BR112019014316B1 - PROCESS FOR PREPARING AN FORMING, FORMING COMPRISING ZINC AND A ZEOLYTIC MATERIAL CONTAINING TITANIUM, AND USE OF AN FORMING - Google Patents

Abstract

A process for preparing a molding comprising zinc and a titanium-containing zeolite material having MWW-type framework, comprising (i) providing a molding comprising a titanium-containing zeolite material having MWW-type framework; (ii) preparing an aqueous suspension comprising a source of zinc and the cast comprising a titanium-containing zeolite material having MWW type scaffold 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, obtaining an aqueous suspension comprising a mold comprising zinc and a zeolite material containing titanium having scaffold type MWW; (iv) separating the molding comprising zinc and a titanium-containing zeolite material having MWW type scaffold from the liquid phase of the suspension obtained in (iii).

Description

[001] The present invention relates to a process for preparing a molding comprising zinc and a titanium-containing zeolite material, wherein the zeolite framework structure of the zeolite material has MWW-type framework. Additionally, the present invention relates to a molding that is obtainable or obtainable by said process, and furthermore relates to the use of said molding as a catalyst.

[002] TiMWW catalysts, for example a ZnTiMWW catalyst, i.e. catalysts comprising a titanium-containing zeolite material having MWW-like scaffold further comprising zinc, are known as excellent catalysts for the epoxidation of propene. Such catalysts are normally prepared in a synthesis process involving a shaping stage such as an extrusion step where molds are prepared which are preferred for catalysts used in industrial scale processes such as the aforementioned epoxidation process. Normally, the process for preparing the moldings, i.e. the molding process, starts from a zeolite material comprising zinc. A process for preparing such castings is described, for example, in WO 2013/117536 A from which process catalysts are obtained which, with respect to a preferred use, i.e. use as an epoxidation catalyst, exhibit the most excellent characteristics . As described in WO 2013/117536 A, the process is a multistage process in which the shaping process is based on a powdered material of a zeolite material comprising zinc. Thus, the shaping process is preferably designed based on the characteristics of said powdered material.

[003] Thus, although the catalysts described in WO 2013/117536 A exhibit excellent characteristics, there was a need to provide a modeling process that was applicable for a general variety of titanium-containing zeolite materials having MWW-type framework. Additionally, there was a certain desire to provide a process that is even more economical than the process described in WO 2013/117536 A. Surprisingly, it was observed that it is possible to incorporate zinc into the mold during the molding step and arrive at a catalyst having equal, or even improved, properties compared to castings of WO 2013/117536 A when used, for example, as an epoxidation catalyst. It was additionally observed that, by doing so, it was possible to eliminate a step from the multistage process of WO 2013/117536 A thus making the overall process more economical which is a highly advantageous feature of a particular preparation process in a technical field where the product respectively obtained is a commercial product used in an industrial scale process, as is the case, for example, for epoxidation catalysts.

[004] Therefore, the present invention relates to a process for preparing a molding comprising zinc and a titanium-containing zeolite material having MWW-type framework, comprising: (i) providing a molding comprising a titanium-containing zeolite material having MWW-type framework; (ii) preparing an aqueous suspension comprising a source of zinc and the cast comprising a titanium-containing zeolite material having MWW type scaffold 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, obtaining an aqueous suspension comprising a mold comprising zinc and a zeolite material containing titanium having scaffold type MWW; (iv) separating the molding comprising zinc and a titanium-containing zeolite material having MWW type scaffold from the liquid phase of the suspension obtained in (iii).

Step (i)

[005] Generally, the molding provided in (i) may consist of the titanium-containing zeolite material having MWW-type framework. Preferably, the molding comprises, in addition to the titanium-containing zeolite material having MWW-type scaffolding, a binder. In addition to the binder and the titanium-containing zeolite material having MWW-type scaffolding, the molding may comprise one or more extra additional components. Preferably at least 90% by weight, more preferably at least 95% by weight, most preferably at least 99% by weight, most preferably at least 99.9% by weight of the molding provided in (i) consists of the titanium-containing zeolite material having MWW type framework and binder. More preferably, apart from any impurities which may be comprised in the binder and/or the titanium-containing zeolite material having MWW type scaffold, the molding does not comprise any further components and therefore it is preferred that the molding essentially consists, more preferably consists, of in the binder and in the zeolite material containing titanium having an MWW type framework. In the molding provided in (i), the ratio by weight of the titanium-containing zeolite material having MWW type scaffold with respect to the binder is not subject to any specific restriction. For example, the weight ratio can be in the range of 0.01:1 to 100:1 or 0.1:1 to 10:1. Preferably, the weight ratio is in the range 1:1 to 9:1, more preferably in the range 2:1 to 7:1, most preferably in the range 3:1 to 5:1. While the chemical nature of the binder is not subject to any specific restriction, it is preferred that the binder comprises, more preferably is, a silica binder.

[006] Therefore, it is preferred that at least 99.9% by weight of the molding provided in (i) consists of the titanium-containing zeolite material having MWW-type scaffold and a silica binder.

[007] The molding geometry provided in (i) is not subject to any specific restriction. Preferably, the molding provided in (i) is in the form of a pellet, a sphere, a cylinder, a star, a filament, or a trilobe, wherein the molding is preferably a filament, more preferably an extruded filament, preferably having cross section rectangular, triangular, hexagonal, quadratic, oval or circular cross section. The preferred circular cross-sectional diameter is preferably in the range 0.0.2 to 0.0 mm, more preferably in the range 0.5 to 3.5 mm, most preferably in the range 1.0 to 2.0 mm.

[008] Preferably, the molding provided in (i) is a calcined molding, wherein the calcination is preferably a calcination carried out in a gaseous atmosphere at a temperature of the gaseous atmosphere preferably in the range of 350 to 650°C, more preferably in the range from 400 to 600°C, more preferably in the range from 450 to 550°C, wherein a preferred gaseous atmosphere comprises air, lean air, or nitrogen such as technical nitrogen, most preferably air.

[009] Preferably, the molding provided in (i) exhibits one or more of the following characteristics (1) to (3), preferably two or more of the following characteristics (1) to (3), more preferably the following characteristics (1) a (3): (1) a BET specific surface area of at least 300 m 2 /g determined as described in Reference Example 1 herein; (2) a pore volume of at least 0.9 mL/g, determined 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, determined as described in Reference Example 3 here.

[0010] Therefore, it is preferred that at least 99.9% by weight of the molding provided in (i) consists of the titanium-containing zeolite material having MWW-type scaffold and a silica binder, wherein the molding exhibits the characteristics (1) to (3) described above.

[0011] There are no specific restrictions on how the impression provided in (i) is prepared. A preferred process for preparing the molding comprises: (i.(1) preparing a mixture comprising the titanium-containing zeolite material having MWW-type scaffold, a binder or a source of a binder, a paste-forming agent and optionally a forming agent pore; (i.(2) mold the mixture prepared in (i.1), obtaining an impression comprising the titanium-containing zeolite material having MWW type scaffold and a binder or a source of a binder: (i.(3) dry the impression obtained in (i.2); (i.(4) calcine the dry impression obtained in (i.3), obtaining the impression comprising the zeolite material containing titanium having MWW type framework and a binder.

[0012] Preferably, the paste forming agent according to (i) comprises one or more of water and a hydrophilic polymer, more preferably one or more of water and a carbohydrate, more preferably water and a carbohydrate. The carbohydrate preferably comprises, more preferably is, one or more of a cellulose and a cellulose derivative, more preferably comprises, most preferably is, one or more of a cellulose, a cellulose ether and a cellulose ester, most preferably comprises, more preferably it is a cellulose ether, more preferably an alkyl cellulose ether, most preferably a methyl cellulose. Therefore, it is preferred that the paste forming agent according to (i.1) comprises, more preferably is, water and a methyl cellulose.

[0013] If the mixture prepared in (i.1) comprises a pore-forming agent, it is preferred that the pore-forming agent comprises, preferably is, a mesopore-forming agent, which is preferably one or more one poly(alkylene oxide) such as poly(ethylene oxide), a polystyrene, a polyacrylate, a polymethacrylate, a polyolefin, a polyamide, and a polyester. Poly(ethylene oxide) may be preferred, which may have an average molecular weight MW (g/mol) in the range of 100,000 to 6,000,000, such as about 4,000,000.

[0014] Preferably, the binder or precursor of a binder of the mixture provided in (i.1) comprises, more preferably is, a silica binder or a precursor of a silica binder. With regard to 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 such silica is amorphous silica, the size of the silica particles being, for example, in the range of 1 to 100 nm and the surface area of the silica particles being in the range of 50 to 500 m 2 /g. Colloidal silica, preferably as an alkaline and/or ammonia solution, more preferably as an ammonia solution, is commercially available, INTER ALIA, for example as Ludox®, Syton®, Nalco® or Snowtex®. “Wet process” silica is commercially available, INTER ALIA, for example, as Hi-Sil®, Ultrasil®, Vulcasil®, Santocel®, Valron-Estersil®, Tokusil® or Nipsil®. “dry process” silica is commercially available, INTER ALIA, for example, as Aerosil®, Reolosil®, Cab-O-Sil®, Fransil® or ArcSilica®. INTER ALIA, an ammonia solution of colloidal silica is preferred in the present invention. Preferably, according to the present invention, the silica binder precursor comprised in the mixture according to (i.1) comprises, more preferably is, one or more of a silica gel, a precipitated silica, a fumed silica, and a colloidal silica. More preferably, the silica binder precursor comprised in the mixture according to (i.1) comprises, preferably is, a colloidal silica. More preferably, the silica binder precursor comprised in the mixture according to (i.1) consists of a colloidal silica, where more preferably, the silica binder or precursor comprises, preferably is, a colloidal silica.

[0015] Preferably, in the mixture prepared in (i.1), the weight ratio of the zeolite material containing titanium having an MWW-type framework with respect to the silica comprised in the binder or in the binder precursor is in the range of 1:1 to 9: 1, more preferably in the range 2:1 to 7:1, most preferably in the range 3:1 to 5:1.

[0016] Preferably, the mixture prepared in (i.1) does not comprise zinc, neither in the binder nor in the titanium-containing zeolite material having MWW-type framework nor in any of the other components of the mixture. The expression “does not contain zinc” does not exclude a minimum amount of zinc that may be present in the mixture due to impurities in one or more components of the mixture that cannot be avoided.

[0017] 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 the titanium-containing zeolite material having scaffold type MWW, the binder or binder precursor, and the paste-forming agent.

[0018] Preferably, preparing the mixture according to (i.1) comprises mechanically stirring, more preferably kneading the mixture, wherein kneading is preferably carried out until the individual components of the mixture which have been added in a suitable sequence form a mixture with each other homogeneous mass.

[0019] Preferably, the shaping according to (i.2) comprises extruding the mixture prepared in (i.1). With regard to extrusion according to (i.2), there are no specific restrictions. Generally, each method of extruding the mixture obtained from (i.1) can be employed. The term "extrusion" as used herein refers to a method from which moldings having an essentially fixed cross-sectional profile are obtained in which the composition obtained from (iv) is suitably pressed through a suitable die exhibiting the desired cross-section. The molding which is obtained from the used extruder can be cut downstream of the respectively used die, for example using a stream of air and/or a suitable mechanical cutting device such as a suitable wire. If it is not necessary to obtain moldings having essentially identical length, it is also possible that the molding obtained from the extruder is not cut, but breaks under its own weight downstream of the die, leading to moldings having different lengths. The cross-section of the molding can be, for example, circle-shaped, oval-shaped, star-shaped, and the like. Preferably, according to the present invention, the molding has a circle-shaped cross-section where the diameter is preferably in the range of 0.0.2 to .0 mm, more preferably in the range of 0.5 to 3.5 mm, more preferably in the range of 1.0 to 2.0 mm.

[0020] Preferably, according to (i.3), the molding is dried. Drying is preferably carried out in a gas atmosphere at a temperature of the gas atmosphere preferably in the range 80 to 200°C, more preferably in the range 90 to 175°C, most preferably in the range 100 to 150°C. Any suitable gaseous atmosphere may be used, a preferred gaseous atmosphere comprising air, lean air, or nitrogen such as technical nitrogen.

[0021] Preferably, according to (i.4), the dry casting obtained from (i.3) is calcined. The calcination is preferably carried out in a gas atmosphere at a temperature of the gas atmosphere preferably in the range of 350 to 650°C, more preferably in the range of 400 to 600°C, most preferably in the range of 450 to 550°C. Any suitable gaseous atmosphere may be used, a preferred gaseous atmosphere comprising air, lean air, or nitrogen such as technical nitrogen.

[0022] With regard to the zeolite material containing titanium having an MWW-type framework comprised in the molding provided in (i), there are no specific restrictions regarding its chemical composition. Therefore, it may be possible that in addition to Ti, Si, O and H, the zeolite material contains additional framework and/or extra-framework elements, e.g. one or more trivalent framework elements, one or more tetravalent, and/or one or more pentavalents such as Al, Em, Ga, B, Ge, Sn, and the like. Preferably, at least 95% by weight, more preferably at least 98% by weight, most preferably at least 99% by weight of the titanium-containing zeolite material having MWW type scaffold comprised in the molding provided in (i) consist of Ti, Si, O , and H in which the backbone of the zeolite material preferably essentially consists of Ti, Si and O. The titanium content of the titanium-containing zeolite material having MWW type backbone comprised in the molding provided in (i) is not subject to any specific restriction . Preferably, the titanium-containing zeolite material having MWW-type framework comprised in the molding 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 zeolite material having MWW type framework. A preferred range may be 1.5 to 2% by weight. Preferably, the titanium-containing zeolite material having MWW type framework comprised in the molding 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, most preferably in the range of 1 to 3% by weight, based on the total weight of the titanium-containing zeolite material having MWW type framework. A preferred range may be 44 to 48% by weight. Therefore, it is preferred that the titanium-containing zeolite material having MWW type framework comprised in the molding provided in (i) has a titanium content in the range of 1 to 3% by weight and a silicon content in the range of 40 to 50% in weight, where it may be preferred that it has a titanium content in the range of 1.5 to 2% by weight and a silicon content in the range of 44 to 48% by weight.

[0023] Preferably, the titanium-containing zeolite material having MWW-type framework comprised in the molding 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 zeolite material having MWW-like framework. Preferably, the titanium-containing zeolite material having MWW type framework comprised in the molding 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, plus preferably at most 0.5%, by weight based on the total weight of the titanium-containing zeolite material having MWW type framework. Preferably, the titanium-containing zeolite material having MWW type framework comprised in the molding provided in (i) has a BET specific surface area of at least 400 m2/g, preferably in the range of 400 to 600 m2/g, more preferably in the range of 450 to 550 m 2 /g, where the specific surface area of BET is determined as described in Reference Example 1 here. Preferably, the titanium-containing zeolite material having MWW-type framework comprised in the molding 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 determined as described in Reference Example 4 here. Preferably, the titanium-containing zeolite material having MWW-type framework comprised in the molding provided in (i) is in the form of a powder having a particle size distribution distinguished 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 10 micrometers, preferably in the range of 7 to 50 micrometers, most 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 determined as described in Reference Example 5 herein. The titanium-containing zeolite material having MWW type scaffold comprised in the molding provided in (i) may be a spray powder, i.e. a powder obtained from a spray drying process, or it may be a powder which is obtained from other processes which may result in a powder having the aforementioned preferred particle size distribution, such as flash drying or may be microwave drying.

[0024] According to preferred embodiments of the present invention, the titanium-containing zeolite material having MWW-type framework comprised in molding prepared in (i), for example comprised in the mixture prepared in (i.1), is obtainable or obtainable by a process comprising: (a) preparing a boron-containing zeolite material having MWW-type scaffold, wherein at least 99% by weight of the zeolite scaffold consists of B, Si, O and H; (b) deburring the boron-containing zeolitic material having MWW-type scaffold prepared in (a), obtaining a deburred zeolite material having MWW-type scaffolding, wherein at least 99% by weight of the zeolite scaffold of the debored zeolite material consists of B, Si, O and H, and wherein the zeolitic framework of the debonded zeolite material has empty framework sites; (c) incorporating titanium into the deboronized zeolite material obtained from (b), comprising preparing an aqueous synthesis mixture containing the deboroned zeolite material obtained from (b), a source of titanium, and an MWW template compound; and hydrothermally synthesizing a titanium-containing zeolitic material having MWW-type framework from the aqueous synthesis mixture prepared in (c), obtaining a mother liquor comprising a titanium-containing zeolite material having MWW-type framework; (d) separating the titanium-containing zeolite material having MWW-like scaffold synthesized in (c) from the mother liquor; (e) treating the separated titanium-containing zeolite material having MWW type scaffold obtained from (d) with an aqueous solution having a pH of at most 5; (f) separating the titanium-containing zeolite material having MWW-type scaffold obtained from (e) from the aqueous solution, optionally followed by washing the titanium-containing zeolite material having separated MWW-type scaffolding; (g) preparing a suspension, preferably an aqueous suspension, containing the titanium-containing zeolite material having MWW-type scaffold obtained from (f), and subjecting the suspension to spray drying; (h) calcining the titanium-containing zeolite material having MWW type scaffold obtained from (g).

[0025] According to a preferred embodiment of the present invention, providing the titanium-containing zeolite material having MWW-type framework comprised in the molding prepared in (i) comprises: (a) preparing a boron-containing zeolite material having MWW-type framework, in which at least at least 99% by weight of the zeolite backbone consists of B, Si, O and H; (b) deburring the boron-containing zeolitic material having MWW-type scaffold prepared in (a), obtaining a deburred zeolite material having MWW-type scaffolding, wherein at least 99% by weight of the zeolite scaffold of the debored zeolite material consists of B, Si, O and H, and wherein the zeolitic framework of the debonded zeolite material has empty framework sites; (c) incorporating titanium into the deboronized zeolite material obtained from (b), comprising preparing an aqueous synthesis mixture containing the deboroned zeolite material obtained from (b), a source of titanium, and an MWW template compound; and hydrothermally synthesizing a titanium-containing zeolitic material having MWW-type framework from the aqueous synthesis mixture prepared in (c), obtaining a mother liquor comprising a titanium-containing zeolite material having MWW-type framework; (d) separating the titanium-containing zeolite material having MWW-like scaffold synthesized in (c) from the mother liquor; (e) treating the separated titanium-containing zeolite material having MWW type scaffold obtained from (d) with an aqueous solution having a pH of at most 5; (f) separating the titanium-containing zeolite material having MWW-type scaffold obtained from (e) from the aqueous solution, optionally followed by washing the separated titanium-containing zeolite material having MWW-type scaffolding; (g) preparing a suspension, preferably an aqueous suspension, containing the titanium-containing zeolite material having MWW-type scaffold obtained from (f), and subjecting the suspension to spray drying; (h) calcining the titanium-containing zeolite material having MWW type scaffold obtained from (g).

[0026] According to a preferred embodiment of the present invention, preparing the boron-containing zeolite material having MWW type scaffold in (a) comprises: (i) 1) preparing an aqueous synthesis mixture comprising a source of silicon, a source of boron , and a mold compound from MWW; (j) 2) hydrothermally synthesizing a boron-containing zeolite material precursor having MWW-type framework from the aqueous synthesis mixture prepared in (a.1), obtaining a mother liquor comprising the boron-containing zeolite material precursor having MWW-type framework; (k) 3) separating the precursor of boron-containing zeolite material having MWW-type framework from the mother liquor, obtaining the separated precursor of boron-containing zeolite material having MWW-type framework; (l) 4) calcining the precursor separated from the boron-containing zeolite material having MWW-type framework, obtaining the boron-containing zeolite material having MWW-type framework.

[0027] In the aqueous synthesis mixture prepared in (a.1), the molar ratio of the MWW template compound with respect to Si, calculated as elemental silicon and comprised in the silicon source, is preferably at least 0.4:1 , more preferably in the range 0.4:1 to 2.0:1, more preferably in the range 0.6:1 to 1.9:1, most preferably in the range 0.9:1 to 1.4: 1. In the aqueous synthesis mixture prepared in (a.1), the molar ratio of water to 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, more preferably in the range 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, with respect 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 0.6:1 to 1.9:1, most preferably in the range 0.9:1 to 1.4:1. In (a.1), the source of boron is preferably one or more of boric acid, a borate, and boron oxide, most preferably boric acid. In (a.1), the silicon source is preferably one or more of fumed silica and colloidal silica, more preferably colloidal silica, most preferably ammonia-stabilized colloidal silica. In (a.1), the MWW template compound is preferably one or more of piperidine, hexamethylene imine, N,N,N,N',N',N'-hexamethyl-1,5-pentanediammonium ion, 1 ,4-bis(N-methylpyrrolidinium)butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, and hexyltrimethylammonium hydroxide, most preferably piperidine. Preferably, at least 99% by weight, more preferably at least 99.5% by weight, most preferably at least 99.9% by weight of the aqueous synthesis mixture prepared in (a.1) consists of water, from the source of boron , the source of silicon, and the molding compound from MWW.

[0028] In (a.2), the hydrothermal synthesis is carried out at an atmosphere of the aqueous synthesis mixture preferably in the range of 160 to less than 180°C, more preferably in the range of 170 to 177°C. In (a.2), the hydrothermal synthesis is carried out for a period of time preferably in the range of 1 to 72 hours, more preferably in the range of 6 to 60 hours, most preferably in the range of 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, most preferably at least 11, and after (a.2) and before (a.3), the pH of the mother liquor is preferably adjusted to a value of at most 10, more preferably at most 9, most preferably at most 8, most preferably in the range of 7 to 8. Preferably, the pH of the liquid phase of the mother liquor is adjusted by subjecting the phase mother liquor liquid to an acid treatment, wherein the acid is preferably an inorganic acid, more preferably one or more of phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid, the acid most preferably being nitric acid.

[0029] The separation according to (a.3) preferably comprises subjecting the mother liquor obtained in (a.2) to filtration. Separation according to (a.3) preferably comprises drying, preferably spray drying.

[0030] In (a.4), the separated precursor of boron-containing zeolite material having MWW type scaffold is calcined at an atmosphere preferably in the range of 400 to 800°C, more preferably 600 to 700°C.

[0031] In (b), the boron-containing zeolite material having MWW-type scaffold prepared in (a) is preferably deslimed by treating the boron-containing zeolite material having MWW-type scaffold with a liquid solvent system, obtaining the deslimed zeolite material having mWW-type scaffold MWW, wherein preferably at least 99% by weight of the zeolite framework of the debored zeolite material consists of B, Si, O and H and wherein the zeolite framework of the debored zeolite material preferably has empty framework sites. Preferably, the deborined zeolite material having MWW type scaffold obtained from (b) has a molar ratio of boron, calculated as B2O3, to silicon, calculated as SiO2, of at most 0.02:1, more preferably at most 0, 01:1, more preferably in the range 0.001:1 to 0.01:1, more preferably in the range 0.001:1 to 0.003:1, wherein preferably at least 99.5% by weight, most preferably at least 99, 9% by weight of the deborined zeolite material having MWW type scaffold 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, wherein preferably, the liquid solvent system does not contain an inorganic acid and an organic acid. Prior to (b), the weight ratio of liquid solvent system to zeolite material having MWW type scaffold is preferably in the range of 5:1 to 40:1, more preferably in the range of 7.5:1 to 30: 1, 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 temperature of the liquid solvent system in the range of 50 to 125°C, more preferably in the range of 90 to 115°C, most preferably in the range of 95°C. at 105°C. In (b), the treatment with the liquid solvent system is preferably carried out for a period in the range of 6 to 20 hours, more preferably in the range of 7 to 17 hours, most preferably in the range of 8 to 12 hours. In (b), 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) comprises drying, more preferably spray drying, the deboned zeolite material having MWW type scaffold. Preferably, the debored zeolite material having MWW type scaffold obtained from (b) is not subjected to calcination before (c).

[0032] In (c), the template compound of MWW is preferably one or more of piperidine, hexamethylene imine, N,N,N,N',N',N'-hexamethyl-1,5-pentanediammonium ion, 1,4-bis(N-methylpyrrolidinium)butane hydroxide, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, and hexyltrimethylammonium hydroxide, most preferably piperidine. In (c), the source of titanium is preferably one or more of tetra-n-butyl orthotitanate, tetraiso-propyl orthotitanate, tetraethyl orthotitanate, titanium dioxide, titanium tetrachloride, and titanium tert-butoxide, the titanium source preferably being tetra-n-butyl orthotitanate. In the aqueous synthesis mixture in (c), the molar ratio of Ti, calculated as TiO2 and comprised in the titanium source, with respect to Si, calculated as SiO2 and comprised in the deboronated zeolite material having MWW type framework, is preferably in the range from 0.005:1 to 0.1:1, more preferably in the range from 0.01:1 to 0.08:1, most preferably in the range from 0.02:1 to 0.06:1, the molar ratio of H2O with respect to Si, calculated as SiO2 and comprised in the deborined zeolite material having MWW type framework, is preferably in the range from 8:1 to 20:1, more preferably in the range from 10:1 to 18:1, most preferably in the range of 12:1 to 16:1, and the molar ratio of the MWW template compound with respect to Si, calculated as SiO2 and comprised in the deborined zeolite material having MWW type scaffolding, is preferably in the range of 0.5:1 to 1, 7:1, more preferably in the range 0.8:1 to 1.5:1, most preferably in the range 1.0:1 to 1.3:1. In (c), hydrothermal sintering is preferably carried out at a temperature in the range 80 to 250°C, more preferably in the range 120 to 200°C, most preferably in the range 160 to 180°C, preferably in a closed system under autogenous pressure. Preferably, neither during (c), nor after (c) and before (d), the titanium-containing zeolite material having MWW-type scaffold is separated from its mother liquor.

[0033] Preferably, the mother liquor subjected to (d) comprising the titanium-containing zeolite material having MWW type scaffold has a solids content, optionally after concentration or dilution, in the range of 5 to 25% by weight, more preferably in the range of 10 to 20% by weight, based on the total weight of the mother liquor comprising the titanium-containing zeolite material having MWW type framework. Preferably, the separation according to (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 from 200 to 350°C, and the drying gas outlet temperature is preferably in the range from 70 to 190°C.

[0034] In (e), the weight ratio of the aqueous solution to the titanium-containing zeolite material having MWW-type scaffold is preferably in the range of 10:1 to 30:1, more preferably in the range of 15:1 to 25: 1, more preferably in the range of 18:1 to 22:1, and the aqueous solution preferably comprises an inorganic acid, more preferably one or more of phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid, most preferably nitric acid. Preferably, after (d) and before (e), the separated titanium-containing zeolite material having MWW-type scaffold obtained from (d) is not subjected to calcination. In (e), the aqueous solution preferably has a pH in the range of 0 to 5, more preferably in the range of 0 to 3, most preferably in the range of 0 to 2. In (e), the titanium-containing zeolite material having scaffold type MWW is preferably treated with the aqueous solution at an aqueous solution temperature in the range of 50 to 175°C, more preferably in the range of 70 to 125°C, most preferably in the range of 95 to 105°C, preferably in a closed system under autogenous pressure.

[0035] Separating the titanium-containing zeolite material having MWW-type framework according to (f) preferably comprises washing the titanium-containing zeolite material having MWW-type framework. Separating the titanium-containing zeolite material having MWW-type framework according to (f) preferably comprises drying the titanium-containing zeolite material having MWW-type framework. The separation of the titanium-containing zeolite material having MWW-type framework according to (f) preferably comprises preparing a suspension, preferably an aqueous suspension containing the titanium-containing zeolite material having MWW-type framework obtained from (e), said suspension having a content of solids preferably in the range of 5 to 25% by weight, more preferably in the range of 10 to 20% by weight, based on the total weight 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 in the range of 200 to 330°C, and the drying gas outlet temperature is preferably in the range of 100 to 180°C, more preferably in the range 120 to 180°C.

[0036] The calcination 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.

Step (ii)

[0037] Generally, there are no specific restrictions regarding the chemical nature of the zinc source used according to (ii). Preferably, the zinc source comprises, more preferably consists of, a zinc compound which 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 of a zinc salt of an organic or inorganic acid, preferably comprises one or more of zinc acetate, zinc benzoate, zinc borate, zinc bromide, zinc chloride, formate zinc, zinc gluconate, zinc lactate, zinc laurate, zinc malate, zinc nitrate, zinc perborate, zinc sulfate, zinc sulfamate, zinc tartrate, most preferably comprises zinc acetate, most preferably comprises di -zinc acetate hydrate. More preferably, the zinc source consists of one or more of a zinc salt of an organic or inorganic acid, preferably it consists of 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 consisting of zinc acetate, more preferably it consists of zinc acetate dihydrate.

[0038] In the aqueous suspension prepared in (ii), the weight ratio of zinc, calculated as elemental zinc and comprised in the zinc source with respect to the zeolite material containing titanium having MWW-type framework comprised in the molding, is preferably in the range of 0.005: 1 to 0.1:1, more preferably in the range 0.01:1 to 0.075:1, more preferably in the range 0.02:1 to 0.05:1, most preferably in the range 0.03:1 to 0.04:1. Additionally in the aqueous suspension prepared in (ii), the weight ratio of the titanium-containing zeolite material having MWW type scaffold comprised in the molding with respect to water is preferably in the range of 0.01:1 to 0.1:1, more preferably in the range of 0.01:1 to 0.1:1. in the range 0.02:1 to 0.075:1, more preferably in the range 0.03:1 to 0.05:1.

[0039] Generally, it is conceivable that, in addition to the water, the zinc source and the titanium-containing zeolite material having MWW-type framework, the aqueous suspension comprises one or more additional suitable components. Preferably at least 99% by weight, more preferably at least 99.5% by weight, most preferably at least 99.9% by weight of the aqueous suspension prepared in (ii) consists of water, the source of zinc and the mold comprising the zeolite material containing titanium having MWW type framework.

[0040] It is conceivable that at least a portion of the water comprised in the aqueous suspension is ammonia stabilized water.

Step (iii)

[0041] According to (iii), it is preferred that the aqueous suspension prepared in (ii) is heated and maintained at a temperature of the liquid phase of the aqueous suspension in the range of 100 to 190°C, more preferably in the range of 110 at 175°C, more preferably in the range 115 to 160°C, most preferably in the range 120 to 150°C. Preferred ranges are, for example, from 120 to 130°C or from 125 to 135°C or from 130 to 140°C or from 135 to 145°C or from 140 to 150°C. Preferably, in (iii), the suspension prepared in (ii) is kept at that temperature for a period of time in the range of 1 to 24 hours, more preferably in the range of 2 to 17 hours, most preferably in the range of 3 to 10 hours .

[0042] Preferably, during heating or during holding or during heating and holding in (iii), the suspension prepared in (ii) is not stirred.

Step (iv)

[0043] Generally, there are no specific restrictions on how the separation in (iv) is performed. Preferably, the separation in (iv) comprises subjecting the aqueous suspension obtained from (iii) to filtration or centrifugation, optionally followed by washing, obtaining the separated cast comprising zinc and a titanium-containing zeolite material having MWW-type framework. All types of filters are conceivable which preferably exhibit, during filtration, a loss of at most 10% by weight of solid material. Conceivable filters include, for example, decanters, slotted sieves, Nutsch-type filters, and the like.

Step (v)

[0044] Preferably, the molding separated according to (iv) is subjected to drying according to (v). Before drying, it is conceivable to subject the separate molding according to (iv) to pre-drying in a suitable gaseous atmosphere such as nitrogen, air or lean air at a temperature of the gaseous atmosphere preferably of at most 50°C, more preferably of at most 40°C, more preferably at most°C, more preferably in the range 10 to 30°C, most preferably in the range 20 to 30°C.

[0045] Preferably, the separate molding comprising zinc and a titanium-containing zeolite material having MWW type scaffold obtained from (iv) is 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. Preferably, in (v), the molding is dried at this temperature for a period of time in the range of 0.5 to 12 hours, more preferably in the range of 1 to 8 hours, most preferably in the range of 2 to 6 hours. Preferably, the separate casting comprising zinc and a titanium-containing zeolite material having MWW type scaffold is dried in a gaseous atmosphere comprising oxygen, preferably air or poor air, more preferably air, wherein the aforementioned drying temperature is the temperature of the gaseous atmosphere used for drying.

Stage (vi)

[0046] Preferably, the separated molding according to (iv) or the molding obtained from drying according to (v), preferably the molding obtained from drying according to (v), is subjected to calcination according to (vi) .

[0047] Preferably, the dry casting preferably comprising zinc and a titanium-containing zeolite material having MWW type scaffold is calcined at a temperature in the range of 300 to 600°C, preferably in the range of 350 to 550°C, more preferably in the range of 400 to 500°C. If calcination is carried out in a batch process, it may be preferable to carry out the calcination for a period of time in the range of 0.1 to 6 hours, more preferably in the range of 0.2 to 4 hours, most preferably in the range of 0. 5 to 3 hours. The calcination can also be carried out in a continuous process using, for example, a rotary kiln, a band calcinator, or the like. Preferably, the dry casting preferably comprising zinc and a titanium-containing zeolite material having MWW-type scaffold is calcined in a gaseous atmosphere comprising oxygen, preferably air or poor air, more preferably air, wherein the aforementioned calcination temperature is the temperature of the atmosphere gas used for calcination.

[0048] According to the present invention, it is preferred that during the entire process, the molding is not subjected to water-spraying, more preferably not subjected to steaming.

Molding and its use

[0049] Furthermore, the present invention relates to a molding comprising zinc and a zeolite material containing titanium having MWW type scaffold, obtainable or obtained by a process as described above, preferably according to a process as described above comprising drying according to (v), more preferably according to process comprising calcining according to (vi), most preferably comprising drying according to (v) and calcining according to (vi).

[0050] Additionally, the present invention relates to a molding comprising zinc and a titanium-containing zeolite material having an MWW-type framework, wherein in the molding, the weight ratio of zinc with respect to the titanium-containing zeolite material having an MWW-type framework is in the in the range 0.005:1 to 0.1:1, preferably in the range 0.01:1 to 0.075:1, more preferably in the range 0.02:1 to 0.05:1, most preferably in the range 0. 03:1 to 0.04:1.

[0051] Preferably, at least 99% by weight, more preferably at least 99.5% by weight of the molding consists of zinc, Ti, Si, O, and H. Preferably, the molding essentially consists of zinc, Ti, Si, O, and H. The expression "essentially consists of" as used in this context of the present invention refers to a molding which, apart from any impurities which cannot be avoided in a given process for preparing the molding, the molding consists of zinc, Ti, Si, O, and H.

[0052] Preferably, the molding has a BET specific surface area of at least 200 m2/g, more preferably at least 225 m2/g, most preferably at least 250 m2/g, wherein the specific surface area of BET is determined as described in Reference Example 1 here.

[0053] Preferably, the molding has a crystallinity of at least 50%, preferably in the range of 50 to 90%, where crystallinity is determined as described in Reference Example 4 herein.

[0054] Preferably, the molding has a porosity of at least 0.9 ml/g, determined as described in Reference Example 2 herein.

[0055] Preferably, the molding 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, determined as described in Reference Example 3 here.

[0056] Preferably, the molding exhibits 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, determined as described in Reference Example 7 here.

[0057] Preferably, the impression exhibits a PO test parameter of at least 8%, preferably at least 9%, determined as described in Reference Example 6 herein.

[0058] The molding of the present invention can be used for any conceivable purpose, including, but not limited to, an absorbent, an adsorbent, a molecular sieve, a catalyst, a catalyst support, or an intermediate for preparing one or more thereof . Preferably, the molding is used as a catalyst, more preferably as a catalyst for converting a hydrocarbon, more preferably for oxidizing a hydrocarbon, more preferably for epoxidizing a hydrocarbon having at least one carbon-carbon double bond, more preferably for epoxidizing an alkene. Preferred alkenes include, but are not limited to, ethene, propene, 1-butene, 2-butene, 1-pentene, and 2-pentene. Propene is most preferred.

[0059] Therefore, the present invention preferably relates to the use of molding as a catalyst for epoxidizing propylene. Preferably, the alkene, more preferably the propylene, is epoxidized in the presence of a solvent, wherein the solvent preferably comprising a nitrile, most preferably comprising acetonitrile. More preferably, the solvent is acetonitrile, optionally in combination with water. Epoxidation can be carried out using any conceivable epoxidation agent including the preferred hydrogen peroxide which can be used as such or can be formed IN SITU in the respective epoxidation reaction.

[0060] Additionally, the present invention relates to a method for catalytically converting a hydrocarbon, preferably for catalytically oxidizing a hydrocarbon, more preferably for catalytically epoxidizing a hydrocarbon having at least one carbon-carbon double bond, more preferably for catalytically epoxidizing an alkene , wherein the hydrocarbon, preferably the hydrocarbon having at least one carbon-carbon double bond, more preferably the alkene, is brought into contact with the molding according to the present invention. Preferred alkenes include, but are not limited to, ethene, propene, 1-butene, 2-butene, 1-pentene, and 2-pentene. Propene is most preferred. Preferably, the alkene, more preferably the propylene, is epoxidized in the presence of a solvent, wherein the solvent preferably comprising a nitrile, most preferably comprising acetonitrile. More preferably, the solvent is acetonitrile, optionally in combination with water. Epoxidation can be carried out using any conceivable epoxidation agent including the preferred hydrogen peroxide which can be used as such or can be formed IN SITU in the respective epoxidation reaction.

[0061] Still further, the present invention relates to a catalytic system comprising a catalyst comprising a cast 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 combinations of at least one inorganic potassium salt and at least one organic potassium salt. At least one potassium salt is preferably 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 consists of potassium formate, potassium acetate, potassium carbonate, and potassium hydrogencarbonate, and a combination of at least one of at least one of the inorganic potassium salts and at least one of the at least one of the organic potassium salts. Preferably, said catalytic system is a catalytic system for the epoxidation of an alkene, preferably propylene. Preferably, said catalyst system is obtainable or obtainable by a preferably continuous process comprising; (i') providing a liquid feed stream comprising an alkene, preferably propene, hydrogen peroxide, a solvent, preferably acetonitrile, water, at least one dissolved potassium salt; (ii') passing the liquid feed stream provided in (i') into an epoxidation reactor comprising the catalyst comprising a mold according to the present invention; wherein in (i'), the molar ratio of potassium to hydrogen peroxide in the liquid feed stream is preferably in the range of 5x10-6:1 to 1000x10-6:1, preferably of 25x10-6:1 to 500x10-6:1, more preferably from 50x10-6:1 to 250x10-6:1; wherein the process preferably comprises: (iii') subjecting the liquid feed stream to epoxidation reaction conditions in the epoxidation reactor, obtaining a reaction mixture comprising an alkene oxide, preferably propylene oxide, solvent, preferably acetonitrile, water , at least one potassium salt, and optionally non-epoxidized alkene, preferably non-epoxidized propylene.

[0062] Still further, the present invention relates to a process for preparing an alkene oxide, preferably propylene oxide, said process comprising: (i') providing a liquid feed stream comprising an alkene, preferably propylene, peroxide, hydrogen, a solvent, preferably acetonitrile, water, at least one dissolved potassium salt; (ii') passing the liquid feed stream provided in (i') into an epoxidation reactor comprising the catalyst comprising a mold according to the present invention; (iii') subjecting the liquid feed stream to epoxidation reaction conditions in the epoxidation reactor, obtaining a reaction mixture comprising an alkene oxide, preferably propylene oxide, solvent, preferably acetonitrile, water, at least one potassium salt , and optionally non-epoxidized alkene, preferably non-epoxidized propylene; wherein in (i'), the molar ratio of potassium to hydrogen peroxide in the liquid feed stream is preferably in the range of 5x10-6:1 to 1000x10-6:1, preferably of 25x10-6:1 to 500x10-6:1, more preferably from 50x10-6:1 to 250x10-6:1.

[0063] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the foregoing dependencies and references as indicated. In particular, note that in each case where a range of modalities is mentioned, for example in the context of an expression such as "The process of any of modalities 1 to 4", each modality in that range must be explicitly described by the versed in the technique, that is, the wording of this expression must be understood by those versed in the technique as being synonymous with “The process of any of the modalities 1, 2, 3 and 4”.

[0064] 1. A process for preparing a molding comprising zinc and a titanium-containing zeolite material having MWW-type framework, comprising: (i) providing a molding comprising a titanium-containing zeolite material having MWW-type framework; (ii) preparing an aqueous suspension comprising a source of zinc and the cast comprising a titanium-containing zeolite material having MWW type scaffold 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, obtaining an aqueous suspension comprising a mold comprising zinc and a zeolite material containing titanium having scaffold type MWW; (iv) separating the molding comprising zinc and a titanium-containing zeolite material having MWW type scaffold from the liquid phase of the suspension obtained in (iii).

[0065] 2. The process of embodiment 1, wherein the molding provided in (i) comprises the titanium-containing zeolite material having MWW-type framework and a binder.

[0066] 3. The process of embodiment 2, wherein at least 90% by weight, preferably at least 95% by weight, more preferably at least 99% by weight, most preferably at least 99.9% by weight of the molding provided in (i) consist of the titanium-containing zeolite material having MWW type scaffold and the binder.

[0067] 4. The process of embodiment 2 or 3, in which, in the molding provided in (i), the weight ratio of the zeolite material containing titanium having MWW-type framework with respect to the binder is in the range of 1:1 to 9 :1, preferably in the range 2:1 to 7:1, more preferably in the range 3:1 to 5:1, wherein the binder is preferably a silica binder.

[0068] 5. The process of any one of embodiments 1 to 4, in which the molding provided in (i) is in the form of a tablet, a sphere, a cylinder, a star, a filament, or a trilobe, in which the molding is preferably a filament, more preferably an extruded filament, preferably having rectangular, triangular, hexagonal, quadratic, oval, or circular cross-section, wherein the diameter of the preferred circular cross-section is preferably in the range of 1.0 to 2.0 mm.

[0069] 6. The process of any one of embodiments 1 to 5, wherein the molding provided in (i) exhibits one or more of the following characteristics (1) to (3), preferably two or more of the following characteristics (1) a (3), more preferably of the following characteristics (1) to (3): (1) a BET specific surface area of at least 300 m 2 /g determined as described in Reference Example 1 herein; (2) a pore volume of at least 0.9 mL/g, determined 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, determined as described in Reference Example 3 here.

[0070] 7. The process of any one of embodiments 1 to 6, preferably of any one of embodiments 2 to 6, wherein the molding comprising the titanium-containing zeolite material having MWW type framework provided in (i) is obtainable or obtainable by a process comprising: (i.(1) preparing a mixture comprising the titanium-containing zeolite material having MWW type scaffold, a binder or a source of a binder, a slurry forming agent and optionally a pore forming agent; (i. (2) modeling the mixture prepared in (i.1), obtaining an impression comprising the titanium-containing zeolite material having MWW type scaffold and a binder or a source of a binder: (i.(3) drying the impression obtained in (i. .2); (i.(4) calcine the dry impression obtained in (i.3), obtaining the impression comprising the zeolite material containing titanium having MWW type framework and a binder.

[0071] 8. The process of any one of embodiments 1 to 6, preferably of any one of embodiments 2 to 6, wherein providing the molding according to (i) comprises: (i.(1) preparing a mixture comprising the titanium-containing zeolite material having MWW-type scaffold, a binder or a source of a binder, and a paste-forming agent; (i.(2) modeling the mixture prepared in (i.1), obtaining a molding comprising the zeolite material containing titanium having MWW type scaffold and a binder or a source of a binder: (i.(3) dry the impression obtained in (i.2); (i.(4) calcine the dry impression obtained in (i.3), obtaining the molding comprising the titanium-containing zeolite material having MWW type scaffold and a binder.

[0072] 9. The process of embodiment 7 or 8, wherein the paste forming agent according to (i.1) comprises one or more of water and a carbohydrate, preferably water and a carbohydrate.

[0073] 10. The process 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 one poly(alkylene oxide) such as poly(ethylene oxide), a polystyrene, a polyacrylate, a polymethacrylate, a polyolefin, a polyamide, and a polyester.

[0074] 11. The process 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 a or more than one poly(alkylene oxide) such as poly(ethylene oxide), a polystyrene, a polyacrylate, a polymethacrylate, a polyolefin, a polyamide, and a polyester.

[0075] 12. The process of any one of embodiments 7 to 11, wherein the binder or precursor of a binder is a silica binder or a precursor of a silica binder, wherein, more preferably, the silica binder or the precursor comprises, preferably is, colloidal silica.

[0076] 13. The process of any of the modalities 7 to 12, in which, in the mixture prepared in (i.1), the weight ratio of the zeolite material containing titanium having MWW-type framework in relation to the silica comprised in the binder or in the binder precursor is in the range 1:1 to 9:1, preferably in the range 2:1 to 7:1, more preferably in the range 3:1 to 5:1.

[0077] 14. The process of any one of embodiments 7 to 13, wherein the mixture prepared in (i.1) does not comprise zinc.

[0078] 15. The process 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) consist of the titanium-containing zeolite material having MWW-type scaffolding, the binder or binder precursor, and the paste-forming agent.

[0079] 16. The process of any one of Embodiments 7 to 15, wherein preparing the mixture according to (i.1) comprises kneading the mixture.

[0080] 17. The process of any one of embodiments 7 to 16, wherein shaping according to (i.2) comprises extruding the mixture prepared in (i.1).

[0081] 18. The process of embodiment 17, wherein, by extrusion, a molding is obtained in the form of a filament, preferably having a diameter in the range of 1.0 to 2.0 mm.

[0082] 19. The process of any one of embodiments 7 to 18, in which, according to (i.3), the molding is dried at a temperature in the range of 80 to 200°C, preferably in the range of 90 to 175°C, more preferably in the range 100 to 150°C.

[0083] 20. The process of any one of embodiments 7 to 19, wherein, according to (i.3), the molding is dried in a gaseous atmosphere comprising oxygen, preferably in air or poor air, more preferably in air .

[0084] 21. The process of any of the embodiments 7 to 20, in which, according to (i.4), the molding is calcined 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 450 to 550°C.

[0085] 22. The process of any one of embodiments 7 to 21, wherein, according to (i.4), the molding is calcined in a gaseous atmosphere comprising oxygen, preferably in air or poor air, more preferably in air .

[0086] 23. The process of any one of embodiments 1 to 22, wherein at least 99% by weight of the titanium-containing zeolite material having MWW-type framework comprised in the molding provided in (i) consists of Ti, Si, O, and H.

[0087] 24. The process of any one of embodiments 1 to 23, in which the zeolite material containing titanium having an MWW-type framework included in the molding provided in (i) has a titanium content, calculated as elemental titanium, in the range of 0 1 to 5% by weight, 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 zeolite material having MWW type scaffold.

[0088] 25. The process of any of the embodiments 1 to 24, in which the zeolite material containing titanium having an MWW-type framework included in the molding 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, most preferably in the range of 1 to 3% by weight, based on the total weight of the titanium-containing zeolite material having MWW type framework.

[0089] 26. The process of any one of embodiments 1 to 25, in which the zeolite material containing titanium having MWW-type framework comprised in the molding provided in (i) has a total organic carbon content of a maximum of 0.1% in weight, based on the total weight of the titanium-containing zeolite material having MWW type scaffold.

[0090] 27. The process of any one of embodiments 1 to 26, in which the zeolite material containing titanium having an MWW-type framework included in the molding provided in (i) has a boron content, calculated as elemental boron, of at most 0 .5% by weight, based on the total weight of the titanium-containing zeolite material having MWW type scaffold.

[0091] 28. The process of any one of embodiments 1 to 27, wherein the zeolite material containing titanium having MWW-type framework comprised in the molding provided in (i) has a BET specific surface area of at least 400 m2/g, preferably in the range of 400 to 600 m2/g, more preferably in the range of 450 to 550 m2/g, wherein the specific surface area of BET is determined as described in Reference Example 1 herein.

[0092] 29. The process of any one of embodiments 1 to 28, in which the zeolite material containing titanium having MWW-type framework comprised in the molding 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%, where crystallinity is determined as described in Reference Example 4 herein.

[0093] 31. The process of any one of embodiments 1 to 30, wherein the titanium-containing zeolite material having MWW-type scaffold comprised in the molding provided in (i) is in the form of a powder having a particle size distribution distinguished 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 micrometers, preferably in the range of 7 to 50 micrometers, 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, most preferably in the range of 13 to 70 micrometers, where the particle size distribution is determined as described in Reference Example 5 here.

[0094] 32. The process of any one of embodiments 1 to 31, wherein the titanium-containing zeolite material having MWW-type framework comprised in the molding provided in (i) is a spray powder.

[0095] 33. The process of any one of embodiments 1 to 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 ).

[0096] 34. The process of any one of embodiments 1 to 33, wherein in (ii), the zinc source comprises one or more of a water-soluble zinc salt preferably being a zinc salt of an organic acid or inorganic, preferably comprising 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, zinc perborate, zinc sulfate, zinc sulfamate, zinc tartrate, more preferably comprises zinc acetate, most preferably comprises zinc acetate dihydrate.

[0097] 35. The process of any one of embodiments 1 to 34, wherein, in (ii), the zinc source comprises zinc acetate, preferably comprises zinc acetate dihydrate, more preferably is zinc acetate dihydrate zinc acetate.

[0098] 36. The process of any one of modalities 1 to 35, in which, in the aqueous suspension prepared in (ii), the weight ratio of zinc included in the zinc source with respect to the zeolite material containing titanium having MWW-type framework comprised in the molding is in the range 0.005:1 to 0.1:1, preferably in the range 0.01:1 to 0.075:1, more preferably in the range 0.02:1 to 0.05:1, most preferably in the range of 0.03:1 to 0.04:1.

[0099] 37. The process of any of the embodiments 1 to 36, in which, in the aqueous suspension prepared in (ii), the weight ratio of the zeolite material containing titanium having MWW-type framework comprised in the molding with respect to water is in in the range 0.01:1 to 0.1:1, preferably in the range 0.02:1 to 0.075:1, more preferably in the range 0.03:1 to 0.05:1.

[00100] 38. The process 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) consist of water, the zinc source and the mold comprising the titanium-containing zeolite material having MWW type framework.

[00101] 39. The process of any one of modalities 1 to 38, in which in (iii), the suspension prepared in (ii) is heated and maintained at 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.

[00102] 40. The process of any of the modalities 1 to 39, in which in (iii), the suspension prepared in (ii) is kept at the temperature for a period of time in the range of 1 to 24 hours, preferably in the range from 2 to 17 hours, more preferably in the range from 3 to 10 hours.

[00103] 41. The process of any one of embodiments 1 to 40, in which during heating and maintenance in (iii), the suspension prepared in (ii) is not stirred.

[00104] 42. The process of any one of embodiments 1 to 41, in which, in (iv), the separation comprises subjecting the aqueous suspension obtained from (iii) to filtration or centrifugation, optionally followed by washing, obtaining the separated molding comprising zinc and a titanium-containing zeolite material having MWW type scaffold.

[00105] 43. The process of any one of embodiments 1 to 42 further comprises: (v) drying the separated molding comprising zinc and a zeolite material containing titanium having MWW type framework obtained from (iv).

[00106] 44. The process of embodiment 43, in which the separate molding comprising zinc and a zeolite material containing titanium having an MWW-type framework is dried at a temperature in the range of 80 to 200°C, preferably in the range of 90 to 175° C, more preferably in the range of 100 to 150°C.

[00107] 45. The process of embodiment 43 or 44, in which the separate molding comprising zinc and a zeolite material containing titanium having MWW type framework is dried for a period of time in the range of 0.5 to 12 hours, preferably in the range from 1 to 8 hours, more preferably in the range from 2 to 6 hours.

[00108] 46. The process of any one of embodiments 43 to 45, wherein the separate molding comprising zinc and a titanium-containing zeolite material having MWW-type scaffold is dried in a gaseous atmosphere comprising oxygen, preferably air or poor air, more preferably air.

[00109] 47. The process of any one of embodiments 43 to 46 further comprises: (vi) calcining the dry molding comprising zinc and a zeolite material containing titanium having MWW type scaffold obtained from (v).

[00110] 48. The process of embodiment 47, in which the dry casting comprising zinc and a zeolite material containing titanium having MWW-type framework is calcined at a temperature in the range of 300 to 600°C, preferably in the range of 350 to 550° C, more preferably in the range of 400 to 500°C.

[00111] 49. The process of embodiment 47 or 48, in which the dry molding comprising zinc and a zeolite material containing titanium having MWW type framework is calcined for a period of time in the range of 0.1 to 6 hours, preferably in the range from 0.2 to 4 hours, more preferably in the range from 0.5 to 3 hours.

[00112] 50. The process of any one of embodiments 47 to 49, in which the dry casting comprising zinc and a titanium-containing zeolite material having MWW-type framework is calcined in a gaseous atmosphere comprising oxygen, preferably air or poor air, more preferably air.

[00113] 51. The process of any one of embodiments 1 to 50, in which the molding comprising zinc and a titanium-containing zeolite material having MWW-type framework is not subjected to water-vaporization, preferably not subjected to vaporization.

[00114] 52. A molding comprising zinc and a zeolite material containing titanium having MWW type scaffold, obtainable or obtained or preparable or prepared by a process according to any one of embodiments 1 to 51, preferably according to any one of embodiments 33 to 51, more preferably according to any one of embodiments 43 to 51, most preferably according to any one of embodiments 47 to 51.

[00115] 53. A molding comprising zinc and a titanium-containing zeolite material having MWW-type framework, preferably the molding according to embodiment 52, wherein in the molding, the weight ratio of zinc with respect to the titanium-containing zeolite material having type framework MWW is in the range 0.005:1 to 0.1:1, preferably in the range 0.01:1 to 0.075:1, more preferably in the range 0.02:1 to 0.05:1, most preferably in the range from 0.03:1 to 0.04:1.

[00116] 54. The molding of embodiment 53, wherein at least 99% by weight, preferably at least 99.5% by weight of the molding consists of zinc, Ti, Si, O, and H.

[00117] 55. The molding of embodiment 53 to 54, having a BET specific surface area of at least 200 to m2/g, preferably at least 250 m2/g, wherein the BET specific surface area is determined as described in Reference Example 1 here.

[00118] 56. The molding 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 determined as described in Reference Example 4 herein.

[00119] 57. The molding of any one of embodiments 53 to 56, having a porosity of at least 0.9 ml/g, determined as described in Reference Example 2 herein.

[00120] 58. The molding of any of the 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, determined as described in Reference Example 3 here.

[00121] 59. The molding of any of the 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, determined as described in Reference Example 7 herein.

[00122] 60. The casting of any one of embodiments 53 to 59, exhibiting a PO test parameter of at least 8%, preferably at least 9%, determined as described in Reference Example 6 herein.

[00123] 61. Use of a molding according to any one of Embodiments 52 to 60 as a catalyst for converting a hydrocarbon, preferably as a catalyst for oxidizing a hydrocarbon, more preferably for epoxidizing a hydrocarbon having at least one carbon-carbon double bond carbon, most preferably to epoxidize an alkene.

[00124] 62. The use of embodiment 61 to epoxide one or more of propylene, ethene, 1-butene, 2-butene, 1-pentene and 2-pentene, preferably to epoxidize propene.

[00125] 63. The use of embodiment 61 or 62, wherein the alkene, preferably propene, is epoxidized in the presence of a solvent preferably comprising a nitrile, more preferably acetonitrile.

[00126] 64. The use of modality 62 or 63, in which propylene is epoxidized with hydrogen peroxide as an epoxidating agent.

[00127] 65. A method for catalytically converting a hydrocarbon, preferably for catalytically oxidizing a hydrocarbon, more preferably for catalytically epoxidizing a hydrocarbon having at least one carbon-carbon double bond, more preferably for catalytically epoxidizing an alkene, wherein the hydrocarbon, preferably the hydrocarbon having at least one carbon-carbon double bond, more preferably the alkene is brought into contact with the molding according to any one of Embodiments 52 to 60 as a catalyst.

[00128] 66. The method of embodiment 65 for catalytically epoxidizing one or more of propylene, ethene, 1-butene, 2-butene, 1-pentene and 2-pentene, preferably for catalytically epoxidizing propene.

[00129] 67. The method of embodiment 66, wherein the alkene, preferably propene, is epoxidized in the presence of a solvent preferably comprising a nitrile, more preferably acetonitrile.

[00130] 68. The method of embodiment 66 or 67, in which propylene is epoxidized with hydrogen peroxide as an epoxidating agent.

[00131] 69. A catalytic system comprising a catalyst comprising a molding according to any one of embodiments 52 to 60, and at least one potassium salt, wherein at least one potassium salt is selected from the group consisting of at least an inorganic potassium salt, at least one organic potassium salt, and combinations of at least one inorganic potassium salt and at least one organic potassium salt.

[00132] 70. The catalytic system of embodiment 69, wherein 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 potassium, at least one organic potassium salt selected from the group consisting of potassium formate, potassium acetate, potassium carbonate, and potassium hydrogen carbonate, and a combination of at least one of at least one of the inorganic potassium salts and at least at least one of at least one of the organic potassium salts.

[00133] 71. The catalytic system of embodiment 69 or 70 for the epoxidation of an alkene, preferably propylene.

[00134] 72. The catalytic system of any one of embodiments 69 to 71, obtainable or obtained by a preferably continuous process comprising: (i') providing a liquid feed stream comprising an alkene, preferably propylene, hydrogen peroxide, a solvent preferably acetonitrile, water, at least one dissolved potassium salt; (ii') passing the liquid feed stream provided in (i') into an epoxidation reactor comprising a catalyst comprising a cast according to any one of embodiments 52 to 60; wherein in (i'), the molar ratio of potassium to hydrogen peroxide in the liquid feed stream is preferably in the range of 5x10-6:1 to 1000x10-6:1, preferably of 25x10-6:1 to 500x10-6:1, more preferably from 50x10-6:1 to 250x10-6:1; wherein the process preferably comprises: (iii') subjecting the liquid feed stream to epoxidation reaction conditions in the epoxidation reactor, obtaining a reaction mixture comprising an alkene oxide, preferably propylene oxide, solvent, preferably acetonitrile, water , at least a portion of the dissolved potassium salt, and optionally non-epoxidized alkene, preferably non-epoxidized propylene.

[00135] 73. A preferably continuous process for preparing an alkene oxide, preferably propylene oxide, said process comprising: (i') providing a liquid feed stream comprising an alkene, preferably propylene, hydrogen peroxide, a solvent, preferably , acetonitrile, water, and preferably a dissolved potassium salt; (ii') passing the liquid feed stream provided in (i') into an epoxidation reactor comprising a catalyst comprising a cast according to any one of embodiments 52 to 60; (iii') subjecting the liquid feed stream to epoxidation reaction conditions in the epoxidation reactor, obtaining a reaction mixture comprising an alkene oxide, preferably propylene oxide, solvent, preferably acetonitrile, water, at least a portion of the potassium dissolved salt, and optionally non-epoxidized alkene, preferably non-epoxidized propylene; wherein in (i'), the molar ratio of potassium to hydrogen peroxide in the liquid feed stream is preferably in the range of 5x10-6:1 to 1000x10-6:1, preferably of 25x10-6:1 to 500x10-6:1, more preferably from 50x10-6:1 to 250x10-6.

[00136] The present invention is further illustrated by the following reference examples, examples and comparative examples.

Examples Reference Example 1: Determination of the specific surface area of BET

[00137] The specific surface area of BET (specific surface area of multipoint BET) referred to in the context of this application was determined by means of nitrogen adsorption at 77 K as described in DIN 66131.

Reference Example 2: Determination of Hg porosimetry data

[00138] The porosimetry data by means of Hg porosimetry were determined as described in DIN 66133.

Reference Example 3: Determination of mechanical strength

[00139] The mechanical strength as referred to in the context of the present invention should be understood as determined by means of a crushing strength testing machine Z2.5/TS1S, supplier Zwick GmbH & Co., D-89079 Ulm, Germany. As the main part of this machine and its operation, reference is made to the respective handbook instructions “Register 1: Betriebsanleitung / Sicherheitshandbuch für matrix Material-Prüfmaschine Z2.5/TS1S”, version 1.5, December 2001 by Zwick GmbH & Co. Tech - nische Dokumentation, August-Nagel-Strasse 11, D-89079 Ulm, Germany. With said machine, a given filament according to the present invention, described in the example here, is subjected to an increasing force by means of a piston having a diameter of 3 mm until the filament is crushed. The force at which the filament crushes is referred to as the crush resistance of the filament. The machine is equipped with a fixed horizontal table on which the filament is positioned. A plunger that is freely movable in a vertical direction drives the filament against the fixed table. The apparatus was operated with a preliminary force of 0.5 N, a shear rate under preliminary force of 10 mm/minute and a subsequent test rate of 1.6 mm/minute. The vertically movable plunger was connected to a load cell for collecting force and, during the measurement, moved towards the fixed rotary table on which the molding (filament) to be investigated is positioned, thus driving the filament against the table. The plunger was applied to the filaments perpendicular to their longitudinal axis. Control of the experiment was carried out by means of a computer that recorded and evaluated the results of the measurements. The values obtained are the average value of the measurements for 10 filaments in each case.

Reference Example 4: Determination of crystallinity

[00140] The crystallinity referred to in the context of the present application was determined according to the method as described in the User Manual DIFFRAC.EVA Version 3, page 105, from Bruker AXS GmbH, Karlsruhe (published February 2003). The respective data were collected on a standard Bruker D8 Advance Diffractometer Series II using a LYNXEYE detector, from 2° to 50° 2theta, using fixed slits, a step size of 0.02° 2theta and a sweep speed of 2.4 without step. The parameters used to estimate background / amorphous content were Curvature = 0 and Threshold = 0.8.

Reference Example 5: Determination of Particle Size Distribution

[00141] The particle size distribution, referred to in the context of the present application based on the respective values of Dv10, Dv50 and Dv90, was determined according to the following method: 1.0 g of a given material was suspended in 100 g of deionized water and agitated for 1 minute. Particle size distribution was then determined using a Mastersizer S long bed version 2.15, ser. No. 33544-325; supplier: Malvern Instruments GmbH, Herrenberg, Germany, with the following parameters: - focal width: 300RF mm - beam length: 10.00 mm - module: MS17 - shading: 16.9% - dispersion model: 3$$D - analysis model: polydisperse - correction: none

[00142] The expression "Dv10 value" as referred to in the context of the present invention describes the average particle size at which 10% by volume of the micropowder particles have a smaller size. Similarly, the expression "Dv50 value" as referred to in the context of the present invention describes the average particle size at which 50% by volume of the micropowder particles have a smaller size, and the expression "Dv90 value" as referred to in the context of the present invention describes the average particle size at which 90% by volume of the micropowder particles are undersized.

Reference Example 6: PO Test

[00143] In the PO test, the moldings of the present invention are tested as catalysts in a miniautoclave by reacting propylene with an aqueous solution of hydrogen peroxide (30% by weight) to produce propylene oxide. In particular, 0.63 g of the impressions of the invention were introduced together with 79.2 g of acetonitrile and 12.4 g of propylene at room temperature, 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 and depressurised, and the liquid phase was analyzed by gas chromatography with respect to its propylene oxide content. The propylene oxide content of the liquid phase (in % by weight) is the result of the PO test.

[00144] The PO test rate was determined by following the pressure progression during the PO test described above. Pressure progression was recorded using an S-11 transmitter (from Wika Alexander Wiegand SE & Co. KG), which was positioned in the pressure line of the autoclave, and a Buddeberg 6100A graph plotter. The respectively obtained data were read and represented in a pressure progression curve. The pressure drop rate, that is, the PO test rate, was determined according to the following equation: PDR = [p(max) - p(minutes)] / delta t where PDR / (bar/minutes) = rate of pressure drop p(max) / bar = maximum pressure at the start of the reaction p(minutes) / bar = minimum pressure observed during the reaction delta t / minutes = time difference from the start of the reaction to the point in time where p(minutes) was observed

Reference Example 7: Determination of Water Adsorption

[00145] Water adsorption/desorption isotherm measurements were performed on a TA Instruments VTI SA instrument following a step-isotherm program. The experiment consisted of a run or series of runs performed on a sample material that was placed on the microbalance pan inside the instrument. Before the measurement was started, residual moisture in the sample was removed by heating the sample to 100°C (heating rise 5°C/minute) and holding it for 6 hours under a stream of N2. After the drying program, the temperature in the cell was lowered to 25°C and kept isothermal during the measurements. The microbalance was calibrated, and the weight of the dry sample was balanced (maximum mass deviation 0.01% by weight). Water uptake by the sample was measured as the increase in weight compared to the dry sample. First, an adsorption curve was measured by increasing the relative humidity (RH) (expressed as weight % water in the atmosphere inside the cell) to which the samples were exposed and measuring the water uptake by the sample at equilibrium. The RH was increased with a step of 10% in weight from 5 to 85% and in each step the system controlled the RH and monitored the weight of the sample until reaching the equilibrium conditions and recording the weight uptake. The total amount of water adsorbed by the sample was taken after the sample was exposed to 85 wt% RH. During the desorption measurement the RH was decreased from 85 wt% to 5 wt% with a 10% step and the change in sample weight (water uptake) was monitored and recorded.

Reference Example 8: Preparation of a titanium-containing zeolite material having MWW type scaffold

[00146] A titanium-containing zeolite (spray powder) was prepared as described in Example 5, 5.1 to 5.3, of WO 2013/117536 A, page 83, line 26 to page 92, line 7.

Reference Example 9: Continuous epoxidation reaction

[00147] Continuous epoxidation reaction was carried out as described in WO 2015/010990 A, in Reference Example 1, page 55, line 14 to page 57, line 10. The reaction temperature was set at a value of 45°C ( see WO 2015/010990 A, page 56, lines 16 to 18). The temperature was adjusted to achieve an essentially constant hydrogen peroxide conversion of 90% (see WO 2015/010990 A, page 56, lines 21 to 23). KH2PO4 was used as an additive (see WO 2015/010990 A, page 56, lines 7 to 10), the concentration of the additive was 130 micromol per mol of hydrogen peroxide. As catalysts, catalysts according to Comparative Example 1 and Example 1 below were employed (see WO 2015/010990 A, page 55, lines 16 to 18).

[00148] Reference Examples 10 to 12 below are examples of how to provide a titanium-containing zeolite material having MWW type scaffold, having a water absorption capacity of at least 11% by weight.

Reference Example 10: Providing a titanium-containing zeolite material having MWW type scaffold, having a water absorption capacity of at least 11% by weight (i) synthesis of B-Ti-MWW

[00149] The synthesis mixture had the following composition: 1.0 (SiO2): 0.04 (TiO2): 0.67 (B2O3): 1.4 piperidine; 19 H2O.

[00150] Batch 0: 1.026 g of deionized water was initially introduced into a beaker, 365 g of piperidine were then added with stirring at 200 rpm, and the mixture was stirred for 10 minutes at pH 13.2 at around 23°C . After that, the batch was divided into two equal parts.

[00151] Batch 1: 695.5 g of the piperidine solution in deionized water were placed in a beaker and, with stirring at 200 rpm, 248.4 g of boric acid were added and stirring continued for 30 minutes, then 90 g of fumed silica (Cab-O-SIL® 5M) were added at around 23°C. The mixture was then stirred for 1 hour at pH 11.4 at around 23°C.

[00152] Batch 2: 695.5 g of the piperidine solution in deionized water were initially introduced into a beaker, stirring at 200 rpm at around 23°C, 43.2 g of tetrabutyl orthotitanate were added and stirring 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 pH 12.2 at around 23°C.

[00153] Batch 3: The two suspensions from batch 1 and 2 were mixed together for 1.5 hours at pH 11.8 at around 23°C to obtain the synthesis mixture and then crystallization was carried out in an autoclave in the following conditions: Heating in 1 hour at 130°C / holding for 24 hours at 100 rpm at a pressure of 0 - 2.7 bar, then heating in 1 h at 150°C / holding for 24 hours at 100 rpm at a pressure of 2.7 - 4.9 bar, then heating in 1 hour at 170°C / holding for 120 hours at 100 rpm at a pressure of 4.9 - 9.4 bar.

[00154] After the above crystallization conditions, the suspension thus obtained having a pH of 11.3 was drained and filtered through a suction filter (giving a clear filtrate) and washed with 10 liters of deionized water (giving a turbid filtrate ). The turbid filtrate was then acidified to pH 7 with 10% aqueous HNO 3 . Subsequently, the wet product (filter cake) was filled into a porcelain dish, dried overnight, then ground. The yield was 192.8g. According to the elemental analysis, the resulting product had the following contents determined by 100 g of substance of 9.6 g of carbon, 0.85 g of B, 21.8 g of Si and 17.8 g of Ti.

(ii) Treatment with B-Ti-MWW HNO3

[00155] The dried and ground material obtained according to item (i) above was washed with HNO3 solution (solid to liquid ratio 1 g: 20 mL) for 20 hours at 100°C: In a glass flask of 10 liters 3600 g HNO3 solution and 180 g B-Ti-MWW according to item (i) were added at 100°C, followed by boiling for 20 hours at reflux with stirring at 250 rpm. The white suspension thus obtained was filtered and washed with 2 x 5 liters of deionized water. Drying: 10 h / 120°C. Calcination: heating at 2 K / minutes at 530°C / holding for 5 hours. The yield was 143g. According to the elemental analysis, the resulting product had the following contents determined per 100 g of substance: < 0.1 g of carbon (TOC), 0.27 g of B, 42 g of Si, and 2 g of Ti. BET surface area was determined to be 532 m2/g. The crystallinity of the product was measured (Reference Example 8) to be 80% and the average crystal size calculated from the XRD diffraction data was determined to be 22 nm.

(iii) Treatment with B-Ti-MWW HNO3

[00156] The material obtained according to item (ii) above was washed with HNO3 solution (solid to liquid ratio 1 g: 20 mL) for 20 hours at 100°C. In a 10 liter glass flask, 2,400 g of HNO3 solution and 120 g of B-Ti-MWW according to item (ii) were added at 100°C, followed by boiling for 20 hours at reflux with stirring at 250 rpm. The white suspension was filtered and washed with 7 x 1 liter of deionized water. Drying: 10 hours / 120°C. Calcination: heating at 2 K / minutes at 530°C / holding for 5 hours. The yield was 117 g. According to elemental analysis the resulting product had the following contents determined per 100 g of substance: <0.03 g of B, 44 g of Si, and 1.8 g of Ti. The specific surface area of BET was determined to be 501 m2/g. The crystallinity of the product was measured to be 94% and the average crystal size calculated from the XRD diffraction data was determined to be 22 nm. The XRD of the resulting product confirmed that the obtained zeolite material had an MWW scaffold structure. The water adsorption capacity as determined by Reference Example 1 herein was 13.2% by weight.

Reference Example 11: Providing a titanium-containing zeolite material having MWW-type scaffold, having a water absorption capacity of at least 11% by weight (i) Synthesis of B-Ti-MWW

[00157] The synthesis mixture had the following composition: 1.0 (SiO2): 0.04 (TiO2): 0.67 (B2O3): 1.4 piperidine; 19 H2O.

[00158] Batch 0: 1.026 g of deionized water was initially introduced into a beaker, 365 g of piperidine were added with stirring at 200 rpm, and the mixture was stirred for 10 minutes at pH 13.2 at around 23°C. After that, the batch was divided into two equal parts.

[00159] Batch 1: 695.5 g of piperidine solution in deionized water were placed in a beaker and, with stirring at 200 rpm, 248.4 g of boric acid were added and stirring continued for 30 minutes, then 90 g of fumed silica (Cab-O-SIL® 5M) were added at around 23°C. The mixture was then stirred for a little over 1 hour at pH 11.4 at around 23°C.

[00160] Batch 2: 695.5 g of piperidine solution in deionized water were initially introduced into a beaker, stirring at 200 rpm at around 23°C, 43.2 g of tetrabutyl orthotitanate were added and stirring continued for another 30 minutes and then 90 g of fumed silica (Cab-O-SIL® 5M) was added. The mixture was then stirred for about 1 hour at pH 12.2 at around 23°C.

[00161] Batch 3: The two suspensions from batch 1 and 2 were mixed together for 1.5 hours at a pH of 11.8 at around 23°C to obtain the synthesis mixture and then crystallization was carried out in an autoclave under the following conditions: heating for 1 hour at 170°C / holding for 120 hours at 120 rpm at a pressure of 0-9.4 bar. After the above crystallization conditions, the suspension thus obtained having a pH of 11.3 was drained and filtered through a suction filter and washed with 10 L of deionized water. Subsequently, the wet product (filter cake) was filled into a porcelain dish, dried overnight, then ground. The yield was 194g.

(ii) Treatment with B-Ti-MWW HNO3

[00162] The dried and ground material according to item (i) was then washed with HNO3 solution (solid to liquid ratio 1 g: 20 mL) for 20 hours at 100°C: In a 10 liter glass flask 3600 g of HNO3 aqueous solution and 180 g of B-Ti-MWW according to item (i) were added at 100°C, followed by boiling for 20 hours at reflux with stirring at 250 rpm. The white suspension thus obtained was filtered and washed with 2 x 5 L of deionized water. Drying: 10 h / 120°C. Calcination: heating at 2 K / minutes at 530°C / holding for 5 hours. The yield was 146g. According to elemental analysis, the resulting product had the following contents determined per 100g of substance: < 0.1 g of carbon (TOC), 0.25 g of B, 43 g of Si and 2.6 g of Ti. specific BET was determined to be 514 m2/g. The crystallinity of the product was measured to be 79% and the average crystal size calculated from the XRD diffraction data was determined to be 22.5 nm. The XRD of the resulting product confirmed that the obtained zeolite material had an MWW scaffold structure. The water adsorption capacity determined by Reference Example 1 here was 17.3% by weight.

Reference Example 12: Providing a titanium-containing zeolite material having MWW type scaffold, having a water absorption capacity of at least 11% by weight (i) synthesis of B-Ti-MWW

[00163] In order to prepare a synthesis mixture having the following composition: 1.0 B2O3/2.0 SiO2/32.8 H2O/2.43 piperidine, deionized water and boric acid were mixed together in a beaker around of 23°C, to which ammonium stabilized silica solution was added with further mixing at around 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 an autoclave for 48 hours at 175°C at autogenous pressure. All excess piperidine was then removed. 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.

(ii) Discoloration

[00164] A slurry of the calcined product thus obtained was then prepared with deionized water, such that the slurry had a solids content of 6.25% by weight. The slurry was heated to 90.5°C and then held at said temperature for 10 hours. The resulting (deborinated) product was then filtered off as a solid, washed with deionized water and dried.

(iii) Insertion of Ti

[00165] A slurry was prepared with the deionized water and the decarbonated product from item (ii) above, which was mixed at 23°C. Said slurry was then transferred to an autoclave, into which a mixture of tetra-n-butyl titanate/piperidine was then added. The mixture thus obtained had the following composition: 0.035 TiO2/1.0 SiO2/17.0 H2O/1.0 Piperidine. Crystallization was then carried out in an autoclave for 48 hours at 170°C under autogenous pressure. All excess piperidine/ethanol was then removed. The resulting product was then filtered as a solid, washed with deionized water and dried.

(iv) Acid treatment

[00166] A slurry was prepared from the product according to item (iii) in a 10% HNO3 solution (aqueous) (907.2 g of HNO3/ 453.6 g of the product of item (iii), thus a Slurry of solids 5% by weight was produced. The slurry was heated to 93.3°C and then held at said temperature for 1 hour. The resulting product was then filtered as a solid, washed with deionized water and dried. rotation was then carried out at 650°C for 2 hours. According to the elemental analysis, the resulting calcined product had the following contents determined by 100 g of substance of 2 g of carbon (TOC), 42 g of Si and 1.6 g The specific surface area of BET was determined to be 420 m2/g. The crystallinity of the product was measured to be 82%. The XRD of the resulting product confirmed that the obtained zeolite material had an MWW scaffold structure. water determined by Reference Example 1 here was 14.1% by weight.

Comparative Example 1: Preparation of an impression of a zeolite material containing titanium and zinc having MWW type scaffold

[00167] Using the titanium-containing zeolite prepared according to Reference Example 8 above, an impression was prepared. In a first CE1.1 step, the titanium-containing zeolite was impregnated with zinc in order to obtain a titanium-zinc-containing zeolite material having an MWW-type framework. In a second step, step CE1.2, the zeolite material containing titanium and zinc having an MWW-type framework was subjected to modeling. The impressions respectively obtained were subjected to a treatment with water in a third step CE1.3.

[00168] CE1.1: The titanium-containing zeolite prepared according to Reference Example 8 was subjected to zinc impregnation. Impregnation was carried out as described in WO 2013/117536 A, example 5.4, page 92, line 9 to page 94, line 8.

[00169] CE1.2: The modeling of the zeolite material containing titanium and zinc having an MWW type framework was carried out as described in WO 2013/117536 A, example 5.5, page 95, lines 10 to 36.

[00170] CE1.3: The treatment with water of the impressions obtained from the second stage was carried out as described in WO 2013/117536 A, example 5.6, page 97, lines 1 to 17.

Example 1: Preparation of a cast comprising zinc and a titanium-containing zeolite material having MWW type framework

[00171] Using the titanium-containing zeolite prepared according to Reference Example 8 above, an impression was prepared. In a first step E1.1, the titanium-containing zeolite was subjected to modelling. In a second step E1.2, the moldings respectively obtained were subjected to a water treatment in which during said water treatment, zinc was incorporated into the moldings.

[00172] E1.1: 60 g of the titanium-containing zeolite prepared according to Reference Example 8 were mixed with 3 g of Walocel(TM) (5%; Wolf Walsrode AG) and 37.5 g of Ludox® AS- 40 (SiO2 20% by weight with respect to the zeolite material) and kneaded for 10 minutes. Then, 160 mL of deionized water was added, and the resulting mixture was kneaded further. The total kneading time was 40 minutes. In a Loomis extruder, filaments were prepared at a machine pressure of 54 bar from the kneaded mass, wherein said filaments had a circular cross-section with a diameter of 1.5 mm. In an oven, the filaments were heated to a temperature of 120°C at a heating rate of 3 K/minute and dried at 120°C for 4 hours under an air atmosphere. Then, the dried filaments were heated to a temperature of 500°C at a heating rate of 2 K/minute and dried at 500°C for 5 hours under an air atmosphere.

[00173] E1.2: 50 g of the filaments of the calcined filaments 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 this temperature for 8 hours under an autogenous pressure of 2.8 bar. The resulting filaments were filtered using a Nutsch-type filter and washed five times with 200 mL of deionized water until the conductivity of the water obtained from the wash was below 30 microSiemens. In an oven, the respectively obtained filaments were heated to a temperature of 120°C in 60 minutes and dried at this temperature for 240 minutes under an air atmosphere. Then, the dried filaments were heated to a temperature of 450°C in 165 minutes and calcined at this temperature for 120 minutes under an air atmosphere.

Comparative Example 2: Preparation of an impression of a zeolite material containing titanium and zinc having MWW type scaffold

[00174] Example 1 was repeated, with the difference that in step E1.2 instead of autogenous pressure, reflux conditions were employed.

[00175] More specifically, 50 g of filaments of the calcined filaments obtained from E1.1 were added to 1,000 g of deionized water and 4.6 g of zinc acetate dihydrate (Merck), which were then heated to 100°C and stirred at reflux for 8 hours. The resulting filaments were filtered using a Nutsch-type filter and washed five times with 200 mL of deionized water until the conductivity of the water obtained from the wash was below 30 microSiemens. In an oven, the respectively obtained filaments were heated to a temperature of 120°C in 60 minutes and dried at this temperature for 240 minutes under an air atmosphere. Then, the dried filaments were heated to a temperature of 450°C in 165 minutes and calcined at this temperature for 120 minutes under an air atmosphere.

[00176] In the following table 1, the results of comparative example 1 (CE1), comparative example 2 (CE2) and Example 1 (E1) are shown. Table 1 Characteristics of impressions a) determined as described in Reference Example 6 here b) determined as described in Reference Example 6 here c) determined as described in Reference Example 3 here d) determined as described in Reference Example 7 here e) determined as described in Reference Example 2 here f) determined as described in Reference Example 1 here g) the selectivity, after a time in the stream of 500 hours, was calculated as 100 times the ratio of moles of propylene oxide in the effluent stream divided by the moles of hydrogen peroxide (consumed) in the feed stream. Continuous reactions were carried out as described in Reference Example 9 here h) not determined

[00177] As shown in Table 1, the zinc content of the molding of the present invention was significantly higher (1.6% by weight) than the zinc content of the prior art moldings (1.1% by weight), although to prepare the filaments of the invention, significantly less zinc acetate dihydrate per zeolite material was employed (11.5%) compared to the prior art according to comparative example 1 (18.4%). Additionally, with regard to the PO test, as well as with regard to the PO test rate, the use of the filaments according to the invention (E1) led to significantly improved values compared to the comparative example CE1 and CE2, i.e. they exhibited improved characteristics for the preferred use of the inventive filaments, since the higher the rate, the higher the catalyst activity, since the propylene starting material is consumed faster.

[00178] Furthermore, as shown in Table 1, E1 (autogenous conditions) show significantly improved physical properties with respect to CE2 (reflux conditions). In particular, the mechanical strength of CE2 is much lower (5.3 N for CE2 compared to 15 N for E1), highlighting that if reflux conditions are employed rather than the autogenous conditions of E1.2, then a product is obtained with inferior physical properties.

Cited Literature

[00179] - WO 2013/117536 A - WO 2015/010990 A

Claims (15)

1. Process for preparing a molding comprising zinc and a titanium-containing zeolite material having an MWW-type framework, characterized in that it comprises: (i) providing a molding comprising a titanium-containing zeolite material having an MWW-type framework; (ii) preparing an aqueous suspension comprising a source of zinc and the cast comprising a titanium-containing zeolite material having MWW type scaffold 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, obtaining an aqueous suspension comprising a mold comprising zinc and the titanium-containing zeolite material having scaffold type MWW; and (iv) separating the molding comprising zinc and the titanium-containing zeolite material having MWW type scaffold from the liquid phase of the suspension obtained in (iii). 2. Process according to claim 1, characterized in that the molding provided in (i) comprises the zeolite material containing titanium having an MWW-type framework and a binder, in which, in the molding provided in (i), the ratio in weight of titanium-containing zeolite material having MWW-type framework with respect to binder is from 1:1 to 9:1. 3. Process according to claim 1, characterized in that the molding provided in (i) exhibits one or more of the following characteristics (1) to (3): (1) a specific surface area of BET of at least 300 m2/g; (2) a pore volume of at least 0.9 mL/g; and (3) a mechanical strength in the range of 5 to 10 N. 4. Process according to claim 1, characterized in that at least 99% by weight of the zeolite material containing titanium having an MWW-type framework included in the molding provided in (i) consists of Ti, Si, O and H. 5. Process according to claim 4, characterized in that the zeolite material containing titanium having an MWW type framework has a titanium content, calculated as elemental titanium, from 0.1 to 5% by weight based on weight total amount of titanium-containing zeolitic material having MWW-type scaffolding. 6. Process according to claim 1, characterized in that the zeolite material containing titanium having MWW type framework comprised in the molding provided in (i) is in the form of a powder having a particle size distribution distinguished by a Dv10 value in the range of 1 to 10 micrometers, and a Dv90 value in the range of 12 to 200 micrometers. 7. Process according to claim 6, characterized in that the Dv10 value is from 1.5 to 10 micrometers, a Dv50 value is from 5 to 50 micrometers, and the Dv90 value is from 12 to 90 micrometers. 8. Process according to claim 1, characterized by the fact that, in the aqueous suspension prepared in (ii), the weight ratio of zinc included in the zinc source in relation to the zeolite material containing titanium having an MWW-type framework included in the molding is in the range of 0.005:1 to 0.1:1. 9. Process according to claim 1, characterized by the fact that, in the aqueous suspension prepared in (ii), the weight ratio of the zeolite material containing titanium having an MWW-type framework included in the molding with respect to water is in the range of 0 .01:1 to 0.1:1. 10. Process according to claim 1, characterized in that, in (iii), the suspension prepared in (ii) is heated and maintained at a temperature of the liquid phase of the aqueous suspension in the range of 110 to 175°C. 11. Process according to claim 1, characterized in that it additionally comprises: (v) drying the separate molding comprising zinc and the titanium-containing zeolite material having MWW type framework obtained from (iv); and (vi) calcining the dry casting comprising zinc and the titanium-containing zeolite material having MWW type scaffold obtained from (v). 12. Molding comprising zinc and a zeolite material containing titanium having an MWW type framework, characterized in that, in the molding, the weight ratio of zinc with respect to the zeolite material containing titanium having an MWW type framework is in the range of 0.005:1 to 0.1:1, wherein the molding has a water absorption capacity of 8 to 12% by weight. 13. Molding according to claim 12, characterized in that it has at least one of the following characteristics: a specific surface area of BET of at least 200 m2/g; a crystallinity of at least 50%; a porosity of at least 0.9 mL/g; a mechanical resistance of 9 to 23 N; a PO test parameter of at least 8%. 14. Use of a molding as defined in claim 12, characterized in that it is as a catalyst for converting a hydrocarbon, preferably as a catalyst for oxidizing a hydrocarbon, more preferably for epoxidizing a hydrocarbon having at least one carbon-carbon double bond , more preferably to epoxidize an alkene, more preferably to epoxidize propene. 15. Use according to claim 14, characterized in that the alkene, preferably propene, is epoxidized in the presence of a solvent preferably comprising a nitrile, more preferably acetonitrile, preferably with hydrogen peroxide as epoxidating agent.