WO2016186162A1 - Method for producing zeolite - Google Patents

Method for producing zeolite Download PDF

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Publication number
WO2016186162A1
WO2016186162A1 PCT/JP2016/064864 JP2016064864W WO2016186162A1 WO 2016186162 A1 WO2016186162 A1 WO 2016186162A1 JP 2016064864 W JP2016064864 W JP 2016064864W WO 2016186162 A1 WO2016186162 A1 WO 2016186162A1
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zeolite
ion exchange
producing
solution
source
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PCT/JP2016/064864
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French (fr)
Japanese (ja)
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豊浩 碓氷
悟史 島田
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イビデン株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • 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
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent

Definitions

  • the present invention relates to a method for producing zeolite.
  • an SCR (Selective Catalytic Reduction) system that uses ammonia to reduce NOx to nitrogen and water has been known as one of the systems for purifying exhaust gas from automobiles.
  • This SCR system uses, as an SCR catalyst carrier, a honeycomb unit in which a large number of longitudinally extending through holes through which exhaust gas passes are arranged.
  • Patent Document 1 discloses heat resistance when used as an SCR catalyst carrier.
  • a Cu ion-exchanged CHA-zeolite having a composition ratio SiO 2 / Al 2 O 3 of less than 15 and a particle diameter of 1.0 to 8.0 ⁇ m is used. Disclosure.
  • Patent Document 2 uses the Na + form zeolite or with a substituted NH 4 + -type zeolite Na + in the zeolite NH 4 +,
  • the present invention has been made in order to solve the above-described problems, and provides a method for producing a zeolite having a CHA structure having a high ion exchange efficiency with Cu and capable of reducing production time and production cost.
  • the purpose is to provide.
  • the method for producing a zeolite of the present invention is a method for producing a zeolite having a CHA structure subjected to Cu ion exchange,
  • the inventors As a result of intensive studies on a method for producing a zeolite capable of improving the ion exchange efficiency of Cu, the inventors first made the synthesized zeolite NH 4 + type zeolite, and this NH 4 + type zeolite was heated to H + The ion exchange efficiency can be increased by performing Cu ion exchange on the obtained H + type zeolite, thereby reducing the number of ion exchange operations and completing the ion exchange process in a short time. I found. That is, in the manufacturing method of the present invention, Cu ion exchange efficiency is high, and manufacturing time and manufacturing cost can be suppressed.
  • the SiO 2 / Al 2 O 3 composition ratio (SAR) in the zeolite obtained in the synthesis step is less than 15.
  • the composition ratio SiO 2 / Al 2 O 3 is less than 15, the NOx purification rate can be further increased.
  • SiO 2 / Al 2 O 3 is less than 15, the amount of alumina increases, and the amount of Cu ion exchange that functions as a catalyst can be increased in proportion to the amount of alumina.
  • the Al source is preferably a dry aluminum hydroxide gel. Since the dry aluminum hydroxide gel has high solubility in an alkaline solution, it is possible to reduce the variation in the particle diameter of the synthesized zeolite and the SiO 2 / Al 2 O 3 molar ratio.
  • the heating temperature of the NH 4 + type zeolite is preferably 350 to 650 ° C. in the heat treatment step.
  • a heating temperature of 350 ° C. or higher NH 3 is easily desorbed from the NH 4 + type zeolite, and can be efficiently converted to H + type zeolite.
  • the heating temperature of 650 degrees C or less de-Al removal from a zeolite is suppressed and ion exchange efficiency can be improved, without impairing the amount of ion exchange of Cu.
  • the pH of the Cu solution used in the Cu ion exchange step is preferably 8-12.
  • the H + ion concentration of the Cu solution is suppressed from being increased by H + ions desorbed from the H + type zeolite by ion exchange, and the progress of Cu ion exchange is not hindered.
  • destruction of the crystal structure of zeolite is prevented when the Cu solution has a pH of 12 or less.
  • the Cu solution to be used is preferably an aqueous copper sulfate solution.
  • an aqueous solution of copper sulfate is low in cost, and the cost of the method for producing a zeolite of the present invention can be further reduced.
  • the Cu / Al (molar ratio) in the zeolite subjected to Cu ion exchange is preferably 0.2 to 0.5.
  • the molar ratio is 0.2 or more, high NOx purification performance can be obtained with a small amount of zeolite.
  • the molar ratio is 0.5 or less, it is possible to prevent a decrease in NOx purification performance due to ammonia oxidation at a high temperature.
  • FIG. 1 is a chart showing the XRD pattern of the zeolite synthesized in Example 1.
  • the method for producing a zeolite of the present invention is characterized by including the following steps.
  • the zeolite produced according to the present invention is named and classified by the structure code of CHA in the International Zeolite Association (IZA), and has a crystal structure equivalent to that of naturally occurring chabazite. Zeolite.
  • a raw material composition comprising a Si source, an Al source, an alkali source, water and a structure directing agent is prepared.
  • the Si source refers to a compound, a salt, and a composition that are raw materials for the silicon component of zeolite.
  • the Si source for example, colloidal silica, amorphous silica, sodium silicate, tetraethylorthosilicate, aluminosilicate gel, and the like can be used, and two or more of these may be used in combination. Of these, colloidal silica is desirable.
  • Al source examples include aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum chloride, aluminosilicate gel, and dry aluminum hydroxide gel. Of these, dry aluminum hydroxide gel is preferred.
  • a Si source and an Al source having a molar ratio (SiO 2 / Al 2 O 3 ) substantially equal to the molar ratio of the zeolite to be produced. It is desirable to use
  • the molar ratio (SiO 2 / Al 2 O 3 ) between the Si source and the Al source in the raw material composition is preferably 5 to 30, and more preferably 10 to 15.
  • the alkali source is a compound containing at least one selected from the group consisting of alkali metals and alkaline earth metals.
  • alkali metals sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium hydroxide, hydroxide Calcium, strontium hydroxide, barium hydroxide, and the like can be used, and two or more of these may be used in combination.
  • potassium hydroxide, sodium hydroxide, and lithium hydroxide are desirable.
  • the amount of water is not particularly limited, but the ratio of the number of moles of water to the total number of moles of Si of Si source and Al of Al source (number of moles of H 2 O). / Total number of moles of Si and Al) is preferably 12 to 30, and the ratio of the number of moles of water to the total number of moles of Si of the Si source and Al of the Al source (H 2 O moles / Si and Al The total number of moles) is more preferably 15-25.
  • the structure-directing agent refers to an organic molecule that defines the pore diameter and crystal structure of zeolite.
  • the structure of the obtained zeolite can be controlled by the type of the structure-directing agent.
  • At least one selected from the group consisting of carbonates, sulfates and nitrates can be used.
  • N, N, N-trimethyladamantanammonium hydroxide hereinafter also referred to as TMAAOH
  • N, N, N-trimethyladamantanammonium halide N, N, N-trimethyladamantanammonium carbonate
  • TMAAOH N, N-trimethyladamantanammonium halide
  • N, N, N-trimethyladamantanammonium carbonate It is preferable to use at least one selected from the group consisting of N, N, N-trimethyladamantanammonium methyl carbonate and N, N, N-trimethyladamantanammonium sulfate, and it is more preferable to use TMAAOH.
  • zeolite seed crystals may be further added to the raw material composition.
  • the crystallization speed of the zeolite is increased, the time for producing the zeolite can be shortened, and the yield is improved.
  • a zeolite seed crystal it is desirable to use a zeolite having a CHA structure.
  • the amount of zeolite seed crystals added is preferably small, but considering the reaction rate and the effect of suppressing impurities, it should be 0.1 to 20% by mass with respect to the silica component contained in the raw material composition. Desirably, 0.5 to 15% by mass is more desirable.
  • the added amount of the seed crystal is less than 0.1% by mass, the contribution of improving the crystallization rate of the zeolite is small, and when it exceeds 20% by mass, impurities are easily contained in the synthesized zeolite.
  • zeolite is synthesized by reacting the prepared raw material composition. Specifically, it is desirable to synthesize zeolite by hydrothermal synthesis of the raw material composition.
  • the reaction vessel used for hydrothermal synthesis is not particularly limited as long as it is used for known hydrothermal synthesis, and may be a heat and pressure resistant vessel such as an autoclave.
  • the zeolite can be crystallized by putting the raw material composition into the reaction vessel, sealing and heating.
  • the raw material mixture When synthesizing the zeolite, the raw material mixture may be in a stationary state, but is preferably in a state of being stirred and mixed.
  • the heating temperature for synthesizing the zeolite is preferably 100 to 200 ° C, more preferably 120 to 180 ° C.
  • the heating temperature is less than 100 ° C., the crystallization rate becomes slow, and the yield tends to decrease.
  • the heating temperature exceeds 200 ° C., impurities are likely to be generated.
  • the heating time in the synthesis process is preferably 10 to 200 hours. If the heating time is less than 10 hours, unreacted raw materials remain and the yield tends to decrease. On the other hand, even when the heating time exceeds 200 hours, the yield and crystallinity are hardly improved.
  • the pressure in the synthesis process is not particularly limited, and the pressure generated when the raw material composition placed in a closed container is heated to the above temperature range is sufficient, but if necessary, an inert gas such as nitrogen gas is added. May be boosted.
  • the zeolite obtained by the synthesis step of the method for producing zeolite of the present invention is sufficiently cooled, solid-liquid separated, and washed with a sufficient amount of water.
  • the zeolite obtained by the synthesis process contains SDA in the pores, it may be removed if necessary.
  • SDA can be removed by a liquid phase treatment using an acidic solution or a chemical solution containing an SDA decomposition component, an exchange treatment using a resin, a thermal decomposition treatment, or the like.
  • the ammonium ion exchange step is a step of obtaining NH 4 + type zeolite by performing ion exchange on the zeolite obtained in the synthesis step using an ammonia solution.
  • the ammonia solution include aqueous ammonia, an aqueous ammonium sulfate solution, an aqueous ammonium nitrate solution, and the like. Among these, an aqueous ammonium sulfate solution is preferable.
  • the ammonia concentration in the ammonia solution is, for example, 1 to 10% by mass, preferably 2 to 5% by mass.
  • An ion exchange method using an ammonia solution can be performed by immersing zeolite in the ammonia solution.
  • the temperature of the ammonia solution is, for example, 4 to 50 ° C.
  • the pressure is, for example, atmospheric pressure
  • the immersion time is, for example, 0.1 to 2 hours. In this way, NH 4 + type zeolite is obtained.
  • the heat treatment step is a step of heating the NH 4 + type zeolite obtained in the ammonium ion exchange step to obtain H + type zeolite.
  • the heating temperature is preferably 350 to 650 ° C. With a heating temperature of 350 ° C. or higher, NH 3 is easily desorbed from the NH 4 + type zeolite, and can be efficiently converted to H + type zeolite. Moreover, by the heating temperature of 650 degrees C or less, de-Al removal from a zeolite is suppressed and ion exchange efficiency can be improved, without impairing the amount of ion exchange of Cu.
  • a more preferable heating temperature is 400 to 600 ° C.
  • the heating time is, for example, 0.5 to 48 hours, preferably 1 to 24 hours.
  • the heating pressure is, for example, atmospheric pressure.
  • a heating means to be used a commercially available heating furnace, for example, trade name KDF-S100 manufactured by Denken Hydental Co., Ltd. may be mentioned.
  • the Cu ion exchange step is a step of obtaining a zeolite subjected to Cu ion exchange by performing ion exchange using a Cu solution on the H + type zeolite obtained in the heat treatment step.
  • the Cu solution include one aqueous solution selected from a copper acetate aqueous solution, a copper nitrate aqueous solution, a copper sulfate aqueous solution, and a copper chloride aqueous solution. Of these, an aqueous copper sulfate solution is preferred.
  • the aqueous copper sulfate solution is lower in cost than the commonly used aqueous copper acetate solution, and can further reduce the cost of the method for producing a zeolite of the present invention.
  • the Cu concentration in the Cu solution is, for example, 0.2 to 5.0% by mass, preferably 0.5 to 2.5% by mass.
  • the pH of the Cu solution used in the Cu ion exchange step of the method for producing zeolite of the present invention is preferably 8 to 12, and more preferably 9 to 11.
  • the Cu solution has a pH of 8 or higher, the H + ion concentration of the Cu solution is prevented from being increased by H + ions desorbed from the H-type zeolite by ion exchange, and the progress of Cu ion exchange is not hindered.
  • destruction of the crystal structure of zeolite is prevented when the Cu solution has a pH of 12 or less.
  • the pH can be adjusted using, for example, aqueous ammonia or NaOH.
  • the ion exchange method in the Cu ion exchange step can be performed by immersing H + type zeolite in the Cu solution.
  • the temperature of the Cu solution is, for example, room temperature to 60 ° C.
  • the pressure is, for example, atmospheric pressure
  • the immersion time is, for example, 0.1 to 24 hours, preferably 0.5 to 12 hours. In this way, a zeolite subjected to Cu ion exchange is obtained.
  • the performance of the zeolite after completion of the Cu ion exchange step can be stabilized by heat aging treatment as necessary.
  • the heating temperature of the heat aging treatment is preferably 900 ° C. or lower. If it exceeds 900 ° C, the crystal structure of the zeolite may be impaired.
  • a preferred heating temperature is 600 to 800 ° C.
  • the heating time is, for example, 1 hour to 10 hours, and the heating pressure is, for example, atmospheric pressure.
  • ⁇ Zeolite> Analysis of the crystal structure of zeolite can be performed using an X-ray diffraction (XRD) apparatus.
  • XRD measurement is performed using an X-ray diffractometer (Uriga IV manufactured by Rigaku Corporation).
  • the sample weight should not be changed by 0.1% or more before and after the XRD measurement.
  • the obtained XRD data is subjected to peak search using the powder X-ray diffraction pattern comprehensive analysis software JADE 6.0, and the half width and integrated intensity of each peak are calculated.
  • the peak search conditions are as follows. Filter type: parabolic filter, K ⁇ 2 peak elimination: yes, peak position definition: peak top, threshold ⁇ : 3, peak intensity% cutoff: 0.1, BG determination range: 1, BG averaging points: 7 .
  • the reason why the integrated intensity of the peaks of the (211) plane, (104) plane, and (220) plane of zeolite is used is that the influence of water absorption of the sample is small.
  • Zeolites synthesized by the present invention is preferably the sum X 0 of the integrated intensity is 55000 or more.
  • the integrated intensity sum X 0 is 55000 or more, a high NOx purification performance can be obtained.
  • the zeolite produced according to the present invention preferably has a Cu / Al (molar ratio) of 0.2 to 0.5.
  • a Cu / Al (molar ratio) of 0.2 to 0.5.
  • the Cu / Al molar ratio can be measured using a fluorescent X-ray analyzer.
  • a more preferable Cu / Al (molar ratio) is 0.25 to 0.5.
  • the zeolite produced according to the present invention preferably has a SiO 2 / Al 2 O 3 composition ratio (SAR) of less than 15.
  • the composition ratio of SiO 2 / Al 2 O 3 means the molar ratio (SAR) of SiO 2 to Al 2 O 3 in the zeolite.
  • the acid sites of the zeolite can be made a sufficient number, and the acid sites can be used for ion exchange with metal ions. As a result, NOx purification performance is excellent.
  • a more preferable SiO 2 / Al 2 O 3 composition ratio is 10 to 14.9.
  • the molar ratio of zeolite (SiO 2 / Al 2 O 3 ) can be measured using fluorescent X-ray analysis (XRF).
  • the average particle size of the zeolite produced according to the present invention is desirably 0.5 ⁇ m or less, and more desirably 0.1 to 0.4 ⁇ m.
  • a honeycomb catalyst is manufactured using zeolite having such a small average particle diameter, the amount of water absorption displacement becomes small. Further, cracks are unlikely to occur during production and use as a catalyst, and heat resistance and durability are excellent.
  • the average particle diameter exceeds 0.5 ⁇ m, the amount of water absorption displacement when the honeycomb catalyst is made increases, and cracks may occur in the honeycomb catalyst.
  • the average particle size of the zeolite was determined by taking an SEM photograph using a scanning electron microscope (SEM, manufactured by Hitachi High-Tech, S-4800), measuring the length of all diagonal lines of 10 particles, and calculating the average value. Ask from. Measurement conditions are as follows: acceleration voltage: 1 kV, emission: 10 ⁇ A, WD: 2.2 mm or less. In general, the CHA-type zeolite particles are cubic, and become a square when two-dimensionally imaged by an SEM photograph. Therefore, there are two diagonal lines of particles.
  • Example 1 Colloidal silica (manufactured by Nissan Chemical Industries, Snowtex) as the Si source, dry aluminum hydroxide gel (manufactured by Tomita Pharmaceutical) as the Al source, sodium hydroxide (manufactured by Tokuyama) and potassium hydroxide (Toagosei Co., Ltd.) as the alkali source N, N, N-trimethyladamantanammonium hydroxide (TMAAOH) 25% aqueous solution (manufactured by Sachem) as a structure directing agent (SDA), SSZ-13 as a seed crystal, and deionized water I prepared something.
  • SDA structure directing agent
  • the molar ratio of the raw material composition was such that SiO 2 : 15 mol, Al 2 O 3 : 1 mol, NaOH: 2.6 mol, KOH: 0.9 mol, TMAAOH: 1.1 mol, H 2 O: 300 mol.
  • the addition of 5.0 wt% of the seed crystal with respect to SiO 2, Al 2 O 3 raw material composition was charged in a 500 L autoclave, and hydrothermal synthesis was performed at a heating temperature of 160 ° C. and a heating time of 48 hours to synthesize zeolite. Subsequently, in order to remove TMAAOH remaining in the zeolite pores, heat treatment was performed in air at 550 ° C. for 4 hours.
  • the zeolite loaded with Cu obtained in the Cu ion exchange step was subjected to a heat aging treatment at 800 ° C. for 2 hours under atmospheric pressure to stabilize the performance of the zeolite.
  • Example 2 The same procedure as in Example 1 was performed except that the pH of the Cu solution in the Cu ion exchange step was adjusted to pH 11 using the aqueous solution shown in Table 1. The results of measuring the amount of Cu ion exchange are shown in Table 1.
  • Example 4-7 The same procedure as in Example 1 was performed except that the Cu solution in the Cu ion exchange step was a copper (II) acetate aqueous solution, and the pH of the solution and the aqueous solution used for pH adjustment were those shown in Table 1. The results of measuring the amount of Cu ion exchange are shown in Table 1.
  • the Cu solution in the Cu ion exchange step was an aqueous copper (II) acetate solution, the Cu concentration was as shown in Table 1, and the same procedure as in Example 1 was performed except that pH adjustment was not performed. The results of measuring the amount of Cu ion exchange are shown in Table 1.
  • Comparative Examples 1 to 4 The same procedure as in Examples 8 to 11 was performed except that the heat treatment step was not performed. The results of measuring the amount of Cu ion exchange are shown in Table 1.
  • the analysis conditions are: filter type: parabolic filter, elimination of K ⁇ 2 peak: yes, peak position definition: peak top, threshold ⁇ : 3, peak intensity% cutoff: 0.1, BG determination range: 1, BG average The number of conversion points was set to 7. As a result, X 0 was 60584.
  • FIG. 1 shows the XRD pattern of the zeolite synthesized in Example 1. From FIG. 1, it was confirmed that the zeolite synthesized in Example 1 was a zeolite having a CHA structure.
  • the zeolites obtained in Examples 1 to 11 were obtained by obtaining NH 4 + type zeolite and then heating the zeolite to obtain H + type zeolite, which was subjected to ion exchange using a Cu solution. As a result, the Cu ion exchange efficiency was high. From this result, it is estimated that the production time and production cost of zeolite can be reduced. In Comparative Examples 1 to 4, since ion exchange using a Cu solution was performed directly on NH 4 + type zeolite, Cu ion exchange efficiency was low.

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Abstract

The purpose of the present invention is to provide a method for producing a zeolite that has a CHA structure loaded with Cu, that has high Cu ion exchange efficiency, and that makes it possible to reduce production time and production costs. The method for producing a zeolite includes: a synthesis step in which a zeolite is synthesized using a starting material composition containing a Si source, an Al source, at least one substance selected from the group consisting of alkali metals and alkaline earth metals, and a structure-directing agent; an ammonium ion exchange step in which the obtained zeolite is subjected to ion exchange using an ammonia solution in order to obtain a zeolite loaded with NH4 +; a heat treatment step in which the zeolite loaded with NH4 + is heated to obtain a zeolite loaded with H+; and a Cu ion exchange step in which the zeolite loaded with H+ is subjected to ion exchange using a Cu solution in order to obtain a zeolite loaded with Cu.

Description

ゼオライトの製造方法Method for producing zeolite
　本発明は、ゼオライトの製造方法に関する。 The present invention relates to a method for producing zeolite.
　従来から、自動車の排ガスを浄化するシステムの１つとして、アンモニアを用いて、ＮＯｘを窒素と水に還元するＳＣＲ（Ｓｅｌｅｃｔｉｖｅ　Ｃａｔａｌｙｔｉｃ　Ｒｅｄｕｃｔｉｏｎ）システムが知られており、Ｃｕイオン交換されたＣＨＡ構造のゼオライトは、ＳＣＲ触媒作用を有するゼオライトとして注目されている。 Conventionally, an SCR (Selective Catalytic Reduction) system that uses ammonia to reduce NOx to nitrogen and water has been known as one of the systems for purifying exhaust gas from automobiles. Has attracted attention as a zeolite having an SCR catalytic action.
　このＳＣＲシステムは、排ガスが通過する多数の長手方向に延びる貫通孔が並設されたハニカムユニットをＳＣＲ触媒担体として用いており、例えば、特許文献１は、ＳＣＲ触媒担体として使用した際の耐熱性、耐久性を上げることを目的として、その組成比ＳｉＯ２／Ａｌ２Ｏ３が１５未満であり、かつ、粒子径が１．０～８．０μｍの、Ｃｕイオン交換されたＣＨＡ構造のゼオライトを開示している。 This SCR system uses, as an SCR catalyst carrier, a honeycomb unit in which a large number of longitudinally extending through holes through which exhaust gas passes are arranged. For example, Patent Document 1 discloses heat resistance when used as an SCR catalyst carrier. In order to increase the durability, a Cu ion-exchanged CHA-zeolite having a composition ratio SiO 2 / Al 2 O 3 of less than 15 and a particle diameter of 1.0 to 8.0 μm is used. Disclosure.
　一方、Ｃｕイオン交換されたＣＨＡ構造のゼオライトの製造方法として、例えば特許文献２は、Ｎａ＋型ゼオライトを用い、または該ゼオライトのＮａ＋をＮＨ４ ＋で置換しＮＨ４ ＋型ゼオライトを用い、Ｃｕ濃度が約０．００１～約０．２５モルのＣｕ溶液でイオン交換する方法を開示している。 On the other hand, as a manufacturing method of the zeolite of Cu ion-exchanged CHA structure, for example, Patent Document 2 uses the Na + form zeolite or with a substituted NH 4 + -type zeolite Na + in the zeolite NH 4 +,, Disclosed is a method of ion exchange with a Cu solution having a Cu concentration of about 0.001 to about 0.25 mol.
日本国特開２０１２－２１１０６６号公報Japanese Unexamined Patent Publication No. 2012-211066 日本国特表２０１３－５１４１６７号公報Japanese National Table 2013-514167
　しかしながら、上記した従来技術には、次のような問題がある。
　すなわち、特許文献２に記載のゼオライトの製造方法では、イオン交換効率が低く、所望のレベルまでＣｕイオン交換されたＣＨＡ構造のゼオライトを製造するには、何回ものイオン交換作業が必要であり、長時間かつ高コストとなるという問題点があった。 However, the above prior art has the following problems.
That is, in the method for producing zeolite described in Patent Document 2, ion exchange efficiency is low, and in order to produce a CHA-structured zeolite in which Cu ions are exchanged to a desired level, many ion exchange operations are required. There was a problem that it was long and expensive.
　本発明は、上記課題を解決するためになされたものであり、Ｃｕのイオン交換効率が高く、製造時間および製造コストの低減を可能とする、Ｃｕイオン交換されたＣＨＡ構造のゼオライトの製造方法を提供することを目的とする。 The present invention has been made in order to solve the above-described problems, and provides a method for producing a zeolite having a CHA structure having a high ion exchange efficiency with Cu and capable of reducing production time and production cost. The purpose is to provide.
　すなわち、本発明のゼオライトの製造方法は、Ｃｕイオン交換されたＣＨＡ構造を有するゼオライトを製造する方法であって、
　Ｓｉ源と、Ａｌ源と、アルカリ金属及びアルカリ土類金属からなる群から選択される少なくとも一種と、並びに構造規定剤とを含む原料組成物を用いてゼオライトを合成する合成工程、
　上記合成工程で得られたゼオライトに対し、アンモニア溶液を用いて、ＮＨ４ ＋型ゼオライトを得るアンモニウムイオン交換工程、
　上記アンモニウムイオン交換工程で得られたＮＨ４ ＋型ゼオライトを加熱し、Ｈ＋型ゼオライトを得る熱処理工程、および
　上記熱処理工程で得られたＨ＋型ゼオライトに対し、Ｃｕ溶液を用いてＣｕイオン交換されたゼオライトを得るＣｕイオン交換工程を含む、
ことを特徴とする。 That is, the method for producing a zeolite of the present invention is a method for producing a zeolite having a CHA structure subjected to Cu ion exchange,
A synthesis step of synthesizing zeolite using a raw material composition comprising a Si source, an Al source, at least one selected from the group consisting of alkali metals and alkaline earth metals, and a structure directing agent;
An ammonium ion exchange step for obtaining NH 4 + type zeolite using an ammonia solution with respect to the zeolite obtained in the synthesis step,
Heating the NH 4 + type zeolite obtained in the ammonium ion exchange step to obtain an H + type zeolite, and Cu ion exchange using a Cu solution for the H + type zeolite obtained in the heat treatment step Including a Cu ion exchange step to obtain a modified zeolite,
It is characterized by that.
　本発明者らはＣｕのイオン交換効率を高め得るゼオライトの製造方法について鋭意検討を行った結果、合成されたゼオライトをまずＮＨ４ ＋型ゼオライトにし、このＮＨ４ ＋型ゼオライトを加熱処理によりＨ＋型ゼオライトにし、得られたＨ＋型ゼオライトに対してＣｕのイオン交換を行うことにより、イオン交換効率が高められ、それによりイオン交換作業の回数を低減でき、イオン交換工程を短時間で終了できることを見出した。すなわち、本発明の製造方法では、Ｃｕのイオン交換効率が高く、製造時間および製造コストを抑制することが可能となる。 As a result of intensive studies on a method for producing a zeolite capable of improving the ion exchange efficiency of Cu, the inventors first made the synthesized zeolite NH 4 + type zeolite, and this NH 4 + type zeolite was heated to H + The ion exchange efficiency can be increased by performing Cu ion exchange on the obtained H + type zeolite, thereby reducing the number of ion exchange operations and completing the ion exchange process in a short time. I found. That is, in the manufacturing method of the present invention, Cu ion exchange efficiency is high, and manufacturing time and manufacturing cost can be suppressed.
　本発明のゼオライトの製造方法においては、上記合成工程で得られるゼオライトにおけるＳｉＯ２／Ａｌ２Ｏ３組成比（ＳＡＲ）が１５未満であることが好ましい。その組成比ＳｉＯ２／Ａｌ２Ｏ３が１５未満であることにより、ＮＯｘの浄化率をさらに高めることができる。その理由は、ＳｉＯ２／Ａｌ２Ｏ３が１５未満であることにより、アルミナ量が増え、それに比例して触媒として機能するＣｕイオン交換量を多くできるからである。 In the method for producing zeolite of the present invention, it is preferable that the SiO 2 / Al 2 O 3 composition ratio (SAR) in the zeolite obtained in the synthesis step is less than 15. When the composition ratio SiO 2 / Al 2 O 3 is less than 15, the NOx purification rate can be further increased. The reason is that when SiO 2 / Al 2 O 3 is less than 15, the amount of alumina increases, and the amount of Cu ion exchange that functions as a catalyst can be increased in proportion to the amount of alumina.
　本発明のゼオライトの製造方法は、上記Ａｌ源が乾燥水酸化アルミニウムゲルであることが好ましい。乾燥水酸化アルミニウムゲルはアルカリ溶液に対する溶解度が高いため、合成されたゼオライトの粒子径及びＳｉＯ２／Ａｌ２Ｏ３モル比のばらつきを小さくすることが可能となる。 In the method for producing zeolite of the present invention, the Al source is preferably a dry aluminum hydroxide gel. Since the dry aluminum hydroxide gel has high solubility in an alkaline solution, it is possible to reduce the variation in the particle diameter of the synthesized zeolite and the SiO 2 / Al 2 O 3 molar ratio.
　本発明のゼオライトの製造方法においては、上記熱処理工程においてＮＨ４ ＋型ゼオライトの加熱温度が３５０～６５０℃であることが好ましい。３５０℃以上の加熱温度により、ＮＨ４ ＋型ゼオライトからＮＨ３が脱離しやすくなり、効率よくＨ＋型ゼオライトに変換することができる。また６５０℃以下の加熱温度により、ゼオライトからの脱Ａｌが抑えられ、Ｃｕのイオン交換量を損なうことなく、イオン交換効率を高めることができる。 In the method for producing zeolite of the present invention, the heating temperature of the NH 4 + type zeolite is preferably 350 to 650 ° C. in the heat treatment step. With a heating temperature of 350 ° C. or higher, NH 3 is easily desorbed from the NH 4 + type zeolite, and can be efficiently converted to H + type zeolite. Moreover, by the heating temperature of 650 degrees C or less, de-Al removal from a zeolite is suppressed and ion exchange efficiency can be improved, without impairing the amount of ion exchange of Cu.
　本発明のゼオライトの製造方法においては、Ｃｕイオン交換工程において使用するＣｕ溶液のｐＨが８～１２であることが好ましい。Ｃｕ溶液が８以上のｐＨであることにより、イオン交換でＨ＋型ゼオライトから脱離したＨ＋イオンによりＣｕ溶液のＨ＋イオン濃度が高くなることを抑え、Ｃｕイオン交換の進行を妨げない。また、Ｃｕ溶液が１２以下のｐＨであることによりゼオライトの結晶構造の破壊が防止される。 In the method for producing zeolite of the present invention, the pH of the Cu solution used in the Cu ion exchange step is preferably 8-12. When the Cu solution has a pH of 8 or higher, the H + ion concentration of the Cu solution is suppressed from being increased by H + ions desorbed from the H + type zeolite by ion exchange, and the progress of Cu ion exchange is not hindered. Moreover, destruction of the crystal structure of zeolite is prevented when the Cu solution has a pH of 12 or less.
　本発明のゼオライトの製造方法においては、使用するＣｕ溶液が硫酸銅水溶液であることが好ましい。一般的に使用される酢酸銅水溶液に比べ硫酸銅水溶液は低コストであり、本発明のゼオライトの製造方法のコストを一層低下させることができる。 In the method for producing zeolite of the present invention, the Cu solution to be used is preferably an aqueous copper sulfate solution. Compared to a commonly used aqueous solution of copper acetate, an aqueous solution of copper sulfate is low in cost, and the cost of the method for producing a zeolite of the present invention can be further reduced.
　本発明のゼオライトの製造方法においては、Ｃｕイオン交換されたゼオライトにおけるＣｕ／Ａｌ（モル比）が０．２～０．５であることが好ましい。該モル比が０．２以上であることにより、少量のゼオライトで高いＮＯｘ浄化性能を得ることができる。また該モル比が０．５以下であることにより、高温でのアンモニア酸化によるＮＯｘ浄化性能の低下を防止できる。 In the zeolite production method of the present invention, the Cu / Al (molar ratio) in the zeolite subjected to Cu ion exchange is preferably 0.2 to 0.5. When the molar ratio is 0.2 or more, high NOx purification performance can be obtained with a small amount of zeolite. Moreover, when the molar ratio is 0.5 or less, it is possible to prevent a decrease in NOx purification performance due to ammonia oxidation at a high temperature.
　以上のように本発明によれば、Ｃｕのイオン交換効率が高く、製造時間および製造コストの低減を可能とする、Ｃｕイオン交換されたＣＨＡ構造のゼオライトの製造方法を提供することができる。 As described above, according to the present invention, it is possible to provide a method for producing a CHA-exchanged zeolite having high ion exchange efficiency of Cu and capable of reducing production time and production cost.
図１は、実施例１で合成したゼオライトのＸＲＤパターンを示すチャートである。FIG. 1 is a chart showing the XRD pattern of the zeolite synthesized in Example 1.
（発明の詳細な説明）
　以下、本発明について具体的に説明する。しかしながら、本発明は、以下の記載に限定されるものではなく、本発明の要旨を変更しない範囲において適宜変更して適用することができる。
　尚、本明細書において、「質量」は「重量」のことを意味するものとする。 (Detailed description of the invention)
Hereinafter, the present invention will be specifically described. However, the present invention is not limited to the following description, and can be appropriately modified and applied without departing from the scope of the present invention.
In the present specification, “mass” means “weight”.
＜Ｃｕイオン交換されたゼオライトの製造方法＞
　本発明のゼオライトの製造方法は、以下の各工程を含むことを特徴とする。
　Ｓｉ源と、Ａｌ源と、アルカリ源としてのアルカリ金属及びアルカリ土類金属からなる群から選択される少なくとも一種と、並びに構造規定剤とを含む原料組成物を用いてゼオライトを合成する合成工程、
　上記合成工程で得られたゼオライトに対し、アンモニア溶液を用いて、ＮＨ４ ＋型ゼオライトを得るアンモニウムイオン交換工程、
　上記アンモニウムイオン交換工程で得られたＮＨ４ ＋型ゼオライトを加熱し、Ｈ＋型ゼオライトを得る熱処理工程、および
　上記熱処理工程で得られたＨ＋型ゼオライトに対し、Ｃｕ溶液を用いてＣｕイオン交換されたゼオライトを得るＣｕイオン交換工程。 <Method for producing Cu ion-exchanged zeolite>
The method for producing a zeolite of the present invention is characterized by including the following steps.
A synthesis step of synthesizing zeolite using a raw material composition comprising a Si source, an Al source, at least one selected from the group consisting of alkali metals and alkaline earth metals as an alkali source, and a structure-directing agent;
An ammonium ion exchange step for obtaining NH 4 + type zeolite using an ammonia solution with respect to the zeolite obtained in the synthesis step,
Heating the NH 4 + type zeolite obtained in the ammonium ion exchange step to obtain an H + type zeolite, and Cu ion exchange using a Cu solution for the H + type zeolite obtained in the heat treatment step Cu ion exchange process to obtain a finished zeolite.
　なお本発明により製造されるゼオライトは、国際ゼオライト学会（Ｉｎｔｅｒｎａｔｉｏｎａｌ　Ｚｅｏｌｉｔｅ　Ａｓｓｏｃｉａｔｉｏｎ：ＩＺＡ）において、ＣＨＡという構造コードで命名され、分類されており、天然に産出するチャバサイト（ｃｈａｂａｚｉｔｅ）と同等の結晶構造を有するゼオライトである。 The zeolite produced according to the present invention is named and classified by the structure code of CHA in the International Zeolite Association (IZA), and has a crystal structure equivalent to that of naturally occurring chabazite. Zeolite.
　まず、本発明のゼオライトの製造方法における、上記合成工程について説明する。
　合成工程においては、まず、Ｓｉ源、Ａｌ源、アルカリ源、水及び構造規定剤からなる原料組成物を準備する。 First, the said synthetic | combination process in the manufacturing method of the zeolite of this invention is demonstrated.
In the synthesis step, first, a raw material composition comprising a Si source, an Al source, an alkali source, water and a structure directing agent is prepared.
　Ｓｉ源とは、ゼオライトのシリコン成分の原料となる化合物、塩及び組成物をいう。
　Ｓｉ源としては、例えば、コロイダルシリカ、無定型シリカ、珪酸ナトリウム、テトラエチルオルトシリケート、アルミノシリケートゲル等を用いることができ、これらを二種以上併用してもよい。これらの中では、コロイダルシリカが望ましい。 The Si source refers to a compound, a salt, and a composition that are raw materials for the silicon component of zeolite.
As the Si source, for example, colloidal silica, amorphous silica, sodium silicate, tetraethylorthosilicate, aluminosilicate gel, and the like can be used, and two or more of these may be used in combination. Of these, colloidal silica is desirable.
　Ａｌ源としては、例えば、硫酸アルミニウム、アルミン酸ナトリウム、水酸化アルミニウム、塩化アルミニウム、アルミノシリケートゲル、乾燥水酸化アルミニウムゲル等が挙げられる。これらの中では、乾燥水酸化アルミニウムゲルが好ましい。 Examples of the Al source include aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum chloride, aluminosilicate gel, and dry aluminum hydroxide gel. Of these, dry aluminum hydroxide gel is preferred.
　本発明のゼオライトの製造方法においては、目的とするＣＨＡ型ゼオライトを製造するためには、ほぼ製造されるゼオライトのモル比（ＳｉＯ２／Ａｌ２Ｏ３）と同じモル比のＳｉ源、Ａｌ源を用いることが望ましい。原料組成物中のＳｉ源とＡｌ源のモル比（ＳｉＯ２／Ａｌ２Ｏ３）は、５～３０であることが望ましく、１０～１５であることがより望ましい。 In the method for producing a zeolite of the present invention, in order to produce the target CHA-type zeolite, a Si source and an Al source having a molar ratio (SiO 2 / Al 2 O 3 ) substantially equal to the molar ratio of the zeolite to be produced. It is desirable to use The molar ratio (SiO 2 / Al 2 O 3 ) between the Si source and the Al source in the raw material composition is preferably 5 to 30, and more preferably 10 to 15.
　アルカリ源は、アルカリ金属及びアルカリ土類金属からなる群から選択される少なくとも一種を含む化合物であり、例えば、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム、水酸化リチウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム等を用いることができ、これらを二種以上併用してもよい。これらの中では、水酸化カリウム、水酸化ナトリウム、水酸化リチウムが望ましい。ゼオライトの単相を得るためには特に水酸化カリウムと水酸化ナトリウムを併用することが好ましい。 The alkali source is a compound containing at least one selected from the group consisting of alkali metals and alkaline earth metals. For example, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium hydroxide, hydroxide Calcium, strontium hydroxide, barium hydroxide, and the like can be used, and two or more of these may be used in combination. Of these, potassium hydroxide, sodium hydroxide, and lithium hydroxide are desirable. In order to obtain a single phase of zeolite, it is particularly preferable to use potassium hydroxide and sodium hydroxide in combination.
　本発明のゼオライトの製造方法においては、水の量は、特に限定されるものではないが、Ｓｉ源のＳｉ及びＡｌ源のＡｌの合計モル数に対する水のモル数の比（Ｈ２Ｏモル数／Ｓｉ及びＡｌの合計モル数）が１２～３０であることが望ましく、Ｓｉ源のＳｉ及びＡｌ源のＡｌの合計モル数に対する水のモル数の比（Ｈ２Ｏモル数／Ｓｉ及びＡｌの合計モル数）が１５～２５であることがより望ましい。 In the method for producing a zeolite of the present invention, the amount of water is not particularly limited, but the ratio of the number of moles of water to the total number of moles of Si of Si source and Al of Al source (number of moles of H 2 O). / Total number of moles of Si and Al) is preferably 12 to 30, and the ratio of the number of moles of water to the total number of moles of Si of the Si source and Al of the Al source (H 2 O moles / Si and Al The total number of moles) is more preferably 15-25.
　構造規定剤（以下、ＳＤＡとも記載する。）とは、ゼオライトの細孔径や結晶構造を規定する有機分子を示す。構造規定剤の種類等によって、得られるゼオライトの構造等を制御することができる。
　本発明のゼオライトの製造方法においては、構造規定剤としては、Ｎ，Ｎ，Ｎ－トリアルキルアダマンタンアンモニウムをカチオンとする水酸化物、ハロゲン化物、炭酸塩、メチルカーボネート塩、硫酸塩及び硝酸塩；及びＮ，Ｎ，Ｎ－トリメチルベンジルアンモニウムイオン、Ｎ－アルキル－３－キヌクリジノールイオン、またはＮ，Ｎ，Ｎ－トリアルキルエキソアミノノルボルナンをカチオンとする水酸化物、ハロゲン化物、炭酸塩、メチルカーボネート塩、硫酸塩及び硝酸塩からなる群から選ばれる少なくとも一種を用いることができる。これらの中では、Ｎ，Ｎ，Ｎ－トリメチルアダマンタンアンモニウム水酸化物（以下、ＴＭＡＡＯＨとも記載する。）、Ｎ，Ｎ，Ｎ－トリメチルアダマンタンアンモニウムハロゲン化物、Ｎ，Ｎ，Ｎ－トリメチルアダマンタンアンモニウム炭酸塩、Ｎ，Ｎ，Ｎ－トリメチルアダマンタンアンモニウムメチルカーボネート塩及びＮ，Ｎ，Ｎ－トリメチルアダマンタンアンモニウム硫酸塩からなる群から選ばれる少なくとも一種を用いることが望ましく、ＴＭＡＡＯＨを用いることがより望ましい。 The structure-directing agent (hereinafter also referred to as SDA) refers to an organic molecule that defines the pore diameter and crystal structure of zeolite. The structure of the obtained zeolite can be controlled by the type of the structure-directing agent.
In the method for producing a zeolite of the present invention, as the structure directing agent, hydroxides, halides, carbonates, methyl carbonate salts, sulfates and nitrates having N, N, N-trialkyladamantanammonium as a cation; and Hydroxides, halides, carbonates, methyls with N, N, N-trimethylbenzylammonium ion, N-alkyl-3-quinuclidinol ion, or N, N, N-trialkylexoaminonorbornane as a cation At least one selected from the group consisting of carbonates, sulfates and nitrates can be used. Among these, N, N, N-trimethyladamantanammonium hydroxide (hereinafter also referred to as TMAAOH), N, N, N-trimethyladamantanammonium halide, N, N, N-trimethyladamantanammonium carbonate It is preferable to use at least one selected from the group consisting of N, N, N-trimethyladamantanammonium methyl carbonate and N, N, N-trimethyladamantanammonium sulfate, and it is more preferable to use TMAAOH.
　本発明のゼオライトの製造方法の合成工程においては、原料組成物に、さらにゼオライトの種結晶を加えてもよい。種結晶を用いることにより、ゼオライトの結晶化速度が速くなり、ゼオライト製造における時間が短縮でき、収率が向上する。 In the synthesis step of the zeolite production method of the present invention, zeolite seed crystals may be further added to the raw material composition. By using the seed crystal, the crystallization speed of the zeolite is increased, the time for producing the zeolite can be shortened, and the yield is improved.
　ゼオライトの種結晶としては、ＣＨＡ構造を有するゼオライトを用いることが望ましい。 As a zeolite seed crystal, it is desirable to use a zeolite having a CHA structure.
　ゼオライトの種結晶の添加量は、少ない方が望ましいが、反応速度や不純物の抑制効果等を考慮すると、原料組成物に含まれるシリカ成分に対して、０．１～２０質量％であることが望ましく、０．５～１５質量％であることがより望ましい。種結晶の添加量が０．１質量％未満であると、ゼオライトの結晶化速度を向上する寄与が小さく、２０質量％を超えると、合成して得られるゼオライトに不純物が入りやすくなる。 The amount of zeolite seed crystals added is preferably small, but considering the reaction rate and the effect of suppressing impurities, it should be 0.1 to 20% by mass with respect to the silica component contained in the raw material composition. Desirably, 0.5 to 15% by mass is more desirable. When the added amount of the seed crystal is less than 0.1% by mass, the contribution of improving the crystallization rate of the zeolite is small, and when it exceeds 20% by mass, impurities are easily contained in the synthesized zeolite.
　合成工程においては、準備した原料組成物を反応させることにより、ゼオライトを合成する。具体的には、原料組成物を水熱合成することによりゼオライトを合成することが望ましい。 In the synthesis step, zeolite is synthesized by reacting the prepared raw material composition. Specifically, it is desirable to synthesize zeolite by hydrothermal synthesis of the raw material composition.
　水熱合成に用いられる反応容器は、既知の水熱合成に用いられるものであれば特に限定されず、オートクレーブなどの耐熱耐圧容器であればよい。反応容器に原料組成物を投入して密閉して加熱することにより、ゼオライトを結晶化させることができる。 The reaction vessel used for hydrothermal synthesis is not particularly limited as long as it is used for known hydrothermal synthesis, and may be a heat and pressure resistant vessel such as an autoclave. The zeolite can be crystallized by putting the raw material composition into the reaction vessel, sealing and heating.
　ゼオライトを合成する際、原料混合物は静置した状態でもよいが、攪拌混合した状態であることが望ましい。 When synthesizing the zeolite, the raw material mixture may be in a stationary state, but is preferably in a state of being stirred and mixed.
　ゼオライトを合成する際の加熱温度は、１００～２００℃であることが望ましく、１２０～１８０℃であることがより望ましい。加熱温度が１００℃未満であると、結晶化速度が遅くなり、収率が低下しやすくなる。一方、加熱温度が２００℃を超えると、不純物が発生しやすくなる。 The heating temperature for synthesizing the zeolite is preferably 100 to 200 ° C, more preferably 120 to 180 ° C. When the heating temperature is less than 100 ° C., the crystallization rate becomes slow, and the yield tends to decrease. On the other hand, when the heating temperature exceeds 200 ° C., impurities are likely to be generated.
　合成工程における加熱時間は、１０～２００時間であることが望ましい。加熱時間が１０時間未満であると、未反応の原料が残存し、収率が低下しやすくなる。一方、加熱時間が２００時間を超えても、収率や結晶性の向上がほとんど見られない。 The heating time in the synthesis process is preferably 10 to 200 hours. If the heating time is less than 10 hours, unreacted raw materials remain and the yield tends to decrease. On the other hand, even when the heating time exceeds 200 hours, the yield and crystallinity are hardly improved.
　合成工程における圧力は特に限定されず、密閉容器中に入れた原料組成物を上記温度範囲に加熱したときに生じる圧力で充分であるが、必要に応じて、窒素ガスなどの不活性ガスを加えて昇圧してもよい。 The pressure in the synthesis process is not particularly limited, and the pressure generated when the raw material composition placed in a closed container is heated to the above temperature range is sufficient, but if necessary, an inert gas such as nitrogen gas is added. May be boosted.
　本発明のゼオライトの製造方法の合成工程により得られたゼオライトは、充分に放冷し、固液分離し、充分量の水で洗浄することが望ましい。 It is desirable that the zeolite obtained by the synthesis step of the method for producing zeolite of the present invention is sufficiently cooled, solid-liquid separated, and washed with a sufficient amount of water.
　合成工程により得られたゼオライトは、細孔内にＳＤＡを含有しているため、必要に応じてこれを除去してもよい。例えば、酸性溶液又はＳＤＡ分解成分を含む薬液を用いた液相処理、レジンなどを用いた交換処理、熱分解処理などにより、ＳＤＡを除去することができる。 Since the zeolite obtained by the synthesis process contains SDA in the pores, it may be removed if necessary. For example, SDA can be removed by a liquid phase treatment using an acidic solution or a chemical solution containing an SDA decomposition component, an exchange treatment using a resin, a thermal decomposition treatment, or the like.
　次に、本発明のゼオライトの製造方法における、アンモニウムイオン交換工程について説明する。
　アンモニウムイオン交換工程は、合成工程により得られたゼオライトに対し、アンモニア溶液を用いてイオン交換を行い、ＮＨ４ ＋型ゼオライトを得る工程である。
　アンモニア溶液としては、例えばアンモニア水、硫酸アンモニウム水溶液、硝酸アンモニウム水溶液等が挙げられ、中でも硫酸アンモニウム水溶液が好ましい。アンモニア溶液中のアンモニア濃度は、例えば、１～１０質量％、好ましくは２～５質量％である。 Next, the ammonium ion exchange step in the method for producing zeolite of the present invention will be described.
The ammonium ion exchange step is a step of obtaining NH 4 + type zeolite by performing ion exchange on the zeolite obtained in the synthesis step using an ammonia solution.
Examples of the ammonia solution include aqueous ammonia, an aqueous ammonium sulfate solution, an aqueous ammonium nitrate solution, and the like. Among these, an aqueous ammonium sulfate solution is preferable. The ammonia concentration in the ammonia solution is, for example, 1 to 10% by mass, preferably 2 to 5% by mass.
　アンモニア溶液を用いたイオン交換方法としては、上記アンモニア溶液にゼオライトを浸漬することで行うことができる。アンモニア溶液の温度は例えば４～５０℃、圧力は例えば大気圧、浸漬時間は例えば０．１時間～２時間である。このようにして、ＮＨ４ ＋型ゼオライトが得られる。 An ion exchange method using an ammonia solution can be performed by immersing zeolite in the ammonia solution. The temperature of the ammonia solution is, for example, 4 to 50 ° C., the pressure is, for example, atmospheric pressure, and the immersion time is, for example, 0.1 to 2 hours. In this way, NH 4 + type zeolite is obtained.
　次に、本発明のゼオライトの製造方法における、熱処理工程について説明する。
　熱処理工程は、アンモニウムイオン交換工程で得られたＮＨ４ ＋型ゼオライトを加熱し、Ｈ＋型ゼオライトを得る工程である。
　加熱温度は、３５０～６５０℃であることが好ましい。３５０℃以上の加熱温度により、ＮＨ４ ＋型ゼオライトからＮＨ３が脱離しやすくなり、効率よくＨ＋型ゼオライトに変換することができる。また６５０℃以下の加熱温度により、ゼオライトからの脱Ａｌが抑えられ、Ｃｕのイオン交換量を損なうことなく、イオン交換効率を高めることができる。
　さらに好ましい加熱温度は、４００～６００℃である。 Next, the heat treatment step in the method for producing zeolite of the present invention will be described.
The heat treatment step is a step of heating the NH 4 + type zeolite obtained in the ammonium ion exchange step to obtain H + type zeolite.
The heating temperature is preferably 350 to 650 ° C. With a heating temperature of 350 ° C. or higher, NH 3 is easily desorbed from the NH 4 + type zeolite, and can be efficiently converted to H + type zeolite. Moreover, by the heating temperature of 650 degrees C or less, de-Al removal from a zeolite is suppressed and ion exchange efficiency can be improved, without impairing the amount of ion exchange of Cu.
A more preferable heating temperature is 400 to 600 ° C.
　加熱時間は、例えば０．５時間～４８時間、好ましくは１時間～２４時間である。加熱圧力は、例えば大気圧である。 The heating time is, for example, 0.5 to 48 hours, preferably 1 to 24 hours. The heating pressure is, for example, atmospheric pressure.
　なお、使用する加熱手段としては、市販されている加熱炉、例えばデンケン・ハイデンタル社製商品名ＫＤＦ－Ｓ１００が挙げられる。 In addition, as a heating means to be used, a commercially available heating furnace, for example, trade name KDF-S100 manufactured by Denken Hydental Co., Ltd. may be mentioned.
　次に、本発明のゼオライトの製造方法における、Ｃｕイオン交換工程について説明する。
　Ｃｕイオン交換工程は、熱処理工程で得られたＨ＋型ゼオライトに対し、Ｃｕ溶液を用いたイオン交換を行い、Ｃｕイオン交換されたゼオライトを得る工程である。
　Ｃｕ溶液としては、酢酸銅水溶液、硝酸銅水溶液、硫酸銅水溶液および塩化銅水溶液から選ばれる１種の水溶液が挙げられる。中でも、硫酸銅水溶液が好ましい。硫酸銅水溶液は一般的に使用される酢酸銅水溶液に比べ低コストであり、本発明のゼオライトの製造方法のコストを一層低下させることができる。 Next, the Cu ion exchange step in the method for producing zeolite of the present invention will be described.
The Cu ion exchange step is a step of obtaining a zeolite subjected to Cu ion exchange by performing ion exchange using a Cu solution on the H + type zeolite obtained in the heat treatment step.
Examples of the Cu solution include one aqueous solution selected from a copper acetate aqueous solution, a copper nitrate aqueous solution, a copper sulfate aqueous solution, and a copper chloride aqueous solution. Of these, an aqueous copper sulfate solution is preferred. The aqueous copper sulfate solution is lower in cost than the commonly used aqueous copper acetate solution, and can further reduce the cost of the method for producing a zeolite of the present invention.
　Ｃｕ溶液中のＣｕ濃度は、例えば、０．２～５．０質量％、好ましくは０．５～２．５質量％である。 The Cu concentration in the Cu solution is, for example, 0.2 to 5.0% by mass, preferably 0.5 to 2.5% by mass.
　また、本発明のゼオライトの製造方法のＣｕイオン交換工程において使用するＣｕ溶液のｐＨは、８～１２であることが好ましく、９～１１であることがさらに好ましい。Ｃｕ溶液が８以上のｐＨであることにより、イオン交換でＨ型ゼオライトから脱離したＨ＋イオンによりＣｕ溶液のＨ＋イオン濃度が高くなることを抑え、Ｃｕイオン交換の進行を妨げない。また、Ｃｕ溶液が１２以下のｐＨであることによりゼオライトの結晶構造の破壊が防止される。ｐＨの調整は、例えばアンモニア水やＮａＯＨ等を用いて行うことができる。 Further, the pH of the Cu solution used in the Cu ion exchange step of the method for producing zeolite of the present invention is preferably 8 to 12, and more preferably 9 to 11. When the Cu solution has a pH of 8 or higher, the H + ion concentration of the Cu solution is prevented from being increased by H + ions desorbed from the H-type zeolite by ion exchange, and the progress of Cu ion exchange is not hindered. Moreover, destruction of the crystal structure of zeolite is prevented when the Cu solution has a pH of 12 or less. The pH can be adjusted using, for example, aqueous ammonia or NaOH.
　Ｃｕイオン交換工程におけるイオン交換方法としては、上記Ｃｕ溶液にＨ＋型ゼオライトを浸漬することで行うことができる。Ｃｕ溶液の温度は例えば室温～６０℃、圧力は例えば大気圧、浸漬時間は例えば０．１時間～２４時間、好ましくは０．５時間～１２時間である。このようにして、Ｃｕイオン交換されたゼオライトが得られる。 The ion exchange method in the Cu ion exchange step can be performed by immersing H + type zeolite in the Cu solution. The temperature of the Cu solution is, for example, room temperature to 60 ° C., the pressure is, for example, atmospheric pressure, and the immersion time is, for example, 0.1 to 24 hours, preferably 0.5 to 12 hours. In this way, a zeolite subjected to Cu ion exchange is obtained.
　本発明のゼオライトの製造方法において、Ｃｕイオン交換工程終了後のゼオライトは、必要に応じて熱エージング処理によりその性能を安定化させることができる。
　熱エージング処理の加熱温度は、９００℃以下が好ましい。９００℃を超えるとゼオライトの結晶構造を損なう恐れがある。好ましい加熱温度は６００～８００℃である。加熱時間は、例えば１時間～１０時間であり、加熱圧力は、例えば大気圧である。 In the method for producing zeolite of the present invention, the performance of the zeolite after completion of the Cu ion exchange step can be stabilized by heat aging treatment as necessary.
The heating temperature of the heat aging treatment is preferably 900 ° C. or lower. If it exceeds 900 ° C, the crystal structure of the zeolite may be impaired. A preferred heating temperature is 600 to 800 ° C. The heating time is, for example, 1 hour to 10 hours, and the heating pressure is, for example, atmospheric pressure.
＜ゼオライト＞
　ゼオライトの結晶構造の解析は、Ｘ線回折（ＸＲＤ）装置を用いて行うことができる。ＣＨＡ型ゼオライトは、粉末Ｘ線解析法によるＸ線回折スペクトルで、２θ＝２０．７°付近、２５．１°付近、２６．１°付近にそれぞれ、ＣＨＡ型ゼオライト結晶の（２１１）面、（１０４）面及び（２２０）面に相当するピークが現れる。 <Zeolite>
Analysis of the crystal structure of zeolite can be performed using an X-ray diffraction (XRD) apparatus. The CHA-type zeolite is an X-ray diffraction spectrum by a powder X-ray analysis method, and the (211) plane of the CHA-type zeolite crystals at 2θ = 20.7 °, 25.1 °, and 26.1 °, respectively ( The peaks corresponding to the (104) plane and the (220) plane appear.
　ＸＲＤ測定は、Ｘ線回折装置（リガク社製　ＵｌｔｉｍａＩＶ）を用いて行う。なお、測定条件は、次の通りとする。
線源：ＣｕＫα（λ＝０．１５４ｎｍ）、測定法：ＦＴ法、回折角：２θ＝５～４８°、ステップ幅：０．０２°、積算時間：１秒、発散スリット、散乱スリット：２／３°、発散縦制限スリット：１０ｍｍ、加速電圧：４０ｋＶ、加速電流：４０ｍＡ。
　ＸＲＤ測定前後でサンプル重量が０．１％以上の変化がないようにする。得られたＸＲＤデータは、粉末Ｘ線回折パターン総合解析ソフトＪＡＤＥ６．０を用いてピークサーチを行い、さらに各ピークの半値幅と積分強度を算出する。なお、ピークサーチの条件は次の通りとする。
フィルタータイプ：放物線フィルター、Ｋα２ピークの消去：あり、ピーク位置定義：ピークトップ、閾値σ：３、ピーク強度％カットオフ：０．１、ＢＧ決定の範囲：１、ＢＧ平均化のポイント数：７。
　得られたデータから、ゼオライトの（２１１）面（２θ＝２０．７°付近）、（１０４）面（２θ＝２５．１°付近）、（２２０）面（２θ＝２６．１°付近）の積分強度の和Ｘ０を求めることができる。
　なお、ゼオライトの（２１１）面、（１０４）面、（２２０）面のピークの積分強度を用いるのは、サンプルの吸水の影響が小さいためである。 XRD measurement is performed using an X-ray diffractometer (Uriga IV manufactured by Rigaku Corporation). The measurement conditions are as follows.
Radiation source: CuKα (λ = 0.154 nm), measurement method: FT method, diffraction angle: 2θ = 5 to 48 °, step width: 0.02 °, integration time: 1 second, divergence slit, scattering slit: 2 / 3 °, divergence length limiting slit: 10 mm, acceleration voltage: 40 kV, acceleration current: 40 mA.
The sample weight should not be changed by 0.1% or more before and after the XRD measurement. The obtained XRD data is subjected to peak search using the powder X-ray diffraction pattern comprehensive analysis software JADE 6.0, and the half width and integrated intensity of each peak are calculated. The peak search conditions are as follows.
Filter type: parabolic filter, Kα2 peak elimination: yes, peak position definition: peak top, threshold σ: 3, peak intensity% cutoff: 0.1, BG determination range: 1, BG averaging points: 7 .
From the obtained data, the (211) plane (near 2θ = 20.7 °), (104) plane (near 2θ = 25.1 °), (220) plane (near 2θ = 26.1 °) of the zeolite. it can be the sum X 0 of the integrated intensity.
The reason why the integrated intensity of the peaks of the (211) plane, (104) plane, and (220) plane of zeolite is used is that the influence of water absorption of the sample is small.
　本発明により合成されたゼオライトは、積分強度の和Ｘ０が５５０００以上であることが好ましい。積分強度が高いほど結晶性が良好であることを示し、積分強度の和Ｘ０が５５０００以上あることで、高いＮＯｘ浄化性能を得ることができる。 Zeolites synthesized by the present invention is preferably the sum X 0 of the integrated intensity is 55000 or more. The higher the integrated intensity, the better the crystallinity. When the integrated intensity sum X 0 is 55000 or more, a high NOx purification performance can be obtained.
　本発明により製造されたゼオライトは、Ｃｕ／Ａｌ（モル比）が０．２～０．５であることが好ましい。
　該モル比が０．２以上であることにより、少量のゼオライトで高いＮＯｘ浄化性能を得ることができる。また該モル比が０．５以下であることにより、高温でのアンモニア酸化によりＮＯｘ浄化性能が低下することを防止できる。Ｃｕ／Ａｌモル比は蛍光Ｘ線分析装置を用いて測定することができる。
　より好ましいＣｕ／Ａｌ（モル比）は、０．２５～０．５である。 The zeolite produced according to the present invention preferably has a Cu / Al (molar ratio) of 0.2 to 0.5.
When the molar ratio is 0.2 or more, high NOx purification performance can be obtained with a small amount of zeolite. Further, when the molar ratio is 0.5 or less, it is possible to prevent NOx purification performance from being deteriorated due to ammonia oxidation at a high temperature. The Cu / Al molar ratio can be measured using a fluorescent X-ray analyzer.
A more preferable Cu / Al (molar ratio) is 0.25 to 0.5.
　また本発明により製造されたゼオライトは、ＳｉＯ２／Ａｌ２Ｏ３組成比（ＳＡＲ）が１５未満であることが好ましい。上記ＳｉＯ２／Ａｌ２Ｏ３組成比とは、ゼオライト中のＡｌ２Ｏ３に対するＳｉＯ２のモル比（ＳＡＲ）を意味している。その組成比ＳｉＯ２／Ａｌ２Ｏ３が１５未満であることにより、ゼオライトの酸点を充分な数とすることができ、その酸点を利用して金属イオンとイオン交換することができ、Ｃｕを多く担持することができるので、ＮＯｘの浄化性能に優れている。
　より好ましいＳｉＯ２／Ａｌ２Ｏ３組成比は、１０～１４．９である。
　なおゼオライトのモル比（ＳｉＯ２／Ａｌ２Ｏ３）は、蛍光Ｘ線分析（ＸＲＦ）を用いて測定することができる。 The zeolite produced according to the present invention preferably has a SiO 2 / Al 2 O 3 composition ratio (SAR) of less than 15. The composition ratio of SiO 2 / Al 2 O 3 means the molar ratio (SAR) of SiO 2 to Al 2 O 3 in the zeolite. When the composition ratio SiO 2 / Al 2 O 3 is less than 15, the acid sites of the zeolite can be made a sufficient number, and the acid sites can be used for ion exchange with metal ions. As a result, NOx purification performance is excellent.
A more preferable SiO 2 / Al 2 O 3 composition ratio is 10 to 14.9.
The molar ratio of zeolite (SiO 2 / Al 2 O 3 ) can be measured using fluorescent X-ray analysis (XRF).
　本発明により製造されたゼオライトの平均粒子径は、０．５μｍ以下であることが望ましく、０．１～０．４μｍであることがより望ましい。このような小さな平均粒子径を有するゼオライトを用いてハニカム触媒を製造した場合、吸水変位量が小さくなる。また、製造時および触媒としての使用時にクラックが生じにくく、耐熱性、耐久性に優れている。一方、平均粒子径が０．５μｍを超えると、ハニカム触媒とした時の吸水変位量が大きくなり、ハニカム触媒にクラックが生じるおそれがある。 The average particle size of the zeolite produced according to the present invention is desirably 0.5 μm or less, and more desirably 0.1 to 0.4 μm. When a honeycomb catalyst is manufactured using zeolite having such a small average particle diameter, the amount of water absorption displacement becomes small. Further, cracks are unlikely to occur during production and use as a catalyst, and heat resistance and durability are excellent. On the other hand, when the average particle diameter exceeds 0.5 μm, the amount of water absorption displacement when the honeycomb catalyst is made increases, and cracks may occur in the honeycomb catalyst.
　ゼオライトの平均粒子径は、走査型電子顕微鏡（ＳＥＭ、日立ハイテク社製、Ｓ－４８００）を用いて、ＳＥＭ写真を撮影し、１０個の粒子の全対角線の長さを測定し、その平均値から求める。なお、測定条件は、加速電圧：１ｋＶ、エミッション：１０μＡ、ＷＤ：２．２ｍｍ以下とする。一般にＣＨＡ型ゼオライトの粒子は立方体であり、ＳＥＭ写真で二次元に撮像した時には正方形となる。そのため粒子の対角線は２本である。 The average particle size of the zeolite was determined by taking an SEM photograph using a scanning electron microscope (SEM, manufactured by Hitachi High-Tech, S-4800), measuring the length of all diagonal lines of 10 particles, and calculating the average value. Ask from. Measurement conditions are as follows: acceleration voltage: 1 kV, emission: 10 μA, WD: 2.2 mm or less. In general, the CHA-type zeolite particles are cubic, and become a square when two-dimensionally imaged by an SEM photograph. Therefore, there are two diagonal lines of particles.
　以下、本発明をより具体的に開示した実施例を示す。なお、本発明はこの実施例のみに限定されるものではない。 Hereinafter, examples that more specifically disclose the present invention will be shown. In addition, this invention is not limited only to this Example.
実施例１
（合成工程）
　Ｓｉ源としてコロイダルシリカ（日産化学工業社製、スノーテックス）、Ａｌ源として乾燥水酸化アルミニウムゲル（富田製薬社製）、アルカリ源として水酸化ナトリウム（トクヤマ社製）と水酸化カリウム（東亜合成社製）、構造規定剤（ＳＤＡ）としてＮ，Ｎ，Ｎ－トリメチルアダマンタンアンモニウム水酸化物（ＴＭＡＡＯＨ）２５％水溶液（Ｓａｃｈｅｍ社製）、種結晶としてＳＳＺ－１３、脱イオン水を混合し、原料組成物を準備した。原料組成物のモル比は、ＳｉＯ２：１５ｍｏｌ、Ａｌ２Ｏ３：１ｍｏｌ、ＮａＯＨ：２．６ｍｏｌ、ＫＯＨ：０．９ｍｏｌ、ＴＭＡＡＯＨ：１．１ｍｏｌ、Ｈ２Ｏ：３００ｍｏｌの割合とした。また原料組成物中のＳｉＯ２、Ａｌ２Ｏ３に対して５．０質量％の種結晶を加えた。原料組成物を５００Ｌオートクレーブに装填し、加熱温度１６０℃、加熱時間４８時間で水熱合成を行い、ゼオライトを合成した。続いて、ゼオイライト細孔内に残存するＴＭＡＡＯＨを除去するために、空気中、５５０℃、４時間、の条件で加熱処理を行った。 Example 1
(Synthesis process)
Colloidal silica (manufactured by Nissan Chemical Industries, Snowtex) as the Si source, dry aluminum hydroxide gel (manufactured by Tomita Pharmaceutical) as the Al source, sodium hydroxide (manufactured by Tokuyama) and potassium hydroxide (Toagosei Co., Ltd.) as the alkali source N, N, N-trimethyladamantanammonium hydroxide (TMAAOH) 25% aqueous solution (manufactured by Sachem) as a structure directing agent (SDA), SSZ-13 as a seed crystal, and deionized water I prepared something. The molar ratio of the raw material composition was such that SiO 2 : 15 mol, Al 2 O 3 : 1 mol, NaOH: 2.6 mol, KOH: 0.9 mol, TMAAOH: 1.1 mol, H 2 O: 300 mol. The addition of 5.0 wt% of the seed crystal with respect to SiO 2, Al 2 O 3 raw material composition. The raw material composition was charged in a 500 L autoclave, and hydrothermal synthesis was performed at a heating temperature of 160 ° C. and a heating time of 48 hours to synthesize zeolite. Subsequently, in order to remove TMAAOH remaining in the zeolite pores, heat treatment was performed in air at 550 ° C. for 4 hours.
（アンモニウムイオン交換工程）
　硫酸アンモニウム１ｍｏｌを１Ｌの水に溶かした後、得られた溶液４ｇ（温度：室温）に対して上記合成工程で得られたゼオライトゼオライトを１ｇの割合で添加し、大気圧で１時間撹拌を行い、ＮＨ４ ＋型ゼオライトを得た。 (Ammonium ion exchange process)
After dissolving 1 mol of ammonium sulfate in 1 L of water, the zeolite zeolite obtained in the above synthesis step is added at a rate of 1 g to 4 g of the resulting solution (temperature: room temperature), and stirred at atmospheric pressure for 1 hour. NH 4 + type zeolite was obtained.
（熱処理工程）
　上記アンモニウムイオン交換工程で得られたＮＨ４ ＋型ゼオライトを、空気中で、４７０℃、４時間の条件で加熱処理を行い、Ｈ＋型ゼオライトを得た。 (Heat treatment process)
The NH 4 + type zeolite obtained in the ammonium ion exchange step was heat-treated in air at 470 ° C. for 4 hours to obtain H + type zeolite.
（Ｃｕイオン交換工程）
　上記熱処理工程で得られたＨ＋型ゼオライトに対し１質量％の濃度の硫酸銅（ＩＩ）水溶液を用い、アンモニア水を用いてｐＨを９に調整して溶液温度５０℃に保ち、Ｈ＋型ゼオライトを大気圧下で、浸漬時間１時間の条件でイオン交換し、Ｃｕイオン交換されたゼオライトを得た。 (Cu ion exchange process)
Using a copper (II) sulfate aqueous solution having a concentration of 1% by mass with respect to the H + type zeolite obtained in the heat treatment step, adjusting the pH to 9 with aqueous ammonia and keeping the solution temperature at 50 ° C., the H + type Zeolite was ion-exchanged under atmospheric pressure at an immersion time of 1 hour to obtain a Cu ion-exchanged zeolite.
（熱エージング処理）
　Ｃｕイオン交換工程で得られたＣｕを担持したゼオライトに対し、大気圧下で、８００℃、２時間の条件で熱エージング処理を行い、ゼオライトの性能を安定化させた。 (Thermal aging treatment)
The zeolite loaded with Cu obtained in the Cu ion exchange step was subjected to a heat aging treatment at 800 ° C. for 2 hours under atmospheric pressure to stabilize the performance of the zeolite.
（Ｃｕイオン交換量の測定）
　実施例１で合成、イオン交換したゼオライトのＣｕイオン交換量を、蛍光Ｘ線分析装置（ＸＲＦ、リガク社製　ＺＳＸ　Ｐｒｉｍｕｓ２）を用いて測定した。測定条件は、Ｘ線管：Ｒｈ、定格最大出力：４ｋＷ、検出元素範囲：Ｆ～Ｕ、定量法：ＳＱＸ法、分析領域：１０ｍｍφとした。
　結果を表１に示す。 (Measurement of Cu ion exchange amount)
The amount of Cu ion exchange of the zeolite synthesized and ion exchanged in Example 1 was measured using a fluorescent X-ray analyzer (XRF, ZSX Primus 2 manufactured by Rigaku Corporation). The measurement conditions were as follows: X-ray tube: Rh, rated maximum output: 4 kW, detection element range: F to U, quantitative method: SQX method, analysis region: 10 mmφ.
The results are shown in Table 1.
実施例２～３
　Ｃｕイオン交換工程におけるＣｕ溶液のｐＨを、表１に示す水溶液を用いてｐＨ１１に調整したこと以外は、実施例１と同様に実施した。
　Ｃｕイオン交換量を測定した結果を表１に示す。 Examples 2 to 3
The same procedure as in Example 1 was performed except that the pH of the Cu solution in the Cu ion exchange step was adjusted to pH 11 using the aqueous solution shown in Table 1.
The results of measuring the amount of Cu ion exchange are shown in Table 1.
実施例４～７
　Ｃｕイオン交換工程におけるＣｕ溶液を酢酸銅（ＩＩ）水溶液とし、溶液のｐＨおよびｐＨ調整に用いた水溶液を表１に示したものにした以外は、実施例１と同様に実施した。
　Ｃｕイオン交換量を測定した結果を表１に示す。 Examples 4-7
The same procedure as in Example 1 was performed except that the Cu solution in the Cu ion exchange step was a copper (II) acetate aqueous solution, and the pH of the solution and the aqueous solution used for pH adjustment were those shown in Table 1.
The results of measuring the amount of Cu ion exchange are shown in Table 1.
実施例８～１１
　Ｃｕイオン交換工程におけるＣｕ溶液を酢酸銅（ＩＩ）水溶液とし、表１に示すＣｕ濃度とし、ｐＨ調整を行わなかったこと以外は、実施例１と同様に実施した。
　Ｃｕイオン交換量を測定した結果を表１に示す。 Examples 8-11
The Cu solution in the Cu ion exchange step was an aqueous copper (II) acetate solution, the Cu concentration was as shown in Table 1, and the same procedure as in Example 1 was performed except that pH adjustment was not performed.
The results of measuring the amount of Cu ion exchange are shown in Table 1.
比較例１～４
　熱処理工程を行わなかったこと以外は、実施例８～１１と同様に実施した。
　Ｃｕイオン交換量を測定した結果を表１に示す。 Comparative Examples 1 to 4
The same procedure as in Examples 8 to 11 was performed except that the heat treatment step was not performed.
The results of measuring the amount of Cu ion exchange are shown in Table 1.
（ゼオライトの結晶構造の解析）
　Ｘ線回折装置（リガク社製、Ｕｌｔｉｍａ　ＩＶ）を用い、実施例１で合成されたゼオライトについて、ＸＲＤ測定を行い、Ｘ線回折スペクトルの（２１１）面、（１０４）面及び（２２０）面の積分強度の和（Ｘ０）を算出した。
　測定条件は、線源：ＣｕＫα（λ＝０．１５４ｎｍ）、測定法：ＦＴ法、回折角：２θ＝５～４８°、ステップ幅：０．０２°、積算時間：１秒、発散スリット、散乱スリット：２／３°、発散縦制限スリット：１０ｍｍ、加速電圧：４０ｋＶ、加速電流：４０ｍＡとした。
　得られたＸＲＤデータの解析は、粉末Ｘ線回折パターン総合解析ソフトＪＡＤＥ６．０を用いて行った。なお、解析条件は、フィルタータイプ：放物線フィルター、Ｋα２ピークの消去：あり、ピーク位置定義：ピークトップ、閾値σ：３、ピーク強度％カットオフ：０．１、ＢＧ決定の範囲：１、ＢＧ平均化のポイント数：７とした。
　その結果、Ｘ０は６０５８４であった。 (Analysis of crystal structure of zeolite)
Using the X-ray diffractometer (Rigaku Corporation, Ultimate IV), the zeolite synthesized in Example 1 was subjected to XRD measurement, and the (211) plane, (104) plane and (220) plane of the X-ray diffraction spectrum were measured. The sum of integral intensities (X 0 ) was calculated.
Measurement conditions are: radiation source: CuKα (λ = 0.154 nm), measurement method: FT method, diffraction angle: 2θ = 5 to 48 °, step width: 0.02 °, integration time: 1 second, divergence slit, scattering Slit: 2/3 °, divergence length limiting slit: 10 mm, acceleration voltage: 40 kV, acceleration current: 40 mA.
Analysis of the obtained XRD data was performed using powder X-ray diffraction pattern comprehensive analysis software JADE 6.0. The analysis conditions are: filter type: parabolic filter, elimination of Kα2 peak: yes, peak position definition: peak top, threshold σ: 3, peak intensity% cutoff: 0.1, BG determination range: 1, BG average The number of conversion points was set to 7.
As a result, X 0 was 60584.
　図１に、実施例１で合成したゼオライトのＸＲＤパターンを示す。
　図１より、実施例１で合成したゼオライトは、ＣＨＡ構造を有するゼオライトであることが確認された。 FIG. 1 shows the XRD pattern of the zeolite synthesized in Example 1.
From FIG. 1, it was confirmed that the zeolite synthesized in Example 1 was a zeolite having a CHA structure.
（Ｃｕ担持量の測定）
　蛍光Ｘ線分析装置（ＸＲＦ、リガク社製　ＺＳＸ　Ｐｒｉｍｕｓ２）を用いて、各実施例および比較例で得られたゼオライトに担持されたＣｕ量を測定した。測定条件は、Ｘ線管：Ｒｈ、定格最大出力：４ｋＷ、検出元素範囲：Ｆ～Ｕ、定量法：ＳＱＸ法、分析領域：１０ｍｍφとした。Ｃｕ担持量の測定値から、Ｃｕ／Ａｌモル比を算出した。
　結果を表１に示す。 (Measurement of Cu loading)
Using an X-ray fluorescence analyzer (XRF, ZSX Primus 2 manufactured by Rigaku Corporation), the amount of Cu supported on the zeolite obtained in each of Examples and Comparative Examples was measured. The measurement conditions were as follows: X-ray tube: Rh, rated maximum output: 4 kW, detection element range: F to U, quantitative method: SQX method, analysis region: 10 mmφ. The Cu / Al molar ratio was calculated from the measured value of the Cu loading.
The results are shown in Table 1.
（ゼオライトのモル比（ＳＡＲ　ＳｉＯ２／Ａｌ２Ｏ３）の測定）
　蛍光Ｘ線分析装置（ＸＲＦ、リガク社製　ＺＳＸ　Ｐｒｉｍｕｓ２）を用いて、実施例１で得られたゼオライト（初期）のモル比（ＳＡＲ　ＳｉＯ２／Ａｌ２Ｏ３）を測定した。測定条件は、Ｘ線管：Ｒｈ、定格最大出力：４ｋＷ、検出元素範囲：Ｆ～Ｕ、定量法：ＳＱＸ法、分析領域：１０ｍｍφとした。その結果は、ＳＡＲは１２．９であった。 (Measurement of molar ratio of zeolite (SAR SiO 2 / Al 2 O 3 ))
Using a fluorescent X-ray analyzer (XRF, ZSX Primus 2 manufactured by Rigaku Corporation), the molar ratio (SAR SiO 2 / Al 2 O 3 ) of the zeolite (initial) obtained in Example 1 was measured. The measurement conditions were as follows: X-ray tube: Rh, rated maximum output: 4 kW, detection element range: F to U, quantitative method: SQX method, analysis region: 10 mmφ. As a result, the SAR was 12.9.
（ゼオライトの粒子径の測定）
　走査型電子顕微鏡（ＳＥＭ、日立ハイテク社製、Ｓ－４８００）を用いて、実施例１で得られたゼオライト（初期）のＳＥＭ写真を撮影し、それらの粒子径を測定した。測定条件は、加速電圧：１ｋＶ、エミッション：１０μＡ、ＷＤ：２．２ｍｍ以下とした。測定倍率は、２００００倍とした。１０個の粒子の２つの対角線から粒子径を測定し、その平均値を求めた。その結果、平均粒子径は０．３３μｍであった。 (Measurement of particle size of zeolite)
Using a scanning electron microscope (SEM, manufactured by Hitachi High-Tech, S-4800), SEM photographs of the zeolite (initial) obtained in Example 1 were taken and their particle sizes were measured. The measurement conditions were acceleration voltage: 1 kV, emission: 10 μA, WD: 2.2 mm or less. The measurement magnification was 20000 times. The particle diameter was measured from two diagonal lines of 10 particles, and the average value was obtained. As a result, the average particle size was 0.33 μm.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１～１１で得られたゼオライトは、ＮＨ４ ＋型ゼオライトを得た後、該ゼオライトを加熱し、Ｈ＋型ゼオライトを得、これに対しＣｕ溶液を用いてイオン交換を行う各工程を経て製造されたものであり、Ｃｕのイオン交換効率が高い結果となった。該結果から、ゼオライトの製造時間および製造コストを低減できることが推測される。
　比較例１～４は、ＮＨ４ ＋型ゼオライトに対し直接、Ｃｕ溶液を用いるイオン交換を行っているので、Ｃｕのイオン交換効率が低い結果となった。 The zeolites obtained in Examples 1 to 11 were obtained by obtaining NH 4 + type zeolite and then heating the zeolite to obtain H + type zeolite, which was subjected to ion exchange using a Cu solution. As a result, the Cu ion exchange efficiency was high. From this result, it is estimated that the production time and production cost of zeolite can be reduced.
In Comparative Examples 1 to 4, since ion exchange using a Cu solution was performed directly on NH 4 + type zeolite, Cu ion exchange efficiency was low.
　本発明を詳細にまた特定の実施形態を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は、２０１５年５月１９日出願の日本特許出願（特願２０１５－１０２００６）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on May 19, 2015 (Japanese Patent Application No. 2015-102006), the contents of which are incorporated herein by reference.

Claims (7)

  1. 　Ｃｕイオン交換されたＣＨＡ構造を有するゼオライトを製造する方法であって、
    　Ｓｉ源と、Ａｌ源と、アルカリ金属及びアルカリ土類金属からなる群から選択される少なくとも一種と、並びに構造規定剤とを含む原料組成物を用いてゼオライトを合成する合成工程、
    　前記合成工程で得られたゼオライトに対し、アンモニア溶液を用いて、ＮＨ４ ＋型ゼオライトを得るアンモニウムイオン交換工程、
    　前記アンモニウムイオン交換工程で得られたＮＨ４ ＋型ゼオライトを加熱し、Ｈ＋型ゼオライトを得る熱処理工程、および
    　前記熱処理工程で得られたＨ＋型ゼオライトに対し、Ｃｕ溶液を用いてＣｕイオン交換されたゼオライトを得るＣｕイオン交換工程を含む
    ゼオライトの製造方法。     A method for producing a zeolite having a CHA structure subjected to Cu ion exchange, comprising:
    A synthesis step of synthesizing zeolite using a raw material composition comprising a Si source, an Al source, at least one selected from the group consisting of alkali metals and alkaline earth metals, and a structure directing agent;
    An ammonium ion exchange step for obtaining NH 4 + type zeolite using an ammonia solution for the zeolite obtained in the synthesis step,
    Heating the NH 4 + type zeolite obtained in the ammonium ion exchange step to obtain an H + type zeolite, and Cu ion exchange using a Cu solution for the H + type zeolite obtained in the heat treatment step A method for producing a zeolite comprising a Cu ion exchange step for obtaining the obtained zeolite.
  2. 　前記合成工程で得られたゼオライトにおけるＳｉＯ２／Ａｌ２Ｏ３組成比（ＳＡＲ）が１５未満である、請求項１に記載のゼオライトの製造方法。 The synthesis step is a SiO 2 / Al 2 O 3 composition ratio (SAR) of less than 15 in the resultant zeolite in the manufacturing method of the zeolite of claim 1.
  3. 　前記Ａｌ源が乾燥水酸化アルミニウムゲルである、請求項１または２に記載のゼオライトの製造方法。 The method for producing a zeolite according to claim 1 or 2, wherein the Al source is a dry aluminum hydroxide gel.
  4. 　前記熱処理工程においてＮＨ４ ＋型ゼオライトの加熱温度が３５０～６５０℃である、請求項１～３のいずれか１項に記載のゼオライトの製造方法。 The method for producing zeolite according to any one of claims 1 to 3, wherein the heating temperature of the NH 4 + type zeolite is 350 to 650 ° C in the heat treatment step.
  5. 　前記Ｃｕイオン交換工程において使用するＣｕ溶液のｐＨが８～１２である、請求項１～４のいずれか１項に記載のゼオライトの製造方法。 The method for producing zeolite according to any one of claims 1 to 4, wherein the Cu solution used in the Cu ion exchange step has a pH of 8 to 12.
  6. 　前記Ｃｕイオン交換工程において使用するＣｕ溶液が硫酸銅水溶液である、請求項１～５のいずれか１項に記載のゼオライトの製造方法。 The method for producing zeolite according to any one of claims 1 to 5, wherein the Cu solution used in the Cu ion exchange step is a copper sulfate aqueous solution.
  7. 　Ｃｕイオン交換されたゼオライトにおけるＣｕ／Ａｌ（モル比）が０．２～０．５である、請求項１～６のいずれか１項に記載のゼオライトの製造方法。 The method for producing zeolite according to any one of claims 1 to 6, wherein the Cu / Al (molar ratio) in the zeolite subjected to Cu ion exchange is 0.2 to 0.5.
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