WO2022264758A1 - ZÉOLITE DE TYPE β ET COMPOSITION DE PURIFICATION DE GAZ D'ÉCHAPPEMENT - Google Patents

ZÉOLITE DE TYPE β ET COMPOSITION DE PURIFICATION DE GAZ D'ÉCHAPPEMENT Download PDF

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WO2022264758A1
WO2022264758A1 PCT/JP2022/021231 JP2022021231W WO2022264758A1 WO 2022264758 A1 WO2022264758 A1 WO 2022264758A1 JP 2022021231 W JP2022021231 W JP 2022021231W WO 2022264758 A1 WO2022264758 A1 WO 2022264758A1
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peak
value
ppm
beta
zeolite
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克彦 林
竜太郎 大橋
秀和 後藤
正剛 小笠原
純雄 加藤
寛治 斎藤
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三井金属鉱業株式会社
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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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • 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
    • 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

  • the present invention relates to a beta zeolite and a composition for purifying exhaust gas.
  • Synthetic zeolite is a crystalline aluminosilicate and has uniform pores due to its crystal structure. Taking advantage of this feature, synthetic zeolites are industrially used as molecular sieve adsorbents that adsorb only molecules with a specific size, adsorption separation agents that adsorb molecules with strong affinity, or as catalyst bases. Beta zeolite, which is one of such zeolites, is used as a catalyst in the petrochemical industry and in exhaust gas purifying compositions because of its excellent ability to adsorb hydrocarbons. Zeolites used in exhaust gas purifying compositions are required to have high crystallinity and catalytic activity that can withstand severe thermal environments of 850° C. or higher.
  • Beta zeolite has been synthesized using an organic structure-directing agent (hereinafter also referred to as "OSDA"). ) has been proposed. Further, Patent Document 2 discloses an exhaust gas purifying composition containing beta zeolite synthesized using OSDA, which contains phosphorus capable of maintaining the structure of beta zeolite.
  • OSDA organic structure-directing agent
  • the zeolite described in Patent Document 1 mentioned above does not contain phosphorus and has a low Si/Al molar ratio, so it is difficult to maintain the crystal structure in a severe thermal environment of, for example, 850°C or higher.
  • the zeolite described in Patent Document 2 contains phosphorus, it has low crystallinity. Therefore, it is difficult to say that the zeolite has the degree of heat resistance required for exhaust gas purification and the like.
  • an object of the present invention is to provide a beta-type zeolite and a composition for purifying exhaust gas that maintain high crystallinity even in a severe thermal environment and further improve heat resistance.
  • the chemical shift value of the peak apex is peak 1: 55.4 ppm or more and 59.0 ppm or less, peak 2: 50.0 ppm or more and 55.4 ppm or less, peak 3: 30.0 ppm or more and 50 .0 ppm or less, peak 4: -15.0 ppm or more -5.0 ppm or less, having a peak separated into four peaks, and the peak area A2 value of peak 1 with respect to the total A1 value of the peak areas of the four peaks A phosphorus-containing beta-type zeolite having an A value of 0.05 or more when the peak area ratio is defined as A (A2/A1) value is proposed.
  • the present invention proposes an exhaust gas purifying composition containing the beta-type zeolite containing phosphorus.
  • beta-type zeolite and a composition for exhaust gas purification that maintain high crystallinity and further improve heat resistance even under the severe thermal environment proposed by the present invention.
  • FIG. 1A shows the 27 Al MAS NMR spectrum of beta zeolite according to Example 1.
  • FIG. 1B shows the 27 Al MAS NMR spectrum of beta zeolite according to Example 2.
  • FIG. 1C shows the 27 Al MAS NMR spectrum of beta zeolite according to Example 3.
  • FIG. 1D shows the 27 Al MAS NMR spectrum of beta zeolite according to Comparative Example 1.
  • FIG. 2A shows the 29 Si DDMAS NMR spectrum of beta zeolite according to Example 1.
  • FIG. 2B shows the 29 Si DDMAS NMR spectrum of beta zeolite according to Example 2.
  • FIG. 2C shows the 29 Si DDMAS NMR spectrum of beta zeolite according to Example 3.
  • FIG. 2D shows the 29 Si DDMAS NMR spectrum of beta zeolite according to Comparative Example 1.
  • FIG. 1A shows the 29 Si DDMAS NMR spectrum of beta zeolite according to Example 1.
  • FIG. 2B shows the 29 Si DDMAS NMR spectrum of beta zeolite
  • FIG. 3A shows the 1 H-side slice spectrum of the 31 P- 1 H two-dimensional NMR spectrum of the beta zeolite according to Example 1.
  • FIG. 3B shows the 1 H side slice spectrum of the 31 P- 1 H two-dimensional NMR spectrum of the beta zeolite according to Example 2.
  • FIG. 3C shows the 1 H-side slice spectrum of the 31 P- 1 H two-dimensional NMR spectrum of the beta zeolite according to Example 3.
  • FIG. 3D shows the 1 H-side slice spectrum of the 31 P- 1 H two-dimensional NMR spectrum of beta zeolite according to Comparative Example 1.
  • FIG. 3A shows the 1 H-side slice spectrum of the 31 P- 1 H two-dimensional NMR spectrum of the beta zeolite according to Example 1.
  • FIG. 3B shows the 1 H side slice spectrum of the 31 P- 1 H two-dimensional NMR spectrum of the beta zeolite according to Example 2.
  • FIG. 3C shows the 1 H-side slice spectrum of the 31 P- 1 H two-dimensional NMR spectrum of the
  • Beta-type zeolite containing phosphorus (P) is a 27 Al MAS NMR spectrum in which the chemical shift value of the peak apex is peak 1: 55.4 ppm or more and 59.0 ppm or less, peak 2: 50.0 ppm. 0 ppm or more and 55.4 ppm or less, peak 3: 30.0 ppm or more and 50.0 ppm or less, peak 4: -15.0 ppm or more and -5.0 ppm or less.
  • Beta zeolite containing phosphorus (P) wherein the A value is 0.05 or more when the peak area ratio of the peak area A2 value of peak 1 to the total A1 value of the peak areas is defined as A (A2/A1) value. I will provide a.
  • a (A2/A1) Value The 27 Al MAS NMR spectrum of beta zeolite for calculating the A value can be measured under the following conditions. Magnetic field: 14.1 T ( 1 H 600MHz) Spectroscope: Bruker AVANCE NEO600 Measurement and data processing software: Bruker TopSpin NMR probe: 3.2 mm MAS probe Sample rotation speed: 20 kHz Standard sample for chemical shift value and radio wave intensity: Potassium alum Standard for chemical shift value: -0.21 ppm for the central peak of potassium alum.
  • Radio wave pulse intensity A value that maximizes the peak of potassium alum when the spectrum center is 51.675 ppm and gives a pulse width of 4.5 ⁇ s.
  • Radio wave pulse width 2.5 ⁇ s
  • Number of spectrum points SI on the above software: 4096 points
  • a 27 Al MAS NMR spectrum is obtained by performing baseline correction on the spectrum obtained as described above using calculation software.
  • the baseline is the point Q1 that is the arithmetic average of the chemical shift values, signal intensities, respectively, of all points from the point closest to 90 ppm to the point closest to 100 ppm and the point Q1 from the point closest to ⁇ 50 ppm to the point closest to ⁇ 40 ppm. It is created by connecting point Q2 obtained by arithmetically averaging chemical shift values and signal intensities of all points up to the point.
  • the spectrum obtained as described above is referred to as "Al measured spectrum".
  • the peaks 1 to 4 of the present invention are obtained by separating peaks from the measured Al spectrum.
  • a calculated spectrum created by summing four pseudo Voigt functions in the measured Al spectrum was divided into a range from the point closest to the 27 Al chemical shift value of -40 ppm to the point closest to 90 ppm (hereinafter, for convenience, "-40 ppm It is described as "the range of 90 ppm or less”.).
  • the pseudo Voigt function is the sum of the same full width half maximum Lorentzian and Gaussian functions.
  • the pseudo Voigt function f(x) used in peak separation is shown in Equation (1) below.
  • the peak area of each peak is obtained from the sum of the signal intensities of the peaks calculated by the pseudo Voigt function at points in the range of -40 ppm to 90 ppm in the measured Al spectrum.
  • the "pseudo Voigt function” is based on “6. Profile function and pattern decomposition method" in Journal of the Crystallographic Society of Japan, 34, 86 (1992), “Special Issue: New Developments in Powder Diffraction Method”.
  • the total A1 value of the peak areas of the four peaks 1 to 4 is positively correlated with the amount of aluminum in the beta zeolite containing phosphorus.
  • the non-patent document Yoshihiro Kubota et. al. ⁇ Effective fabrication of catalysts from large-pore,multi-dimensional zeolites synthesized without using organic structure-directing agents ⁇ Chemistry of Materials ⁇ 2014 ⁇ 26(2) ⁇ 1250-1259( ⁇ Yoshihiro ⁇ ), there are silicon sites T1 to T9.
  • the area A2 value of peak 1 has a positive correlation with the amount of aluminum substituted at the silicon sites T3 to T9 among the nine silicon sites T1 to T9 equivalently present in the crystal structure of beta-type zeolite. . Note that if the area A2 value of peak 1 is large, the amount of ammonia (NH 3 ) adsorbed by the temperature programmed desorption method (TPD) increases. It is considered that O bonded to aluminum substituted at the silicon site of ⁇ T9 tends to become a strong acid site. Peak 1 represents a peak derived from aluminum substituted at silicon sites T3 to T9 among the nine silicon sites T1 to T9 equivalently present in the crystal structure of beta-type zeolite as described above.
  • Peak 2 represents a peak derived from aluminum substituted at the T1 and/or T2 silicon sites among the nine silicon sites T1 to T9 equivalently present in the beta zeolite crystal structure.
  • Peak 3 represents a peak derived from tetracoordinated aluminum in the vicinity of phosphoric acid.
  • Peak 4 represents a peak derived from hexacoordinated aluminum outside the zeolite framework.
  • NH 3 ammonia
  • the A (A2/A1) value is a value that shows a positive correlation with the abundance ratio of aluminum that tends to form acid sites with respect to the total amount of aluminum in the sample.
  • Silicon sites T3 to T9 belonging to peak 1 and silicon sites T1 and T2 belonging to peak 2 have a site number ratio of 3:1.
  • the number of silicon sites T1 to T9 in one unit cell of beta zeolite is 4 for each of T7 and T9, and 8 for each of T1 to T6 and T8.
  • the total of T3 to T9 is 48 sites, and the total of T1 and T2 is 16 sites.
  • a large A value which is the area ratio of peak 1
  • the A (A2/A1) value of such a beta-type zeolite containing phosphorus is 0.05 or more, it has high crystallinity and high heat resistance, but has a large number of Bronsted acid sites, resulting in severe heat. It becomes a highly active catalyst even when placed under the environment.
  • the relationship between the beta-type zeolite crystal structure and the 27 Al MAS NMR spectrum is described in the above-mentioned non-patent document Yoshihiro.
  • the A value is preferably in the range of 0.05 or more and 0.75 or less, and more preferably in the range of 0.14 or more and 0.5 or less from the viewpoint of excellent balance between high crystallinity and catalytic activity. Preferably, it is more preferably 0.14 or more and 0.3 or less.
  • the A value is 0.75 or less, the crystallinity is easily maintained at a high level, and the crystal structure is stabilized, so that the catalytic activity is suitable even in a severe thermal environment.
  • beta zeolite has high crystallinity, the pore size of beta zeolite is easily maintained, and the adsorption of the target substance is improved.
  • the A value can be suitably obtained by measuring the phosphorus-containing beta zeolite produced by the below-described production method by the below-described measurement method.
  • the pseudo Voigt function f(x) used in the peak separation of the pseudo Voigt spectrum can be derived from the following formula (1).
  • x is the value of the horizontal axis of the NMR spectrum (chemical shift value)
  • x 0 is the chemical shift value of the peak apex
  • S is the scaling factor to match the actual measurement
  • ⁇ is - ⁇ (minus infinity) is the peak area ratio of the Lorentzian function (first term) in the range from to + ⁇ (plus infinity)
  • ⁇ is the full width at half maximum of the peak
  • ⁇ is the circumference constant
  • ln is the natural logarithm function
  • exp is the natural exponential function.
  • the chemical shift value of the peak apex is peak 5: -100 ppm or more and -106 ppm or less, peak 6: -106 ppm or more and -112 ppm or less, peak 7: It has a peak separated into three peaks of -112 ppm or more and -118 ppm or less, and the B value is 9.8 ppm or less when the full width at half maximum represented by the chemical shift value of peak 5 is taken as the B value.
  • the unit (ppm) of the B value is the horizontal axis unit (chemical shift value) in the 29 Si DDMAS NMR spectrum.
  • the B value is a value representing the heterogeneity of the structure near the acid site of beta zeolite.
  • the B value can be suitably obtained by measuring the phosphorus-containing beta zeolite produced by the below-described production method by the below-described measurement method.
  • the 29 Si DDMAS NMR spectrum of beta zeolite containing phosphorus for calculating the B value can be measured under the following conditions.
  • Radio wave pulse intensity The value is such that the pulse width that maximizes the peak on the low magnetic field side of Q8M8 when the spectrum center is 0.0 ppm is 4 ⁇ s.
  • Radio wave pulse width 4 ⁇ s 1 H decouple irradiation center (O2 value - 1 H SR value (chemical shift notation)): 4.7 ppm 1 H decoupling strength: 62.5 kHz
  • the spectrum obtained as described above is referred to as "Si measured spectrum".
  • the peaks 5 to 7 of the present invention are obtained by separating peaks from the measured spectrum of Si. Peak separation is performed by fitting a calculated spectrum created by summing the three above-mentioned pseudo Voigt functions to the measured Si spectrum in the range of 29 Si chemical shift values from -123 ppm to -92 ppm.
  • the B value is the full width at half maximum of peak 5 obtained by fitting.
  • peak 5 is a chemical bond of beta-type zeolite in which three —O (oxygen)—Si are continuously bonded and one —O—Al is bonded. It represents a peak derived from silicon (hereinafter referred to as “Si(1Al)”).
  • Si(1Al) a peak derived from silicon
  • Peak 6 represents a peak derived from silicon in which --O--Si is tetra-coordinated to silicon sites T3 to T6.
  • Peak 7 represents a peak derived from silicon in which --O--Si is tetra-coordinated to the silicon sites of T1 and T2.
  • the B value is 9.8 ppm or less, preferably in the range of 0.07 ppm or more and 9.8 ppm or less, and more preferably in the range of 1.0 ppm or more and 8.4 ppm or less. The lower the heterogeneity of the structure in the vicinity of the acid site serving as the active center, the higher the catalytic activity. be.
  • the beta-type zeolite containing phosphorus has an E (C ⁇ D) value, which is the product of the C value and the D value, of 1.0. 1 or more, a phosphorus-containing beta zeolite is provided.
  • E (C ⁇ D) value which is the product of the C value and the D value, of 1.0. 1 or more
  • a phosphorus-containing beta zeolite is provided.
  • the chemical shift value of the peak apex of the 1 H side slice spectrum at the peak is 8: 5.0 ppm or more and 6.0 ppm or less, and the peak 9: 4.4 ppm.
  • peak 10 has a peak separated into three peaks of 3.0 ppm or more and 4.4 ppm or less, and the peak area C2 value of peak 8 with respect to the total C1 value of the peak areas of the three peaks
  • the peak area ratio is defined as (C2/C1).
  • the D value is the peak intensity of the zeolite (302) plane relative to the peak intensity D1 of the (116) plane of ⁇ -Al 2 O 3 in the X-ray diffraction spectrum measured by XRD using CuK ⁇ rays. Let the ratio be (D2/D1).
  • the C value represents the amount of hydrogen (H) bonded to Bronsted acid sites
  • the D value represents the crystallinity of beta-type zeolite
  • the E (C ⁇ D) value is 1.1 or more.
  • the beta zeolite has a good balance of heat resistance and acid sites, and preferably maintains the acid sites even after durability.
  • the C (C2/C1) value, D (D2/D1) value, and E (C ⁇ D) value are obtained by measuring the phosphorus-containing beta zeolite produced by the production method described below by the measurement method described below. can be suitably obtained.
  • C(C2/C1) Value The 31 P- 1 H two-dimensional NMR spectrum of phosphorus-containing beta zeolite for calculating the C value can be measured under the following conditions. Magnetic field: 14.1 T ( 1 H 600MHz) Spectroscope: Bruker AVANCE NEO600 Measurement and data processing software: Bruker TopSpin NMR probe: 3.2 mm MAS probe Sample rotation speed: 20 kHz Standard sample for chemical shift value and radio wave intensity: Diammonium hydrogen phosphate Standard for chemical shift value: The peak of diammonium hydrogen phosphate on the low magnetic field side is 1.5 ppm.
  • the beta zeolite containing phosphorus has a peak apex chemical shift value of 8:5. It has three calculated peaks separated from 0 ppm to 6.0 ppm, peak 9 from 4.4 ppm to 5.0 ppm, and peak 10 from 3.0 ppm to 4.4 ppm.
  • the peak area of each peak is determined by the sum of the signal intensities of the calculated peaks at points in the entire range of the slice spectrum on the 1 H side at the vertex of the 31 P- 1 H two-dimensional NMR spectrum.
  • the calculated peak here is the peak calculated by the above-mentioned pseudo Voigt function.
  • the total C1 value of the peak areas of the three peaks, peaks 8-10 represents the amount of hydrogen near phosphorus in beta zeolite.
  • the peak area C2 value of peak 8 is Bronsted It represents the amount of H bound to the acid sites.
  • Peak 8 represents a peak derived from hydrogen bound to Bronsted acid points in the vicinity of phosphorus contained in beta-type zeolite.
  • Peak 9 represents a peak derived from hydrogen of water molecules in the vicinity of phosphorus contained in beta-type zeolite.
  • Peak 10 represents a peak derived from hydrogen at a Lewis acid site near P contained in beta-type zeolite.
  • the C (C2/C1) value represents the amount of hydrogen bonded to the Bronsted acid points near phosphorus relative to the amount of hydrogen near phosphorus contained in beta-type zeolite, and the higher the C value, the more phosphorus
  • the amount of hydrogen bonding to Bronsted acid sites in the vicinity of increases, and the value represents the amount of acid sites.
  • the C value is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more. As the C value increases, the amount of acid sites increases. However, if the acid sites are too large, the amount of aluminum forming acid sites increases and the crystallinity deteriorates.
  • D ( D2/D1) value Zeolite's ( 302) Let the peak intensity ratio of the peak intensity D2 value of the plane 302) be the D(D2/D1) value.
  • the D value is an index of the crystallinity of beta-type zeolite, and it can be said that the larger the D value, the higher the crystallinity of the zeolite and the better the heat resistance.
  • ⁇ -Al 2 O 3 is reference material 674a distributed by the National Institute of Standards and Technology. When the crystallinity is high, the crystal structure tends to be stable, and the catalytic activity tends to be improved.
  • the D value is preferably 1.3 or more, more preferably 1.8 or more.
  • the D value is obtained by subjecting a sample obtained by mixing the beta-type zeolite containing phosphorus to be measured and ⁇ -Al 2 O 3 as a standard substance in the same volume to X-ray diffraction measurement.
  • the peak intensity D1 of the (116) plane of Al 2 O 3 and the peak intensity D2 of the (302) plane of beta-type zeolite obtained by X-ray diffraction measurement are obtained, and the D (D2/D1) value is calculated.
  • the diffraction peak of ⁇ -Al 2 O 3 which is a standard substance, is generally observed in the range of the diffraction angle 2 ⁇ of 57.40° or more and 57.60° or less.
  • the reason for adopting the diffraction peak of the (116) plane as the diffraction peak of ⁇ -Al 2 O 3 is that the diffraction peak of the zeolite was not observed in the vicinity of the diffraction peak of the (116) plane and the diffraction peak of the (116) plane was not observed. This is because the accuracy of measurement is enhanced due to the high intensity.
  • the diffraction peak of the (302) plane of beta-type zeolite is generally observed in the range of the diffraction angle 2 ⁇ of 22.10° or more and 23.58° or less. XRD can be measured by the method described in Examples below.
  • E (C ⁇ D) value If the E (C ⁇ D) value is 1.1 or more, the crystallinity of beta-type zeolite is high and excellent even when the amount of hydrogen bonded to the acid sites is small. Alternatively, the crystallinity of beta-type zeolite is maintained to some extent and the amount of hydrogen bonded to acid sites is large, so that not only heat resistance but also excellent catalytic activity is exhibited.
  • the E(C ⁇ D) value is an index representing the quality of the catalytic activity in consideration of the amount of Bronsted acid sites in the vicinity of phosphorus of the phosphorus-containing beta-zeolite and the crystallinity of the phosphorus-containing beta-zeolite.
  • the E(CxD) value is less than 1.1, the amount of Bronsted acid sites near phosphorus or the crystallinity of the beta-type zeolite decreases, resulting in a decrease in heat resistance and a decrease in catalytic activity.
  • the E(CxD) value is preferably 1.2 or more, more preferably 1.5 or more. Also, the E(C ⁇ D) value may be 1.8 or less.
  • the peak area of the peak area A2 value of peak 1 with respect to the total A3 value of the peak areas of peaks 1 and 2 Provided is a phosphorus-containing beta zeolite having an F (A2/A3) ratio of 0.22 or more.
  • the 27 Al MAS NMR spectrum and peak area of beta-type zeolite containing phosphorus can be measured in the same manner as the A value described above.
  • the total A3 value of the peak areas of peaks 1 and 2 was replaced by nine silicon sites from T1 to T9 in the crystal structure of beta zeolite.
  • the F(A2/A3) value is a numerical value that shows a positive correlation with the abundance ratio of aluminum, which tends to form Bronsted acid sites, among aluminum substituted for silicon sites in the crystal structure of beta-type zeolite.
  • a beta-type zeolite containing phosphorus with an F(A2/A3) value of 0.22 or more has high crystallinity and excellent heat resistance.
  • the F value can be suitably obtained by measuring the phosphorus-containing beta-type zeolite produced by the production method described below by the measurement method described above.
  • the total A3 of the peak areas of peaks 1 and 2 is 4-coordinated aluminum contained within the structural framework of the crystal structure of beta-type zeolite (framework aluminum).
  • the peak area A2 is the same as the peak area A2 described above, and is positive to the amount of aluminum substituted at the silicon sites T3 to T9 among the nine silicon sites T1 to T9 equivalently present in the beta crystal structure.
  • the F (A2/A3) value is the total number of sites (64 sites) of T1 to T9 of silicon sites in one unit cell of beta-type zeolite and the total number of T3 to T9 of silicon sites that can be substituted by aluminum. As the ratio of (48 sites) approaches 0.75, beta zeolite has high crystallinity and excellent heat resistance, and aluminum is more uniformly dispersed in beta zeolite.
  • the F value is preferably 0.22 or more, and 0.4 or more. more preferred. If the F-value of the beta-type zeolite containing phosphorus is 0.22 or more, the aluminum of the beta-type zeolite containing phosphorus is more uniformly dispersed in the sample, and the catalytic activity is improved. If the F value is larger than 0.75, which is the site number ratio of the crystal structure, it indicates that the distribution of aluminum is biased or the crystal structure has changed. Therefore, the F value is preferably 0.75 or less, and may be 0.6 or less.
  • the G value is the ratio of the molar amount of aluminum to the total molar amount of aluminum, silicon and phosphorus constituting the phosphorus-containing beta zeolite.
  • Silicon and aluminum contained in beta-type zeolite serve as central atoms of TO4 units (T is the central atom) having a tetrahedral structure.
  • the molar ratio of aluminum contained in beta-type zeolite containing phosphorus, the molar ratio of phosphorus and the molar ratio of silicon described later are measured using a scanning fluorescent X-ray spectrometer as in the method of the examples described later. be able to.
  • the G value is preferably 0.5 mol % or more and 20 mol % or less.
  • the I value is the ratio of the molar amount of phosphorus to the total molar amount of aluminum, silicon and phosphorus constituting the phosphorus-containing beta zeolite. Phosphorus contained in beta zeolite containing phosphorus binds to acid sites of aluminum. The I value is preferably 0.1 mol % or more and 40 mol % or less.
  • the J value is the ratio of the molar amount of silicon to the total molar amount of aluminum, silicon and phosphorus constituting beta zeolite containing phosphorus. Silicon constitutes the structural framework of beta zeolites. The J value is preferably 60 mol % or more and 95 mol % or less.
  • the phosphorus-containing beta zeolite preferably has an I/G value of 0.7 or more and 1.0 or less.
  • the I/G value can also be expressed as the P/Al molar ratio.
  • the acid sites other than the acid site that is the center of catalytic activity (Lewis acid site) are modified with phosphorus, and the acid site that is the center of catalytic activity (Bronsted acid site) is maintained. . If the I/G value is 0.7 or more, the beta-type zeolite containing phosphorus can improve the catalytic activity while maintaining high crystallinity.
  • the I/G value exceeds 1.0 and is large, the acid site that is the center of catalytic activity is also modified with phosphorus, the amount of hexacoordinated aluminum increases, the crystal structure of beta-type zeolite changes, and the crystallinity deteriorates. may decrease.
  • the I / G value is in the range of 0.7 or more and 1.0 or less, the acid sites other than the acid sites that are the centers of catalytic activity are modified with phosphorus, and the acid sites that are the centers of catalytic activity are maintained. , it is possible to maintain high crystallinity and improve catalytic activity even in a severe thermal environment.
  • the I/G value is preferably 0.8 or higher.
  • the beta-type zeolite containing phosphorus preferably has a J/G value of 5 or more and 30 or less.
  • the J/G value can also be expressed as the Si/Al molar ratio. If the beta-type zeolite containing phosphorus has a J/G value of 5 or more and 30 or less, it has high crystallinity and can maintain catalytic activity even when placed in a severe thermal environment. If the J/G value is too large, the amount of aluminum contained in the phosphorus-containing beta-type zeolite is small, and the acid sites that are the center of catalytic activity may decrease, resulting in a decrease in catalytic activity.
  • the J/G value is preferably 10 or more, more preferably 15 or more, and preferably 25 or less.
  • the beta zeolite is preferably an OSDA-free beta zeolite synthesized using seed crystals and without using OSDA.
  • a method for producing OSDA-free beta zeolite is described, for example, in the above-mentioned Patent Document 1.
  • OSDA-free beta-type zeolite has a small J/G value (Si/Al molar ratio) and high crystallinity. If it is possible to retain aluminum that contributes to the formation of acid sites and remove aluminum that does not contribute to the formation of acid sites (dealuminization) while maintaining high crystallinity, the J / G value (Si / Al molar ratio) can be maintained to improve the catalytic activity while maintaining high crystallinity.
  • the OSDA-free beta-type zeolite containing dealuminated phosphorus has an A value of 0.05 or more, the aluminum that does not contribute to the formation of acid sites is dealuminated, resulting in high crystallinity and high catalytic activity.
  • the OSDA-free beta zeolite containing dealuminated phosphorus further has at least one of B value, E (C ⁇ D) value, F value, and I / G value (P / Al molar ratio) , it can be confirmed that when the above numerical range is satisfied, the crystallinity is high and the catalytic activity is high.
  • the OSDA-free beta-type zeolite may be proton-type, ammonium-type, sodium-type, potassium-type, or lithium-type.
  • the ion exchange sites may be exchanged with transition metal ions.
  • Transition metals that can be ion-exchanged include, for example, iron (Fe), copper (Cu), cobalt (Co), nickel (Ni), chromium (Cr), molybdenum (Mo), manganese (Mn), vanadium (V), At least one selected from the group consisting of titanium (Ti), cerium (Ce), ruthenium (Ru), platinum (Pt), silver (Ag) and iridium (Ir).
  • Ion exchange with transition metal ions can be performed, for example, by dispersing beta-type zeolite in an ammonium nitrate aqueous solution to obtain ammonium-type beta-type zeolite, and then performing the method described in JP-A-2014-019601.
  • the phosphorus-containing beta zeolite is obtained by dealuminating OSDA-free beta zeolite and then contacting it with a phosphorus-containing compound so that the aforementioned A value is 0.05 or more. It is possible to obtain a beta-type zeolite containing phosphorus.
  • the phosphorus-containing beta zeolite having an A value of 0.05 or more is dealuminated OSDA-free beta zeolite, unlike the case where phosphorus is present in the form of an oxide on the surface of OSDA-free beta zeolite.
  • the acid sites other than the acid sites that are the centers of catalytic activity remaining after dealumination are modified with phosphorus, and the acid sites that are the centers of catalytic activity are maintained. Catalytic activity can be improved while still being kept high.
  • an ammonium salt it is preferable to bring the zeolite into contact with an ammonium salt to remove aluminum that does not contribute to the formation of acid sites without reducing the crystallinity of the beta-type zeolite as much as possible.
  • a method for dealuminizing beta zeolite can be performed, for example, by the method described in International Publication No. 2021/002322.
  • the A value, B value, E (C ⁇ D) value, F value, I / G value (P / Al molar ratio) and J / G value (Si / Al molar ratio) can be easily adjusted to a desired numerical range.
  • a dealuminated OSDA-free beta zeolite can be brought into contact with a phosphorus-containing compound to obtain a phosphorus-containing beta zeolite with an A value of 0.05 or more.
  • methods for bringing the dealuminated OSDA-free beta-type zeolite into contact with a phosphorus-containing compound include a vapor deposition method, an impregnation method, a precipitation method, an ion exchange method, and the like.
  • the vapor deposition method beta-type zeolite and a phosphorus-containing compound are placed in a container, and the phosphorus-containing compound is evaporated at room temperature or by heating to adhere the phosphorus-containing compound to the beta-type zeolite. mentioned.
  • beta zeolite is immersed in a liquid mixture of a phosphorus-containing compound and a solvent, and the mixture is dried by heating under normal pressure or reduced pressure to attach the phosphorus-containing compound to the beta zeolite.
  • the impregnation method includes incipient wetness method, evaporation to dryness method, pore-filling method, spray method, equilibrium adsorption method and the like. Examples of precipitation methods include a kneading method and a deposition method.
  • trimethyl phosphate When phosphorus is attached to beta-type zeolite, trimethyl phosphate, triethyl phosphate, trimethyl phosphite, triethyl phosphite, or the like can be used as the phosphorus-containing compound. Trimethyl phosphate is preferred because of its low boiling point.
  • the phosphorus-containing compound is preferably water-soluble, such as trimethyl phosphate, triethyl phosphate, trimethyl phosphite, triethyl phosphite, phosphoric acid , dihydrogen phosphates such as ammonium dihydrogen phosphate, sodium dihydrogen phosphate and potassium dihydrogen phosphate, and hydrogen phosphates such as diammonium hydrogen phosphate and dipotassium hydrogen phosphate.
  • Examples of phosphoric acid include orthophosphoric acid (H 3 PO 4 ), pyrophosphoric acid (H 4 P 2 O 7 ), triphosphoric acid (H 5 P 3 O 10 ), polyphosphoric acid, metaphosphoric acid (HPO 3 ), ultraphosphoric acid, and the like. are mentioned.
  • Phosphoric acid such as orthophosphoric acid, ammonium phosphate such as trimethyl phosphate, ammonium dihydrogen phosphate, or diammonium hydrogen phosphate is preferred from the viewpoint of ease of drying.
  • Examples of the solvent to be mixed with the phosphorus-containing compound include polar organic solvents such as deionized water, ethanol, 2-propanol, and acetone. Deionized water and ethanol are preferably used because they are easy to handle and dry.
  • the phosphorus-containing compound may be in the range of 1% by mass or more and 25% by mass or less, or in the range of 2% by mass or more and 20% by mass or less with respect to 100% by mass of the total amount of the mixed liquid. It may be in the range of 5% by mass or more and 15% by mass or less.
  • the time for impregnating the mixed liquid with the beta zeolite can be 0.5 hours or more and 2 hours or less.
  • the beta zeolite containing a phosphorus-containing compound may be dried, the drying temperature may be 80° C. or higher and 200° C. or lower, and the drying time may be 0.5 hours or longer5. can be done within hours.
  • the pressure during drying is not particularly limited, and may be atmospheric pressure (0.1 MPa) or under reduced pressure of 0.1 MPa or less.
  • heat treatment is performed to obtain a beta zeolite containing phosphorus.
  • the heat treatment temperature is preferably in the range of 200° C. or higher and 800° C. or lower, more preferably in the range of 400° C. or higher and 700° C. or lower, in order to maintain the framework structure of beta zeolite.
  • the atmosphere for the heat treatment may be an air atmosphere or an inert gas atmosphere such as nitrogen.
  • Exhaust gas purifying composition The phosphorus-containing beta zeolite having an A value of 0.05 or more obtained as described above can be used in an exhaust gas purifying composition.
  • An exhaust gas purifying composition containing a phosphorus-containing beta zeolite with an A value of 0.05 or more is exposed to a severe thermal environment in a temperature range of, for example, 900° C. or higher and 1000° C. or lower. Since beta zeolite has high crystallinity and high catalytic activity, the skeleton structure of beta zeolite is maintained, it has stable hydrocarbon (HC) adsorption capacity, and exhibits stable high purification performance.
  • HC hydrocarbon
  • Such an exhaust gas purifying composition can exhibit stable and high exhaust gas purifying performance as an exhaust gas purifying catalyst for internal combustion engines powered by fossil fuels such as gasoline engines and diesel engines.
  • the exhaust gas purifying composition can be suitably used for purifying exhaust gas discharged from internal combustion engines such as four-wheeled motor vehicles and motorcycles.
  • Exhaust gas purifying compositions are effectively used to purify particularly hydrocarbons (HC) in exhaust gas.
  • the exhaust gas purifying composition can be suitably used for purifying hydrocarbons (HC) contained in the exhaust gas flowing through the exhaust passage of an internal combustion engine, and can also provide an exhaust gas purifying method.
  • a beta zeolite containing phosphorus with an A value of 0.05 or more further has a B value, E (C ⁇ D) value, F value, I / G value (P / Al molar ratio) and J / G value ( Si/Al molar ratio) preferably satisfies the above numerical range.
  • the exhaust gas purifying composition may be an exhaust gas purifying composition made of phosphorus-containing beta zeolite with an A value of 0.05 or more, and may contain other components other than phosphorus-containing beta zeolite. may contain.
  • Other components include conventionally known catalyst materials and the like.
  • the exhaust gas purifying composition may be in any form such as powder, paste or granules.
  • the exhaust gas purifying composition can be used as a catalyst layer formed on a catalyst support.
  • a catalyst support for example, a support made of ceramics or metal materials can be used. Ceramics used as catalyst supports include alumina (Al 2 O 3 ), mullite (3Al 2 O 3 -2SiO 2 ), cordierite (2MgO-2Al 2 O 3 -5SiO 2 ), aluminum titanate (Al 2 TiO 5 ), silicon carbide (SiC), and the like.
  • Metal materials used as catalyst supports include, for example, stainless steel.
  • the shape of the catalyst support is not particularly limited, but examples thereof include a honeycomb shape, a plate shape, a pellet shape, and the like.
  • the catalyst structure using the exhaust gas purifying composition for the catalyst layer may include a catalyst layer made of a conventionally known catalyst material other than the exhaust gas purifying composition.
  • a catalyst structure using an exhaust gas purifying composition for a catalyst layer can also be used as a DPF (Diesel Particulate Filter) or a GPF (Gasoline Particulate Filter).
  • Example 1 According to the method described in the example of WO2021/002322, specifically as follows, a dealuminated OSDA-free beta zeolite is prepared, phosphorus is attached to A beta zeolite containing (1) Preparation of Seed Crystal Tetraethylammonium hydroxide was used as an OSDA, sodium aluminate was used as an alumina source, and fine powdered silica (manufactured by Mizusawa Chemical Industry Co., Ltd., P707) was used as a silica source, and these were stirred and heated at 165 ° C. for 96 hours. was performed to synthesize a beta zeolite having a Si/Al molar ratio of 12. The resulting beta-type zeolite was calcined at 550° C. for 10 hours in an electric furnace while air was circulated to produce seed crystals containing no organic matter.
  • OSDA Seed Crystal Tetraethylammonium hydroxide
  • sodium aluminate was used as an
  • OSDA-free beta-type zeolite was prepared according to the method described in the examples of Japanese Patent No. 4904417, specifically as follows.
  • An aqueous solution was obtained by dissolving 2.35 g of sodium aluminate and 18.28 g of 36 mass % sodium hydroxide in 139 g of deionized water.
  • a mixture of 20.24 g of finely powdered silica (M-5, manufactured by CABOT) and 2.02 g of the seed crystal was added little by little to the aqueous solution and mixed with stirring to obtain a SiO 2 /Al 2 O 3 molar ratio.
  • the reaction mixture was placed in a 60 mL stainless steel sealed vessel and heated statically under autogenous pressure at 140° C. for 46 hours without aging and stirring. After cooling the closed container, the product was filtered and washed with warm water to obtain a white powder. It was confirmed by the X-ray diffraction measurement described later that the resulting white powder was sodium-type OSDA-free beta-type zeolite containing no impurities. As a result of ICP emission spectroscopic analysis, which will be described later, the Si/Al molar ratio was 5.5.
  • Preparation of phosphorus-containing beta zeolite Phosphorus was attached to the obtained dealuminated OSDA-free beta zeolite by the incipient wetness method to obtain a phosphorus-containing OSDA-free beta zeolite. . Specifically, 3.5 g (dry weight) of dealuminated OSDA-free beta zeolite and 0.613 g of 99% by mass trimethyl phosphate were placed in a closed container, and the pressure was reduced to 0.01 MPa, and then the pressure was reduced to 80°C. to obtain an OSDA-free beta-type zeolite on which a phosphorus-containing compound was vapor-deposited.
  • the obtained OSDA-free beta zeolite powder containing the compound containing phosphorus was dried at 120° C. for 3 hours in an air atmosphere of 0.1013 MPa to obtain a powder.
  • the dried powder was heat-treated at 600° C. for 1 hour in an air atmosphere of 0.1013 MPa (heating rate of 5° C./min) to obtain OSDA-free beta zeolite containing phosphorus.
  • a phosphorus-containing OSDA-free beta-type zeolite having an I/G value (P/Al molar ratio) of 0.95 and a J/G value (Si/Al molar ratio) of 11.8 as measured by the evaluation method described later. got
  • Example 2 After carrying out the steps (1) to (4) of Example 1, an acid treatment using nitric acid was carried out as a post-treatment as shown below. That is, 5.5 g of dealuminated OSDA-free beta-type zeolite powder was dispersed in 25 mL of an aqueous nitric acid solution having a concentration of 1 mol/L, and the mixture was mixed at 95° C. for 15 hours for acid treatment. Filtration and washing with deionized water were then repeated five times. The obtained hydrous powder was dried at 100° C. for 12 hours or longer. Thus, a dealuminated OSDA-free beta zeolite powder having a Si/Al ratio of 20.4 as measured by the evaluation method described later was obtained.
  • the OSDA-free beta-type zeolite containing P was performed in the same manner as in the step (5) of Example 1, except that the amount of trimethyl phosphate was changed to 0.365 g. got The beta zeolite had an I/G value (P/Al molar ratio) of 0.95 and a J/G value (Si/Al molar ratio) of 20.4.
  • Example 3 After carrying out the steps (1) to (4) of Example 1, an acid treatment using nitric acid was carried out as a post-treatment as shown below. That is, 5.0 g of dealuminated OSDA-free beta-type zeolite powder was dispersed in 25 mL of an aqueous nitric acid solution having a concentration of 1 mol/L, and the mixture was mixed at 100° C. for 20 hours for acid treatment. Filtration and washing with deionized water were then repeated five times. The obtained hydrous powder was dried at 100° C. for 12 hours or longer. Thus, a dealuminated OSDA-free beta zeolite powder having a Si/Al ratio of 22.6 as measured by the evaluation method described later was obtained.
  • the beta zeolite had an I/G value (P/Al molar ratio) of 0.95 and a J/G value (Si/Al molar ratio) of 22.6.
  • Comparative example 1 A commercially available proton-type beta-type zeolite (HSZ-940, manufactured by Tosoh Corporation, Si/Al molar ratio: 17.5) was prepared.
  • step (5) of Example 1 3.5 g (dry weight) of dealuminated OSDA-free beta zeolite was changed to 3.5 g (dry weight) of commercially available proton-type beta zeolite, and trimethyl phosphate was
  • a beta-type zeolite containing P was obtained in the same manner as in step (5) of Example 1, except that the amount was changed to 0.401 g.
  • the beta zeolite had an I/G value (P/Al molar ratio) of 0.95 and a J/G value (Si/Al molar ratio) of 18.5.
  • a Value, F Value, B Value, C Value The A value and F value of each beta zeolite of Examples and Comparative Examples were calculated by measuring 27 Al MAS NMR spectra as described above. The A1 value, A2 value and A3 value for calculating the A value and the F value were obtained as relative values when the A1 value of Comparative Example 1 was normalized to 1. Further, the C1 value and C2 value for calculating the C value were obtained as relative values when C1 of Comparative Example 1 was normalized to 1.
  • 27 Al MAS NMR spectra of the beta-type zeolites of Examples and Comparative Examples for which peak separation was performed are shown in FIGS. 1A to 1D.
  • Table 2 shows the variables (x 0 , ⁇ , ⁇ , S) of the pseudo Voigt function of peaks 1 to 4 obtained by peak separation.
  • the B value of each beta zeolite of Examples and Comparative Examples was calculated by measuring the 29 Si DDMAS NMR spectrum as described above. 29 Si DDMAS NMR spectra of the beta zeolites of Examples and Comparative Examples for which peak separation was performed are shown in FIGS. 2A to 2D.
  • Table 3 shows the variables (x 0 , ⁇ , ⁇ , S) of the pseudo Voigt function of peaks 5 to 7 obtained by peak separation.
  • the C value of each beta zeolite of Examples and Comparative Examples was calculated by measuring the 31 P- 1 H two-dimensional NMR spectrum as described above.
  • 3A to 3D show slice spectra on the 1 H side of 31 P- 1 H two-dimensional NMR spectra of beta-type zeolites of Examples and Comparative Examples for which peak separation was performed.
  • Table 4 shows the variables (x 0 , ⁇ , ⁇ , S) of the pseudo Voigt function of peaks 8 to 10 obtained by peak separation.
  • D value XRD was measured using an X-ray diffractometer (RINT-TTR III, manufactured by Rigaku Corporation) using CuK ⁇ rays (0.15406 nm, 50 kV, 300 mA) as an X-ray source.
  • the measurement range was measured under the conditions of a diffraction angle 2 ⁇ of 5° to 80°, a scan speed of 20°/min, and a scan step width of 0.02°.
  • the software "PDXL2" was used for the diffraction intensity analysis. After removing the background, the intensity of the diffraction peak was obtained by fitting with a split-type pseudo-Voigt function using the K ⁇ 1 position as the peak position.
  • the peak intensity D1 of the (116) plane was obtained from the XRD that measured ⁇ -Al 2 O 3 , which is the standard material 674a distributed by the National Institute of Standards and Technology, and the XRD that measured each beta-type zeolite of Examples and Comparative Examples.
  • the peak intensity D2 of the (302) plane was determined from Diffraction peaks of ⁇ -Al 2 O 3 , which is a standard substance, were generally observed in a range of diffraction angle 2 ⁇ of 57.40° or more and 57.60° or less.
  • the diffraction peak of the (302) plane of beta zeolite was observed in the range of the diffraction angle 2 ⁇ of 22.10° or more and 23.58° or less.
  • E (C ⁇ D) Value The E (C ⁇ D) value, which is the product of the C and D values described above, was determined.
  • the amounts of aluminum, phosphorus, and silicon in beta zeolite were measured. From the measured amount of aluminum, the molar ratio of aluminum in the phosphorus-containing beta-type zeolite was calculated and used as the G value. From the measured amount of phosphorus, the molar ratio of phosphorus in the beta-type zeolite containing phosphorus was calculated and used as the I value.
  • Measurement samples were prepared as follows. Method for preparing measurement sample A vinyl chloride tube having a diameter of 30 mm was filled with beta-type zeolite and compression-molded to prepare a measurement sample.
  • Crystallinity retention rate The XRD spectrum of each exhaust gas purifying composition (beta-type zeolite) before and after the thermal durability test was measured according to the above-described XRD measurement.
  • the peak intensity of the strongest peak corresponding to the (302) plane of beta zeolite in the range of diffraction angle 2 ⁇ 22.10 ° or more and 23.58 ° or less in the XRD spectrum before the heat durability test is defined as the XRD crystallinity, and the following formula ( b) was used to calculate the XRD retention rate (crystallinity retention rate).
  • XRD retention rate (%) (XRD crystallinity after thermal durability test/XRD crystallinity before thermal durability test) x 100
  • the phosphorus-containing beta zeolites of Examples 1 to 3 had an A value of 0.05 or more and a large amount of acid sites.
  • the phosphorus-containing beta zeolites of Examples 1 to 3 have an A value of 0.05 or more, a B value of 9.8 ppm or less, and an E (C ⁇ D) value of 1.1.
  • each NMR spectrum satisfying an F value of 0.22 or more was measured.
  • the exhaust gas purifying compositions using the beta zeolite of Examples 1 to 3 had a higher specific surface area retention rate after the heat durability test than the exhaust gas purifying composition using the beta zeolite of Comparative Example 1. and maintained high crystallinity even after the heat durability test.
  • the exhaust gas purifying compositions using the beta zeolite of Examples 2 and 3 had a higher XRD retention rate after the thermal endurance test than the exhaust gas purifying composition using the beta zeolite of Comparative Example 1. , maintained high crystallinity after the thermal endurance test.
  • the beta-type zeolite containing phosphorus according to the present disclosure and the exhaust gas purifying composition using the same maintain high crystallinity and further improve heat resistance even when placed in a severe thermal environment. can do.
  • the phosphorus-containing beta-type zeolite and exhaust gas purification composition according to the present disclosure can be suitably used to purify exhaust gases emitted from internal combustion engines such as four-wheeled motor vehicles and motorcycles.

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Abstract

L'invention concerne une zéolite de type β qui maintient une cristallinité élevée et une résistance à la chaleur améliorée même dans un environnement thermique difficile, et une composition de purification de gaz d'échappement.　Un spectre RMN sous rotation à l'angle magique (MAS) de 27Al de la zéolite de type β présente des pics qui sont séparés en quatre pics comportant : un pic (1) présentant une valeur de déplacement chimique du sommet de pic de 55,4 à 59,0 ppm inclus ; un pic (2) présentant une valeur de déplacement chimique du sommet de pic de 50,0 à 55,4 ppm inclus ; un pic (3) présentant une valeur de déplacement chimique du sommet de pic de 30,0 à 50,0 ppm inclus ; et un pic (4) présentant une valeur de déplacement chimique du sommet de pic de -15,0 à -5,0 ppm inclus. Lorsque le rapport d'aire de premier pic de l'aire de pic (A2) du pic (1) à la somme des aires de pics des quatre pics (A1) est désigné par A (A2/A1), alors A est supérieur ou égal à 0,05. La zéolite de type β contient du phosphore.　
PCT/JP2022/021231 2021-06-14 2022-05-24 ZÉOLITE DE TYPE β ET COMPOSITION DE PURIFICATION DE GAZ D'ÉCHAPPEMENT WO2022264758A1 (fr)

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WO2024204696A1 (fr) * 2023-03-31 2024-10-03 三井金属鉱業株式会社 Zéolithe de type bea

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JP2015000828A (ja) * 2013-06-14 2015-01-05 ユニゼオ株式会社 Ｍｎ＋置換ベータ型ゼオライト、それを含むガス吸着剤及びその製造方法、並びに一酸化窒素の除去方法
WO2019082990A1 (fr) * 2017-10-25 2019-05-02 三井金属鉱業株式会社 Zéolite bêta substituée par un métal et sa méthode de production
WO2021002322A1 (fr) * 2019-07-03 2021-01-07 三井金属鉱業株式会社 Zéolite de type bêta et catalyseur la contenant
WO2021044687A1 (fr) * 2019-09-05 2021-03-11 三井金属鉱業株式会社 Composition de purification de gaz d'échappement et procédé de production associé

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WO2019082990A1 (fr) * 2017-10-25 2019-05-02 三井金属鉱業株式会社 Zéolite bêta substituée par un métal et sa méthode de production
WO2021002322A1 (fr) * 2019-07-03 2021-01-07 三井金属鉱業株式会社 Zéolite de type bêta et catalyseur la contenant
WO2021044687A1 (fr) * 2019-09-05 2021-03-11 三井金属鉱業株式会社 Composition de purification de gaz d'échappement et procédé de production associé

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Publication number Priority date Publication date Assignee Title
WO2024204696A1 (fr) * 2023-03-31 2024-10-03 三井金属鉱業株式会社 Zéolithe de type bea

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