemical nature of the zinc source used according to formula (ii). Preferably, the zinc source comprises, and more preferably consists of, a zinc compound that is soluble in water, preferably at the temperature and pressure of the liquid aqueous phase according to (iii). More preferably, the zinc source comprises one or more zinc salts of an organic or inorganic acid, preferably one or more of zinc acetate, zinc benzoate, zinc borate, zinc bromide, zinc chloride, zinc formate, zinc gluconate, zinc lactate, zinc laurate, zinc malate, zinc nitrate, zinc perborate, zinc sulfate, zinc sulfamate, and zinc tartrate, more preferably zinc acetate, more preferably zinc acetate dihydrate. More preferably, the zinc source comprises one or more zinc salts of an organic or inorganic acid, preferably one or more of zinc acetate, zinc benzoate, zinc borate, zinc bromide, zinc chloride, zinc formate, zinc gluconate, zinc lactate, zinc laurate, zinc malate, zinc nitrate, zinc perborate, zinc sulfate, zinc sulfamate, zinc tartrate, more preferably zinc acetate, more preferably zinc acetate dihydrate.

[0039] In the aqueous suspension prepared in (ii), the mass ratio of zinc contained in the zinc source to the titanium-containing zeolite material having framework MWW contained in the formed product, calculated as elemental zinc, is preferably in the range of 0.005:1 to 0.1:1, more preferably 0.01:1 to 0.075:1, more preferably 0.02:1 to 0.05:1, and even more preferably 0.03:1 to 0.04:1. Furthermore, in the aqueous suspension prepared in (ii), the mass ratio of the titanium-containing zeolite material having framework MWW contained in the formed product to water is preferably in the range of 0.01:1 to 0.1:1, more preferably 0.02:1 to 0.075:1, and even more preferably 0.03:1 to 0.04:1.

[0040] In general, in addition to water, a zinc source, and a titanium-containing zeolitic material having an MWW framework type, the aqueous suspension may comprise one or more further suitable components. Preferably, at least 99% by weight, more preferably at least 99.5% by weight, and even more preferably at least 99.9% by weight of the aqueous suspension prepared in (ii) consists of shaped articles comprising water, a zinc source, and a titanium-containing zeolitic material having an MWW framework type.

[0041] It is believed that at least a portion of the water contained in the aqueous suspension is ammonia-stabilized water.

[0042] Process (iii) According to (iii), the aqueous suspension prepared in (ii) is preferably heated to a liquid phase temperature of the aqueous suspension in the range of 100 to 190°C, more preferably 110 to 175°C, more preferably 115 to 160°C, and even more preferably 120 to 150°C, and maintained at that temperature. Suitable ranges are, for example, 120 to 130°C, or 125 to 135°C, or 130 to 140°C, or 135 to 145°C, or 140 to 150°C. Preferably, in (iii), the suspension prepared in (ii) is maintained at this temperature for a period of 1 to 24 hours, more preferably 2 to 17 hours, and even more preferably 3 to 10 hours.

[0043] In (iii), it is preferable not to stir the suspension prepared in (ii) during heating, or during holding the temperature, or during heating and holding the temperature.

[0044] Process (iv) In general, there are no particular limitations on how the separation in (iv) is carried out. Preferably, the separation in (iv) comprises filtering or centrifuging the aqueous suspension obtained from (iii), optionally followed by washing, to obtain a separated extrusion containing zinc and the titanium-containing zeolite material with framework MWW. Any type of filter is contemplated, preferably exhibiting a maximum solid material loss of 10% by weight during filtration. Possible filters include, for example, decanters, slotted sieves, and nut-type filters.

[0045] Process (v) The extrusions separated according to (iv) are preferably subjected to drying according to (v). Prior to drying, the extrusions separated according to (iv) may be pre-dried in a suitable gas atmosphere such as nitrogen, air or diluted air at a temperature of the gas atmosphere, preferably at a maximum of 50°C, more preferably at a maximum of 40°C, more preferably at a maximum of 10 to 30°C, more preferably at a temperature of 20 to 30°C.

[0046] Preferably, the separated shaped product containing zinc and the titanium-containing zeolite material having a framework MWW obtained in (iv) is dried at a temperature in the range of 80 to 200°C, more preferably in the range of 90 to 175°C, and more preferably in the range of 100 to 150°C. Preferably, in (v), the shaped product is dried at this temperature for a period in the range of 0.5 to 12 hours, more preferably in the range of 1 to 8 hours, and even more preferably in the range of 2 to 6 hours. Preferably, the separated shaped product containing zinc and the titanium-containing zeolite material having a framework MWW is dried in an oxygen-containing gas atmosphere, preferably in air or diluted air, and more preferably in air. Here, the drying temperature is the temperature of the gas atmosphere used for drying.

[0047] Process (vi) The moldings isolated according to (iv) or obtained by drying according to (v), preferably the moldings obtained by drying according to (v), are preferably calcined according to (vi).

[0048] Preferably, a dried shaped product containing zinc and a titanium-containing zeolite material having a framework MWW is calcined at a temperature in the range of 300 to 600°C, more preferably 350 to 550°C, and more preferably 400 to 500°C. When calcination is performed by a batch process, it may be preferable to perform the calcination for a period of 0.1 to 6 hours, more preferably 0.2 to 4 hours, and more preferably 0.5 to 3 hours. Calcination can also be performed by a continuous method using, for example, a rotary kiln or a band calciner. Preferably, a dried shaped product containing zinc and a titanium-containing zeolite material having a framework MWW is calcined in an oxygen-containing gas atmosphere, preferably air or diluted air, and more preferably air. Here, the calcination temperature is the temperature of the gas atmosphere used for calcination.

[0049] According to the invention, it is preferred that the moldings are not water-steamed, more preferably not steamed, during all process steps.

[0050] Moldings and their uses Furthermore, the present invention relates to a shaped article comprising zinc and a titanium-containing zeolitic material with framework type MWW, which is obtainable or obtained by the process as described above, preferably by the process as described above comprising drying according to (v), more preferably by the process comprising calcining according to (vi), more preferably by the process comprising drying according to (v) and calcining according to (vi).

[0051] The present invention also relates to a shaped article containing zinc and a titanium-containing zeolite material having a framework MWW, wherein the mass ratio of zinc to the titanium-containing zeolite material having a framework MWW is in the range of 0.005:1 to 0.1:1, preferably in the range of 0.01:1 to 0.075:1, more preferably in the range of 0.02:1 to 0.05:1, and even more preferably in the range of 0.03:1 to 0.04:1.

[0052] Preferably, at least 99% by weight of the molding consists of zinc, Ti, Si, O, and H, more preferably at least 99.5% by weight. Preferably, the molding consists essentially of zinc, Ti, Si, O, and H. The expression "essentially consists of" as used in the context of the present invention relates to moldings in which, apart from impurities that cannot be avoided in a given method for preparing the molding, the molding consists of zinc, Ti, Si, O, and H.

[0053] The molding is preferably at least 200 mm 2 / g, more preferably at least 225m 2 / g, more preferably at least 250m 2 / g, where the BET specific surface area is measured as described in Reference Example 1.

[0054] The molded product preferably has a crystallinity of at least 50%, preferably in the range of 50 to 90%, where the crystallinity is measured as described in Reference Example 4.

[0055] Preferably, the extrusions have a porosity of at least 0.9 mL / g, as measured as described in Example 2.

[0056] Preferably, the molded article has a mechanical strength in the range of 9 to 23 N, preferably in the range of 11 to 18 N, more preferably in the range of 15 to 18 N. This was measured as described in Reference Example 3.

[0057] Preferably, the extruded product exhibits a water adsorption capacity in the range of 5 to 14% by mass, preferably in the range of 6 to 13% by mass, more preferably in the range of 8 to 12% by mass, as measured as described in Reference Example 7.

[0058] Preferably, the extrusions exhibit a PO test parameter of at least 8%, preferably at least 9%, as measured as described in Example 6.

[0059] The molded articles of the present invention can be used for any conceivable purpose, including, but not limited to, absorbents, adsorbents, molecular sieves, catalysts, catalyst supports, or intermediates for preparing one or more of these. The molded articles are preferably used as catalysts, more preferably as catalysts for converting hydrocarbons, even more preferably as catalysts for oxidizing hydrocarbons, even more preferably as catalysts for epoxidizing hydrocarbons having at least one carbon-carbon double bond, and even more preferably as catalysts for epoxidizing alkenes. Suitable alkenes include, but are not limited to, ethene, propene, 1-butene, 2-butene, 1-pentene, and 2-pentene. Propene is more preferred. Thus, the present invention relates to the use of the molded articles as catalysts for epoxidizing propene. Preferably, alkenes, more preferably propene, are epoxidized in the presence of a solvent, preferably comprising a nitrile, more preferably acetonitrile. More preferably, the solvent is acetonitrile, optionally combined with water. Epoxidation can be carried out using any conceivable epoxidizing agent, including suitable hydrogen peroxide, which can be used as such or formed in situ in the respective epoxidation reaction.

[0060] Furthermore, the present invention relates to a method for catalytically converting hydrocarbons, preferably a method for catalytically oxidizing hydrocarbons, more preferably a method for catalytically epoxidizing hydrocarbons having at least one carbon-carbon double bond, more preferably a method for catalytically epoxidizing alkenes, wherein a hydrocarbon, preferably a hydrocarbon having at least one carbon-carbon double bond, more preferably an alkene, is contacted with the shaped article of the present invention. Suitable alkenes include, but are not limited to, ethene, propene, 1-butene, 2-butene, 1-pentene, and 2-pentene. Propene is more preferred. Preferably, the alkene, more preferably propene, is epoxidized in the presence of a solvent, preferably a nitrile, more preferably acetonitrile. More preferably, the solvent is acetonitrile, optionally in combination with water. Epoxidation can be carried out using any conceivable epoxidizing agent, including suitable hydrogen peroxide, which can be used by itself or formed in situ in the respective epoxidation reaction.

[0061] Furthermore, the present invention relates to a catalyst system comprising a catalyst comprising the shaped article according to any one of embodiments 52 to 60 and at least one potassium salt, wherein the at least one potassium salt is selected from the group consisting of at least one inorganic potassium salt, at least one organic potassium salt, and a combination of at least one inorganic potassium salt and at least one organic potassium salt. Preferably, the at least one potassium salt is selected from the group consisting of at least one inorganic potassium salt selected from the group consisting of potassium hydroxide, potassium chloride, and potassium nitrate, at least one organic potassium salt selected from the group consisting of potassium formate, potassium acetate, potassium carbonate, and potassium bicarbonate, and a combination of at least one of the at least one inorganic potassium salt and at least one of the at least one organic potassium salt. Preferably, the catalyst system is for the epoxidation of an alkene, preferably propene. Preferably, the catalyst system is obtainable or obtainable by a preferably continuous process comprising the following steps:

[0062] (i') providing a liquid feed stream comprising an alkene, preferably propene, hydrogen peroxide, a solvent, preferably acetonitrile, water, and at least one dissolved potassium salt of the above; (ii') passing the liquid feed stream provided in (i') through an epoxidation reactor containing a catalyst comprising a shaped article according to the present invention; wherein in (i'), the molar ratio of potassium to hydrogen peroxide in the liquid feed stream is preferably 5×10 -6 :1~1000×10 -6 :1, preferably 25 x 10 -6 :1~500×10 -6 :1, more preferably 50×10 -6 :1~250×10 -6 :1 range.

[0063] Also, the method preferably comprises the steps of: (iii') subjecting the liquid feed stream to epoxidation reaction conditions in an epoxidation reactor to obtain a reaction mixture comprising an alkene oxide, preferably propylene oxide, a solvent, preferably acetonitrile, water, the at least one potassium salt described above, and, optionally, a non-epoxidized alkene, preferably a non-epoxidized propene. Includes.

[0064] Furthermore, the present invention relates to a process for preparing an alkene oxide, preferably propylene oxide, comprising the steps of: (i') providing a liquid feed stream comprising an alkene, preferably propene, hydrogen peroxide, a solvent, preferably acetonitrile, water, and at least one dissolved potassium salt of said compound; (ii') passing the liquid feed stream provided in (i') into an epoxidation reactor containing a catalyst comprising a shaped article according to the present invention; (iii') subjecting the liquid feed stream to epoxidation reaction conditions in an epoxidation reactor to obtain a reaction mixture comprising an alkene oxide, preferably propylene oxide, a solvent, preferably acetonitrile, water, the at least one potassium salt described above, and, optionally, a non-epoxidized alkene, preferably non-epoxidized propene; Includes. wherein in (i'), the molar ratio of potassium to hydrogen peroxide in the liquid feed stream is preferably 5×10 -6 :1~1000×10 -6 :1, preferably 25 x 10 -6 :1~500×10 -6 :1, more preferably 50×10 -6 :1~250×10 -6 :1 range.

[0065] The present invention will be further described by the following series of embodiments and combinations of embodiments resulting from explicit dependencies and backward references. In particular, in each case where the scope of an embodiment is explicitly stated, for example, in connection with the term "the method of any one of embodiments 1 to 4," it should be noted that all embodiments within this scope are clearly disclosed to those skilled in the art. In other words, this expression should be understood by those skilled in the art to be synonymous with "the method of any one of embodiments 1, 2, 3, and 4."

[0066] 1. A method for producing a shaped article comprising zinc and a titanium-containing zeolite material having a framework MWW, comprising: (i) providing a molded article comprising a titanium-containing zeolite material having a framework type MWW; (ii) preparing an aqueous suspension comprising a zinc source and a molding comprising the titanium-containing zeolite material having framework type MWW prepared in (i); (iii) heating the aqueous suspension prepared in (ii) under autogenous pressure to a liquid phase temperature of the aqueous suspension in the range of 100 to 200°C to obtain an aqueous suspension containing extrudates containing zinc and a titanium-containing zeolite material having a framework type MWW; (iv) separating from the liquid phase of the suspension obtained in (iii) a shaped product comprising zinc and a titanium-containing zeolitic material having a framework type MWW. A method comprising:

[0067] 2. The process of embodiment 1, wherein the shaped article provided in (i) comprises a titanium-containing zeolitic material having framework type MWW and a binder.

[0068] 3. The process of embodiment 2, wherein at least 90% by weight of the shaped article provided in (i) consists of the titanium-containing zeolitic material with framework type MWW and the binder, more preferably at least 95% by weight, even more preferably at least 99% by weight, and even more preferably at least 99.9% by weight.

[0069] 4. The process of embodiment 2 or 3, wherein in the shaped article provided in (i), the mass ratio of titanium-containing zeolitic material with framework MWW to binder is in the range of 1:1 to 9:1, more preferably in the range of 2:1 to 7:1, even more preferably in the range of 3:1 to 5:1, and the binder is preferably a silica binder.

[0070] 5. The process of any one of embodiments 1 to 4, wherein the shaped bodies provided in (i) are in the form of tablets, spheres, cylinders, stars, strands, or trilobes, wherein the shaped bodies are preferably strands, more preferably extruded strands, and preferably have a rectangular, triangular, hexagonal, square, oval, or circular cross section, and the diameter of the preferred circular cross section is preferably in the range of 1.0 to 2.0 mm.

[0071] 6. The method of any one of embodiments 1 to 5, wherein the molded article provided in (i) exhibits one or more of the following properties (1) to (3), preferably two or more of the following properties (1) to (3), more preferably the following properties (1) to (3): (1) At least 300 m, measured as described in Reference Example 1 of this document. 2 BET specific surface area in / g; (2) a pore volume of at least 0.9 mL / g, measured as described in Reference Example 2 herein; (3) A mechanical strength in the range of 5 to 10 N, preferably in the range of 6 to 9 N, measured as described in Reference Example 3 herein.

[0072] 7. The molded article comprising the titanium-containing zeolite material having framework MWW prepared in (i) is (i.1) preparing a mixture comprising a titanium-containing zeolite material having framework type MWW, a binder or binder source, a pasting agent, and optionally a pore-forming agent; (i.2) shaping the mixture prepared in (i.1) to obtain a shaped product comprising a titanium-containing zeolite material having framework type MWW and a binder or a binder source; (i.3) Drying the extrusions obtained in (i.2); (i.4) Calcining the dried molded product obtained in (i.3) to obtain a molded product containing a titanium-containing zeolite material having an MWW framework and a binder. The method of any one of embodiments 1 to 6, preferably any one of embodiments 2 to 6, which is obtained or has been obtained by a method comprising:

[0073] 8.(i) is prepared by: (i.1) preparing a mixture comprising a titanium-containing zeolite material having a framework type MWW, a binder or a binder source, and a pasting agent; (i.2) shaping the mixture prepared in (i.1) to obtain a shaped product comprising a titanium-containing zeolite material having framework type MWW and a binder or a binder source; (i.3) Drying the extrusions obtained in (i.2); (i.4) Calcining the dried molded product obtained in (i.3) to obtain a molded product containing a titanium-containing zeolite material having an MWW framework and a binder. The method of any one of embodiments 1 to 6, preferably any one of embodiments 2 to 6, comprising:

[0074] 9. The method of embodiment 7 or 8, wherein the paste according to (i.1) comprises one or more of water and carbohydrates, preferably water and carbohydrates.

[0075] 10. The method of any one of embodiments 7 to 9, wherein the mixture prepared in (i.1) comprises a pore-forming agent, preferably a mesopore-forming agent, which is preferably one or more of a polyalkylene oxide, such as polyethylene oxide, polystyrene, polyacrylate, polymethacrylate, polyolefin, polyamide, and polyester.

[0076] 11. The method of any one of embodiments 7 to 10, wherein the mixture prepared in (i.1) does not comprise a mesopore-forming agent, preferably does not comprise a pore-forming agent, which is preferably one or more of a polyalkylene oxide, such as polyethylene oxide, polystyrene, polyacrylate, polymethacrylate, polyolefin, polyamide, and polyester.

[0077] 12. The method of any one of embodiments 7-11, wherein the binder or binder precursor is a silica binder or a silica binder precursor, more preferably the silica binder or precursor comprises, and preferably is, colloidal silica.

[0078] 13. The method of any one of embodiments 7 to 12, wherein the mass ratio of titanium-containing zeolitic material with framework MWW to silica present in the binder or binder precursor in the mixture prepared in (i.1) is in the range of 1:1 to 9:1, more preferably in the range of 2:1 to 7:1, even more preferably in the range of 3:1 to 5:1.

[0079] 14. The method of any one of embodiments 7 to 13, wherein the mixture prepared in (i.1) does not contain zinc.

[0080] 15. The method of any one of embodiments 7 to 14, wherein at least 99% by weight, preferably at least 99.5% by weight, more preferably at least 99.9% by weight of the mixture prepared in (i.1) consists of the titanium-containing zeolitic material having framework type MWW, the binder or a precursor to the binder, and the pasting agent.

[0081] 16. The method of any one of embodiments 7 to 15, wherein preparing the mixture according to (i) comprises kneading the mixture.

[0082] 17. The method of any one of embodiments 7 to 16, wherein the shaping according to (i.2) comprises extruding the mixture prepared in (i.1).

[0083] 18. The process of embodiment 17, wherein extrusion results in extrusions in the form of strands, preferably having a diameter in the range of 1.0 to 2.0 mm.

[0084] 19. The process of any one of embodiments 7 to 18, wherein the extrusion is dried according to (i.3) at a temperature in the range of 80 to 200°C, more preferably in the range of 90 to 175°C, more preferably in the range of 100 to 150°C.

[0085] 20. The process according to any one of embodiments 7 to 19, wherein the extrusion is dried in accordance with (i.3) in an oxygen-containing gas atmosphere, preferably in air or lean air, more preferably in air.

[0086] 21. The process of any one of embodiments 7 to 20, wherein the shaped product is calcined according to (i.4) at a temperature in the range of 350 to 650°C, preferably in the range of 400 to 600°C, more preferably in the range of 450 to 550°C.

[0087] 22. The process according to any one of embodiments 7 to 21, wherein the shaped article is calcined in accordance with (i.4) in an oxygen-containing gas atmosphere, preferably in air or lean air, more preferably in air.

[0088] 23. The method of any one of embodiments 1 to 22, wherein at least 99% by weight of the titanium-containing zeolitic material having framework type MWW contained in the molding provided in (i) consists of Ti, Si, O, and H.

[0089] 24. The process of any one of embodiments 1 to 23, wherein the titanium-containing zeolitic material with framework MWW contained in the shaped article provided in (i) has a titanium content, calculated as elemental titanium, in the range of 0.1 to 5% by weight, more preferably in the range of 0.5 to 3% by weight, more preferably in the range of 1 to 3% by weight, based on the total weight of the titanium-containing zeolitic material with framework MWW.

[0090] 25. The process of any one of embodiments 1 to 24, wherein the titanium-containing zeolitic material with framework MWW contained in the shaped article provided in (i) has a silicon content, calculated as elemental silicon, in the range of 30 to 60% by weight, preferably in the range of 35 to 55% by weight, more preferably in the range of 40 to 50% by weight, more preferably in the range of 1 to 3% by weight, based on the total weight of the titanium-containing zeolitic material with framework MWW.

[0091] 26. The method of any one of embodiments 1 to 25, wherein the titanium-containing zeolitic material with framework MWW contained in the molding provided in (i) has a total organic carbon content of at most 0.1 wt. %, based on the total weight of the titanium-containing zeolitic material with framework MWW.

[0092] 27. The method of any one of embodiments 1 to 26, wherein the titanium-containing zeolitic material with framework MWW contained in the molding provided in (i) has a boron content of at most 0.5% by weight, calculated as elemental boron, based on the total weight of the titanium-containing zeolitic material with framework MWW.

[0093] 28. (i) The titanium-containing zeolite material having framework MWW contained in the molding prepared in (i) is at least 400 m 2 / g, preferably 400 to 600m 2 / g, more preferably 450 to 550 m2 28. The method of any one of embodiments 1 to 27, wherein the BET specific surface area is in the range of / g, wherein the BET specific surface area is measured as described in Reference Example 1 herein.

[0094] 29. The method of any one of embodiments 1 to 28, wherein the titanium-containing zeolitic material having framework MWW contained in the extrusion provided in (i) has a crystallinity of at least 70%, preferably in the range of 70 to 90%, more preferably in the range of 70 to 80%, wherein the crystallinity is measured as described in Reference Example 4 herein.

[0095] 31. The method of any one of embodiments 1 to 30, wherein the titanium-containing zeolitic material with framework MWW contained in the shaped article provided in (i) is in the form of a powder having a particle size distribution characterized by a Dv10 value in the range of 1 to 10 micrometers, preferably in the range of 1.5 to 10 micrometers, more preferably in the range of 2 to 6 micrometers, a Dv50 value in the range of 5 to 50 micrometers, preferably in the range of 7 to 50 micrometers, even more preferably in the range of 8 to 30 micrometers, and a Dv90 value in the range of 12 to 200 micrometers, preferably in the range of 12 to 90 micrometers, more preferably in the range of 13 to 70 micrometers, wherein the particle size distribution is measured as described in Reference Example 5 herein.

[0096] 32. The method of any one of embodiments 1 to 31, wherein the titanium-containing zeolitic material having framework type MWW contained in the molding provided in (i) is a spray powder.

[0097] 33. The method of any one of embodiments 1-32, wherein in (ii), the zinc source comprises a zinc compound that is soluble in water at the temperature and pressure of the liquid aqueous phase according to (iii).

[0098] 34. The method of any one of embodiments 1-33, wherein the zinc source comprises one or more zinc salts soluble in water, preferably zinc salts of an organic or inorganic acid, preferably one or more of zinc acetate, zinc benzoate, zinc borate, zinc bromide, zinc chloride, zinc formate, zinc gluconate, zinc lactate, zinc laurate, zinc malate, zinc nitrate, zinc perborate, zinc sulfate, zinc sulfamate, zinc tartrate, more preferably zinc acetate, more preferably zinc acetate dihydrate.

[0099] 35. The method of any one of embodiments 1-34, wherein in (ii), the zinc source comprises zinc acetate, preferably zinc acetate dihydrate, more preferably zinc acetate dihydrate.

[0100] 36. The method of any one of embodiments 1 to 35, wherein in the aqueous suspension prepared in (ii), the mass ratio of zinc contained in the zinc source to the titanium-containing zeolitic material with framework MWW contained in the extrusion is in the range of 0.005:1 to 0.1:1, more preferably in the range of 0.01:1 to 0.075:1, more preferably in the range of 0.02:1 to 0.05:1, and even more preferably in the range of 0.03:1 to 0.04:1.

[0101] 37. The process of any one of embodiments 1 to 36, wherein the mass ratio of titanium-containing zeolitic material having framework type MWW contained in the extrusion to water in the aqueous suspension prepared in (ii) is in the range of 0.01:1 to 0.1:1, preferably in the range of 0.02:1 to 0.075:1, more preferably in the range of 0.03:1 to 0.05:1.

[0102] 38. The method of any one of embodiments 1 to 37, wherein at least 99% by weight, preferably at least 99.5% by weight, more preferably at least 99.9% by weight, of the aqueous suspension prepared in (ii) consists of moldings comprising water, a zinc source, and a titanium-containing zeolitic material having framework type MWW.

[0103] 39. The method of any one of embodiments 1 to 38, wherein in (iii), the suspension prepared in (ii) is heated to a temperature of the liquid phase of the aqueous suspension in the range of 110 to 175°C, preferably in the range of 120 to 150°C, and maintained at that temperature.

[0104] 40. The method of any one of embodiments 1 to 39, wherein in (iii), the suspension prepared in (ii) is kept at said temperature for a period in the range of 1 to 24 hours, preferably in the range of 2 to 17 hours, more preferably in the range of 3 to 10 hours.

[0105] 41. The method of any one of embodiments 1 to 40, wherein the suspension prepared in (ii) is not stirred during the heating and temperature holding in (iii).

[0106] 42. The process of any one of embodiments 1 to 41, wherein in (iv), the separating comprises filtering or centrifuging the aqueous suspension obtained from (iii), optionally followed by washing, to obtain a separated molding comprising zinc and titanium-containing zeolitic material having framework type MWW.

[0107] 43.Furthermore, (v) The process of any one of embodiments 1 to 42, comprising drying the separated extrusions comprising zinc and titanium-containing zeolitic material with framework type MWW obtained from (iv).

[0108] 44. The process of embodiment 43, wherein the separated extrusions comprising zinc and titanium-containing zeolitic material having framework type MWW are dried at a temperature in the range of 80 to 200°C, more preferably in the range of 90 to 175°C, more preferably in the range of 100 to 150°C.

[0109] 45. The process of embodiment 43 or 44, wherein the separated extrusions comprising zinc and titanium-containing zeolitic material having framework type MWW are dried for a period in the range of 0.5 to 12 hours, more preferably in the range of 1 to 8 hours, and even more preferably in the range of 2 to 6 hours.

[0110] 46. ​​The method of any one of embodiments 43 to 45, wherein the separated shaped product comprising zinc and titanium-containing zeolitic material having framework type MWW is dried in an oxygen-containing gas atmosphere, preferably in air or lean air, more preferably in air.

[0111] 47.Furthermore, (vi) The process of any one of embodiments 43 to 46, comprising calcining the dried shaped product comprising zinc and titanium-containing zeolitic material with framework type MWW obtained from (v).

[0112] 48. The method of embodiment 47, wherein the dried shaped product comprising zinc and titanium-containing zeolitic material having framework type MWW is calcined at a temperature in the range of 300 to 600°C, more preferably in the range of 350 to 550°C, more preferably in the range of 400 to 500°C.

[0113] 49. The method of embodiment 47 or 48, wherein the dried shaped product comprising zinc and titanium-containing zeolitic material having framework type MWW is calcined for a period in the range of 0.1 to 6 hours, more preferably in the range of 0.2 to 4 hours, more preferably in the range of 0.5 to 3 hours.

[0114] 50. The method of any one of embodiments 47 to 49, wherein the dried shaped product comprising zinc and titanium-containing zeolitic material having framework type MWW is calcined in an oxygen-containing gas atmosphere, preferably in air or lean air, more preferably in air.

[0115] 51. The method of any one of embodiments 1-50, wherein the molding comprising zinc and the titanium-containing zeolitic material having framework type MWW is not steamed, preferably not steamed.

[0116] 52. A shaped article comprising zinc and a titanium-containing zeolitic material having framework type MWW, the shaped article being obtainable or obtained or produced or produced by the method according to any one of embodiments 1 to 51, preferably any one of embodiments 33 to 51, more preferably any one of embodiments 43 to 51, and even more preferably any one of embodiments 47 to 51.

[0117] 53. A shaped article comprising zinc and a titanium-containing zeolitic material having a framework MWW, preferably the shaped article according to embodiment 52, wherein the mass ratio of zinc to titanium-containing zeolitic material having a framework MWW in the shaped article is in the range of 0.005:1 to 0.1:1, preferably in the range of 0.01:1 to 0.075:1, more preferably in the range of 0.02:1 to 0.05:1, and even more preferably in the range of 0.03:1 to 0.04:1.

[0118] 54. The molding of embodiment 53, wherein at least 99% by weight, more preferably at least 99.5% by weight, of the molding consists of zinc, Ti, Si, O, and H.

[0119] 55. At least 200m 2 / g, preferably at least 250m 2 / g, wherein the BET specific surface area is measured as described in Reference Example 1 herein.

[0120] 56. The molded article of any one of embodiments 53 to 55, having a crystallinity of at least 50%, preferably in the range of 50 to 90%, wherein the crystallinity is measured as described in Reference Example 4 herein.

[0121] 57. The molded article of any one of embodiments 53-56, having a porosity of at least 0.9 mL / g, measured as described in Reference Example 2 herein.

[0122] 58. The molded article of any one of embodiments 53 to 57, having a mechanical strength in the range of 9 to 23 N, preferably in the range of 11 to 18 N, more preferably in the range of 15 to 18 N, measured as described in Reference Example 3 herein.

[0123] 59. The molded article of any one of embodiments 53 to 57, exhibiting a water adsorption capacity in the range of 5 to 14% by weight, preferably in the range of 6 to 13% by weight, more preferably in the range of 8 to 12% by weight, measured as described in Reference Example 7 herein.

[0124] 60. The molded article of any one of embodiments 53-59, exhibiting a PO test parameter of at least 8%, preferably at least 9%, measured as described in Reference Example 6 herein.

[0125] 61. Use of the molding according to any one of embodiments 52 to 60 as a catalyst for converting hydrocarbons, preferably as a catalyst for oxidizing hydrocarbons, more preferably as a catalyst for epoxidizing hydrocarbons having at least one carbon-carbon double bond, more preferably as a catalyst for epoxidizing alkenes.

[0126] 62. The use of embodiment 61 for epoxidizing one or more of propene, ethene, 1-butene, 2-butene, 1-pentene and 2-pentene, preferably for epoxidizing propene.

[0127] 63. The use of embodiment 61 or 62, wherein an alkene, preferably propene, is epoxidized in the presence of a solvent, preferably comprising a nitrile, more preferably comprising acetonitrile.

[0128] 64. The use according to embodiment 62 or 63, wherein propene is epoxidized using hydrogen peroxide as the epoxidizing agent.

[0129] 65. A method for catalytically converting hydrocarbons, preferably a method for catalytically oxidizing hydrocarbons, more preferably a method for catalytically epoxidizing hydrocarbons having at least one carbon-carbon double bond, more preferably a method for catalytically epoxidizing alkenes, wherein the hydrocarbon, preferably a hydrocarbon having at least one carbon-carbon double bond, more preferably an alkene, is contacted with the shaped article of any one of embodiments 52 to 60 as a catalyst.

[0130] 66. The process of embodiment 65, wherein one or more of propene, ethene, 1-butene, 2-butene, 1-pentene, and 2-pentene are catalytically epoxidized, preferably propene is catalytically epoxidized.

[0131] 67. The process of embodiment 66, wherein the alkene, preferably propene, is epoxidized in the presence of a solvent, preferably comprising a nitrile, more preferably comprising acetonitrile.

[0132] 68. The method of embodiment 66 or 67, wherein propene is epoxidized using hydrogen peroxide as the epoxidizing agent.

[0133] 69. A catalyst system comprising a catalyst comprising the shaped article of any one of embodiments 52-60 and at least one potassium salt, wherein the at least one potassium salt is selected from the group consisting of at least one inorganic potassium salt, at least one organic potassium salt, and a combination of at least one inorganic potassium salt and at least one organic potassium salt.

[0134] 70. The catalyst system of embodiment 69, wherein the at least one potassium salt is selected from the group consisting of at least one inorganic potassium salt selected from the group consisting of potassium hydroxide, potassium chloride, potassium nitrate, at least one organic potassium salt selected from the group consisting of potassium formate, potassium acetate, potassium carbonate, and potassium bicarbonate, and a combination of at least one of the at least one inorganic potassium salt with at least one of the at least one organic potassium salt.

[0135] 71. The catalyst system of embodiment 69 or 70 for the epoxidation of alkenes, preferably propene.

[0136] 72. The catalytic system of any one of embodiments 69 to 71, preferably obtained or obtained by a continuous process, wherein the process comprises: (i') providing a liquid feed stream comprising an alkene, preferably propene, hydrogen peroxide, a solvent, preferably acetonitrile, water, and at least one dissolved potassium salt; (ii') passing the liquid feed stream provided in (i') to an epoxidation reactor containing a catalyst comprising the shaped article of any one of embodiments 52-60; wherein in (i'), the molar ratio of potassium to hydrogen peroxide in the liquid feed stream is preferably 5×10 -6 :1~1000×10 -6 :1, preferably 25 x 10 -6 :1~500×10 -6 :1, more preferably 50×10 -6 :1~250×10 -6 :1 range; Including, Also, the method preferably comprises the following steps: (iii') subjecting the liquid feed stream to epoxidation reaction conditions in an epoxidation reactor to obtain a reaction mixture comprising an alkene oxide, preferably propylene oxide, a solvent, preferably acetonitrile, water, the at least one potassium salt as described above, and, optionally, a non-epoxidized alkene, preferably a non-epoxidized propene. A catalyst system comprising:

[0137] 73. A preferably continuous process for producing an alkene oxide, preferably propylene oxide, comprising: (i') providing a liquid feed stream comprising an alkene, preferably propene, hydrogen peroxide, a solvent, preferably acetonitrile, water, and preferably a dissolved potassium salt; (ii') passing the liquid feed stream provided in (i') to an epoxidation reactor containing a catalyst comprising the shaped article of any one of embodiments 52-60; (iii') subjecting the liquid feed stream to epoxidation reaction conditions in an epoxidation reactor to obtain a reaction mixture comprising an alkene oxide, preferably propylene oxide, a solvent, preferably acetonitrile, water, at least a portion of the dissolved potassium salt, and, optionally, a non-epoxidized alkene, preferably a non-epoxidized propene. Including, wherein in (i'), the molar ratio of potassium to hydrogen peroxide in the liquid feed stream is preferably 5×10 -6 :1~1000×10 -6 :1, preferably 25 x 10 -6 :1~500×10 -6 :1, more preferably 50×10 -6 :1~250×10 -6 The method is in the range of

[0138] The present invention will be further explained using the following Reference Examples, Examples and Comparative Examples. [Example]

[0139] Reference Example 1: Measurement of BET specific surface area The BET specific surface areas referred to in the context of this application (multipoint BET specific surface areas) were determined via nitrogen adsorption at 77 K as described in DIN 66131.

[0140] Reference Example 2: Measurement of Hg porosimetry data Porosimetry data by Hg porosimetry were determined as described in DIN 66133.

[0141] Reference Example 3: Measurement of mechanical strength The mechanical strength referred to in the context of the present invention is understood to be measured using a crush strength testing machine Z2.5 / TS1S, supplied by Zwick GmbH & Co., D-89079 Ulm, Germany. Regarding the principle of this device and its operation, reference is made to the respective instruction manual "Registration 1: Instructions / Safety Handbook for Materials Testing Machines Z2.5 / TS1S," version 1.5, December 2001, by Zwick GmbH & Co., Technische Dokumentation, August-Nagel-Strasse 11, D-89079 Ulm, Germany. Using this machine, a given strand according to the present invention, as described in the examples herein, is subjected to increasing forces via a 3 mm diameter plunger until the strand breaks. The force at which the strand breaks is referred to as the strand's crush strength. The machine is equipped with a fixed horizontal table on which the strand is positioned. A vertically movable plunger is actuated to press the strand against the fixed table. The device is operated with a preload of 0.5 N, a shear rate of 10 mm / min under preload, and then a test speed of 1.6 mm / min. The vertically movable plunger is connected to a load cell to increase the force and, during the measurement, is actuated to move the plunger towards a fixed turntable on which the molded article (strand) to be tested is positioned, thus pressing the strand against the table. The plunger is applied perpendicular to the longitudinal axis of the strand. The experiment is controlled by a computer, which records and evaluates the measurement results. The obtained value is the average of the measurements on 10 strands in each case.

[0142] Reference Example 4: Measurement of crystallinity Crystallinity values ​​referred to in the context of this application were measured according to the method described in the User Manual DIFFRAC.EVA, 3rd Edition, p. 105, published by Bruker AXS GmbH, Karlsruhe (issued February 2003). Data were collected on a standard Bruker D8 Advance diffractometer series II using a LYNXEYE detector, 2°-50° 2-theta, with a fixed slit, a step size of 0.02° 2-theta, and a scan rate of 2.4 seconds per step. The parameters used to estimate the background / amorphous content were curvature=0 and threshold=0.8.

[0143] Reference Example 5: Measurement of particle size distribution The particle size distributions referred to in the context of this application, based on Dv10, Dv50 and Dv90 values, were measured according to the following method: 1.0 g of a given material was suspended in 100 g deionized water and stirred for 1 minute. Measurements of the particle size distribution were then carried out using a Mastersizer S Long Bed Version 2.15, serial number 33544-325; supplier: Malvern Instruments GmbH (Herrenberg, Germany). The instrument had the following parameters:

[0144] - Focal width: 300RFmm - Beam length: 10.00mm - Module: MS17 - Shadowing: 16.9% - Dispersion model: 3D - Analytical model: polydispersity - Correction: None

[0145] The term "Dv10 value" referred to in the context of the present invention denotes the average particle size below which 10% by volume of the particles of the fine powder (micropowder) have a smaller size. Similarly, the term "Dv50 value" referred to in the context of the present invention denotes the average particle size below which 50% by volume of the particles of the fine powder have a smaller size, and the term "Dv90 value" referred to in the context of the present invention denotes the average particle size below which 90% by volume of the particles of the fine powder have a smaller size.

[0146] Reference Example 6: PO Exam In the PO test, the inventive moldings were tested as catalysts in the reaction of propene with aqueous hydrogen peroxide (30% by weight) to produce propylene oxide in a mini-autoclave. Specifically, 0.63 g of the inventive moldings were introduced at room temperature together with 79.2 g of acetonitrile and 12.4 g of propene, and 22.1 g of hydrogen peroxide (30% by weight in water) were introduced into a steel autoclave. After a reaction time of 4 hours at 40°C, the mixture was cooled, decompressed, and the liquid phase was analyzed for propylene oxide content by gas chromatography. The propylene oxide content (% by weight) of the liquid phase was the result of the PO test.

[0147] The PO test rate was measured according to the pressure change during the PO test described above. This pressure change was recorded using an S-11 transmitter (manufactured by Wika Alexander Wiegand SE & Co. KG) installed in the autoclave's pressure line and a Buddeberg 6100A graphic plotter. The obtained data was read out and displayed as a pressure change curve. The pressure drop rate, i.e., the PO test rate, was determined according to the following formula:

[0148] PDR = [p(max)-p(min)] / Delta t During the ceremony, PDR / (bar / min) = Pressure Drop Rate p(max) / bar = maximum pressure at the start of the reaction p(min) / bar = minimum pressure observed during the reaction Delta t / min = time difference between the start of the reaction and the point at which p (min) is observed

[0149] Reference Example 7: Measurement of water adsorption capacity Water adsorption / desorption isotherm measurements were performed on a TA Instruments VTI SA instrument according to a step-isotherm program. The experiment consisted of a single run or a series of runs performed on sample material placed in the microbalance pan inside the instrument. Before the measurement began, the sample was heated to 100 °C (heating ramp 5 °C / min) and held under a N2 flow for 6 h to remove residual moisture. After the drying program, the temperature inside the cell was reduced to 25 °C and kept isothermal throughout the measurement. The microbalance was calibrated, and the mass of the dried sample was balanced (maximum mass deviation 0.01 wt%). Water uptake by the sample was measured as the increase in mass over the mass of the dried sample. Adsorption curves were first measured by exposing the sample to increasing relative humidity (RH) (expressed as the mass % of the moisture in the atmosphere inside the cell) and measuring the amount of water uptake by the sample at equilibrium. The RH was increased from 5% to 85% in 10% by weight steps, and the mass of the sample was monitored at each step until the system controlled the RH and reached equilibrium, recording the mass uptake. After the sample was exposed to 85% by weight RH, the total amount of water adsorbed by the sample was measured. During the desorption measurements, the RH was decreased from 85% to 5% by weight in 10% by weight steps. The change in sample mass (water uptake) was monitored and recorded.

[0150] Reference Example 8: Preparation of titanium-containing zeolite material with framework type MWW Titanium-containing zeolite (spray powder) was prepared as described in Example 5, 5.1 to 5.3, from page 83, line 26 to page 92, line 7, of WO2013 / 117536A.

[0151] Reference Example 9: Continuous epoxidation reaction A continuous epoxidation reaction was carried out as described in WO 2015 / 010990A, Reference Example 1, page 55, line 14 to page 57, line 10. The reaction temperature was set to 45°C (see WO 2015 / 010990A, page 56, lines 16-18). The temperature was adjusted to achieve an essentially constant hydrogen peroxide conversion of 90% (see WO 2015 / 010990A, page 56, lines 21-23). ​​KH2PO4 was used as an additive (see WO 2015 / 010990A, page 56, lines 7-10), and the additive concentration was 130 micromoles per mole of hydrogen peroxide. The catalyst used was the catalyst according to Comparative Example 1 and Example 1 below (see WO 2015 / 010990A, page 55, lines 16-18).

[0152] The following Examples 10 to 12 are specific examples of how to prepare titanium-containing zeolitic materials having framework MWW and a water adsorption capacity of at least 11 wt. %.

[0153] Reference Example 10: Preparation of titanium-containing zeolite material having framework MWW and water adsorption capacity of at least 11% by mass (i) B-Ti-MWW synthesis The synthesis mixture had the following composition: 1.0 (SiO2): 0.04 (TiO2): 0.67 (B2O3): 1.4 piperidine: 19H2O.

[0154] Batch 0: First, 1,026 g of deionized water was introduced into a beaker, then 365 g of piperidine was added with stirring at 200 rpm, and the mixture was stirred for 10 minutes at about 23° C. and pH 13.2. The batch was then divided into two equal portions.

[0155] Batch 1: 695.5 g of the deionized water-piperidine solution was placed in a beaker and, while stirring at 200 rpm, 248.4 g of boric acid was added, stirring was continued for 30 minutes, and 90 g of fumed silica (Cab-O-SIL® 5M) was added at about 23° C. The mixture was then stirred for 1 hour at about 23° C. and pH 11.4.

[0156] Batch 2: First, 695.5 g of a deionized water-piperidine solution was introduced into a beaker while stirring at 200 rpm at about 23° C., 43.2 g of tetrabutyl orthotitanate was added, stirring was continued for another 30 minutes, and then 90 g of fumed silica (Cab-O-SIL® 5M) was added. The mixture was then stirred for 1 hour at about 23° C. and pH 12.2.

[0157] Batch 3: The two suspensions from batches 1 and 2 were mixed together for 1.5 hours at about 23°C and pH 11.8 to obtain a synthesis mixture, which was then crystallized in an autoclave under the following conditions: Heat to 130°C for 1 hour / hold for 24 hours at 100 rpm, 0-2.7 bar pressure, then heat to 150°C for 1 hour / hold for 24 hours at 100 rpm, 2.7-4.9 bar pressure, then heat to 170°C for 1 hour / hold for 120 hours at 100 rpm, 4.9-9.4 bar pressure.

[0158] After the above crystallization conditions, the resulting suspension, with a pH of 11.3, was dehydrated, filtered through a suction filter (to obtain a clear filtrate), and washed with 10 liters of deionized water (to obtain a cloudy filtrate). The cloudy filtrate was then acidified to pH 7 with 10% aqueous HNO3 solution. The wet product (filter cake) was then filled into a porcelain dish, dried overnight, and then crushed. The yield was 192.8 g. Elemental analysis of the resulting product revealed the following contents per 100 g of material: 9.6 g carbon, 0.85 g boron, 21.8 g silicon, and 17.8 g titanium.

[0159] (ii) B-Ti-MWW HNO3 treatment The dried ground material obtained according to item (i) above was washed with HNO3 solution (solid to liquid ratio 1 g:20 ml) at 100°C for 20 hours. 3600 g of HNO3 solution and 180 g of B-Ti-MWW according to item (i) were added to a 10-liter glass flask at 100°C, followed by boiling under reflux for 20 hours with stirring at 250 rpm. The white suspension thus obtained was filtered off and washed with 2 x 5 liters of deionized water. Drying: 10 hours / 120°C. Calcination: 2 K / min to 530°C / hold for 5 hours. The yield was 143 g. Elemental analysis showed that the following contents were determined per 100 g of material for the obtained product: <0.1 g of carbon (TOC), 0.27 g of B, 42 g of Si, and 2 g of Ti. The BET surface area was measured to be 532 m 2 The crystallinity of the product was measured (Reference Example 8) to be 80% and the average crystal size calculated from XRD diffraction data was determined to be 22 nm.

[0160] (iii) B-Ti-MWW HNO3 treatment The material obtained according to (ii) above was washed with HNO3 solution (solid to liquid ratio 1 g:20 ml) at 100°C for 20 hours. 2,400 g of HNO3 solution and 120 g of B-Ti-MWW according to (ii) were added to a 10-liter glass flask at 100°C, followed by boiling under reflux for 20 hours with stirring at 250 rpm. The white suspension was filtered off and washed with 7 x 1-liter deionized water. Drying: 10 hours / 120°C. Calcination: heating to 530°C at 2 K / min / holding for 5 hours. The yield was 117 g. Elemental analysis showed that the following contents were determined per 100 g of material for the obtained product: <0.03 g B, 44 g Si, and 1.8 g Ti. The BET specific surface area was measured to be 501 m 2 / g. The crystallinity of the product was measured to be 94%, and the average crystal size calculated from XRD diffraction data was determined to be 22 nm. XRD of the resulting product confirmed that the resulting zeolitic material had an MWW framework structure. Its water adsorption capacity, measured according to Reference Example 1 herein, was 13.2 wt.%.

[0161] Reference Example 11: Preparation of titanium-containing zeolite material having framework MWW and water adsorption capacity of at least 11% by mass (i) B-Ti-MWW synthesis The synthesis mixture had the following composition: 1.0 (SiO2): 0.04 (TiO2): 0.67 (B2O3): 1.4 piperidine: 19H2O.

[0162] Batch 0: First, 1,026 g of deionized water was introduced into a beaker, 365 g of piperidine was added while stirring at 200 rpm, and the mixture was stirred for 10 minutes at about 23° C. and pH 13.2. The batch was then divided into two equal portions.

[0163] Batch 1: 695.5 g of the deionized water-piperidine solution was placed in a beaker and, while stirring at 200 rpm, 248.4 g of boric acid was added, stirring was continued for 30 minutes, and then 90 g of fumed silica (Cab-O-SIL® 5M) was added at about 23° C. The mixture was then stirred for an additional hour at about 23° C. and pH 11.4.

[0164] Batch 2: First, 695.5 g of a deionized water-piperidine solution was introduced into a beaker while stirring at 200 rpm at about 23° C., 43.2 g of tetrabutyl orthotitanate was added, stirring was continued for another 30 minutes, and then 90 g of fumed silica (Cab-O-SIL® 5M) was added. The mixture was then stirred for another hour at about 23° C. and pH 12.2.

[0165] Batch 3: The two suspensions from batches 1 and 2 were mixed together at approximately 23°C and pH 11.8 for 1.5 hours to obtain a synthesis mixture, which was then crystallized in an autoclave under the following conditions: heating to 170°C for 1 hour, holding at 120 rpm at 0-9.4 bar for 120 hours. After the above crystallization conditions, the resulting suspension with a pH of 11.3 was dehydrated, filtered through a suction filter, and washed with 10 L of deionized water. The wet product (filter cake) was then filled into a porcelain dish, dried overnight, and then crushed. The yield was 194 g.

[0166] (ii) B-Ti-MWW HNO3 treatment The dried and ground material according to item (i) above was then washed with HNO3 solution (solid to liquid ratio 1 g:20 ml) at 100°C for 20 hours. 3,600 g of HNO3 aqueous solution and 180 g of B-Ti-MWW according to item (i) were added to a 10-liter glass flask at 100°C, followed by boiling under reflux for 20 hours with stirring at 250 rpm. The white suspension thus obtained was filtered off and washed with 2 x 5 L of deionized water. Drying: 10 hours / 120°C. Calcination: heating to 530°C at 2 K / min / holding for 5 hours. The yield was 146 g. Elemental analysis showed that the obtained product contained the following contents per 100 g of material: <0.1 g of carbon (TOC), 0.25 g of B, 43 g of Si, and 2.6 g of Ti. The BET specific surface area was measured to be 514 m 2 / g. The crystallinity of the product was measured to be 79%, and the average crystal size calculated from XRD diffraction data was determined to be 22.5 nm. XRD of the resulting product confirmed that the resulting zeolitic material had an MWW framework structure. Its water adsorption capacity, measured according to Reference Example 1 herein, was 17.3 wt.%.

[0167] Reference Example 12: Preparation of titanium-containing zeolite material having framework MWW and water adsorption capacity of at least 11% by mass (i) B-Ti-MWW synthesis To prepare a synthesis mixture having the following composition: 1.0B2O3 / 2.0SiO2 / 32.8H2O / 2.43piperidine, deionized water and boric acid were mixed together in a beaker at about 23°C, to which ammonium-stabilized silica sol was added with further mixing at about 23°C. The mixture thus obtained was then transferred to an autoclave, and piperidine was then added with further mixing. Crystallization was then carried out in the autoclave at 175°C under autogenous pressure for 48 hours. Excess piperidine was then flashed off. The resulting product was then filtered as a solid, washed with deionized water, and dried. Rotary calcination was then carried out at 650°C for 2 hours.

[0168] (ii) Deboronation A slurry of the calcined product thus obtained was then prepared using deionized water so that the slurry had a solids content of 6.25% by weight. The slurry was heated to 90.5°C and then held at this temperature for 10 hours. The resulting (deboronated) product was then filtered off as a solid, washed with deionized water, and dried.

[0169] (iii) Ti insertion A slurry was prepared from deionized water and the deboronated product from item (ii) above, and mixed at 23°C. The slurry was then transferred to an autoclave, to which a tetra-n-butyl titanate / piperidine mixture was then added. The mixture thus obtained had the following composition: 0.035TiO2 / 1.0SiO2 / 17.0HO / 1.0piperidine. Crystallization was then carried out in the autoclave at 170°C under autogenous pressure for 48 hours. The excess piperidine / ethanol was then removed by evaporation. The resulting product was then filtered off as a solid, washed with deionized water, and dried.

[0170] (iv) Acid treatment A slurry was prepared from the product from item (iii) in 10% HNO3 (aqueous) solution (907.2 g HNO3 / 453.6 g product from item (iii)), thus producing a slurry with a 5% solids content by weight. The slurry was heated to 93.3°C and then held at this temperature for 1 hour. The resulting product was then filtered off as a solid, washed with deionized water, and dried. Rotary calcination was then carried out at 650°C for 2 hours. Elemental analysis determined that the calcined product contained 2 g of carbon (TOC), 42 g of Si, and 1.6 g of Ti per 100 g of material. The BET specific surface area was determined to be 420 m 2 / g. The crystallinity of the product was measured to be 82%. XRD of the resulting product confirmed that the resulting zeolitic material had an MWW framework structure. The water adsorption capacity, measured according to Reference Example 1 herein, was 14.1 wt.%.

[0171] Comparative Example 1: Preparation of extrusions of zinc- and titanium-containing zeolitic materials with framework type MWW Extruded articles were produced using the titanium-containing zeolite prepared according to Reference Example 8 above. In a first step CE1.1, the titanium-containing zeolite was impregnated with zinc to obtain a zinc- and titanium-containing zeolite material having an MWW framework. In a second step CE1.2, the zinc- and titanium-containing zeolite material having an MWW framework was shaped. Each of the resulting extruded articles was subjected to a water treatment in a third step CE1.3.

[0172] CE1.1: Zinc impregnation was carried out on the titanium-containing zeolite prepared according to Reference Example 8. The impregnation was carried out as described in WO2013 / 117536A, Example 5.4, page 92, line 9 to page 94, line 8.

[0173] CE1.2: The shaping of zinc- and titanium-containing zeolitic material with framework type MWW was carried out as described in WO2013 / 117536A, Example 5.5, page 95, lines 10-36.

[0174] CE1.3: The water treatment of the extrusions obtained from the second step was carried out as described in WO2013 / 117536A, Example 5.6, page 97, lines 1-17.

[0175] Example 1: Preparation of a molding containing zinc and a titanium-containing zeolite material with framework type MWW Extruded products were produced using the titanium-containing zeolite prepared according to Reference Example 8. In the first step E1.1, the titanium-containing zeolite was extruded. In the second step E1.2, each of the extruded products was subjected to a water treatment, during which zinc was incorporated into the extruded products.

[0176] E1.1: 60 g of titanium-containing zeolite prepared according to Reference Example 8 was mixed with 3 g of Walocel™ (5%; Wolf Walsrode AG) and 37.5 g of Ludox® AS-40 (20% by weight SiO2 relative to the zeolite material) and kneaded for 10 minutes. 160 mL of deionized water was then added, and the resulting mixture was further kneaded. The total kneading time was 40 minutes. Strands were produced from the kneaded mass in a Loomis extruder at a mechanical pressure of 54 bar. The strands had a circular cross section with a diameter of 1.5 mm. In an oven, the strands were heated to a temperature of 120°C at a heating rate of 3 K / min and dried at 120°C for 4 hours under air. The dried strands were then heated to a temperature of 500°C at a heating rate of 2 K / min and dried at 500°C for 5 hours under air.

[0177] E1.2: 50 g of the calcined strands obtained from E1.1 were added to 1,000 g of deionized water and 4.6 g of zinc acetate dihydrate (Merck) in an autoclave without stirring. The mixture was heated to a temperature of 145°C and maintained at that temperature for 8 hours under an autogenous pressure of 2.8 bar. The resulting strands were filtered through a nut-shaped filter and washed five times with 200 mL of deionized water until the conductivity of the water obtained from the washes was less than 30 microsiemens. In an oven, each resulting strand was heated to a temperature of 120°C within 60 minutes and dried at that temperature for 240 minutes in an air atmosphere. The dried strands were then heated to a temperature of 450°C within 165 minutes and calcined at that temperature for 120 minutes in an air atmosphere.

[0178] Comparative Example 2: Preparation of extrusions of zinc- and titanium-containing zeolitic material with framework type MWW Example 1 was repeated except that in step E1.2 reflux conditions were used instead of autogenous pressure.

[0179] More specifically, 50 g of the calcined strands obtained from E1.1 were added to 1,000 g of deionized water and 4.6 g of zinc acetate dihydrate (Merck), then heated to 100°C and stirred at reflux for 8 hours. The resulting strands were filtered through a nut-shaped filter and washed five times with 200 mL of deionized water until the conductivity of the water obtained from the washings was less than 30 microsiemens. In an oven, each resulting strand was heated to a temperature of 120°C within 60 minutes and dried at that temperature for 240 minutes in an air atmosphere. The dried strands were then heated to a temperature of 450°C within 165 minutes and calcined at that temperature for 120 minutes in an air atmosphere.

[0180] Table 1 below shows the results of Comparative Example 1 (CE1), Comparative Example 2 (CE2), and Example 1 (E1).

[0181] [Table 1]

[0182] a) Measured as described in Reference Example 6 herein b) Measured as described in Reference Example 6 herein c) Measured as described in Reference Example 3 herein d) Measured as described in Reference Example 7 herein e) Measured as described in Reference Example 2 herein f) Measured as described in Reference Example 1 herein g) Selectivity after 500 hours on stream was calculated as the ratio of the moles of propylene oxide in the effluent stream divided by the moles of hydrogen peroxide (consumed) in the feed stream multiplied by 100. A continuous reaction was carried out as described in Reference Example 9 herein. h) Not measured

[0183] As shown in Table 1, the zinc content of the extrusions of the present invention was significantly higher (1.6% by mass) than that of the extrusions of the prior art (1.1% by mass), even for the production of strands of the present invention. Furthermore, the amount of zinc acetate dihydrate used per zeolite material was significantly lower (11.5%) compared to the prior art (18.4%) according to Comparative Example 1. Furthermore, the use of the strands of the present invention (E1) resulted in significantly improved values ​​for the PO test and PO test rate compared to Comparative Examples CE1 and CE2. This indicates that the higher the rate, the faster the propene starting material is consumed and the higher the catalytic activity, improving the properties for the preferred use of the strands of the present invention.

[0184] Furthermore, E1 (autogenous conditions) exhibits significantly improved physical properties over CE2 (reflux conditions), as shown in Table 1. In particular, the mechanical strength of CE2 is much lower (15 N for E1 compared to 5.3 N for CE2), which highlights the inferior physical properties of the resulting product when reflux conditions are used instead of the autogenous conditions of E1.2.

Claims

1. 1. A method for producing a catalytic molding for epoxidizing hydrocarbons, comprising zinc and a titanium-containing zeolitic material having a framework MWW, the method comprising: (i) providing a shaped article comprising a titanium-containing zeolite material having a framework MWW; (ii) preparing an aqueous suspension comprising a zinc source and a shaped article comprising the titanium-containing zeolitic material with framework MWW prepared in (i); (iii) heating the aqueous suspension prepared in (ii) under autogenous pressure to a temperature of the liquid phase of the aqueous suspension in the range of 100 to 200°C to obtain an aqueous suspension containing extrudates comprising zinc and a titanium-containing zeolitic material having a framework MWW; (iv) separating from the liquid phase of the suspension obtained in (iii) a shaped product comprising zinc and a titanium-containing zeolitic material having a framework MWW. and In (ii), the zinc source comprises a zinc compound that is soluble in water at the temperature and pressure of the liquid aqueous phase described in (iii); the zinc compound includes one or more of zinc acetate, zinc benzoate, zinc borate, zinc bromide, zinc chloride, zinc formate, zinc gluconate, zinc lactate, zinc laurate, zinc malate, zinc nitrate, zinc perborate, zinc sulfate, zinc sulfamate, and zinc tartrate; (i) the titanium-containing zeolitic material having a framework MWW contained in the formed article is at least 99% by weight of Ti, Si, O, and H; The result of a PO test of the molded product is at least 9%, and the PO test is carried out by reacting propene with an aqueous hydrogen peroxide solution in the presence of the molded product in an autoclave, and the propylene oxide content of the liquid phase is measured on a mass % basis using a pressure transition curve, and the pressure drop rate (PDR) is calculated by the following formula: PDR = [p(max) - p(min)] / delta t (In the formula, PDR / (bar / min) = Pressure Drop Rate p(max) / bar = maximum pressure at the start of the reaction p(min) / bar = minimum pressure observed during the reaction Delta t / min = time difference from the start of the reaction to the time p (min) is observed is required by, and A manufacturing method characterized in that the molded product has a mechanical strength of 15 to 18 N.

2. The method of claim 1 , wherein the zinc compound comprises zinc acetate.

3. The method of claim 1 or 2, wherein the zinc compound comprises zinc acetate dihydrate.

4. 4. The method of claim 1, wherein the shaped article provided in (i) comprises a titanium-containing zeolite material having a framework MWW and a binder, and wherein the mass ratio of the titanium-containing zeolite material having a framework MWW to the binder in the shaped article provided in (i) is in the range of 1:1 to 9:

1.

5. The method according to any one of claims 1 to 4, wherein the molded article provided in (i) exhibits one or more of the following properties (1) or (2): (1) At least 300 m ２ BET specific surface area in g / g; (2) A pore volume of at least 0.9 mL / g.

6. 6. The method of any one of claims 1 to 5, wherein the titanium-containing zeolitic material with framework MWW contained in the formed product provided in (i) is in the form of a powder having a particle size distribution characterized by a Dv10 value in the range of 1 to 10 micrometers, a Dv50 value in the range of 5 to 50 micrometers, and a Dv90 value in the range of 12 to 200 micrometers.

7. 7. The process according to claim 1, wherein the mass ratio of zinc contained in the zinc source in the aqueous suspension prepared in (ii) to the titanium-containing zeolitic material with framework MWW contained in the extrusion is in the range of 0.01:1 to 0.075:

1.

8. 8. The process according to claim 1, wherein the mass ratio of zinc contained in the zinc source in the aqueous suspension prepared in (ii) to the titanium-containing zeolitic material with framework MWW contained in the extrusion is in the range of 0.02:1 to 0.05:

1.

9. 9. The process according to claim 1, wherein the mass ratio of zinc contained in the zinc source in the aqueous suspension prepared in (ii) to the titanium-containing zeolitic material with framework MWW contained in the extrusion is in the range of 0.03:1 to 0.04:

1.

10. 10. The process according to claim 1, wherein the weight ratio of titanium-containing zeolitic material having framework MWW contained in the extrusion to water in the aqueous suspension prepared in (ii) is in the range of 0.01:1 to 0.1:

1.

11. The method according to any one of claims 1 to 10, wherein in (iii), the suspension prepared in (ii) is heated to and maintained at a temperature of the liquid phase of the aqueous suspension in the range of 110 to 175°C.

12. The method further comprises: (v) drying the separated extrusions comprising zinc and titanium-containing zeolitic material with framework MWW obtained from (iv); and (vi) calcining the dried shaped product comprising zinc and titanium-containing zeolitic material with framework MWW obtained from (v); The method according to any one of claims 1 to 11, comprising:

13. A molding as a catalyst for epoxidizing hydrocarbons, comprising zinc and a titanium-containing zeolitic material having a framework MWW, wherein the mass ratio of zinc to titanium-containing zeolitic material having a framework MWW in the molding is in the range of 0.01:1 to 0.075:1; At least 99% by mass of the molding consists of Ti, Si, O, and H; The molded product has a water adsorption capacity in the range of 8 to 12 mass %, The PO test result of the molded article is at least 9%; The PO test is carried out by reacting propene with an aqueous hydrogen peroxide solution in the presence of the molded product in an autoclave, and the propylene oxide content in the liquid phase is measured in mass % using a pressure transition curve. The pressure drop rate (PDR) is calculated using the following formula: PDR = [p(max) - p(min)] / delta t (In the formula, PDR / (bar / min) = Pressure Drop Rate p(max) / bar = maximum pressure at the start of the reaction p(min) / bar = minimum pressure observed during the reaction Delta t / min = time difference from the start of the reaction to the time p (min) is observed is required by, and A molded product characterized in that the molded product has a mechanical strength of 15 to 18N.

14. 13 moldings having one or more of the following characteristics: - at least 200m ２ BET specific surface area in g / g; - a degree of crystallinity in the range of at least 50%; - A porosity of at least 0.9 mL / g.

15. A method for using a molded product obtained by the production method according to any one of claims 1 to 12 or a molded product according to claim 13 or 14 as a catalyst for epoxidizing a hydrocarbon having at least one carbon-carbon double bond.

16. 16. The use of claim 15, wherein the alkene is epoxidized in the presence of a solvent.

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