Molded body containing Ti-MWW zeolite and having a specific Lewis acidity

Abstract

The present invention relates to a shaped body comprising a zeolitic material having an MWW-type framework, the framework structure comprising Ti, Si, and O, the zeolitic material further comprising Zn and an alkaline earth metal M, the shaped body further comprising a binder, and the shaped body exhibiting a specific Lewis acidity. The present invention also relates to a method for producing the shaped body and a method for using the same.

Description

[Technical Field]

[0001] The present invention relates to a shaped body comprising a zeolite material having an MWW-type framework, wherein the framework structure comprises Ti, Si, and O, the zeolite material further comprises Zn and an alkaline earth metal M, the shaped body further comprises a binder, and the shaped body exhibits a specific Lewis acidity. [Background technology]

[0002] Titanium-containing zeolites are typically used as catalysts in the intentional production of propylene oxide by epoxidation of propylene oxide. Because hydrogen peroxide is typically used as the oxidizing agent, this industrial process is referred to as the hydrogen peroxide to propylene oxide process (also abbreviated herein as HPPO). In particular, two specific HPPO processes are known, one based on TS-1 zeolite and the other on a Zn / Ti-MWW zeolite catalyst. The latter has been found to exhibit significantly improved performance over first-generation catalysts. Recent activity has focused on increasing the catalyst's performance through the addition of a second metal, e.g., Ba and / or La.

[0003] CN105854933A discloses TS-1 zeolite modified by impregnation with barium and, optionally, additional zinc and / or lanthanum. The resulting zeolite exhibited catalytic activity in the conversion of propylene to propylene oxide, using hydrogen peroxide as the oxidant and methanol as the solvent.

[0004] CN106115732A also discloses TS-1 zeolite modified with barium, zinc, and optionally additional lanthanum. The produced zeolite has been shown to have catalytic activity in liquid-phase propylene epoxidation using acetonitrile as a solvent.

[0005] Y. Yu et al. have published studies on the efficiency of hydrogen peroxide utilization over titanosilicate / H2O2 systems. Two different TS-1 zeolites, lamellar Ti-MWW, B-MWW, F-Ti-MWW zeolites, Re-Ti-MWW, and amorphous silica-alumina were prepared as catalysts for these studies and tested in the epoxidation of alkenes, particularly 1-hexene.

[0006] The object of the present invention is to provide novel shaped bodies comprising a zeolitic material having an MWW-type framework, whereby the zeolitic material is modified to contain, in particular, Zn and alkaline earth metals, and the shaped bodies have advantageous characteristics. In particular, it was an object to provide novel shaped bodies having improved propylene oxide selectivity when used as catalysts or catalyst components, especially in the epoxidation reaction of propene to propylene oxide. A further object of the present invention was to provide a process for the production of such shaped bodies, particularly a process which preferably results in shaped bodies having advantageous properties when used as catalysts or catalyst components, particularly in oxidation or epoxidation reactions. A further object of the present invention was to provide an improved process for the epoxidation of propene using hydrogen peroxide as an oxidizing agent, which shows very low selectivity with respect to by-products and by-products of the epoxidation reaction, while at the same time allowing very high propylene selectivity.

[0007] It has surprisingly been found that when a given shaped body comprising a zeolitic material having the framework structure MWW is subjected to a specific subsequent water treatment, which results in the shaped body exhibiting, among other things, a specific Lewis acidity as determined via FTIR using pyridine as a probe gas as described herein, such a shaped body can be provided that exhibits the above-mentioned advantageous characteristics.

[0008] It has been surprisingly observed that when the precursor shaped bodies are treated with water, the resulting novel shaped bodies, comprising a zeolitic material having the framework structure MWW, exhibit improved performance when used as a catalyst in the epoxidation of propene to propylene oxide, due to increased selectivity for propylene oxide. Furthermore, an increase in the lifespan of the novel shaped bodies has also been observed. In particular, it has been surprisingly found that shaped bodies can be provided that, when used as a catalyst in the epoxidation of propene to propylene oxide, exhibit significantly increased propylene oxide selectivity and yield, and further exhibit excellent lifespan characteristics, when compared to shaped bodies of the prior art. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] CN 105854933 A [Patent Document 2] CN 106115732 A [Non-patent literature]

[0010] [Non-Patent Document 1] Y. Yu et al., "Insights into the efficiency of hydrogen peroxide utilization over titanosilicate / H2O2 systems," Journal of Catalysis 2020, Vol. 381, pp. 96-107 Summary of the Invention [Problem to be solved by the invention]

[0011] In the present invention, a compact is understood as a three-dimensional entity resulting from a molding process, and therefore the term "compact" is used as a synonym for the term "molded object". [Means for solving the problem]

[0012] Accordingly, the present invention provides a shaped body, preferably a shaped body obtainable or obtained by the method of any one of the embodiments disclosed herein, comprising a zeolitic material having an MWW-type framework and having a framework structure comprising Ti, Si and O, wherein the zeolitic material further comprises Zn and an alkaline earth metal M, and the shaped body further comprises a binder, and wherein the shaped body has a viscosity of 1490 cm -1 The molded article has an integrated extinction unit of 8 or less in the IR band at 1490 cm -1 The integrated extinction units of the IR band at 1000 nm is preferably determined as described in Reference Example 1 disclosed herein.

[0013] The present invention further provides a method for producing a shaped body, preferably a shaped body according to any one of the embodiments disclosed herein, comprising a zeolitic material having an MWW-type framework and a binder material, the method comprising: (i) providing a shaped body comprising a zeolitic material having an MWW-type framework and a framework structure comprising Ti, Si and O, wherein the zeolitic material further comprises Zn, an alkaline earth metal M, and optionally a rare earth metal, and the shaped body further comprises a binder for said zeolitic material; (ii) preparing a mixture containing the molded body according to (i) and water, subjecting the mixture to a water treatment under hydrothermal conditions to obtain a water-treated molded body, and calcining the water-treated molded body in a gas atmosphere. The present invention relates to a method comprising:

[0014] Still further, the present invention relates to a shaped body comprising a zeolitic material with an MWW-type framework and a binder material obtainable or obtained by a method according to any one of the embodiments disclosed herein.

[0015] Still further, the present invention relates to a method of using the shaped article according to any one of the embodiments disclosed herein as an adsorbent, absorbent, catalyst or catalyst component, preferably as a catalyst or catalyst component, more preferably as a Lewis acid catalyst or Lewis acid catalyst component, an isomerization catalyst or isomerization catalyst component, an oxidation catalyst or oxidation catalyst component, an aldol condensation catalyst or aldol condensation catalyst component, or a Prins reaction catalyst or Prins reaction catalyst component, more preferably as an oxidation catalyst or oxidation catalyst component, more preferably as an epoxidation catalyst or epoxidation catalyst component, more preferably as an epoxidation catalyst.

[0016] Still further, the present invention relates to a method for oxidizing an organic compound, comprising contacting the organic compound with a catalyst comprising the shaped body according to any one of the embodiments disclosed herein to preferably epoxidize the organic compound, more preferably an organic compound having at least one C-C double bond, preferably a C2-C10 alkene, more preferably a C2-C5 alkene, more preferably a C2-C4 alkene, more preferably a C2 or C3 alkene, more preferably propene.

[0017] Still further, the present invention relates to a method for producing propylene oxide, comprising reacting propene with hydrogen peroxide in an acetonitrile solution in the presence of a catalyst comprising the shaped body according to any one of the embodiments disclosed herein to obtain propylene oxide.

[0018] Regarding the molded article of the present invention, 1490 cm -1 The integrated extinction unit of the IR band of the molded article at 1490 cm is preferably in the range of 0.05 to 8.0, more preferably in the range of 0.1 to 7.5, more preferably in the range of 0.5 to 7.0, more preferably in the range of 1.0 to 6.9, and more preferably in the range of 1.5 to 6.9. -1 The integrated extinction units in the IR band at 1000 nm are preferably determined as described in Reference Example 1 disclosed herein.

[0019] The molded article has an integrated extinction unit of the Lewis acid IR band in the range of preferably 1 to 100, more preferably 5 to 90, more preferably 8 to 88, and even more preferably 9.0 to 79.0. The integrated extinction unit of the Lewis acid IR band is preferably determined as described in Reference Example 1 disclosed herein.

[0020] The molded article preferably has an integrated extinction unit of Bronsted acid IR band of not more than 1, preferably not more than 0.5, more preferably not more than 0.2, more preferably not more than 0.1, more preferably not more than 0.05. The integrated extinction unit of Bronsted acid IR band is preferably determined as described in Reference Example 1.

[0021] The molded article preferably has a torsion parameter with respect to water in the range of 1.0 to 5.0, preferably in the range of 1.5 to 3.0, more preferably in the range of 1.7 to 2.5, more preferably in the range of 1.9 to 2.1 The torsion parameter is preferably determined as described in Reference Example 12 disclosed herein.

[0022] According to the present invention, Bronsted acidity and Lewis acidity were determined using IR-spectroscopy, in particular by utilizing an FTIR cell, in which pyridine was used as a probe gas. Preferably, the sample was compressed into a pellet. The measurement conditions preferably included heating the sample to about 350°C for about 1 hour in air, so that water and any volatile substances could be removed from the sample. Furthermore, the measurement conditions preferably included applying low pressure (about 10 -5 The cell was then cooled to approximately 80°C (0.01, 0.1, 1, and 3 mbar "high vacuum"). During the application of the low pressure, the sample was preferably cooled to approximately 80°C. The measurements were preferably carried out at approximately 80°C for the entire duration of the measurements. This prevented condensation of pyridine in the cell. Pyridine was then preferably introduced into the cell in successive steps (0.01, 0.1, 1, and 3 mbar). This ensured controlled and complete exposure of the sample.

[0023] The molded body contains Si in an amount, calculated as an element, of preferably 20 to 60 mass %, more preferably 30 to 55 mass %, more preferably 35 to 50 mass %, and more preferably 41 to 44 mass %, relative to the total mass of the molded body.

[0024] The compact contains Ti in an amount, calculated as an element, preferably in the range of 0.1 to 5 mass %, more preferably in the range of 0.5 to 2.0 mass %, and more preferably in the range of 1.0 to 1.5 mass %, relative to the total mass of the compact.

[0025] The molded body contains Zn in an amount, calculated as the element, preferably in the range of 0.1 to 5 mass %, more preferably in the range of 0.25 to 2.0 mass %, and more preferably in the range of 0.5 to 1.0 mass %, relative to the total mass of the molded body.

[0026] The alkaline earth metal M is preferably one or more of Mg, Ca, Sr and Ba, more preferably one or more of Mg, Ca and Ba, and particularly preferably Ba.

[0027] The molded body contains the alkaline earth metal M, calculated as the element, in an amount preferably in the range of 0.1 to 5 mass %, more preferably in the range of 0.5 to 2.0 mass %, and more preferably in the range of 1.0 to 1.5 mass %, relative to the total mass of the molded body.

[0028] The molded body is preferably composed of Si, O, Ti, Zn, M, and optionally H, at 98 to 100 mass %, preferably 99 to 100 mass %, and more preferably 99.5 to 100 mass %.

[0029] The zeolitic material preferably further comprises a rare earth metal, more preferably one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, more preferably one or more of Y, La, Ce, Pr, and Nd, more preferably one or more of Y, La, and Ce, more preferably La.

[0030] When the molded body further contains a rare earth metal, the molded body contains the rare earth metal in an amount, calculated as the element, preferably in the range of 0.1 to 5 mass %, more preferably in the range of 0.25 to 2.5 mass %, and more preferably in the range of 0.5 to 1.0 mass %, relative to the total mass of the molded body.

[0031] When the molded body further contains a rare earth metal, preferably 98 to 100 mass%, more preferably 99 to 100 mass%, and more preferably 99.5 to 100 mass% of the molded body is composed of Si, O, Ti, Zn, M, the rare earth metal, and optionally H.

[0032] The binder preferably contains Si and O.

[0033] The binder contained in the molded body is preferably composed of Si and O in an amount of 95 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably at least 99.5 to 100 mass%, and more preferably 99.9 to 100 mass%.

[0034] The molded body contains the binder in an amount preferably in the range of 1 to 75 mass %, more preferably in the range of 5 to 50 mass %, more preferably in the range of 10 to 40 mass %, more preferably in the range of 15 to 25 mass %, relative to the total mass of the molded body.

[0035] Preferably, 95 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably at least 99.5 to 100 mass%, more preferably 99.9 to 100 mass% of the molded body is composed of the zeolite material having an MWW-type framework and the binder.

[0036] The molded body preferably has a total pore volume in the range of 0.5 to 3.0 mL / g, more preferably 0.75 to 2.5 mL / g, more preferably 1.0 to 2.0 mL / g, and more preferably 1.25 to 1.75 mL / g. The pore volume is preferably determined according to DIN66133.

[0037] The molded body preferably exhibits a water uptake in the range of 1 to 20% by weight, more preferably in the range of 6 to 15% by weight, more preferably in the range of 8 to 12% by weight. The water uptake is preferably determined as described in Reference Example 7.

[0038] The compact contains acidic sites at a concentration of preferably 0.05 to 1.00 mmol / g, more preferably 0.10 to 0.50 mmol / g, and even more preferably 0.15 to 0.30 mmol / g at temperatures below 200° C. The concentration of acidic sites is preferably determined by temperature-programmed desorption of ammonia (NH3-TPD) according to Reference Example 5 disclosed herein.

[0039] The compact contains acidic sites at a concentration of preferably 0.05 mmol / g or less, more preferably 0.02 mmol / g or less, at a temperature in the range of 200 to 400° C. The concentration of acidic sites is preferably determined by temperature-programmed desorption of ammonia (NH3-TPD) according to Reference Example 5 disclosed in this specification.

[0040] The compact contains acidic sites at a concentration preferably in the range of 0.001 to 0.5 mmol / g, more preferably in the range of 0.01 to 0.10 mmol / g, at temperatures above 500° C. The concentration of acidic sites is preferably determined by temperature-programmed desorption of ammonia (NH3-TPD) according to Reference Example 5 disclosed herein.

[0041] The shaped bodies are preferably strands, preferably having a hexagonal, rectangular, quadratic, triangular, oval or circular cross section, more preferably a circular cross section.

[0042] The formed body is a strand having a circular cross section with a diameter preferably in the range of 0.5 to 5 mm, more preferably in the range of 1 to 3 mm, and more preferably in the range of 1.5 to 2 mm.

[0043] Preferably, the shaped body is an extrudate.

[0044] The shaped article is preferably an extrudate, more preferably a strand as disclosed herein, and preferably exhibits a crush strength in the range of 5 to 50 N, more preferably in the range of 10 to 30 N, more preferably in the range of 15 to 25 N. The crush strength is preferably determined as described in Reference Example 6 disclosed herein.

[0045] The molded body preferably exhibits a propylene oxide activity of at least 6.2% by weight, more preferably in the range of 7.5 to 15% by weight, more preferably in the range of 10 to 13% by weight. The propylene oxide activity is preferably determined as described in Reference Example 8 disclosed herein.

[0046] The molded body preferably exhibits a propylene oxide selectivity in the range of 96 to 100%, more preferably in the range of 97 to 100%, and more preferably in the range of 98 to 100%. The propylene oxide activity is preferably determined as described in Reference Example 9 disclosed herein.

[0047] The molded body is preferably 100 mm 2 / g or more, more preferably 200m 2 / g or more, more preferably 250m 2 / g or more, preferably 280m 2 The BET specific surface area is preferably determined in accordance with DIN 66131.

[0048] The molded body is preferably used as a catalyst or catalyst component in a reaction for producing propylene oxide from propene and hydrogen peroxide, more preferably in a reaction for continuously producing propylene oxide from propene and hydrogen peroxide, more preferably in a continuous epoxidation reaction, more preferably in the continuous epoxidation reaction described in Reference Example 9 disclosed herein.

[0049] The present invention further provides a method for producing a shaped body comprising a zeolitic material having an MWW-type framework and a binder material, preferably a shaped body according to any one of the embodiments disclosed herein, comprising: (i) providing a shaped body comprising a zeolitic material having an MWW-type framework and a framework structure comprising Ti, Si, and O, wherein the zeolitic material further comprises Zn, an alkaline earth metal M, and optionally a rare earth metal, and the shaped body further comprises a binder for the zeolitic material; (ii) preparing a mixture containing the molded body according to (i) and water, subjecting the mixture to a water treatment under hydrothermal conditions to obtain a water-treated molded body, and calcining the water-treated molded body in a gas atmosphere. The present invention relates to a method comprising:

[0050] In this method, (i) (i.1) providing a zeolitic material having an MWW-type framework and a framework structure comprising Ti, Si, and O; (i.2) providing an aqueous solution of a Zn source; (i.3) providing an aqueous solution of a source of an alkaline earth metal M; (i.4) optionally providing an aqueous solution of a rare earth metal source; (i.5) impregnating the zeolitic material provided by (i.1) with the aqueous solution provided by (i.2), the aqueous solution provided by (i.3), and optionally the aqueous solution provided by (i.4) to obtain an impregnated zeolitic material; (i.6) preparing a mixture comprising the impregnated zeolitic material obtained from (i.5) and a binder precursor, (i.7) A step of molding the mixture obtained from (i.6) It is preferred that the compound contains:

[0051] If the method includes (i.5) as defined herein, then (i.5) is (i.5.a) providing a mixture comprising the aqueous solution provided by (i.2), the aqueous solution provided by (i.3), and optionally the aqueous solution provided by (i.4); (i.5.b) Impregnating the zeolite material prepared in (i.1) with the mixture prepared in (i.5.a). It is preferred that the composition further comprises:

[0052] Alternatively, if the method includes (i.5) as defined herein, (i.5) may be (i.5.1) impregnating the zeolite material prepared in (i.1) with the aqueous solution prepared in (i.2); (i.5.2) Impregnating the zeolite material obtained from (i.5.1) with the aqueous solution prepared in (i.3) to obtain an impregnated zeolite material. It is preferred that the compound contains:

[0053] Alternatively, if the method includes (i.5) as defined herein, (i.5) may be (i.5.1') impregnating the zeolite material prepared in (i.1) with the aqueous solution prepared in (i.3); (i.5.2') Impregnating the zeolite material obtained from (i.5.1') with the aqueous solution prepared in (i.2) to obtain an impregnated zeolite material. It is preferred that the compound contains:

[0054] If the method comprises (i.5.1) or (i.5.1') as defined herein, the method further comprises: (i.5.3) optionally impregnating the zeolitic material with the aqueous solution provided by (i.4) before (i.5.1) or before (i.5.1'); (i.5.4) optionally impregnating the zeolitic material with the aqueous solution provided by (i.4) after (i.5.1) and before (i.5.2), or after (i.5.1') and before (i.5.2'); (i.5.5) After (i.5.2) or after (i.5.2'), optionally impregnating the zeolite material with the aqueous solution prepared by (i.4). It is preferred that the composition further comprises:

[0055] Alternatively, if the method includes (i.5) as defined herein, (i.5) may be (i.zn.1) impregnating the zeolitic material provided by (i.1) with the aqueous solution provided by (i.2) and, optionally, with the aqueous solution provided by (i.4) to obtain an impregnated zeolitic material; (i.zn.2) preparing a mixture comprising the impregnated zeolitic material obtained from (i.zn.1) and a binder precursor, (i.zn.3) A step of molding the mixture obtained from (i.zn.2) to obtain a first molded body; (i.zn.4) A step of impregnating the first molded body obtained from (i.zn.3) with the aqueous solution prepared in (i.3) and optionally with the aqueous solution prepared in (i.4) to obtain a precursor molded body; It is preferred that the compound contains:

[0056] Preferably, at least one of (i.5), (i.5.b), (i.5.1), (i.5.2), (i.5.1'), (i.5.2'), (i.5.3), (i.5.4), (i.5.5), (i.zn.1), and (i.zn.4) is performed n times, where n is a natural number greater than 1, and n is preferably equal to 2, 3, 4, or 5.

[0057] Preferably, the method includes heat treatment in a gas atmosphere after one or more of (i.5), (i.5.b), (i.5.1), (i.5.2), (i.5.1'), (i.5.2'), (i.5.3), (i.5.4), (i.5.5), (i.zn.1), and (i.zn.4).

[0058] If the method further comprises a heat treatment after one or more of (i.5), (i.5.b), (i.5.1), (i.5.2), (i.5.1'), (i.5.2'), (i.5.3), (i.5.4), (i.5.5), (i.zn.1), and (i.zn.4), the heat treatment comprises: (i.5.6) optionally drying at a temperature of a gas atmosphere preferably in the range of 50 to 200°C, and / or preferably and (i.5.7) Optionally calcining at a temperature in a gas atmosphere preferably in the range of 400 to 700°C It is preferred that the compound contains:

[0059] Furthermore, when the method further comprises one or more of (i.5), (i.5.b), (i.5.1), (i.5.2), (i.5.1'), (i.5.2'), (i.5.3), (i.5.4), (i.5.5), (i.zn.1), and (i.zn.4) after the heat treatment, it is preferred that the gas atmosphere comprises one or more of nitrogen, oxygen, or mixtures thereof, and more preferably the gas atmosphere is oxygen, air, or lean air.

[0060] The compact prepared in (i) contains Si in an amount, calculated as an element, of preferably 20 to 60 mass %, more preferably 30 to 55 mass %, more preferably 35 to 50 mass %, more preferably 40 to 45 mass %, and more preferably 41 to 44 mass %, relative to the total mass of the compact.

[0061] The compact prepared in (i) contains Ti, calculated as an element, in an amount of preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, more preferably 0.5 to 2 mass %, more preferably 1.0 to 1.5 mass %, and more preferably 1.1 to 1.4 mass %, relative to the total mass of the compact.

[0062] The molded body prepared in (i) contains Zn, calculated as an element, in an amount of preferably 0.01 to 5 mass %, more preferably 0.1 to 2.5 mass %, more preferably 0.25 to 1.1 mass %, and more preferably 0.5 to 0.9 mass %, relative to the total mass of the molded body.

[0063] The alkaline earth metal M contained in the molded body prepared in (i) is preferably one or more of Mg, Ca, Sr and Ba, more preferably one or more of Mg, Ca and Ba, and more preferably the alkaline earth metal M is Ba.

[0064] The compact prepared in (i) contains the alkaline earth metal M, calculated as the element, in an amount of preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, more preferably 0.5 to 2 mass %, more preferably 1.0 to 1.5 mass %, more preferably 1.1 to 1.4 mass %, relative to the total mass of the compact.

[0065] The compact provided in (i) preferably further comprises a rare earth metal, preferably one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, more preferably one or more of Y, La, Ce, Pr, and Nd, more preferably one or more of Y, La, and Ce, more preferably La.

[0066] The molded body prepared in (i) preferably further contains a rare earth metal, calculated as the element, in an amount of preferably 0.01 to 5 mass %, more preferably 0.1 to 2 mass %, more preferably 0.25 to 1.25 mass %, and more preferably 0.5 to 1.0 mass %, relative to the total mass of the molded body.

[0067] The molded body prepared in (i) contains the binder in an amount of preferably 1 to 50 mass %, more preferably 5 to 30 mass %, more preferably 15 to 25 mass %, more preferably 18 to 23 mass %, more preferably 19 to 22 mass %, relative to the total mass of the molded body.

[0068] The compact prepared in (i) preferably has a bulk density in the range of 200 to 500 g / mL, more preferably in the range of 300 to 400 g / mL, and more preferably in the range of 325 to 375 g / mL.

[0069] The shaped bodies prepared in (i) are strands having a circular cross section with a diameter preferably in the range of 0.5 to 5 mm, more preferably in the range of 1 to 3 mm, more preferably in the range of 1.5 to 2 mm, and the shaped bodies preferably exhibit a crushing strength, when determined as described in Reference Example 6, of at least 1.5 N, preferably in the range of 5 to 30 N, more preferably in the range of 15 to 25 N.

[0070] The compact prepared in (i) preferably has a pore volume of at least 1.0 g / mL, more preferably in the range of 1.3 to 2.0 g / mL. The pore volume is preferably determined as described in Reference Example 2 disclosed herein.

[0071] The compact prepared in (i) was 1490 cm -1 The integrated extinction units of the IR band at 1490 cm is preferably in the range of 5 to 15, more preferably in the range of 7.5 to 13.0, more preferably in the range of 10.0 to 12.0, and more preferably in the range of 11.0 to 11.6. -1The integrated extinction unit of the IR band in is preferably determined as described in Reference Example 1.

[0072] The molded article prepared in (i) preferably has an integrated extinction unit of the Lewis acid IR band in the range of 1 to 100, more preferably in the range of 50 to 200, more preferably in the range of 75 to 150, more preferably in the range of 101 to 125, and more preferably in the range of 105 to 120. The integrated extinction unit of the Lewis acid IR band is preferably determined as described in Reference Example 1.

[0073] The molded article prepared in (i) preferably has an integrated extinction unit of the Brønsted acid IR band of 1 or less, more preferably 0.5 or less, more preferably 0.2 or less, more preferably 0.1 or less, more preferably 0.05 or less. The Brønsted acid IR band is preferably determined as described in Reference Example 1.

[0074] The compact prepared in (i) contains acidic sites at a concentration of preferably 0.05 to 1.00 mmol / g, more preferably 0.10 to 0.50 mmol / g, and even more preferably 0.15 to 0.25 mmol / g at a temperature lower than 200° C. The concentration of acidic sites is preferably determined by temperature-programmed desorption of ammonia (NH3-TPD) according to Reference Example 5.

[0075] The compact prepared in (i) contains acidic sites at a concentration of preferably 0.05 mmol / g or less, more preferably 0.02 mmol / g or less, at a temperature in the range of 200 to 400° C. The concentration of acidic sites is preferably determined by temperature-programmed desorption of ammonia (NH3-TPD) according to Reference Example 5.

[0076] The compact prepared in (i) contains acidic sites at a concentration of preferably 0.005 to 0.1 mmol / g, more preferably 0.01 to 0.05 mmol / g, and even more preferably 0.02 to 0.03 mmol / g at a temperature higher than 500° C. The concentration of acidic sites is preferably determined by temperature-programmed desorption of ammonia (NH3-TPD) according to Reference Example 5.

[0077] If the method further comprises (i.1), the zeolitic material provided by (i.1) preferably comprises Si in an amount, calculated as the element, relative to the total mass of the zeolitic material, in the range of 20 to 60% by mass, more preferably in the range of 30 to 55% by mass, more preferably in the range of 35 to 50% by mass, more preferably in the range of 40 to 45% by mass, more preferably in the range of 41 to 44% by mass.

[0078] If the method further comprises (i.1), the zeolitic material provided by (i.1) preferably comprises Ti in an amount, calculated as the element, in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, more preferably in the range of 1 to 2% by mass, more preferably in the range of 1.2 to 1.8% by mass, based on the total mass of the zeolitic material.

[0079] If the method further comprises (i.1), the zeolitic material provided by (i.1) preferably comprises Zn in an amount, calculated as the element, in the range of 0.1 to 2.5% by mass, more preferably in the range of 0.5 to 1.3% by mass, more preferably in the range of 0.7 to 1.1% by mass, based on the total mass of the shaped body.

[0080] If the method further comprises (i.1), the alkaline earth metal M comprised in the zeolitic material provided by (i.1) is preferably one or more of Mg, Ca, Sr and Ba, more preferably one or more of Mg, Ca and Ba, more preferably the alkaline earth metal M is Ba.

[0081] If the method further comprises (i.1), the zeolitic material provided by (i.1) preferably comprises an alkaline earth metal M in an amount, calculated as the element, relative to the total mass of the shaped body, in the range of 0.1 to 7.5 mass%, more preferably in the range of 0.25 to 5 mass%, more preferably in the range of 0.5 to 2.5 mass%, more preferably in the range of 1.2 to 2.0 mass%.

[0082] If the method further comprises (i.1), then the zeolitic material provided by (i.1) preferably further comprises a rare earth metal, more preferably one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, more preferably one or more of Y, La, Ce, Pr and Nd, more preferably one or more of Y, La and Ce, more preferably La.

[0083] If the method further comprises (i.1), the zeolitic material provided by (i.1) preferably further comprises a rare earth metal, more preferably in an amount in the range of 0.1 to 5% by mass, preferably in the range of 0.25 to 2% by mass, more preferably in the range of 0.5 to 1.5% by mass, more preferably in the range of 0.8 to 1.2% by mass, calculated as the element, relative to the total mass of the shaped body.

[0084] If the method further comprises (i.1), the zeolitic material provided by (i.1) preferably has a crystallite size in the range of 15 to 40 nm. The crystallite size is preferably determined as described in Reference Example 4 disclosed herein.

[0085] If the method further comprises (i.1), the zeolitic material provided by (i.1) preferably has a BET specific surface area of ​​250 m 2 / g or more, preferably 275m 2 / g or more, more preferably 300m 2 The BET specific surface area is preferably determined in accordance with DIN 66131.

[0086] If the method further comprises (i.1), the zeolitic material provided by (i.1) preferably has a C value in the range of −150 to −40, more preferably in the range of −125 to −50, more preferably in the range of −100 to −60. The C value is preferably determined as described in Reference Example 10 disclosed herein.

[0087] If the method further comprises (i.1), the zeolitic material provided by (i.1) preferably has a crystallinity of at least 50%, more preferably at least 75%, more preferably at least 80%, preferably determined as described in Example 4 disclosed herein.

[0088] If the method further comprises (i.1), the zeolitic material provided by (i.1) preferably has a water uptake in the range of 8 to 20 wt. %, more preferably in the range of 9 to 17.5 wt. %, more preferably in the range of 10 to 15 wt. The water uptake is preferably determined as described in Reference Example 7 disclosed herein.

[0089] If the method further comprises (i.1), the zeolitic material provided by (i.1) preferably exhibits a propylene oxide activity in the range of at least 10 wt.%, more preferably in the range of 10-15 wt.%, more preferably in the range of 11-14 wt.%, preferably determined as described in Reference Example 8 disclosed herein.

[0090] If the method further comprises (i.1), the zeolite material prepared by (i.1) has a viscosity of (3700-3750) + / - 20 cm -1 and a band with a maximum in the region of (3670~3690) + / - 20 cm -1 Preferably, the infrared spectrum includes a band having a maximum in the region of (3700-3750) + / - 20 cm -1 Band area: (3670~3690) + / - 20cm -1 The intensity ratio for the band in the region of is at most 1.7, preferably at most 1.6. The infrared spectrum is preferably determined as described in Reference Example 11 disclosed herein.

[0091] Additionally, when the method further comprises (i.1), the Zn source is preferably a salt, more preferably one or more of nitrate, halide, hydroxide, acetate, more preferably nitrate.

[0092] When the method further comprises (i.1), the alkaline earth metal in the alkaline earth metal source is preferably one or more of Mg, Ca, Sr and Ba, more preferably one or more of Mg, Ca and Ba. It is particularly preferred that the alkaline earth metal M is Ba.

[0093] If the method further comprises (i.1), then the alkaline earth metal source is preferably a salt, more preferably one or more of a nitrate, a halide, an acetate, a hydroxide, more preferably a nitrate.

[0094] If the method further comprises (i.2), the mixture according to (i.2) comprises a rare earth metal source, and the rare earth metal is preferably one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, more preferably one or more of Y, La, Ce, Pr, and Nd, more preferably one or more of Y, La, and Ce, more preferably La.

[0095] When the mixture according to (i.2) comprises a rare earth metal source, and the rare earth metal is one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, it is preferred that the rare earth metal source is a salt, more preferably one or more of a nitrate, a halide, and a hydroxide, more preferably a nitrate.

[0096] If the method further comprises (i.5), it is preferred that the impregnation according to (i.5) comprises one or more of spray impregnation, adhesive impregnation, incipient impregnation, wet impregnation adhesive techniques, and agitation, more preferably mechanical agitation, more preferably stirring, more preferably for a period in the range of 0.1 to 5 hours, more preferably in the range of 0.5 to 2 hours.

[0097] If the method further comprises (i.5), the impregnation with (i.5) preferably comprises keeping the mixture at the same temperature, more preferably at a temperature in the range of 15 to 40°C, for a period in the range of 1 to 50 hours, more preferably in the range of 30 to 40 hours.

[0098] If the method further comprises (i.5) and (i.6), then after (i.5) and before (i.6), the method comprises: (a) optionally isolating the impregnated zeolitic material obtained in (i.5), preferably by filtration, and / or preferably by and (b) optionally washing the impregnated zeolitic material obtained in (i.5) or (a), preferably with deionized water, and / or preferably with and (c) optionally drying the impregnated zeolitic material obtained in (i.5), (a) or (b) in a gas atmosphere, and / or preferably (d) optionally, calcining the impregnated zeolitic material obtained in (i.5), (a), (b) or (c) in a gas atmosphere. It is preferred that the compound contains:

[0099] If the method further comprises (c), the drying is carried out according to (c) at a gas atmosphere temperature preferably in the range of 70 to 150°C, more preferably in the range of 90 to 130°C, more preferably in the range of 100 to 120°C.

[0100] If the method further comprises (c), the gas atmosphere for drying in (c) preferably comprises nitrogen, oxygen, or a mixture thereof, and the gas atmosphere is more preferably oxygen, air, or lean air.

[0101] If the method further comprises (d), the calcination is carried out in accordance with (d) at a temperature in the gas atmosphere preferably in the range of 510 to 590°C, more preferably in the range of 530 to 570°C, more preferably in the range of 540 to 560°C.

[0102] If the method further comprises (d), the gas atmosphere for the calcination in (d) preferably comprises nitrogen, oxygen, or a mixture thereof, and the gas atmosphere is more preferably oxygen, air, or lean air.

[0103] If the method further comprises (i.6), the binder precursor in (i.6) is preferably selected from the group consisting of silica sol, colloidal silica, wet-process silica, dry-process silica, and mixtures of two or more thereof; the binder precursor is more preferably colloidal silica.

[0104] In this context, both colloidal silicas can be used, so-called "wet process" silicas and so-called "dry process" silicas. Colloidal silicas, preferably as alkaline and / or ammoniacal solutions, more preferably as ammoniacal solutions, are commercially available, for example Ludox®, Syton®, Nalco® or Snowtex®, among others. "Wet process" silicas are commercially available, for example Hi-Sil®, Ultrasil®, Vulcasil®, Santocel®, Valron-Estersil®, Tokusil® or Nipsil®, among others. "Dry process" silicas are commercially available, for example Aerosil®, Reolosil®, Cab-O-Sil®, Fransil® or ArcSilica®, among others. According to the present invention, ammoniacal solutions of colloidal silica are preferred.

[0105] If the method further comprises (i.6), the mass ratio of the zeolitic material obtained from (i.5) to the binder precursor in the mixture according to (i.6) is preferably in the range of 1:1 to 10:1, more preferably in the range of 3:1 to 5:1, more preferably in the range of 3.5:1 to 4.5:1.

[0106] If the method further comprises (i.5) and (i.6), preferably 95-100% by weight, more preferably 98-100% by weight, more preferably 99-100% by weight of the mixture produced according to (i.6) consists of the impregnated zeolitic material from (i.5) and the binder precursor.

[0107] If the method further comprises (i.6), it is preferred that the mixture produced according to (i.6) further comprises one or more viscosity adjusting and / or mesopore forming agents.

[0108] If the mixture prepared according to (i.6) further comprises one or more viscosity-adjusting and / or mesopore-forming agents, the one or more viscosity-adjusting and / or mesopore-forming agents are preferably selected from the group consisting of water, alcohols, organic polymers, and mixtures of two or more thereof, the organic polymers more preferably selected from the group consisting of cellulose, cellulose derivatives, starch, polyalkylene oxides, polystyrene, polyacrylates, polymethacrylates, polyolefins, polyamides, polyesters, and mixtures of two or more thereof, the organic polymers more preferably selected from the group consisting of cellulose derivatives, polyalkylene oxides, polystyrene, and mixtures of two or more thereof, the organic polymers more preferably selected from the group consisting of methylcellulose, carboxymethylcellulose, polyethylene oxide, polystyrene, and mixtures of two or more thereof, and more preferably the one or more viscosity-adjusting and / or mesopore-forming agents comprise water and methylcellulose.

[0109] Furthermore, if the mixture prepared according to (i.6) further comprises one or more viscosity modifying and / or mesopore forming agents, the mass ratio of zeolitic material to one or more viscosity modifying and / or mesopore forming agents in the mixture prepared according to (i.6) is preferably in the range of 10:1 to 20:1, more preferably in the range of 15:1 to 16:1, more preferably in the range of 15.5:1 to 15.7:1.

[0110] If the method further comprises (i.5) and (i.6), preferably 95-100% by weight, more preferably 98-100% by weight, more preferably 99-100% by weight of the mixture produced according to (i.6) consists of the impregnated zeolitic material from (i.5), the binder precursor, and one or more viscosity modifying and / or mesopore forming agents.

[0111] If the method further comprises (i.7), in (i.7) the mixture is preferably shaped into strands, more preferably strands having a circular cross section.

[0112] When the mixture is formed into strands having a circular cross section, the strands having a circular cross section preferably have a diameter in the range of 0.2 to 10 mm, more preferably in the range of 0.5 to 5 mm, more preferably in the range of 1 to 3 mm, more preferably in the range of 1.5 to 2 mm, more preferably in the range of 1.6 to 1.8 mm.

[0113] Regarding the shaping in (i.7), there is no particular limitation, and the shaping can be carried out by any conceivable means. When the method further comprises (i.7), it is preferred that in (i.7), the shaping comprises extruding the mixture.

[0114] Suitable extrusion equipment is described, for example, in "Ullmann's Enzyklopaedie der Technischen Chemie", 4th edition, Vol. 2, pp. 295 et seq., 1972. In addition to using an extruder, an extrusion press can also be used to produce shaped bodies. If necessary, the extruder can be appropriately cooled during the extrusion process. The strands leaving the extruder through the extruder die head can be mechanically cut by a suitable wire or via a discontinuous gas flow.

[0115] If the method further comprises (i.7), then after (i.7) and before (ii), the method comprises: (e) optionally drying the shaped body obtained from (i.7) in a gas atmosphere, and / or preferably (f) optionally, calcining the shaped body obtained from (i.7) or (e) in a gas atmosphere. It is preferred that the composition further comprises:

[0116] When the method further comprises (e), the drying in (e) is carried out at a gas atmosphere temperature preferably in the range of 80 to 160°C, more preferably in the range of 100 to 140°C, more preferably in the range of 110 to 130°C.

[0117] If the method further comprises (e), the gas atmosphere for drying in (e) preferably comprises nitrogen, oxygen, or a mixture thereof, and the gas atmosphere is preferably oxygen, air, or lean air.

[0118] If the method further comprises (f), the calcination according to (f) is preferably carried out at a temperature in the gas atmosphere in the range of 460-540°C, more preferably in the range of 480-520°C, more preferably in the range of 490-510°C.

[0119] If the method further comprises (f), the gas atmosphere for the calcination in (f) preferably comprises nitrogen, oxygen, or a mixture thereof, and the gas atmosphere is preferably oxygen, air, or lean air.

[0120] The mixture (ii) is preferably prepared in a kneader or a mix muller.

[0121] The mixture (ii) contains the molded body according to (i) and water in a mass ratio preferably in the range of 5:1 to 1:100, more preferably in the range of 1:1 to 1:50, more preferably in the range of 1:10 to 1:30, more preferably in the range of 1:15 to 1:25.

[0122] The water treatment according to (ii) preferably involves a temperature of the mixture in the range of 100 to 200°C, more preferably in the range of 125 to 175°C, more preferably in the range of 130 to 160°C, more preferably in the range of 135 to 155°C, more preferably in the range of 140 to 150°C.

[0123] The water treatment according to (ii) is preferably carried out under autogenous pressure, more preferably in an autoclave.

[0124] The water treatment in (ii) is carried out for preferably 6 to 10 hours, more preferably 7 to 9 hours.

[0125] After the water treatment in (ii) and before calcination, the water-treated shaped body is preferably separated from the mixture obtained from the water treatment, wherein the separation preferably includes filtering or centrifuging the mixture obtained from the water treatment, and more preferably, the separation further includes washing the water-treated shaped body at least once with a liquid solvent system, wherein the liquid solvent system preferably includes one or more of water, alcohol, and mixtures of two or more thereof, and the water-treated shaped body is more preferably washed with water.

[0126] Preferably, after subjecting the mixture to the water treatment and before calcining the water-treated shaped body, (ii) further comprises drying the shaped body in a gas atmosphere.

[0127] If the method further comprises drying, the drying is preferably carried out at a temperature of the gas atmosphere in the range of 80 to 160°C, more preferably in the range of 100 to 140°C, more preferably in the range of 110 to 130°C.

[0128] If the method further comprises drying, the gas atmosphere preferably comprises nitrogen, oxygen or a mixture thereof, and the gas atmosphere is preferably oxygen, air or lean air.

[0129] Calcination of the precursor body, preferably the dried precursor body according to any one of the embodiments disclosed herein, with (ii) is preferably carried out in a gas atmosphere.

[0130] When the calcination of the precursor molded body by (ii) is carried out in a gas atmosphere, the calcination is carried out at a temperature in the gas atmosphere preferably in the range of 410 to 490°C, more preferably in the range of 430 to 470°C, more preferably in the range of 440 to 460°C.

[0131] Furthermore, when the calcination of the precursor body with (ii) is carried out in a gas atmosphere, the gas atmosphere preferably contains nitrogen, oxygen, or a mixture thereof, and the gas atmosphere is more preferably oxygen, air, or lean air.

[0132] Still further, the present invention relates to a shaped body comprising a zeolitic material with an MWW-type framework and a binder material obtainable or obtained by a method according to any one of the embodiments disclosed herein.

[0133] Still further, the present invention relates to a method of using the shaped article according to any one of the embodiments disclosed herein as an adsorbent, absorbent, catalyst or catalyst component, preferably as a catalyst or catalyst component, more preferably as a Lewis acid catalyst or Lewis acid catalyst component, an isomerization catalyst or isomerization catalyst component, an oxidation catalyst or oxidation catalyst component, an aldol condensation catalyst or aldol condensation catalyst component, or a Prins reaction catalyst or Prins reaction catalyst component, more preferably as an oxidation catalyst or oxidation catalyst component, more preferably as an epoxidation catalyst or epoxidation catalyst component, more preferably as an epoxidation catalyst.

[0134] The shaped bodies are preferably used for the epoxidation reaction of an organic compound having at least one C-C double bond, preferably a C2-C10 alkene, more preferably a C2-C5 alkene, more preferably a C2-C4 alkene, more preferably a C2 or C3 alkene, more preferably propene, more preferably for the epoxidation of propene using hydrogen peroxide as oxidizing agent, more preferably for the epoxidation of propene in a solvent comprising acetonitrile using hydrogen peroxide as oxidizing agent.

[0135] Still further, the present invention relates to a method for oxidizing an organic compound, comprising the step of contacting the organic compound with a catalyst comprising the shaped body according to any one of the embodiments disclosed herein to preferably epoxidize the organic compound, more preferably an organic compound having at least one C-C double bond, preferably a C2-C10 alkene, more preferably a C2-C5 alkene, more preferably a C2-C4 alkene, more preferably a C2 or C3 alkene, more preferably propene.

[0136] Hydrogen peroxide is preferably used as the oxidizing agent, and the oxidation reaction is more preferably carried out in a solvent, more preferably a solvent comprising acetonitrile.

[0137] Still further, the present invention relates to a method for producing propylene oxide, preferably the method of any one of the embodiments disclosed herein, more preferably the method for oxidizing an organic compound of any one of the embodiments disclosed herein, comprising reacting propene with hydrogen peroxide in an acetonitrile solution in the presence of a catalyst comprising the shaped body of any one of the embodiments disclosed herein to obtain propylene oxide.

[0138] The unit bar (abs) is 10 5 Refers to absolute pressure in Pa.

[0139] The present invention further exemplifies the following set of embodiments and combinations of embodiments that can be obtained from the indicated substates and the following description. In particular, it should be noted that in each case, within the scope of the described embodiments, for example, in the context of the term "molded body according to any one of embodiments 1 to 4," all embodiments within this scope are intended to be explicitly disclosed to those skilled in the art, i.e., this expression is understood by those skilled in the art to be synonymous with "molded body according to any one of embodiments 1, 2, 3, and 4." Furthermore, it should be noted that the following set of embodiments expressly represents a properly structured portion of the specification that is directed to the general and preferred aspects of the present invention, rather than a set of claims that determines the scope of protection.

[0140] 1. Preferably, the zeolite material has an MWW-type framework and a framework structure containing Ti, Si, and O, wherein the zeolite material further contains Zn and an alkaline earth metal M, and the molded body further contains a binder, and the molded body has a viscosity of 1490 cm when determined as described in Reference Example 1. -1 101. A molded body obtainable or obtained by the method according to any one of embodiments 31 to 100, having an integrated extinction unit in the IR band in the range of 100 to 8.

[0141] 2. The molded product has a viscosity of 1490 cm when determined as described in Reference Example 1. -1The molded article according to embodiment 1, wherein the integrated extinction unit of the IR band in the range of 0.05 to 8.0, preferably 0.1 to 7.5, more preferably 0.5 to 7.0, more preferably 1.0 to 6.9, more preferably 1.5 to 6.9.

[0142] 3. The molded article according to embodiment 1 or 2, wherein the molded article has an integrated extinction unit of the Lewis acid IR band in the range of 1 to 100, more preferably in the range of 5 to 90, more preferably in the range of 8 to 88, more preferably in the range of 9.0 to 79.0, when determined as described in Reference Example 1.

[0143] 4. The molded article according to any one of embodiments 1 to 3, wherein the molded article has an integrated extinction unit of the Bronsted acid IR band of 1 or less, preferably 0.5 or less, more preferably 0.2 or less, more preferably 0.1 or less, more preferably 0.05 or less, when determined as described in Reference Example 1.

[0144] 5. The molded article according to any one of embodiments 1 to 4, wherein the molded article has a torsion parameter for water in the range of 1.0 to 5.0, preferably in the range of 1.5 to 3.0, more preferably in the range of 1.7 to 2.5, preferably when determined as described in Reference Example 12.

[0145] 6. A molded body according to any one of embodiments 1 to 5, containing Si in an amount, calculated as an element, in the range of 20 to 60 mass%, preferably in the range of 30 to 55 mass%, more preferably in the range of 35 to 50 mass%, and more preferably in the range of 41 to 44 mass%, relative to the total mass of the molded body.

[0146] 7. A molded body according to any one of embodiments 1 to 6, containing Ti in an amount, calculated as the element, in the range of 0.1 to 5 mass%, preferably in the range of 0.5 to 2.0 mass%, and more preferably in the range of 1.0 to 1.5 mass%, relative to the total mass of the molded body.

[0147] 8. A molded body according to any one of embodiments 1 to 7, containing Zn in an amount, calculated as the element, in the range of 0.1 to 5 mass%, preferably in the range of 0.25 to 2.0 mass%, and more preferably in the range of 0.5 to 1.0 mass%, relative to the total mass of the molded body.

[0148] 9. The molded body according to any one of embodiments 1 to 8, wherein the alkaline earth metal M is one or more of Mg, Ca, Sr and Ba, preferably one or more of Mg, Ca and Ba, more preferably the alkaline earth metal M is Ba.

[0149] 10. The molded body according to any one of embodiments 1 to 9, containing an alkaline earth metal M in an amount, calculated as the element, in the range of 0.1 to 5 mass %, preferably in the range of 0.5 to 2.0 mass %, more preferably in the range of 1.0 to 1.5 mass %, relative to the total mass of the molded body.

[0150] 11. The molded body according to any one of embodiments 1 to 10, wherein 98 to 100 mass %, preferably 99 to 100 mass %, more preferably 99.5 to 100 mass % of the molded body is composed of Si, O, Ti, Zn, M, and optionally H.

[0151] 12. The shaped body of any one of embodiments 1 to 11, wherein the zeolitic material further comprises a rare earth metal, preferably one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, more preferably one or more of Y, La, Ce, Pr, and Nd, more preferably one or more of Y, La, and Ce, more preferably La.

[0152] 13. The molded body according to embodiment 12, containing rare earth metals in an amount, calculated as the element, in the range of 0.1 to 5 mass %, preferably in the range of 0.25 to 2.5 mass %, and more preferably in the range of 0.5 to 1.0 mass %, relative to the total mass of the molded body.

[0153] 14. The molded body according to embodiment 12 or 13, wherein 98 to 100 mass %, preferably 99 to 100 mass %, more preferably 99.5 to 100 mass % of the molded body is composed of Si, O, Ti, Zn, M, rare earth metals, and optionally H.

[0154] 15. The molded body of any one of embodiments 1 to 14, wherein the binder comprises Si and O.

[0155] 16. The molded body according to any one of embodiments 1 to 15, wherein 95 to 100% by mass, preferably 98 to 100% by mass, more preferably 99 to 100% by mass, more preferably at least 99.5 to 100% by mass, more preferably 99.9 to 100% by mass of the binder contained in the molded body is composed of Si and O.

[0156] 17. The molded body according to any one of embodiments 1 to 16, comprising a binder in an amount in the range of 1 to 75% by mass, preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 40% by mass, more preferably in the range of 15 to 25% by mass, based on the total mass of the molded body.

[0157] 18. The molded body according to any one of embodiments 1 to 17, wherein 95 to 100% by weight, preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably at least 99.5 to 100% by weight, more preferably 99.9 to 100% by weight of the molded body is composed of the zeolitic material having an MWW-type framework and the binder.

[0158] 19. The molded body according to any one of embodiments 1 to 18, wherein the molded body has a total pore volume in the range of 0.5 to 3.0 mL / g, preferably in the range of 0.75 to 2.5 mL / g, more preferably in the range of 1.0 to 2.0 mL / g, more preferably in the range of 1.25 to 1.75 mL / g, the pore volume preferably being determined according to DIN 66133.

[0159] 20. The molded body according to any one of embodiments 1 to 19, wherein the molded body exhibits a water uptake in the range of 1 to 20% by weight, preferably in the range of 6 to 15% by weight, more preferably in the range of 8 to 12% by weight, the water uptake being preferably determined as described in Reference Example 7.

[0160] 21. The molded body according to any one of embodiments 1 to 20, wherein the molded body contains acidic sites at a concentration in the range of 0.05 to 1.00 mmol / g, preferably in the range of 0.10 to 0.50 mmol / g, more preferably in the range of 0.15 to 0.30 mmol / g, and this concentration is determined by temperature-programmed desorption of ammonia (NH3-TPD) at a temperature below 200°C, preferably according to Reference Example 5.

[0161] 22. A molded body according to any one of embodiments 1 to 21, wherein the molded body contains acidic sites at a concentration of 0.05 mmol / g or less, preferably 0.02 mmol / g or less, and this concentration is determined by temperature-programmed desorption of ammonia (NH3-TPD) at a temperature in the range of 200 to 400°C, preferably according to Reference Example 5.

[0162] 23. The molded body according to any one of embodiments 1 to 22, wherein the molded body contains acidic sites at a concentration in the range of 0.001 to 0.5 mmol / g, preferably in the range of 0.01 to 0.10 mmol / g, and this concentration is determined by temperature-programmed desorption of ammonia (NH3-TPD) at a temperature higher than 500°C, preferably according to Reference Example 5.

[0163] 24. The molded body according to any one of embodiments 1 to 23, wherein the molded body is a strand, preferably a strand having a hexagonal, rectangular, quadratic, triangular, elliptical or circular cross section, more preferably a circular cross section.

[0164] 25. The molded body according to any one of embodiments 1 to 24, wherein the molded body is a strand having a circular cross section with a diameter in the range of 0.5 to 5 mm, more preferably in the range of 1 to 3 mm, more preferably in the range of 1.5 to 2 mm.

[0165] 26. The molded article of any one of embodiments 1 to 25, wherein the molded article is an extrudate.

[0166] 27. The molded body according to any one of embodiments 1 to 26, preferably embodiment 24 or 25, more preferably embodiment 24, wherein the molded body exhibits a crushing strength in the range of 5 to 50 N, preferably in the range of 10 to 30 N, more preferably in the range of 15 to 25 N, and this crushing strength is preferably determined as described in Reference Example 6.

[0167] 28. The molded body according to any one of embodiments 1 to 27, wherein the molded body exhibits a propylene oxide activity of at least 6.2% by weight, preferably in the range of 7.5 to 15% by weight, more preferably in the range of 10 to 13% by weight, and wherein the propylene oxide activity is preferably determined as described in Reference Example 8.

[0168] 29. The molded body according to any one of embodiments 1 to 28, wherein the molded body exhibits a propylene oxide selectivity in the range of 96 to 100%, preferably in the range of 97 to 100%, more preferably in the range of 98 to 100%, and the propylene oxide selectivity is preferably determined in a continuous epoxidation reaction as described in Reference Example 9.

[0169] 30. 100m, preferably determined according to DIN 66131 2 / g or more, preferably 200m 2 / g or more, more preferably 250m 2 / g or more, preferably 280m 2 30. The molded article according to any one of embodiments 1 to 29, having a BET specific surface area of ​​1 / g or more.

[0170] 31. The molded article according to any one of embodiments 1 to 30, for use as a catalyst or catalyst component, preferably in a reaction for producing propylene oxide from propene and hydrogen peroxide, more preferably in a reaction for continuously producing propylene oxide from propene and hydrogen peroxide, more preferably in the continuous epoxidation reaction described in Reference Example 9.

[0171] 32. A method for producing a shaped body, preferably a shaped body according to any one of embodiments 1 to 31, comprising the steps of: (i) providing a shaped body comprising a zeolitic material having an MWW-type framework and a framework structure comprising Ti, Si and O, wherein the zeolitic material further comprises Zn, an alkaline earth metal M, and optionally a rare earth metal, and the shaped body further comprises a binder for said zeolitic material; (ii) preparing a mixture containing the molded body according to (i) and water, subjecting the mixture to a water treatment under hydrothermal conditions to obtain a water-treated molded body, and calcining the water-treated molded body in a gas atmosphere. A method comprising:

[0172] 33.(i) is (i.1) providing a zeolitic material having an MWW-type framework and a framework structure comprising Ti, Si, and O; (i.2) providing an aqueous solution of a Zn source; (i.3) providing an aqueous solution of a source of an alkaline earth metal M; (i.4) optionally providing an aqueous solution of a rare earth metal source; (i.5) impregnating the zeolitic material provided by (i.1) with the aqueous solution provided by (i.2), the aqueous solution provided by (i.3), and optionally the aqueous solution provided by (i.4) to obtain an impregnated zeolitic material; (i.6) preparing a mixture comprising the impregnated zeolitic material obtained from (i.5) and a binder precursor, (i.7) A step of molding the mixture obtained from (i.6) 33. The method of embodiment 32, comprising:

[0173] 34.(i.5) is (i.5.a) providing a mixture comprising the aqueous solution provided by (i.2), the aqueous solution provided by (i.3), and optionally the aqueous solution provided by (i.4); (i.5.b) impregnating the zeolite material prepared in (i.1) with the mixture prepared in (i.5.a). 34. The method of embodiment 33, comprising:

[0174] 35. The method according to any one of embodiments 32 to 34, wherein the compact provided in (i) contains Si in an amount, calculated as the element, in the range of 20 to 60% by mass, preferably in the range of 30 to 55% by mass, more preferably in the range of 35 to 50% by mass, more preferably in the range of 40 to 45% by mass, more preferably in the range of 41 to 44% by mass, relative to the total mass of the compact.

[0175] 36. The method of any one of embodiments 32 to 35, wherein the compact provided in (i) contains Ti in an amount, calculated as the element, in the range of 0.01 to 10% by weight, preferably in the range of 0.1 to 5% by weight, more preferably in the range of 0.5 to 2% by weight, more preferably in the range of 1.0 to 1.5% by weight, more preferably in the range of 1.1 to 1.4% by weight, relative to the total weight of the compact.

[0176] 37. The method of any one of embodiments 32 to 36, wherein the molded body provided in (i) contains Zn in an amount, calculated as the element, in the range of 0.01 to 5% by weight, preferably in the range of 0.1 to 2.5% by weight, more preferably in the range of 0.25 to 1.1% by weight, more preferably in the range of 0.5 to 0.9% by weight, relative to the total weight of the molded body.

[0177] 38. The method of any one of embodiments 32 to 37, wherein the alkaline earth metal M contained in the compact provided in (i) is one or more of Mg, Ca, Sr, and Ba, preferably one or more of Mg, Ca, and Ba, more preferably the alkaline earth metal M is Ba.

[0178] 39. The method according to any one of embodiments 32 to 38, wherein the compact provided in (i) comprises an alkaline earth metal M in an amount, calculated as the element, in the range of 0.01 to 10% by weight, preferably in the range of 0.1 to 5% by weight, more preferably in the range of 0.5 to 2% by weight, more preferably in the range of 1.0 to 1.5% by weight, more preferably in the range of 1.1 to 1.4% by weight, relative to the total weight of the compact.

[0179] 40. The method of any one of embodiments 32-39, wherein the compact provided in (i) further comprises a rare earth metal, preferably one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, more preferably one or more of Y, La, Ce, Pr, and Nd, more preferably one or more of Y, La, and Ce, more preferably La.

[0180] 41. The method of any one of embodiments 32 to 40, wherein the compact provided in (i) further comprises a rare earth metal, calculated as the element, in an amount, relative to the total mass of the compact, preferably in the range of 0.01 to 5 mass%, more preferably in the range of 0.1 to 2 mass%, more preferably in the range of 0.25 to 1.25 mass%, more preferably in the range of 0.5 to 1.0 mass%.

[0181] 42. The method of any one of embodiments 32 to 41, wherein the molded body provided in (i) comprises the binder in an amount in the range of 1 to 50% by weight, preferably in the range of 5 to 30% by weight, more preferably in the range of 15 to 25% by weight, more preferably in the range of 18 to 23% by weight, more preferably in the range of 19 to 2221% by weight, based on the total weight of the molded body.

[0182] 43. The method according to any one of embodiments 32 to 42, wherein the compact provided in (i) has a bulk density in the range of 200 to 500 g / mL, preferably in the range of 300 to 400 g / mL, more preferably in the range of 325 to 375 g / mL.

[0183] 44. The method according to any one of embodiments 32 to 43, wherein the shaped bodies provided in (i) are strands having a circular cross section with a diameter in the range of 0.5 to 5 mm, preferably in the range of 1 to 3 mm, more preferably in the range of 1.5 to 2 mm, and wherein the shaped bodies exhibit a crushing strength of at least 1.5 N, preferably in the range of 5 to 30 N, more preferably in the range of 15 to 25 N, preferably when determined as described in Reference Example 6.

[0184] 45. The method of any one of embodiments 32 to 44, wherein the molded body provided in (i) has a pore volume, preferably determined as described in Reference Example 2, of at least 1.0 g / mL, preferably in the range of 1.3 to 2.0 g / mL.

[0185] The compact prepared in 46.(i) had a viscosity of 1490 cm when determined as described in Reference Example 1. -1 46. ​​The method according to any one of embodiments 32 to 45, wherein the integrated extinction units in the IR band in the range of 5 to 15, more preferably in the range of 7.5 to 13.0, more preferably in the range of 10.0 to 12.0, more preferably in the range of 11.0 to 11.6.

[0186] 47. The method of any one of embodiments 32 to 46, wherein the molded body provided in (i) has an integrated extinction unit of the Lewis acid IR band in the range of 50 to 200, more preferably in the range of 75 to 150, more preferably in the range of 101 to 125, more preferably in the range of 105 to 120, when determined as described in Reference Example 1.

[0187] 48. The method of any one of embodiments 32 to 47, wherein the molded body provided in (i) has an integrated extinction unit of the Bronsted acid IR band of 1 or less, preferably 0.5 or less, more preferably 0.2 or less, more preferably 0.1 or less, more preferably 0.01 or less, when determined as described in Reference Example 1.

[0188] 49. The method of any one of embodiments 32 to 48, wherein the shaped body provided in (i) contains acidic sites at a concentration in the range of 0.05 to 1.00 mmol / g, preferably in the range of 0.10 to 0.50 mmol / g, as determined by temperature-programmed desorption of ammonia (NH3-TPD) preferably according to Reference Example 5 at a temperature below 200°C.

[0189] 50. The method of any one of embodiments 32 to 49, wherein the shaped body provided in (i) contains acidic sites at a concentration of at most 0.05 mmol / g, preferably at most 0.02 mmol / g, as determined by temperature-programmed desorption of ammonia (NH3-TPD), preferably according to Reference Example 5, at a temperature in the range of 200 to 400 °C.

[0190] 51. The method of any one of embodiments 32 to 50, wherein the formed body provided in (i) contains acidic sites at a concentration in the range of 0.005 to 0.1 mmol / g, preferably in the range of 0.01 to 0.05 mmol / g, more preferably in the range of 0.02 to 0.03 mmol / g, as determined by temperature-programmed desorption of ammonia (NH3-TPD) preferably according to Reference Example 5 at a temperature above 500°C.

[0191] 52. The method of any one of embodiments 33 to 51, wherein the zeolitic material provided by (i.1) comprises Si in an amount, calculated as element, in the range of 20 to 60% by weight, preferably in the range of 30 to 55% by weight, more preferably in the range of 35 to 50% by weight, more preferably in the range of 40 to 45% by weight, more preferably in the range of 41 to 44% by weight, relative to the total weight of the zeolitic material.

[0192] 53. The method of any one of embodiments 33 to 52, wherein the zeolitic material provided by (i.1) comprises Ti in an amount, calculated as element, in the range of 0.1 to 10% by weight, preferably in the range of 0.5 to 5% by weight, more preferably in the range of 1 to 2% by weight, more preferably in the range of 1.2 to 1.8% by weight, relative to the total weight of the zeolitic material.

[0193] 54. The method of any one of embodiments 33 to 53, wherein the zeolitic material provided by (i.1) comprises Zn in an amount, calculated as element, in the range of 0.1 to 2.5% by weight, preferably in the range of 0.5 to 1.3% by weight, more preferably in the range of 0.7 to 1.1% by weight, relative to the total weight of the shaped body.

[0194] 55. The method of any one of embodiments 33-54, wherein the alkaline earth metal M comprised in the zeolitic material provided by (i.1) is one or more of Mg, Ca, Sr and Ba, preferably one or more of Mg, Ca and Ba, more preferably the alkaline earth metal M is Ba.

[0195] 56. The method according to any one of embodiments 33 to 55, wherein the zeolitic material provided by (i.1) comprises an alkaline earth metal M in an amount, calculated as element, in the range of 0.1 to 7.5% by weight, preferably in the range of 0.25 to 5% by weight, more preferably in the range of 0.5 to 2.5% by weight, more preferably in the range of 1.2 to 2.0% by weight, relative to the total weight of the shaped body.

[0196] 57. The method of any one of embodiments 33-56, wherein the zeolitic material provided by (i.1) further comprises a rare earth metal, preferably one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, more preferably one or more of Y, La, Ce, Pr and Nd, more preferably one or more of Y, La and Ce, more preferably La.

[0197] 58. The method of any one of embodiments 33 to 57, wherein the zeolitic material provided by (i.1) further comprises a rare earth metal, calculated as the element, preferably in an amount in the range of 0.1 to 5% by weight, preferably in the range of 0.25 to 2% by weight, more preferably in the range of 0.5 to 1.5% by weight, more preferably in the range of 0.8 to 1.2% by weight, relative to the total weight of the shaped body.

[0198] 59. The method of any one of embodiments 33 to 58, wherein the zeolitic material provided by (i.1) preferably has a crystallite size in the range of 15 to 40 nm, as determined as described in Reference Example 4.

[0199] 60. The zeolitic material prepared according to (i.1) preferably has a BET specific surface area of ​​250 m, as determined according to DIN 66131. 2 / g or more, preferably 275m 2 / g or more, more preferably 300m 2 / g or more.

[0200] 61. The method of any one of embodiments 33 to 60, wherein the zeolitic material provided by (i.1) has a C value in the range of −150 to −40, preferably in the range of −125 to −50, more preferably in the range of −100 to −60, preferably when determined as described in Reference Example 10.

[0201] 62. The method of any one of embodiments 33 to 61, wherein the zeolitic material provided by (i.1) has a crystallinity of at least 50%, preferably at least 75%, more preferably at least 80%, preferably determined as described in Reference Example 4.

[0202] 63. The method of any one of embodiments 33 to 62, wherein the zeolitic material provided by (i.1) has a water uptake, preferably determined as described in Reference Example 7, in the range of 8 to 20% by weight, preferably in the range of 9 to 17.5% by weight, more preferably in the range of 10 to 15% by weight.

[0203] 64. The method of any one of embodiments 33 to 63, wherein the zeolitic material provided by (i.1) exhibits a propylene oxide activity of at least 10 wt.%, preferably in the range of 10 to 15 wt.%, more preferably in the range of 11 to 14 wt.%, preferably determined as described in Reference Example 8.

[0204] 65. The zeolite material prepared by (i.1) has a viscosity of (3700-3750) + / - 20 cm -1 and a band with a maximum in the region of (3670~3690) + / - 20 cm -1 and preferably has an infrared spectrum including a band having a maximum in the region of (3700-3750) + / - 20 cm when determined as described in Reference Example 11. -1 Band area: (3670~3690) + / - 20cm -1 65. The method according to any one of embodiments 33 to 64, wherein the intensity ratio of the region to the band is at most 1.7, preferably at most 1.6.

[0205] 66. The method of any one of embodiments 33 to 65, wherein the Zn source is a salt, preferably one or more of a nitrate, a halide, a hydroxide, an acetate, preferably a nitrate.

[0206] 67. The method of any one of embodiments 33-66, wherein the alkaline earth metal in the alkaline earth metal source is one or more of Mg, Ca, Sr, and Ba, preferably one or more of Mg, Ca, and Ba, more preferably, the alkaline earth metal M is Ba.

[0207] 68. The method of any one of embodiments 33-67, wherein the alkaline earth metal source is a salt, preferably one or more of a nitrate, a halide, an acetate, a hydroxide, more preferably a nitrate.

[0208] 69. The method of any one of embodiments 33-68, wherein the mixture according to (i.2) comprises a rare earth metal source, and the rare earth metal is one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, more preferably one or more of Y, La, Ce, Pr, and Nd, more preferably one or more of Y, La, and Ce, more preferably La.

[0209] 70. The method of embodiment 69, wherein the rare earth metal source is a salt, preferably one or more of a nitrate, a halide, and a hydroxide, more preferably a nitrate.

[0210] 71. The method according to any one of embodiments 33 to 70, wherein the impregnation according to (i.5) comprises one or more of spray impregnation, adhesive impregnation, incipient impregnation, wet impregnation adhesive techniques, and agitation, preferably mechanical agitation, more preferably stirring, more preferably for a period in the range of 0.1 to 5 hours, more preferably in the range of 0.5 to 2 hours.

[0211] 72. The method according to any one of embodiments 33 to 71, wherein the impregnation with (i.5) comprises keeping the mixture at the same temperature, preferably at a temperature in the range of 15 to 40°C, for a period in the range of 1 to 50 hours, preferably in the range of 30 to 40 hours.

[0212] 73. After (i.5) and before (i.6), (a) optionally isolating the impregnated zeolitic material obtained in (i.5), preferably by filtration, and / or preferably by and (b) optionally washing the impregnated zeolitic material obtained in (i.5) or (a), preferably with deionized water, and / or preferably with and (c) optionally drying the impregnated zeolitic material obtained in (i.5), (a) or (b) in a gas atmosphere, and / or preferably (d) optionally, calcining the impregnated zeolitic material obtained in (i.5), (a), (b) or (c) in a gas atmosphere. 73. The method of any one of embodiments 33 to 72, comprising:

[0213] 74. The method of embodiment 73, wherein drying is carried out according to (c) at a temperature of the gas atmosphere in the range of 70 to 150°C, preferably in the range of 90 to 130°C, more preferably in the range of 100 to 120°C.

[0214] 75. The method of embodiment 73 or 74, wherein the gas atmosphere for drying in (c) comprises nitrogen, oxygen, or a mixture thereof, and the gas atmosphere is preferably oxygen, air, or lean air.

[0215] 76. The method of any one of embodiments 73 to 75, wherein the calcination is carried out according to (d) at a temperature in the gas atmosphere in the range of 510 to 590°C, preferably in the range of 530 to 570°C, more preferably in the range of 540 to 560°C.

[0216] 77. The method of embodiment 73 or 76, wherein the gas atmosphere for calcination in (d) comprises nitrogen, oxygen, or a mixture thereof, and the gas atmosphere is preferably oxygen, air, or lean air.

[0217] 78. The method of any one of embodiments 33-77, wherein the binder precursor is selected from the group consisting of silica sol, colloidal silica, wet-process silica, dry-process silica, and mixtures of two or more thereof, and the binder precursor is more preferably colloidal silica.

[0218] 79. The method of any one of embodiments 33 to 78, wherein in the mixture according to (i.6), the mass ratio of the zeolitic material obtained from (i.5) to the binder precursor is in the range of 1:1 to 10:1, preferably in the range of 3:1 to 5:1, more preferably in the range of 3.5:1 to 4.5:1.

[0219] 80. The method of any one of embodiments 33 to 79, wherein 95 to 100% by weight, preferably 98 to 100% by weight, more preferably 99 to 100% by weight of the mixture produced according to (i.6) consists of the impregnated zeolitic material from (i.5) and binder precursor.

[0220] 81. The method of any one of embodiments 33 to 80, wherein the mixture produced according to (i.6) further comprises one or more viscosity-adjusting and / or mesopore-forming agents.

[0221] 82. The method of embodiment 81, wherein the one or more viscosity adjusting and / or mesopore forming agents are selected from the group consisting of water, alcohols, organic polymers, and mixtures of two or more thereof; the organic polymer is preferably selected from the group consisting of cellulose, cellulose derivatives, starch, polyalkylene oxides, polystyrene, polyacrylates, polymethacrylates, polyolefins, polyamides, polyesters, and mixtures of two or more thereof; the organic polymer is more preferably selected from the group consisting of cellulose derivatives, polyalkylene oxides, polystyrene, and mixtures of two or more thereof; the organic polymer is more preferably selected from the group consisting of methylcellulose, carboxymethylcellulose, polyethylene oxide, polystyrene, and mixtures of two or more thereof; more preferably the one or more viscosity adjusting and / or mesopore forming agents comprise water and methylcellulose.

[0222] 83. The method of embodiment 81 or 82, wherein in the mixture prepared according to (i.6), the mass ratio of zeolitic material to one or more viscosity-adjusting and / or mesopore-forming agents is in the range of 10:1 to 20:1, preferably in the range of 15:1 to 16:1, more preferably in the range of 15.5:1 to 15.7:1.

[0223] 84. The method of any one of embodiments 33 to 83, wherein 95 to 100% by weight, preferably 98 to 100% by weight, more preferably 99 to 100% by weight of the mixture produced according to (i.6) consists of the impregnated zeolitic material from (i.5), the binder precursor, and one or more viscosity-adjusting and / or mesopore-forming agents.

[0224] 85. The method of any one of embodiments 33 to 84, wherein in (i.7), the mixture is shaped into strands, preferably strands having a circular cross section.

[0225] 86. The method according to embodiment 85, wherein the strands having a circular cross section have a diameter in the range of 0.2 to 10 mm, preferably in the range of 0.5 to 5 mm, more preferably in the range of 1 to 3 mm, more preferably in the range of 1.5 to 2 mm, more preferably in the range of 1.6 to 1.8 mm.

[0226] 87. The method of any one of embodiments 33 to 86, wherein in (i.7), shaping comprises extruding the mixture.

[0227] 88. After (i.7) and before (ii), (e) optionally drying the shaped body obtained from (i.7) in a gas atmosphere, and / or preferably (f) optionally, calcining the shaped body obtained from (i.7) or (e) in a gas atmosphere. 88. The method of any one of embodiments 33 to 87, further comprising:

[0228] 89. The method of embodiment 88, wherein the drying in (e) is carried out at a temperature of the gas atmosphere in the range of 80 to 160°C, preferably in the range of 100 to 140°C, more preferably in the range of 110 to 130°C.

[0229] 90. The method of embodiment 88 or 89, wherein the gas atmosphere for drying in (e) comprises nitrogen, oxygen, or a mixture thereof, and the gas atmosphere is preferably oxygen, air, or lean air.

[0230] 91. The method of any one of embodiments 88 to 90, wherein the calcination according to (f) is carried out at a temperature in the gas atmosphere in the range of 460 to 540°C, preferably in the range of 480 to 520°C, more preferably in the range of 490 to 510°C.

[0231] 92. The method of any one of embodiments 88-91, wherein the gas atmosphere for calcination in (f) comprises nitrogen, oxygen, or a mixture thereof, and the gas atmosphere is preferably oxygen, air, or lean air.

[0232] 93. The method of any one of embodiments 32-92, wherein the mixture of (ii) is produced in a kneader or mix muller.

[0233] 94. The method of any one of embodiments 32 to 93, wherein the mixture of (ii) comprises the shaped body according to (i) and water in a mass ratio ranging from 5:1 to 1:100, preferably ranging from 1:1 to 1:50, more preferably ranging from 1:10 to 1:30, more preferably ranging from 1:15 to 1:25.

[0234] 95. The method of any one of embodiments 32 to 94, wherein the water treatment according to (ii) comprises a temperature of the mixture in the range of 100 to 200°C, preferably in the range of 125 to 175°C, more preferably in the range of 130 to 160°C, more preferably in the range of 135 to 155°C, more preferably in the range of 140 to 150°C.

[0235] 96. The method according to any one of embodiments 32 to 95, wherein the water treatment according to (ii) is carried out under autogenous pressure, preferably in an autoclave.

[0236] 97. The method according to any one of embodiments 32 to 96, wherein the water treatment according to (ii) is carried out for 6 to 10 hours, preferably 7 to 9 hours.

[0237] 98. The method of any one of embodiments 32 to 97, wherein after the water treatment in (ii) and before calcination, the water-treated shaped body is separated from the mixture obtained from the water treatment, and wherein the separation preferably comprises filtering or centrifuging the mixture obtained from the water treatment, and more preferably, the separation further comprises washing the water-treated shaped body at least once with a liquid solvent system, and the liquid solvent system preferably comprises one or more of water, alcohol, and a mixture of two or more thereof, and the water-treated shaped body is more preferably washed with water.

[0238] 99. The method of any one of embodiments 32-98, wherein after subjecting the mixture to the water treatment and before calcining the water-treated shaped body, (ii) further comprises drying the shaped body in a gas atmosphere.

[0239] 100. The method of embodiment 99, wherein the drying is carried out at a temperature of the gas atmosphere in the range of 80 to 160°C, preferably in the range of 100 to 140°C, more preferably in the range of 110 to 130°C.

[0240] 101. The method of embodiment 99 or 100, wherein the gas atmosphere comprises nitrogen, oxygen, or a mixture thereof, and the gas atmosphere is preferably oxygen, air, or lean air.

[0241] 102. The method according to any one of embodiments 32 to 101, preferably any one of embodiments 93 to 101, wherein the calcination of the shaped body according to (ii), preferably the dried shaped body according to any one of embodiments 86 to 90, is carried out in a gas atmosphere.

[0242] 103. The method of embodiment 102, wherein the calcination is carried out at a temperature in the gas atmosphere in the range of 410 to 490°C, preferably in the range of 430 to 470°C, more preferably in the range of 440 to 460°C.

[0243] 104. The method of embodiment 102 or 103, wherein the gas atmosphere comprises nitrogen, oxygen, or a mixture thereof, and the gas atmosphere is preferably oxygen, air, or lean air.

[0244] 105. A shaped body comprising a zeolitic material with an MWW-type framework and a binder material, obtainable or obtained by the method according to any one of embodiments 32 to 104.

[0245] 106. Use of the shaped article according to any one of embodiments 1 to 31 or embodiment 105 as an adsorbent, absorbent, catalyst, or catalyst component, preferably as a catalyst or catalyst component, more preferably as a Lewis acid catalyst or Lewis acid catalyst component, an isomerization catalyst or isomerization catalyst component, an oxidation catalyst or oxidation catalyst component, an aldol condensation catalyst or aldol condensation catalyst component, or a Prins reaction catalyst or Prins reaction catalyst component, more preferably as an oxidation catalyst or oxidation catalyst component, more preferably as an epoxidation catalyst or epoxidation catalyst component, more preferably as an epoxidation catalyst.

[0246] 107. The method according to embodiment 106, wherein the epoxidation reaction of an organic compound having at least one C-C double bond, preferably a C2-C10 alkene, more preferably a C2-C5 alkene, more preferably a C2-C4 alkene, more preferably a C2 or C3 alkene, more preferably propene, more preferably for the epoxidation of propene using hydrogen peroxide as oxidant, more preferably for the epoxidation of propene in a solvent comprising acetonitrile using hydrogen peroxide as oxidant.

[0247] 108. A method for oxidizing an organic compound, comprising contacting the organic compound with a catalyst comprising the shaped body described in any one of embodiments 1-31 or embodiment 105, to preferably epoxidize the organic compound, more preferably an organic compound having at least one C-C double bond, preferably a C2-C10 alkene, more preferably a C2-C5 alkene, more preferably a C2-C4 alkene, more preferably a C2 or C3 alkene, more preferably propene.

[0248] 109. The method according to embodiment 108, wherein hydrogen peroxide is used as the oxidizing agent and the oxidation reaction is preferably carried out in a solvent, more preferably in a solvent comprising acetonitrile.

[0249] 110. A process for producing propylene oxide, preferably a process according to embodiment 108 or 109, comprising reacting propene with hydrogen peroxide in an acetonitrile solution in the presence of a catalyst comprising the shaped body according to any one of embodiments 1 to 31 or embodiment 105, to obtain propylene oxide.

[0250] The invention is further illustrated by the following examples and reference examples.

[0251] [Reference example 1] Determination of Bronsted and Lewis acidities In the examples, pyridine was used as a probe gas to determine Bronsted acidity and Lewis acidity. Measurements were performed using a Nicolet 6700 IR spectrometer, which utilizes an FTIR cell. For the measurements, the sample was compressed into a pellet that was placed in the FTIR cell. After being placed in the FTIR cell, the sample was then heated to 350°C in air and held at temperature for 1 hour to remove water and any volatiles from the sample. The apparatus was then placed under high vacuum (10 -5 The cell was placed under a constant pressure of 1000 kJ / cm² and allowed to cool to 80° C. The cell was kept at this temperature for the entire duration of the measurement to avoid condensation of pyridine within the cell.

[0252] Pyridine was then dosed to the cell in successive steps (0.01, 0.1, 1, and 3 mbar) to ensure controlled and complete exposure of the sample.

[0253] 80℃ and 10 -5 The irradiation spectrum of the activated sample at mbar was used as background for the absorption spectrum to correct for the influence of matrix bands.

[0254] For analysis, the samples were at stable equilibrium, so spectra were used at a pressure of 1 mbar. For quantification, extinction spectra were used, as they allow for the cancellation of matrix effects.

[0255] The integral extinction units were determined as follows: the characteristic signal for pyridine absorption was integrated and the area thus determined was scaled according to the thickness of the pellet. To allow a better comparison, the determined values ​​were multiplied by a constant factor, said factor being 1000. Therefore, based on the measured spectrum, the integral extinction units were calculated according to formula I: Integrated extinction units = (area under the extinction band at 1 mbar / thickness value of the degraded pellet in μm) x 1000.

[0256] The integral extinction units of the IR bands at a pressure of 1 mbar are used herein as values ​​defining the Lewis acidity of the respective material. -1 The integrated extinction units of the IR band at 1000 .ANG. are used herein as a further value to define the acidity of the respective material.

[0257] [Table 1]

[0258] In the example, the Lewis acid site is determined at 1450 cm -1 The Brønsted acid site is determined by considering the band at 1545 cm -1 This was decided taking into consideration the band.

[0259] [Reference example 2] Determination of total pore volume The total pore volume was determined via mercury intrusion porosimetry according to DIN 66133.

[0260] [Reference example 3] Determination of BET specific surface area The BET specific surface area was determined according to the method disclosed in DIN 66131 via nitrogen physical adsorption at 77 K. N sorption isotherms at liquid nitrogen temperature were measured using a Micrometrics ASAP 2020M, and the BET specific surface area was determined using a Tristar system.

[0261] [Reference example 4] Powder X-ray diffraction and crystallinity determination Powder X-ray diffraction (PXRD) data were collected using a diffractometer (D8 Advance Series II, Bruker AXS GmbH) equipped with a LYNXEYE detector operated with a copper anode X-ray tube running at 40 kV and 40 mA. The geometry was Bragg-Brentano, and an atmospheric scattering shield was used to reduce atmospheric scattering.

[0262] Calculating Crystallinity: The crystallinity of the samples was determined using the software DIFFRAC.EVA provided by Bruker AXS GmbH, Karlsruhe. The method is described on page 121 of the user manual. Default parameters for the calculation were used.

[0263] Calculation of phase composition: The phase composition was calculated for the raw data using the modeling software DIFFRAC.TOPAS provided by Bruker AXS GmbH, Karlsruhe. The identified crystal structures of the phases, the instrumental parameters, and the crystallite sizes of the individual phases were used to simulate the diffraction patterns, which were fitted to the data in addition to a function to model the background intensity.

[0264] Data collection: The sample was homogenized in a mortar and then compressed into a standard flat sample holder provided by Bruker AXS GmbH for Bragg-Brentano geometric data collection. A glass plate was used to press and flatten the sample powder to achieve a flat surface. Data were collected from an angle range of 2 to 70°2θ with a step size of 0.02°2θ, while the variable divergence slit was set at an angle of 0.1°. The crystalline content expresses the intensity of the crystalline signal relative to the total scattered intensity. (User Manual for DIFFRAC.EVA, Bruker AXS GmbH, Karlsruhe.)

[0265] [Reference example 5] Determination of acidic sites: Temperature-programmed desorption of ammonia (NH3-TPD) Temperature-programmed desorption of ammonia (NH3-TPD) was performed on an automated chemisorption analysis unit (Micromeritics AutoChem II 2920) with a thermal conductivity detector. Continuous analysis of the desorbed species was achieved using an online mass analyzer (OmniStar QMG200, Pfeiffer Vacuum). Samples (0.1 g) were introduced into a quartz tube and analyzed using the program described below. The temperature was measured using a Ni / Cr / Ni thermocouple directly above the sample in the quartz tube. He with a purity of 5.0 was used for the analysis. A blank sample was analyzed for calibration before every measurement.

[0266] 1. Preparation: Start recording; measure once per second. Wait for 10 minutes at 25°C. Helium flow rate is 30 cm 3 / min (room temperature (approximately 25°C) and 1 atm); heat to 600°C at a heating rate of 20 K / min; hold for 10 min. He flow (30 cm 3 Cool to 100 °C under a cooling rate of 20 K / min (furnace ramp temperature); He flow (30 cm 3 / min) to 100 °C (sample ramp temperature) at a cooling rate of 3 K / min. 2. Saturation with NH3: Start recording; one measurement per second. At 100 °C, change the gas flow to a mixture of 10% NH3 in He (75 cm 3 / min; 100 °C and 1 atm); hold for 30 min. 3. Remove excess: Start recording; measure once per second. Gas flow 75cm at 100°C. 3 Change to He flow (100° C. and 1 atm) / min; hold for 60 min. 4. NH3-TPD: Start recording; one measurement per second. He flow (flow rate: 30 cm 3 / min) to 600°C at a heating rate of 10 K / min; hold for 30 min. 5. Measurement complete.

[0267] Desorbed ammonia was measured using an online mass spectrometer, which demonstrated that the signal from the thermal conductivity detector was caused by desorbed ammonia. This involved monitoring the desorption of ammonia using the m / z = 16 signal from ammonia. Through integration of the TPD signal with a horizontal baseline, the amount of adsorbed ammonia (mmol / g of sample) was determined using Micromeritics software.

[0268] [Reference example 6] Determination of hardness The crushing force referred to in this context is understood to be determined using the crushing force test machine Z2.5 / TS1S, manufactured by Zwick GmbH & Co., D-89079 Ulm, Germany. For information about this machine and its operating principle, reference is made to the respective instructions in the handbook "Register1: Betriebsanleitung / Sicherheitshandbuch für die Material-Prüfmaschine Z2.5 / TS1S," 1.5th edition, December 2001, Zwick GmbH & Co., Technische Dokumentation, August-Nagel-Strasse 11, D-89079 Ulm, Germany. The machine had a fixed, horizontal table on which the strand was placed. A freely movable plunger with a diameter of 3 mm in the vertical direction moved the strand against the fixed table. The device was operated with an initial force of 0.5 N and a shear rate of 10 mm / min at the initial force, followed by a test rate of 1.6 mm / min. The vertically movable plunger, connected to a load cell for sensing force, moved toward a fixed turntable on which the compact (strand) under investigation was placed during the measurement, thereby moving the strand toward the table. The plunger applied the strand perpendicular to their longitudinal axis. Using the above-described device, a given strand, as described below, was subjected to increasing force via the plunger until the strand shattered. The force at which the strand shattered is referred to as the strand's crushing strength.

[0269] The control of the experiment was carried out by means of a computer, which registered and evaluated the results of the measurements, the values ​​obtained being in each case the average value of measurements on 10 strands.

[0270] [Reference example 7] Determination of water uptake Water adsorption / desorption isotherm measurements were performed using a VTI SA instrument (TA Instruments) according to a step isotherm program. Experiments consisted of a run or series of runs performed on sample material placed on a microbalance pan inside the instrument. Before the start of the measurements, the sample was heated to 100 °C (5 °C / min ramp) and held under a N2 flow for 6 hours to remove residual moisture. After the drying program, the temperature inside the cell was reduced to 25 °C and maintained isothermal throughout the measurement. The microbalance was calibrated, and the mass of the dried sample was balanced (maximum mass deviation 0.01 wt%). Water uptake by the sample was measured as the mass increase from the dry sample mass. Adsorption curves were measured by first exposing the sample to increasing relative humidity (RH) (expressed as the mass % of water in the atmosphere inside the cell) and measuring the water uptake by the sample at equilibrium. The RH was increased from 5% to 85% in 10% steps, and at each step, the system controlled the RH and monitored the sample mass until equilibrium was reached and the mass uptake was recorded. After the sample was exposed to 85% RH, the total amount of water adsorbed by the sample was collected. During the desorption measurements, the RH was reduced from 85% to 5% in 10% steps, and the change in sample mass (water uptake) was monitored and recorded.

[0271] [Reference example 8] Determination of propylene oxide activity and pressure drop rate (PO test) The PO test disclosed below represents a preliminary test procedure for evaluating the potential suitability of the molded bodies as catalysts for the epoxidation of propene. In the PO test, the molded bodies were tested as catalysts in a small autoclave for the reaction of propene with hydrogen peroxide, which was provided as an aqueous hydrogen peroxide solution (30% by weight) to produce propylene oxide. Specifically, 0.63 g of the molded bodies was introduced into a steel autoclave together with 79.2 g of acetonitrile and 12.4 g of propene at room temperature, and 22.1 g of aqueous hydrogen peroxide. After a reaction time of 4 hours at 40°C, the mixture was cooled and depressurized, and the liquid phase was analyzed by gas chromatography for its propylene oxide content. The propylene oxide content (% by weight) of the liquid phase was the result of the PO test.

[0272] [Reference example 9] Determination of propylene oxide activity in sequential epoxidation reactions. The continuous epoxidation reaction was carried out as described in Reference Example 1 of WO 2015 / 010990A, page 55, line 14 to page 57, line 10. The reaction temperature was set to 45°C (see WO 2015 / 010990A, page 56, lines 16 to 18). The temperature was adjusted to achieve a constant hydrogen peroxide conversion rate of essentially 90% (see WO 2015 / 010990A, page 56, lines 21 to 23). KH2PO4 was used as an additive (see WO 2015 / 010990A, page 56, lines 7 to 10), and the additive concentration was 130 micromoles per mole of hydrogen peroxide. As catalysts, catalysts according to Comparative Example 22, Reference Example 20 and Example 23 described herein below were used (see WO2015 / 010990A, page 55, lines 16 to 18).

[0273] [Reference example 10] Determination of C value (BET C constant) As known to those skilled in the art, the C value was determined by the usual calculation ((slope / intercept) + 1) based on a plot of the BET value 1 / (V((p / p)-1)) against p / p, where p is the partial vapor pressure of the adsorbate gas in equilibrium with the surface at 77.4 K (bp of liquid nitrogen) in Pa, p is the saturation pressure of the adsorbate gas in Pa, and V is the pressure at standard temperature and pressure (STP) [273.15 K and atmospheric pressure (1.013 × 10 5 is the volume of gas adsorbed at 1000 kJ / s (unit: mL).

[0274] [Reference example 11] IR measurements IR measurements were carried out on a Nicolet 6700 spectrometer. The zeolite material was compressed into a self-supporting pellet without any additives. The pellet was introduced into a high vacuum cell and placed in the IR instrument. Before the measurements, the sample was placed under high vacuum (10 -5 The cell was pre-treated at 300°C for 3 hours under a pressure of 1000 mbar. After cooling the cell to 50°C, the spectrum was collected. The spectrum was recorded at 4000 cm -1 ~800cm -1 In the range of 2cm -1 The spectra were recorded with a resolution of 100 kHz. The x-axis represents wave numbers (cm -1 ), plotted with absorbance (arbitrary units) on the y-axis. For quantitative determination of peak heights and peak height ratios, baseline correction was performed.

[0275] [Reference example 12] Determination of torsional parameters for water Samples for NMR analysis were prepared by drying a small amount (0.05–0.2 g) of catalyst in an NMR tube under vacuum overnight at T > 350 °C. The sample was then loaded with nanopure water (Millipore Advantage A10) via a vacuum line to 90% of the catalyst support's pore volume (determined by Hg-porosimetry). The loaded sample was then flame-sealed in the tube and allowed to stand overnight before measurement.

[0276] The self-diffusion coefficient for water in the catalyst material (D effTo determine the PFG NMR (H) band, NMR analysis was performed using a Bruker Avance III NMR spectrometer at 20 °C and 1 bar with a 400 MHz H resonance frequency. A Bruker Diff50 probehead was used with a Bruker Great 60A gradient amplifier. A temperature of 20 °C was maintained with a water-cooled gradient coil. The pulse program used for the PFG NMR self-diffusion analysis was stimulated spin echo with pulsed field gradients according to Figure 1b of US20070099299A1. For each sample, spin echo extinction curves were measured at different diffusion times (between 20 and 100 ms) with stepwise increases in field gradient strength (up to a maximum gmax = 3 T / m). The gradient pulse length was 1 ms. The spin echo extinction curves were fitted to Equation 6 of US2007 / 0099299A. As an example, a double logarithmic plot of data from a catalyst support at various diffusion times is shown in Figure X. The slope of each line corresponds to the diffusion rate. The tortuosity for each catalyst support was calculated using the average diffusivity over all diffusion times according to Equation II (see Reference Example 2).

[0277] PFG NMR allows for non-destructive examination of molecular thermal motions of adsorbed molecules in free gases and liquids, in macro- and supramolecular solutions, and in porous systems. The principles and applications are described in US20070099299A1. The tortuosity was calculated from the diffusivities obtained by NMR according to Reference Example 4. The tortuosity of a porous material is given by the tortuosity of the porous system (D eff ) and the self-diffusion coefficient of the free liquid (D0) (see S. Kolitcheff, E. Jolimaitre, A. Hugon, J. Verstraete, M. Rivallan, P. L. Carrette, F. Couenne and M. Tayakout-Fayolle, Catal. Sci. Technol., 2018, vol. 8, pp. 4537; and F. Elwinger, P. Pourmand and I. Furo, J. Phys. Chem. C., 2017, vol. 121, pp. 13757-13764):

[0278]

number

[0279] The free diffusion coefficient for water is 2.02 x 10 at 20°C. -9 m 2 s -1 (See M. Holz, S.R. Heil and A. Sacco. Phys. Chem. Chem. Phys., 2000, vol. 2, pp. 4740-4742).

[0280] [Reference example 12] Manufacturing of Ti-MWW A zeolite material having an MWW framework structure and containing Ti (also abbreviated as Ti-MWW in this specification) was provided that was similar to the zeolite material produced according to Example 5, 5.1 to 5.3, page 83, line 26 to page 92, line 7 of WO 2013 / 117536A. The produced zeolite material had a crystallinity of 89% and a BET specific surface area of ​​353 m. 2 / g, C value -94, Ti content 1.5gTi / 100g. Furthermore, the produced zeolite material showed a water adsorption of 12 wt%.

[0281] [Reference example 14:] Fabrication of Zn-impregnated Ti-MWW A zeolite material having a framework structure MWW, containing Ti, and impregnated with Zn was provided according to Reference Example 1, pages 57-66 of WO2013 / 117536A2.

[0282] [Reference example 15] Fabrication of Ba-impregnated Ti-MWW 1.2 g of barium nitrate (Ba(NO3)2) was dissolved in 60 g of deionized water in a beaker with stirring for 1 hour. Then, 40.0 g of Ti-MWW from Reference Example 12 was added to the mixture, and the mixture was kept at room temperature for 40 hours. The resulting solid was dried in air at 110°C for 5 hours and then calcined in air at 550°C for 8 hours to obtain the product. The yield was 39.6 g.

[0283] The resulting material had a Ba content of 1.6 g / 100 g, a Si content of 43 g / 100 g, and a Ti content of 1.5 g / 100 g.

[0284] [Reference example 16] Fabrication of Ba and Zn impregnated Ti-MWW 1.20 g of barium nitrate (Ba(NO3)2) and 1.64 g of zinc nitrate (Zn(NO3)2·6H2O) were dissolved in 60.00 g of deionized water in a beaker with stirring for 1 hour. Then, 40.00 g of Ti-MWW from Reference Example 12 was added to the mixture, which was then kept at room temperature for 36 hours. The resulting solid was dried in air at 110°C for 5 hours and then calcined in air at 550°C for 8 hours to obtain the product. The yield was 40.3 g.

[0285] The resulting material had a Ba content of 1.6 g / 100 g, a Si content of 42 g / 100 g, a Ti content of 1.5 g / 100 g and a Zn content of 0.88 g / 100 g.

[0286] [Reference example 17] Fabrication of Ba, Zn, and La-impregnated Ti-MWW 1.20 g of barium nitrate (Ba(NO3)2), 1.64 g of zinc nitrate (Zn(NO3)2·6H2O), and 1.24 g of lanthanum nitrate (La(NO3)3·6H2O) were dissolved in 60.00 g of deionized water in a beaker with stirring for 1 hour. Then, 40.00 g of Ti-MWW from Reference Example 12 was added to the mixture, which was then kept at room temperature for 36 hours. The resulting solid was dried in air at 110°C for 5 hours and then calcined in air at 550°C for 8 hours to obtain the product. The yield was 40.9 g.

[0287] The resulting material had a Ba content of 1.6 g / 100 g, a La content of 1.0 g / 100 g, a Si content of 42 g / 100 g, a Ti content of 1.5 g / 100 g and a Zn content of 0.88 g / 100 g.

[0288] [Reference example 18] Forming of Zn-impregnated Ti-MWW 30 g of Ti-MWW impregnated with Zn according to Reference Example 14 and 1.92 g of methylcellulose (Walocel MW 15000 GB, Wolff Cellulosics GmbH & Co. KG, Germany) were placed in a kneader and mixed for 5 minutes. 60 mL of deionized water was then added along with 18.75 g of colloidal silica (Ludox® AS40), and the mixture was mixed for a further 10 minutes. 10 mL of deionized water was then added, and the mixture was mixed for a further 15 minutes. The total mixing time was 45 minutes.

[0289] The mixed mass was extruded at a pressure of 120 bar (abs) to obtain strands with a circular cross section of 1.7 mm in diameter. The extruded strands were then dried and calcined in air according to the following program: 1. Heat to a temperature of 120°C within 40 minutes; 2. Maintain the temperature at 120℃ for 6 hours; 3. Heat to a temperature of 500°C within 380 minutes; 4. Maintain the temperature at 500°C for 5 hours.

[0290] The resulting material had a TOC of less than 0.1 g / 100 g, a Zn content of 1.1 g / 100 g, a Si content of 43 g / 100 g, and a Ti content of 1.9 g / 100 g. The Lewis acidity was determined according to Reference Example 1, which gave an integrated extinction unit of the IR band of the Lewis acid site of 14.2, which gave an IR band of 1490 cm. -1 The integrated extinction units of the IR band at 100°C was determined to be 0. Furthermore, the integrated extinction units of Bronsted acid sites was observed to be 0.23, which was determined according to Reference Example 1. Additionally, the Lewis acid site density was determined by temperature-programmed desorption of ammonia according to Reference Example 5. Thus, the density of Lewis acid sites was determined via NH3-TPD to be 0.26 mmol / g at temperatures below 200°C, no Lewis acid sites were observed in the temperature range between 200 and 400°C, and a Lewis acid site density of 0.01 mmol / g was observed at temperatures above 500°C.

[0291] [Reference example 19] Forming of Ba-impregnated Ti-MWW 30 g of Ti-MWW impregnated with Ba according to Reference Example 15 and 1.92 g of methylcellulose (Walocel MW 15000 GB, Wolff Cellulosics GmbH & Co. KG, Germany) were placed in a kneader and mixed for 5 minutes. 60 mL of deionized water was then added along with 18.75 g of colloidal silica (Ludox® AS40), and the mixture was mixed for a further 10 minutes. 10 mL of deionized water was then added, and the mixture was mixed for a further 15 minutes. The total mixing time was 45 minutes.

[0292] The mixed mass was extruded at a pressure of 120 bar (abs) to obtain strands with a circular cross section of 1.7 mm in diameter. The extruded strands were then dried and calcined in air according to the following program: 1. Heat to a temperature of 120°C within 40 minutes; 2. Maintain the temperature at 120℃ for 6 hours; 3. Heat to a temperature of 500°C within 380 minutes; 4. Maintain the temperature at 500°C for 5 hours.

[0293] The resulting material had a TOC of less than 0.1 g / 100 g, a Ba content of 1.3 g / 100 g, a Si content of 43 g / 100 g, and a Ti content of 1.2 g / 100 g. The Lewis acidity was determined according to Reference Example 1, which gave an integrated extinction unit of the IR band of the Lewis acid sites of 100.7, which gave an IR band of 1490 cm at 1 mbar pressure. -1 The integrated extinction units of the IR band at 100°C was determined to be 9.77. Furthermore, no Bronsted acid sites were observed, as determined in accordance with Reference Example 1. Additionally, the Lewis acid site density was determined by temperature-programmed desorption of ammonia in accordance with Reference Example 5. Thus, the Lewis acid site density was determined via NH3-TPD to be 0.15 mmol / g at temperatures below 200°C, no Lewis acid sites were observed in the temperature range between 200 and 400°C, and a Lewis acid site density of 0.02 mmol / g was observed at temperatures above 500°C.

[0294] [Reference example 20] Forming of Ti-MWW impregnated with Ba and Zn 30 g of Ti-MWW and 1.92 g of methylcellulose (Walocel MW 15000 GB, Wolff Cellulosics GmbH & Co. KG, Germany), impregnated with Ba and Zn according to Reference Example 16, were placed in a kneader and mixed for 5 minutes. 60 mL of deionized water was then added along with 18.75 g of colloidal silica (Ludox® AS 40), and the mixture was mixed for a further 10 minutes. 10 mL of deionized water was then added, and the mixture was mixed for a further 15 minutes. The total mixing time was 45 minutes.

[0295] The mixed mass was extruded at a pressure of 120 bar (abs) to obtain strands with a circular cross section of 1.7 mm in diameter. The extruded strands were then dried and calcined in air according to the following program: 1. Heat to a temperature of 120°C within 40 minutes; 2. Maintain the temperature at 120℃ for 6 hours; 3. Heat to a temperature of 500°C within 380 minutes; 4. Maintain the temperature at 500°C for 5 hours.

[0296] The resulting material had a TOC of less than 0.1 g / 100 g, a Ba content of 1.2 g / 100 g, a Si content of 43 g / 100 g, a Ti content of 1.2 g / 100 g, and a Zn content of 0.69 g / 100 g. The Lewis acidity was determined according to Reference Example 1, whereby the integrated extinction units of the IR band of the Lewis acid sites was determined to be 108.9, whereby the IR band at 1490 cm at 1 mbar pressure -1 The integrated extinction units of the IR band at 100°C was determined to be 11.05. Furthermore, no Bronsted acid sites were observed, as determined in accordance with Reference Example 1. Additionally, the Lewis acid site density was determined by temperature-programmed desorption of ammonia in accordance with Reference Example 5. Thus, the Lewis acid site density was determined via NH3-TPD to be 0.23 mmol / g at temperatures below 200°C, no Lewis acid sites were observed in the temperature range between 200 and 400°C, and a Lewis acid site density of 0.02 mmol / g was observed at temperatures above 500°C.

[0297] [Reference example 21] Forming of Ti-MWW impregnated with Ba, Zn and La 30 g of Ti-MWW and 1.92 g of methylcellulose (Walocel MW 15000 GB, Wolff Cellulosics GmbH & Co. KG, Germany), impregnated with Ba, Zn, and La according to Reference Example 17, were placed in a kneader and mixed for 5 minutes. 60 mL of deionized water was then added along with 18.75 g of colloidal silica (Ludox® AS40), and the mixture was mixed for a further 10 minutes. 10 mL of deionized water was then added, and the mixture was mixed for a further 15 minutes. The total mixing time was 45 minutes.

[0298] The mixed mass was extruded at a pressure of 120 bar (abs) to obtain strands with a circular cross section of 1.7 mm in diameter. The extruded strands were then dried and calcined in air according to the following program: 1. Heat to a temperature of 120°C within 40 minutes; 2. Maintain the temperature at 120℃ for 6 hours; 3. Heat to a temperature of 500°C within 380 minutes; 4. Maintain the temperature at 500°C for 5 hours.

[0299] The resulting material had a TOC of less than 0.1 g / 100 g, a Ba content of 1.2 g / 100 g, a La content of 0.78 g / 100 g, a Si content of 42 g / 100 g, a Ti content of 1.2 g / 100 g, and a Zn content of 0.68 g / 100 g. The Lewis acidity was determined according to Reference Example 1, which gave an integrated extinction unit of the IR band of the Lewis acid sites of 118.3, which gave an IR band of 1490 cm at 1 mbar pressure. -1The integrated extinction units of the IR band at 100°C was determined to be 11.53. Furthermore, no Bronsted acid sites were observed, which was determined according to Reference Example 1. Additionally, the Lewis acid site density was determined by temperature-programmed desorption of ammonia according to Reference Example 5. Thus, the Lewis acid site density was determined via NH3-TPD to be 0.23 mmol / g at temperatures below 200°C, no Lewis acid sites were observed in the temperature range between 200 and 400°C, and a Lewis acid site density of 0.01 mmol / g was observed at temperatures above 500°C.

[0300] [Comparative Example 22] Zn-impregnated, molded Ti-MWW for water treatment 7 g of strands prepared according to Example 18 were mixed with 140 g of deionized water. The resulting mixture was heated in an autoclave at a temperature of 145° C. for 8 hours. The resulting water-treated strands were then separated and sieved on a 0.8 mm sieve. The resulting strands were then washed with deionized water and pre-dried in a nitrogen stream at ambient temperature. The washed and pre-dried strands were subsequently dried and calcined in air according to the following program: 1. Heat to 120°C within 60 minutes; 2. Maintain the temperature at 120℃ for 4 hours; 3. Heat to 450°C within 165 minutes; 4. Maintain the temperature at 450°C for 2 hours.

[0301] The resulting material has a BET specific surface area of ​​283 m 2 / g, TOC less than 0.1 g / 100 g, Zn content 1.9 g / 100 g, Si content 42 g / 100 g, and Ti content 1.9 g / 100 g, each determined as described hereinabove. The resulting material exhibited a water uptake of 10.2 wt.%, determined as described hereinabove. The strand crush strength, determined as described hereinabove, was 19 N, and the pore volume, determined as described hereinabove, was 1.0 mL / g. The tortuosity parameter for water was observed to be 1.6, determined according to Reference Example 12. The Lewis acidity was determined according to Reference Example 1, whereby the integrated extinction units of the IR band of the Lewis acid sites was determined to be 77.8, whereby the integrated extinction units of the IR band of the Lewis acid sites at 1490 cm at 1 mbar pressure were determined. -1 The integrated extinction units of the IR band at 100°C was determined to be 8.1. Furthermore, no Bronsted acid sites were observed, as determined in accordance with Reference Example 1. Additionally, the Lewis acid site density was determined by temperature-programmed desorption of ammonia in accordance with Reference Example 5. Thus, the Lewis acid site density was determined via NH3-TPD to be 0.24 mmol / g at temperatures below 200°C, no Lewis acid sites were observed in the temperature range between 200 and 400°C, and a Lewis acid site density of 0.05 mmol / g was observed at temperatures above 500°C.

[0302] [Example 23] Water treatment of formed Ti-MWW impregnated with Ba and Zn 21 g of strands prepared according to Example 20 were divided into four portions of 7 g each and mixed with 140 g of deionized water per portion. The resulting mixture was heated in an autoclave at a temperature of 145° C. for 8 hours. The resulting water-treated strands were then separated and sieved on a 0.8 mm sieve. The resulting strands were then washed with deionized water and pre-dried at ambient temperature in a nitrogen stream. The washed and pre-dried strands were subsequently dried and calcined in air according to the following program: 1. Heat to 120°C within 60 minutes; 2. Maintain the temperature at 120℃ for 4 hours; 3. Heat to 450°C within 165 minutes; 4. Maintain the temperature at 450°C for 2 hours.

[0303] The resulting material has a BET specific surface area of ​​284 m 2 The resulting material exhibited a TOC of less than 0.1 g / 100 g, a Ba content of 1.2 g / 100 g, a Si content of 43 g / 100 g, a Ti content of 1.2 g / 100 g, and a Zn content of 0.7 g / 100 g, each determined as described herein above. The resulting material exhibited a water uptake of 10.4 wt.%, determined as described in Reference Example 7. The resulting material exhibited an acid site concentration of 0.25 at temperatures below 200°C, an acid site concentration of 0 at temperatures between 200 and 400°C, and an acid site concentration of 0.05 at temperatures above 500°C, determined by temperature-programmed desorption of ammonia (NH3-TPD) as described in Reference Example 5. The strand crush strength, determined as described herein above, was 9 N, and the pore volume, determined as described herein above, was 1.5 mL / g. The tortuosity parameter for water was observed to be 2.0, determined as described in Reference Example 12. The Lewis acidity was determined according to Reference Example 1, and the integrated extinction unit of the IR band of the Lewis acid site was determined to be 78.5, which gave the IR band at 1490 cm at a pressure of 1 mbar. -1 The integrated extinction units of the IR band at 100°C was determined to be 6.8. Furthermore, no Bronsted acid sites were observed, as determined in accordance with Reference Example 1. Additionally, the Lewis acid site density was determined by temperature-programmed desorption of ammonia in accordance with Reference Example 5. Thus, the Lewis acid site density was determined via NH3-TPD to be 0.25 mmol / g at temperatures below 200°C, no Lewis acid sites were observed in the temperature range between 200 and 400°C, and a Lewis acid site density of 0.05 mmol / g was observed at temperatures above 500°C.

[0304] [Example 24] Water treatment of formed Ti-MWW impregnated with Ba, Zn and La 21 g of strands prepared according to Example 21 were divided into four portions of 7 g each and mixed with 140 g of deionized water per portion. The resulting mixture was heated in an autoclave at a temperature of 145° C. for 8 hours. The resulting water-treated strands were then separated and sieved on a 0.8 mm sieve. The resulting strands were then washed with deionized water and pre-dried at ambient temperature in a nitrogen stream. The washed and pre-dried strands were subsequently dried and calcined in air according to the following program: 1. Heat to 120°C within 60 minutes; 2. Maintain the temperature at 120℃ for 4 hours; 3. Heat to 450°C within 165 minutes; 4. Maintain the temperature at 450°C for 2 hours.

[0305] The resulting material had a TOC of less than 0.1 g / 100 g, a Ba content of 1.2 g / 100 g, a La content of 0.75 g / 100 g, a Si content of 42 g / 100 g, a Ti content of 1.1 g / 100 g, and a Zn content of 0.68 g / 100 g, each determined as described hereinabove. The resulting material had a BET specific surface area of ​​334 m 2 / g. The pore volume, determined as described herein above, was 1.7 mL / g. The tortuosity parameter for water was observed to be 2.0, as determined in accordance with Reference Example 12. The resulting material exhibited a water uptake of 11.5 wt. %, as determined in accordance with Reference Example 7. The Lewis acidity was determined in accordance with Reference Example 1, whereby the integrated extinction units of the IR band of the Lewis acid sites was determined to be 9.95, whereby the IR band at 1490 cm at 1 mbar pressure was -1 The integrated extinction units of the IR band at 100°C was determined to be 1.6. Furthermore, no Bronsted acid sites were observed, as determined in accordance with Reference Example 1. Additionally, the Lewis acid site density was determined by temperature-programmed desorption of ammonia in accordance with Reference Example 5. Thus, the Lewis acid site density was determined via NH3-TPD to be 0.19 mmol / g at temperatures below 200°C, no Lewis acid sites were observed in the temperature range between 200 and 400°C, and a Lewis acid site density of 0.02 mmol / g was observed at temperatures above 500°C.

[0306] [Example 25] Catalyst Testing Example 25.1 Preliminary Exam - PO Exam The example molded bodies were preliminarily tested for their general suitability as epoxidation catalysts according to the PO test described in Reference Example 8. The respective resulting values ​​of propylene oxide activity are shown in Table 2 below.

[0307] [Table 2]

[0308] Clearly, the molded body according to Comparative Example 22 shows very good propylene oxide activity according to the PO test. Therefore, it can be expected that the molded body according to the present invention is also a promising candidate for catalyst in industrial continuous epoxidation reaction.

[0309] Example 25.2 Continuous epoxidation of propylene a) Results for Comparative Example 22 shown in Figure 1 Conversion was observed to be approximately 99% for the first 200 hours of test time, then dropped to approximately 95% around 400 hours, then increased again to approximately 99%, before dropping to approximately 86% within approximately 1500 hours. After reaching a maximum conversion of approximately 98% for approximately 50 hours, conversion then dropped to less than 84% after 2000 hours. Propylene oxide selectivity based on H2O2 ranged from approximately 97 to approximately 99% over the entire run. Propylene oxide selectivity based on propene (C3) ranged from approximately 99% to nearly 100% over the entire run. Temperature ranged from approximately 32 to approximately 37°C over the entire run.

[0310] b) Results for Reference Example 20 shown in Figure 2 The total run time was approximately 500 hours. Conversion was observed to range from approximately 87 to 96%, reaching a maximum after approximately 320 hours and a minimum after approximately 50 and 360 hours. Propylene oxide selectivity based on H2O2 ranged from approximately 97 to approximately 98% over the entire run time. Propylene oxide selectivity based on propene (C3) ranged from approximately 97 to approximately 99% over the entire run time. The temperature increased from approximately 35 to approximately 44°C over the entire run time.

[0311] c) Results for Example 23 shown in Figure 3 The total run time was about 900 hours. The conversion was observed to be at least 92% over the entire run time, with the conversion being about 99% for the first about 250 hours, then slowly decreasing to a minimum of 92% before increasing again. The propylene oxide selectivity based on H2O2 was about 99% over the entire run time. The propylene oxide selectivity based on propene (C3) ranged from about 99% to nearly 100% over the entire run time. The temperature was about 35°C over the entire run time.

[0312] In summary, for the continuous epoxidation reaction of propene, the shaped bodies of the invention are particularly suitable for industrial-scale processes, and are therefore of interest for commercial purposes, since it has been convincingly shown that the shaped bodies of the invention according to Example 23 are ideal catalysts, allowing excellent selectivity for propylene oxide, in particular for propylene oxide based on propene, at continuously high conversions of at least 92%.

[0313] In particular, when compared with a molded body representative of the prior art according to Reference Example 20 as discussed hereinabove in item b), it is shown that the molded body of the present invention exhibited a conversion of at least 92%, whereas the conversion observed for Reference Example 20 was in the range of about 87-96%. Of course, higher temperatures were required to achieve said results. Furthermore, the selectivity based on H2O2 and on propene was higher for the molded body of the present invention over the entire operating time.

[0314] Similarly, the molded body according to Example 23 showed improved conversion at a high level of about 99% within the first about 250 hours of testing, whereas the molded body according to Comparative Example 22 showed a decreasing conversion, particularly within 200-250 hours of operation, as discussed in section a) herein above. [Brief explanation of the drawings]

[0315] [Figure 1] The results of the continuous epoxidation reaction according to Reference Example 9 for the molded body of Comparative Example 22 are shown in terms of the conversion of the valuable product propylene oxide and hydrogen peroxide. The propylene oxide selectivity based on HO (S(PO)HO) (%) (middle gray line) is defined as the moles of propylene oxide formed per unit of time divided by the moles of HO consumed per unit of time × 100. The propylene oxide selectivity based on propylene (S(PO)C) (%) (light gray line) is defined as the moles of propylene oxide formed per unit of time divided by the moles of propylene consumed per unit of time × 100. The HO conversion rate C (%) (left vertical axis) is defined as the moles of HO consumed per unit of time divided by the moles of HO fed to the reactor per unit of time × 100. The inlet temperature T (°C) (right vertical axis) is the inlet temperature of the heat transfer medium. The time t (unit: hours) for the flow is given on the abscissa. The starting point (t=0) is the time point when the H2O2 metering pump is started (all other pumps have been started before). [Figure 2]The results of the continuous epoxidation reaction according to Example 9 for the molded body of Example 20 are shown in terms of the conversion rates of the valuable products propylene oxide and hydrogen peroxide. The propylene oxide selectivity based on HO (S(PO)HO) (%) (middle gray line) is defined as the moles of propylene oxide formed per unit time divided by the moles of HO consumed per unit time × 100. The propylene oxide selectivity based on propylene (S(PO)C) (%) (light gray line) is defined as the moles of propylene oxide formed per unit time divided by the moles of propylene consumed per unit time × 100. The HO conversion rate C (%) (left vertical axis) is defined as the moles of HO consumed per unit time divided by the moles of HO fed to the reactor per unit time × 100. The inlet temperature T (units: °C) (right ordinate) is the inlet temperature of the heat transfer medium. The time (units: hours) for the flow t is given on the abscissa. The starting point (t=0) is the time point when the H2O2 metering pump is started (all other pumps have been started previously). [Figure 3]The results of the continuous epoxidation reaction according to Reference Example 9 for the molded body of Example 23 are shown in terms of the conversion rates of the valuable products propylene oxide and hydrogen peroxide. The propylene oxide selectivity based on HO (S(PO)HO) (units: %) (middle gray line) is defined as the moles of propylene oxide formed per unit time divided by the moles of HO consumed per unit time × 100. The propylene oxide selectivity based on propylene (S(PO)C) (units: %) (light gray line) is defined as the moles of propylene oxide formed per unit time divided by the moles of propylene consumed per unit time × 100. The HO conversion rate C (units: %) (left vertical axis) is defined as the moles of HO consumed per unit time divided by the moles of HO fed to the reactor per unit time × 100. The inlet temperature T (unit: °C) (right vertical axis) is the inlet temperature of the heat transfer medium. The time t (unit: hours) for the flow is given on the abscissa. The starting point (t=0) is the time point when the H2O2 metering pump is started (all other pumps have been started before). References - CN 105854933 A - CN 106115732 A - Y. Yu et al. "Insights into the efficiency of hydrogen peroxide utilization over titanosilicate / H2O2 systems" in Journal of Catalysis 2020, vol. 381, pp. 96-107

Claims

1. A shaped body comprising a zeolite material having an MWW-type framework and a framework structure containing Ti, Si, and O, wherein the zeolite material further contains Zn and an alkaline earth metal M, and the shaped body further contains a binder; the binder comprises Si and O; The molded product had a viscosity of 1490 cm when determined as described in Reference Example 1. －１ the integrated extinction units in the IR band are in the range of 0.1 to 7.5, the molded article has an integrated extinction unit of the Lewis acid IR band in the range of 1 to 100, as determined as described in Reference Example 1; the molded article has an integrated extinction unit of the Bronsted acid IR band of 1 or less, when determined as described in Reference Example 1; The alkaline earth metal M is contained in an amount in the range of 0.5 to 5 mass% relative to the total mass of the molded body, calculated as the element, the alkaline earth metal M is one or more of Mg, Ca, and Ba; The molded body exhibits a water uptake in the range of 6 to 15% by weight, the water uptake being determined as described in Reference Example 7.

2. The molded body according to claim 1, containing Si in an amount in the range of 20 to 60 mass% based on the total mass of the molded body, calculated as an element.

3. 3. The molded body according to claim 1, which contains Ti in an amount in the range of 0.1 to 5 mass % when calculated as an element.

4. The molded body according to any one of claims 1 to 3, containing Zn in an amount in the range of 0.1 to 5 mass% relative to the total mass of the molded body, calculated as the element.

5. A molded body described in any one of claims 1 to 4, wherein the alkaline earth metal M includes Ba.

6. 6. The molded body according to claim 1, wherein the zeolitic material further comprises a rare earth metal.

7. A molded body described in any one of claims 1 to 6, wherein the torsion parameter for water, when determined as described in Reference Example 12, is in the range of 1.0 to 5.

0.

8. 8. The molded body according to claim 1, wherein the molded body has a total pore volume in the range of 0.5 to 3.0 mL / g, the pore volume being determined according to DIN 66133.

9. The molded body contains acidic sites at a concentration of 0.05 to 1.00 mmol / g at a temperature lower than 200°C, and / or the molded body contains acidic sites at a concentration of 0.001 to 0.5 mmol / g at a temperature higher than 500°C, and the concentration of the acidic sites is higher than that of the temperature-programmed desorption of ammonia (NH ３ The molded body according to any one of claims 1 to 8, wherein the tensile strength is determined by a tensile strength (TpD) of 1000 ppm or less.

10. 10. A method for producing a shaped body according to any one of claims 1 to 9, comprising a zeolitic material having an MWW-type framework and a binder material, comprising: (i) providing a shaped body comprising a zeolitic material having an MWW-type framework and a framework structure comprising Ti, Si and O, wherein the zeolitic material further comprises Zn, an alkaline earth metal M, and optionally a rare earth metal, the zeolitic material comprising the alkaline earth metal M in an amount, calculated as the element, in the range of 0.5 to 5 mass % relative to the total mass of the shaped body, the alkaline earth metal M being one or more of Mg, Ca and Ba, and the shaped body further comprising a binder for the zeolitic material; (ii) preparing a mixture comprising the precursor shaped body according to (i) and water, subjecting the mixture to a water treatment under hydrothermal conditions to obtain a water-treated shaped body, and calcining the water-treated shaped body in a gas atmosphere, wherein the water treatment according to (ii) comprises a temperature of the mixture in the range of 100 to 200°C, the water treatment according to (ii) is carried out under autogenous pressure, and the water treatment according to (ii) is carried out for 6 to 10 hours. Including, (i) is (i.1) providing a zeolitic material having a framework structure with an MWW-type framework and comprising Ti, Si, and O; (i.2) providing an aqueous solution of a Zn source; (i.3) providing an aqueous solution of a source of alkaline earth metal M; (i.4) optionally providing an aqueous solution of a rare earth metal source; (i.5) impregnating the zeolitic material provided by (i.1) with the aqueous solution provided by (i.2), the aqueous solution provided by (i.3), and optionally the aqueous solution provided by (i.4) to obtain an impregnated zeolitic material; (i.6) preparing a mixture comprising the impregnated zeolitic material obtained from (i.5) and a binder precursor, (i.7) Molding the mixture obtained from (i.6) Including, The binder precursor is selected from the group consisting of silica sol, colloidal silica, wet-process silica, dry-process silica, and mixtures of two or more thereof; method.

11. A shaped body comprising a zeolitic material with an MWW-type framework and a binder material, obtained by the method of claim 10.

12. 12. Use of the shaped body according to any one of claims 1 to 9 or claim 11 as an adsorbent, absorbent, catalyst or catalyst component.

13. A method for oxidizing an organic compound, comprising contacting an organic compound having at least one C-C double bond with a catalyst comprising the molded body of any one of claims 1 to 9 or claim 11.

14. 12. A method for producing propylene oxide, comprising reacting propene with hydrogen peroxide in an acetonitrile solution in the presence of a catalyst comprising the shaped body of any one of claims 1 to 9 or claim 11 to obtain propylene oxide.

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