JP6461807B2 - Use of zeolitic materials in methods for producing zeolitic materials and in converting oxygen-containing materials to olefins - Google Patents

Description

The present invention, MFI, relates zeolitic material having MEL and / or M WW-type skeletal structure. Furthermore, the present invention is, MFI, relates zeolitic material itself having a MEL and / or M WW-type skeletal structure, and to the use of the zeolite materials in the conversion process of an oxygen-containing material to olefins. Finally, the present invention, when MFI, relates to the use of a zeolite material having MEL and / or M WW-type skeletal structure (hereinafter, referred to as zeolitic material having NWW- type skeletal structure herein, MWW- type backbone A zeolite having a structure) .

  Considering that the reserves of petroleum, the raw material for the production of short-chain hydrocarbons and their derivatives, are decreasing, the importance of alternative methods for producing such basic chemicals has increased. ing. An alternative method for the production of such short chain hydrocarbons and their derivatives is to convert other raw materials and / or chemicals into hydrocarbons and their derivatives (especially short chain hydrocarbons), where there are very specialized catalysts. Is used. A notable attempt in such a process is not only the optimal selection of reaction parameters, but also a special one that allows a very efficient and selective conversion to the desired hydrocarbon or derivative (eg in particular an olefin fraction). A catalyst is used. From this point of view, the process using methanol as a starting material is particularly important, and its catalytic conversion usually gives a mixture of hydrocarbons and their derivatives (especially olefins, paraffins and aromatics).

  Thus, a notable attempt in such catalytic conversion is to optimize and fine-tune the catalyst used and the architecture and parameters of the process so that high selectivity to as little product as possible is obtained. There is. For this reason, such methods are often named after products for which a particularly high selectivity has been achieved in the method. Thus, the process that has been performed over the past decade for the conversion of oxygen-containing materials to olefins, particularly the conversion of methanol to olefins, which has gained importance from the standpoint of reducing petroleum reserves, is methanol-to-olefins. -Methanol-to-olefin-processes (MTO-processes for methanol to olefins).

  Of the catalyst materials found for use in such conversions, zeolitic materials have proven to be highly efficient, especially the pentasil type, more particularly the MFI-MFL-intergrowth type. Zeolite having MFI- and MFL-type framework structures including zeolites exhibiting framework structures are used. Regarding the specific use of zeolitic materials, especially the pentasil type, and more particularly the method of converting oxygen-containing substances to olefins such as the MTO-method discussed above, EP 2460784 A1 (patent document 1) is a long term in the production process. A technique relating to a process for producing propylene from an oxygen-containing compound using a catalyst capable of maintaining the stable activity of the above is described. DD 238733 A1 (Patent Document 2) describes a technique relating to a synthesis procedure for the production of a selective olefin catalyst. McIntosh et al. In Applied Catalysis 1983, vol. 6, pp. 307-314 (Non-Patent Document 1) describes magnesium and olefin-rich products for conversion from methanol to olefin-rich products. Techniques relating to the properties of zinc oxide treated ZSM-5 catalysts are described. Similarly, Cyanberry et al., “Catalytic acid-base catalyst in the conversion of methanol to olefins over Mg-modified ZSM-5 zeolites”, Successful Design of Catalysis (Ciambelli et al. In “Acid-Base Catalysis In the Conversion of Methanol to Olefins over Mg-Modified ZSM-5 Zeolite ”, Successful Design of Catalysts, edited by T. Inui, Elsevier Science Publishers BV, Amsterdam 1988) (Non-Patent Document 2), Studies have been made on the effect of magnesium in 5 catalysts, in particular its acid-base nature and its effect on olefin selectivity in the MTO process.

  In order to further improve such catalysts, methods of further treatment with specific compounds have been investigated, particularly methods of loading different compounds into typical ones of these microporous systems of zeolitic materials. Therefore, Okada et al., Applied Catalysis 1988, vol. 41, pp. 121-135 (Non-Patent Document 3) shows resistance of ZSM-5 type zeolite containing alkaline earth metal. Techniques relating to deactivation and its use for conversion to methanol are described. Similarly, Goriainova et al., Goryainova et al. In Petroleum Chemistry 2011, vol. 51, pp. 169-173 (Non-Patent Document 4) contain magnesium for the synthesis of lower olefins from dimethyl ether. Zeolite catalysts are described. On the other hand, U.S. Pat. No. 4,049,573 (Patent Document 3) relates to a zeolite catalyst containing an oxide of boron or magnesium.

  On the other hand, with respect to the synthesis of general zeolitic materials, efforts are being made to optimize economically and for increasing environmental reasons. In this regard, the ion exchange procedure normally required to obtain the so-called H-form by crystallization of aluminum silicate in the absence of an alkali source can be omitted. In the ion exchange procedure, the alkali metal present in the material obtained as a non-skeleton element is exchanged for protons. Ion exchange requires an additional step in the manufacturing process that significantly reduces the space-time yield of the zeolite, creating a large volume of wastewater, thereby increasing the overall manufacturing cost. Therefore, an alkali-free synthesis method is extremely beneficial because it simplifies the synthesis method to fewer steps and is therefore more economical and industrially feasible. Such a production method can also reduce the amount of waste liquid during catalyst production.

  For this reason, Liu et al., Chemistry Letters (Liu et al. In Chemistry Letters 2007, vol. 36, pp. 916 and 917) (Non-Patent Document 5), NWW-type metallosilicate production is carried out under conditions that do not contain alkali. Techniques relating to synthesis procedures for are described. Micro-porous and Mesoporous Materials (De Baerdemaeker et al. In Microporous and Mesoporous Materials 2011, vol. 143, pp. 477-481) (Non-patent Document 6) does not contain alkalis and fluorine. Techniques relating to the synthesis of MTW-type zeolites that are carried out in a synthesis procedure that does not contain any are described. Takeguchi et al., Journal of Catalysis 1998, vol. 175, pp. 1-6 (Non-Patent Document 7) describes an alkali-free Ga-substituted MCM-41 catalyst. Has been. Ahedi et al., Journal of Materials Chemistry (Ahedi et al. In Journal of Materials Chemistry 1998, vol. 8, pp. 1685-1686) (Non-Patent Document 8) does not contain non-aqueous alkali. Techniques for the synthesis of FER titanosilicates from the system are described. Dodwell et al., Zeolite (Dodwell et al. In Zeolites 1985, vol. 5, pp. 153-157) (Non-Patent Document 9) includes EU-1 and EU-2 in an alkaline system and an alkali-free system. Techniques relating to crystallization are described. On the other hand, Shibata et al., Applied Catalysis A (General 1997, vol. 162, pp. 93-102) (Non-Patent Document 10) synthesizes an MFI borosilicate containing no alkali. The route is described.

  Furthermore, it is known that the formation of the zeolite catalyst obtained in an alkali-free process is adjusted by adjusting the temperature, the stirring speed, the concentration of the synthesis mixture and the duration of crystallization, especially with respect to the diameter. This may be important to adjust the dispersibility for a particular catalyst application and to optimize the shape and properties of the resulting molded body. In particular, suitable shaped bodies often need to be prepared prior to introducing the catalyst into the reactor for catalytic conversion.

  In this regard, DE 10356184A1 (Patent Document 4) discloses a pentasil-type zeolite material having a molar ratio of Si to Al of 250 to 1500, and at least 90% of the primary particles of the zeolite material are spherical, Techniques relating to zeolitic materials where 95% by weight have a diameter of 1 μm or less are described. Further, this document discloses a technique for performing a specific treatment of ZSM-5 powder with demineralized water under self-generated pressure, and when used in the synthesis of tetraethylenediamine from piperazine and ethylenediamine, It is taught that both selectivity will be improved by water treatment of ZSM-5 powder under hydrothermal conditions. On the other hand, DE41131448A1 (Patent Document 5) describes a technique related to a boron silicate having a zeolite structure and having a size of 2 to 150 μm and substantially not containing alkali.

  Reading, et al., Reding et al. In Microporous and Mesoporous Materials 2003, vol. 57, pp. 83-92 (Non-Patent Document 11) uses nano-crystalline zeolite ZSM-5. We are studying synthetic procedures to obtain. Similarly, Van Gleeken et al., Van Grieken in Microporous and Mesoporous Materials 2000, vol. 39, pp. 135-147 (Non-patent Document 12) is a nano-crystalline zeolite. We are studying the crystallization mechanism in the synthesis of ZSM-5. On the other hand, Rivas-Cardona et al. (Rivas-Cardona in Microporous and Mesoporous Materials 2012, vol. 155, pp. 56-64,) (Non-Patent Document 13) has a degree of dilution. Different silicate-1 precursor mixtures are being studied.

  On the one hand, despite the considerable efforts in the prior art relating to the synthesis of new zeolitic materials by using a new and improved synthesis procedure and on the other hand to its various applications, especially in the catalytic field, New that exhibits further improved properties, especially in the ever-increasing number of applications in which zeolitic materials are used, especially in the ever-increasing number of applications used in critical areas of catalytic processes Demand for new zeolitic materials

EP2460784A1 DD238733A1 US4049573 DE10356184A1 DE41131448A1

Applied catalysis such as Macintosh (McIntosh et al. In Applied Catalysis 1983, vol. 6, pp. 307-314) Cyanberry et al., “Catalytic acid-base catalyst in the conversion of methanol to olefins over Mg-modified ZSM-5 zeolite”, Successful Design of Catalysts (Ciambelli et al. In “Acid-Base Catalysis in the Conversion of Methanol to Olefins over Mg-Modified ZSM-5 Zeolite ”, Successful Design of Catalysts, edited by T. Inui, Elsevier Science Publishers BV, Amsterdam 1988) Okada et al., Applied Catalysis 1988, vol. 41, pp. 121-135 Goliainova et al., Petroleum Chemistry (Goryainova et al. In Petroleum Chemistry 2011, vol. 51, pp. 169-173) Liu et al., Chemistry Letters (Liu et al. In Chemistry Letters 2007, vol. 36, pp. 916 and 917) Bear maker, etc., microporous and mesoporous materials (De Baerdemaeker et al. In Microporous and Mesoporous Materials 2011, vol. 143, pp. 477-481) Takeguchi et al., Journal of Catalysis 1998, vol. 175, pp. 1-6 Ahedi et al. In Journal of Materials Chemistry 1998, vol. 8, pp. 1685-1686 Dodwell et al., Zeolite (Dodwell et al. In Zeolites 1985, vol. 5, pp. 153-157) Shibata et al., Applied Catalysis A: General 1997, vol. 162, pp. 93-102 Redding et al., Microporous and Mesoporous Materials (Reding et al. In Microporous and Mesoporous Materials 2003, vol. 57, pp. 83-92) Van Grieken in Microporous and Mesoporous Materials 2000, vol. 39, pp. 135-147 Rivas Cardona in Microporous and Mesoporous Materials 2012, vol. 155, pp. 56-64

  Accordingly, it is an object of the present invention to provide an improved zeolitic material which is used in particular for its specific catalytic applications, in particular for the conversion of oxygen-containing substances to olefins. Furthermore, the object of the present invention provides an improved process for the conversion of oxygen-containing materials to olefins.

  In particular, it has been found that an unexpected synergistic effect is achieved by using a specific zeolitic material having specific characteristics for the particle size distribution of the primary particles, together with one or more alkaline earth metal elements. This is quite amazing. In this regard, certain zeolitic materials, such as those obtained from alkali-free synthesis procedures, show technical effects when used with one or more alkaline earth metal elements, particularly from the aforementioned zeolitic materials, themselves. It was completely unexpected to clearly show a strong synergy that could not be expected from the technical characteristics, especially the chemical properties, which is a possible feature. More specifically, such a zeolitic material of the present invention is used in a catalyst application, particularly in a process for the conversion of an oxygen-containing material to an olefin, and the life of the catalyst when used in such an application. It is quite surprising to have brought a considerable improvement over time).

Accordingly, the present invention is a method for producing a zeolitic material having MFI, MEL and / or NWW-type framework structure containing YO ₂ and X ₂ O ₃ ,
(1) Step of preparing a mixture containing one or more YO ₂ sources, one or more X ₂ O ₃ sources, and one or more solvents (2) Crystallizing the mixture obtained in step (1) A step of obtaining a zeolite material having a MEL and / or NWW-type framework structure, and (3) impregnating the zeolite material obtained in step (2) with one or more elements selected from alkaline earth metals Including steps, and
Y is a tetravalent element, X is a trivalent element, and the mixture crystallized in step (2) is one or more elements of 3% by mass or less with respect to 100% by mass of YO ₂ The present invention relates to a production method comprising M (M represents sodium).

1A shows an X-ray diffraction pattern (measured using CuKα-1 line) of the crystalline material obtained in Reference Example 1. FIG. In the figure, the angle 2θ in ° is shown on the horizontal axis, and the intensity of the count is plotted along the vertical axis. FIG. 1B shows a scanning electron micrograph (SEM) of the ZSM-5 powder obtained in Reference Example 1. In the figure, the magnification is 75000: 1 and is shown in the lower left corner of the image. In the lower right corner of the SEM micrograph, the unit is shown as a grid of sub-units with a unit length of 0.1 μm corresponding to 0.5 μm. FIG. 1C shows the IR spectrum of the crystalline material obtained in Reference Example 1. In the figure, the wave number in cm ⁻¹ is plotted along the horizontal axis and the absorbance in arbitrary units is plotted along the vertical axis. FIG. 2A shows an X-ray diffraction pattern (measured using a CuKα-1 line) of the crystalline material obtained in Reference Example 2. In the figure, the angle 2θ in ° is shown on the horizontal axis, and the intensity of the count is plotted along the vertical axis. FIG. 2B shows a scanning electron micrograph (SEM) of the ZSM-5 powder obtained in Reference Example 2. In the figure, the magnification is 75000: 1 and is shown in the lower left corner of the image. In the lower right corner of the SEM micrograph, the unit is shown as a grid of sub-units with a unit length of 0.1 μm corresponding to 0.5 μm. FIG. 2C shows an IR spectrum of the crystalline material obtained in Reference Example 2. In the figure, the wave number in cm ⁻¹ is plotted along the horizontal axis and the absorbance in arbitrary units is plotted along the vertical axis. FIG. 3A shows an X-ray diffraction pattern (measured using a CuKα-1 line) of the crystalline material obtained in Reference Example 3. In the figure, the angle 2θ in ° is shown on the horizontal axis, and the intensity of the count is plotted along the vertical axis. FIG. 3B shows a scanning electron micrograph (SEM) of the ZSM-5 powder obtained in Reference Example 3. In the figure, the magnification is 75000: 1 and is shown in the lower left corner of the image. In the lower right corner of the SEM micrograph, the unit is shown as a grid of sub-units with a unit length of 0.1 μm corresponding to 0.5 μm. FIG. 4A shows an X-ray diffraction pattern (measured using CuKα-1 line) of the crystalline material obtained in Reference Example 4. In the figure, the angle 2θ in ° is shown on the horizontal axis, and the intensity of the count is plotted along the vertical axis. FIG. 4B shows a scanning electron micrograph (SEM) of the ZSM-5 powder obtained in Reference Example 4. In the figure, the magnification is 75000: 1 and is shown in the lower left corner of the image. In the lower right corner of the SEM micrograph, the unit is shown as a grid of sub-units with a unit length of 0.1 μm corresponding to 0.5 μm. FIG. 4C shows an IR spectrum of the crystalline material obtained in Reference Example 4. In the figure, the wave number in cm ⁻¹ is plotted along the horizontal axis and the absorbance in arbitrary units is plotted along the vertical axis.

According to the method of the present invention, one or more YO ₂ sources are supplied in step (1). In general, in step (2), one or more sources (source materials) provided that the zeolitic material having MFI, MEL and / or NWW-type framework structure containing YO ₂ can be crystallized. Can be provided in a conceivable form. Preferably, YO ₂ is provided by itself and / or as a chemical component and / or as a compound that is chemically (partially or fully) converted to YO ₂ during the performance of the method of the invention. Is done.

Zeolite material having MFI, MEL and / or NWW-type framework structure whose element is tetravalent and crystallized in step (2) with respect to YO ₂ and / or its precursor used in the method of the present invention As long as the condition that it is contained in is satisfied, there is no limitation on one or more elements represented by Y. In particular, within the meaning of the present invention, YO ₂ is at least partially, preferably completely, included as a structural component in the MFI, MEL and / or NWW-type framework structure of the zeolitic material. This is in contrast to the non-skeletal elements present in the pores and cavities (holes) that are typical of zeolitic materials in general. Therefore, considering the above, Y may be any of the possible tetravalent elements, and Y represents one or more elements. Preferred tetravalent elements of the present invention include Si, Sn, Ti, Zr, Ge, and mixtures thereof. According to a preferred embodiment of the present invention, Y is Si.

  Thus, in a preferred embodiment of the invention, Y is selected from Si, Sn, Ti, Zr, Ge, and mixtures thereof, preferably Si.

In a preferred embodiment of the invention, Y represents Si or a combination of Si and one or more other tetravalent elements, and the SiO ₂ source preferably used in step (1) is any conceivable It can be a source. For example, silica and / or silica derivatives can be used, preferably the one or more YO ₂ sources are fumed silica, silica hydrosol, reactive amorphous solid silica, silica gel, silicic acid, water glass, sesquisilicate. , One or more compounds selected from disilicate, colloidal silica, calcined silica, silicate esters, or mixtures of two or more of these compounds may be used as well. Alternatively, elemental silicon can be used in addition to one or more of the aforementioned SiO ₂ sources. According to a particularly preferred embodiment, the one or more YO ₂ sources used in step (1) of the present invention are fumed silica, reactive amorphous solid, reactive amorphous solid silica, silica gel, colloidal silica, calcined silica, Also included are mixtures of two or more of these compounds selected from tetraalkoxysilanes. In accordance with the above particularly preferred embodiment, the one or more YO ₂ sources are further selected from fumed silica, reactive amorphous solid silica, silica gel, calcined silica, tetraalkoxysilane, and mixtures of two or more of these compounds. Preferably, the one or more YO ₂ sources are preferably selected from fumed silica, tetraalkoxysilane, or a mixture of two or more of these compounds, on which one or more YO ₂ sources are It preferably contains one or more tetraalkoxysilanes.

With respect to the silicate esters that can be used in particularly and preferred embodiments of the present invention, it is preferred that the one or more esters have the following composition:

Si (OR) _4-x (OR ') _x

In the above formula,
x is 0, 1, 2, 3 or 4 and may be used as SiO ₂ , R and R ′ may be different from each other, each of C ₁ -C ₈ alkyl, eg methyl, ethyl , n- propyl, isopropyl, n- butyl, isobutyl, tert- butyl, pentyl, hexyl, heptyl or _octyl; C 4 -C ₈ cycloalkyl, e.g., cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl; aryl, alkyl May be aryl or arylalkyl, or R and R ′ may be the same, each of hydrogen, C ₁ -C ₈ alkyl, eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, tert-butyl, pentyl, hexyl, heptyl or octyl; C ₄ -C ₈ cycloalkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl or octyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl; aryl, alkyl or It may be aryl.

According to a preferred embodiment of the method of the present invention, the one or more YO ₂ sources, in particular the SiO ₂ source, comprise compounds of the following general composition:

Si (OR) ₄

Or

Si (OR) ₃ (OR ')

In the above formula,
R ′ is hydrogen and R is C ₁ -C ₈ alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl or octyl.

According to a particularly preferred embodiment in which the one or more YO ₂ sources, in particular the SiO ₂ source, is one or more tetraalkoxysilanes, the one or more sources contain the following general composition with one or more compounds: More preferably it contains:

Si (OR) ₄

In the above formula,
R is _C 1 -C ₈ alkyl, e.g., methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, tert- butyl, pentyl, hexyl, heptyl or octyl, more preferably methyl, ethyl, n- Propyl, isopropyl, n-butyl, isobutyl or tert-butyl, more preferably methyl, ethyl, n-propyl or isopropyl, more preferably methyl or ethyl, particularly preferably ethyl.

According to the invention, the mixture provided in step (1) further comprises one or more X ₂ O ₃ (X is a tetravalent element). Regarding the element that can be used as the tetravalent element X contained in one or more kinds of X ₂ O ₃ provided in the step (1), MFI, MEL, and / or NWW- containing YO ₂ and X ₂ O ₃ as skeleton elements Any element or element mixture may be used as long as the condition that the zeolitic material having a type skeleton structure can be obtained by crystallization in the step (2) is not particularly limited. According to a preferred embodiment of the present invention, X is selected from Al, B, In, Ga and mixtures of two or more thereof, preferably X is Al and / or B. According to a particularly preferred embodiment of the invention, X comprises Al, more preferably X is Al. X ₂ O ₃ contained in a zeolitic material having an MFI, MEL and / or NWW-type framework structure is within the scope of the present invention, and X ₂ O ₃ is also at least partly, preferably completely zeolitic material Are included as structural constituent elements that are the opposite of non-skeletal elements that can be present in the pores and cavities that are formed of the skeletal structure and that are typically typical of zeolitic materials.

  For this reason, X is selected from Al, B, In, Ga and a mixture of two or more thereof, and the aspect of the present invention is preferably such that X is Al and / or Ga, more preferably Al.

According to a particularly preferred embodiment of the present invention, X represents Al or Al and one or more other trivalent elements, and an Al ₂ O ₃ source preferably provided in step (1) is a possible source. You can also. In general, possible sources that enable the production of zeolitic materials according to the present invention can be used as the aluminum source. Thus, for example, the one or more aluminum sources can include one or more compounds selected from aluminum, aluminum alkoxides, alumina, aluminates, and aluminum salts. In the method of the present invention, it is particularly preferable to use aluminum nitrate, aluminum sulfate or trialkoxy aluminate of the composition Al (OR) ₃ or a mixture of two or more of these compounds as the aluminum source. With respect to the trialkoxyaluminate of the composition Al (OR) ₃ , R may be the same or different from each other and may be C ₁ -C ₈ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl. , tert- butyl, pentyl, hexyl, heptyl or _octyl; C 4 -C ₈ cycloalkyl, e.g., cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl; aryl, alkylaryl or arylalkyl. According to a particularly preferred embodiment of the invention, the aluminum source used is aluminum sulfate. With regard to the aluminum salts preferably used, they can be used in their dehydrated form and / or one or more hydrates or hydrated forms thereof.

One or more YO ₂ sources and X ₂ O ₃ sources may be MFI, MEL and / or NWW-type comprising YO ₂ and X ₂ O ₃ with respect to their amount provided in step (1) of the method of the invention. There is no limitation as long as the condition that the zeolitic material having a framework structure can be obtained by crystallization in the step (2) is satisfied. The same is true for the relative ratio of the YO ₂ source and the X ₂ O ₃ source. These YO ₂ and X ₂ O ₃ sources are generally calculated for the mixture produced in step (1) based on the respective amounts of one or more YO ₂ and X ₂ O ₃ sources. It can be used for the production of the mixture in step (1) so as not to be particularly limited with respect to YO ₂ : X ₂ O ₃ . Thus, for example, with respect to the amount of one or more YO ₂ sources provided in the mixture of step (1), the YO ₂ : X ₂ O ₃ molar ratio of the mixture is in the range of 10 to 1500, and the preferred molar ratio is It is in the range of 30 to 1200, more preferably in the range of 50 to 900, more preferably in the range of 70 to 700, more preferably in the range of 80 to 500, and particularly preferably in the range of 90 to 300. In a particularly preferred embodiment, the mixture provided in step (1) has a YO ₂ : X ₂ O ₃ molar ratio in the range of 100-250.

Therefore, as an embodiment of the method of the present invention, the YO ₂ : X ₂ O ₃ molar ratio of the mixture produced by the mixture of step (1) is in the range of 10 to 1500, preferably in the range of 30 to 1200, more preferably. Is in the range of 70 to 700, more preferably in the range of 80 to 500, more preferably in the range of 90 to 300, and still more preferably in the range of 100 to 250.

However, in an alternative preferred embodiment of the method of the invention, the YO ₂ : X ₂ O ₃ molar ratio of the mixture is in the range of 10-300, the preferred molar ratio is in the range of 30-220, more preferably Is in the range of 50 to 180, more preferably in the range of 70 to 150, still more preferably in the range of 90 to 120, still more preferably in the range of 95 to 105. In another embodiment of the method of the present invention that is preferred instead of the above, the YO ₂ : X ₂ O ₃ molar ratio of the mixture is in the range of 50-500, the preferred molar ratio is in the range of 100-400, and more Preferably it is in the range of 150 to 350, more preferably in the range of 200 to 300, more preferably in the range of 220 to 280, even more preferably in the range of 240 to 260.

  According to the method of the present invention, the mixture provided in step (1) further comprises one or more solvents. In general, as long as the condition that the zeolitic material having MFI, MEL and / or NWW-type framework structure can be obtained by crystallization in step (2) is satisfied, about the kind of solvent and / or the number of kinds of solvent There is no restriction | limiting in particular in this invention, Moreover, there is no restriction | limiting in particular regarding the quantity of the solvent used by this invention. However, in the method of the present invention, it is preferred that the one or more solvents include one or more polar solvents. The one or more polar solvents are preferably selected from alkanols, water and mixtures of two or more thereof. In a particularly preferred embodiment, the one or more polar solvents are selected from methanol, ethanol and / or propanol, isopropanol, water and a mixture of two or more thereof, further methanol, ethanol, water and two or more thereof. It is preferable to select from a mixture of However, in the present invention, it is further preferred that the one or more solvents, particularly the one or more polar solvents, contain water, particularly distilled water. Also in a particularly preferred embodiment, distilled water is used as a single solvent in the mixture provided in step (1) and crystallized in step (2).

  Thus, in an embodiment of the method of the present invention, the one or more solvents include one or more polar solvents, and the one or more polar solvents are selected from alkanols, water, and mixtures of two or more thereof. It is preferable.

In the method of the invention, the mixture produced in step (1) is then crystallized in step (2), and the mixture crystallized in this step (2) is based on 100% by weight YO ₂ . One or more elements M of 3 mass% or less are included. In general, M represents sodium that may be present in the mixture provided in step (1) and crystallized in step (2). According to a preferred embodiment of the process of the invention, the mixture crystallized in step (2) contains not more than 3% by weight of both sodium and potassium with respect to 100% by weight YO ₂ , so that M is Represents sodium and potassium. However, according to a particularly preferred embodiment of the method of the present invention, the mixture produced in step (1) and crystallized in step (2) is an alkali metal other than sodium and potassium (the amount of which is The total amount of alkali metal elements in 1) does not exceed 3% by mass with respect to 100% by mass of YO ₂ . Therefore, according to the above particularly preferred embodiment, the mixture provided in step (1) and crystallized in step (2) contains 3% by mass or less of alkali metal element, and further 3% by mass or less of alkali metal element. It preferably contains a metal element and an alkaline earth metal element.

  Therefore, according to a preferred embodiment of the method of the present invention, M represents sodium and potassium, preferably represents an alkali metal group, and M preferably represents an alkali and alkaline earth metal group.

According to a more preferred embodiment of the invention, the mixture provided in step (1) and crystallized in step (2) is 1% according to a particularly preferred or preferred embodiment of the invention with respect to 100% by weight of YO ₂ . % Of one or more elements M, more preferably 0.5% by mass or less, more preferably 0.1% by mass or less, more preferably 0% with respect to 100% by mass of YO ₂ . 0.05% by mass or less, more preferably 0.01% by mass or less, more preferably 0.005% by mass or less, more preferably 0.001% by mass or less, more preferably 0.0005% by mass or less. The element M is included. According to a particularly preferred embodiment, the mixture provided in step (1) and crystallized in step (2) contains 0.0003% by weight or less of one or more elements M with respect to 100% by weight of YO ₂ . The mixture which contains and is crystallized in step (2) of the process of the present invention contains not more than 0.0001% by weight of one or more elements M and is therefore a particularly preferred or preferred embodiment of the present invention. According to the above, it is even more preferable that one or more elements M are not substantially included.

According to a preferred embodiment of the present invention, the mixture provided in step (1) and crystallized in step (2) further comprises one or more organic templates. In general, according to the present invention, as long as the condition that the zeolitic material having MFI, MEL and / or NWW-type framework structure is crystallized in step (2) from the mixture obtained in step (1) is satisfied, There are no particular limitations on the types of one or more organic templates and the number of types used. However, it is preferred in the present invention that the one or more organic templates include one or more compounds selected from tetraalkylammonium and alkenyltrialkylammonium compounds. With respect to the alkyl moiety that can be included in the tetraalkylammonium and alkenyltrialkylammonium compounds, again the condition that the zeolitic material with MFI, MEL and / or NWW-type framework structure is crystallized in step (2) is met. As long as it is, there is no particular limitation. Thus, possible alkyl moieties including combinations of two or more alkyl moieties are those that can be included in each of one or more tetraalkylammonium and / or one or more alkenyltrialkylammonium compounds, and preferred alkyl moieties. Is selected from C ₁ -C ₈ alkyl, preferably C ₁ -C ₆ alkyl, more preferably C ₁ -C ₅ alkyl, and even more preferably C ₁ -C ₄ alkyl. According to a particularly preferred embodiment of the present invention, the alkyl moiety contained in each of the one or more tetraalkylammonium and / or one or more alkenyl trialkylammonium compound is selected from C ₁ -C ₃ alkyl.

With regard to the alkenyl moiety contained in the alkenyltrialkylammonium cation of one or more alkenyltrialkylammonium compounds preferably contained between one or more organic templates, again a zeolite having an MFI, MEL and / or NWW-type framework structure There is no particular limitation as long as the condition that the material is crystallized in (2) is satisfied in the process. However, according to a particularly preferred embodiment of the present invention, the alkenyl portion of the alkenyl tri-alkyl ammonium cation is selected from _C 2 -C ₆ alkenyl, more preferably _C 2 -C ₅ alkenyl, more preferably _C 2 -C ₄ alkenyl , even more preferably selected from _C 2 -C ₃ alkenyl. According to a particularly preferred embodiment of the present invention, the alkenyl part of the alkenyltrialkylammonium cation contained in one or more alkenyltrialkylammonium compounds preferably contained between one or more organic templates is 2-propene-1- Yl, 1-propen-1-yl or 1-propen-2-yl, and in a particularly preferred embodiment, the alkenyl moiety is 2-propen-1-yl or 1-propen-1-yl.

  Therefore, the mixture of step (1) further comprises one or more organic templates, preferably the one or more organic templates are preferably one or more compounds selected from tetraalkylammonium and alkenyltrialkylammonium compounds. The method aspect of the present invention is preferred.

  According to an even more preferred embodiment of the present invention, the one or more organic templates contained in the mixture produced in step (1) comprises one or more tetraalkylammonium compounds, which compounds are tetraethylammonium compounds, triethylpropyl. Preferably, the compound is selected from an ammonium compound, a diethyldipropylammonium compound, an ethyltripropylammonium compound, a tetrapropylammonium compound, and a mixture of the two, and the one or more organic templates are one or more tetrapropylammonium compounds. It is particularly preferable that

Similarly, with respect to a particularly preferred embodiment of the invention wherein the one or more organic templates preferably contained in the mixture produced in step (1) comprises one or more alkenyltrialkylammonium compounds, these compounds are N- _(C 2 -C ₅₎ - alkenyl - tri - _{(C 1} -C ₅₎ alkyl ammonium compound, more preferably N- _(C 2 -C ₄₎ - alkenyl - tri - _{(C 1} -C ₄₎ alkylammonium compounds , even more preferably N- _(C 2 -C ₃₎ - alkenyl - tri - _{(C 2} -C ₄₎ is preferably selected from alkyl ammonium compound, even more preferably those compounds N-(2-propene -1-yl) -tri-n-propylammonium compound, N- (1-propen-1-yl) -tri-n-propylammonium Compounds, N-(1-propen-2-yl) - tri -n- propyl ammonium compounds, and mixtures of two or more thereof. According to this particularly preferred embodiment, the one or more alkenyltrialkylammonium compounds contained in the mixture produced in step (1) are N- (2-propen-1-yl) -tri-n-propylammonium compounds. , N- (1-propen-1-yl) -tri-n-propylammonium compound, and mixtures of two or more thereof.

  With respect to one or more tetraalkylammonium and / or alkenyltrialkylammonium compounds further added to the mixture produced in step (1) according to a particularly preferred embodiment of the present invention, the one or more compounds are suitably in salt form. Provided in. Regarding the counter ion of one or more tetraalkylammonium and / or alkenyltrialkylammonium compounds contained in the one or more compounds, a zeolitic material having an MFI, MEL and / or NWW-type skeleton structure is used again. As long as the condition that it can be crystallized in step (2) of the method is satisfied, there is no particular limitation in the present invention. Accordingly, any possible counterion of the one or more cations can be used to provide one or more tetraalkylammonium and / or alkenyltrialkylammonium compounds. Thus, for example, the one or more counter-ions of one or more tetraalkylammonium compounds and / or alkenyltrialkylammonium compounds are chloride, fluoride, bromide, bicarbonate, hydroxide, nitrate, phosphate, It contains one or more anions selected from hydrogen phosphate, dihydrogen phosphate, sulfate, hydrogen sulfate, acetate, formate, oxalate, cyanate and mixtures of two or more thereof. More preferably chloride, fluoride, bromide, bicarbonate, hydroxide, nitrate, dihydrogen phosphate, hydrogen sulfate, acetate, formate, oxalate, and mixtures of two or more thereof One or more anions selected from the group consisting of chlorides, bromides, hydroxides, nitrates and mixtures of two or more thereof. It can contain on.

  According to a particularly preferred embodiment of the present invention, one or more tetraalkylammonium salts and / or alkenyls preferably added to the mixture produced in step (1) of the method of the present invention and crystallized in step (2). Trialkylammonium salts are, independently of one another, hydroxide and / or halide salts, preferably salts selected from hydroxides, chlorides, bromides and mixtures of two or more thereof. Even more preferably, the salt comprises a hydroxide. Thus, according to a particularly preferred embodiment of the present invention, the one or more organic templates comprise one or more tetraalkylammonium, and the one or more organic templates comprise one or more tetraalkylammonium hydroxides and / or chlorides. It is particularly preferable that the product contains a tetraalkylammonium hydroxide. Similarly, according to a particularly preferred embodiment of the present invention, the one or more organic templates preferably added to the mixture produced in step (1) of the method of the present invention are one or more alkenyltrialkylammonium compounds. In particular, the one or more organic templates are N- (2-propen-1-yl) -tri-n-propylammonium and / or N- (1-propen-1-yl) -tri-n-propylammonium. Hydroxides and / or chlorides are preferred, and N- (2-propen-1-yl) -tri-n-propylammonium and / or N- (1-propen-1-yl) -tri-n- More preferred is propylammonium hydroxide.

One or more organic templates are included in the mixture produced in step (1) of the process of the present invention, preferably provided for crystallization of zeolitic materials having MFI, MEL and / or NWW-type framework structures. There is no particular limitation on the amount of organic template above the seed. Thus, for example, the molar ratio of the total amount of one or more organic templates of the mixture obtained in step (1) to YO ₂ is 1: 0.1 to 1:30, preferably 1: 0.5 to 1:20. More preferably 1: 1 to 1:15, still more preferably 1: 3 to 1:10, and even more preferably 1: 4 to 1: 7. In a particularly preferred embodiment, the molar ratio of the total amount of one or more organic templates to YO ₂ is 1: 5 to 1: 5.6.

Therefore, the molar ratio of the total amount of one or more organic templates contained in the mixture produced in step (1) to YO ₂ is 1: (0.1-30), preferably 1: (0.5-20). ), More preferably 1: (1-15), more preferably 1: (3-10), more preferably 1: (4-7), and still more preferably 1: (5-5.6). And the method aspect of the present invention is preferred.

According to the method of the present invention, the mixture according to step (1) is one or more OH ⁻ sources for crystallizing the MFI, MEL and / or NWW-type framework structure in step (2) of the method of the present invention. Is included. For a particular type of one or more OH ^- sources that can be used in the present invention, the OH ^- anion in the mixture produced in step (1) and crystallized in step (2) of the method of the invention There is no particular limitation as long as the condition that is generated directly or indirectly is satisfied. Within the contemplation of the present invention, the OH ^- anion is indirectly provided by a chemical reaction that results in the formation of an OH ^- anion (eg, reaction of a Lewis acid with water), and the protonated form of the base and OH ^- anion produced by the former chemical reaction.

According to the present invention, the one or more OH ⁻ sources further preferably included in the mixture according to step (1) comprises one or more sources directly comprising OH ⁻ , in particular one or more Bronsted bases, and even more preferred one or more OH ^- source in accordance with particularly preferred or preferred embodiment of the present invention comprises one or more hydroxides of further organic template contained in the mixture produced in step (1). Thus, according to certain preferred embodiments thereof, the one or more OH ⁻ sources are tetraalkylammonium hydroxide and / or alkenyltrialkylammonium hydroxide, more preferably tetraethylammonium hydroxide, triethylpropyl hydroxide. Ammonium, diethyldipropylammonium hydroxide, ethyltripropylammonium hydroxide, tetrapropylammonium hydroxide, N- (2-propen-1-yl) -tri-n-propylammonium hydroxide, N- (1- One or more selected from propen-1-yl) -tri-n-propylammonium hydroxide, N- (1-propen-2-yl) -tri-n-propylammonium hydroxide, and mixtures of two or more thereof The hydroxide. Even more preferably, the one or more hydroxides are tetrapropylammonium hydroxide, N- (2-propen-1-yl) -tri-n-propylammonium hydroxide, N- (1-propene-hydroxide). 1-yl) -tri-n-propylammonium and mixtures of two or more thereof. According to certain preferred embodiments, the one or more OH ^- sources comprises tetrapropylammonium hydroxide, even more preferably the one or more OH ^- sources are tetrapropylammonium hydroxide.

Thus, in a preferred embodiment of the process of the present invention, the mixture according to step (1) is 1 or more OH ^- comprises a source, the one or more OH ^- source preferably comprises a hydroxide of the organic template, and more Preferably, one or more hydroxides selected from tetraalkylammonium hydroxides and / or alkenyltrialkylammonium hydroxides are included.

With respect to the amount of OH ^- source that can be included in the mixture produced in step (1) of the method of the present invention, zeolitic materials having MFI, MEL and / or NWW-type framework structure are included in the step of the method of the present invention (2). There is no particular limitation in the present invention as long as the condition that it can be crystallized is satisfied. Thus, for example, according to the above preferred embodiment, the OH ⁻ : YO ₂ molar ratio of the mixture obtained in step (1) is preferably in the range of 0.01 to 5, more preferably in the range of 0.05 to 2, more preferably. Is in the range of 0.1 to 1, more preferably in the range of 0.12 to 0.5, and preferably in the range of 0.15 to 0.3. According to a particularly preferred embodiment of the invention, according to a particularly preferred embodiment of the invention, the OH ⁻ : YO ₂ molar ratio of the mixture obtained in step (1) is in the range of 0.18 to 0.2.

  In step (1) of the present invention, the mixture can be produced by any conceivable means, preferably vigorous mixing, more preferably mixing by stirring.

  Regarding the crystallization performed in step (2) of the present invention, the actual means used to crystallize the zeolitic material having MFI, MEL and / or NWW-type framework structure from the mixture obtained in step (1) In the present invention, there is no particular limitation. Accordingly, any means can be used, but crystallization is preferably performed by heating the mixture of step (1). According to this preferred embodiment, the temperature for achieving the crystallization in the step (2) is not particularly limited, but the crystallization is preferably performed under heating at a temperature in the range of 80 to 250 ° C. The range is preferably in the range of 100 to 220 ° C, more preferably in the range of 120 to 200 ° C, further in the range of 140 to 180 ° C, and further in the range of 145 to 175 ° C. According to a particularly preferred embodiment of the present invention, preference is given to the mixture provided in step (2) for crystallization of the zeolitic material obtained in step (1) and having an MFI, MEL and / or NWW-type framework structure. Heating is performed at a temperature in the range of 150-170 ° C.

  As a means for crystallization of a zeolitic material having an MFI, MEL and / or NWW-type framework structure, it relates to the heating preferably used in step (2) of the method of the invention, which heating is generally achieved by crystallization Any suitable pressure may be used as long as the conditions are satisfied. In a preferred embodiment of the invention, the mixture of step (1) is subjected to a pressure higher than normal pressure in step (2). The “normal pressure” used in the present invention is a pressure of 101325 Pa in an ideal case. However, this pressure can be varied within a range known to those skilled in the art. For example, this pressure can be in the range of 95000-106000 Pa, or 96000-105000 Pa, or 97000-104000 Pa, or 98000-103000 Pa, or 99000-102000 Pa.

  In a preferred embodiment of the process according to the invention, the solvent is present in the mixture of step (1) and furthermore the heating of step (2) is carried out under solvothermal conditions (ie under the self-generated pressure of the solvent used). Preferably crystallized). This can be done, for example, by heating the mixture obtained in step (1) in an autoclave or other crystallization vessel that meets the generated solvothermal (solvent heat) conditions. In a particularly preferred embodiment, the solvent comprises water, preferably distilled water, with the result that the heating in step (2) is carried out under hydrothermal conditions.

  The apparatus used in the present invention for crystallization is particularly limited as long as the desired parameters of crystallization satisfy the condition that they can be realized in a preferred embodiment, particularly where specific crystallization conditions are required. It is not something. In a preferred embodiment performed under solvothermal conditions, any type of autoclave or any type of digestion vessel can be used.

  Furthermore, regarding the period during which the preferred heating in step (2) of the method of the present invention is performed for crystallization of the zeolitic material, the heating period is crystallization of the zeolitic material having an MFI, MEL and / or NWW-type framework structure. As long as it is suitable for achieving the above, there is no particular limitation. Thus, for example, heating can be carried out for a period of at least 3 hours, with a preferred heating period being 6 hours to 15 days, more preferably 9 hours to 10 days, more preferably 12 hours to 7 days. More preferably, it is 15 hours to 5 days, more preferably 18 hours to 4 days, and more preferably 21 hours to 3 days. In a particularly preferred embodiment, the heating period in step (2) of the present invention is 1-2 days.

  According to a preferred embodiment of the invention, the mixture is heated in step (2), but this heating can be carried out in the entire crystallization step or in one or more parts thereof as long as the zeolitic material is crystallized. . Preferably, heating is performed during the entire crystallization step.

  Furthermore, with regard to the crystallization means of step (2) of the present invention, it is usually possible in the present invention to perform crystallization by means of static conditions or by stirring the mixture in accordance with the present invention. According to the aspect including stirring the mixture, the means for stirring is not particularly limited. The agitation can be performed for the crystallization by using any one means of vibration means, rotation of the reaction vessel and / or mechanical stirring of the reaction mixture. It is preferably achieved by mechanical stirring. However, in an alternative preferred embodiment, the crystallization is performed under static conditions, i.e. without any agitation means during the crystallization process.

  In general, the method of the present invention optionally involves a separate step for work-up and / or the zeolitic material crystallized in step (2) from the mixture provided in step (1). Additional steps for further chemical and / or physical transformations can be included. The post-treatment is performed before the step (3) of impregnating the zeolite material. The zeolitic material can be subjected to, for example, any series of isolation and / or washing procedures, and the zeolitic material obtained in the crystallization of step (2) has at least one isolation treatment and at least It is preferable to perform one washing process.

  Isolation of the crystallized product can be accomplished by any conceivable means. Preferably isolation of the crystallized product can be accomplished by means of filtration, ultrafiltration, diafiltration, centrifugation and / or decantation. The filtration method can include a suction step and / or a pressure filtration step. According to a preferred embodiment, prior to isolation, first the pH of the reaction mixture is in the range of 5-9, more preferably in the range of 6-8, more preferably in the range of 6.5-7.8, more preferably 7. It is preferable to adjust to the range of -7.6. Within the scope of the intention of the present invention, the pH value is preferably determined by a standard glass electrode.

  For any one or more optional cleaning methods, any conceivable solvent can be used. Examples of usable cleaning agents include water, alcohol (eg, methanol, propanol), or a mixture of two or more of these. Examples of mixtures include a mixture of two or more alcohols (eg, methanol and ethanol, or methanol and propanol, or ethanol and propanol, methanol, ethanol and propanol), a mixture of water and at least one alcohol (eg, water). And methanol, water and ethanol, water and propanol, water and methanol and ethanol, water and methanol and propanol, water and ethanol and propanol, water, methanol, ethanol, and propanol). Water or a mixture of water and at least one alcohol, particularly water and methanol, are preferred, and distilled water is particularly preferred as a single cleaning agent.

  The separated zeolitic material is washed until the pH of the detergent (preferably wash water) is in the range of 6-8, preferably in the range of 6.5-7.5.

  Further, the method of the present invention can optionally include one or more drying steps. In general, any conceivable drying means can be used. In general, any stationary drying process or continuous drying process (for example, use of a band dryer) can be used as a drying method. Dry-milling and spinflash processes can also be mentioned as alternatives. Examples of the drying treatment include heating the zeolitic material and / or evacuating the zeolitic material. In contemplated embodiments of the invention, one or more drying steps may also include spray drying, which can be achieved by spray granulation of the zeolitic material.

  In an embodiment including at least one drying step, the drying temperature is preferably in the range of 25 to 150 ° C, more preferably in the range of 60 to 140 ° C, more preferably in the range of 70 to 130 ° C, and still more preferably in the range of 75 to 125. It is in the range of ° C. The drying period is preferably in the range of 2 to 24 hours, more preferably in the range of 2.5 to 10 hours, further preferably in the range of 3 to 7 hours, and still more preferably in the range of 3.5 to 5 hours.

  According to an alternative embodiment of the preferred method of the invention, the zeolitic material crystallized in step (2) is preferably directly subjected to at least one drying step, preferably without prior isolation, washing or drying of the zeolitic material. Is subjected to spray drying and / or spray granulation. Subjecting the mixture obtained in step (2) of the method of the present invention directly to a spray drying or spray granulation step has the advantage that isolation and drying can be carried out in a single step. As a result, this aspect of the present invention provides a more preferred method that not only avoids removal of the organic template, but can also minimize the number of post-treatment steps after synthesis, and as a result. The zeolitic material can be obtained in a very simple manner.

  In general, the optional washing and / or isolation and / or ion exchange treatments in the methods of the present invention can be performed in any conceivable order and can be repeated as often as desired.

  According to a further preferred embodiment, in addition to the one or more post-treatment steps described above that can be performed after step (2) and before step (3), in addition to one or more optional drying steps, Alternatively, instead of one or more optional drying steps, the optionally washed zeolitic material is subjected to one or more calcination steps. According to the present invention, one or more of the calcination steps described above are particularly preferred from the standpoint of a particular embodiment of the method of the present invention, wherein the mixture produced in step (1) is an MFI, MEL and / or NWW-type skeleton. It includes an organic template that is removed after the synthesis of the zeolitic material having a structure. In the preferred embodiment where one or more calcination steps are performed after step (2) of the method of the present invention and before step (3), the number of repetitions of the calcination step that can be performed, in particular the number of repetitions. However, the temperature used in the calcination treatment and the duration of the calcination treatment are not particularly limited. In a particularly preferred embodiment of the process according to the invention, one or more organic templates are further included in the mixture produced in step (1) and the conditions of calcination, in particular temperature and / or duration and / or calcination. The number of process iterations is preferably selected such that one or more organic templates are substantially removed from the pore structure of the zeolitic material having an MFI, MEL and / or NWW-type framework structure.

Within the meaning of the invention, the use of the term “substantially”, in particular the amount of one or more organic templates present in the pore structure of the zeolitic material at most after calcination, is at most zeolitic material. The residual amount of carbon and / or nitrogen derived from one or more organic templates existing in the pore structure of the present invention is shown. More particularly, the zeolitic material crystallized in step (2) of the process of the present invention in the presence of one or more organic templates is substantially free of the intention of the present invention. In this case, the content of carbon and / or nitrogen is 1.0% by mass or less, preferably 0 with respect to 100% by mass of YO ₂ contained in the zeolite material having MFI, MEL and / or NWW-type skeleton structure. 0.5 mass% or less, more preferably 0.2 mass% or less, more preferably 0.1 mass% or less, more preferably 0.05 mass% or less, more preferably 0.01 mass% or less, more preferably 0. 0.005 mass% or less, more preferably 0.001 mass% or less.

  Regarding one or more calcination steps of a preferred embodiment of the method of the present invention, the temperature of the calcination treatment used in the method of the present invention is in the range of 300-850 ° C., and the calcination temperature in step (2d) is 350 The range of -700 degreeC is preferable, and the range of 400-600 degreeC is more preferable. According to a particularly preferred embodiment of the method of the invention, the calcination in step (2d) is performed at a temperature in the range of 450 to 550 ° C. There is no particular limitation regarding the period of one or more calcination steps in step (2d), but the calcination can be performed for a time in the range of 1 to 80 hours. According to any of the particularly preferred embodiments described herein, the calcination time ranges from 2 to 24 hours, during which the calcination temperature is maintained. This calcination time is preferably in the range of 2.5-12 hours, more preferably in the range of 3-10 hours, more preferably in the range of 3.5-8 hours, more preferably in the range of 4-7 hours. is there. In a particularly preferred embodiment comprising the calcination treatment of the method of the invention, the calcination period is in the range of 4.5 to 6 hours, and the selected calcination temperature is maintained during this period.

  Regarding the number of times of the calcination treatment in the step (2d), the calcination treatment is preferably performed 1 to 3 times in the step (2d). More preferably, it is once or twice. According to a particularly preferred embodiment of the invention, the calcination treatment is carried out once in step (2d) of the method of the invention.

  According to the present invention, the zeolitic material is preferably subjected to a hydrothermal treatment step (2e). As long as the hydrothermal treatment changes the physical and / or chemical properties of the zeolitic material, there is generally no particular limitation on how the hydrothermal treatment is performed. It is particularly preferred to reduce the hydrophobicity of the zeolitic material by hydrothermal treatment.

  Accordingly, in general, the preferable hydrothermal treatment may be performed under any suitable conditions, and is preferably performed at a particularly suitable pressure and temperature. However, according to the present invention, the hydrothermal treatment is carried out under self-generated pressure and can be achieved, for example, using an autoclave or a suitable pressure digestion vessel.

  With respect to the temperature at which the hydrothermal treatment in the step (2e) is performed, any temperature can be used as appropriate. The hydrothermal treatment in the step (2e) is preferably performed under heating, and the heating is preferably a temperature range of 80 to 250 ° C, more preferably a temperature range of 100 to 220 ° C, more preferably a temperature of 120 to 200 ° C. It is carried out in the range, more preferably in the temperature range of 140 to 190 ° C, more preferably in the temperature range of 160 to 185 ° C. However, in the present invention, the hydrothermal treatment in the step (2e) is particularly preferably performed at a temperature included in the range of 170 to 180 ° C.

  With regard to the duration of the hydrothermal treatment step, in particular the duration of heating according to preferred and particularly preferred embodiments of the method of the invention, the duration depends on the selected physical and / or chemical properties of the zeolitic material, in particular its hydrophobicity, There is no particular limitation as long as it is sufficient to bring about a change, particularly under conditions of selected temperature and pressure. Therefore, for example, the duration of the hydrothermal treatment step is in the range of 2 to 72 hours, preferably the treatment in the step (2e) is performed in the period of 4 to 48 hours, and more preferably in the range of 8 to 36 hours. More preferably, it is performed in the range of 12 to 30 hours. In the present invention, it is particularly preferable that the hydrothermal treatment step (2e) is performed in a period in the range of 18 to 24 hours.

  Regarding the effect of the hydrothermal treatment preferably performed according to the step (2e), there is no particular limitation with respect to the change in physical and / or chemical properties of the zeolitic material to be achieved. It is particularly preferred that the hydrothermal treatment conditions according to the preferred and particularly preferred embodiments of the process of the invention, in particular the temperature, pressure and duration, lead to an increase in the hydrophobicity of the zeolitic material. Therefore, according to the present invention, the zeolitic material obtained in step (2e) preferably exhibits a reduced water absorption compared to the zeolitic material before the treatment in step (2e). As a result, for the specific water absorption of the zeolitic material obtained in step (2e), there is generally no limitation in the above preferred embodiments of the present invention as long as the hydrophobicity of the zeolitic material increases. That is, the water absorption of the zeolitic material decreases as a result of the treatment in step (2e). Therefore, in general, the water absorption of the zeolitic material obtained in the step (2e) is not particularly limited, but the water absorption of the zeolitic material obtained in the above step shows, for example, 10.0% by mass or less. The hydrothermally treated zeolitic material obtained in step (2e) preferably exhibits a water absorption of 7.4% by weight or less, more preferably 6.2% by weight or less, more preferably 6.0% by weight or less, more preferably Represents 5.0% by mass or less, more preferably 4.5% by mass or less, more preferably 4.2% by mass or less, more preferably 3% by mass or less, and more preferably 2.2% by mass or less. According to the invention, it is particularly preferred that the hydrothermally treated zeolitic material obtained in step (2e) exhibits a water absorption of 2% by weight or less, more preferably 1.5% by weight or less.

  Within the intent of the present invention, the water absorption of a material defined in any of the preferred and particularly preferred embodiments of the present invention expressed in mass%, in particular a zeolitic material, is measured in a dry sample (ie 0% RH). Refers to the water absorption of the material at 85% by weight relative humidity (RH) expressed as an increase in weight relative to the weight of the sample. According to the present invention, the mass of the sample measured at 0% RH is the sample from which residual moisture has been removed by heating the sample to 100 ° C. (5 ° C./min heating ramp) and maintaining under nitrogen flow for 6 hours. Is preferably pointed to. According to the present invention, the water absorption of the material defined in a particularly preferred embodiment of the method of the present invention is the water absorption of the material at 85% RH obtained according to the water absorption / desorption isotherm measurement procedure defined in the experimental section of the present application. Particularly preferably, it refers to the water absorption of the zeolitic material.

For this reason, the method of the present invention is further performed after step (2) and before step (3).
(2a) The pH of the product mixture obtained in step (2) is in the range of 5-9, preferably in the range of 6-8, more preferably in the range of 6.5-7.8, more preferably 7-7. And / or (2b) isolating the zeolitic material from the product mixture obtained in step (2), preferably filtration, ultrafiltration, diafiltration (diafiltration) And / or (2c) washing the zeolitic material; and / or (2d) drying and / or calcining the zeolitic material; and / or Or (2e) hydrothermal treatment (hydrothermal treatment) of the zeolitic material;
Is a preferred embodiment of the present invention.

  In the step (3) of the present invention, the zeolite material obtained in the step (2) is impregnated with one or more metals selected from alkaline earth metals. With respect to the means for impregnating the zeolitic material that can be used in the method of the present invention, the pores of the zeolitic material in which one or more elements selected from alkaline earth metals have an MFI, MEL and / or NWW-type framework structure There is no limitation as long as the condition that it is efficiently supplied is satisfied. Therefore, any suitable impregnation method can be used in step (3) of the present invention. For example, impregnation by treatment including the step of immersing the zeolitic material in a solution and / or suspension of one or more compounds containing one or more elements selected from alkaline earth metals and spray impregnation and / or initial An impregnation method by an incipient wetness can be mentioned, and these impregnation methods can be used by themselves, but two or more kinds may be used in combination. However, in the present invention, it is particularly preferred that the impregnation of the zeolitic material is achieved by spray impregnation.

  With respect to one or more elements selected from the alkaline earth metals impregnated in the zeolitic material obtained in step (2) of the method of the present invention, that element allows its inclusion in the pore structure of the zeolitic material It may be used in any form. Accordingly, the one or more elements can generally be used in the form of a simple substance and / or one or more compounds, particularly one or more salts thereof. In the method of the present invention, one or more elements selected from alkaline earth metals are preferably used in the form of one or more salts in order to impregnate the zeolitic material. Regarding preferred salts of one or more elements selected from alkaline earth metals that can be used in step (3), there is no particular limitation on the number of types of salts used. The one or more salts of one or more elements are preferably halides, carbonates, hydroxides, nitrates, phosphates, sulfates, acetates, formates, oxalates, cyanides, and these 2 Selected from a mixture of more than one species, more preferably the one or more salts are chloride, fluoride, bromide, bicarbonate, hydroxide, nitrate, hydrogen phosphate, dihydrogen phosphate, hydrogen sulfate Selected from salts, acetates and mixtures of two or more, more preferably the one or more salts are selected from chlorides, bromides, nitrates, acetates and mixtures of two or more. In a particularly preferred embodiment of the process according to the invention, the one or more elements selected from alkaline earth metals preferably used in step (3) for impregnation of the zeolitic material obtained in step (2) are 1 Contains more than one species of nitrate.

  Regarding one or more elements selected from the alkaline earth metals used in step (3), in general, any one or more alkaline earth metals can be impregnated in the zeolitic material, particularly two or more kinds. It is preferable to impregnate a combination of alkaline earth metals. However, in the method of the present invention, in step (3), the zeolitic material is preferably impregnated with one or more elements selected from Mg, Ca, Ba, Sr and a mixture of two or more thereof, The zeolitic material is preferably impregnated with one or more elements selected from Mg and / or Ca and mixtures of two or more thereof.

  With respect to the amount of one or more elements selected from the alkaline earth metals impregnated in the zeolitic material obtained in step (2), the present invention is particularly limited as long as possible amounts can be impregnated in the zeolitic material. Not. Thus, for example, the impregnation of the zeolitic material is carried out in such a way that one or more elements selected from alkaline earth metals are 0.1 to 15% by mass (calculated as elements) with respect to the total amount of zeolitic material. To be impregnated. However, in a preferred embodiment, the zeolitic material having an MFI, MEL and / or NWW-type framework structure includes at least one selected from 0.5 to 10% by weight of an alkaline earth metal in step (3). More preferably 1 to 7% by mass, more preferably 2 to 5% by mass, more preferably 3 to 4.5% by mass, and more preferably 3.5 to 4.3% by mass. Impregnated with elements. In a particularly preferred embodiment of the process according to the invention, the zeolitic material obtained in step (2) is selected from 3.8 to 4.1% by weight of alkaline earth metal in step (3) relative to the total amount of zeolitic material. One or more elements to be impregnated.

  In general, the zeolitic material obtained according to the method of the present invention may be any conceivable zeolitic material having an MFI, MEL and / or NWW-type framework structure, preferably the above-mentioned zeolite formed in step (2) The material includes one or more zeolitic materials having an MFI-type framework structure. Among zeolitic materials having a preferred MFI-type framework structure, there is no particular limitation on the type and / or the number of types and the amount in the zeolitic material.

  In an embodiment of the method of the present invention that the resulting zeolitic material contains one or more zeolites having an NWW-type framework structure, the kind of one or more zeolites having an NWW-type framework structure contained in the zeolite material, There is no particular limitation on the number of types. Thus, for example, one or more zeolites having an NWW-type framework structure obtainable according to the method of the present invention include MCM-22, [Ga-Si-O] -MWW, [Ti-Si-O]-. Mention may be made of one or more zeolites selected from MWW, ERB-1, ITQ-1, PSH-3, SSZ-25, and mixtures of two or more thereof. One or more zeolites that can be used for the conversion of oxygen-containing materials to olefins are preferably included in the zeolitic material obtained according to the process of the invention, in particular the zeolitic material comprises MCM-22 and / or MCM-36. It is preferable.

  The same is true for one or more zeolites having a MEL-type framework structure that can be included in the zeolite material obtained according to the method of the present invention. Thus, for example, one or more zeolites having a MEL-type framework structure that can be included in the zeolitic material obtained according to the method of the present invention include ZSM-11, [Si—B—O] -MEL, Bor-D. (MFI / MEL-intergrowth), Boralite D, SSZ-46, Silicalite 2, TS-2 and zeolites selected from a mixture of two or more of these. In this case, one or more zeolites having a MEL-type framework structure can be used for the conversion of oxygen-containing substances to olefins, and in a particularly preferred embodiment of the process of the invention, the resulting zeolitic material is ZSM-11. including.

  However, as mentioned above, it is preferred that the zeolitic material obtained according to the process of the invention comprises one or more zeolites having an MFI-type framework structure, in particular the zeolitic material is used for the conversion of oxygen-containing substances to olefins. It is preferable to include a zeolite having an MFI-type framework structure. Further, there is no particular limitation on the type of zeolite having an MFI-type framework structure that can be included in the zeolite material obtained according to the method of the present invention, and the number of types thereof. Examples of the zeolite material include ZSM-5, ZBM- 10, [As-Si-O] -MFI, [Fe-Si-O] -MFI, (Ga-Si-O) -MFI, AMS-1B, AZ-1, Bor-C, Boralite C, Encilite, FZ -1, LZ-105, monoclinic H-ZSM-5, Mutinaite, NU-4, NU-5, Silicalite, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, Mention may be made of one or more zeolites selected from ZKQ-1B, ZMQ-TB, and mixtures of two or more thereof. That. However, the zeolitic material obtained according to the method of the present invention comprises ZSM-5 and / or ZBM-10 as one or more zeolites having an MFI-type framework structure contained therein. Zeolite ZBM-10 and in particular its production process are disclosed in EP 070708 A1 and EP 0034727 A2, respectively. In a particularly preferred embodiment of the process according to the invention, the resulting zeolitic material comprises ZSM-5 as one or more zeolites having an MFI-type framework structure.

  Furthermore, in addition to the process for producing a zeolitic material having an MFI, MEL and / or NWW-type framework structure, the present invention also provides an MFI, MEL and / or NWW obtainable by the process according to the present invention or by the process of the present invention. It also relates to a zeolitic material having an MFI, MEL and / or NWW-type skeletal structure obtained by a possible method resulting in a zeolitic material having a skeletal structure. Particularly preferred inventive methods are particularly preferred embodiments of the invention as defined herein.

Furthermore, the present invention also provides a zeolite having an MFI, MEL and / or NWW-type framework structure comprising YO ₂ and X ₂ O ₃ (as such, Y is a tetravalent element and X is a trivalent element). In terms of materials, the zeolitic material comprises not more than 3% by weight of one or more elements M with respect to 100% by weight of YO ₂ , where M represents sodium and the zeolitic material is further selected from alkaline earth metals 1 It contains more than seed elements, and more than 95 mass% of the primary particles have a diameter of less than 1 μm.

  According to the present invention, the zeolitic material of the present invention having the MFI, MEL and / or NWW-type framework structure defined in a particularly preferred and preferred embodiment in the present application is the method of the present invention or the zeolitic material of the present invention. In particular, it is obtained by the possible methods that can lead to the particularly preferred embodiments defined therein.

According to the present invention, the zeolitic material having MFI, MEL and / or NWW-type framework structure comprises YO ₂ . In general, Y represents a possible tetravalent element, and Y represents one or more types of tetravalent elements. Preferred tetravalent elements of the present invention include Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof. However, it is particularly preferred that Y contains Si, more preferably Y is Si.

Regarding X ₂ O ₃ contained in a zeolitic material having an MFI, MEL and / or NWW-type framework structure according to the present invention, X represents a trivalent element that can be generally considered, and X represents one or more trivalent elements. Represents an element. Preferred trivalent elements of the present invention include Al, B, In, Ga, or a mixture of two or more of the above trivalent elements. More preferably, X represents Al, B, Ga, or a mixture of two or more of the above trivalent elements, and more preferably X contains Al and / or Ga. In a particularly preferred embodiment of the invention, X comprises Al, more preferably X represents Al.

  In a preferred embodiment of the present invention, 96% by mass or more, more preferably 97% by mass or more, more preferably 98% by mass or more, particularly 99% by mass or more of the primary particles of the zeolitic material has a diameter of 1 μm or less.

  There are no particular limitations on the crystalline phase of the primary particles of the present invention. In the present invention, at least a part of the primary particles is preferably spherical.

The term “spherical” as used in the present invention refers to that of a scanning electron microscope (SEM) at a magnification of 0.5 × 10 ⁴ to 2.0 × 10 ⁴ , preferably 2.0 × 10 ⁴ to 75 × 10 ⁴ . As a result of the investigation, it is the name of a primary particle that does not substantially contain a sharp end (acute angle). Therefore, the term “spherical” is, for example, the name of a primary particle of a pure sphere or a deformed sphere (eg, an ellipse or a rectangular parallelepiped). The end is circular and not sharp.

  In a preferred embodiment of the present invention in which at least a part of the primary particles are spherical, 50% or more of the primary particles, more preferably 60% or more, more preferably 70% or more, more preferably 80% or more, More preferably, it is 85% or more, and more preferably 90% or more is spherical. In a more preferred embodiment, 91% or more, more preferably 92% or more, more preferably 93% or more, more preferably 94% or more, more preferably 95% or more, more preferably 96%, of the primary particles of the zeolitic material. More preferably, 97% or more, more preferably 98% or more is spherical.

  Regarding the primary particles of the zeolitic material, the diameter of less than 1 μm is preferably 95% by mass or more, and in a preferable embodiment in which at least a part of the primary particles is spherical, 95% by mass or more of the spherical primary particles Particularly preferably has a diameter of 1 μm or less. More preferably, the diameter is 900 nm or less, more preferably 800 nm or less, more preferably 700 nm or less, more preferably 600 nm or less, and more preferably 500 nm or less. More preferably, the primary particles of the zeolitic material have a diameter in the range of 5 nm or more, more preferably 10 nm or more, more preferably 20 nm or more, more preferably 30 nm or more, particularly preferably 50 nm or more. The diameter is particularly preferably in the range of 5 to 800 nm, more preferably 10 to 500 nm, more preferably 20 to 400 nm, more preferably 30 to 300 nm, more preferably 40 to 250 nm, more preferably 50 to 200 nm. .

  For this reason, in the present invention, 95% by mass or more of primary particles are 5 to 800 nm, more preferably 10 to 500 nm, more preferably 20 to 400 nm, more preferably 30 to 300 nm, more preferably 40 to 250 nm, and more. An embodiment having a diameter in the range of 50 to 200 nm is preferable.

  Furthermore, in the present invention, 90% or more of primary particles are spherical, and 95% by mass or more of spherical primary particles are 1 μm or less, more preferably 5 to 800 nm, more preferably 10 to 500 nm, more preferably An embodiment having a diameter of 20 to 400 nm, more preferably 30 to 300 nm, more preferably 40 to 250 nm, and more preferably 50 to 200 nm is preferable.

  The diameter of the primary particles in the present invention can be measured by, for example, electron microscopy SEM (scanning electron microscope) and TEM (transmission electron microscope). The diameter in the present invention was measured by SEM.

In the present invention, the zeolitic material having an MFI, MEL and / or NWW-type skeleton structure contains 3% by mass or less of one or more kinds of atoms M with respect to 100% by mass of YO ₂ . With respect to one or more atoms M, M represents sodium. In a preferred embodiment of the invention, the zeolitic material contains up to 3% by weight of both sodium and potassium with respect to 100% by weight YO ₂ . With respect to the quantity measured by the mass of element M of the present invention, the quantity is for one or more elements measured as elements rather than as oxides thereof. In the present invention, the one or more elements M contained in the zeolitic material at 3 mass% or less represent alkali metals, particularly Li, Na, K, Rb, and Cs. In a further preferred embodiment, M is an alkali metal and an alkaline earth metal, the alkaline earth metal being in particular the elements Mg, Ca, Sr and Ba, and in the above particularly preferred embodiment of the invention, the zeolitic material is an alkaline earth metal. 1 or more elements M containing 3% by mass or less, and the one or more alkaline earth metals M are the one or more elements further contained in the zeolite material of the particularly preferred and preferred embodiments of the present invention. Does not contain. Furthermore, for a particularly preferable embodiment of the present invention, for example, the zeolitic material having MFI, MEL and / or NWW-type skeleton structure further contains Mg as one or more elements selected from alkaline earth metals. Particularly preferably contains 3% by mass or less of alkali metal and alkaline earth metal M (M does not contain Mg).

In the present invention, the zeolitic material having an MFI, MEL and / or NWW-type skeleton structure contains 1% by mass or less of one or more kinds of atoms M with respect to YO ₂ . 0.5% by mass or less, more preferably 0.1% by mass or less, more preferably 0.05% by mass or less, further preferably 0.02% by mass or less, more preferably 0.01% by mass or less, and further preferably 0% or less. 0.005% by mass or less, more preferably 0.001% by mass or less, further preferably 0.0005% by mass or less, and further preferably 0.0003% by mass or less. In a particularly preferred embodiment of the invention, the zeolitic material is substantially free of one or more elements M, i.e. contains at most trace amounts of one or more elements M; less than 0.0001% by mass with respect to YO ₂ of 100 mass% contained in the material.

In addition to the skeleton elements YO ₂ and X ₂ O ₃ , the one or more alkaline earth metals are any alkaline earths with respect to one or more elements selected from the alkaline earth metals further contained in the zeolitic material It may be a metal or a combination of two or more alkaline earth metals, preferably the one or more elements selected from alkaline earth metals are Mg, Ca, Ba and Sr and mixtures of these two or more. It is preferred that the one or more elements include Mg and / or Ca. According to a particularly preferred embodiment of the present invention, the one or more alkaline earth metals comprise Mg, more preferably Mg is further included in the zeolitic material as one or more elements selected from alkaline earth metals. included.

  There is no particular limitation on the amount of one or more elements selected from alkaline earth metals contained in the zeolite material having an MFI, MEL and / or NWW-type framework structure, and generally conceivable amounts are included therein. included. Thus, for example, one or more elements selected from alkaline earth metals contained in the zeolitic material are generally included in the zeolitic material in an amount ranging from 0.1 to 15% by weight relative to the total amount of the zeolitic material. Preferably, the one or more elements are in the range of 0.5 to 10% by weight, more preferably in the range of 0.5 to 10% by weight, and still more preferably in the range of 0.5 to 10% by weight. Zeolite material in an amount in the range of -7% by weight, more preferably in the range of 2-5% by weight, more preferably in the range of 3-4.5% by weight, more preferably in the range of 3.5-4.3% by weight. Generally contained within. In a particularly preferred embodiment of the present invention, one or more elements selected from alkaline earth metals are further included in or contained in the zeolitic material in an amount ranging from 3.8 to 4.1% by weight. Is done. With respect to one or more alkaline earth metals further contained in the zeolitic material, there is no particular limitation as to how one or more elements are contained in the zeolitic material. Thus, for example, one or more alkaline earth metals may be included in the outer surface of the zeolitic material particles and / or within the pore structure of the zeolitic material particles, and at least one of the one or more alkaline earth metals. The portion is preferably contained in the pore structure of the zeolite material particles, particularly as a non-framework element of the zeolite material. Non-framework elements do not constitute one or more skeletal structures of the zeolitic material and are therefore generally present in each skeletal structure of the zeolitic material and the pores and / or cavities (holes) formed by it.

Regarding YO ₂ and X ₂ O ₃ contained in zeolite material having MFI, MEL and / or NWW-type framework structure, the amount of each contained in the zeolite material, molar ratio of YO ₂ to X ₂ O _{3 in the} zeolite material There is no particular limitation with regard to. Thus, for example, the zeolitic material exhibits a YO ₂ : X ₂ O ₃ atomic ratio in the range of 10-1500, preferably an atomic ratio in the range of 30-1200, more preferably an atomic ratio in the range of 50-900, and more. An atomic ratio in the range of 70 to 700 is preferable, an atomic ratio in the range of 80 to 500 is more preferable, and an atomic ratio in the range of 90 to 300 is more preferable. In a particularly preferred embodiment of the invention, the zeolitic material having MFI, MEL and / or NWW-type framework structure exhibits a YO ₂ : X ₂ O ₃ atomic ratio in the range of 100-250.

  There is no particular limitation on the specific MFI, MEL and / or NWW-type framework structure regarding the specific zeolitic material having the MFI, MEL and / or NWW-type framework structure of the present invention, which may be considered Zeolite materials having such MFI, MEL and / or NWW-type framework structures may also be included. Thus, for example, in an embodiment of the invention where the zeolitic material includes an NWW-type framework structure, the one or more zeolites containing the NWW-type framework structure include MCM-22, [Ga-Si-O] -MWW, [Ti -Si-O] -MWW, ERB-1, ITQ-1, PSH-3, SSZ-25 and one or more zeolites selected from a mixture of two or more thereof. However, in an embodiment of the invention, the zeolitic material comprises one or more zeolites having one or more NWW-type framework structures that can be used for the conversion of oxygen-containing substances to olefins, more preferably the above The preferred embodiment zeolitic material comprises MCM-22 and / or MCM-36.

  The same is true for one or more zeolitic materials having a MEL-type framework structure that can be included in the zeolitic material of the present invention. Thus, for example, one or more zeolites containing a MEL-type framework structure that can be included in the zeolite material include ZSM-11, [Si-B-O] -MEL, Bor-D (MFI / MEL-intergrowth), Boralite. And one or more zeolites selected from D, SSZ-46, Silicalite 2, TS-2 and mixtures of two or more thereof. Again, one or more zeolites having a MEL-type framework structure can be used for the conversion of oxygen-containing substances to olefins, particularly preferably the zeolitic material comprises ZSM-11.

  However, as mentioned above, the zeolitic material of the present invention comprises one or more zeolites having an MFI-type framework structure, and in particular, has an MFI-type framework structure that can be used for the conversion of oxygen-containing materials to olefins. It is particularly preferred that it contains one or more zeolites. In a preferred embodiment of the zeolitic material, there is no particular limitation on the kind of one or more zeolites having an MFI-type framework structure that can be included therein, and examples of the zeolitic material include ZSM-5, ZBM-10, [As-Si-O] -MFI, [Fe-Si-O] -MFI, [Ga-Si-O] -MFI, AMS-1B, AZ-1, Bor-C, Boralite C, Encilite, FZ-1 , LZ-105, monoclinic H-ZSM-5, Mutinaite, NU-4, NU-5, Silicalite, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ- One or more zeolites selected from 1B, ZMQ-TB, and a mixture of two or more thereof may be mentioned. Preferably, however, the zeolitic material comprises ZSM-5 and / or ZBM-10 as one or more zeolites having an MFI-type framework structure. Thus, in a particularly preferred embodiment of the invention, the zeolitic material comprises ZSM-5.

Furthermore, there are no particular limitations on the preferred physical and / or chemical properties of the zeolitic material of the present invention. Thus, for example, any conceivable value can be used for the porosity and / or surface area of the material of the invention. In particular, for the BET surface area of the zeolitic material measured according to DIN 66131, the BET surface area is in the range of 200 to 900 m ² / g, preferably the BET surface area is in the range of 250 to 700 m ² / g, more preferably Is 300 to 600 m ² / g, more preferably 350 to 550 m ² / g, more preferably 380 to 500 m ² / g, more preferably 400 to 470 m ² / g, and still more preferably 420 to 450 m ^2. / G. In a particularly preferred embodiment of the invention, the BET surface area of the zeolitic material determined according to DIN 66131 is in the range of 425 to 440 m ² / g.

  According to the invention, it is further preferred that the zeolitic material has a low water absorption, ie a high hydrophobicity, for example the water absorption of the zeolitic material can be 10.0% by weight or less. However, the zeolitic material of the present invention preferably exhibits a water absorption of 10.0% by mass or less, more preferably 7.4% by mass or less, more preferably 6.2% by mass or less, more preferably 6.0% by mass or less. More preferably, it is 5.0% by mass or less, more preferably 4.5% by mass or less, more preferably 4.2% by mass or less, more preferably 3% by mass or less, more preferably 2.2% by mass or less. Indicates. In the present invention, it is particularly preferable that the zeolitic material exhibits a water absorption of 2% by mass or less, more preferably 1.5% by mass or less.

  In accordance with the specific requirements of the present application, the zeolitic material of the present invention is used in the form of a powder, sprayed powder, or sprayed granule obtained by the above-described separation techniques such as decantation, filtration, centrifugation or spraying. can do.

  In many industrial applications, it is often desirable on the part of the user not to use zeolitic material as a powder or spray material. That is, such a zeolitic material is obtained by separating the material from the mother liquor of the material, optionally washing and drying, followed by calcination, but further processed into a molded body. The material is excluded. Such shaped bodies are particularly required in many industrial processes, for example in many processes in which the zeolitic material of the invention is used as a catalyst or adsorbent.

  The invention therefore also relates to shaped bodies comprising the zeolitic material of the invention in a particularly preferred and preferred embodiment as defined herein. Therefore, this invention relates to the molded object containing the above-mentioned zeolitic material.

  In general, the shaped body can comprise any conceivable compound in addition to the zeolitic material of the invention, so long as the resulting shaped body is suitable for the desired application.

  In the present invention, it is preferable to use at least one suitable binder material in the production of the molded body. In this preferred embodiment, it is more preferred to produce a mixture of zeolitic material and at least one binder material.

Therefore, the present invention also describes a method for producing a molded body containing a zeolitic material as described above, and the production method includes the following steps:
(A) The process of producing the mixture containing the above-mentioned zeolite material or the zeolite material obtained by the above-mentioned method, and at least 1 sort (s) of binder material.

Suitable binder materials are generally all compounds that provide adhesion and / or cohesion between particles of the zeolitic material to be bonded, the adhesion and / or cohesion being the physical properties that exist without the binder material. Beyond adsorption. Examples of such binder materials include metal oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZrO ₂ or MgO, or clay, or a mixture of two or more of these compounds.

Clay minerals and natural or synthetic aluminas (eg, α-, β-, γ-, δ-, η-, κ-, χ- or θ-alumina), and inorganic or organic precursors thereof as Al ₂ O ₃ binder materials The body (eg, gibbsite, buyerite, boehmite, pseudoboehmite, or trialkoxy aluminate (eg, aluminum triisopropylate)) is particularly preferred. Further preferred binder materials include amphiphilic compounds and graphite having polar and nonpolar moieties. Furthermore, examples of the binder material include clay (eg, montmorillonite, kaolin, bentonite, halosite, dickite, nakurite, anaxite).

  These binders can be used by themselves. In the present invention, it is also possible to use a compound capable of forming a binder in at least one other step of manufacturing a molded body. Examples of such binder material precursors include tetraalkoxysilane, tetraalkoxytitanate, tetraalkoxyzirconate, a mixture of two or more different tetraalkoxysilanes, a mixture of two or more different tetraalkoxytitanates, or two or more. A mixture of different tetraalkoxy zirconates, a mixture of one or more tetraalkoxysilanes and one or more tetraalkoxytitanates, a mixture of one or more tetraalkoxysilanes and one or more tetraalkoxyzirconates, one or more tetra Mention may be made of a mixture of an alkoxy titanate and one or more tetraalkoxy zirconates, or a mixture of one or more tetraalkoxy silanes, one or more tetraalkoxy titanates and one or more tetraalkoxy zirconates. That.

In the present invention, a binder material which is a precursor of SiO ₂ which can form SiO ₂ in at least one other step of manufacturing a molded body, or a binder material containing SiO ₂ completely or partially is very particularly preferable. preferable. In the present invention, colloidal silica, wet silica and dry silica can be used. These are very particularly preferably amorphous silica. The particle diameter of these silica particles is in the range of 5 to 100 nm, and the surface area of the silica particles is in the range of 50 to 500 m ² / g.

Preferably as alkali and / or ammonia solution, and more preferably colloidal silica used as an ammonia solution is available in the market, especially Ludox ^R, Syton ^R, include Nalco ^R or Snowtex ^R. Wet silica is also available in the market, especially ^{Hi-Sil R, Ultrasil R,} Vulcasil R, Santocel R, Valron-Estersil R, include Tokusil ^R or Nipsil ^R. Dry silica is also available in the market, especially ^{Aerosil R, Reolosil R, Cab-} O-Sil R, include Fransil ^R or ArcSilica ^R. Of these, an ammonia solution of colloidal silica is preferred in the present invention.

Accordingly, the present invention also relates to the above-mentioned molded body, and further to a molded body containing SiO ₂ as a binder material.

The present invention also relates to binder materials used in accordance with (A) is a SiO ₂ content or forming binder material, the above-mentioned method. Accordingly, the present invention also relates to the above-described method wherein the binder material is colloidal silica.

  It is preferred to use the binder material in an amount that will result in the final molded body. The binder content is 80% by mass or less, more preferably 5 to 80% by mass, more preferably 10 to 70% by mass, more preferably 10 to 60% by mass, based on the total amount of the molded body finally obtained. More preferably, it is 15-50 mass%, More preferably, it is 15-45 mass%, Most preferably, it is 15-40 mass%.

  The mixture of binder material or binder material precursor and zeolitic material can be further processed and mixed with at least one other compound to form a plastic mass. In particular, a pore former is preferred here. The pore formers that can be used in the process of the invention are all compounds that give a certain pore size, a certain pore size distribution and / or a certain pore volume with respect to the shaped bodies to be produced.

  Preferred pore formers used in the method of the present invention include polymers that are dispersible, suspendable or emulsifiable in water or in aqueous solvent mixtures. Preferred polymers here are vinyl polymer compounds such as polyalkylene oxides (eg polyethylene oxide), polystyrene, polyacrylates, polymethacrylates, polyolefins, polyamides and polyesters, carbohydrates (eg cellulose or cellulose derivatives (eg methylcellulose)) ), Sugar or natural fiber. Further suitable pore formers are, for example, pulp, graphite.

  When the pore former is used in the preparation of the mixture according to (A), the polymer content of the mixture of (A) is from 5 to 90% by weight, based on the amount of zeolitic material in the mixture of (A), It is preferably 15 to 75% by mass, particularly preferably 25 to 55% by mass. If it is desired to achieve a pore size distribution, it is also possible to use a mixture of two or more pore formers.

  In a particularly preferred embodiment of the present invention as described above, the pore-forming agent is removed by calcination in step (E) to obtain a porous molded body. In a preferred embodiment of the process according to the invention, the pores determined according to DIN 66134 are at least 0.6 ml / g, preferably 0.6-0.8 ml / g, particularly preferably 0.6-0.7 ml / g. A certain shaped body is obtained.

The specific surface area of the shaped bodies according to the invention determined according to DIN 66131 is generally at least 250 m ² / g, preferably at least 290 m ² / g, particularly preferably at least 300 m ² / g. For example, the specific surface area may be 250~400m ² / g or 290~450m ² / g or 300~500m ² / g.

Accordingly, the present invention also relates to the above-mentioned shaped body comprising pores having a specific surface area of at least 250 m ² / g and a pore volume of at least 0.6 ml / g.

  In the preparation of the mixture according to (A), at least one pasting agent is added in a further preferred embodiment of the process according to the invention. The pasting agents used are all compounds suitable for this purpose. These are preferably organic, in particular hydrophilic polymers such as cellulose, cellulose derivatives (eg methylcellulose), starch (eg potato starch), wallpaper pastes, polyacrylates, polymethacrylates, polyvinyl alcohol, Polyvinyl pyrrolidone, polyisobutene, polyethylene glycol or polytetrahydrofuran is preferred. In particular, compounds that also act as pore-forming agents can be used as paste agents. In a particularly preferred embodiment of the method of the present invention, as described below, these pastes are removed by calcination in step (E) to obtain a porous shaped body.

  In a further aspect of the invention, at least one acidic additive is added during the preparation of the mixture according to (A). Organic acidic compounds are very particularly preferred since they can be removed by calcination in the preferred step (E) as described below. As the carboxylic acid, for example, oxalic acid and / or citric acid is particularly preferable. Mixtures of two or more of these acidic compounds can also be used.

  The order of addition of the components of the mixture according to (A) containing the zeolitic material is not critical. It is possible to first add at least one binder material, then add at least one pore former, at least one acidic compound, and finally add at least one paste. It is also possible to change the order of at least one binder material, at least one pore former, at least one acidic compound and at least one paste.

  After addition of the binder material to the zeolite-containing solid (optionally at least one compound as described above has already been added to the zeolite-containing solid), the mixture of (A) is generally homogenized for 10 to 180 minutes. The Among these, a kneader (kneader), an edge mill, or an extruder is particularly preferably used for homogenization. The mixture is preferably kneaded. On an industrial scale, treatment with an edge mill is preferable for homogenization.

Accordingly, the present invention also describes a method comprising the following steps:
(A) A step of producing a mixture containing the above-mentioned zeolitic material or the zeolitic material obtained by the above-mentioned method, and at least one binder material;
(B) A step of kneading the mixture.

  In the homogenization, generally, a temperature from about 10 ° C. to the boiling point of the paste and a pressure slightly exceeding atmospheric pressure (overpressure) is used. Then at least one of the above-mentioned compounds can optionally be added. The resulting mixture is homogenized, preferably kneaded, until an extrudable plastic mass is formed. The homogenized mixture is shaped according to a preferred embodiment of the present invention.

  In the present invention, a preferable molding method is a method in which a molded body is obtained by a conventional extruder, for example, by giving an extrudate, preferably an extrudate having a diameter of 1 to 10 mm, particularly preferably 2 to 5 mm. . Such a method is described, for example, in Ullmann's Enzyklopadie der Technischen Chemie, 4th Edition, Vol. 2, page 295 et seq., 1972. In addition to the use of an extruder, it is further preferred to use a ram extruder for molding.

In general, however, all known and / or suitable kneading and shaping devices and methods can be used for shaping. Examples of these include:
(A) Briquetting, ie mechanical pressing with or without additional binder material;
(B) pelletization, ie pelletization by circulation and / or rotational movement;
(C) calcination, i.e. subjecting the material to be molded to a heat treatment.

  For example, the molding can be selected from the following groups that explicitly include a combination of at least two of these methods: ram press, roll press, ring-roll press briquetting, binderless briquetting; pelletizing Melting, spinning technology, deposition, foaming, spray-drying; blast furnace combustion, convection furnace, moving grid, rotary furnace, edge mill.

  Compacting can be carried out at normal pressure or overpressure, for example from 1 bar to several hundred bar. Further, the compression can be performed at room temperature or higher than room temperature, for example, 20 to 300 ° C. Finally, when drying and / or combustion is part of the molding process, temperatures below 1500 ° C. can be envisaged, compression can be carried out at normal or controlled atmospheric pressure. The controlled atmospheric pressure is, for example, an inert gas atmospheric pressure or a reducing and / or oxidizing atmospheric pressure.

Accordingly, the present invention also describes a method for producing the above-mentioned shaped body comprising the following steps:
(A) A step of producing a mixture containing the above-mentioned zeolite material or the zeolite material obtained by the above-mentioned method, and at least one binder material;
(B) a step of kneading the mixture;
(C) A step of molding the kneaded mixture to obtain at least one molded body.

  According to the invention, the shape of the shaped body can be selected as desired. In particular, spherical, oval, cylindrical or tablets are possible.

  In the present invention, the molding is particularly preferably performed by extrusion of the kneaded mixture obtained in (B). More preferred substantially cylindrical extrudates having a diameter in the range of 1-20 mm, preferably in the range of 1-10 mm, more preferably in the range of 2-10 mm, particularly preferably in the range of 2-5 mm, are extrudates. As obtained.

  In this invention, it is preferable to perform at least 1 drying process following a process (C). This at least one drying step is generally achieved at a temperature in the range of 80-160 ° C., preferably in the range of 90-145 ° C., particularly preferably in the range of 100-130 ° C., and the duration of the drying is generally over 6 hours, For example, it is performed in 6 to 24 hours. However, depending on the moisture content of the material being dried, shorter drying times are possible, for example about 1, 2, 3, 4, or 5 hours.

  Before and / or after the drying step, the preferably obtained extrudate can be ground, for example. It is preferable to obtain granules or chips having a particle size of 0.1 to 5 mm, especially 0.5 to 2 mm.

Accordingly, the present invention also describes a method for producing the above-mentioned shaped body comprising the following steps:
(A) A step of producing a mixture containing the above-mentioned zeolite material or the zeolite material obtained by the above-mentioned method, and at least one binder material;
(B) a step of kneading the mixture;
(C) forming a kneaded mixture to obtain at least one shaped body;
(D) The process of drying at least 1 type of molded object.

  In the present invention, it is preferable to perform at least one calcination step subsequent to step (D). Calcination is generally carried out at a temperature in the range of 350 to 750 ° C, preferably in the range of 450 to 600 ° C.

  Calcination can be performed under a suitable gas pressure, preferably air and / or lean air. Furthermore, the calcination is preferably performed in a muffle furnace, a rotary furnace and / or a belt calcination furnace, and the calcination period is generally 1 hour or longer, for example, 1 to 24 hours, or 3 to 12 hours. Thus, in the method of the present invention, it is possible, for example, to calcine the compact once, twice or more, each time for at least 1 hour, for example 3 to 12 hours, and The temperature during the calcination process can be maintained at the same temperature or can be changed to continuous or discontinuous. When calcination is carried out twice or more, the calcination temperatures in the individual steps may be the same or different.

Therefore, the present invention also relates to a method for producing the above-mentioned molded body, which includes the following steps:
(A) A step of producing a mixture containing the above-mentioned zeolite material or the zeolite material obtained by the above-mentioned method, and at least one binder material;
(B) a step of kneading the mixture;
(C) forming a kneaded mixture to obtain at least one shaped body;
(D) drying at least one molded article;
(E) A step of calcining at least one dried molded body.

  After the calcination step, the calcined material can be crushed, for example. It is preferable to obtain granules or chips having a particle size of 0.1 to 5 mm, especially 0.5 to 2 mm.

  Treating at least one shaped body with a concentrated or diluted Bronsted acid or a mixture of two or more Bronsted acids before and / or after drying and / or before and / or after calcination. Can do. Preferred acids include, for example, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or carboxylic acid, dicarboxylic acid or oligo- or polycarboxylic acid (eg, nitrilotriacetic acid, sulfosalicylic acid or ethylenediaminotetraacetic acid).

  This treatment with at least one Bronsted acid is followed by at least one drying step and / or at least one calcination step, in each case under the conditions described above.

  In a further preferred embodiment of the process according to the invention, it is preferred that the catalyst extrudate can be subjected to steam treatment for better curing and then again dried at least once and / or calcined at least once. . For example, after at least one drying step and at least one subsequent calcination step, the calcined form is subjected to steam treatment and then again dried and / or calcined at least once.

  The molded body obtained in the present invention generally has a hardness in the range of 2 to 40N, preferably 5 to 40N, particularly preferably 10 to 40N.

  Accordingly, the present invention also relates to the above-described molded body having a cutting hardness of 2 to 40N.

  In the present invention, the above-mentioned hardness is measured using a Zwick, type BZ2.5 / TS1S device, which measures 0.5 N initial force, 10 mm / min feed rate under initial force, and Performed at a test speed of 6 mm / min. The apparatus has a fixed turntable and a free moving punch with a built-in blade of 0.3 mm thickness. This movable punch with a blade is connected to a force pick-up load cell and moves to a fixed turntable on which a catalyst molded body to be investigated exists during measurement. The test apparatus is controlled by a computer that registers and evaluates test results. The value obtained is the average of the measured values of 10 catalyst compacts in each case. The catalyst molded body has a cylindrical shape, the average length of which corresponds to about 2 to 3 times the diameter, and the force (force) is increased with a 0.3 mm thick blade until the molded body is cut. A load is applied. The blade is applied perpendicular to the long axis of the shaped body. The force for this is the cutting hardness (unit N).

  Therefore, the present invention also relates to a molded body obtained by the method of any one of the above embodiments.

  The at least one shaped body according to the invention and / or the shaped body produced according to the invention is generally characterized by the properties of the shaped body, in particular the nature of the zeolitic material of the invention contained in the shaped body or the zeolite produced according to the invention. It can be used in any method or operation where the nature of the material is desired. It is very particularly preferred that at least one shaped body according to the invention or a shaped body produced according to the invention is used as a catalyst in a chemical reaction.

  In general, the zeolitic materials having MFI, MEL and / or NWW-type framework structures described in the present invention and particularly preferred and preferred embodiments herein can be used for any suitable application. . The zeolitic material is preferably used as a molecular sieve, catalyst, catalyst support, and / or absorbent. For example, the zeolitic material of the present invention can be used as a molecular sieve to dry a gas or liquid for selective separation of molecules (eg, separation of hydrocarbons or amines), as an ion exchanger, as a chemical carrier, as an adsorbent (particularly , An adsorbent for the separation of hydrocarbons or amines), or as a catalyst. The zeolitic material of the present invention is most preferably used as a catalyst and / or catalyst support.

  According to a preferred embodiment of the invention, the zeolitic material is used in a catalytic process, preferably as a catalyst and / or catalyst support, more preferably as a catalyst. In general, the zeolitic material of the present invention can be used in a possible catalytic process, preferably a process comprising the conversion of at least one organic compound, more preferably at least one carbon-carbon bond and / or carbon. Conversion of organic compounds containing oxygen bonds and / or carbon-nitrogen bonds, more preferably conversion of organic compounds containing at least one carbon-carbon bond and / or carbon-oxygen bond, even more preferably at least one kind A method involving the conversion of an organic compound containing a carbon-oxygen bond.

  Thus, in a particularly preferred embodiment of the invention, the zeolitic material is converted from an oxygen-containing material to an olefin, a process for converting methanol to gasoline (MTG), a process for converting biomass to olefins and / or converting biomass to aromatics. Used as a catalyst in a process, a process for converting methanol to benzene, an aromatic alkylation process, or a fluid catalytic cracking (FCC) process. According to the invention, the zeolitic material is particularly preferably used in a process for the conversion of oxygen-containing substances to olefins, further a process for the conversion of dimethyl ether to olefins (DTO), a process for the conversion of methanol to olefins (MTO). It is preferably used as a catalyst in a process for the conversion of methanol to propylene (MTP) and / or for the conversion of methanol to propylene / butylene (MT3 / 4).

In addition to relating to zeolitic materials having an MFI, MEL and / or NWW-type framework structure and methods for producing such zeolitic materials, the present invention also relates to a method for converting oxygen-containing materials to olefins. In particular, the present invention also relates to a process for converting an oxygen-containing material to an olefin comprising the following steps:
(I) supplying a gas stream containing one or more oxygen-containing materials;
(II) contacting the gas stream with a catalyst comprising the zeolitic material of the invention, in particular a zeolitic material according to a particularly preferred and preferred embodiment of the invention.

  With respect to the catalyst used in the process of the present invention, as long as it contains the zeolitic material of the present invention and it is suitable for converting one or more oxygen-containing materials to one or more olefins, particular limitations are Absent. This is also applicable to particularly preferred and preferred aspects of the invention as defined herein. However, in a particularly preferred embodiment of the process for converting oxygen-containing materials to olefins of the present invention, the catalyst comprises a shaped body according to any of the particularly preferred and preferred embodiments of the present invention, and therefore the shaped body is the present invention. A zeolitic material according to any of the particularly preferred and preferred embodiments.

For the gas stream of step (I), as long as it satisfies the condition that one or more oxygen-containing materials are converted to at least one olefin in contact with the catalyst of the invention and particularly preferred and preferred embodiments of the invention, There is no particular limitation in the present invention regarding one or more oxygen-containing substances contained in the gas stream. However, in the present invention, the one or more oxygen-containing substances contained in the gas stream supplied in step (I) are oxygen-containing selected from aliphatic alcohols, ethers, carbonyl compounds, and mixtures of two or more thereof. Contains substances. In the inventive conversion method of oxygen-containing materials to olefins, the one or more oxygen-containing materials contained in the gas stream are C ₁ -C ₆ -alcohol, di-C ₁ -C ₃ -alkyl ether, C _1- It is preferably selected from C ₆ -aldehyde, C ₂ -C ₆ -ketone, and mixtures of two or more thereof, more preferably C ₁ -C ₄ -alcohol, di-C ₁ -C ₂ -alkyl ether , C ₁ -C ₄ -aldehyde, C ₂ -C ₄ -ketone, and mixtures of two or more thereof. In an even more preferred embodiment of the present invention, the one or more oxygen-containing substances contained in the gas stream are methanol, ethanol, n-propanol, isopropanol, butanol, dimethyl ether, diethyl ether, ethyl methyl ether, diisopropyl ether, di-n. -Selected from propyl ether, formaldehyde, dimethyl ketone and mixtures of two or more thereof. One or more oxygen-containing substances contained in the gas stream are methanol, ethanol, n-propanol, isopropanol, butanol, dimethyl ether, diethyl ether, ethyl methyl ether, diisopropyl ether, di-n-propyl ether, formaldehyde, dimethyl ketone and It is even more preferable to select from a mixture of two or more of these, and it is more preferable to select from a mixture of methanol, ethanol, dimethyl ether, diethyl ether, ethyl methyl ether and a mixture of two or more thereof. According to a particularly preferred embodiment of the process of the present invention for converting oxygen-containing materials to olefins, the gas stream supplied in step (I) comprises methanol and / or dimethyl ether, in particular of the gas stream supplied in (I). The one or more oxygen-containing materials preferably include dimethyl ether.

  Regarding the content of the oxygen-containing substance in the gas stream of (I) in the process of the present invention for converting oxygen-containing substances to olefins, the contact of the gas stream of (II) with the catalyst containing the zeolitic material of the present invention is one type. There is no particular limitation as long as the above oxygen-containing material can be converted to one or more olefins. In a preferred embodiment of the process according to the invention, the content of oxygen-containing substances in the gas stream of (I) is in the range of 30 to 100% by volume with respect to the total volume of the gas stream, and the content is in particular: Gas flow at a temperature in the range of 200-700 ° C and a pressure of 101.3 kPa, more preferably in the range of 250-650 ° C, more preferably in the range of 300-600 ° C, more preferably in the range of 350-560 ° C, Preferably for a gas stream at a temperature in the range of 400-540 ° C, more preferably in the range of 430-520 ° C, more preferably in the range of 450-500 ° C and a pressure of 101.3 kPa. In the present invention, the oxygen-containing substance content of the gas stream (I) is 30 to 99.9% by volume, more preferably 30 to 99% by volume, and more preferably 30 to 95% by volume, based on the total volume of the gas stream. More preferably, it is 30 to 90% by volume, more preferably 30 to 80% by volume, still more preferably 30 to 70% by volume, still more preferably 30 to 60% by volume, and even more preferably 30 to 50% by volume. In a particularly preferred embodiment of the process according to the invention, the content of at least one oxygen-containing substance in the gas stream (I) is between 30 and 45% by volume.

  For this reason, as an aspect of the conversion method of the present invention for converting an oxygen-containing material into an olefin, the gas stream supplied in the step (I) contains 30 to 100% by volume of the oxygen-containing material with respect to the total gas flow capacity Embodiments are preferred.

  Regarding the additional components that may be included in the gas stream of (I) in the process of the present invention, generally at least one or more oxygen-containing substances when the gas stream is contacted with the zeolitic material of the invention in step (II) As long as one can be converted to at least one olefin, there is no particular limitation regarding the number and amount of one or more additional component types for the one or more oxygen-containing materials. Thus, in addition to one or more oxygen-containing materials, for example, one or more inert gases can be included in the gas stream (I), examples of inert gases include one or more noble gases, Nitrogen gas, carbon monoxide, carbon dioxide, water and a mixture of two or more of these may be mentioned. Alternatively, in addition to these, the one or more inert gases may be recycled unwanted by-products such as paraffin, olefinic compounds having 5 or more carbon atoms, aromatics, or a mixture of two or more of these. Which are produced according to any of the particularly preferred and preferred embodiments of the process of the present invention for converting oxygen-containing materials to olefins. In a particularly preferred embodiment of the present invention, the gas stream of (I) of the method of the present invention further comprises water in addition to one or more oxygen-containing materials.

  According to a particularly preferred embodiment of the process of the invention, in addition to the one or more oxygen-containing substances, water is included in the gas stream of (I) and at least one oxygen-containing substance is in step (II) The amount of water that can be included in the gas stream is not particularly limited as long as it satisfies the condition that it is converted to at least one olefin by contacting the gas stream with the catalyst of the present invention. Thus, for example, the gas stream supplied in step (I) can contain up to 60% by volume of water with respect to the total volume of the gas stream, and in a particularly preferred embodiment, 5% with respect to the total volume of the gas stream. It contains ˜60% by volume of water, and the water content is preferably in the range of 10 to 55% by volume and more preferably in the range of 20 to 50% by volume with respect to the total volume of the gas stream. In a particularly preferred embodiment of the invention, in addition to the one or more oxygen-containing substances, water is included in the gas stream (I) in the range of 30 to 45% by volume.

  However, in another preferred embodiment, no or very close amount of water is contained in the gas stream supplied in step (I), in particular the water content is not more than 5% by volume, more preferably not more than 3% by volume. More preferably, it is 1% by volume or less, more preferably 0.5% by volume or less, more preferably 0.1% by volume or less, further preferably 0.05% by volume or less, more preferably 0.01% by volume or less, Preferably it is 0.005 volume% or less, More preferably, it is 0.001 volume% or less.

  For this reason, an embodiment of the method of the present invention is preferred in which the gas stream supplied to (I) contains 60% or less by volume of water relative to the total volume of the gas stream.

In a particularly preferred embodiment of the process of the invention for converting oxygen-containing materials to olefins, the gas stream of (I) results from a pre-reaction, preferably from the conversion of one or more alcohols to one or more ethers, in particular Preferred alcohols are selected from methanol, ethanol, n-propanol, isopropanol and mixtures of two or more thereof, and more preferred alcohols are selected from methanol, ethanol, n-propanol and mixtures of two or more thereof. The gas stream of (I) arises from a pre-reaction of methanol and / or ethanol, preferably from a pre-reaction of methanol and at least part of which is one or more di-C ₁ -C ₂ -alkyl ethers, Converted to one or more di-C ₁ -C ₂ -alkyl ethers selected from dimethyl ether, diethyl ether, ethyl methyl ether and mixtures of two or more thereof. In a particularly preferred embodiment of the process according to the invention, the gas stream of (I) results from a pre-reaction and at least part of the methanol is converted to dimethyl ether.

  In a particularly preferred embodiment of the present invention, the gas stream fed in step (I) results from a pre-reaction of one or more alcohols, and in step (II) is contacted with the catalyst of the present invention and at least one As long as the gas stream containing the one or more oxygen-containing materials that converts the oxygen-containing material into at least one olefin satisfies the condition that its pre-reaction is effected, the reaction of the conversion of one or more alcohols and 1 There are no particular limitations on the reaction product from the conversion of more than one species of alcohol. In said preferred embodiment, the pre-reaction for the conversion of at least one alcohol preferably results in at least one ether, in particular a dialkyl ether. In particular, the preliminary reaction is preferably a dehydration reaction, and water is preferably produced as a secondary product in a condensation reaction that results in one or more dialkyl ethers. In a particularly preferred and preferred embodiment of the invention in which the gas stream fed in step (I) occurs in a pre-reaction, in the process according to the invention, the gas stream obtained from such a pre-reaction It is particularly preferred that it is fed directly to step (I) of the method of the present invention without undergoing post-treatment.

  For the specific conditions in which the gas stream is contacted with the catalyst of the invention in step (II), there is no particular limitation as long as the conversion of at least one oxygen-containing material to at least one olefin is realized. For example, this condition is a temperature at which the contact in the step (II) is performed. Thus, the contact with the gas stream of step (II) can be carried out according to the method of the invention at a temperature in the range of 200-700 ° C., the contact in the temperature range of 250-650 ° C., more preferably 300. The temperature is preferably in the range of ˜600 ° C., more preferably in the range of 350 to 560 ° C., more preferably in the range of 400 to 540 ° C., and still more preferably in the range of 430 to 520 ° C. In a particularly preferred embodiment of the process according to the invention, the contact with the gas stream in step (II) is carried out at a temperature in the range from 450 to 500 ° C.

  Thus, in the process aspect of the present invention, the contact of the gas stream in step (II) with the zeolitic material is carried out at a temperature in the range of 200-700 ° C.

  Therefore, the same is true for the pressure at which the gas stream is brought into contact with the catalyst of the present invention in step (II) of the process of the present invention. Thus, as long as the gas stream can be contacted with the catalyst of the present invention to convert at least one oxygen-containing material to at least one olefin, the contacting can be carried out at any conceivable pressure. . Thus, for example, the contact in step (II) can be carried out at a pressure in the range of 0.1 to 10 bar, and the pressure of the present invention is 1.03 kPa at the pressure of 1 bar when contacting the gas stream and the catalyst. Absolute pressure is shown to correspond to the normal pressure. In the method of the present invention, the contact in step (II) is preferably carried out at a pressure of 0.3-7 bar, more preferably 0.5-5 bar, more preferably 0.7-3 bar, more preferably 0.8 to 2.5 bar, more preferably 0.9 to 2.2 bar. In a particularly preferred embodiment of the process according to the invention, the contact with the gas stream of step (II) is carried out at a pressure of 1 to 2 bar.

  For this reason, the embodiment of the present invention is preferably such that the contact between the gas stream and the zeolitic material in step (II) is carried out at a pressure in the range of 0.1 to 10 bar.

  Further, the process of the present invention can be in both discontinuous mode and continuous mode, and there is no particular limitation on the manner in which the process of the present invention for converting oxygen-containing materials to olefins is carried out. The discontinuous method can be performed by, for example, a batch method. However, in the present invention, it is preferred that the process of the present invention for converting oxygen-containing materials to olefins be carried out at least in part in a continuous mode.

With regard to a preferred embodiment of the process of the present invention, when at least partly in the continuous mode, the weight hourly space velocity (WHSV) per unit time in carrying out the process, as long as the conversion of the oxygen-containing material to olefin is realized There is no special limitation. Accordingly, the weight space velocity per unit time is selected in consideration of the contact in the step (II), and is generally 0.5 to 50 hours ⁻¹ , preferably the weight space velocity per unit time is 1 to 30 hours. ^-1 , more preferably 2 to 20 hours ⁻¹ , more preferably 3 to 15 hours ⁻¹ , more preferably 4 to 10 hours ⁻¹ . In a particularly preferred embodiment of the process according to the invention, it is carried out at least partly in a continuous mode, the contact between the gas stream of step (II) and the catalyst according to the invention being a weight space per unit time of 5-7 hours- ^1. Speed is selected.

  With regard to the preferred weight hourly space velocity per unit time in a preferred embodiment of the method of the present invention for the conversion of oxygen-containing materials to olefins, this weight space velocity per unit time is provided in step (I) of the method of the present invention. Is adjusted as a function of the conversion of one or more oxygen-containing substances contained in the gas stream being adjusted, and in particular adjusted to achieve a certain level of conversion falling within a particular range. Thus, in a particularly preferred and preferred embodiment of the process according to the invention, the weight hourly space velocity can be adjusted so that the conversion of one or more oxygen-containing substances is in the range of 50 to 99.9%. . In the present invention, the weight space velocity per unit time is in accordance with a particularly preferred and preferred embodiment of the present invention, preferably the conversion of one or more oxygen-containing materials is 70-99.5%, more preferably 90-99%. More preferably, it is 95-98.5%, More preferably, it is 96-98%, More preferably, it is 96.5-97.5%. However, in the present invention, the weight space velocity per unit time when the gas stream of step (II) is in contact with the catalyst of the present invention ensures a sufficient conversion of sufficient oxygen-containing material, ie 96 0.5-99.9% conversion thereof, more preferably 97.5-99.9% conversion of oxygen-containing material, more preferably 98-99.9% conversion thereof, more preferably 99-99.9%. % Oxygen-containing material, and more preferably adjusted to ensure 99.5-99.9% oxygen-containing material conversion.

Accordingly, the weight space velocity per unit time of the gas stream of step (II) is selected in consideration of the contact of step (II), and the embodiment of the present invention generally in the range of 0.5 to 50 hours ⁻¹ Further preferred.

Determination of crystallinity The crystallinity of the zeolitic material of the present example was determined by XRD analysis. That is, the crystallinity of a given material is expressed relative to a reference zeolitic material, where the reflective surfaces of the two zeolitic materials are compared. The reference zeolitic material was commercial H-ZSM-5 with a SiO ₂ / Al ₂ O ₃ ratio of 100 or 250. The crystallinity was determined using a D8 Advance series 2 diffractometer manufactured by Bruker AXS. The diffractometer consists of an aperture with a divergence aperture of 0.1 ° and a Lynxey detector. Samples and reference zeolitic material were measured in the range of 21 ° to 25 ° (2θ). After correcting the baseline, the reflective surface was determined using evaluation software EVA (manufactured by Bruker AXS). The ratio of the reflective surfaces is obtained in%.

FT-IR measurement The IR measurement of the Example of this application was performed with the Nicolet 6700 spectrometer. Zeolite material was compressed without additives to obtain self-supporting pellets. This pellet was introduced into a high vacuum cell in an IR measuring instrument. Prior to measurement, the sample was pretreated at 300 ° C. under high vacuum (10-5 mbar) for 3 hours. Spectra were collected after cooling the cell to 50 ° C. Spectra were recorded with a resolution of ^{2 cm -1} in the range of ^{4000cm -1 ~1400cm} -1. The obtained spectrum is represented by the wave number (cm ⁻¹ ) of the x axis and the absorbance (arbitrary unit) of the y axis. Baseline corrections were made for quantitative determination of band height and ratio between bands. Analyzing the changes in 3000cm ^-1 ~3900cm ^-1, in order to compare the number of samples was a standard band of 1880 ± ^{5 cm -1.}

Measurement of water adsorption / desorption Water adsorption / desorption isotherms in the examples of the present application were obtained with a VTI SA measuring instrument manufactured by TA Instruments. The experiment consisted of one run or a series of runs made on the sample material placed in a microbalance dish inside the measuring instrument. Before starting the measurement, residual moisture in the sample was removed by heating the sample to 100 ° C. (5 ° C./min ramp) and maintaining for 6 hours under nitrogen flow. After the drying program, the cell temperature was lowered to 25 ° C. and kept constant during the measurement. The microbalance was calibrated and the mass of the dried sample was weighed (maximum mass deviation 0.01% by mass). The water absorption of the sample was measured as an increase in mass compared to the dry sample. First, the adsorption curve was measured by increasing the relative humidity (RH) at which the sample was exposed (expressed as mass% water at atmospheric pressure inside the cell) and measuring the water absorption of the sample as an equilibrium. . The RH was increased from 5% to 85% every 10% step and the system controlled the RH at each step and monitored the sample mass until the sample reached equilibrium conditions and recorded the water absorption mass. After the sample was exposed to 85% by weight RH, the total adsorbed water of the sample was obtained. During the desorption measurement, RH was decreased from 85% to 5% in 10% steps and the change in mass of the sample (water absorption) was recorded.

Determination of Crushing Strength of Molded Body It should be understood that the crushing strength of the examples of the present application was determined by a crushing strength tester Z2.5 / TS1S manufactured by Zwick GmbH & Co., D.89070 Ulm. The basics of this device and its operation are described in the instructions “Register 1: Betriebsanleungung / Sicherheithandbuch furdie-Material-Purfmaskine Z2.5 / TS1S”, December 2001, Zwick TchGb. Reference is made to Documentation, August-Nagel-Strasse 11, D-89079 Ulm, Germany. Using this equipment, the force produced by the 3 mm diameter plunger was increased until the strands of the given (final) 2.5 mm diameter made in Examples 5-11 were crushed. give. The force that the strands crush is called the strand crushing strength. The instrument is mounted on a fixed horizontal table on which the strands are placed. A plunger that moves freely in the vertical direction actuates the strand against a fixed floor table. The device operates with an initial force of 0.5 N, a shear rate of 10 mm / min under the initial force, and a subsequent test speed of 1.6 mm / min. A vertically movable plunger was connected to the force pick-up load cell and moved during the measurement relative to a fixed turntable on which the shaped body (strand) to be investigated was placed, thus actuating the strand against the table. . A plunger was applied to the strand perpendicular to its long axis. The experiment was controlled by a computer that registered and evaluated the measurement results. The value obtained is the average of the measured values of 25 strands each.

Reference Example 1: Synthesis of ZSM-5 zeolite having a SiO ₂ : Al ₂ O ₃ molar ratio of 100 Tetraethylorthosilicate (757 g) was stirred in a four-necked flask. Water (470 g) and tetrapropylammonium hydroxide (40% by weight aqueous solution, 366 g) were added. The mixture was stirred for 60 minutes, during which time the temperature was raised to 60 ° C. This is due to the hydrolysis of tetraethylorthosilicate resulting in the formation of alcohol. The ethanol was removed by distillation until the drain temperature reached 95 ° C. This removed 817 g of ethanol from the mixture. The mixture was then cooled to 40 ° C. with stirring, 817 g of water was added, and the resulting gel was filled into an autoclave. A solution of aluminum sulfate 18 hydrate (24.2 g) and water (40 g) was added to the autoclave. The autoclave was closed and heated to 170 ° C.

  After stirring the gel at 170 ° C. for 48 hours, the autoclave was cooled to room temperature and the mixture was removed. It was treated with nitric acid (10 wt% aqueous solution, 173 g) until pH was 7.3. The resulting suspension was filtered. The filter cake was washed three times with water (1000 mL each time), dried (4 hours, 120 ° C.) and calcined (5 hours, 500 ° C.) to give 217 g of ZSM-5. The primary particle size determined by SEM was in the range of 100-200 nm.

Elemental analysis:
Si 43.5 mass%
Al 0.87 mass%
Na <100 ppm
K <100ppm

Thus, by chemical analysis, the calcined material exhibited a SiO ₂ : Al ₂ O ₃ molar ratio of 96.

  FIG. 1A shows an XRD of a crystalline product obtained by the synthesis of Reference Example 1 and displaying a typical line pattern of the MFI skeleton structure. The crystallinity according to Reference Example 1 was 98%.

FIG. 1B shows an electron micrograph of the product obtained by SEM at a magnification of 75 × 10 ⁴ . As can be seen from the electron micrographs, in particular, spherical primary particles were observed even at this high magnification and the primary particle size was determined to be in the range of 100-170 nm.

This material exhibited a BET surface area of 426 m ² / g. The pore volume is 0.17 cm ³ / g at p / p ₀ = 0.302 and the median pore width is 0.58 nm, respectively, by argon adsorption using the Horvath-Kawazoe method. It has been determined. The total intrusion volume determined by Hg porosimetry (porosity measurement) according to DIN 66133 was 1.24 ml / g (milliliter / gram) and each total pore area was 40.5 m ² / g.

  Temperature programmed desorption of ammonia was 0.43 mmol / g when performed at 152 ° C. and 0.24 mmol / g when performed at 378 ° C.

  The material had 6.3% by weight water absorption at 85% relative humidity.

  FIG. 1C shows the IR-OH band of the sample obtained in Reference Example 1. The band regions along the band height are as follows:

  Therefore, the IR-band ratio of the absorbance intensity of the silanol nest to the absorbance intensity of the surface silanol reaches 1.45.

Reference Example 2: Synthesis of ZSM-5 zeolite having a SiO ₂ : Al ₂ O ₃ molar ratio of 250 Tetraethylorthosilicate (757 kg) was stirred in a container. Water (470 kg) and tetrapropylammonium hydroxide (40% by weight aqueous solution, 333 kg) were added. The mixture was stirred for 60 minutes, during which time the temperature was raised to 60 ° C. This is due to the hydrolysis of tetraethylorthosilicate resulting in the formation of alcohol. The ethanol was removed by distillation until the drain temperature reached 95 ° C. This removed 832 kg of ethanol from the mixture. 832 kg of water and a solution of aluminum sulfate 18 hydrate (9.4 kg) and water (20 kg) were added to the container. The vessel was closed and heated to 150 ° C.

  After the gel was stirred at 150 ° C. for 24 hours, the autoclave was cooled to room temperature and the mixture was removed. It was treated with nitric acid (10% by weight aqueous solution) until the pH was 7.1. The resulting suspension was filtered. The filter cake was washed with water and dried (120 ° C.). The dry powder was ground and then calcined (5 hours, 500 ° C.).

Elemental analysis:
Si 43.5 mass%
Al 0.36 mass%
Na <100 ppm
K <100ppm

Thus, by chemical analysis, the calcined material exhibited a SiO ₂ : Al ₂ O ₃ molar ratio of 233.

  FIG. 2A shows an XRD of the crystalline product obtained by the synthesis of Reference Example 2 and displaying a typical pattern of the MFI skeleton structure. The crystallinity according to Reference Example 2 was 96%.

FIG. 2B shows an electron micrograph of the product obtained by SEM at a magnification of 75 × 10 ⁴ . As can be seen from the electron micrographs, in particular spherical primary particles were observed even at this high magnification, and the primary particle size was determined to be in the range of 50-150 nm.

This material exhibited a BET surface area of 441 m ² / g. The pore volume is 0.18 cm ³ / g at p / p ₀ = 0.301 and the median pore width is 0.54 nm, respectively, by argon adsorption using the Horvath-Kawazoe method. It has been determined. The total intrusion volume determined by Hg porosimetry (porosity measurement) according to DIN 66133 was 1.45 ml / g (milliliter / gram) and each total pore area was 71.3 m ² / g.

The temperature programmed desorption (NH ₃ -TPD) of ammonia was 0.24 mmol / g when performed at 107 ° C. and 0.12 mmol / g when performed at 343 ° C.

  The material had 7.1 wt% water absorption at 85% relative humidity.

FIG. 2C shows the IR-OH band of the sample obtained in Reference Example 2. The band regions along the band height are as follows:

  Therefore, the IR-band ratio of the absorbance intensity of the silanol nest to the absorbance intensity of the surface silanol reaches 1.36.

Reference Example 3: Synthesis of ZSM-5 zeolite having a SiO ₂ : Al ₂ O ₃ molar ratio of 320 Tetraethyl orthosilicate (757 g) was stirred in a four-necked flask. Water (470 g) and tetrapropylammonium hydroxide (40% by weight aqueous solution, 333 g) were added. The mixture was stirred for 60 minutes, during which time the temperature was raised to 60 ° C. This is due to the hydrolysis of tetraethylorthosilicate resulting in the formation of alcohol. The ethanol was removed by distillation until the drain temperature reached 95 ° C. This removed 805 g of ethanol from the mixture. The mixture was then cooled to 40 ° C. with stirring, 805 g of water was added, and the resulting gel was filled into an autoclave. A solution of aluminum sulfate 18 hydrate (7.6 g) and water (25 g) was added to the autoclave. The autoclave was closed and heated to 170 ° C.

  After the gel was stirred at 170 ° C. for 24 hours, the autoclave was cooled to room temperature and the mixture was removed. It was treated with nitric acid (10 wt% aqueous solution, 203 g) until the pH was 7.6. The resulting suspension was filtered. The filter cake was washed 3 times with water (each time 1000 mL), dried (4 hours, 120 ° C.) and calcined (5 hours, 500 ° C.) to give 222 g of calcined zeolite ZSM-5.

Elemental analysis:
Si 44% by mass
Al 0.26% by mass
Na <100 ppm
K <100ppm

Thus, by chemical analysis, the calcined material exhibited a SiO ₂ : Al ₂ O ₃ molar ratio of 325.

  FIG. 3A shows an XRD of the crystalline product obtained by the synthesis of Reference Example 3 and displaying a typical pattern of the MFI skeleton structure.

FIG. 3B shows an electron micrograph of the product obtained by SEM at a magnification of 75 × 10 ⁴ . As can be seen from the electron micrographs, in particular, spherical primary particles were observed even at this high magnification, and the primary particle size was determined to be in the range of 100-200 nm.

This material exhibited a BET surface area of 442 m ² / g. The pore volume is 0.18 cm ³ / g at p / p ₀ = 0.301 and the median pore width is 0.58 nm, respectively, by argon adsorption using the Horvath-Kawazoe method. It has been determined. The temperature programmed desorption (NH ₃ -TPD) of ammonia was 0.19 mmol / g when performed at 108 ° C. and 0.067 mmol / g when performed at 340 ° C.

Reference Example 4: Water Treatment of ZSM-5 Zeolite with a SiO ₂ : Al ₂ O ₃ Molar Ratio of 100 Starting from the calcined powder obtained in Reference Example 1, the post-treatment was performed as follows:
100 g of the calcined powder obtained in Reference Example 1 was suspended in 2000 g of deionized water. The mixture was filled into a container and the container was closed (consolidated). The mixture was then heated at 145 ° C. within 1.5 hours, and this temperature was maintained at self-generated pressure (about 4 bar) for 8 hours. The water treatment powder was filtered and washed with deionized water. The obtained filter cake was dried at 120 ° C. for 4 hours. The dried material was then heated under air to a temperature of 500 ° C. within 4 hours and maintained at this temperature for 5 hours. The yield after that was 85 g.

The resulting water-treated zeolite powder had a Si content of 45% by weight and an Al content of 0.87% by weight (corresponding to 99 SiO ₂ : Al ₂ O ₃ molar ratio).

  The crystallinity determined by XRD was 101-114%. The XRD of the material is shown in FIG. 4A. Therefore, the water treatment of the present invention increased the above value from 98% (Reference, Reference Example 1) to 101-114%.

FIG. 4B shows an electron micrograph of the product obtained by SEM at 50 × 10 ⁴ magnification. As can be seen from the electron micrographs, in particular, spherical primary particles were observed even at this high magnification, and the primary particle size was determined to be in the range of 70-150 nm.

This powder exhibited a multipoint BET surface area of 427 m ² / g. The BET surface area was determined by nitrogen adsorption at 77K according to DIN 66133. The pore volume is 0.17 cm ³ / g at p / p ₀ = 0.281 and the median pore width is 0.51 nm, respectively, by argon adsorption using the Horvath-Kawazoe method. It has been determined. The total intrusion volume determined by Hg porosimetry (porosity measurement) according to DIN 66133 was 1.11 ml / g (milliliter / gram) and each total pore area was 40.7 m ² / g.

  The total amount of adsorbed water determined was 3.8 to 4.1% by mass (compared to 6.3% of the starting material mass of the reference example). For this reason, it is clear that the water treatment of the present invention increases the hydrophobicity of the powder.

FIG. 4C shows the IR spectrum of the powder obtained in Reference Example 4. The band regions along the band height of the powder obtained in Reference Example 4 are as follows:

  Therefore, the IR-band ratio of the absorbance intensity of the silanol nest to the absorbance intensity of the surface silanol reaches 1.00.

Comparative Example 5: Molding of ZSM-5 zeolite of Reference Example 1 ZSM-5 (100 g) obtained in Reference Example 1 was converted to Pural SB (86.5 g) and formic acid (2.6 g in 20 mL of water). Dissolved) and Walocel (5 g). The mass of the raw material was chosen so that the ratio of the resulting calcined shaped body to zeolite to binder was 60:40. The mixture was homogenized with a kneader by adding water (100 g). The resulting plastic mixture was made into strands (O 2.5 mm) using a strand press (pressure ~ 100 bar). The strands were dried (16 hours, 120 ° C.) and calcined (4 hours, 500 ° C.), thereby obtaining an extrudate having a cutting hardness of 11.1 N.

Elemental analysis:
Si 25.6 mass%
Al 19.6% by mass

The BET surface area of this extrudate was determined to be 362 m ² / g, the pore volume obtained by Hg porosimetry (porosity measurement) was 0.46 cm ³ / g, and the total pore area was 117.0 m ² / g. Was decided.

Comparative Example 6: Molding of ZSM-5 zeolite of Reference Example 2 ZSM-5 (100 g) obtained in Reference Example 2 was converted to Pural SB (86.5 g) and formic acid (2.6 g in 20 mL of water). Dissolved) and Walocel (5 g). The mass of the raw materials was chosen such that the ratio of the resulting calcined shaped body to the zeolite binder was 60:40. The mixture was homogenized with a kneader by adding water (83 g). The resulting plastic mixture was made into strands (O 2.5 mm) using a strand press (pressure ~ 100 bar). The strands were dried (16 hours, 120 ° C.) and calcined (4 hours, 500 ° C.), thereby obtaining an extrudate having a cutting hardness of 21.6 N.

Elemental analysis:
Si 25.7% by mass
Al 19.1% by mass

The BET surface area of this extrudate was determined to be 374 m ² / g, the pore volume obtained by Hg porosimetry (porosity measurement) was 0.36 cm ³ / g, and each total pore area was 119.5 m ² / g. Was decided.

Example 7 : Magnesium impregnation of ZSM-5 zeolite of Reference Example 1 and molding thereof ZSM-5 powder obtained in Reference Example 1 was spray impregnated with a magnesium nitrate solution. The amount of magnesium nitrate was selected so that the Mg after calcination of the zeolite was 4% by weight. For this implementation, the zeolite powder (98.2 g) obtained in Reference Example 1 was introduced into a round bottom flask connected to a rotary evaporator. Magnesium nitrate (44.0 g) was dissolved in water to give a 77 mL solution. 68.9 mL of the solution was slowly sprayed onto the rotating zeolite using a spray nozzle (100 l / hour N ₂ flow). This corresponds to 90% of the maximum water absorption capacity of the zeolite. After the finished solution was sprayed onto the zeolite, the latter was rotated for 10 minutes. The treated powder was dried (16 hours, 120 ° C.), calcined (4 hours, 500 ° C.), ground, and sieved (1 mm size).

Elemental analysis:
Mg 4.0% by mass

  An Mg-impregnated zeolite was molded to give an extrudate that had a 60/40 ratio of zeolite to binder in the calcined body. ZSM-5 powder (100 g) was mixed with Pural SB (86.5 g), formic acid (2.6 g dissolved in 20 mL water) and Walocel (5 g). The mixture was homogenized with a kneader by adding water (95 g). The resulting plastic mixture was made into strands (O 2.5 mm) using a strand press (pressure ~ 150 bar). The strands were dried (16 hours, 120 ° C.) and calcined (4 hours, 500 ° C.), thereby obtaining an extrudate having a cutting hardness of 10.2 N.

Elemental analysis:
Si 23.8 mass%
Al 19.4% by mass
Mg 2.3 mass%

The BET surface area of this extrudate was determined to be 309 m ² / g, the pore volume obtained by Hg porosimetry (porosity measurement) was 0.84 cm ³ / g, and the total pore area was 102.9 m ² / g. Was decided.

Example 8: Magnesium impregnation and molding of ZSM-5 zeolite of Reference Example 2 The ZSM-5 powder obtained in Reference Example 2 was spray impregnated with a magnesium nitrate solution. The amount of magnesium nitrate was selected so that the Mg after calcination of the zeolite was 4% by weight. For this implementation, the zeolite powder (120 g) obtained in Reference Example 2 was introduced into a round bottom flask connected to a rotary evaporator. Magnesium nitrate (53.8 g) was dissolved in water to obtain an 82 mL solution. 73 mL of the solution was slowly sprayed onto the rotating zeolite using a spray nozzle (100 l / hr N ₂ flow). This corresponds to 90% of the maximum water absorption capacity of the zeolite. After the finished solution was sprayed onto the zeolite, the latter was rotated for 10 minutes. The treated powder was dried (16 hours, 120 ° C.), calcined (4 hours, 500 ° C.), ground, and sieved (1 mm size).

Elemental analysis:
Mg 4.1% by mass

The BET surface area of the impregnated ZSM-5 zeolite was determined to be 318 m ² / g.

  Thereafter, an Mg-impregnated zeolite was formed, and an extrudate having a ratio of zeolite to binder of 60/40 in the calcined body was obtained. For this practice, impregnated ZSM-5 powder (100 g) was mixed with Pural SB (86.5 g), formic acid (2.6 g dissolved in 20 mL water) and Walocel (5 g). The mixture was homogenized with a kneader by adding water (85 g). The resulting plastic mixture was made into strands (O 2.5 mm) using a strand press (pressure ~ 130 bar). The strands were dried (16 hours, 120 ° C.) and calcined (4 hours, 500 ° C.), thereby obtaining an extrudate having a cutting hardness of 11.0 N.

Elemental analysis:
Si 24.3 mass%
Al 19.2 mass%
Mg 2.4% by mass

The BET surface area of this extrudate was determined to be 310 m ² / g and the pore volume obtained by Hg porosimetry (porosity measurement) was determined to be 0.67 cm ³ / g.

Example 9: Magnesium impregnation of water-treated ZSM-5 zeolite of Reference Example 4 and its molding The ZSM-5 powder obtained in Reference Example 4 was spray impregnated with a magnesium nitrate solution. The amount of magnesium nitrate was selected so that the Mg after calcination of the zeolite was 4% by weight. For this implementation, zeolite powder (100 g) was introduced into a round bottom flask connected to a rotary evaporator. Magnesium nitrate (44.8 g) was dissolved in water. 61.2 mL of this solution was slowly sprayed onto the rotating zeolite using a spray nozzle (100 L / hr N ₂ flow). This corresponds to 90% of the maximum water absorption capacity of the zeolite. After the finished solution was sprayed onto the zeolite, the latter was rotated for 10 minutes. The treated powder was dried (16 hours, 120 ° C.), calcined (4 hours, 500 ° C.), ground, and sieved (1 mm size).

  The powder obtained has a Mg content of 3.9% by weight.

  Mg-ZSM-5 powder (98.9 g) was mixed with Pural SB (90.3 g), formic acid (2.7 g dissolved in 20 mL water) and Walocel (5 g). The mass of the raw material was chosen so that the ratio of the resulting calcined shaped body to zeolite to binder was 60:40. The mixture was homogenized with a kneader by adding water (90 g). The resulting plastic mixture was made into strands (O 2.5 mm) using a strand press (pressure ~ 100 bar). The strands were dried (16 hours, 120 ° C.) and calcined (4 hours, 500 ° C.). The strand was divided into 1.6-2.0 mm fractions using a sieve equipped with two steel balls (O 2.5 mm) before being applied to the addition of methanol to the olefin.

The resulting extrudate has a Si content of 23.7% by weight, an Al content of 20.7% by weight, an Mg content of 2.3% by weight, and a multipoint BET surface area of 77K according to DIN 66133. Of 307 m ² / g.

  The crushing strength determined by the method using the crushing strength tester Z2.5 / TS1S described in Reference Example 4 was 8.7N.

The total intrusion volume determined by Hg porosimetry (porosity measurement) according to DIN 66133 was 0.88 ml / g (milliliter / gram) and each total pore area was 124.7 m ² / g.

Comparative Example 10: Molding of Commercial ZSM-5 Zeolite with a SiO ₂ : Al ₂ O ₃ Molar Ratio of 100 For comparison with the material of the present invention, the procedure of Reference Example 5 was changed to SiO ₂ : Al ₂ O ₃ mol. commercially available ZSM-5 zeolite (PZ / 2-100 H, ZEOCHEM made ^R) with a ratio 100 was repeated using. Prior to performing the procedure, the zeolitic material was analyzed to obtain a BET surface area of 412 m ² / g. The pore volume is 0.16 cm ³ / g at p / p ₀ = 0.304 and the median pore width is 0.55 nm, respectively, by argon adsorption using the Horvath-Kawazoe method. It has been determined. Temperature programmed desorption (NH ₃ -TPD) of ammonia was 0.41 mmol / g when performed at 161 ° C. and 0.25 mmol / g when performed at 355 ° C. The primary particle size of commercial ZSM-5 zeolite determined by SEM was in the range of 200-500 nm.

  After repeating the procedure of Comparative Example 5 using commercial ZSM-5 zeolite, the resulting extrudate was shown to have a cutting hardness of 26.4N.

Elemental analysis:
Si 25.9 mass%
Al 19.7% by mass

The BET surface area of this extrudate was determined to be 310 m ² / g and the pore volume obtained by Hg porosimetry (porosity measurement) was determined to be 0.36 cm ³ / g.

Comparative Example 11: Magnesium Impregnation of Commercial ZSM-5 Zeolite and Its Molding For comparison with the material of the invention, the procedure of Example 7 was used with the commercial ZSM-5 zeolite used in Comparative Example 10. Repeatedly, the extrudate thus obtained had a cutting hardness of 10.5N.

Elemental analysis:
Si 24.8% by mass
Al 19.3 mass%
Mg 2.2 mass%

The BET surface area of this extrudate was determined to be 283 m ² / g and the pore volume obtained by Hg porosimetry (porosity measurement) was determined to be 0.44 cm ³ / g.

Example 12: Catalysts tested in the conversion of methanol to olefins The extrudates obtained in Examples 7-9 and Comparative Examples 5, 6, 10 and 11 were treated with two steel balls (O 2 cm, 258 g / ball). Each catalyst sample was obtained by dividing into 1.6 to 2.0 mm fractions. Then 2 g of each catalyst sample was diluted with 23 g of silicon carbide to obtain each catalyst charge used in the test.

The methanol was evaporated and mixed with nitrogen to give a gas stream containing 75% by volume methanol and 25% by volume nitrogen. The methanol in the gas stream was then converted to dimethyl ether in a heated pre-reactor (275 ° C.) packed with alumina split (34 mL). The resulting stream was then converted in a continuously operating, electrically heated tubular reactor filled with each zeolite catalyst to be tested (2 g, diluted with 23 g of SiC). The MTO reaction was carried out at 450-500 ° C. and 1-2 bar pressure (absolute) at a weight hourly space velocity per unit time of 6 hours- ¹ based on the volume of methanol in the initial gas stream. After the methanol conversion rate was below 97%, the reaction mixture was analyzed. The gas product mixture was analyzed by on-line gas chromatography and the results are shown in the table below.

  As can be seen from the results of Comparative Examples 5 and 10 in the table above, when using a sodium-free synthesis procedure for the preparation of the catalyst of Comparative Example 5, there was a slight increase in working time when> 97% conversion based on methanol was achieved. The improvement was seen. However, when Mg of Comparative Example 11 was further used, there was an improvement of the factor of about 4 compared to Comparative Example 10, and a considerable improvement in working time was observed. However, when applying the catalyst obtained in the sodium-free synthesis, the use of Mg shows an improvement in the working time by a factor of 6, as can be seen from Example 7 of the present invention compared to Comparative Example 5, It was unexpected.

Thus, it was very surprising that the special use of the zeolite material Mg obtained from the sodium-free synthesis procedure provides a strong synergistic effect in the catalyst of the present invention. Such very unexpected technical effects have also been observed in materials having a high SiO ₂ : Al ₂ O ₃ ratio. Thus, the inventive catalyst of Example 8 showing a SiO ₂ : Al ₂ O ₃ ratio of 233 has the same SiO ₂ : Al ₂ O ₃ ratio but compared to the catalyst of Comparative Example 6 which does not contain Mg. There is almost 10 times improvement in working time.

  However, more surprisingly, as can be seen from the results of the process of the present invention using the extrudate of Example 9, both the propylene and butylene were obtained by the use of a water treatment procedure to increase the hydrophobicity of the zeolitic material. There was a considerable improvement in selectivity. This effect is obtained because the hydrophobicity of the water treatment material increases as the water absorption of the zeolite material decreases. Furthermore, a surprisingly large increase in the service life of the catalyst is also observed for the water-treated zeolitic material contained in the extrudate of Example 9.

Claims (44)

A method for producing a zeolitic material having MFI, MEL and / or MWW-type framework structure containing YO ₂ and X ₂ O ₃ , comprising:
(1) Step of preparing a mixture containing one or more YO ₂ sources, one or more X ₂ O ₃ sources, and one or more solvents (2) Crystallizing the mixture obtained in step (1) , A step of obtaining a zeolite material having an MFI, MEL and / or MWW-type framework structure, and (3) one or more elements selected from alkaline earth metals in the zeolite material obtained in step (2) Impregnating, and
After step (2) and before (3),
(2e) hydrothermally treating the zeolite material;
Including
Y is a tetravalent element, X is a trivalent element, and the mixture crystallized in step (2) is one or more elements of 3% by mass or less with respect to 100% by mass of YO ₂ M (M represents sodium)
A production method characterized in that the impregnation of the zeolite material in step (3) is achieved by spray impregnation. The process according to claim 1 crystallized mixture in step (2) is, containing sodium below 1 wt% with respect to 100 wt% of YO _2.   The production method according to claim 1 or 2, wherein in the step (3), the zeolite material is impregnated with one or more elements selected from Mg, Ca, Ba, Sr and a mixture of two or more thereof. The process according to the molar ratio of X 2 _{O 3} is any one of claims 1 to 3 in the range of 10 to _{1500: YO} 2 of the mixture prepared in step (1).   The manufacturing method according to any one of claims 1 to 4, wherein Y is selected from Si, Sn, Ti, Zr, Ge, and a mixture of two or more thereof.   The manufacturing method according to any one of claims 1 to 5, wherein X is selected from Al, B, In, Ga, and a mixture of two or more thereof.   The production method according to claim 1, wherein the one or more solvents include one or more polar solvents.   The manufacturing method of any one of Claims 1-7 in which the mixture of a process (1) contains 1 or more types of organic templates.   One or more organic templates are selected from tetraethylammonium compounds, triethylpropylammonium compounds, diethyldipropylammonium compounds, ethyltripropylammonium compounds, tetrapropylammonium compounds, and mixtures of two or more thereof. The manufacturing method of Claim 8 containing a tetraalkylammonium compound. One or more organic _{template, N- (C 2 -C 5)} - alkenyl - tri - _{(C 1} -C ₅₎ according to claim 8 comprising one or more alkenyl trialkyl ammonium compound selected from alkylammonium compounds Or the manufacturing method of 9. The total amount molar ratio of the one or more organic template of the mixture obtained in step (1) with respect to YO ₂ is 1: any one of claims 8 to 10 in the range of (0.1 to 30) The manufacturing method as described in. The method according to any one of claims 1 to 11, wherein the mixture of step (1) further comprises one or more OH ^- sources. The production method according to claim 12, wherein the mixture obtained in step (1) has a molar ratio of OH ⁻ : YO ₂ in the range of 0.01 to 5.   The manufacturing method of any one of Claims 1-13 in which the crystallization of a process (2) includes the heating of a mixture.   The manufacturing method of any one of Claims 1-14 by which crystallization of a process (2) is performed on solvothermal conditions.   The method according to any one of claims 1 to 15, wherein the crystallization in step (2) comprises heating the mixture for at least 3 hours. After step (2) and before (2e) and (3), further (2a) adjusting the pH of the mixed product obtained in step (2) to a pH in the range of 5-9; and / or (2b) isolating the zeolitic material from the mixed product obtained in step (2); and / or (2c) washing the zeolitic material; and / or (2d) drying and / or zeolitic material. Baking process ;
The method according to any one of claims 1 to 16 comprising.   The production method according to claim 17, wherein the calcination of (2d) is performed at a temperature in the range of 300 to 850 ° C. The manufacturing method according to any one of claims 1 to 18, wherein the hydrothermal treatment of (2e) is performed under a self-generated pressure. The manufacturing method according to any one of claims 1 to 19, wherein the hydrothermal treatment of (2e) is performed using an aqueous solvent system. The production method according to any one of claims 1 to 20, wherein the hydrothermal treatment of (2e) is performed under heating. The production method according to any one of claims 1 to 21, wherein the hydrothermal treatment of (2e) is performed in a period of 2 to 72 hours. The production method according to any one of claims 1 to 22, wherein the hydrothermally treated zeolite material obtained in (2e) exhibits a water absorption of 10.0% by mass or less.   24. The process according to any one of claims 1 to 23, wherein in the step (3), the zeolitic material is impregnated with one or more elements selected from alkaline earth metals in an amount of 0.1 to 15% by mass relative to the total mass of the zeolitic material. The production method according to claim 1. A zeolitic material having MFI, MEL and / or MWW-type framework structure containing YO ₂ and X ₂ O ₃ ,
Y is a tetravalent element, X is a trivalent element, and the zeolitic material contains 3% by mass or less of one or more elements M with respect to 100% by mass of YO ₂ , Sodium
The zeolitic material further comprises one or more elements selected from alkaline earth metals;
95% by mass or more of the primary particles of the zeolitic material have a diameter of 1 μm or less,
The zeolitic material, wherein the zeolitic material exhibits water absorption of 10.0% by mass or less.   The zeolitic material according to claim 25, wherein 90% by mass or more of the primary particles are spherical.   27. The zeolitic material according to claim 25 or 26, wherein 95% by mass or more of the primary particles have a diameter of 5 to 800 nm. The zeolitic material according to any one of claims 25 to 27, comprising 1% by mass or less of sodium with respect to 100% by mass of YO ₂ .   One or more elements selected from alkaline earth metals further contained in the zeolitic material are contained in the zeolitic material in an amount ranging from 0.1 to 15% by mass relative to the total mass of the zeolitic material. Item 29. The zeolitic material according to any one of Items 25 to 28.   30. One or more elements selected from alkaline earth metals further contained in the zeolitic material are selected from Mg, Ca, Ba, Sr and mixtures of two or more thereof. The zeolitic material described in 1. The zeolitic material according to any one of claims 25 to 30, wherein the YO ₂ : X ₂ O ₃ atomic ratio of the zeolitic material is in the range of 10 to 1500.   The zeolitic material according to any one of claims 25 to 31, wherein Y is selected from Si, Sn, Ti, Zr, Ge, and a mixture of two or more thereof.   The zeolitic material according to any one of claims 25 to 32, wherein X is selected from Al, B, In, Ga, and a mixture of two or more thereof.   The zeolitic material according to any one of claims 25 to 33, wherein the zeolitic material contains ZSM-5. The zeolitic material according to any one of claims 25 to 34, wherein the zeolitic material has a BET surface area determined according to DIN 66131 in the range of 200 to 900 m ² / g. (I) supplying a gas stream containing one or more oxygen-containing materials;
(II) contacting the gas stream with a catalyst comprising the zeolitic material according to any one of claims 25 to 35;
A method for converting an oxygen-containing substance containing olefin into an olefin.   37. The method of claim 36, wherein the gas stream supplied in step (I) comprises one or more oxygen-containing materials selected from aliphatic alcohols, ethers, carbonyl compounds, and mixtures of two or more thereof.   38. A method according to claim 36 or 37, wherein the gas stream supplied in step (I) comprises from 30 to 100% by volume of oxygen-containing material relative to the total gas stream volume.   39. A method according to any one of claims 36 to 38, wherein the gas stream supplied in step (I) comprises 60% or less water by volume relative to the total gas stream volume.   40. A process according to any one of claims 36 to 39, wherein the contact between the gas stream and the catalyst in step (II) is carried out at a temperature of 200 to 700 <0> C.   41. A process according to any one of claims 36 to 40, wherein the contact between the gas stream and the catalyst in step (II) is carried out at a pressure of 0.1 to 10 bar.   The method according to any one of claims 36 to 41, wherein at least a part of the method is performed in a continuous mode. 43. The method of claim 42, wherein the weight hourly space velocity (WHSV) of the gas stream in step (II) is in the range of 0.5 to 50 hours- ¹ .   36. A method of using the zeolitic material according to any one of claims 25 to 35 as a molecular sieve, a catalyst, a catalyst support and / or an adsorbent.

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