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WO2025204912A1 - Zéolite et son procédé de production - Google Patents

Zéolite et son procédé de production

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Publication number
WO2025204912A1
WO2025204912A1 PCT/JP2025/009324 JP2025009324W WO2025204912A1 WO 2025204912 A1 WO2025204912 A1 WO 2025204912A1 JP 2025009324 W JP2025009324 W JP 2025009324W WO 2025204912 A1 WO2025204912 A1 WO 2025204912A1
Authority
WO
WIPO (PCT)
Prior art keywords
zeolite
calcium
ratio
less
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/009324
Other languages
English (en)
Japanese (ja)
Inventor
雅人 伊藤
智也 石川
雄哉 阪口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tosoh Corp
Original Assignee
Tosoh Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tosoh Corp filed Critical Tosoh Corp
Priority to JP2025524318A priority Critical patent/JP7758250B1/ja
Publication of WO2025204912A1 publication Critical patent/WO2025204912A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • 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

Definitions

  • This disclosure relates to zeolites containing calcium and copper.
  • Zeolites are used in a wide range of applications, including as catalysts, adsorbents, and ion exchangers.
  • zeolites with pores formed by eight-membered oxygen rings and a framework structure of six-membered oxygen double rings have attracted attention as selective catalytic reduction catalysts (hereinafter also referred to as "SCR catalysts") for removing nitrogen oxides contained in automobile exhaust gases.
  • SCR catalysts selective catalytic reduction catalysts
  • Patent Document 1 discloses a copper-containing GME/CHA intergrowth zeolite as a zeolite having pores formed from eight-membered oxygen rings and containing double six-membered rings in its framework structure.
  • the copper-containing GME/CHA intergrowth zeolite disclosed in Patent Document 1 has poor hydrothermal durability, and therefore has the problem that when exposed to a high-temperature, moist atmosphere, its activity in reducing nitrogen oxides (hereinafter also referred to as "SCR catalytic activity") decreases.
  • SCR catalytic activity reducing nitrogen oxides
  • the treatment of exposing the zeolite to a high-temperature, moist atmosphere will also be referred to as hydrothermal durability treatment.
  • the present disclosure aims to provide at least one of a zeolite that has excellent hydrothermal durability and exhibits excellent SCR catalytic activity even after hydrothermal durability treatment, a method for producing the same, and a selective reduction catalyst containing the same.
  • the inventors investigated zeolites with nitrogen oxide reduction properties that are practical for use as SCR catalysts. As a result, they discovered that when copper and calcium coexist in a specific state in zeolites with a specific crystalline structure (intergrowth structure), they exhibit excellent SCR catalytic activity even after hydrothermal durability treatment.
  • the present invention is as defined in the claims, and the gist of the present disclosure is as follows.
  • [1] Having an intergrowth structure including a CHA structure and a GME structure, It has at least the peaks in the table below in a powder X-ray diffraction pattern, Contains calcium and copper, A zeolite having an XPS spectrum in which the ratio of the spectral area in the range of 930.0 eV to 933.0 eV to the spectral area in the range of 930.0 eV to 940.0 eV is less than 34%.
  • Al aluminum
  • Si silicon
  • O oxygen
  • aluminosilicate also includes a structure consisting of a repeating network of aluminum (Al) and silicon (Si) via oxygen (O), in which a portion of the aluminum (e.g., 30% or less of the aluminum as T atoms) is replaced with another metal atom.
  • aluminosilicates those that have crystalline XRD peaks in their powder X-ray diffraction (hereinafter also referred to as "XRD") patterns are "crystalline aluminosilicates," while those that do not have crystalline XRD peaks are “amorphous aluminosilicates.”
  • zeolites in which the T atoms are essentially composed of aluminum (Al) and silicon (Si) fall under the category of "crystalline aluminosilicates.”
  • T atoms substantially consisting of aluminum (Al) and silicon (Si) does not only mean that the T atoms consist only of aluminum (Al) and silicon (Si), but also means that the T atoms may contain T atoms other than aluminum (Al) and silicon (Si) as long as the effects of the present invention are achieved.
  • the XRD pattern can be measured using a general powder X-ray diffractometer (e.g., Ultima IV, manufactured by Rigaku Corporation).
  • the crystalline XRD peak is a peak detected by identifying the 2 ⁇ of the peak top in an XRD pattern analysis using general analysis software (e.g., SmartLab Studio II, manufactured by Rigaku Corporation).
  • general analysis software e.g., SmartLab Studio II, manufactured by Rigaku Corporation.
  • the "regular structure (hereinafter also referred to as "skeletal structure”)" of zeolites and zeolite-like substances is a skeletal structure identified by the skeletal structure code (hereinafter also simply referred to as "skeletal code”) established by the Structure Commission of the International Zeolite Association.
  • a "CHA structure” is a skeletal structure that corresponds to the CHA type in the skeletal code
  • a "GME structure” is a skeletal structure that corresponds to the GME type in the skeletal code.
  • the skeletal structure of zeolites and zeolite-like substances can also be expressed by dividing it into structural units (repeating units), and such structural units are generally called composite building units (CBUs).
  • a composite building unit is a unit formed by connecting several (e.g., several to several tens) TOx units (e.g., TO4 units), each consisting of a T atom and oxygen (O) bonded to it.
  • An "intergrowth structure including a CHA structure and a GME structure” exhibits a characteristic XRD pattern, and can therefore be identified from the XRD pattern.
  • the XRD patterns of zeolites having an "intergrowth structure including a CHA structure and a GME structure” have similar characteristics, but exhibit different XRD patterns depending on the ratio of CHA units to GME units (hereinafter also referred to as "intergrowth ratio").
  • Some zeolites (with a predetermined intergrowth ratio) among those having an "intergrowth structure including a CHA structure and a GME structure” exhibit XRD patterns including at least each peak in Table 2 below. Therefore, zeolites showing XRD patterns including each peak in Table 2 below can be determined to have an "intergrowth structure including a CHA structure and a GME structure.”
  • the zeolite of this embodiment has an intergrowth structure including a CHA structure and a GME structure, and has at least the peaks shown in Table 3 below in its XRD pattern.
  • the zeolite of this embodiment also contains calcium and copper, and in its XPS spectrum, the spectral area ratio in the range of 930.0 eV to 933.0 eV to the spectral area in the range of 930.0 eV to 940.0 eV (hereinafter also referred to as "XPS area ratio”) is less than 34%.
  • Table 3 below is the same as Table 2 above.
  • the zeolite of this embodiment contains calcium. By containing calcium, the zeolite of this embodiment can exhibit excellent hydrothermal durability.
  • the molar ratio of calcium to aluminum (hereinafter also referred to as the "Ca/Al ratio") is not particularly limited, but from the viewpoint of further improving hydrothermal durability, it is preferably 0.01 or more, more preferably 0.015 or more, and even more preferably 0.02 or more.
  • the Ca/Al ratio in the zeolite of this embodiment is preferably 0.3 or less, more preferably 0.25 or less, and even more preferably 0.15 or less.
  • the upper and lower limit values of the Ca/Al ratio may be any combination of the upper and lower limit values described above, but are preferably 0.01 or more and 0.3 or less, more preferably 0.015 or more and 0.25 or less, and even more preferably 0.02 or more and 0.15 or less.
  • the zeolite of this embodiment contains copper.
  • the molar ratio of copper to aluminum (hereinafter also referred to as the "Cu/Al ratio") is not particularly limited, but from the viewpoint of further improving hydrothermal durability, it is preferably 0.05 or greater, more preferably 0.10 or greater, and even more preferably 0.12 or greater.
  • the Cu/Al ratio in the zeolite of this embodiment is preferably 0.4 or less, more preferably 0.35 or less, and even more preferably 0.30 or less.
  • the zeolite of this embodiment may contain calcium and copper, and the form in which they are contained is not particularly limited. However, from the perspective of further improving hydrothermal durability, it is preferable that at least one of calcium and copper be supported on the zeolite.
  • containing a specific element means that the specific element is contained in the zeolite, and the specific element may be contained in any state and at any location.
  • supporting a specific element means that the specific element is contained as a component other than the T atom of the zeolite. Examples of the form in which the specific element is supported include a form in which the specific element is supported on at least one of the outer surface of the zeolite (the surface of the zeolite excluding the inner surfaces of the pores) and the inner surfaces of the pores.
  • the state of the calcium and copper contained in the zeolite of this embodiment is not particularly limited as long as the XPS area ratio (described below) is less than 34%, and examples include compounds (e.g., oxides), metals, ions, alloys, or two or more of these.
  • the states of calcium and copper may be the same or different.
  • the zeolite of this embodiment may contain other substances in addition to calcium and copper.
  • examples of such other substances include alkali metals, alkaline earth metals, and transition metals.
  • the ratio of the spectral area in the range of 930.0 eV to 933.0 eV to the spectral area in the range of 930.0 eV to 940.0 eV is less than 34%.
  • the XPS area ratio of the zeolite of this embodiment is preferably 10% to less than 34%, more preferably 15% to 33%, and even more preferably 25% to 33%.
  • the XPS area ratio is a value expressed as a percentage, obtained by dividing the spectral area from 930.0 eV to 933.0 eV by the spectral area from 930.0 eV to 940.0 eV.
  • the peak area of an XPS spectrum can be calculated from the sum of the areas of the trapezoids between data points. More specifically, the measured XPS spectrum is divided using multiple virtual lines spaced at 0.10 eV intervals, and the area of each of the divided XPS spectra is calculated assuming that it is a trapezoid (a right-angled trapezoid bounded by two adjacent virtual lines, a line connecting the intersection of the two virtual lines with the XPS spectrum curve, and the horizontal axis). The areas of the individual trapezoids are then added together to calculate the peak area of the XPS spectrum.
  • a trapezoid a right-angled trapezoid bounded by two adjacent virtual lines, a line connecting the intersection of the two virtual lines with the XPS spectrum curve, and the horizontal axis.
  • the molar ratio of silica to alumina (hereinafter also referred to as the " SiO2 / Al2O3 ratio ”) is not particularly limited, but from the viewpoint of further improving the SCR catalytic activity over a low temperature range (e.g., 150°C) to a high temperature range (e.g., 600°C), it is preferably 5.0 or more, more preferably 5.5 or more, and even more preferably 6.0 or more.
  • the SiO2 / Al2O3 ratio is preferably 15 or less, more preferably 10 or less, and even more preferably 9.5 or less.
  • the upper and lower limit values of the SiO 2 /Al 2 O 3 ratio may be any combination of the upper and lower limit values described above, but from the viewpoint of further improving the SCR catalytic activity over a range from a low temperature (e.g., 150°C) to a high temperature (e.g., 600°C), the upper and lower limit values are preferably 5.0 to 15, more preferably 5.5 to 10, and even more preferably 6.0 to 9.5.
  • the T atoms that make up the framework structure are not particularly limited as long as they are composed of at least either metal atoms or metalloid atoms, but from the perspective of further improving hydrothermal durability, they are preferably composed of aluminum (Al) and silicon (Si).
  • the zeolite of this embodiment is preferably a crystalline aluminosilicate having an intergrowth structure including a CHA structure and a GME structure.
  • the nitrogen oxides contained in the nitrogen oxide-containing fluid may include, for example, nitric oxide, nitrogen dioxide, dinitrogen trioxide, dinitrogen tetroxide, and dinitrogen monoxide, and two or more of these may be used.
  • the nitrogen oxide-containing fluid may be one or more selected from the group consisting of liquid, gas, and a mixed fluid of liquid and gas, but from the perspective of further improving the reduction rate of nitrogen oxides, a gas is preferred.
  • Production method (1) is a method in which zeolite is synthesized from a raw material composition and then calcium is incorporated into the zeolite.
  • Production method (1) comprises a crystallization step (hereinafter also referred to as “crystallization step (1)”) in which a raw material composition containing at least an alumina source, a silica source, an alkali source, and water is crystallized in the presence of seed crystals, and a calcium-containing step (hereinafter also referred to as “calcium-containing step (1)") in which calcium is contained in the raw material zeolite obtained in crystallization step (1). Calcium-containing zeolite can be obtained by production method (1) including these steps.
  • the alumina source contained in the raw material composition is at least one of alumina (Al 2 O 3 ) and its precursor, and examples thereof include one or more selected from the group consisting of alumina, aluminum sulfate, aluminum nitrate, sodium aluminate, aluminum hydroxide, aluminum chloride, amorphous aluminosilicate, metallic aluminum, crystalline aluminosilicate, and aluminum alkoxide.
  • An amorphous aluminum compound is preferred, at least one of aluminum hydroxide and amorphous aluminosilicate is more preferred, and amorphous aluminosilicate is even more preferred.
  • substances containing aluminum (Al) and silicon (Si), such as amorphous aluminosilicate can be used not only as an alumina source but also as a silica source, which will be described later.
  • the silica source contained in the raw material composition is at least one of silica (SiO 2 ) or a precursor thereof, and examples thereof include one or more selected from the group consisting of colloidal silica, amorphous silica, sodium silicate, tetraethoxysilane, tetraethyl orthosilicate, precipitated silica, fumed silica, amorphous aluminosilicate, and crystalline aluminosilicate, and is preferably an amorphous silicon compound, more preferably an amorphous aluminosilicate.
  • alumina source and silica source contained in the raw material composition do not contain crystalline aluminosilicate, production costs tend to be lower, which is industrially advantageous.
  • the alkali source contained in the raw material composition is an alkali metal or a compound containing an alkali metal element, and examples thereof include one or more selected from the group consisting of alkali metal hydroxides, carbonates, sulfates, chlorides, bromides, and iodides.
  • alkali metal hydroxides One or more selected from the group consisting of alkali metal hydroxides, chlorides, bromides, and iodides are preferred, and alkali metal hydroxides are more preferred.
  • the alkali metal (alkali metal element) contained in the alkali source includes one or more selected from the group consisting of sodium, potassium, rubidium, and cesium, and at least one of sodium and potassium is more preferred.
  • a particularly preferred alkali source is at least one of sodium hydroxide and potassium hydroxide.
  • the raw material composition does not contain calcium.
  • a manufacturing method in which calcium is contained in the raw material composition corresponds to manufacturing method (2) described below.
  • the raw material composition preferably does not contain an organic structure-directing agent, since the raw material zeolite obtained by crystallization is likely to have an intergrowth structure containing a CHA structure and a GME structure.
  • the raw material composition preferably does not contain fluorine (F) or phosphorus (P), since this makes it easier to use manufacturing equipment made of general-purpose materials.
  • free from a specified substance means that the content determined by general compositional analysis such as ICP measurement is 100 ppm by mass or less, preferably 10 ppm by mass or less, and even more preferably below the measurement limit.
  • the SiO2 / Al2O3 ratio of the raw material composition is preferably 24 or less, more preferably 22 or less, and even more preferably 20 or less.
  • the SiO2 / Al2O3 ratio of the raw material composition is preferably 8 or more, more preferably 10 or more, and even more preferably 13 or more.
  • the upper and lower limit values of the SiO2 / Al2O3 ratio of the raw material composition may be any combination of the above-mentioned upper and lower limit values, but are preferably 8 or more and 24 or less, more preferably 10 or more and 22 or less, and even more preferably 13 or more and 20 or less.
  • the SiO 2 /Al 2 O 3 ratio of the raw material zeolite obtained by crystallizing the raw material composition tends to be lower than the SiO 2 /Al 2 O 3 ratio of the raw material composition. Therefore, when the SiO 2 /Al 2 O 3 ratio of the raw material composition is 24 or less, a calcium-containing zeolite having the SiO 2 /Al 2 O 3 ratio described below is more easily obtained, and a zeolite having better SCR catalytic activity over a range from low temperatures (e.g., 150°C) to high temperatures (e.g., 600°C) is more easily obtained.
  • low temperatures e.g. 150°C
  • high temperatures e.g., 600°C
  • the molar ratio of alkali metal to silica in the raw material composition (hereinafter also referred to as the "M/ SiO2 ratio") is preferably 0.30 or more, more preferably 0.35 or more, and even more preferably 0.40 or more. Furthermore, in the crystallization step (1), the M/SiO2 ratio of the raw material composition is preferably 0.70 or less, more preferably 0.65 or less, and even more preferably 0.60 or less.
  • the upper and lower limits of the M/ SiO2 ratio of the raw material composition may be any combination of the above-mentioned upper and lower limits, but are preferably 0.30 or more and 0.70 or less, more preferably 0.35 or more and 0.65 or less, and even more preferably 0.40 or more and 0.60 or less.
  • the M/ SiO2 ratio of the raw material composition is within the above-mentioned range, the peaks in Table 3 are more likely to be included in the XRD pattern of the raw material zeolite obtained by crystallization, making it easier to produce the zeolite of this embodiment.
  • the molar ratio of water to silica in the raw material composition (hereinafter also referred to as the " H2O / SiO2 ratio") is preferably 3 or more, more preferably 5 or more, and even more preferably 8 or more. Furthermore, in the crystallization step (1), the H2O /SiO2 ratio of the raw material composition is preferably 50 or less, more preferably 30 or less, and even more preferably 25 or less.
  • the upper and lower limits of the H2O / SiO2 ratio of the raw material composition may be any combination of the upper and lower limits described above, but are preferably 3 or more and 50 or less, more preferably 5 or more and 30 or less, and even more preferably 8 or more and 25 or less.
  • the molar ratio of hydroxide ions to silica in the raw material composition (hereinafter also referred to as the "OH/ SiO2 ratio") is preferably 0.30 or more, more preferably 0.35 or more, and even more preferably 0.40 or more. Furthermore, in the crystallization step (1), the OH/SiO2 ratio of the raw material composition is preferably 0.70 or less, more preferably 0.65 or less, and even more preferably 0.60 or less.
  • the upper and lower limits of the OH/ SiO2 ratio of the raw material composition may be any combination of the upper and lower limits described above, but are preferably 0.30 or more and 0.70 or less, more preferably 0.35 or more and 0.65 or less, and even more preferably 0.40 or more and 0.60 or less.
  • the peaks in Table 3 are more likely to be included in the XRD pattern of the raw material zeolite obtained by crystallization, making it easier to produce the zeolite of this embodiment.
  • the raw material composition in the crystallization step (1) preferably has any combination of the following molar compositions.
  • M represents the molar amount of alkali metals.
  • M represents the molar amount of that alkali metal.
  • M represents the total molar amount of those two or more alkali metals.
  • the M/SiO2 ratio is the (Na + K)/ SiO2 ratio.
  • the raw material composition is crystallized in the presence of seed crystals.
  • An example of a method for crystallizing the raw material composition in the presence of seed crystals is a method in which seed crystals are added to the raw material composition and the raw material composition to which the seed crystals have been added is crystallized.
  • the seed crystals are preferably one or more selected from the group consisting of CHA-type zeolite, AFX-type zeolite, GME-type zeolite, LEV-type zeolite, and OFF-type zeolite, and are more preferably CHA-type zeolite, since this makes it more likely that the peaks in Table 3 will be included in the XRD pattern of the raw material zeolite obtained by crystallization.
  • the ratio of the total mass of silicon (Si) and aluminum (Al) of the seed crystals, converted into SiO2 and Al2O3 , respectively, to the total mass of silicon (Si) and aluminum (Al ) of the raw material composition (excluding seed crystals), converted into SiO2 and Al2O3 , respectively (hereinafter also referred to as the "seed crystal content”) is preferably greater than 0 mass%, more preferably greater than 0.5 mass%, and even more preferably greater than 1 mass%.
  • the seed crystal content is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 3 mass% or less.
  • the upper and lower limits of the seed crystal content may be any combination of the aforementioned upper and lower limits, but are preferably greater than 0 mass% and 10 mass% or less, more preferably 0.5 mass% or more and 5 mass% or less, and even more preferably 1 mass% or more and 3 mass% or less.
  • the peaks shown in Table 3 are more likely to be included in the XRD pattern of the raw material zeolite obtained by crystallization, making it easier to produce the zeolite of this embodiment.
  • the crystallization method of the raw material composition may be any method that crystallizes the raw material composition, and for example, a hydrothermal synthesis method in which the raw material composition is subjected to a hydrothermal treatment can be used.
  • the following conditions can be exemplified as conditions for the hydrothermal treatment. Crystallization temperature: 120°C or higher, 130°C or higher, or 135°C or higher, and 200°C or lower, 180°C or lower, or 160°C or lower.
  • Crystallization time 1 hour or higher, 5 hours or higher, or 10 hours or higher, and 7 days or less, 5 days or less, 3 days or less, or 2 days or less
  • Crystallization state At least one of a stirring state and a static state, or a stirring state
  • Crystallization pressure Autogenous pressure
  • the raw zeolite obtained in the crystallization step (1) described above is used in the calcium-containing step described below.
  • the raw zeolite obtained in the crystallization step (1) may be used in the calcium-containing step (1) as is, or may be further subjected to one or more treatments selected from the group consisting of a washing treatment, a drying treatment, and an ion exchange treatment before being used in the calcium-containing step (1).
  • the ion exchange treatment is preferably an ion exchange treatment that changes the cation type of the raw zeolite to a proton (H + ) type or an ammonium (NH 4 + ) type.
  • the cation type of the raw zeolite is a proton (H + ) type or an ammonium (NH 4 + ) type
  • calcium is more easily incorporated in the calcium-containing step described below compared to when the cation type is other than the proton (H + ) type.
  • the calcium source brought into contact with the raw zeolite is a substance containing calcium, and examples include salts and compounds containing calcium. Since this makes it easier for calcium to be incorporated into the raw zeolite, the calcium source brought into contact with the raw zeolite is preferably one or more selected from the group consisting of calcium chloride, calcium iodide, calcium bromide, calcium hydroxide, calcium oxide, and calcium nitrate, more preferably one or more selected from the group consisting of calcium chloride, calcium bromide, and calcium nitrate, and even more preferably calcium nitrate.
  • the contact between the calcium source and the raw zeolite is preferably carried out by contacting the raw zeolite with a solution containing the calcium source (hereinafter also referred to as the "calcium solution"), as this allows the raw zeolite to more easily incorporate calcium.
  • a solution containing the calcium source hereinafter also referred to as the "calcium solution”
  • the solvent contained in the calcium solution include at least one of water and alcohol, with water being preferred.
  • the calcium concentration in the calcium solution is not particularly limited and can be adjusted appropriately taking into account the Ca/Al ratio and other factors so that the zeolite of this embodiment can be produced. From the perspective of making it easier to produce the zeolite of this embodiment, the calcium concentration in the calcium solution is preferably such that the Ca/Al ratio of the calcium-containing zeolite obtained by the calcium contact treatment is 0.01 or more and 0.3 or less.
  • the contact conditions between the calcium source and the raw zeolite are not particularly limited, and may be adjusted appropriately taking into account the Ca/Al ratio and other factors so that the zeolite of this embodiment can be produced. From the perspective of making it easier to produce the zeolite of this embodiment, the contact conditions between the calcium source and the raw zeolite are preferably such that the Ca/Al ratio of the calcium-containing zeolite obtained by the calcium contact treatment is 0.01 or more and 0.3 or less.
  • the contact time between the raw zeolite and the calcium source may be 10 minutes or more and 24 hours or less.
  • the contact temperature between the raw zeolite and the calcium source may be 20°C or more and 110°C or less.
  • the contact pressure between the raw zeolite and the calcium source may be 0.0 MPa or more and 1.0 MPa or less (gauge pressure).
  • calcium-containing step (1) calcium is incorporated into the raw zeolite, thereby producing a calcium-containing zeolite (calcium-containing zeolite obtained by the production method (1)).
  • the calcium-containing zeolite obtained by the production method (1) may be used directly in the copper-containing step described above, or may be subjected to one or more treatments selected from the group consisting of a washing treatment, a drying treatment, a calcination treatment, and an ion exchange treatment before being used in the copper-containing step described above.
  • the ion exchange treatment is preferably an ion exchange treatment that changes the cation type of the calcium-containing zeolite to a proton (H + ) type or an ammonium (NH 4 + ) type.
  • the cation type of the calcium-containing zeolite is a proton (H + ) type or an ammonium (NH 4 + ) type
  • copper is more likely to be incorporated in the copper-containing step compared to calcium-containing zeolite of other cation types.
  • the alumina source, silica source, alkali source, and water contained in the raw material composition can be the same as those contained in the raw material composition in the crystallization step (1), respectively.
  • the raw material composition preferably does not contain an organic structure-directing agent, since the calcium-containing zeolite obtained by crystallization is likely to have an intergrowth structure containing a CHA structure and a GME structure. Furthermore, in the crystallization step (2), the raw material composition preferably does not contain fluorine (F) or phosphorus (P), since this makes it easier to use manufacturing equipment made of general-purpose materials.
  • the OH/ SiO2 ratio of the raw material composition is preferably 0.30 or more, more preferably 0.35 or more, and even more preferably 0.40 or more. Furthermore, in the crystallization step (2), the OH/ SiO2 ratio of the raw material composition is preferably 0.70 or less, more preferably 0.65 or less, and even more preferably 0.60 or less.
  • the upper and lower limits of the OH/ SiO2 ratio of the raw material composition may be any combination of the above-mentioned upper and lower limits, but are preferably 0.30 or more and 0.70 or less, more preferably 0.35 or more and 0.65 or less, and even more preferably 0.40 or more and 0.60 or less.
  • the ion exchange treatment is preferably an ion exchange treatment that changes the cation type of the zeolite to a proton (H + ) type or an ammonium (NH 4 + ) type.
  • the cation type of the calcium-containing zeolite is a proton (H + ) type or an ammonium (NH 4 + ) type, copper is more likely to be contained in the copper-containing step compared to when other cation types are used.
  • the Ca/Al ratio of the calcium-containing zeolite obtained by Production Method (1) or Production Method (2) is preferably 0.01 or more and 0.3 or less, more preferably 0.015 or more and 0.25 or less, and even more preferably 0.02 or more and 0.15 or less.
  • the SCR catalytic activity (SCR catalytic activity after hydrothermal durability treatment) of the zeolite of this embodiment is excellent from low temperatures (e.g., 150°C) to high temperatures (e.g., 600°C).
  • the zeolite of this embodiment has superior SCR catalytic activity (SCR catalytic activity after hydrothermal durability treatment) at temperatures of 200°C or less, and even superior SCR catalytic activity (SCR catalytic activity after hydrothermal durability treatment) at temperatures of 150°C to 200°C, compared to zeolites having the same composition as the zeolite of this embodiment except that they do not contain calcium, and zeolites having the same composition as the zeolite of this embodiment except that they have an XPS area ratio of 34% or more.
  • composition analysis The composition of the sample was analyzed using a general inductively coupled plasma optical emission spectrometer (instrument name: OPTIMA 7300DV, manufactured by Perkin Elmer). The sample was dissolved in a mixed solution of hydrofluoric acid and nitric acid to prepare a measurement solution. The obtained measurement solution was used to analyze the composition of the sample ( SiO2 / Al2O3 ratio , Ca/Al ratio, Cu/Al ratio).
  • the peak area of the XPS spectrum was calculated by dividing the measured XPS spectrum using multiple virtual lines spaced at 0.10 eV intervals, and assuming that each divided XPS spectrum is a trapezoid (a right-angled trapezoid bounded by two adjacent virtual lines, a line connecting the intersection of the two virtual lines with the XPS spectrum curve, and the horizontal axis), and then adding up the areas of the individual trapezoids.
  • a trapezoid a right-angled trapezoid bounded by two adjacent virtual lines, a line connecting the intersection of the two virtual lines with the XPS spectrum curve, and the horizontal axis
  • the crystallized product was a calcium-containing zeolite with a SiO2 / Al2O3 ratio of 7.0 and a Ca/Al ratio of 0.02.
  • a copper nitrate solution was added dropwise to the obtained calcium-containing zeolite so that the copper content was 4 mass %, and the mixture was mixed in a mortar for 10 minutes.
  • the zeolite was dried overnight at 110°C in an air atmosphere and then calcined at 550°C in an air atmosphere for 1 hour to obtain a zeolite containing calcium and copper (hereinafter also referred to as "Ca-Cu zeolite”) of this example.
  • the Ca-Cu zeolite of this example had a SiO 2 /Al 2 O 3 ratio of 7.0, a Ca/Al ratio of 0.02, and a Cu/Al ratio of 0.18.
  • the Ca-Cu zeolite of this example had a binding energy peak position (eV) in the XPS spectrum ranging from 930.0 eV to 940.0 eV, with an XPS area ratio of 31%.
  • Example 2 A raw material composition having the following molar composition was obtained by changing the amounts of the raw materials added in Example 1. A crystallized product was obtained in the same manner as in Example 1, except that the obtained raw material composition was used.
  • the crystallized product was a calcium-containing zeolite with a SiO2 / Al2O3 ratio of 7.7 and a Ca/Al ratio of 0.05. Furthermore, the XRD pattern of the crystallized product confirmed that the crystallized product was a calcium-containing zeolite (calcium-containing crystalline aluminosilicate) having an intergrowth structure including a CHA structure and a GME structure.
  • the Ca-Cu zeolite of this example had a SiO 2 /Al 2 O 3 ratio of 7.7, a Ca/Al ratio of 0.05, and a Cu/Al ratio of 0.19.
  • the Ca-Cu zeolite of this example was a Ca-Cu zeolite (crystalline aluminosilicate containing calcium and copper) having an intergrowth structure including a CHA structure and a GME structure.
  • the Ca-Cu zeolite of this example had a binding energy peak position (eV) in the XPS spectrum ranging from 930.0 eV to 940.0 eV, with an XPS area ratio of 28%.
  • the crystallized product was a calcium-containing zeolite with a SiO2 / Al2O3 ratio of 7.4 and a Ca/Al ratio of 0.05. Furthermore, the XRD pattern of the crystallized product confirmed that the crystallized product was a calcium-containing zeolite (calcium-containing crystalline aluminosilicate) having an intergrowth structure including a CHA structure and a GME structure.
  • the Ca-Cu zeolite of this example was a Ca-Cu zeolite (crystalline aluminosilicate containing calcium and copper) having an intergrowth structure including a CHA structure and a GME structure.
  • the Ca-Cu zeolite of this example had a binding energy peak position (eV) in the XPS spectrum ranging from 930.0 eV to 940.0 eV, with an XPS area ratio of 31%.
  • the Ca-Cu zeolite of this example had a binding energy peak position (eV) in the XPS spectrum ranging from 930.0 eV to 940.0 eV, with an XPS area ratio of 31%.
  • Comparative Example 1 A raw material composition having the following molar composition was obtained by changing the amounts of the raw materials added and not using the calcium source in Example 1. A crystallized product was obtained in the same manner as in Example 1, except that the obtained raw material composition was used.
  • Ca/ SiO2 ratio 0
  • the crystallized product was a zeolite with a SiO2 / Al2O3 ratio of 7.3 and a Ca/Al ratio of 0.
  • the obtained zeolite was doped with copper in the same manner as in Example 1, to obtain the copper-containing zeolite of this comparative example.
  • the copper-containing zeolite of this comparative example had a SiO2 / Al2O3 ratio of 7.3, a Ca/Al ratio of 0, and a Cu/Al ratio of 0.19.
  • the copper-containing zeolite of this comparative example was a copper-containing zeolite (copper-containing crystalline aluminosilicate) having an intergrowth structure including a CHA structure and a GME structure.
  • Comparative Example 2 A crystallized product was obtained in the same manner as in Example 5.
  • the crystallized product was a zeolite having a SiO2 / Al2O3 ratio of 6.5 and a Ca/Al ratio of 0.
  • the Ca-Cu zeolite of this comparative example had a SiO 2 /Al 2 O 3 ratio of 6.5, a Ca/Al ratio of 0.05, and a Cu/Al ratio of 0.18.
  • the Ca-Cu zeolite of this comparative example had a binding energy peak position (eV) in the range of 930.0 eV to 940.0 eV in its XPS spectrum, and the XPS area ratio was 34%.
  • the Ca-Cu zeolite of this comparative example had a SiO 2 /Al 2 O 3 ratio of 7.7, a Ca/Al ratio of 0.05, and a Cu/Al ratio of 0.34.
  • the Ca-Cu zeolite of this comparative example had a binding energy peak position (eV) in the XPS spectrum ranging from 930.0 eV to 940.0 eV, with an XPS area ratio of 45%.
  • the zeolites of each Example and Comparative Example were subjected to hydrothermal durability treatment.
  • the hydrothermal durability treatment was carried out in the following manner.
  • the zeolite of each Example and Comparative Example was molded and pulverized to form agglomerated particles having an agglomeration diameter of 12 to 20 mesh. 3 mL of the obtained agglomerated particles was packed into an atmospheric pressure fixed-bed flow reactor, and then air containing 10% by volume of moisture was passed through the reactor, and the resulting mixture was subjected to a hydrothermal durability treatment under the following conditions: Air flow rate: 300 mL/min Processing temperature: 650°C Processing time: 100 hours
  • the nitrogen oxide reduction rate (%) of the zeolite of each example and each comparative example that had been subjected to hydrothermal durability treatment was determined.
  • the nitrogen oxide reduction rate was determined by the following method.
  • the zeolites of each example and comparative example that had been subjected to hydrothermal durability treatment were molded and crushed to form agglomerated particles with an agglomerate diameter of 12 to 20 mesh.
  • 1.5 mL of the agglomerated particles were packed into an atmospheric pressure fixed-bed flow-type reactor tube, and a nitrogen oxide-containing gas was passed through while maintaining the temperature at the following measurement temperature.
  • the nitrogen oxide concentrations at the inlet and outlet of the atmospheric pressure fixed-bed flow-type reactor tube were measured to determine the nitrogen oxide reduction rate.
  • the flow conditions for the nitrogen oxide-containing gas are as follows: The space velocity below is the flow rate of the nitrogen oxide-containing gas per volume of the zeolite-shaped catalyst. Composition of nitrogen oxide-containing gas: NO 200 ppm by volume NH3 200 ppm by volume O2 10% by volume H2O 3% by volume Flow rate of nitrogen oxide-containing gas: 1.5 L/min Space velocity: 60,000hr -1 Measurement temperature: 600°C or 150°C Gauge pressure: 0.01 MPa
  • Nitrogen oxide reduction rate (%) ⁇ ([NOx]in-[NOx]out)/[NOx]in ⁇ 100...(1)
  • [NOx]in is the nitrogen oxide concentration (ppm) of the nitrogen oxide-containing gas at the inlet of the atmospheric pressure fixed-bed flow-type reactor
  • [NOx]out is the nitrogen oxide concentration (ppm) of the nitrogen oxide-containing gas at the outlet of the atmospheric pressure fixed-bed flow-type reactor.
  • Table 16 below shows the nitrogen oxide reduction rates at 150°C for the zeolites of each Example and Comparative Example that were subjected to hydrothermal durability treatment (hereinafter also referred to as "100-hour durability-treated samples").

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Abstract

Le but de la présente invention est de fournir au moins l'un parmi : une zéolite qui présente une excellente durabilité hydrothermique et qui, même après avoir subi un traitement de durabilité hydrothermique, présente une excellente activité catalytique SCR ; un procédé de production de la zéolite ; ainsi qu'un catalyseur de réduction sélective comprenant la zéolite.　La présente zéolite a une structure d'intercroissance comprenant une structure CHA et une structure GME, donne un motif de diffraction des rayons X sur poudre qui présente au moins les pics présentés dans la table, contient du calcium et du cuivre, et donne un spectre XPS dans lequel la proportion de la zone pour la plage spectrale de 930,0-933,0 eV à la zone pour la plage spectrale de 930,0-940,0 eV est inférieure à 34 %.　
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US20190217280A1 (en) * 2016-11-10 2019-07-18 Haldor Topsøe A/S Catalyst comprising a molecular sieve belonging to the abc-6 framework family with disorder in the abc stacking sequence and use of the catalyst
JP2019524606A (ja) * 2016-06-08 2019-09-05 ビーエーエスエフ コーポレーション ＮＯｘの選択的接触還元における銅で促進されたグメリン沸石およびその使用
JP2020193135A (ja) * 2019-05-30 2020-12-03 東ソー株式会社 ゼオライトｚｔｓ−６及びその製造方法
JP2022525280A (ja) * 2019-03-28 2022-05-12 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 「ｓｆｗ－ＧＭＥ尾部」を有するｃｈａとａｆｔとのモレキュラーシーブ連晶調製及び使用の方法

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Publication number Priority date Publication date Assignee Title
JP2012148968A (ja) * 2010-12-28 2012-08-09 Tosoh Corp 銅及びアルカリ土類金属を担持したゼオライト
JP2017081809A (ja) * 2014-11-21 2017-05-18 三菱化学株式会社 Ａｅｉ型ゼオライト及びその製造方法と用途
JP2018510837A (ja) * 2015-04-09 2018-04-19 ピーキュー コーポレイション 安定化されたマイクロポーラス結晶性物質、それを作成する方法、およびＮＯｘの選択的触媒還元のためのその使用
JP2019524606A (ja) * 2016-06-08 2019-09-05 ビーエーエスエフ コーポレーション ＮＯｘの選択的接触還元における銅で促進されたグメリン沸石およびその使用
US20190217280A1 (en) * 2016-11-10 2019-07-18 Haldor Topsøe A/S Catalyst comprising a molecular sieve belonging to the abc-6 framework family with disorder in the abc stacking sequence and use of the catalyst
JP2022525280A (ja) * 2019-03-28 2022-05-12 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 「ｓｆｗ－ＧＭＥ尾部」を有するｃｈａとａｆｔとのモレキュラーシーブ連晶調製及び使用の方法
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