TW201526988A - A tin-containing zeolitic material having a BEA framework structure - Google Patents

Abstract

A process for preparing a tin-containing zeolitic material having a BEA framework structure comprising providing a zeolitic material having a BEA framework structure having vacant tetrahedral framework sites, providing a tin-ion source in solid form, incorporating tin into the zeolitic material via solid-state ion exchange, calcining the zeolitic material, and treating the calcined zeolitic material with an aqueous solution having a pH of at most 5.

Description

Tin-containing zeolitic material with BEA framework structure

This invention relates to a solid state ion exchange process for the preparation of tin-containing zeolitic materials having a BEA framework structure. The method of the present invention comprises providing a zeolitic material having a BEA framework structure having an empty tetrahedral framework site and further comprising a source of tin ions providing a solid form. In the solid state ion exchange stage, tin is incorporated into the zeolitic material and the resulting zeolitic material is calcined. In the post-treatment stage, the thus obtained calcined material is treated with an acidic aqueous solution which imparts a specific desired characteristic to the zeolite material having the BEA framework structure, which is advantageously different from the known BEA framework structure. Zeolite material.

When used as a catalytically active material in certain applications such as the Bayeyer Villiger type oxidation reaction, isomerization reaction and the like, the zeolite (zeolite beta) having a framework structure BEA doped with tin has Show promising results.

According to the known literature, a tin-containing zeolite having a BEA framework structure BEA is usually prepared by hydrolyzing a zeolitic material having an empty tetrahedral skeleton site in the presence of a tin ion source to incorporate tin into the zeolite framework. However, with regard to this hydrothermal incorporation into tin, considerations such as longer synthesis periods, crystallization aids such as HF or cost intensive templating agents must be considered. Still further, only tin-containing zeolites having BEA having a lower tin content can be obtained.

Hammond et al. describe the preparation of zeolites having a framework structure of BEA. The zeolite is prepared by incorporating tin into a zeolite framework having an empty tetrahedral framework site by a specific solid state ion exchange method, wherein the zeolite skeleton having an empty tetrahedral framework site is together with a solid tin ion source. Mix properly. Although the method described in Hammond et al. provides certain advantages over previously known methods for preparing tin-containing zeolites having a BEA framework structure, it is explicitly mentioned in Baymondi in Hammond et al. Testing of the materials obtained in the lattice oxidation reaction did not show the desired selectivity of the reaction product. Furthermore, the process itself comprises certain reaction steps, in particular in the case of an industrial scale process for the preparation of a zeolite BEA framework having empty tetrahedral framework sites, which are not necessarily practical choices, such as removal by acid treatment. aluminum.

Accordingly, it is an object of the present invention to provide a tin-containing zeolitic material having a BEA framework structure which, when used as a catalytically active material, is specifically used as, for example, Bayerville type oxidation (e.g., cyclic ketone) The catalytically active material in the oxidation reaction of Bayer Welige oxidizes exhibits improved characteristics.

Accordingly, it is another object of the present invention to provide an improved process for preparing a tin-containing zeolitic material having a BEA framework structure comprising incorporating tin into a BEA framework structure having an empty tetrahedral site via a solid state ion exchange stage.

Surprisingly, it has been found that such a goal can be achieved by subjecting a zeolitic material having a BEA framework structure to the incorporation of tin into a BEA framework structure having an empty tetrahedral site via a solid ion exchange stage to a specific post-treatment stage. .

It has further been found that such objects can be achieved by subjecting the zeolitic material having the BEA framework structure to a particular stage of formation of the empty tetrahedral framework sites. In this context, it has further been found that a certain zeolite material having a BEA framework structure is specifically suitable.

Accordingly, the present invention is directed to a method of preparing a tin-containing zeolitic material having a BEA framework structure comprising (i) providing a zeolitic material having a BEA framework structure comprising X ₂ O ₃ and YO ₂ wherein Y is selected from the group consisting of Si, Ti a tetravalent element of a group consisting of Zr, Ge, and a combination of two or more thereof, and X is selected from the group consisting of Al, B, In, Ga, Fe, and a combination of two or more thereof. a trivalent element having an empty tetrahedral framework site; (ii) providing a source of tin ions in solid form; (iii) by solid state ion exchange conditions by subjecting the zeolitic material provided in (i) to The tin ion source provided in (ii) is contacted to incorporate tin into the zeolitic material provided in (i) to obtain a tin-containing zeolitic material having a BEA framework structure; (iv) a zeolitic material obtained from (iii) Subject to heat treatment; (v) treating the heat treated zeolite material obtained from (iv) with an aqueous solution having a pH of at most 5.

As mentioned above, it has been found that a particular post-treatment stage allows the preparation of advantageous zeolite materials having a BEA framework structure. This particular post-treatment stage is a step (v) of the method of the invention, according to which a BEA framework structure is prepared by incorporating tin into a BEA framework structure having an empty tetrahedral site via a solid state ion exchange stage. A tin-containing zeolitic material which is subjected to treatment with an aqueous solution of an acidic aqueous solution, in particular having a pH of at most 5. The pH value as referred to in the context of the present invention is understood to be determined by measurement with a pH selective glass electrode.

Step (i)

According to step (i) of the method of the present invention, a zeolitic material having a BEA framework structure comprising X ₂ O ₃ and YO ₂ is provided, wherein Y is selected from the group consisting of Si, Ti, Zr, Ge, and two or more thereof. a tetravalent element of a group consisting of, and X is a trivalent element selected from the group consisting of Al, B, In, Ga, Fe, and a combination of two or more thereof, the BEA skeleton structure having an empty tetrahedral skeleton Site.

Preferably, the tetravalent element Y is Si. Accordingly, the present invention relates to a method wherein, according to (i), a zeolitic material having a BEA framework structure comprising X ₂ O ₃ and YO ₂ is provided, wherein Y is Si and X is selected from the group consisting of Al, B, In, Ga a trivalent element of a group consisting of Fe, a combination thereof, or a combination of two or more thereof, the BEA skeleton structure having an empty tetrahedral skeleton site.

Preferably, the trivalent element X is B. Accordingly, the present invention is directed to a method wherein, according to (i), a zeolitic material having a BEA framework structure comprising X ₂ O ₃ and YO ₂ is provided, wherein Y is selected from the group consisting of Si, Ti, Zr, Ge, and both A tetravalent element of a group consisting of two or more, and X is B, and the BEA skeleton structure has an empty tetrahedral skeleton site.

More preferably, the tetravalent element Y is Si and the trivalent element X is B. Accordingly, the present invention is directed to a method wherein, according to (i), a zeolitic material having a BEA framework structure comprising X ₂ O ₃ and YO ₂ wherein Y is Si and wherein X is B is provided.

Generally, there are no specific restrictions on how to provide such a zeolite material having an empty tetrahedral site. For example, it is contemplated to purchase a suitable commercially available zeolitic material having an empty tetrahedral site. Further, for example, any conceivable method of preparing the zeolitic material can be used to provide the zeolitic material. By way of example, it is conceivable, in the presence or absence of a suitable template compound, with or without the use of suitable seed crystals, for example in hydrothermal synthesis, from suitable sources of X ₂ O ₃ and YO ₂ The zeolitic material having the BEA framework structure is suitably synthesized as the starting zeolitic material, and the starting zeolitic material is subjected to a suitable method stage after the washing and/or drying and/or calcination as appropriate, in which the method X At least a portion of it is removed from the zeolite framework and an empty tetrahedral site is formed. For example, at least a portion of X can be removed from the zeolite framework by treatment with steam and/or by treatment with an acid. For example, in Hammond et al., the removal of aluminum from the BEA zeolite framework by treatment of the zeolite material with a ₁₃ M aqueous HNO ₃ solution is described in the experimental section. In the context of the present invention, it has been found that, especially when X is B, a zeolite framework for a subsequent solid ion exchange process having an empty tetrahedral site is advantageously prepared by removing X from the zeolite framework in an extremely mild manner, This extremely mild process uses neither steam nor acid. In particular, it has been found that X, preferably B, can be removed by treating the zeolite starting material with a liquid solvent system, preferably under reflux, wherein the liquid solvent system is preferably selected from the group consisting of: Water, methanol, ethanol, propanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, propane-1,2,3-triol and two thereof Or a mixture of two or more, the liquid solvent system is more preferably water, and more preferably, the liquid solvent system does not contain an inorganic or organic acid or a salt thereof, and wherein the treatment is preferably at 50 to 125 ° C, more preferably The temperature is carried out at a temperature in the range of 90 to 115 ° C, more preferably 95 to 105 ° C, and preferably for a period of time ranging from 6 to 20 h, more preferably from 7 to 17 h, still more preferably from 8 to 12 h.

Preferably, according to (i), a zeolitic material having a BEA framework structure having a hollow tetrahedral skeleton site is provided by the method comprising: (i.1) providing a zeolite starting material having a BEA framework structure, wherein the zeolite The skeleton structure of the starting material comprises X ₂ O ₃ and YO ₂ , preferably B ₂ O ₃ and SiO ₂ , and the molar ratio X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ is greater than SiO _{2 by} more than 0.02: 1, preferably at least 0.03:1, more preferably in the range of 0.03:1 to 0.07:1, more preferably 0.03:1 to 0.06:1, more preferably 0.03:1 to 0.05:1; (i.2) by The zeolite starting material provided in (i.1) is treated with a liquid solvent system, preferably under reflux, to produce an empty tetrahedral framework site, thereby obtaining a molar ratio of X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ is at most 0.02:1 zeolitic material than SiO ₂ , wherein the liquid solvent system is preferably selected from the group consisting of water, methanol, ethanol, propanol, ethane-1,2-diol. a propane-1,2-diol, a propane-1,3-diol, a propane-1,2,3-triol, and a mixture of two or more thereof, the liquid solvent system being more preferably water, wherein More preferably, the liquid solvent system Containing an inorganic or organic acid or a salt thereof, and wherein the treatment is preferably carried out at a temperature in the range of 50 to 125 ° C, more preferably 90 to 115 ° C, still more preferably 95 to 105 ° C, and preferably lasts 6 to 20 hours, more Preferably, the time period is from 7 to 17 hours, more preferably from 8 to 12 hours.

Step (i.1)

Generally, there is no particular limitation on how to provide a zeolite material having a BEA skeleton structure in (i.1). For example, it is contemplated to purchase a suitable commercially available zeolitic material having a BEA framework structure. Further, for example, any conceivable method of synthesizing the zeolite can be used to provide the zeolitic material. Preferably, the zeolitic material is provided by the use of a suitable source of X ₂ O ₃ and YO ₂ as a starting material in the presence of a suitable template compound (also known as a structure directing agent).

Typically, the framework structure of the zeolitic material provided in (i.1) comprises X ₂ O ₃ and YO ₂ . Preferably, a suitable source of X ₂ O ₃ and YO ₂ is used in an amount such that at least 75% by weight, more preferably at least 90% by weight, more preferably at least 95% by weight, still more preferably at least 98% by weight, more preferably at least 99 The skeletal structure of the zeolitic material provided in (i.1) is composed of X ₂ O ₃ and YO ₂ .

In general, X ₂ O ₃ and YO ₂ may be greater than 0.02:1, preferably at least 0.03:1, more preferably 0.03:1 to 0.07:1, more preferably 0.03:1 to 0.06:1, still more preferably 0.03:1 to 0.05. The molar ratio X ₂ O ₃ :YO ₂ in the range of 1 is contained in the zeolite material having the BEA framework structure.

Accordingly, it is preferred in (i.1) to provide a zeolitic material having a BEA framework structure wherein at least 90% by weight, more preferably at least 95% by weight, more preferably at least 98% by weight, still more preferably at least 99% by weight of the framework structure % consists of B ₂ O ₃ and SiO ₂ , and wherein the molar ratio B ₂ O ₃ :SiO _{2 is} greater than 0.02:1, more preferably at least 0.03:1, more preferably 0.03:1 to 0.07:1, more preferably 0.03 :1 to 0.06:1, more preferably 0.03:1 to 0.05:1. This material is also known as B-BEA.

Preferably, the zeolitic material provided in (i.1) is obtained by a synthesis comprising: (i.1.1) preparing at least one template compound, at least one YO ₂ source, and at least one X ₂ O ₃ source. a mixture, and (i.1.2) a crystalline zeolitic material from a mixture prepared in (i.1.1).

According to the invention, at least one of the template compounds used in (i.1.1) may be any suitable template compound (structural directing agent). Suitable template compounds include piperidine, hexamethyleneimine, N,N,N-trimethyl-1-hard stone-ammonium hydroxide, piperidine, hexamethyleneimine, diphenylmethyl-1 4-Dinitro-bicyclo-[2,2,2]octane, diphenylmethylammonium, tetraethylammonium hydroxide, and mixtures thereof. Preferably, tetraethylammonium hydroxide is used.

In general, YO ₂ can be provided in (i.1.1) in any conceivable form, provided that the zeolitic material having the BEA framework structure comprising YO ₂ can be crystallized in (i.1.2). Preferably, YO ₂ is provided as such and/or in the form of a compound comprising YO ₂ as a chemical moiety and/or in the form of a compound which is partially or completely chemically converted to YO ₂ during (i.1.2). Preferably, the source of SiO ₂ provided in (i.1.1) is any conceivable source when Y is a combination of Si or Si with one or more other tetravalent elements. Generally, all types of cerium oxide and ceric acid salts can be used, preferably smoky cerium oxide, cerium oxide hydrosol, reactive amorphous solid cerium oxide, cerium, citric acid, water glass, metafluoric acid. A mixture of sodium hydrate, sesquiterpene or dicaprate, colloidal cerium oxide, pyrogenic cerium oxide, decanoate or tetraalkoxy decane or at least two of such compounds.

Preferably, when the mixture according to (i.1.1) comprises at least one source of SiO ₂ , the source comprises at least one compound selected from the group consisting of cerium oxide and ceric acid salt, preferably ceric acid salt, more preferably It is an alkali metal citrate. In preferred alkali metal silicates, the at least one source preferably comprises water glass, more preferably sodium citrate and/or potassium citrate, more preferably sodium citrate. More preferably, the source of SiO ₂ is sodium citrate. Asphalt erbium dioxide may also be preferred.

In general, X ₂ O ₃ may be provided in any conceivable form, provided that the zeolitic material having the BEA framework structure comprising X ₂ O ₃ is crystallizable in (i.1.2). Preferably, X ₂ O ₃ is as such and/or in the form of a compound comprising X ₂ O ₃ as a chemical moiety and/or a compound which is partially or completely chemically converted to X ₂ O ₃ during the process of the invention The form is provided. Preferably, when X represents a combination of B or B with one or more other trivalent elements such as free boronic acid and/or borate and/or borate esters, such as triethyl borate or trimethyl borate, The starting material is used as the at least one source of X ₂ O ₃ .

As preferred sources of titanium, mention may be made of titanium oxide, titanium halide and tetraalkyl orthotitanate. Among them, titanium halide and tetraalkyl orthotitanate are more preferable. More preferred are titanium tetrafluoride, tetraethyl orthotitanate, tetrapropyl orthotitanate and tetrabutyl orthotitanate, of which tetrabutyl orthotitanate is particularly preferred. As the preferred zirconium source, mention may be made of zirconium oxide, zirconium halide and zirconium tetraalkoxide. Among them, zirconium halides and zirconium tetraalkoxides are more preferable. More preferred are zirconium tetrafluoride, zirconium tetraethoxide and zirconium tetrabutoxide. As regards preferred sources, mention may be made of cerium oxide, cerium chloride and cerium isopropoxide. As regards a preferred source of aluminum, mention may be made of aluminum oxide or aluminum nitrate, of which aluminum nitrate is particularly preferred. Regarding a preferred source of indium, mention may be made of indium oxide, Indium halides and indium dialkoxides, of which indium trichloride, indium trifluoride and indium triisopropoxide are particularly preferred. As preferred gallium sources, gallium oxide, gallium halide and gallium nitrate can be mentioned, of which gallium nitrate, gallium trichloride and gallium trifluoride are particularly preferred. As the preferred iron source, iron oxide, iron halide, iron acetate and iron nitrate can be mentioned, with ferric nitrate being especially preferred.

In general, the crystallization procedure according to (i.1.2) can be carried out in any conceivable manner, provided that the zeolite material having the BEA framework structure is crystallized from a mixture according to (i.1.1). The mixture may be crystallized in any type of container, wherein agitation is preferred, preferably by rotating the vessel and/or agitating, and more preferably by stirring the mixture.

Preferably, the mixture is heated during at least a portion of the crystallization treatment in (i.1.2). Generally, the mixture can be heated to any conceivable crystallization temperature, provided that the zeolite material having the BEA framework structure crystallizes from the mixture. Preferably, the mixture is heated to a temperature in the range of 80 to 200 ° C, more preferably 90 to 190 ° C, still more preferably 100 to 185 ° C, still more preferably 120 to 180 ° C, still more preferably 140 to 175 ° C, still more preferably 150 to 165 ° C. Crystallization temperature.

The preferred heating in (i.1.2) of the present invention can be carried out in any conceivable manner for crystallizing a zeolitic material having a BEA framework structure. Generally, the heating can be carried out at a crystallization temperature or between different temperatures. Preferably, a heating ramp is used to achieve a crystallization temperature, wherein the heating rate is preferably in the range of 5 to 100 K/h, more preferably 10 to 70 K/h, still more preferably 15 to 50 K/h, still more preferably 20 to 30 K/h.

In general, the duration of the crystallization treatment in (i.1.2) of the process of the present invention is not particularly limited. Preferably, the crystallization treatment is carried out for a period of time ranging from 10 to 200 h, more preferably from 20 to 190 h, more preferably from 40 to 170 h, still more preferably from 60 to 160 h, still more preferably from 80 to 150 h, still more preferably from 110 to 130 h.

Preferably, the heating in (i.1.2) is carried out during the entire crystallization treatment or only during one or more of its parts, provided that the zeolitic material crystals have a BEA framework structure. Preferably, the heating is carried out during the entire duration of the crystallization.

Preferably, the crystalline material obtained from (i.1.2) is subjected to a series of separation and/or washing steps, wherein the zeolitic material obtained from the crystallization in (i.1.2) is preferably subjected to at least one separation and at least one washing step. Accordingly, step (i.1) of the method of the invention preferably comprises (i.1.1) preparing a mixture comprising at least one template compound, at least one source of YO ₂ and at least one source of X ₂ O ₃ , and (i. 1.2) Crystalline zeolitic material of the mixture prepared from (i.1.1); (i.1.3) Separation and/or washing, preferably separating and washing the crystalline material obtained from (i.1.2).

Separation of the crystalline zeolite material can be achieved by any conceivable method. Such methods include, for example, filtration, ultrafiltration, diafiltration, and centrifugation and/or decantation methods, or, for example, spray drying methods and spray granulation methods, wherein the filtration process can involve aspiration and/or pressure filtration steps. Two or a combination of two or more of these methods may be applied.

For the purpose of separation, in particular filtration, the pH of the mother liquor containing the crystalline zeolite material obtained from (i.1.2) is preferably adjusted to 6 to 9 by adding acid to the mother liquor, preferably under agitation. Preferably, the value in the range of 6.5 to 8.5, more preferably 7 to 8, wherein the acid addition is preferably carried out at a temperature of the mother liquor, the temperature being 20 to 70 ° C, more preferably 30 to 65 ° C, still more preferably 40 to 60 Within the °C range. The acid is preferably an inorganic acid, preferably an aqueous solution containing a mineral acid, wherein the inorganic acid is preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof, and wherein the inorganic The acid is more preferably nitric acid.

For any one or more washing procedures selected as appropriate, any conceivable Solvent. The detergent which can be used is, for example, water, an alcohol such as methanol, ethanol or propanol, or a mixture of two or more thereof. Examples of mixtures are mixtures of two or more alcohols, such as methanol and ethanol or methanol with propanol or ethanol and propanol or a mixture of methanol with ethanol and propanol, or a mixture of water and at least one alcohol, such as water and Methanol or water and ethanol or water and propanol or water and methanol and ethanol or water and methanol and propanol or water and ethanol and propanol or water and methanol and ethanol and propanol mixture. Water or water is preferably a mixture of at least one alcohol, preferably water and ethanol, and distilled water is extremely particularly preferred as the sole detergent.

The crystalline zeolitic material is preferably isolated in (i.1.3) by filtration from a suspension obtained from (i.1.2) to obtain a filter cake which is preferably subjected to washing, preferably with water. If washing is applied, the washing process is preferably continued until the wash water has a conductivity of at most 1,000 microsiemens per centimeter, more preferably up to 850 microsiemens per centimeter, more preferably up to 700 microsiemens per centimeter.

Preferably, the zeolitic material obtained from (i.1.3) is subjected to a heat treatment stage, wherein the zeolitic material obtained from (i.1.3) is preferably subjected to pre-drying and/or drying and/or calcination. Accordingly, step (i.1) of the method of the invention preferably comprises (i.1.1) preparing a mixture comprising at least one template compound, at least one source of YO ₂ and at least one source of X ₂ O ₃ , and (i. 1.2) a mixture of crystalline zeolite materials prepared in (i.1.1); (i.1.3) separated and/or washed, preferably separated and washed from (i.1.2) obtained crystalline material; (i.1.4) The zeolitic material obtained from (i.1.3) is subjected to a heat treatment stage.

Preferably, the zeolitic material obtained from (i.1.3) is subjected to pre-drying for a period of time preferably in the range of 4 to 10 h, more preferably 5 to 8 h, for example by subjecting the zeolitic material to Suitable air streams, such as air, lean air or industrial nitrogen.

The pre-dried filter cake is preferably dried, as appropriate. Preferably, the drying is carried out in a suitable atmosphere such as industrial nitrogen, air or dilute air at a temperature in the range of 100 to 300 ° C, more preferably 150 to 275 ° C, more preferably 200 to 250 ° C. The drying can be carried out, for example, in a suitable drying oven or by spray drying, wherein in the case of spray drying, it is preferred to prepare a preferred aqueous suspension from the pre-dried filter cake. If the drying is completed by spray drying, the drying gas inlet temperature is preferably in the range of 200 to 250 ° C, more preferably 220 to 250 ° C, and the drying gas outlet temperature is preferably in the range of 100 to 175 ° C, more preferably 120 to 150 ° C. Inside.

If spray drying is carried out, it is conceivable that the mother liquor containing the zeolitic material obtained from (i.1.2) is subjected to spray drying directly after concentration, as appropriate. Furthermore, it is envisaged that the isolated and washed zeolite material is subjected to spray drying after suitable resuspension of the washed and optionally predried zeolitic material, wherein the aqueous suspension is preferably based on the total weight of the suspension. It is prepared to have a preferred solid content range of from 2 to 35% by weight, preferably from 5 to 25% by weight, more preferably from 10 to 20% by weight.

Preferably, the heat treatment according to (i.1.4) comprises calcining the zeolitic material, wherein the zeolitic material is optionally subjected to spray drying as before. Preferably, at least one template compound is at least partially, more preferably substantially removed from the framework structure during calcination. Calcination generally involves heating the zeolitic material to a temperature of at least 350 ° C in a suitable atmosphere such as industrial nitrogen, air or dilute air, preferably to a temperature in the range of 400 to 700 ° C, more preferably 450 to 550 ° C. . Preferably, the calcination is carried out for a period of time ranging from 1 to 10 h, preferably from 3 to 6 h. Therefore, the calcination is preferably carried out at a temperature in the range of from 400 to 700 ° C, preferably from 450 to 550 ° C, for a period of time ranging from 1 to 10 h, preferably from 3 to 6 h.

Accordingly, the present invention relates to the above method, wherein the step (i.1) comprises (i.1.1) preparing a mixture comprising at least one template compound, at least one YO ₂ source, preferably SiO ₂ , and at least one X ₂ O ₃ source, preferably B ₂ O ₃ ; (i.1.2) a crystalline zeolitic material having a mixture prepared from (i.1.1); (i.1.3) separated from the separated zeolite material by filtration and washing ( I.1.2) obtained zeolitic material; (i.1.4) subjecting the separated zeolitic material obtained from (i.1.3) to a heat treatment stage comprising pre-drying the zeolitic material, resuspending the pre-dried zeolitic material; The suspended zeolite material is dried and the spray dried zeolite material is calcined.

Step (i.2)

According to step (i.2) of the process of the invention, an empty tetrahedral framework site is created by treating the zeolite starting material provided in (i.1) with a liquid solvent system. Preferably, the separated, spray dried and calcined zeolitic material provided in (i.1) is subjected to treatment with a liquid solvent system according to (i.2) from which Mohrby X ₂ O _{3 is obtained.} : YO ₂ , preferably B ₂ O ₃ : SiO _{2 is} at most 0.02:1 zeolite material.

Generally, there are no specific restrictions regarding the chemical nature of the liquid solvent system used in (i.2). Therefore, it is conceivable to use an acidic water system for reducing the molar ratio of the zeolitic material X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ :SiO ₂ to a value of at most 0.02:1. In terms of acid, the liquid solvent system can comprise, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid or tartaric acid. Preferably, the liquid solvent system used in (i.2) is selected from the group consisting of water, monohydric alcohol, polyhydric alcohol, and a mixture of two or more thereof. There are no specific restrictions regarding such monohydric alcohols and polyhydric alcohols. Preferably, the alcohols contain from 1 to 6 carbon atoms, more preferably from 1 to 5 carbon atoms, still more preferably from 1 to 4 carbon atoms, and still more preferably from 1 to 3 carbon atoms. The polyol preferably contains 2 to 5 hydroxyl groups, more preferably 2 to 4 hydroxyl groups, preferably 2 or 3 hydroxyl groups. Particularly preferred monohydric alcohols are methanol, ethanol and propanol such as 1-propanol and 2-propanol. Particularly preferred polyols are ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, propane-1,2,3-triol. If a mixture of two or more of the above compounds is used, preferably the mixtures comprise water and at least one monohydric alcohol and/or at least one polyhydric alcohol. Optimally, the liquid solvent system consists of water. Accordingly, the present invention relates to a process as defined above and a zeolitic material obtainable therefrom or obtained therefrom, wherein the liquid solvent system is selected from the group consisting of water, methanol, ethanol, propanol, ethane - 1,2-diol, propane-1,2-diol, propane-1,3-diol, propane-1,2,3-triol, and a mixture of two or more thereof, preferably water .

Further, it is particularly preferred that the liquid solvent system does not contain a mineral acid or an organic acid or a salt thereof, and the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid, and tartaric acid. Accordingly, the present invention is also directed to the above method, wherein the liquid solvent system is selected from the group consisting of water, methanol, ethanol, propanol, ethane-1,2-diol, propane-1,2-diol a propane-1,3-diol, a propane-1,2,3-triol, a mixture of two or more thereof, preferably water, and wherein the liquid solvent system does not contain an inorganic or organic acid or The salt, the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid, and tartaric acid. Even more preferably, the invention relates to the above method, wherein the liquid solvent system is selected from the group consisting of water, methanol, ethanol, propanol, ethane-1,2-diol, propane-1,2 a diol, a propane-1,3-diol, a propane-1,2,3-triol, and a mixture of two or more thereof, preferably water, and wherein the liquid solvent system does not contain inorganic or organic Acid or its salt.

The reaction conditions according to (i.2) are not particularly limited, provided that the solvent system described above is in its liquid state and the molar ratio of X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ :SiO _{2 is} lowered. Up to a value of 0.02:1. In particular, with regard to the preferred temperatures described below, those skilled in the art will select the respective pressures to be processed in order to maintain the solvent system in its liquid state. There are no specific restrictions regarding the duration of processing according to (i.2). The above time is understood to be the time during which the liquid solvent system is maintained at the processing temperatures described below. Preferably, in (i.2), the treatment is carried out for a period of time of 6 to 20 h, more preferably 7 to 17 h, still more preferably 8 to 12 h. The preferred treatment temperature is in the range of 50 to 125 ° C, preferably 90 to 115 ° C, more preferably 95 to 105 ° C. Most preferably, the treatment according to (i2) is carried out at the boiling point of the solvent system. If the solvent system consists of two or more components, the treatment according to (i.2) is preferably carried out at the boiling point of the component having the lowest boiling point.

Preferably, the treatment according to (i.2) is carried out under reflux. Therefore, a preferred container for processing according to (i.2), which represents an open system, is preferably equipped with a reflux condenser. During the treatment according to (i.2), the temperature of the liquid solvent system remains substantially constant or varies, so treatment with a liquid solvent system is carried out at two or more different temperatures. Most preferably, the temperature remains substantially constant over the range defined above.

Accordingly, the present invention relates to the above method comprising (i2) treating the zeolitic material provided in (i.1) with a liquid solvent system, preferably with water, thereby being in the open system at 95 to 105 ° C under reflux A zeolite material having a molar ratio of X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ :SiO _{2 of} at most 0.02:1 is obtained at the internal temperature, and the zeolite material is at least partially separated from the liquid solvent system.

There is no particular limitation as to the amount of zeolitic material used relative to the amount of liquid solvent system. Preferably, the weight ratio of the zeolitic material to the liquid solvent system is from 1:5 to 1:50, more preferably from 1:10 to 1:35, more preferably from 1:10 to 1:20, even more preferably from 1:12 to Within the range of 1:18.

It is further preferred during the treatment according to (i.2) to properly agitate the liquid solvent system. During (i.2), the agitation rate remains substantially constant or varies, so the treatment is carried out at two or more different agitation rates. Most preferably, the zeolitic material is suspended in the liquid solvent system at a first agitation rate, and during the above temperature (a.2), the agitation rate varies, preferably increased. Thus, the agitation rate can be appropriately selected depending on, for example, the volume of the liquid solvent system, the amount of the zeolitic material used, the desired temperature, and the like. Preferably, the stirring rate of the zeolite material suspended in the liquid solvent system is from 5 to 200 r.pm (per minute), more preferably from 10 to 200 r.pm, still more preferably from 20 to 55 r.pm, still more preferably from 30 to 50 r. Within the pm range. The agitation rate at which the treatment at the temperature described above is carried out is preferably in the range of 50 to 100 r.p.m., more preferably 55 to 90 r.p.m., still more preferably 60 to 80 r.p.m.

After the treatment according to (i.2), the resulting zeolitic material is preferably separated from the liquid solvent system. Accordingly, the present invention is also directed to the above method, further comprising (i.3) separating the zeolitic material obtained from (i.2) at least in part from a liquid solvent system, optionally including drying.

Step (i.3)

All methods of separating zeolite materials from liquid solvent systems are envisioned. Such methods include, for example, filtration, ultrafiltration, diafiltration, and centrifugation methods, or, for example, spray drying methods and spray granulation methods, wherein the filtration process can involve aspiration and/or pressure filtration steps. Two or a combination of two or more of these methods may be applied.

Any conceivable solvent can be used in connection with one or more washing procedures selected as appropriate. The detergent which can be used is, for example, water, an alcohol such as methanol, ethanol or propanol, or a mixture of two or more thereof. An example of a mixture is a mixture of two or more alcohols, Such as methanol and ethanol or methanol and propanol or ethanol and propanol or a mixture of methanol and ethanol and propanol, or a mixture of water and at least one alcohol, such as water and methanol or water and ethanol or water and propanol or water and methanol And a mixture of ethanol or water with methanol and propanol or water with ethanol and propanol or water with methanol and ethanol and propanol. Water or water is preferably a mixture of at least one alcohol, preferably water and ethanol, and distilled water is extremely particularly preferred as the sole detergent. If washing is applied, the washing treatment can preferably be continued until the washing water has a conductivity of at most 1,000 microsiemens per centimeter, more preferably up to 850 microsiemens per centimeter, more preferably up to 700 microsiemens per centimeter.

According to the invention, the zeolitic material is preferably separated from the suspension by filtration to obtain a filter cake which is preferably subjected to washing, preferably with water.

The zeolite material obtained in (ii) is optionally subjected to drying after separation of the zeolite material having the BEA framework structure from the liquid solvent system by filtration, and after washing. The drying procedure may optionally include one or more drying steps. In general, any conceivable drying method can be used. The drying procedure preferably includes heating and/or applying a vacuum to the zeolitic material having the BEA framework structure.

Preferably, the separated and washed zeolitic material is subjected to pre-drying for a period of time preferably in the range of 4 to 10 h, more preferably 5 to 8 h, for example by subjecting the filter cake to a suitable gas flow, such as air, thin Air or nitrogen.

Preferably, the zeolitic material is subjected to drying, preferably spray drying, after optionally pre-drying, wherein the drying gas inlet temperature is preferably in the range of 200 to 250 ° C, more preferably 220 to 250 ° C, and the drying gas The outlet temperature is preferably in the range of 100 to 175 ° C, more preferably 120 to 150 ° C. If spray drying is carried out, it is conceivable that the suspension containing the zeolitic material is subjected to spray drying directly after concentration, as appropriate. In addition, it is conceivable to compare the separated and washed zeolite materials. Preferably, it is subjected to spray drying after suitable resuspension of the washed and optionally predried zeolitic material, preferably in deionized water. Preferably, the aqueous suspension has a solids content of from 2 to 35% by weight, preferably from 5 to 25% by weight, more preferably from 10 to 20% by weight, based on the total weight of the suspension.

Preferably, the zeolitic material obtained from (i.3) is in powder form, preferably in the form of a spray powder, wherein the spray powder can be spray dried from (i.1) and/or (i.3) Spray drying is produced.

Therefore, according to (i), the zeolitic material having the BEA framework structure having a hollow tetrahedral skeleton site is preferably provided by the method comprising: (i.1) providing a zeolite starting material having a BEA framework structure, wherein the starting material of the skeleton structure comprising zeolite X ₂ O ₃ and YO _2, preferably B ₂ O ₃ and SiO _2, and the molar ratio of X ₂ O _3: YO _2, preferably B ₂ O ₃ SiO ₂ ratio greater than 0.02 :1, preferably at least 0.03:1, more preferably in the range of 0.03:1 to 0.07:1, more preferably 0.03:1 to 0.06:1, more preferably 0.03:1 to 0.05:1; (i.2) The empty tetrahedral skeleton site is produced by treating the zeolite starting material provided in (i.1) with a liquid solvent system preferably under reflux to obtain a molar ratio X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ : SiO _{2 is} at most 0.02:1 zeolite material, wherein the liquid solvent system is preferably selected from the group consisting of water, methanol, ethanol, propanol, ethane-1,2-diol, propane -1,2-diol, propane-1,3-diol, propane-1,2,3-triol, and a mixture of two or more thereof, the liquid solvent system is more preferably water, more preferably Ground, the liquid solvent system does not An inorganic or organic acid or a salt thereof, and wherein the treatment is preferably carried out at a temperature in the range of 50 to 125 ° C, more preferably 90 to 115 ° C, still more preferably 95 to 105 ° C, and preferably lasts 6 to 20 hours, more preferably a period of time ranging from 7 to 17 h, more preferably from 8 to 12 h; (i.3) a zeolite material obtained from (i.2) at least partially separated from the liquid solvent system, optionally including drying, preferably spray drying .

According to the invention, the isolated zeolitic material obtained from (i.3) is subjected to calcination in step (i.4) as appropriate.

Step (i.4)

Preferably, the calcination according to (i.4) is carried out in a suitable atmosphere such as air, dilute air or nitrogen at a temperature in the range of 400 to 700 ° C, preferably 500 to 600 ° C, for 1 to 10 h, Good time range from 2 to 6h.

Therefore, according to (i), the zeolitic material having the BEA framework structure having a hollow tetrahedral skeleton site is preferably provided by the method comprising: (i.1) providing a zeolite starting material having a BEA framework structure, wherein the starting material of the skeleton structure comprising zeolite X ₂ O ₃ and YO _2, preferably B ₂ O ₃ and SiO _2, and the molar ratio of X ₂ O _3: YO _2, preferably B ₂ O ₃ SiO ₂ ratio greater than 0.02 :1, preferably at least 0.03:1, more preferably in the range of 0.03:1 to 0.07:1, more preferably 0.03:1 to 0.06:1, more preferably 0.03:1 to 0.05:1; (i.2) The empty tetrahedral skeleton site is produced by treating the zeolite starting material provided in (i.1) with a liquid solvent system preferably under reflux to obtain a molar ratio X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ : SiO _{2 is} at most 0.02:1 zeolite material, wherein the liquid solvent system is preferably selected from the group consisting of water, methanol, ethanol, propanol, ethane-1,2-diol, propane -1,2-diol, propane-1,3-diol, propane-1,2,3-triol, and a mixture of two or more thereof, the liquid solvent system is more preferably water, more preferably Ground, the liquid solvent system does not An inorganic or organic acid or a salt thereof, and wherein the treatment is preferably carried out at a temperature in the range of 50 to 125 ° C, more preferably 90 to 115 ° C, still more preferably 95 to 105 ° C, and preferably lasts 6 to 20 hours, more preferably a period of time ranging from 7 to 17 h, more preferably from 8 to 12 h; (i.3) a zeolite material obtained from (i.2) at least partially separated from the liquid solvent system, optionally including drying, preferably spray drying (i.4) calcining the isolated zeolite material obtained from (i.3) as appropriate, preferably at a temperature in the range of 400 to 700 ° C, more preferably 450 to 550 ° C, and preferably lasting 1 to 10 h. More preferably, the time period is in the range of 3 to 6 hours.

Preferably, the zeolitic material obtained in (i.3) is not subjected to calcination prior to (iii).

Therefore, according to (i), the zeolitic material having the BEA framework structure having a hollow tetrahedral skeleton site is preferably provided by the method comprising: (i.1) providing a zeolite starting material having a BEA framework structure, wherein the starting material of the skeleton structure comprising zeolite X ₂ O ₃ and YO _2, preferably B ₂ O ₃ and SiO _2, and the molar ratio of X ₂ O _3: YO _2, preferably B ₂ O ₃ SiO ₂ ratio greater than 0.02 :1, preferably at least 0.03:1, more preferably in the range of 0.03:1 to 0.07:1, more preferably 0.03:1 to 0.06:1, more preferably 0.03:1 to 0.05:1; (i.2) The empty tetrahedral skeleton site is produced by treating the zeolite starting material provided in (i.1) with a liquid solvent system preferably under reflux to obtain a molar ratio X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ : SiO _{2 is} at most 0.02:1 zeolite material, wherein the liquid solvent system is preferably selected from the group consisting of water, methanol, ethanol, propanol, ethane-1,2-diol, propane -1,2-diol, propane-1,3-diol, propane-1,2,3-triol, and a mixture of two or more thereof, the liquid solvent system is more preferably water, more preferably Ground, the liquid solvent system does not An inorganic or organic acid or a salt thereof, and wherein the treatment is preferably carried out at a temperature in the range of 50 to 125 ° C, more preferably 90 to 115 ° C, still more preferably 95 to 105 ° C, and preferably lasts 6 to 20 hours, more preferably a period of time ranging from 7 to 17 h, more preferably from 8 to 12 h; (i.3) a zeolite material obtained at least partially from the liquid solvent system from (i.2), preferably including drying, preferably spray drying Wherein after (i.3) and prior to (iii), preferably the dried, more preferably spray dried zeolitic material is not subjected to a temperature in the range of from 450 to 550 ° C and a period of from 3 to 6 h The calcination, preferably not subjected to calcination at a temperature in the range of from 400 to 700 ° C and in the range of from 1 to 10 h, is more preferably uncalcined.

According to the present invention, the treatment with the liquid solvent system according to (ii) reduces the molar ratio of the zeolitic material X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ :SiO ₂ ; therefore, it is used for self The BEA framework removes at least a portion of X and creates a program of empty tetrahedral sites in the zeolite framework. Therefore, the molar ratio X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ :SiO ₂ of the zeolitic material having the BEA skeleton structure obtained from (ii) is higher than that of the BEA skeleton structure provided in (i) The molar ratio of the zeolitic material is X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ :SiO ₂ . According to a preferred embodiment of the present invention, the molar ratio X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ :SiO ₂ obtained in (ii) is at most 0.02:1, preferably at most 0.01:1. More preferably, it is in the range of 0.0005:1 to 0.01:1, more preferably 0.0009:1 to 0.003:1.

Accordingly, the present invention relates to the above method, wherein in the framework structure of the zeolitic material provided in (i), the molar ratio X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ :SiO ₂ is at most 0.02:1 Preferably, it is at most 0.01:1, more preferably in the range of 0.0005:1 to 0.01:1, more preferably 0.0009:1 to 0.003:1.

According to the present invention, it is preferred to provide a zeolitic material having a BEA framework structure based on a source of SiO _{2 and a} source of B ₂ O ₃ . Particularly preferably, the zeolitic material having the BEA framework structure is free of aluminum. The term "free of aluminum" as used in this context of the present invention relates to a zeolitic material having a BEA framework structure which may contain only aluminum in trace amounts in the form of impurities, which may be present, for example, by use. Aluminum impurities are produced in the starting materials in the synthesis mixture for the preparation of the zeolitic material, i.e., in the form of impurities in the ruthenium source, boron source, template compound, and water. In particular, no source of aluminum is used in the synthesis mixture in (i.1).

Preferably, at least 95% by weight, preferably at least 98% by weight, more preferably at least 99% by weight of the framework structure of the zeolitic material provided in (i) consists of X ₂ O ₃ and YO ₂ , preferably B ₂ O ₃ And SiO ₂ composition. More preferably, at least 99.5% by weight, more preferably at least 99.8% by weight, more preferably at least 99.9% by weight of the framework structure of the zeolitic material provided in (i) consists of X ₂ O ₃ and YO ₂ , preferably B ₂ O ₃ And SiO ₂ composition.

Based on the composition of the zeolitic material having the BEA framework structure which is subjected to the removal of X, preferably B from the zeolite framework, and further based on the composition of the zeolitic material having the BEA framework structure obtained by removing X, preferably B from the zeolite framework The amount of moiré of the empty tetrahedral skeleton site formed by the removal stage can be easily calculated.

Step (ii)

According to step (ii) of the process of the invention, a source of tin ions in solid form is provided.

Generally, there is no particular limitation with respect to the source of tin ions, provided that the tin can be incorporated into the zeolite framework according to (iii) by solid state ion exchange.

Preferably, the source of tin ions is selected from the group consisting of tin (II) alkoxides, tin (IV) alkoxides, tin (II) salts of organic acids, tin (IV) salts of organic acids, and a mixture of two or more of them. More preferably, the source of tin ions is selected from the group consisting of tin (II) alkane having 1 to 4 carbon atoms, such as 1 carbon atom, 2 carbon atoms, 3 carbon atoms or 4 carbon atoms. An oxide; a tin (IV) alkoxide having 1 to 4 carbon atoms, such as 1 carbon atom, 2 carbon atoms, 3 carbon atoms or 4 carbon atoms; having 1 to 6 carbon atoms, such as 1 a tin (II) salt of an organic acid having 2 carbon atoms, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms or 6 carbon atoms; having 1 to 6 carbon atoms, such as 1 carbon a tin (IV) salt of an organic acid having an atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms or 6 carbon atoms; and a mixture of two or more thereof. More preferably, the tin ion source comprises organic a tin (II) salt of an acid having from 1 to 6 carbon atoms, such as 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms or 6 carbon atoms, or organic A tin (IV) salt of an acid having from 1 to 6 carbon atoms, such as 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms or 6 carbon atoms. More preferably, the source of tin ions comprises a tin (II) salt of an organic acid having from 1 to 6 carbon atoms, such as 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbons. Atom or 6 carbon atoms. More preferably, the source of tin ions comprises tin (II) acetate.

Accordingly, the present invention relates to the above method, wherein the source of tin ions provided in (ii) is selected from the group consisting of tin (II) alkoxide, tin (IV) alkoxide, tin of an organic acid ( II) a salt, a tin (IV) salt of an organic acid, and a mixture of two or more thereof, preferably selected from the group consisting of tin (II) alkoxides having 1 to 4 carbon atoms, a tin (IV) alkoxide having 1 to 4 carbon atoms, a tin (II) salt of an organic acid having 1 to 6 carbon atoms, a tin (IV) salt of an organic acid having 1 to 6 carbon atoms, and A mixture of two or more thereof, more preferably, the source of tin ions provided in (ii) is tin (II) acetate.

Step (iii)

In accordance with step (iii) of the method of the present invention, tin is incorporated in (i) by contacting the zeolitic material provided in (i) with the source of tin ions provided in (ii) under solid state ion exchange conditions. In the zeolitic material provided, thereby obtaining a tin-containing zeolitic material having a BEA framework structure.

There is no particular limitation regarding the amount of the tin ion source used in (iii) and the amount of the zeolitic material. Generally, the amount of tin ion source will be selected depending on the desired tin content of the prepared tin-containing zeolite material. Preferably, a tin-containing zeolitic material having a higher tin content is prepared in accordance with the present invention. Thus, preferably, the source of tin ions is used in an amount relative to the amount of zeolitic material having an empty tetrahedral framework site such that up to 100% of the empty tetrahedral sites can be filled with tin. Due to the removal phase The molar amount of the formed empty tetrahedral skeleton sites can be easily calculated as described above, and then the necessary amount of the tin ion source can be easily determined. Preferably, according to (iii), the molar ratio of tin contained in the source of tin ions in contact with the zeolitic material relative to the empty tetrahedral framework site of the zeolitic material is at most 1:1.

Accordingly, the present invention is directed to the above method wherein, according to (iii), the molar ratio of tin contained in the source of tin ions in contact with the zeolitic material relative to the empty tetrahedral framework site of the zeolitic material is at most 1:1.

Depending on the amount of the tetrahedral framework sites, the preferred tin-containing material is prepared to have from 2 to 20% by weight, preferably from 5 to 18% by weight, more preferably, based on the total weight of the tin-containing zeolitic material. A tin content in the range of 8 to 16% by weight.

The method of how to contact the zeolitic material provided in (i) with the tin ion source provided in (ii) under the solid ion exchange conditions according to (iii) is not subject to any particular limitation. Preferably, in (iii), contacting the zeolitic material provided in (i) with the source of tin ions provided in (ii) under solid state ion exchange conditions comprises the zeolitic material to be provided in (i) The tin ion source is mixed.

Any suitable mixing method can be applied. For example, the mixing can be done manually or using a suitable mixing device. Manual mixing can be carried out, for example, in a suitable stucco, for example by grinding the zeolitic material provided in (i) together with the source of tin ions provided in (ii). Suitable mixing equipment includes, for example, high energy mixers; grinding machines such as ball mills, rod mills, self-grinding mills, semi-autogenous mills, pebble mills, high pressure grinding rolls, stone mills, straight shaft impact mills or tower mills .

Preferably, the mixing is carried out in a suitable device that provides a high energy input during mixing, preferably at 100 to 1,000 W, more preferably 200 to 800 W, still more preferably 300. Up to 600W. If the mixing is carried out in a mixing apparatus which provides mixing energy by stirring the mixture, the mixing is preferably carried out under stirring with a stirring energy input in the range of 100 to 1000 W, preferably 200 to 800 W, more preferably 300 to 600 W.

Preferably, in (iii), the zeolitic material is mixed with a source of tin ions for a period of time ranging from 2 min to 5 h, preferably from 5 min to 3 h, more preferably from 10 min to 2 h.

Accordingly, the present invention is also directed to the above method, wherein in (iii), the tin is contacted by contacting the zeolitic material provided in (i) with the source of tin ions provided in (ii) under solid state ion exchange conditions. Into the zeolitic material provided in (i) to obtain a tin-containing zeolitic material having a BEA framework structure comprising the zeolitic material to be provided in (i) and (ii) under energy input Provided by a source of tin ions provided, preferably provided by stirring a mixture of the zeolitic material provided in (i) and the source of tin ions provided in (ii), at 100 to 1000 W, preferably 200 to 800 W More preferably in the range of 300 to 600W.

Accordingly, the present invention is also directed to the above method, wherein in (iii), the tin is contacted by contacting the zeolitic material provided in (i) with the source of tin ions provided in (ii) under solid state ion exchange conditions. Into the zeolitic material provided in (i) to obtain a tin-containing zeolitic material having a BEA framework structure comprising mixing the zeolitic material provided in (i) with energy input and (ii) Providing a source of tin ions for a period of time ranging from 2 min to 5 h, preferably from 5 min to 3 h, more preferably from 10 min to 2 h, preferably by stirring the zeolite material provided in (i) with (ii) A mixture of tin ion sources provided is provided in the range of 100 to 1000 W, preferably 200 to 800 W, more preferably 300 to 600 W.

According to the method of the present invention, it is possible that either the zeolitic material and/or the tin ion source alone has been mixed prior to mixing the zeolitic material provided in (i) with the source of tin ions provided in (ii). Grind or mill. Accordingly, the present invention is also directed to the above method comprising grinding and/or grinding a zeolitic material prior to grinding the zeolitic material along with a source of tin ions, or grinding and/or grinding a source of tin ions prior to grinding the zeolitic material together with a source of tin ions, or The zeolitic material is ground and/or ground prior to grinding the zeolitic material along with the source of tin ions and the source of tin ions is ground and/or ground prior to grinding the zeolitic material along with the source of tin ions.

Step (iv)

The zeolitic material obtained from (iii) is subjected to a heat treatment in accordance with step (iv) of the process of the invention.

Optionally, the heat treatment comprises drying the zeolitic material obtained from (iii). The drying can be carried out at a temperature in the range of 50 to 200 ° C, preferably 75 to 175 ° C, more preferably 100 to 150 ° C. The drying can be carried out for a period of time ranging from 0.5 to 48 h, preferably from 1 to 24 h, more preferably from 2 to 12 h. Further, the drying may be carried out under an atmosphere containing oxygen such as pure oxygen, air or dilute air, or under an inert atmosphere such as argon or nitrogen, preferably industrial nitrogen. Preferably, the drying is carried out in an atmosphere containing oxygen.

According to the invention, it is envisaged that step (iv) of the process according to the invention is carried out to subject the zeolitic material obtained from (iii) to a heat treatment consisting of the drying. Accordingly, the present invention relates to the above method, wherein according to (iv), the zeolitic material obtained from (iii) is subjected to heat treatment by drying the zeolitic material obtained from (iii), preferably at 50 to 200 ° C, more preferably Performing at a temperature in the range of 75 to 175 ° C, more preferably 100 to 150 ° C, preferably for a period of 0.5 to 48 h, more preferably 1 to 24 h, more preferably 2 to 12 h, preferably containing oxygen, such as pure It is carried out under an atmosphere of oxygen, air or dilute air, or under an inert atmosphere such as argon or nitrogen, preferably industrial nitrogen, more preferably in an atmosphere containing oxygen such as pure oxygen, air or dilute air.

Drying can be carried out in any suitable equipment such as a static oven, or in a continuous drying apparatus. Drying can include spray drying the zeolitic material obtained from (iii), preferably after preparing a preferred aqueous suspension comprising the zeolitic material obtained from (iii). Preferably, the aqueous suspension has a solids content of from 2 to 35% by weight, preferably from 5 to 25% by weight, more preferably from 10 to 20% by weight, based on the total weight of the suspension.

Preferably, the zeolitic material obtained from (iii) is subjected to a heat treatment comprising calcining the zeolitic material in accordance with step (iv) of the process of the invention. According to a specific embodiment of the invention, the heat treatment according to (iv) consists of calcined zeolitic material. According to another embodiment of the present invention, the heat treatment according to (iv) comprises drying the zeolitic material obtained from (iii), followed by calcining the dried zeolitic material, wherein preferably, the heat treatment according to (iv) is dried from (iii) The obtained zeolitic material is subsequently calcined to form the dried zeolitic material.

According to the invention, it is conceivable to carry out the calcination in one, two or more subsequent calcination stages, wherein in each stage the calcination conditions may be the same or different from each other. Preferably, the calcination is carried out in at least one stage in an atmosphere comprising oxygen, such as pure oxygen, air or dilute air. Therefore, preferably, the calcination according to (iv) is carried out at least partially in an atmosphere containing oxygen.

Therefore, the heat treatment according to (iv) preferably comprises calcination, wherein the calcination is preferably at a temperature of from 400 to 700 ° C, more preferably from 450 to 650 ° C, more preferably from 500 to 600 ° C, preferably from 1 to 10 h, more preferably. The period of time in the range of 2 to 8 h, more preferably 3 to 6 hours, is preferably carried out at least partially in an atmosphere containing oxygen, wherein the calcination according to (iv) can be carried out partially in an inert gas atmosphere.

According to a preferred embodiment of the preferred calcination of the invention, the calcination according to (iv) is carried out in at least one calcination stage, wherein in each calcination stage, calcination is carried out in an atmosphere containing oxygen Row. In each of the calcination stages, the calcination temperature is preferably in the range of 400 to 700 ° C, more preferably 450 to 650 ° C, still more preferably 500 to 600 ° C, wherein the calcination temperatures may be different in different stages. The total calcination time of the at least one calcination stage is preferably in the range of from 1 to 10 h, more preferably from 2 to 8 h, still more preferably from 3 to 6 hours. Preferably, the zeolitic material obtained from (iii) is heated to a calcination temperature under a heating ramp in the range of 0.2 to 5 K/min, more preferably 0.5 to 4 K/min, more preferably 1 to 3 K/min. Preferably, if the calcination according to (iv) is carried out completely in an atmosphere containing oxygen, it is preferred to carry out calcination in one calcination stage.

Accordingly, the present invention relates to the above method, wherein according to (iv), the zeolitic material obtained from (iii) is subjected to a heat treatment, which is contained in one calcination stage, preferably at 400 to 700 ° C, more preferably 450 to Calcining the zeolitic material in a calcination time preferably in the range of from 1 to 10 h, more preferably from 2 to 8 h, more preferably from 3 to 6 hours, at a calcination temperature in the range of from 650 ° C, more preferably from 500 to 600 ° C, wherein the heat treatment is performed Preferably, the zeolitic material obtained from (iii) is heated to a calcination temperature under a heating ramp in the range of from 0.2 to 5 K/min, more preferably from 0.5 to 4 K/min, more preferably from 1 to 3 K/min.

According to another preferred calcination embodiment of the invention, the calcination according to (iv) is carried out in at least 2 calcination stages, wherein in at least one calcination stage, calcination is carried out in an atmosphere comprising oxygen, and wherein at least one calcination is carried out In the stage, calcination is carried out in an inert atmosphere. In each of the calcination stages, the calcination temperature is preferably in the range of 400 to 700 ° C, more preferably 450 to 650 ° C, still more preferably 500 to 600 ° C, wherein the calcination temperatures may be different in different stages. The total calcination time of the at least two calcination stages is preferably in the range of from 1 to 10 h, more preferably from 2 to 8 h, still more preferably from 3 to 6 hours. Preferably, the zeolitic material obtained from (iii) is heated to a calcination temperature under a heating ramp in the range of 0.2 to 5 K/min, more preferably 0.5 to 4 K/min, more preferably 1 to 3 K/min. Preferably, If the calcination according to (iv) is carried out in an atmosphere containing oxygen and in an inert atmosphere, it is preferably calcined in two calcination stages, wherein in the first calcination stage, the calcination is carried out in an atmosphere containing oxygen and In the second calcination stage, calcination is carried out in an inert atmosphere, or wherein in the first calcination stage, calcination is carried out in an inert atmosphere and in the second calcination stage, calcination is carried out in an atmosphere containing oxygen.

Accordingly, the present invention relates to the above method, wherein according to (iv), the zeolitic material obtained from (iii) is subjected to a heat treatment which is contained in two calcination stages, preferably in each stage of from 400 to 700 ° C, more Calcining the zeolitic material in a total calcination time preferably in the range of from 1 to 10 h, more preferably from 2 to 8 h, more preferably from 3 to 6 hours, at a calcination temperature in the range of from 450 to 650 ° C, more preferably from 500 to 600 ° C. Wherein the heat treatment preferably comprises heating the zeolitic material obtained from (iii) to a calcination temperature under a heating ramp in the range of 0.2 to 5 K/min, more preferably 0.5 to 4 K/min, more preferably 1 to 3 K/min, and Wherein in the first calcination stage, the calcination is carried out in an inert atmosphere, preferably nitrogen, and in the second calcination stage, the calcination is carried out in an atmosphere containing oxygen, preferably air or dilute air.

Accordingly, the present invention relates to the above method, wherein according to (iv), the zeolitic material obtained from (iii) is subjected to a heat treatment which is contained in two calcination stages, preferably in each stage of from 400 to 700 ° C, more Calcining the zeolitic material in a total calcination time preferably in the range of from 1 to 10 h, more preferably from 2 to 8 h, more preferably from 3 to 6 hours, at a calcination temperature in the range of from 450 to 650 ° C, more preferably from 500 to 600 ° C. Wherein the heat treatment preferably comprises heating the zeolitic material obtained from (iii) to a calcination temperature under a heating ramp in the range of 0.2 to 5 K/min, more preferably 0.5 to 4 K/min, more preferably 1 to 3 K/min, and Wherein in the first calcination stage, the calcination is carried out in an atmosphere containing oxygen, preferably air or dilute air, and in the second calcination stage, calcined in an inert atmosphere, It is preferably carried out in nitrogen.

Calcination can be carried out in any suitable equipment such as a static oven, or in a continuous calcining apparatus.

Step (v)

According to step (v) of the process of the invention, the heat treated zeolite material obtained from (iv) is treated with an aqueous solution having a pH of at most 5.

Preferably, the aqueous solution having a pH of at most 5 comprises at least one organic acid, or at least one inorganic acid, or at least one organic acid and at least one inorganic acid. The organic acid is preferably selected from the group consisting of oxalic acid, acetic acid, citric acid, methanesulfonic acid, and a mixture of two or more thereof. The inorganic acid is preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof. Accordingly, the present invention relates to the above method, wherein in (v), the aqueous solution comprises an organic acid, which is preferably selected from the group consisting of oxalic acid, acetic acid, citric acid, methanesulfonic acid, and a mixture of two or more thereof. And/or comprising a mineral acid, preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof. More preferably, the aqueous solution contains a mineral acid, which is preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof. More preferably, the aqueous solution comprises a mineral acid, which is preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof, and does not comprise a material selected from the group consisting of oxalic acid, acetic acid, citric acid, and methanesulfonic acid. The organic acid of the group consisting of an acid and a mixture of two or more thereof preferably does not contain an organic acid. More preferably, the aqueous solution comprises nitric acid. More preferably, the aqueous solution contains nitric acid and does not contain an organic acid selected from the group consisting of oxalic acid, acetic acid, citric acid, methanesulfonic acid, and a mixture of two or more thereof, and more preferably does not contain an organic acid. More preferably, the aqueous solution contains only nitric acid in the form of an acidic compound.

Accordingly, the present invention is also directed to the above method, wherein in (v), the aqueous solution comprises an organic acid, preferably selected from the group consisting of oxalic acid, acetic acid, citric acid, methanesulfonic acid, and a mixture of two or more thereof. And/or comprising a mineral acid, preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof, more preferably nitric acid.

Preferably, in (v), the pH of the aqueous solution is from 0 to 5, preferably from 0 to 4.5, more preferably from 0 to 4, still more preferably from 0 to 3.5, more preferably from 0 to 3, still more preferably from 0 to 2.5, more Good range from 0 to 2.

Regarding the temperature of the treatment with the aqueous solution according to (v), there is no particular limitation. Preferably, in (v), the heat treated zeolite material is treated with an aqueous solution at a temperature ranging from 20 ° C to 130 ° C, preferably from 50 ° C to 120 ° C, more preferably from 90 to 110 ° C. Although there is no particular limitation with regard to the type of vessel in which the treatment in (v) is carried out, the vessel is suitably selected to allow treatment of the zeolitic material at the temperatures described above, at which temperature the aqueous solution is in its liquid state. Thus, in the case of higher temperatures, the treatment in (v) is carried out under autogenous pressure in a closed system.

Regarding the period of time in which the treatment with the aqueous solution according to (v) is carried out, there is no particular limitation. Preferably, in (v), the heat treated zeolite material is treated with an aqueous solution for a period of time ranging from 10 minutes to 40 hours, preferably from 30 minutes to 30 hours, more preferably from 1 hour to 25 hours.

There is no particular limitation with respect to the amount of aqueous solution used in (v). Preferably, the weight ratio of the aqueous solution to the heat treated zeolite material is in the range of 2:1 to 50:1, preferably 8:1 to 40:1, more preferably 10:1 to 35:1.

Accordingly, the present invention relates to the above process, wherein in (v), the heat-treated zeolitic material obtained from (iv) is treated with an aqueous solution having a pH in the range of 0 to 5, preferably 0 to 3.5, more preferably 0 to 2. The treatment is carried out at a temperature ranging from 20 ° C to 130 ° C, preferably from 50 ° C to 120 ° C, more preferably from 90 to 110 ° C, and for from 10 min to 40 h, preferably from 30 min to 30 h, more preferably a time period in the range of 1 h to 25 h, wherein the weight ratio of the aqueous solution to the heat-treated zeolitic material is in the range of 2:1 to 50:1, preferably 8:1 to 40:1, more preferably 10:1 to 35:1. Inside.

During the treatment according to (v), it is preferred to suitably stir the aqueous solution containing the zeolitic material. During (v), the agitation rate remains substantially constant or varies. Thus, the stirring rate can be appropriately selected depending on, for example, the volume of the aqueous solution, the amount of the zeolitic material used, the desired temperature, and the like. Preferably, the agitation rate at which the treatment at the temperature described above is carried out is preferably in the range of 50 to 300 r.p.m. (revolution per minute), more preferably 100 to 250 r.p.m., still more preferably 180 to 220 r.p.m.

After treating the zeolitic material obtained from (iv) with an aqueous solution having a pH of at most 5 according to (v), it is preferred to separate the tin-containing zeolitic material having a BEA framework structure from the aqueous solution. All conceivable methods for separating zeolite materials from aqueous solutions are generally possible. Such methods include, for example, filtration, ultrafiltration, diafiltration, and centrifugation methods, or, for example, spray drying methods and spray granulation methods. Two or a combination of two or more of these methods may be applied. According to a specific example conceivable in one of the inventions, the zeolitic material is separated from the aqueous solution by direct spray drying. Prior to spray drying, it is possible to increase the zeolite material content in the aqueous solution by concentrating the suspension, or to reduce the zeolite material content in the aqueous solution by diluting the suspension. Preferably, the zeolitic material is separated from the aqueous solution by suitable filtration, and the material thus obtained, for example in the form of a filter cake, is optionally subjected to washing.

Any of the spray dried materials is preferably subjected to washing with at least one suitable detergent. The detergent which can be used is, for example, water, an alcohol such as methanol, ethanol or propanol, or a mixture of two or more thereof. Examples of mixtures are mixtures of two or more alcohols, such as methanol and ethanol or methanol and propanol or a mixture of ethanol and propanol or methanol with ethanol and propanol, or a mixture of water and at least one alcohol, such as water and methanol or water and ethanol or water and propanol or water and methanol and ethanol or water and methanol and propanol or water and ethanol and propanol or water and methanol and ethanol and propanol a mixture. Water or water is preferably a mixture of at least one alcohol, preferably water and ethanol, and distilled water is extremely particularly preferred as the sole detergent. Preferably, the washing is carried out at a temperature of up to 50 ° C, more preferably from 15 to 50 ° C, more preferably from 15 to 35 ° C, still more preferably from 20 to 30 ° C. Preferably, the washing is carried out until the pH of the water obtained from the washing has a pH in the range of 6.5 to 7.5, preferably 6.7 to 7.3, more preferably 6.9 to 7.1.

Preferably, the washed zeolitic material is subjected to step (vi), according to which the zeolitic material is dried and/or calcined. More preferably, the optionally washed zeolitic material is subjected to step (vi), according to which the zeolitic material is dried and calcined.

Step (vi)

Regarding the drying conditions, there are no specific restrictions. Preferably, the drying is carried out at a temperature in the range of 100 to 180 ° C, more preferably 110 to 165 ° C, still more preferably 120 to 150 ° C. Preferably, the drying is carried out for a period of time ranging from 10 h to 70 h, more preferably from 12 to 40 h, still more preferably from 15 h to 25 h. Drying can be carried out in an atmosphere containing oxygen, such as pure oxygen, air or dilute air, or in an inert atmosphere such as nitrogen or argon, preferably in an atmosphere containing oxygen, more preferably in air or dilute air. . Drying can be carried out in a static oven or in a continuous drying unit.

There are no specific restrictions regarding the calcination conditions. Preferably, the calcination is carried out at a temperature in the range of 550 to 700 ° C, more preferably 575 to 690 ° C, still more preferably 600 to 680 ° C. Preferably, the calcination is carried out for a period of time ranging from 1 to 10 h, more preferably from 1.5 to 7.5 h, still more preferably from 2 h to 5 h. The calcination may be carried out in an atmosphere containing oxygen such as pure oxygen, air or dilute air, or in an inert atmosphere such as nitrogen or argon, preferably in an atmosphere containing oxygen, more preferably in air or Performed in dilute air. Calcination can be carried out in a static oven or in a continuous drying unit.

Accordingly, the present invention relates to the above method, which further comprises (vi) drying and/or calcining the zeolitic material obtained from (v) after washing, wherein the drying is preferably from 100 to 180 ° C, preferably from 120 to 150. The temperature is in the range of ° C for a period of time ranging from 10 to 70 h, preferably from 15 to 25 h, and the calcination is preferably carried out at a temperature in the range of 550 to 700 ° C, preferably 600 to 680 ° C, for 1 to A time period in the range of 10 h, preferably 2 to 5 h.

Tin-containing zeolite material itself

According to the present invention, a tin-containing zeolite having a BEA framework structure is prepared which is used as a catalytically active material when compared with a tin-containing zeolite having a BEA framework structure known in the art prepared by solid state ion exchange. It is preferred to exhibit improved characteristics in the oxidation reaction, specifically in the Bayerville-type oxidation reaction of Bayerville-type oxidation such as cyclic ketone. As shown in the examples, it has surprisingly been found that the selectivity of the product can be significantly improved by the application of the post-treatment stage (v) of the present invention, so that it clearly has a significant effect on the chemical and/or physical properties of the zeolitic material, which in turn It becomes obvious in other uses.

Accordingly, the present invention is also directed to a tin-containing zeolitic material having a BEA framework structure, which may be by a method as described above, preferably by including steps (i) through (v), preferably steps (i) through The method of (vi) is obtained or obtained by the above method.

Surprisingly, it has been found that by applying the post-treatment stage (v) of the present invention, the crystallinity of the zeolitic material obtained from (iv) can be increased, preferably by up to 5 percentage points or by up to 10 percentage points or by up to 15 percentage points. Accordingly, the invention also relates to the use of a treatment of a tin-containing zeolitic material having a BEA framework structure, preferably prepared by solid state tin ion exchange. The use of a treatment of a tin-containing zeolite material of a BEA framework structure for increasing the crystallinity of the tin-containing zeolite material.

Surprisingly, it has been found that the hydrophobicity of the zeolitic material obtained from (iv) can be increased by applying the post-treatment stage (v) of the present invention. The measure of the hydrophobicity of the zeolitic material is the amount of water absorbed by the zeolitic material, wherein the higher the amount of water absorbed, the lower the hydrophobicity. According to the present invention, it has been found that a tin-containing zeolitic material having a BEA framework structure having a water absorption of up to 12% by weight, preferably up to 11% by weight, preferably up to 10% by weight, can be obtained.

Accordingly, the present invention also relates to a tin-containing zeolitic material having a BEA framework structure comprising X ₂ O ₃ and YO ₂ , wherein Y is selected from the group consisting of Si, Ti, Zr, Ge, and a combination of two or more thereof. a tetravalent element, Y is preferably Si, and X is a trivalent element selected from the group consisting of Al, B, In, Ga, Fe, and a combination of two or more thereof, and X is preferably B, wherein The skeleton structure additionally comprises tin, wherein in the framework structure of the zeolitic material, the molar ratio X ₂ O ₃ :YO _{2 is} at most 0.02:1, preferably at most 0.011, more preferably 0.0005:1 to 0.01:1. More preferably, in the range of from 0.0009:1 to 0.003:1, at least 95% by weight, preferably at least 98% by weight, more preferably at least 99% by weight, more preferably at least 99.5% by weight, even more preferably at least 99.8 by weight of the framework structure of the zeolitic material More preferably, at least 99.9% by weight consists of X, Y, O, H and tin, and wherein the tin-containing zeolitic material has a water uptake of up to 12% by weight, preferably up to 11% by weight, preferably up to 10% by weight. .

Preferably, the tin-containing zeolitic material of the present invention has a tin content in the range of 2 to 20% by weight, preferably 5 to 18% by weight, more preferably 8 to 16% by weight, based on the total weight of the tin-containing zeolite material. . Preferably, the tin content can be greater than 10% by weight, such as in the range of 11 to 16% by weight or 12 to 16% by weight.

Preferably, the tin-containing zeolitic material of the present invention has a range of from 200 to 220 nm. The maximum UV/Vis spectrum is displayed inside.

Preferably, the tin-containing zeolitic material of the present invention has (21.5±0.2)°, (22.6±0.2)°, (25.5±0.2)°, (26.6±0.2)°, (28.8±0.2)°, The XRD spectrum of the peak was exhibited at 2 θ values of 29.7±0.2)°, (32.2±0.2)°, (34.0±0.2)°, and (37.9±0.2)°. More preferably, the tin-containing zeolitic material of the present invention has (21.5 ± 0.2) °, (22.6 ± 0.2) °, (25.5 ± 0.2) °, (26.6 ± 0.2) °, (28.8 ± 0.2) °, ( 29.7±0.2)°, (32.2±0.2)°, (34.0±0.2)°, (36.1±0.2)°, (37.9±0.1)°, (38.9±0.2)°, (43.7±0.2)° 2 The XRD spectrum of the peak is exhibited at the value of θ. More preferably, the tin-containing zeolitic material of the present invention has (11.7±0.2)°, (13.5±0.2)°, (14.8±0.2)°, (21.5±0.2)°, (22.6±0.2)°, 25.5±0.2)°, (26.6±0.2)°, (28.8±0.2)°, (29.7±0.2)°, (32.2±0.2)°, (34.0±0.2)°, (36.1±0.2)°, (37.9 The XRD spectrum of the peak is exhibited at 2 θ values of ±0.2)°, (38.9±0.2)°, and (43.7±0.2)°.

Furthermore, the present invention relates to the tin-containing zeolitic material of the present invention, which can be obtained by the method as described above, preferably by including step (i) to step (v), preferably step (i) to step ( The method of vi) is obtained or obtained by the above method.

Further, the present invention relates to the use of a tin-containing zeolitic material having a BEA framework structure as described above, which is preferably used as a catalytically active material in an oxidation reaction in a Bayerville type oxidation reaction, and is preferably used for a catalytically active material. Bayer Welige oxidation of cyclic ketones.

Still further, the present invention relates to an oxidation reaction, preferably a Bayerville type oxidation reaction, more preferably a Bayerville oxidation of a cyclic ketone, wherein the tin-containing zeolite having a BEA framework structure as described above The material is used as a catalytically active material.

Other method steps

Usually, it is possible to use it as it is without any other modifications. The zeolitic material according to the invention is present in the form of a stone powder or a zeolite spray powder, for example in the form of a catalyst, in the form of a catalyst support, in the form of a molecular sieve, in the form of a sorbent, in the form of a filler or the like.

It is also conceivable to prepare a shaped product containing the zeolitic material based on the zeolitic material of the present invention. In this method, the zeolitic material is suitably shaped and post-treated as appropriate after further modification, as appropriate. Accordingly, the present invention is also directed to a method as described above, further comprising (vii) A tin-containing zeolite material having a BEA skeleton structure obtained from (v) or (vi), preferably from (vi), is molded to obtain a molded article.

For shaping in (vii), the zeolitic material may be admixed with at least one binder and/or with at least one binder precursor, and optionally with at least one pore former and/or at least one plasticizer.

Examples of such binders are metal oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZrO ₂ or MgO or clay or a mixture of two or more of these oxides, or Si, Al, Ti a mixed oxide of at least two of Zr and Mg. Clay minerals and naturally occurring or synthetically produced aluminas, such as alpha-, beta-, gamma-, delta-, eta-, κ-, χ- or θ-alumina, and inorganic or organometallic precursor compounds thereof, for example A gibbsite, bayerite, gibbsite or pseudo-boehmite, or a trialkoxy aluminate such as aluminum triisopropoxide is particularly preferred as the Al ₂ O ₃ binder. Other conceivable binders may be two carbophilic compounds having polar and non-polar moieties and graphite. Other binders may be, for example, clays such as montmorillonite, kaolin, metakaolin, laponite, bentonite, halloysite, dickite, pearlite or vermiculite. These binders can be used as such or in the form of a suitable precursor compound which forms the desired binder during either spray drying and/or subsequent calcination. Examples of such binder precursors are tetraalkoxy decane, tetraalkoxy titanate, tetraalkoxy zirconate, or a mixture of two or more different tetraalkoxy decanes, or two a mixture of two or more different tetraalkoxy titanates, or a mixture of two or more different tetraalkoxy zirconates, or at least one tetraalkoxy decane and at least one tetraalkoxy a mixture of titanates, or a mixture of at least one tetraalkoxy decane and at least one tetraalkoxy zirconate, or a mixture of at least one tetraalkoxy titanate and at least one tetraalkoxy zirconate Or a mixture of at least one tetraalkoxynonane and at least one tetraalkoxy titanate and at least one tetraalkoxy zirconate. In the context of the present invention, the fully or partially comprising SiO ₂ or (formed from SiO ₂₎ of SiO ₂ of the binder precursor may be preferable. In this context, colloidal cerium oxide can be used with both the so-called "wet process" cerium oxide and the so-called "dry process" cerium oxide. Particularly preferably, the cerium oxide is amorphous cerium oxide, the size of the cerium oxide particles is, for example, in the range of 5 to 100 nm, and the surface area of the cerium oxide particles is in the range of 50 to 500 m ² /g. Preferably, it is in the form of a basic and/or ammonia solution, preferably a colloidal cerium oxide in the form of an ammonia solution, especially for example Ludox ^® , Syton ^® , Nalco ^® or Snowtex ^® . "Wet" cerium oxide is commercially available, especially for example Hi-Sil ^® , Ultrasil ^® , Vulcasil ^® , Santocel ^® , Valron-Estersil ^® , Tokusil ^® or Nipsil ^® . "Dry" cerium oxide is commercially available, for example, as Aerosil ^® , Reolosil ^® , Cab-O-Sil ^® , Fransil ^® or ArcSilica ^® . In particular, an ammonia solution of colloidal cerium oxide is preferred in the present invention.

Pore forming agents include, but are not limited to, polymers such as polymeric vinyl compounds such as polyoxyalkylenes such as polyethylene oxide, polystyrene, polyacrylates, polymethacrylates, polyolefins, polyamines, and polyesters. Carbohydrates, such as cellulose or cellulose derivatives, such as methyl cellulose, or sugar or natural fibers. Other suitable pore formers can be, for example, pulp or graphite. If To achieve the pore characteristics, a mixture of two or more pore formers can be used. In a particularly preferred embodiment of one of the methods according to the invention, the pore former is removed by calcination according to (viii) and/or (x).

The ratio of the amount of the tin-containing zeolitic material used to prepare the shaped article to the amount of the binder is usually freely selectable. Generally, the weight ratio of the tin-containing zeolitic material to the binder is in the range of from 20:1 to 1:20, preferably from 10:1 to 1:10, more preferably from 1:1 to 1:10.

To prepare a shaped article based on a tin-containing zeolitic material, at least one viscous agent can be used to provide improved processability of the moldable mixture. Conceivable thickeners are, in particular, organic, in particular hydrophilic polymers, such as carbohydrates, such as cellulose, cellulose derivatives, such as methylcellulose, and starches, such as potato starch; wallpaper plaster; polyacrylate; Polymethacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyisobutylene or polytetrahydrofuran. Mention may be made of the use of water, alcohols or glycols or mixtures thereof, such as water and alcohol or a mixture of water and ethylene glycol, such as water and methanol or water and ethanol or water and propanol or a mixture of water and propylene glycol as a viscosity agent. Preferably, a carbohydrate, such as cellulose, a cellulose derivative, water, and a mixture of two or more of these compounds, such as water and cellulose or a mixture of water and a cellulose derivative, is used as a thickener. In a particularly preferred embodiment of one of the methods according to the invention, the at least one viscous agent is removed by drying and/or calcination, as further described below.

The ratio of the amount of the tin-containing zeolitic material used to prepare the shaped article to the amount of the thickener is usually freely selectable. Generally, the weight ratio of the tin-containing zeolitic material to the binder is in the range of from 20:1 to 1:50, preferably from 10:1 to 1:40, more preferably from 1:1 to 1:30.

Preferably, step (vii) comprises (vii.1) a preparation mixture comprising a tin-containing zeolite material having a BEA framework structure and a pH An aqueous solution having a value of at most 5; (vii.2) a binder or a precursor thereof, preferably a cerium oxide binder or a precursor thereof, preferably a pore former, is added to the mixture obtained from (vii.1). And optionally as a plasticizer; (vii.3) subjecting the mixture obtained from (vii.2) to shaping.

The aqueous solution having a pH of at most 5 used in (vii.1) comprises at least one organic acid, or at least one inorganic acid, or at least one organic acid and at least one inorganic acid. The organic acid is preferably selected from the group consisting of oxalic acid, acetic acid, citric acid, methanesulfonic acid, and a mixture of two or more thereof. The inorganic acid is preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof. Accordingly, the present invention relates to the above method, wherein in (v), the aqueous solution comprises an organic acid, which is preferably selected from the group consisting of oxalic acid, acetic acid, citric acid, methanesulfonic acid, and a mixture of two or more thereof. And/or comprising a mineral acid, preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof. More preferably, the aqueous solution contains a mineral acid, which is preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof. More preferably, the aqueous solution comprises a mineral acid, which is preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof, and does not comprise a material selected from the group consisting of oxalic acid, acetic acid, citric acid, and methanesulfonic acid. The organic acid of the group consisting of an acid and a mixture of two or more thereof preferably does not contain an organic acid. More preferably, the aqueous solution comprises nitric acid. More preferably, the aqueous solution contains nitric acid and does not contain an organic acid selected from the group consisting of oxalic acid, acetic acid, citric acid, methanesulfonic acid, and a mixture of two or more thereof, and more preferably does not contain an organic acid. More preferably, the aqueous solution contains only nitric acid in the form of an acidic compound.

The shaped articles of the present invention may be shaped in (vii) in each conceivable geometry such as, for example, having a rectangular shape, a triangular hexagon, a square, an ellipse a strand of a shape or a circular cross section; a star shape; a flat plate shape; a spherical shape; a hollow cylindrical shape and the like. Depending on the particular geometry, the shaping method according to (vii) will be selected. If a strand is prepared in accordance with a preferred embodiment of the invention, the shaping according to (vii) preferably comprises extrusion. Suitable extrusion equipment is described, for example, in "Ullmann's Enzyklopädie der Technischen Chemie", 4th edition, Vol. 2, page 295 and below, 1972. In addition to using an extruder, an extruder can also be used to prepare the shaped article. If desired, the extruder can be cooled as appropriate during the extrusion process. An extrusion method is conceivable in which the power consumption is in the range of 1 to 10 A, preferably 1.5 to 6 A, more preferably 2 to 4 A, depending on the batch. The strands exiting the extruder through the die end of the extruder can be mechanically cut by a suitable wire or via a non-continuous gas stream.

The shaped article obtained from (vii) is dried and/or calcined as appropriate. There are no specific restrictions regarding drying and calcination conditions. Drying is preferably carried out at a temperature usually in the range of 75 to 200 ° C, preferably 90 to 170 ° C, more preferably 100 to 150 ° C, and preferably in the range of 6 to 24 h, more preferably 10 to 20 h. . Drying can be effected in any suitable gas atmosphere, with nitrogen, air and/or lean air being preferred.

The calcination is preferably carried out at a temperature usually in the range of from 400 to 650 ° C, preferably from 450 to 600 ° C, more preferably from 475 to 550 ° C, and preferably in the range of from 0.25 to 6 h, more preferably from 0.5 to 2 h. . Calcination can be achieved in any suitable gas atmosphere, with air and/or lean air being preferred.

Furthermore, it is conceivable to subject the shaped bodies comprising the tin-containing zeolitic material to a treatment with a water system having a pH in the range of 5.5 to 8.

Preferably, the shaped body is treated with a water system at a temperature in the range of 80 to 220 ° C, preferably 90 to 210 ° C, more preferably 100 to 200 ° C. In addition, the water system treatment is better to continue A time period in the range of 1 to 20 h, more preferably 4 to 15 h, more preferably 6 to 10 h. Preferably, at least 95% by weight, more preferably at least 99% by weight, and even more preferably at least 99.9% by weight of the water system consists of water. More preferably, the water system is water.

Preferably, the treatment of the water system is carried out in a closed system under autogenous pressure with or without agitation. According to another embodiment of the present invention, the treatment with the water system is carried out in an open system, preferably under reflux, with or without agitation.

After the shaped product is treated with a water system, the shaped article is preferably suitably separated from the suspension. All methods of separating the shaped articles from the suspension are conceivable. Such methods include, for example, filtration and centrifugation methods. Two or a combination of two or more of these methods may be applied. According to the present invention, the molded product is preferably separated from the water system by filtration, and it is preferred that the molded article thus obtained is subjected to a temperature of at most 50 ° C, preferably 15 to 35 ° C, more preferably 20 to 30 ° C. Washing, preferably subjected to washing with water.

After the treatment with the water system, the shaped article is preferably subjected to drying and/or calcination, wherein drying is preferably carried out at a temperature in the range of from 100 to 180 ° C, preferably from 130 to 150 ° C, for from 10 to 70 h, preferably from 15 to The time period in the range of 25 h, and calcination is preferably carried out at a temperature in the range of 550 to 700 ° C, preferably 600 to 680 ° C, for a period of time ranging from 1 to 10 h, preferably from 2 to 5 h.

In general, the invention further relates to a zeolitic material, optionally contained in a shaped article, obtainable by or by the process according to the invention.

Furthermore, the invention relates to a shaped body comprising the zeolitic material of the invention or a zeolitic material obtainable by the process of the invention or obtained by the process, the shaped form optionally comprising a binder.

Accordingly, the present invention is also directed to the above method, which further comprises (vii) shaping the tin-containing zeolitic material having the BEA framework structure obtained from (v) or (vi), preferably from (vi), thereby obtaining a shaped article (viii) drying and/or calcining the shaped article obtained from (vii); (ix) subjecting the shaped article obtained from (vii) or (viii), preferably from (viii), to water treatment, where The water treatment comprises treating the shaped body with liquid water in an autoclave at a temperature ranging from 100 to 200 ° C under autogenous pressure; (x) drying and/or calcining the water-treated shaped product obtained from (ix) as appropriate.

Preferably, this stage (vii) comprises (vii.1) a preparation mixture comprising a tin-containing zeolitic material having a BEA framework structure and an aqueous solution having a pH of at most 5; (vii.2) to (vii.1) The obtained mixture is added with a binder or a precursor thereof, preferably a cerium oxide binder or a precursor thereof, preferably a pore former, and optionally a plasticizer; (vii.3) from (vii.2) The obtained mixture was subjected to shaping.

Further, the present invention relates to the above method, wherein (viii) comprises (viii.1) dried at (iv) at a temperature in the range of 75 to 200 ° C, preferably 90 to 170 ° C, more preferably 100 to 150 ° C. Molded product; (viii.2) A dried molded product obtained from (viii.1) is calcined at a temperature in the range of 400 to 650 ° C, preferably 450 to 600 ° C, more preferably 475 to 550 ° C.

Accordingly, the present invention is also directed to a tin-containing zeolitic material comprising a BEA framework structure as described above contained in a shaped article, the molded article preferably further comprising a binder, preferably a cerium oxide binder. Further, the present invention Also related to a molded article comprising the same as described above The tin-containing zeolitic material of the BEA framework structure, which optionally comprises at least one binder, preferably a cerium oxide binder. Further, the present invention relates to the use of a molded article as a catalyst, preferably in an oxidation reaction, preferably in a Bayerville type oxidation reaction, and more preferably in Bayerville oxidation of a cyclic ketone. Further, the present invention relates to an oxidation reaction, preferably a Bayerville type oxidation reaction, more preferably Bayervilleg oxidation of a cyclic ketone, wherein the molded article as described above contains as described above The tin-containing zeolitic material of the BEA framework structure described is used as a catalyst.

Accordingly, the present invention also relates to the use of a tin-containing zeolitic material having the BEA framework structure of the present invention, or the use of the molded article of the present invention comprising a tin-containing zeolitic material having the BEA framework structure of the present invention, which is used as a Bayerville a catalyst in a lattice oxidation reaction, or a Bayer Welig type oxidation reaction, wherein the tin-containing zeolite material having the BEA framework structure of the present invention or the tin-containing zeolite material of the present invention comprising the BEA framework structure of the present invention is formed Used as a catalyst, according to formula (I)

The organic carbonyl compound is oxidized, and wherein R ₁ and R ₂ are each independently a linear or branched alkyl residue, a linear or branched alkenyl residue, an aryl or heteroaryl residue or a hydrogen atom, The limitation is that R ₁ and R _{2 are} not hydrogen atoms at the same time, and the method comprises (i) optionally containing a tin-containing zeolitic material having a BEA framework according to the present invention in the presence of a solvent or comprising the present invention. The compound of the formula (I) is peroxidized in the presence of a shaped article of the tin-containing zeolitic material of the BEA framework structure, preferably at a temperature in the range of 50 to 150 ° C, preferably 70 to 120 ° C, more preferably 90 to 110 ° C. Hydrogen reaction to obtain a compound of formula (II)

Wherein, if R ₁ and R ₂ are not both a hydrogen atom, then R ₁ and R ₂ may form a ring together with a carbonyl group or a carboxyl group, and the formula (I) compound

And the compound of formula (II) is (ii) separating the compound of the formula (II) from the mixture obtained in (i) as appropriate; preferably, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 20 carbon atoms. a straight or branched alkenyl residue having 2 to 20 carbon atoms, an aryl or heteroaryl residue having 4 to 20 carbon atoms or a hydrogen atom, and wherein neither R ₁ nor R ₂ As a hydrogen atom, R ₁ and R ₂ may form a ring having 4 to 20 carbon atoms together with a carbonyl group or a carboxyl group.

The present invention preferably relates to a method of oxidizing a cyclic ketone of formula (I)

Wherein the ring formed by R _{1 ,} R ₂ and a carbonyl carbon atom has 4 to 20, preferably 4 to 18, more preferably 5 to 16 carbon atoms, preferably 5, 6, 8, 12, 15 or 16 a carbon atom, the method comprising (i) providing a liquid mixture comprising a compound of formula (I), hydrogen peroxide, at least one at least partially dissolved potassium salt, and optionally a solvent; (ii) a compound of formula (I) Reacting with hydrogen peroxide in a liquid mixture in the presence of a catalyst comprising a tin-containing zeolitic material to obtain a compound of formula (II)

Further, the present invention relates to the use or the method, wherein the cyclic ketone of the formula (I) is selected from the group consisting of cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and ring twelve. Alkanone, cyclopentadecanone, cyclohexadecanone, 2-pentylcyclopentanone, 2-heptylcyclopentanone, cyclohexadec-8-en-1-one, and two or more thereof The mixture, the cyclic ketone of formula (I) is preferably cyclohexanone.

The invention is further illustrated by the following examples and comparative examples.

Example Reference Example 1: Determination of water absorption

After the step isotherm procedure, a water adsorption/desorption isotherm was performed on a VTI SA instrument from a TA instrument (TA Instrument). The experiment consists of a run or series of runs performed on the sample material that has been placed on a microbalance pan within the instrument. Prior to the start of the measurement, the sample was removed by heating the sample to 100 ° C (heating ramp of 5 ° C / min) and the sample was held under a stream of nitrogen for 6 h. After the drying procedure, the temperature in the cell was lowered to 25 °C and isothermally maintained during the measurement. The microbalance was calibrated and the weight of the dried sample was equalized (maximum mass deviation was 0.01% by weight). The water uptake of the sample was measured as an increase in weight compared to the weight of the dried sample. First, the adsorption curve is increased by the relative exposure of the sample. Humidity (RH) (which is expressed as weight % water in the atmosphere in the cell), and the amount of water absorbed by the sample was measured as a balance. RH is increased from 5% to 85% in steps of 10% by weight, and at each step, the system controls RH and monitors the sample weight until the sample reaches equilibrium after exposure from 85% to 5% by weight in 10% steps Conditions, and monitoring and recording changes in sample weight (water absorption).

Reference Example 2: Determination of crystallinity

The crystallinity of the zeolitic material according to the invention was determined by XRD analysis using the EVA method as described in User Manual DIFFRAC. EVA version 3, page 105 by Bruker AXS GmbH of Karlsruhe. Sol-X detector on standard Bruker D8 Advance Diffractometer Series II, from 2° to 50°2 θ, using variable slit (V20), 0.02°2 θ step size and 2.4s per step scan Speed collection of individual data. Preset parameters were used to estimate background/amorphous content (curvature = 1, margin = 1).

Reference Example 3: FT-IR measurement

FT-IR (Fourier-Transformed-Infrared) measurements were performed on a Nicolet 6700 spectrometer. The powdered material is pressed into self-supporting pellets without using any additives. The pellets were introduced into a high vacuum (HV) unit cell placed in an FT-IR instrument. Samples were pretreated at 300 ° C for 3 h under high vacuum (10 ^-5 mbar) prior to measurement. The spectra were collected after cooling the unit cell to 50 °C. Spectra were recorded in the range 4000 to 800cm ^-1 at a resolution of 2cm ^-1. The resulting spectrum is represented by a graph having a wave number (cm ^-1 ) on the x-axis and absorbance (arbitrary unit, au) on the y-axis. To quantify the peak height and the ratio between these peaks, a baseline correction was made. The change in the region of 3000 to 3900 cm ^-1 was analyzed, and in order to compare a plurality of samples, a band at 1880 ± 5 cm ^-1 was taken as a reference.

Reference Example 4: Determination of compressive strength of the molded article of the present invention

The compressive strength mentioned in the context of the present invention is to be understood as determined by the compressive strength tester Z2.5/TS1S, supplier Zwick GmbH & Co., D-89079 Ulm, Germany. For the basic principle of this machine and its operation, refer to the respective manual "Register 1: Betriebsanleitung / Sicherheitshandbuch für die Material-Prüfmaschine Z2.5/TS1S", version 1.5, December 2001, from Zwick GmbH & Co. Technische Dokumentation , August-Nagel-Strasse 11, D-89079Ulm, Germany. With this machine, a given strand having a diameter of 1.5 mm as described in Example 5 was subjected to an increased force via a plunger having a diameter of 3 mm until the strand was crushed. The force that breaks the strand is called the compressive strength of the strand. The machine is equipped with a fixed water platform on which the strands are positioned. A plunger that is free to move in the vertical direction causes the strand to abut the fixed table. The apparatus was operated with a preliminary force of 0.5 N, a shear rate of 10 mm/min under preliminary force, and a subsequent test rate of 1.6 mm/min. A vertically movable plunger is attached to the dynamometer for force picking, and it moves toward the fixed turret on which the shaped article (strand) to be studied is positioned during the measurement, thus causing the strand to abut the table. The plunger is applied to the bracket perpendicular to the longitudinal axis of the stent. Control of the experiment was performed by means of a computer that recorded and evaluated the measurement results. In each case, the value obtained is the average of the measurements for the 10 strands.

Reference Example 5: Preparation of deborated zeolite material having a BEA framework structure 5.1 Preparation of boron-containing zeolitic material with BEA framework structure

209 kg of deionized water was provided in the vessel. Under stirring at 120 rpm (revolution per minute), 355 kg of tetraethylammonium hydroxide was added and the suspension was stirred at room temperature for 10 minutes. Thereafter, 61 kg of boric acid was suspended in water and the suspension was stirred at room temperature for further 30 minutes. Subsequently, 555 kg of Ludox® AS-40 was added, and the resulting mixture was further stirred at 70 rpm for one hour at room temperature. The pH of the liquid gel was 11.8 as determined by pH electrode measurements. The resulting mixture was transferred to a crystallization vessel and heated to 160 ° C in 6 h under a pressure of 7.2 bar and with stirring (140 rpm). Subsequently, the mixture was allowed to cool to room temperature. The mixture was again heated to 160 ° C over 6 h and stirred for an additional 55 h at 140 rpm. The mixture was allowed to cool to room temperature, and then the mixture was further heated at a temperature of 160 ° C under stirring at 140 rpm for 45 h. 7800 kg of deionized water was added to 380 kg of this suspension. The suspension was stirred at 70 rpm and 100 kg of a 10% by weight aqueous solution of HNO _{3 was added} . The boron-containing zeolitic material having the BEA framework structure is separated from the suspension by filtration. The filter cake was then washed with deionized water at room temperature until the wash water had a conductivity of less than 150 microsiemens per centimeter. The filter cake thus obtained was subjected to pre-drying in a stream of nitrogen.

The zeolitic material thus obtained, after having been prepared using deionized water to prepare an aqueous suspension having a solids content of 15% by weight (based on the total weight of the suspension), was subjected to spray drying in a spray tower, the spray drying conditions being as follows: drying Gas, nozzle gas: industrial nitrogen

Dry gas temperature:

nozzle:

The spray tower consists of a vertically arranged cylinder of length 2,650 mm and a diameter of 1,200 mm which is conically narrowed at the bottom. The length of the cone is 600 mm. At the top end of the cylinder, an atomizing member (two-component nozzle) is disposed. The spray dried material is separated from the drying gas in a filter downstream of the spray tower, and then the drying gas is passed through the scrubber. The suspension is passed through the internal opening of the nozzle and the nozzle gas is passed through an annular slit surrounding the opening.

The spray dried material was then subjected to calcination at 500 ° C for 5 h. The calcined material had a B ₂ O ₃ :SiO ₂ molar ratio of 0.045, a total carbon content (TOC) of 0.08% by weight, a crystallinity of 56% as determined by XRD, and a BET specific surface area as determined by DIN 66131. It is 498 m ² /g.

5.2 Deboration - formation of empty tetrahedral sites

840 kg of deionized water was provided in a vessel equipped with a reflux condenser. At a stirring of 40 rpm, 28 kg of the spray dried and calcined zeolitic material described in 5.1 was used. Subsequently, the vessel is sealed and the reflux condenser begins to operate. The agitation rate was increased to 70 rpm. The contents of the vessel were heated to 100 ° C in 1 h with stirring at 70 rpm and held at this temperature for 20 h. Subsequently, the contents of the vessel were allowed to cool to a temperature below 50 °C. The deboronated zeolite material having the BEA framework structure obtained from the suspension separation was washed four times with nitrogen gas under a pressure of 2.5 bar and washed with deionized water at room temperature four times. After filtration, the filter cake was dried under a stream of nitrogen for 6 h.

After the zeolite material has been resuspended in deionized water, the resulting deboronated zeolite material is subjected to spray drying under the conditions as described in 5.1. The solids content of the aqueous suspension was 15% by weight, based on the total weight of the suspension. The obtained zeolite material had a B ₂ O ₃ :SiO ₂ molar ratio of less than 0.002, a water absorption of 15% by weight, a crystallinity of 48% as determined by XRD and a BET specific surface area of 489 m ² /g as determined by DIN 66131. .

Comparative Example 1: Preparation of a tin-containing zeolitic material having a BEA framework structure without acid treatment

25 g of deborated zeolite material having a BEA framework structure as described in Reference Example 5, Section 5.2 and 5.5 g of tin(II) acetate (Sn(OAc) ₂ [CAS-Nr:638-39-1]) They were added together to a mixer (Microton MB550 type grinder), and the mixture was ground at 14,000 rpm (revolution per minute) for 15 minutes. After grinding, the mixture was transferred to a porcelain basket and calcined in air at 550 ° C for 5 h with a heating ramp of 2 K/min.

The obtained powder material had a Sn content of 9.6% by weight, a cerium (Si) content of 38% by weight and a TOC of less than 0.1% by weight. The BET specific surface area measured by DIN 66131 was 423 m ² /g, the crystallinity measured by XRD was 51%, and the water absorption amount was 18% by weight. The UV/Vis spectrum shows two maxima, one at a wavelength of 200 nm and the second around 250 nm. Intensity ratio between the first maximum value of the second suction belt has a maximum adsorption between 3600 to 3690cm ^-1 in the FT-IR spectrum having between 3701 to 3741cm ^-1 was 1.49.

Comparative Example 2: Preparation of a tin-containing zeolitic material having a BEA framework structure without acid treatment

50 g of deborated zeolite material having a BEA framework structure as described in Reference Example 5, Section 5.2 and 14.2 g of tin(II) acetate (Sn(OAc) ₂ [CAS-Nr:638-39-1]) They were added together to a mixer (Microton MB550 type grinder), and the mixture was ground at 14,000 rpm (revolution per minute) for 15 minutes. After grinding, the mixture was transferred to a porcelain basket and calcined in air at 500 ° C for 3 h with a heating ramp of 2 K/min.

The obtained powder material had a Sn content of 12.0% by weight, a cerium (Si) content of 35 wt% and a TOC of less than 0.1% by weight. The BET specific surface area measured by DIN 66131 was 391 m ² /g, the crystallinity measured by XRD was 44%, and the water absorption amount was 15% by weight. The UV/Vis spectrum shows two maxima, one at a wavelength of 200 nm and a shoulder at about 250 nm. In the FT-IR spectrum having between 3701 to 3741cm ^-1 is the intensity ratio between the first maximum value of the second adsorption suction belt having a maximum value between 3600 to 3690cm ^-1 is 1.32.

Comparative Example 3: Preparation of a tin-containing zeolitic material having a BEA framework structure without acid treatment

50 g of deborated zeolite material having a BEA framework structure as described in Reference Example 5, Section 5.2 and 14.2 g of tin(II) acetate (Sn(OAc) ₂ [CAS-Nr:638-39-1]) They were added together to a mixer (Microton MB550 type grinder), and the mixture was ground at 14,000 rpm (revolution per minute) for 15 minutes. After grinding, the mixture was transferred to a porcelain basket and calcined in air at 500 ° C for 3 h under N ₂ , followed by calcination under air for 3 h with a heating ramp of 2 K/min.

The obtained powder material had a Sn content of 13.1% by weight, a cerium (Si) content of 38% by weight and a TOC of less than 0.1% by weight. The BET specific surface area measured by DIN 66131 was 442 m ² /g, the crystallinity measured by XRD was 44%, and the water absorption amount was 11.5% by weight. The UV/Vis spectrum shows two maxima, one at a wavelength of 200 nm and a shoulder at about 250 nm. Intensity ratio between the first maximum value of the second suction belt has a maximum adsorption between 3600 to 3690cm ^-1 in the FT-IR spectrum having between 3701 to 3741cm ^-1 is 1.62.

Comparative Example 4: Preparation of a tin-containing zeolitic material having a BEA framework structure without acid treatment

50 g of deborated zeolite material having a BEA framework structure as described in Reference Example 5, Section 5.2 and 14.2 g of tin(II) acetate (Sn(OAc) ₂ [CAS-Nr:638-39-1]) They were added together to a ball mill (17 balls, the total weight of the balls was 904 g), and the mixture was ground at 80 r.pm (revolution per minute) for 15 minutes. After grinding, the mixture was transferred to a porcelain basket and calcined in air at 500 ° C for 3 h with a heating ramp of 2 K/min.

The obtained powder material had a Sn content of 12.4% by weight, a cerium (Si) content of 36% by weight and a TOC of less than 0.1% by weight. The BET specific surface area measured by DIN 66131 was 426 m ² /g, the crystallinity measured by XRD was 42%, and the water absorption amount was 12% by weight.

Example 1: Preparation of a tin-containing zeolitic material having a BEA framework structure under acid treatment

10 g of the zeolitic material obtained according to Comparative Example 1 was supplied in a round bottom flask, and 300 g of a 30% by weight aqueous solution of HNO ₃ having a pH in the range of 0 to 1 was added. The mixture was stirred at a temperature of 100 ° C for a period of 20 h (200 rpm). The suspension was filtered and the filter cake was then washed with deionized water at room temperature until the pH of the wash water was approximately 7.

The resulting zeolitic material was dried at 120 ° C for 10 h and calcined by heating to 550 ° C (2 K/min) and subsequent heating at 550 ° C for 10 h. The dried and calcined zeolitic material had a Si content of 36% by weight, a Sn content of 9.3% by weight and a crystallinity of 53% as determined by XRD. Further, the BET specific surface area of the zeolitic material measured according to DIN 66131 is 380 m ² /g, and the water absorption amount is 6% by weight. The UV/Vis spectrum shows two maximum values at 208 nm and 250 nm. Intensity ratio between the first maximum value of the second suction belt has a maximum adsorption between 3600 to 3690cm ^-1 in the FT-IR spectrum having between 3701 to 3741cm ^-1 is 0.93.

Example 2: Preparation of a tin-containing zeolite having a BEA framework structure by acid treatment material

12 g of the zeolitic material obtained according to Comparative Example 2 was supplied in a round bottom flask, and 360 g of a 30% by weight aqueous solution of HNO ₃ having a pH in the range of 0 to 1 was added. The mixture was stirred at a temperature of 100 ° C for a period of 20 h (200 rpm). The suspension was filtered and the filter cake was then washed with deionized water at room temperature until the pH of the wash water was approximately 7.

The resulting zeolitic material was dried at 120 ° C for 10 h and calcined by heating to 550 ° C (2 K/min) and subsequent heating at 550 ° C for 5 h. The dried and calcined zeolitic material had a Si content of 37% by weight, a Sn content of 12.7% by weight, a TOC of less than 0.1% by weight, and a crystallinity of 48% as determined by XRD. Further, the BET specific surface area of the zeolitic material measured according to DIN 66131 was 395 m ² /g, and the water absorption amount was 9% by weight. The UV/Vis spectrum has a maximum at 208 nm and a shoulder at about 257 nm. Intensity ratio between the first maximum value of the second suction belt has a maximum adsorption between 3600 to 3690cm ^-1 in the FT-IR spectrum having between 3701 to 3741cm ^-1 is 1.33.

The XRD spectrum of the resulting calcined zeolitic material exhibits the following characteristics:

Example 3: Preparation of a tin-containing zeolitic material having a BEA framework structure under acid treatment

12 g of the zeolitic material obtained according to Comparative Example 3 was supplied in a round bottom flask, and 360 g of a 30% by weight aqueous solution of HNO ₃ having a pH in the range of 0 to 1 was added. The mixture was stirred at a temperature of 100 ° C for a period of 20 h (200 rpm). The suspension was filtered and the filter cake was then washed with deionized water at room temperature until the pH of the wash water was approximately 7.

The resulting zeolitic material was dried at 120 ° C for 10 h and calcined by heating to 550 ° C (2 K/min) and subsequent heating at 550 ° C for 5 h. The dried and calcined zeolite material had a Si content of 37% by weight, a Sn content of 12.6% by weight, a TOC of less than 0.1% by weight, and a crystallinity of 49% as determined by XRD. Further, the BET specific surface area of the zeolitic material measured according to DIN 66131 was 405 m ² /g, and the water absorption amount was 8.7% by weight. The UV/Vis spectrum has a maximum at 210 nm and a shoulder at about 257 nm. Intensity ratio between the first maximum value of the second suction belt has a maximum adsorption between 3600 to 3690cm ^-1 in the FT-IR spectrum having between 3701 to 3741cm ^-1 was 1.5.

Example 4: Preparation of a tin-containing zeolitic material having a BEA framework structure under acid treatment

900 g of a 30% by weight aqueous solution of HNO ₃ having a pH in the range of 0 to 1 was supplied in a 2 L stirring apparatus, and 30 g of the zeolitic material obtained according to Comparative Example 4 was added. The mixture was stirred at a temperature of 100 ° C for a period of 20 h (200 rpm). The suspension was filtered and the filter cake was then washed with deionized water at room temperature until the pH of the wash water was approximately 7.

The resulting zeolitic material was dried at 120 ° C for 10 h (3 K/min) and calcined in air by heating to 550 ° C (2 K/min) and subsequent heating at 550 ° C for 10 h. The dried and calcined zeolitic material had a Si content of 36% by weight, a Sn content of 12.8% by weight, a TOC of less than 0.1% by weight, and a crystallinity of 46% as determined by XRD. Further, the BET specific surface area of the zeolitic material measured according to DIN 66131 was 374 m ² /g, and the water absorption amount was 8% by weight.

Comparative Example 5: Use of tin-containing zeolitic material according to Comparative Example 1 to Comparative Example 4

Bayerville oxidation of cyclohexanone to ε-caprolactone in 1,4-dioxane using an aqueous solution of hydrogen peroxide.

Comparative Example 5.1: Use of the tin-containing zeolitic material according to Comparative Example 1

The zeolitic material prepared according to Comparative Example 1 was fed into a 100 mL glass flask as a catalyst (0.1 g, Sn loading = 9.6 wt%) and 1,4-dioxane (45 g). The mixture was heated to 95 °C. An aqueous solution of hydrogen peroxide (70% by weight, 0.5 g) was then added, and the reaction mixture was stirred for 4 hours. After cooling to room temperature, the solution was filtered and used by GC The butyl ether was used as an internal standard to analyze the filtrate. The concentration of ε-caprolactone and cyclohexanone in the product mixture was determined by using quantitative GC analysis using di-n-butyl ether as an internal standard. Using these data, the selectivity of cyclohexanone and hydrogen peroxide based on ε-caprolactone and the conversion of cyclohexanone were calculated. The results are shown in Table 1 below.

Comparative Example 5.2: Use of tin-containing zeolitic material according to Comparative Example 2

The zeolitic material prepared according to Comparative Example 2 was fed into a 100 mL glass flask as a catalyst (0.1 g, Sn loading = 12.0% by weight) and 1,4-dioxane (45 g). The mixture was heated to 95 °C. An aqueous solution of hydrogen peroxide (70% by weight, 0.5 g) was then added, and the reaction mixture was stirred for 4 hours. After cooling to room temperature, the solution was filtered and the filtrate was analyzed by GC using di-n-butyl ether as an internal standard. The concentration of ε-caprolactone and cyclohexanone in the product mixture was determined by using quantitative GC analysis using di-n-butyl ether as an internal standard. Using these data, the selectivity of cyclohexanone and hydrogen peroxide based on ε-caprolactone and the conversion of cyclohexanone were calculated. The results are shown in Table 1 below.

Comparative Example 5.3: Use of the tin-containing zeolitic material according to Comparative Example 3

The zeolitic material prepared according to Comparative Example 3 was fed with a cyclohexanone (1.5 g) into a 100 mL glass flask as a catalyst (0.1 g, Sn loading = 13.1% by weight) and 1,4-dioxane (45 g). The mixture was heated to 95 °C. An aqueous solution of hydrogen peroxide (70% by weight, 0.5 g) was then added, and the reaction mixture was stirred for 4 hours. After cooling to room temperature, the solution was filtered and the filtrate was analyzed by GC using di-n-butyl ether as an internal standard. The concentration of ε-caprolactone and cyclohexanone in the product mixture was determined by using quantitative GC analysis using di-n-butyl ether as an internal standard. Using these data, the selectivity of cyclohexanone and hydrogen peroxide based on ε-caprolactone and the conversion of cyclohexanone were calculated. The results are shown in Table 1 below.

Comparative Example 5.4: Use of a tin-containing zeolitic material according to Comparative Example 4

The zeolitic material prepared according to Comparative Example 4 was fed with a cyclohexanone (1.5 g) into a 100 mL glass flask as a catalyst (0.1 g, Sn loading = 12.4% by weight) and 1,4-dioxane (45 g). The mixture was heated to 95 °C. An aqueous solution of hydrogen peroxide (70% by weight, 0.5 g) was then added, and the reaction mixture was stirred for 4 hours. After cooling to room temperature, the solution was filtered and the filtrate was analyzed by GC using di-n-butyl ether as an internal standard. The concentration of ε-caprolactone and cyclohexanone in the product mixture was determined by using quantitative GC analysis using di-n-butyl ether as an internal standard. Using these data, the selectivity of cyclohexanone and hydrogen peroxide based on ε-caprolactone and the conversion of cyclohexanone were calculated. The results are shown in Table 1 below.

Example 5: Use of tin-containing zeolitic material according to Examples 1 to 4

Bayerville oxidation of cyclohexanone to ε-caprolactone in 1,4-dioxane by aqueous solution of hydrogen peroxide

Example 5.1: Use of a tin-containing zeolitic material according to Example 1

The zeolitic material prepared according to Example 1 was fed with a cyclohexanone (1.5 g) into a 100 mL glass flask as a catalyst (0.1 g, Sn loading = 9.3 wt%) and 1,4-dioxane (45 g). The mixture was heated to 95 °C. An aqueous solution of hydrogen peroxide (70% by weight, 0.5 g) was then added, and the reaction mixture was stirred for 4 hours. After cooling to room temperature, the solution was filtered and the filtrate was analyzed by GC using di-n-butyl ether as an internal standard. The concentration of ε-caprolactone and cyclohexanone in the product mixture was determined by using quantitative GC analysis using di-n-butyl ether as an internal standard. Using these data, the selectivity of cyclohexanone and hydrogen peroxide based on ε-caprolactone and the conversion of cyclohexanone were calculated. The results are shown in Table 1 below.

Example 5.2: Use of a tin-containing zeolitic material according to Example 2

The zeolitic material prepared according to Example 2 was fed with a cyclohexanone (1.5 g) into a 100 mL glass flask as a catalyst (0.1 g, Sn loading = 12.7% by weight) and 1,4-dioxane (45 g). The mixture was heated to 95 °C. An aqueous solution of hydrogen peroxide (70% by weight, 0.5 g) was then added, and the reaction mixture was stirred for 4 hours. After cooling to room temperature, the solution was filtered and the filtrate was analyzed by GC using di-n-butyl ether as an internal standard. The concentration of ε-caprolactone and cyclohexanone in the product mixture was determined by using quantitative GC analysis using di-n-butyl ether as an internal standard. Using these data, the selectivity of cyclohexanone and hydrogen peroxide based on ε-caprolactone and the conversion of cyclohexanone were calculated. The results are shown in Table 1 below.

Example 5.3: Use of a tin-containing zeolitic material according to Example 3

The zeolitic material prepared according to Example 3 was fed with a cyclohexanone (1.5 g) into a 100 mL glass flask as a catalyst (0.1 g, Sn loading = 12.6% by weight) and 1,4-dioxane (45 g). The mixture was heated to 95 °C. An aqueous solution of hydrogen peroxide (70% by weight, 0.5 g) was then added, and the reaction mixture was stirred for 4 hours. After cooling to room temperature, the solution was filtered and the filtrate was analyzed by GC using di-n-butyl ether as an internal standard. The concentration of ε-caprolactone and cyclohexanone in the product mixture was determined by using quantitative GC analysis using di-n-butyl ether as an internal standard. Using these data, the selectivity of cyclohexanone and hydrogen peroxide based on ε-caprolactone and the conversion of cyclohexanone were calculated. The results are shown in Table 1 below.

Example 5.4: The tin-containing zeolitic material of Example 4 of way

The zeolitic material prepared according to Example 4 was fed with a cyclohexanone (1.5 g) into a 100 mL glass flask as a catalyst (0.1 g, Sn loading = 12.8% by weight) and 1,4-dioxane (45 g). The mixture was heated to 95 °C. An aqueous solution of hydrogen peroxide (70% by weight, 0.5 g) was then added, and the reaction mixture was stirred for 4 hours. After cooling to room temperature, the solution was filtered and di-n-butyl was used by GC. The ether was used as an internal standard to analyze the filtrate. The concentration of ε-caprolactone and cyclohexanone in the product mixture was determined by using quantitative GC analysis using di-n-butyl ether as an internal standard. Using these data, the selectivity of cyclohexanone and hydrogen peroxide based on ε-caprolactone and the conversion of cyclohexanone were calculated. The results are shown in Table 1 below.

These examples and comparative examples clearly show that by subjecting a tin-containing zeolitic material having a BEA framework structure prepared by solid state ion exchange to step (v) according to the invention, that is, to treatment with an acidic aqueous solution, The catalytic properties and selectivity of the zeolitic material with respect to the most important parameters are significantly improved. In particular, although the selectivity of ε-caprolactone based on hydrogen peroxide remains constant at an extremely high level of 99%, the selectivity of ε-caprolactone based on the starting material cyclohexanone is according to the steps according to the (v) Comparative Example 1 increased from 82% to 99% when treating the catalyst, from 83% to 98% when the catalyst was treated according to Comparative Example 2 according to step (v), according to according to step (v) Comparative Example 3 treated the catalyst with an increase of 82% to 91% and increased from 90% to 99% when the catalyst was treated according to Comparative Example 4 according to step (v).

Example 6: Preparation of a molding based on a tin-containing zeolitic material having a BEA framework structure in the case of acid treatment 6.1 Preparation of zeolitic materials

150 g of deborated zeolite material having a BEA framework structure as described in Reference Example 5, Section 5.2 and 42.6 g of tin(II) acetate (Sn(OAc) ₂ [CAS-Nr:638-39-1]) They were added together to a mixer (Microton MB550 type grinder), and the mixture was ground at 14,000 rpm (revolution per minute) for 15 minutes. After grinding, the mixture was transferred to a porcelain basket and calcined in air at 500 ° C for 3 h with a heating ramp of 2 K/min. The obtained powder material had a Sn content of 12.0% by weight, a Si content of 37.0% by weight, and a TOC of less than 0.1% by weight. The BET specific surface area measured by DIN 66131 was 464 m ² /g, and the crystallinity measured by XRD was 51%.

6.2 acid treatment

In a round bottom flask, 165 g of the zeolitic material obtained according to 6.1 above was supplied, and 4,950 g of a 30% by weight aqueous solution of HNO ₃ having a pH in the range of 0 to 1 was added. The mixture was stirred at a temperature of 100 ° C for a period of 20 h (200 rpm). The suspension was filtered and the filter cake was then washed with deionized water at room temperature until the pH of the wash water was approximately 7. The resulting zeolitic material was dried at 120 ° C for 10 h and calcined by heating to 550 ° C (2 K/min) and subsequent heating at 550 ° C for 5 h. The dried and calcined zeolitic material had a Si content of 37.0% by weight, a Sn content of 12.4% by weight, a TOC of less than 0.1% by weight, and a crystallinity of 62% as determined by XRD. Furthermore, the BET specific surface area of the zeolitic material determined according to DIN 66131 is 391 m ² /g.

6.3 shaping

In a kneader, 34 g of the zeolitic material obtained according to 6.2 above was added and mixed with an acidic solution prepared by dissolving 3.9 g of HNO ₃ (65 wt%) in 15 ml of distilled water. The suspension was kneaded (kneaded) for 10 min. And the mixture was added 6.5g Walocel ^TM 108.3g Ludox® AS-40 and then to the resulting mixture 30min. Finally, 45 ml of distilled water was added to the mixture and mixed for another 20 min. The paste is then extruded in a Loomis extruder at a pressure of 100 to 110 bar (equipment pressure) and an extrudate mass pressure of 32 to 49 bar. An extrudate of 1.5 mm was obtained and dried in a static oven at 120 °C for 5 h, followed by calcination at 500 ° C for 5 h at air and a heating rate of 2 K/min. The calcined extrudate had a bulk density of 535 g/L and a mechanical strength of 11.2 N. The basic composition was 9.2% by weight of Sn, 41% by weight of Si and 0.12% by weight of TOC. Furthermore, the shaped material has a BET specific surface area of 55 m ² /g as determined according to DIN 66131, a water absorption of 8% by weight, and a total pore volume of 0.5 ml/g as determined by Hg porosimetry according to DIN 66133. The UV/Vis spectrum has a maximum at 208 nm and a shoulder at about 259 nm. Intensity ratio between the first maximum value of the second suction belt has a maximum adsorption between 3600 to 3690cm ^-1 in the FT-IR spectrum having between 3701 to 3741cm ^-1 was 3.3.

Cited literature

- Hammond C., et al., Simple and Scalable Preparation of Highly Active Lewis Acidic Sn-beta; Angw. Chem. Int. Ed. 2012 (51), pp. 11736-11739

Claims (30)

A method of preparing a tin-containing zeolitic material having a BEA framework structure, comprising: (i) providing a zeolitic material having a BEA framework structure comprising X ₂ O ₃ and YO ₂ , wherein Y is selected from the group consisting of Si, Ti, Zr, Ge, and a tetravalent element of a group consisting of a combination of two or more thereof, and X is a trivalent element selected from the group consisting of Al, B, In, Ga, Fe, and a combination of two or more thereof, The BEA framework structure has an empty tetrahedral framework site; (ii) provides a source of tin ions in solid form; (iii) by using the zeolite material provided in (i) with the source of tin ions provided in (ii) Contacting under solid ion exchange conditions to incorporate tin into the zeolitic material provided in (i) to obtain a tin-containing zeolitic material having a BEA framework structure; (iv) subjecting the zeolitic material obtained from (iii) to Heat treatment; (v) treating the heat treated zeolite material obtained from (iv) with an aqueous solution having a pH of at most 5. The method of claim 1, wherein Y is Si and X is B. The method of claim 1 or 2, wherein the zeolite material having a BEA framework structure having a hollow tetrahedral skeleton site is provided by the following method according to (i): (i.1) a zeolite starting material having a BEA framework structure, wherein the framework structure of the zeolite starting material comprises X ₂ O ₃ and YO ₂ , and the molar ratio X ₂ O ₃ :YO _{2 is} greater than 0.02:1, preferably at least 0.03 :1, more preferably in the range of 0.03:1 to 0.07:1, more preferably 0.03:1 to 0.06:1, more preferably 0.03:1 to 0.05:1; (i.2) preferably by using a liquid solvent system The zeolite starting material provided in (i.1) is treated under reflux to produce an empty tetrahedral framework site, thereby obtaining a zeolitic material having a molar ratio of X ₂ O ₃ :YO _{2 of} at most 0.02:1, wherein the liquid The solvent system is preferably selected from the group consisting of water, methanol, ethanol, propanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, a propane-1,2,3-triol and a mixture of two or more thereof, the liquid solvent system being more preferably water, and more preferably, the liquid solvent system does not contain an inorganic or organic acid or And wherein the treatment is preferably at a temperature in the range of 50 to 125 ° C, more preferably 90 to 115 ° C, more preferably 95 to 105 ° C, preferably 6 to 20 h, more preferably 7 to 17 h, still more preferably 8 to 12 h. a period of time within the range; (i.3) at least partially separated from the liquid solvent system from the zeolitic material obtained from (i.2), optionally including drying; (i.4) optionally calcined from (i.3) The isolated zeolitic material obtained is preferably at a temperature in the range of from 400 to 700 ° C, more preferably from 450 to 550 ° C, and preferably for a period of from 1 to 10 h, more preferably from 3 to 6 h. The method of any one of claims 1 to 3, wherein the molar ratio X ₂ O ₃ :YO _{2 is} at most 0.02 in the skeleton structure of the zeolitic material provided in (i) :1, preferably at most 0.011, more preferably in the range of 0.0005:1 to 0.01:1, more preferably 0.0009:1 to 0.003:1. The method of any one of claims 1 to 4, wherein at least 95% by weight, preferably at least 98% by weight, more preferably at least 99% of the framework structure of the zeolitic material provided in (i) The weight % consists of X ₂ O ₃ and YO ₂ . The method of any one of clauses 1 to 5, wherein the source of tin ions provided in (ii) is selected from the group consisting of tin (II) alkoxide, tin (IV) An alkoxide, a tin (II) salt of an organic acid, a tin (IV) salt of an organic acid, and both or both The above mixture is preferably selected from the group consisting of tin (II) alkoxide having 1 to 4 carbon atoms, tin (IV) alkoxide having 1 to 4 carbon atoms, having 1 to a tin (II) salt of an organic acid of 6 carbon atoms, a tin (IV) salt of an organic acid having 1 to 6 carbon atoms, and a mixture of two or more thereof, more preferably, in (ii) The source of tin ions provided in the middle is tin (II) acetate. The method of any one of clauses 1 to 6, wherein the tin contained in the source of tin ions in contact with the zeolitic material is relative to the empty tetrahedron of the zeolitic material according to (iii) The molar ratio of the skeleton sites is at most 1:1. The method of any one of claims 1 to 7, wherein in (iii), the zeolitic material provided in (i) and the source of tin ions provided in (ii) are in a solid state Contacting under ion exchange conditions comprises mixing the zeolitic material provided in (i) with the source of tin ions. The method of claim 8, wherein in (iii), the zeolitic material is mixed with the source of tin ions for a period of time ranging from 2 min to 5 h, preferably from 5 min to 3 h, more preferably from 10 min to 2 h. The method of claim 8 or 9, wherein the mixing is carried out under stirring with an agitation energy input in the range of 100 to 1000 W, preferably 200 to 800 W, more preferably 300 to 600 W. The method of any one of clauses 8 to 10, comprising: grinding and/or grinding the zeolitic material prior to grinding the zeolitic material together with the source of tin ions, or grinding the zeolitic material together with the tin Ionizing and/or grinding the source of tin ions prior to the ion source, or grinding and/or grinding the zeolitic material prior to grinding the zeolitic material along with the source of tin ions and grinding prior to grinding the zeolitic material along with the source of tin ions / or grinding the source of tin ions. The method of any one of clauses 1 to 11, wherein the heat treatment according to (iv) comprises calcination, wherein the calcination is preferably from 400 to 700 ° C, more preferably from 450 to 650 ° C, more preferably 500. The period of time in the range of from 1 to 10 h, more preferably from 2 to 8 h, more preferably from 3 to 6 hours, preferably at least partially in an atmosphere containing oxygen, is carried out at a temperature in the range of from 600 °C. The method of any one of claims 1 to 12, wherein the calcined portion according to (iv) is carried out in an inert gas atmosphere. The method of any one of clauses 1 to 13, wherein in (v), the aqueous solution comprises an organic acid, preferably selected from the group consisting of oxalic acid, acetic acid, citric acid, methanesulfonic acid, and the like. Or a mixture of a mixture of two or more, and/or comprising a mineral acid, preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof, the inorganic acid being more preferably nitric acid . The method of any one of clauses 1 to 14, wherein in (v), the aqueous solution has a pH in the range of 0 to 5, preferably 0 to 3.5, more preferably 0 to 2. The method of any one of clauses 1 to 15, wherein in the (v), the heat-treated material is used in the aqueous solution at 20 to 130 ° C, preferably 50 to 120 ° C, more preferably 90 to Treatment at a temperature in the range of 110 °C. The method of any one of claims 1 to 16, wherein in (v), the heat-treated zeolite material is treated with the aqueous solution for 10 to 40 hours, preferably 30 to 30 hours, more preferably 1 hour. Time period up to 25h. The method of any one of clauses 1 to 17, wherein in the (v), the heat-treated zeolite material is in the range of 2:1 to 50:1, preferably 8:1 to 40:1. Better 10:1 to 35:1 The aqueous solution is treated with the aqueous solution in a weight ratio relative to the heat treated zeolite material. The method of any one of clauses 1 to 18, further comprising (vi) drying and/or calcining the zeolitic material obtained from (v) after washing, wherein the drying is preferably It is carried out at a temperature in the range of 100 to 180 ° C, preferably 120 to 150 ° C, for a period of time ranging from 10 to 70 h, preferably from 15 to 25 h, and the calcination is preferably from 550 to 700 ° C, preferably from 600 to 680. The temperature is in the range of °C for a period of time ranging from 1 to 10 h, preferably from 2 to 5 h. The method of any one of claims 1 to 19, further comprising (vii) the tin-containing structure having a BEA framework structure obtained from (v) or (vi), preferably from (vi) The zeolitic material is shaped to obtain a shaped article; (viii) dried and/or calcined from the molded article obtained from (vii); (ix) as obtained from (vii) or (viii), preferably from (viii) The shaped article is subjected to a water treatment, wherein the water treatment comprises treating the shaped body with liquid water in an autoclave at a temperature ranging from 100 to 200 ° C under autogenous pressure; (x) drying and/or calcining as appropriate (ix) The water treatment molded article obtained. The method of claim 20, wherein (vii) comprises (vii.1) a preparation mixture comprising the tin-containing zeolite material having a BEA framework structure and an aqueous solution having a pH of at most 5; (vii.2) The binder obtained from (vii.1) is added with a binder or a precursor thereof, preferably a cerium oxide binder or a precursor thereof, preferably a pore former, and optionally a plasticizer; (vii.3) The mixture obtained from (vii.2) was subjected to shaping. The method of claim 20 or 21, wherein (viii) comprises (viii.1) drying at a temperature in the range of 75 to 200 ° C, preferably 90 to 170 ° C, more preferably 100 to 150 ° C. (vii) the molded article obtained; (viii.2) calcined from (viii.1) at a temperature in the range of 400 to 650 ° C, preferably 450 to 600 ° C, more preferably 475 to 550 ° C. Things. A tin-containing zeolitic material having a BEA framework structure comprising X ₂ O ₃ and YO ₂ , wherein Y is a tetravalent element selected from the group consisting of Si, Ti, Zr, Ge, and a combination of two or more thereof, Y is preferably Si, and X is a trivalent element selected from the group consisting of Al, B, In, Ga, Fe, and a combination of two or more thereof, and X is preferably B, wherein the skeleton structure additionally contains tin. Wherein in the framework structure of the zeolitic material, the molar ratio X ₂ O ₃ :YO ₂ , preferably B ₂ O ₃ :SiO ₂ is at most 0.02:1, preferably at most 0.011, more preferably 0.0005 a range of from 1 to 0.01:1, more preferably from 0.0009:1 to 0.003:1, wherein at least 95% by weight, preferably at least 98% by weight, more preferably at least 99% by weight of the framework structure of the zeolitic material is from X, Y And O, H and tin, preferably consisting of B, Si, O and tin, and wherein the tin-containing zeolitic material has a water adsorption of up to 12% by weight, preferably up to 10% by weight. A tin-containing zeolitic material according to claim 23, which has a total weight of the tin-containing zeolitic material in the range of 2 to 20% by weight, preferably 5 to 18% by weight, more preferably 8 to 16% by weight. Tin content. A tin-containing zeolitic material as claimed in claim 23 or 24, which has a UV/Vis spectrum exhibiting a maximum in the range of 200 to 220 nm. The tin-containing zeolitic material according to any one of claims 23 to 25, which has (21.5 ± 0.2) °, (22.6 ± 0.2) °, (25.5 ± 0.2) °, (26.6 ± 0.2) °, (28.8 ± 0.2) °, (29.7 The XRD spectra of the peaks were exhibited at 2 θ values of ±0.2)°, (32.2±0.2)°, (34.0±0.2)°, and (37.9±0.2)°. The tin-containing zeolitic material according to any one of claims 23 to 26, which is obtained or obtained by the method of any one of claims 1 to 19. The tin-containing zeolitic material according to any one of claims 23 to 27, which is contained in a molded article, which preferably further comprises a binder, preferably a cerium oxide binder. A use of a tin-containing zeolitic material having a BEA framework structure (Sn-BEA) according to any one of claims 23 to 28, which is used as a catalytically active material, preferably as a catalytic activity in an oxidation reaction The material is more preferably used for the oxidation of the Bayeyer Villiger of cyclic ketones. A molded article comprising the tin-containing zeolitic material having a BEA framework structure according to any one of claims 23 to 27, and preferably comprising a binder, more preferably a cerium oxide binder, The case is used as a catalyst, preferably used in an oxidation reaction, and more preferably used in Bayerville oxidation of a cyclic ketone.