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• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/026—After-treatment
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/7007—Zeolite Beta
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/26—Mordenite type
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/38—Base treatment
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Definitions

• the present invention relates to a method for producing zeolite.
• Synthetic zeolite is a crystalline aluminosilicate and has sub-nano-sized uniform pores due to its crystal structure. Taking advantage of this feature, synthetic zeolite is industrially used as a molecular sieve adsorbent that adsorbs only molecules having a specific size, an adsorption separator that adsorbs molecules having a strong affinity, or a catalyst base. Beta-type zeolite, which is one of such zeolites, is currently used in large quantities all over the world as a catalyst in the petrochemical industry and as an adsorbent for treating automobile exhaust gas.
• beta-type zeolite has been synthesized using an organic structure-regulating agent (hereinafter, also referred to as “OSDA”), but in recent years, a method for synthesizing beta-type zeolite without using OSDA has been proposed (see Patent Document 1). .. Similarly, mordenite zeolites are currently used in large quantities worldwide as catalysts in the petrochemical industry. A method for synthesizing a mordenite-type zeolite without OSDA is described in, for example, Patent Document 2.
• OSDA organic structure-regulating agent
• OSDA-free zeolite Zeolites synthesized without using OSDA (hereinafter, also referred to as “OSDA-free zeolite”) have a low Si / Al ratio and exhibit high crystallinity. Due to this, the OSDA-free zeolite is characterized by high ion exchange ability derived from a low Si / Al ratio and high durability and high selectivity derived from high crystallinity.
• affinity with the reactant difference in affinity hydrophobicity and polarity
• Si / Al ratio to suit the purpose of use. Is. That is, in order to utilize the high crystallinity of OSDA-free zeolite in a wide range of applications, a technique for adjusting the Si / Al ratio by dealuminum while maintaining the crystallinity is required.
• Patent Document 3 As a conventional technique for adjusting the Si / Al ratio of beta-type zeolite, for example, the one described in Patent Document 3 is known.
• the beta-type zeolite is converted to ammonium type by ion exchange, then the beta-type zeolite is exposed to water vapor, and the exposed beta-type zeolite is subjected to acid treatment to obtain Si / of the beta-type zeolite.
• the Al ratio is adjusted.
• Patent Document 3 describes only examples in which the Si / Al ratio exceeds 40.
• the present inventor retested the technique described in Patent Document 3, it is not easy to obtain a beta zeolite having a Si / Al ratio in a relatively low range of 40 or less while maintaining crystallinity. found.
• Zeolites having a relatively low Si / Al ratio of 40 or less contain a large amount of Al as compared with zeolites having a Si / Al ratio of more than 40, and thus have high ion exchange capacity and high acidity. It is important for application from the viewpoint. Therefore, an object of the present invention is to provide a method capable of producing a zeolite having high crystallinity in a range of a relatively low Si / Al ratio.
• zeolite synthesized without using an organic structure defining agent is ion-exchanged to form sodium type, proton type or ammonium type.
• the present invention provides a method for producing a zeolite, which comprises a step of contacting a zeolite after ion exchange with an ammonium salt solution to remove aluminum.
• the "relatively low Si / Al ratio range” is a range in which the Si / Al ratio is 40 or less.
• the production method of the present invention includes a step of contacting a zeolite synthesized without using OSDA with an ammonium salt solution, that is, a step of dealuminating. Methods for producing OSDA-free zeolite are known in the art, and are described, for example, in Patent Documents 1 and 2 described above.
• the OSDA-free zeolite When removing aluminum from OSDA-free zeolite, it is desirable not to reduce the crystallinity of zeolite as much as possible.
• the zeolite is preferably a beta-type zeolite or a mordenite-type zeolite.
• ammonium salt either an organic ammonium salt or an inorganic ammonium salt can be used.
• organic ammonium salt include an organic acid ammonium salt such as ammonium oxalate.
• inorganic ammonium salt include ammonium fluoride, ammonium silica fluoride, ammonium bobofluoride, ammonium phosphate, ammonium titanium fluoride and ammonium zircon fluoride.
• ammonium salts can be used alone, or two or more thereof can be used in combination.
• Dealuminum using ammonium salt can be performed by adding ammonium salt to the aqueous dispersion of zeolite.
• concentration of zeolite in the aqueous dispersion is preferably 0.0033 g / mL or more and 1 g / mL or less, and is 0.01 g / mL or more and 0. It is more preferably 66 g / mL or less, and further preferably 0.033 g / mL or more and 0.33 g / mL or less.
• the form of adding the ammonium salt to the aqueous dispersion may be a solution or a powder. However, when the ammonium salt is used in a powder state, it must be dissolved in an aqueous dispersion. From an industrial point of view, it is preferable to add an ammonium salt in the form of an aqueous solution to the aqueous dispersion of zeolite.
• the concentration of ammonium salt in the aqueous solution after adding the ammonium salt solution to the aqueous dispersion of zeolite is 0.01 mol / L or more and 3 mol / L or less from the viewpoint of smooth dealumination while maintaining the crystallinity of zeolite. It is more preferably 0.05 mol / L or more and 2 mol / L or less, and even more preferably 0.1 mol / L or more and 1 mol / L or less.
• the ammonium salt may be directly produced in the aqueous solution by a neutralization reaction with an appropriate acid aqueous solution and a base aqueous solution.
• ammonium silicate powder is produced by neutralizing an aqueous solution of silicic acid (H 2 SiF 6 ) with an aqueous solution of ammonia (NH 3 ) to directly produce ammonium silicate ((NH 4 ) 2 SiF 6 ) in the solution.
• H 2 SiF 6 silicic acid
• NH 3 ammonia
• the contact between the ammonium salt solution and the zeolite after ion exchange is performed so that the Si / Al ratio of the obtained zeolite is the ratio described later.
• the aqueous dispersion of zeolite and the ammonium salt solution may be mixed under heating or under heating.
• the temperature of the liquid is preferably 0 ° C. or higher and 100 ° C. or lower, preferably 25 ° C. or higher and 90 ° C. or lower, from the viewpoint of smoothly removing aluminum while maintaining the crystallinity of zeolite. It is more preferable that the temperature is 25 ° C. or higher and 80 ° C. or lower.
• the zeolite may be pretreated prior to dealumination of the zeolite. Then, after that, the zeolite is dealuminated. Examples of the pretreatment include steam treatment of zeolite. Dealumination can be promoted by applying the pretreatment to the zeolite.
• the above pretreatment is preferably performed after the zeolite is in the sodium type, proton type or ammonium type.
• the zeolite may be allowed to stand in a steam atmosphere, or the zeolite may be arranged in the steam flow.
• Zeolites can be exposed to water vapor using, for example, the apparatus shown in FIG. 1 of US2017 / 368539A1.
• the temperature of steam is preferably 90 ° C. or higher and 800 ° C. or lower, more preferably 200 ° C. or higher and 700 ° C. or lower, and even more preferably 300 ° C. or higher and 700 ° C. or lower.
• the exposure time to water vapor is preferably 1 hour or more and 50 hours or less, more preferably 2 hours or more and 20 hours or less, provided that the temperature of water vapor is in this range, and is 5 hours or more and 20 hours. The following is more preferable.
• Acid treatment is suitable as the post-treatment.
• a zeolite having high crystallinity and a adjusted Si / Al ratio can be obtained more easily.
• the acid used for the acid treatment include various mineral acids such as nitric acid, hydrochloric acid and sulfuric acid. Of these mineral acids, it is preferable to use nitric acid.
• the concentration of the acid aqueous solution used for the acid treatment is preferably 0.001N or more and 20N or less, more preferably 0.01N or more and 13N or less, and further preferably 0.1N or more and 3N or less. Note that "N" represents the normality.
• the amount of the acid aqueous solution added is preferably 10 mL or more and 500 mL or less, more preferably 10 mL or more and 300 mL or less, and further preferably 10 mL or more and 30 mL or less with respect to 1 g of zeolite after dealumination.
• the zeolite or the aqueous dispersion of zeolite and the aqueous acid solution may be mixed under heating or under heating.
• the temperature of the liquid is preferably 40 ° C. or higher and 100 ° C. or lower, more preferably 60 ° C. or higher and 100 ° C. or lower, and further preferably 80 ° C. or higher and 100 ° C. or lower. ..
• the zeolite produced in this manner may be of a proton type, an ammonium type, or a sodium type, a potassium type, or a lithium type. Further, the zeolite produced by the method of the present invention may be ion-exchanged to exchange the ion exchange site with a transition metal ion. Examples of transition metals that can be ion-exchanged include iron, copper, cobalt, nickel, chromium, molybdenum, manganese, vanadium, titanium, cerium, ruthenium, platinum, silver, and iridium. When the zeolite of the present invention is in a state of being ion-exchanged with a transition metal, the performance as a catalyst for various reactions may be further improved.
• Ion exchange with transition metal ions can be carried out, for example, by dispersing zeolite in an aqueous ammonium nitrate solution to obtain ammonium-type beta zeolite, and then using the method described in JP-A-2014-019601.
• a step of allowing an oxide of phosphorus, zirconium, zinc or silicon to be present on the surface of the zeolite may be further performed before and after the above-mentioned ion exchange.
• Zeolites having oxides of these elements on their surfaces have an appropriately controlled amount of acid on the surface, and are more useful as adsorbents for various compounds and catalysts for various reactions.
• an impregnation method, an evaporative drying method, or a surface modification method using a coupling agent such as a silane coupling agent or a zirconium coupling agent is adopted. do it.
• Whether or not oxides of these elements are present on the surface can be confirmed by, for example, X-ray photoelectron spectroscopy.
• a step of adding at least one element M selected from titanium, tin, zinc, niobium, tantalum and zirconium to zeolite may be carried out.
• the element M can be an active site for various chemical reactions.
• a known method such as an impregnation method or an evaporation to dryness method may be adopted.
• a step of including these at least one element M in the skeleton structure of zeolite may be performed. This is because it has an excellent carrying capacity for polyvalent metal cations and can be an active site for various chemical reactions.
• the value of Si / (M + Al) expressed in atomic ratio is preferably 4 or more and 2000 or less, more preferably 4 or more and 300 or less, and further preferably 4 or more and 40 or less.
• a known method such as a hydrothermal synthesis method, a dry gel conversion method, or a solid phase crystallization method may be adopted.
• the zeolite produced by the method of the present invention preferably has a high peak intensity obtained by X-ray diffraction measurement.
• the intensity of the peak obtained by X-ray diffraction measurement is mainly related to the crystallinity of zeolite.
• the diffraction intensity of the main peak of the zeolite observed by the X-ray diffraction measurement is set to A, and the standard substance 674a distributed by the American National Institute of Standards and Technology, which is measured by X-ray diffraction under the same conditions as described above.
• the value of A / B which is the intensity ratio of A to B, can be used as a measure of crystallinity.
• the A / B value can be obtained by subjecting a sample obtained by mixing the zeolite to be measured and ⁇ -alumina, which is a standard substance, in the same volume to X-ray diffraction measurement.
• the intensity A of the main peak of zeolite obtained by this X-ray diffraction measurement and the diffraction intensity B of the (116) plane of ⁇ -alumina, which is a standard substance, are obtained, and A / B is calculated from the values of A and B. ..
• Intensities A and B are peak heights obtained by X-ray diffraction measurements.
• the reason why the diffraction peak of the (116) plane is adopted as the diffraction peak of the ⁇ -alumina is that the diffraction peak of zeolite is not observed in the vicinity of the diffraction peak of the (116) plane and the diffraction peak of the (116) plane is high intensity. This is because the measurement accuracy can be improved.
• X-ray diffraction is measured using, for example, RINT-TTR III manufactured by Rigaku Co., Ltd. and Cu K ⁇ (0.15406 nm, 50 kV, 300 mA) as an X-ray source.
• the software "PDXL2" is used for the analysis of the diffraction intensity. After removing the background, the K ⁇ 1 position is set as the peak position and fitted with a split-type pseudo Voigt function to obtain a value of diffraction intensity.
• the Si / Al ratio of the zeolite produced by the method of the present invention is preferably 4 or more and 40 or less, and particularly preferably 5 or more and 35 or less.
• the Si / Al ratio can be determined by quantitative analysis of Si and Al using ICP emission spectroscopy using an aqueous solution in which zeolite is dissolved as a sample.
• the zeolite of the present invention thus obtained has high crystallinity in a range where the Si / Al ratio is relatively low, for example, in the range of 4 or more and 40 or less. Taking advantage of this property, the zeolite of the present invention is suitably used as an adsorbent for various compounds and as a catalyst for various chemical reactions.
• the form of the catalyst is not particularly limited, and for example, a film-like or pellet-like form can be adopted.
• Example 1 (1) Preparation of Seed Crystal Using a conventionally known method using tetraethylammonium hydroxide as an organic structure-determining agent, sodium aluminate as an alumina source, and fine silica (Mizukasil P707) as a silica source, at 165 ° C. for 96 hours. Stirring and heating were carried out to synthesize a beta-type zeolite having a Si / Al ratio of 9. These were calcined at 550 ° C. for 10 hours while flowing air in an electric furnace to produce seed crystals containing no organic matter.
• the product was filtered and washed with warm water to obtain a white powder.
• X-ray diffraction measurements confirmed that the product was a sodium-type beta-zeolite containing no impurities.
• the Si / Al ratio was 5.
• Example 2 The concentration of the ammonium silicate aqueous solution used for dealuminum in Example 1 was 0.1 mol / L. Other than this, the same as in Example 1.
• Example 3 The concentration of the ammonium silicate aqueous solution used for dealuminum in Example 1 was set to 0.3 mol / L. Other than this, the same as in Example 1.
• Example 4 The concentration of the ammonium silicate aqueous solution used for dealuminum in Example 1 was 0.5 mol / L. Other than this, the same as in Example 1.
• Example 5 The concentration of the ammonium silicate aqueous solution used for dealuminum in Example 1 was set to 1 mol / L. Other than this, the same as in Example 1.
• Example 6 The concentration of the ammonium silicate aqueous solution used for dealuminum in Example 1 was set to 3 mol / L. Other than this, the same as in Example 1.
• Example 7 In Example 5, after dealuminating the OSDA free beta zeolite, acid treatment with nitric acid was performed as a post-treatment. Nitric acid was dispersed in water to obtain a 1 mol / L aqueous solution. 1 g of the dealuminated OSDA free beta zeolite powder was mixed with 30 mL of a 1 mol / L nitric acid aqueous solution and treated with acid. The mixing temperature was 80 ° C. and the mixing time was 20 hours. Other than this, the same as in Example 5.
• Example 8 The amount of ammonium-type OSDA-free beta-type zeolite used for dealuminum in Example 1 was 10 g.
• the concentration of the ammonium silicate aqueous solution used for dealumination was 0.1 mol / L
• the heating temperature with the ammonium silicate aqueous solution was 80 ° C.
• the heating time was 10 hours.
• 1 g of the dealuminated OSDA free beta zeolite powder was mixed with 30 mL of a 1 mol / L nitric acid aqueous solution for acid treatment.
• the mixing temperature was 80 ° C. and the mixing time was 20 hours.
• Example 9 The amount of ammonium-type OSDA-free beta-type zeolite used for dealuminum in Example 1 was 10 g.
• the concentration of the ammonium silicate aqueous solution used for dealumination was 0.25 mol / L
• the heating temperature with the ammonium silicate aqueous solution was 80 ° C.
• the heating time was 10 hours.
• 1 g of the dealuminated OSDA free beta zeolite powder was mixed with 30 mL of a 1 mol / L nitric acid aqueous solution for acid treatment.
• the mixing temperature was 80 ° C. and the mixing time was 20 hours.
• Example 10 The amount of ammonium-type OSDA-free beta-type zeolite used for dealuminum in Example 1 was 10 g.
• the concentration of the ammonium silicate aqueous solution used for dealuminum was set to 1 mol / L. Other than this, the same as in Example 1.
• 1 g of the dealuminated OSDA free beta zeolite powder was mixed with 30 mL of a 1 mol / L nitric acid aqueous solution for acid treatment.
• the mixing temperature was 80 ° C. and the mixing time was 20 hours.
• Example 11 Instead of performing the dealumination step of (4) OSDA free beta type zeolite of Example 1, the following step was carried out. After mixing 40 wt% of the fluorosilicate acid (H 2 SiF 6) solution 1.695ml pure water 8.25 ml, neutralized fluorosilicate acid aqueous solution was slowly added dropwise 25 wt% NH 3 aq 1.263Ml, Ammonium silicate was produced in the solution. 2.75 g of ammonium-type OSDA-free beta-type zeolite was dispersed in this neutralizing solution to obtain a dispersion. This dispersion was heated at 60 ° C. for 3 hours to remove aluminum. Then, filtration and washing with pure water were repeated. The obtained hydrous powder was dried at 100 ° C. for 12 hours or more. In this way, an OSDA-free beta-type zeolite powder having a Si / Al ratio of 8 was obtained. Other than this, the same as in Example 1.
• Example 12 In Example 11, after dealuminating the OSDA free beta zeolite, acid treatment with nitric acid was performed. Specifically, 1 g of dealuminated OSDA-free beta-type zeolite powder was mixed with 30 mL of a 1 mol / L nitric acid aqueous solution and treated with acid. The mixing temperature was 80 ° C. and the mixing time was 20 hours. Other than this, the same as in Example 11.
• Example 13 In Example 5, before dealuminating the OSDA free beta zeolite, the zeolite was pretreated to be exposed to water vapor. The zeolite was exposed at 500 ° C. for 20 hours under an air flow of 1.2 L / min with a water vapor partial pressure of about 7 kPa. Other than this, the same as in Example 5.
• Example 14 In Example 5, before dealuminating the OSDA free beta zeolite, the zeolite was pretreated to be exposed to water vapor. The zeolite was exposed at 700 ° C. for 20 hours under an air flow of 1.2 L / min with a water vapor partial pressure of about 7 kPa. Other than this, the same as in Example 5.
• Example 1 A dealuminated OSDA free beta zeolite was produced in accordance with the prior art US2017 / 368539A1 (Patent Document 3 in the background technology section). That is, nitric acid was dispersed in water to obtain a 0.4 mol / L aqueous solution. Similar to Example 1, OSDA free beta zeolite was synthesized using seed crystals. After exposing the zeolite to water vapor under the same conditions as in Example 13, 1 g of OSDA-free beta-type zeolite was dispersed in 17.5 mL of a 0.4 mol / L nitric acid aqueous solution, mixed, and subjected to acid treatment. The mixing temperature was 60 ° C. and the mixing time was 1 hour.
• Example 15 (1) Preparation of OSDA-free mordenite type zeolite The reaction mixture was placed in a 60 mL stainless steel airtight container, and the temperature was 150 ° C. and the time was 100 hours when the reaction mixture was allowed to stand and heated under self-sustaining pressure without aging and stirring. A white powder was obtained by performing the same procedure as that described in (1) and (2) of Example 1 except for the above. X-ray diffraction measurements and ICP emission spectroscopy confirmed that the product was a sodium-type mordenite-type zeolite. As a result of ICP emission spectroscopic analysis, the Si / Al ratio was 5.
• Example 16 The concentration of the aqueous nitric acid solution used for the acid treatment in Example 15 was set to 3 mol / L. Other than this, the same as in Example 15.
• Example 15 No dealumination was performed in Example 15. Other than this, the same as in Example 15.
• the beta-zeolite obtained in Example 1 had a strength ratio A / B similar to that of the reference example even though the beta-zeolite obtained in Reference Example 1 was dealuminated. It can be seen that a beta-type zeolite with high crystallinity has been realized. Similarly, it can be seen that beta-type zeolite having high crystallinity can be realized in Examples 2 to 12. As shown in Table 2, it can be seen that the beta-zeolites of Examples 13 and 14 that have been pretreated to be exposed to water vapor also have a high intensity ratio A / B and highly crystalline beta-zeolites.
• the beta-type zeolite of Comparative Example 1 dealuminated by the acid treatment according to the prior art has a lower strength ratio A / B than the beta-type zeolite obtained in Examples 1 to 14. , It can be seen that the crystallinity is low.
• the mordenite-type zeolites obtained in Examples 15 and 16 also have a higher strength ratio A / B than the mordenite-type zeolite of Comparative Example 2 dealuminated by acid treatment, which is a conventional technique. It can be seen that a mordenite-type zeolite with high crystallinity has been realized.
• a method capable of producing a zeolite having high crystallinity in a range of a relatively low Si / Al ratio is provided.

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