JP2023033143A - Method of manufacturing copper-containing cha-type zeolite - Google Patents

Abstract

To provide a method of manufacturing copper-containing CHA-type zeolite which does not essentially require a post-treatment process and also has higher yield than a conventional method of crystallization of a copper-containing CHA-type zeolite.SOLUTION: Disclosed is a method of manufacturing a CHA-type zeolite including a step of obtaining a crystallized product by crystallization of a composition containing at least a structure directing agent source including N,N,N-trialkylcyclohexylammonium cations, a polyamine source, a copper source, an alumina source, a silica source, a sodium source, and water, wherein a molar ratio of silica to alumina is 24 or under, a molar ratio of sodium to silica is 0.10 or over and 0.23 or under, and also, a molar ratio of N,N,N-trialkylcyclohexylammonium cation hydroxides to N,N,N-trialkylcyclohexylammonium cations is 0.7 or under.SELECTED DRAWING: None

Description

The present disclosure relates to copper-containing CHA-type zeolites, and to CHA-type zeolites crystallized from compositions containing a copper source.

CHA-type zeolite is an artificially synthesized zeolite reported in Patent Document 1, and CHA-type zeolite containing copper is widely used as a nitrogen oxide reduction catalyst.

A common method for adding copper to CHA-type zeolite is to crystallize CHA-type zeolite and then perform post-treatment such as liquid-phase ion exchange or impregnation. However, in these post-treatment containing methods, after the copper is contained in the CHA-type zeolite, an additional firing step is required to fix the copper to the CHA-type zeolite. On the other hand, a method for producing CHA-type zeolite has been proposed in which copper is incorporated into CHA-type zeolite during crystallization by using a tetraethylenepentamine copper complex as an organic structure directing agent instead of the method of containing by post-treatment (non Patent document 1).

U.S. Pat. No. 4,544,538

Chem. Commun, 2011, 47, 9789-9791

In the method for producing copper-containing CHA-type zeolite according to Patent Document 1, there is a problem that the production cost increases because an additional calcination step is required for fixing copper to the CHA-type zeolite.

In the method for producing a copper-containing CHA-type zeolite proposed in Non-Patent Document 1, the yield of the copper-containing CHA-type zeolite after crystallization is very low.

An object of the present disclosure is to provide a method for producing a copper-containing CHA-type zeolite that does not require a post-treatment step and has a higher yield than conventional methods for crystallizing a copper-containing CHA-type zeolite. and

The present inventors have investigated a method for producing a copper-containing CHA-type zeolite that does not require a copper-containing step as a post-treatment step in the method for producing a CHA-type zeolite. As a result, the inventors have found that the above problems can be solved by specific crystallization conditions.

That is, the present invention is as set forth in the claims, and the gist of the present disclosure is as follows.
[1] A structure directing agent source containing at least an N,N,N-trialkylcyclohexylammonium cation, a polyamine source, a copper source, an alumina source, a silica source, a sodium source and water, wherein the molar ratio of silica to alumina is 24. or less, the molar ratio of sodium to silica is 0.10 or more and 0.23 or less, and the N,N,N-trialkylcyclohexylammonium cation hydroxide to the N,N,N-trialkylcyclohexylammonium cation crystallizing a composition having a molar ratio of 0.7 or less to obtain a crystallized product.
[2] The production method according to [1] above, wherein the composition contains at least amorphous aluminosilicate.
[3] The production method according to [1] or [2] above, wherein the polyamine source is at least one of tetraethylenepentamine and N,N'-bis(3-aminopropyl)ethylenediamine.
[4] The production method according to any one of [1] to [3] above, wherein the N,N,N-trialkylcyclohexylammonium cation is an N,N,N-dimethylethylcyclohexylammonium cation.
[5] The copper content of the CHA-type zeolite is more than 0% by mass and 6.0% by mass or less, and the area of the TPR spectrum at 450 ° C. or higher and 800 ° C. or lower with respect to the area of the TPR spectrum at 100 ° C. or higher and 800 ° C. or lower The manufacturing method according to any one of the above [1] to [4], wherein the area ratio is 0.05 or more and 0.60 or less.
[6] The copper content is more than 0% by mass and 6.0% by mass or less, and the ratio of the area of the TPR spectrum at 450°C or higher and 800°C or lower to the area of the TPR spectrum at 100°C or higher and 800°C or lower is 0. A CHA-type zeolite of .05 or more and 0.60 or less.

According to the present disclosure, to provide a method for producing a copper-containing CHA-type zeolite that does not require a post-treatment step and has a higher yield than conventional methods for crystallizing a copper-containing CHA-type zeolite. can.

FIG. 10 is a diagram showing the TPR spectrum of the CHA-type zeolite of Example 8;

Hereinafter, a method for producing a CHA-type zeolite of the present disclosure will be described by showing an example of an embodiment. Each term in this embodiment is as shown below.

"Zeolite" means a compound having a regular structure in which skeletal atoms (hereinafter also referred to as "T atoms") are interposed with oxygen (O), and the T atoms are composed of at least one of a metal atom and a metalloid atom. It is a compound that As metal atoms, one or more selected from the group of aluminum (Al), iron (Fe) and gallium (Ga) can be exemplified. Examples of metalloid atoms include one or more selected from the group consisting of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb) and tellurium (Te).

A "zeolite-like substance" is a compound having a regular structure in which T atoms are oxygen-mediated, and in which T atoms contain at least atoms other than metals and metalloids (hereinafter also referred to as "non-metallic atoms"). is. Phosphorus (P) is an example of a nonmetallic atom, and complex phosphorus compounds such as aluminophosphate (AlPO) and silicoaluminophosphate (SAPO) can be exemplified as zeolite-like substances.

The “regular structure in which T atoms are interposed by oxygen (hereinafter also referred to as “zeolite structure”)” in zeolite and zeolite-like substances is defined by the structure code (hereinafter , also simply referred to as “structural code”). For example, "CHA structure" is the backbone structure specified as structure code "CHA". The zeolite structure can be identified by comparison with the XRD pattern (hereinafter also referred to as "reference pattern") of each structure described in Collection of simulated XRD powder patterns for zeolites, Fifth revised edition (2007). In this embodiment, framework structure, crystalline structure and crystalline phase are each used interchangeably.

“Aluminosilicate” is a composite oxide having a structure consisting of repeating networks of aluminum (Al) and silicon (Si) via oxygen (O). In the present embodiment, aluminum (Al) and silicon (Si) have a structure consisting of a repeating network via oxygen (O), and a part of aluminum (for example, 30 atoms of aluminum as T atoms % or less) substituted with other metal atoms is also included in the aluminosilicate. Among aluminosilicates, those having a crystalline XRD peak in the powder X-ray diffraction (hereinafter also referred to as “XRD”) pattern are “crystalline aluminosilicates” and do not have a crystalline XRD peak. The thing is "amorphous aluminosilicate". In this embodiment, the crystalline XRD peak is an XRD peak with a full width at half maximum (FWHM) of 5° or less.

The XRD pattern in this embodiment is measured using a CuKα ray as a radiation source, and measurement conditions include the following conditions.

Accelerating current/voltage: 40mA/40kV
Radiation source: CuKα ray (λ = 1.5405 Å)
Measurement mode: Continuous scan
Scan condition: 40°/min
Measurement range: 2θ = 3° to 43°
Divergence longitudinal limiting slit: 10mm
Divergence/Entrance Slit: 1°
Light receiving slit: open
Receiving solar slit: 5°
Detector: Semiconductor detector (D/teX Ultra)
Filter: Ni filter The XRD pattern can be measured using a general powder X-ray diffractometer (eg, Ultima IV, manufactured by Rigaku). In addition, the crystalline XRD peak is a peak whose peak top 2θ is specified and detected in XRD pattern analysis using general analysis software (for example, SmartLab Studio II, manufactured by Rigaku). Conditions for XRD pattern analysis include the following conditions.

Fitting conditions: automatic, refine background
Dispersive pseudo-Voigt function (peak shape)
Background removal method: Fitting method
Kα2 removal method: Kα1/Kα2 ratio = 0.497
Smoothing method: B-Spline curve
Smoothing conditions: Second derivative method, σ cut value = 3, χ threshold = 1.5
The composition in this embodiment, such as the molar ratio of silica to alumina, may be measured by ICP analysis using a general inductively coupled plasma emission spectrometer (for example, OPTIMA7300DV, manufactured by Perkin Elmer).

[Method for producing CHA-type zeolite]
The method for producing CHA-type zeolite of the present embodiment includes a structure-directing agent source containing at least an N,N,N-trialkylcyclohexylammonium cation, a polyamine source, a copper source, an alumina source, a silica source, a sodium source, and water. , the molar ratio of silica to alumina is 24 or less, the molar ratio of sodium to silica is 0.10 or more and 0.23 or less, and N,N,N to N,N,N-trialkylcyclohexylammonium cations - Crystallizing a composition having a trialkylcyclohexylammonium cation hydroxide molar ratio of 0.7 or less to obtain a crystallized product. As a result, CHA-type zeolite containing copper (hereinafter also referred to as "copper-containing CHA-type zeolite"), and further CHA-type zeolite with copper supported (hereinafter also referred to as "copper-supported CHA-type zeolite") ) can be obtained.

"Containing copper" means that the CHA-type zeolite contains copper. Preferably, it means a state in which copper does not exist as a T atom and is contained in at least one of the surface and pores of the zeolite.

A composition comprising a structure-directing agent source containing at least an N,N,N-trialkylcyclohexylammonium cation, a polyamine source, a copper source, an alumina source, a silica source, a sodium source and water (hereinafter also referred to as a "raw material composition") ) to obtain a crystallized product (hereinafter also referred to as “crystallization step”) directly crystallizes copper-containing CHA-type zeolite having high hot water resistance and high catalytic activity.

The method for producing CHA-type zeolite of the present embodiment crystallizes a raw material composition containing a copper source, a polyamine source and a sodium source. Therefore, it is believed that crystallization proceeds while copper interacts with the polyamine source and the sodium source, and as a result, a CHA-type zeolite containing monovalent copper and divalent copper can be obtained.

The alumina source is at least one of alumina (Al ₂ O ₃ ) and its precursors, such as alumina, aluminum sulfate, aluminum nitrate, sodium aluminate, aluminum hydroxide, aluminum chloride, amorphous aluminosilicate, metal One or more selected from the group of aluminum, crystalline aluminosilicate and aluminum alkoxide, further amorphous aluminum compound, further at least one of aluminum hydroxide and amorphous aluminosilicate, further amorphous It is preferably a pure aluminosilicate.

The silica source is at least one of silica (SiO ₂ ) and its precursors, such as colloidal silica, amorphous silica, sodium silicate, tetraethoxysilane, tetraethylorthosilicate, precipitated silica, fumed silica, amorphous One or more selected from the group consisting of amorphous aluminosilicate and crystalline aluminosilicate can be mentioned, and amorphous aluminosilicate is preferred.

The raw material composition preferably contains at least an amorphous alumina source and a silica source, and at least an amorphous aluminosilicate. Since the raw material composition does not contain crystalline aluminosilicate as an alumina source and a silica source, the manufacturing cost tends to be lower, which is industrially advantageous. Therefore, the alumina source and silica source are preferably only amorphous compounds, more preferably amorphous aluminosilicate.

Sodium sources include salts or compounds containing sodium. One or more selected from the group of sodium chlorides, iodides, bromides, hydroxides and oxides, one or more selected from the group of sodium chlorides, bromides and hydroxides, and sodium hydroxide It is mentioned that it is. Sodium contained in other starting materials can also be considered a sodium source. The raw material composition preferably contains at least sodium hydroxide.

The raw material composition may contain alkali metals other than sodium, that is, one or more selected from the group of potassium, rubidium and cesium, and further potassium, as long as the amount is sufficiently small relative to sodium.

The structure directing agent source contains at least N,N,N-trialkylcyclohexylammonium cations (TACH ⁺ ). TACH ⁺ functions as a structure-directing agent (hereinafter also referred to as "SDA") that directs the CHA structure. The SDA source is one or more selected from the group of TACH ⁺ hydroxides, halides, carbonate monoesters and sulfate monoesters; one or more selected from the group of hydroxides, chlorides, bromides and iodides; One or more selected from the group of hydroxides, bromides and iodides, at least one of hydroxides and bromides, and bromides can be exemplified.

TACH ⁺ contained in the SDA source is N,N,N-trimethylcyclohexylammonium cation (hereinafter also referred to as “TMCH ⁺ ”), N,N,N-dimethylethylcyclohexylammonium cation (hereinafter also referred to as “DMECH ⁺ ”). ), N,N,N-methyldiethylcyclohexylammonium cation (hereinafter also referred to as “MDECH ⁺ ”) and N,N,N-triethylcyclohexylammonium cation (hereinafter also referred to as “TECH ⁺ ”). one or more selected from, at least one of DMECH ⁺ and MDECH ⁺ , or DMECH ⁺ . In order to crystallize the copper-containing CHA-type zeolite having the SiO ₂ /Al ₂ O ₃ ratio of this embodiment, the TACH ⁺ contained in the SDA source is preferably TACH ⁺ other than TMCH ⁺ , such as DMECH ⁺ and MDECH ⁺ and preferably DMECH ⁺ .

The copper source may be any compound containing copper, one or more selected from the group consisting of copper sulfate, copper nitrate, copper acetate, copper oxide and copper hydroxide, further copper sulfate, copper nitrate, copper acetate and copper oxide One or more selected from the group of, and copper sulfate can be exemplified. Copper contained in other starting materials such as polyamine sources can also be considered a copper source. The raw material composition preferably contains at least copper sulfate.

The polyamine source may be any compound containing polyalkylpolyamine, such as tetraethylenepentamine (hereinafter also referred to as "TEPA"), N,N'-bis(3-aminopropyl)ethylenediamine (hereinafter also referred to as "EDPTA"). ), one or more selected from the group consisting of triethylenetetramine, diethylenetriamine, ethylenediamine, diethylenetriamine and pentaethylenehexamine, and at least one of TEPA and EDPTA. The polyalkylpolyamine may be at least one or more selected from the group of linear, branched and cyclic polyamines. The polyamine source may contain ethyleneamine as an impurity, that is, it may be a polyalkylamine containing ethyleneamine.

The copper source and the polyamine source in the raw material composition are preferably different compounds, such as copper sulfate and at least one of TEPA and EDPTA.

The water contained in the raw material composition includes deionized water, pure water, structural water, water as a solvent, etc., and even water (H ₂ O) contained in other starting materials. good.

The raw material composition preferably does not contain fluorine (F) or phosphorus (P), and the contents of fluorine and phosphorus in the raw material composition are each less than the measurement limit (for example, the fluorine content is 1 mass ppm or less, The phosphorus content is 1 mass ppm or less, or the fluorine content and phosphorus content are 1 mass ppm or less).

The molar ratio of silica to alumina in the raw material composition (SiO ₂ /Al ₂ O ₃ ratio) is 24 or less, preferably 22 or less or 20 or less. The crystallized product obtained in the crystallization process tends to have a lower SiO ₂ /Al ₂ O ₃ ratio than the raw material composition. Since the SiO ₂ /Al ₂ O ₃ ratio of the raw material composition is these values, when it is used as a nitrogen oxide reduction catalyst, it has high catalytic activity over a low temperature range of 150 ° C. to a high temperature range of 600 ° C. A copper-containing CHA-type zeolite is obtained. Also, the SiO ₂ /Al ₂ O ₃ ratio may be 8 or more, 10 or more, 13 or more, or 16 or more.

In order to suppress crystallization of zeolites other than CHA-type zeolite, the molar ratio of N,N,N-trialkylcyclohexylammonium hydroxide (hereinafter also referred to as "TACHOH") to TACH ⁺ of the raw material composition (hereinafter, "TACHOH /TACH ⁺ ratio") is 0.7 or less, preferably 0.5 or less or 0.4 or less. The TACHOH/TACH ⁺ ratio may be 0 (zero) (i.e., the feed composition may contain no TACHOH), but the feed composition contains TACHOH and the TACHOH/TACH ⁺ ratio is greater than 0 or It may be 0.25 or more.

The molar ratio of sodium to silica in the raw material composition is 0.10 or more and 0.23 or less, preferably 0.13 or more or 0.15 or more, and 0.22 or less or 0.21 or less .

Preferred compositions of the raw material composition include the following molar compositions. In the following, SDA is TACH ⁺ , and when TACH ⁺ is DMECH ⁺ or the like, the SDA/ _SiO2 ratio may be regarded as the DMECH ⁺ / _SiO2 ratio or the like. In addition, M is an alkali metal other than sodium, and when the raw material composition contains two or more kinds of alkali metals other than sodium (for example, potassium and cesium), the M / SiO ₂ ratio is (K + Cs) / SiO ₂ ratio, etc. You should consider it. In addition, TACH ⁺ in the TACHOH/TACH ⁺ ratio includes TACH ⁺ dissociated from TACHOH.

SiO ₂ /Al ₂ O ₃ ratio = 8 or more, 10 or more, 13 or more, or 16 or more, and
24 or less, 22 or less, or 20 or less SDA/SiO ₂ ratio = 0.02 or more, 0.04 or more, or 0.08 or more, and
0.5 or less, 0.3 or less, or 0.2 or less TACHOH/TACH ⁺ ratio = 0 or more, greater than 0, or 0.25 or more, and
0.7 or less, 0.5 or less, or 0.4 or less polyamine/SiO ₂ ratio = 0.01 or more, 0.02 or more, or 0.03 or more, and
0.5 or less, 0.3 or less, or 0.2 or less Cu/SiO ₂ ratio = 0.01 or more, 0.02 or more, or 0.03 or more, and
0.5 or less, 0.3 or less, or 0.2 or less Na/SiO ₂ ratio = 0.10 or more, 0.13 or more, or 0.15 or more, and
0.23 or less, 0.22 or less, or 0.21 or less
M / Na ratio = 0 or more, 0.001 or more, or 0.005 or more, and
Less than 0.05, 0.03 or less, or 0.01 or less H ₂ O/SiO ₂ ratio = 3 or more, 5 or more, 10 or more, or 15 or more, and
50 or less, 30 or less, or 20 or less In order to promote the crystallization of CHA-type zeolite, the raw material composition may contain seed crystals as long as the amount is sufficiently small relative to the alumina source and silica source. The seed crystal can be exemplified by one or more selected from the group consisting of CHA-type zeolite, AFX-type zeolite, ERI-type zeolite, CHA-type zeolite, LEV-type zeolite and OFF-type zeolite, and further CHA-type zeolite. The _seed crystals contained _{in the} raw material composition are the silicon The ratio of the total mass of (Si) and aluminum (Al) converted to SiO ₂ and Al ₂ O ₃ (hereinafter also referred to as "seed crystal content") is more than 0% by mass and 0.5% by mass or more or 1% by mass or more and 10% by mass or less, 5% by mass or less, or 3% by mass or less. The raw material composition may contain no seed crystals, that is, the seed crystal content may be 0% by mass.

In the crystallization step, the raw material composition is crystallized. The method of crystallization may be any method as long as the raw material composition is crystallized, and may be hydrothermal synthesis. The following conditions can be illustrated as conditions of hydrothermal synthesis.

Crystallization temperature: 130°C or higher, 140°C or higher, 150°C or higher, or 155°C or higher, and
200° C. or less, 180° C. or less, or 170° C. or less Crystallization time: 1 hour or more, 10 hours or more, or 24 hours or more, and
7 days or less, 5 days or less, 3 days or less, or 2 days or less Crystallization state: At least one of stirring state and stationary state, or stirring state Crystallization pressure: Autogenous pressure, for example, SiO ₂ /Al ₂ O ₃ ratio When crystallizing a copper-containing CHA zeolite with a of 24 or less, if the crystallization temperature is 150° C. or higher, a single-phase CHA zeolite can be crystallized in a crystallization time of 3 days or less.

The production method of the present embodiment can produce a copper-containing CHA-type zeolite with a higher yield than the conventional copper-containing CHA-type zeolite crystallization method.

The yield is the total mass W _Raw of Al converted to _Al2O3 and Si mass converted to _SiO2 in the raw material composition, and _Al2O3 in _the copper-containing CHA-type zeolite obtained by _the production method of the present embodiment. It refers to the ratio of the total mass W _Cry of the converted Al and the Si mass converted to SiO ₂ ((W _Cry /W _Raw )×100). The yield of the production method of the present embodiment is 100% or less, further 99% or less, and 85% or more, 90% or more, further 95% or more.

The production method of this embodiment may include at least one of a washing step, a drying step, an SDA removal step, and an ion exchange step.

In the washing step, the CHA-type zeolite and the liquid phase are solid-liquid separated. In the washing step, solid-liquid separation is performed by a known method, and the CHA-type zeolite obtained as a solid phase is washed with pure water.

The drying step removes water physically adsorbed on the CHA-type zeolite. Drying conditions are arbitrary, and the CHA-type zeolite can be dried in the air at 50° C. or higher and 150° C. or lower for 2 hours or more, or by a spray dryer.

The SDA removal step removes SDA contained in the CHA-type zeolite. Examples of methods for removing SDA include one or more selected from the group of liquid phase treatment with an acidic aqueous solution, exchange treatment with a resin, thermal decomposition treatment, and calcination treatment. From the viewpoint of production efficiency, the SDA removal step is preferably at least one of thermal decomposition treatment and calcination treatment.

The ion exchange step converts the CHA-type zeolite to any cation type. For example, when the cation type is an ammonium (NH ₄ ⁺ ) type, CHA-type zeolite is mixed with an ammonium chloride aqueous solution and stirred to perform ion exchange. Further, when the cation type is proton (H ⁺ ) type, calcination of ammonium (NH ₄ ⁺ ) type CHA-type zeolite in the atmosphere can be mentioned.

The copper content refers to the total mass of Al in terms of Al ₂ O ₃ , Si mass in terms of SiO ₂ and Cu mass (W _Cry-Cu ) in the CHA-type zeolite obtained by the production method of the present embodiment. It refers to the ratio of mass W _Cu [% by mass] ((W _Cu /W _Cry-Cu )×100).

In the production method of the present embodiment, the upper and lower limits of parameters such as the SiO ₂ /Al ₂ O ₃ ratio and other compositions, seed crystal content, crystallization temperature, crystallization time and yield may be any combination of the above. I wish I had.

[CHA-type zeolite]
The CHA-type zeolite of the present embodiment has a copper content of more than 0% by mass and 6.0% by mass or less, and a TPR spectrum at 450 ° C. or higher and 800 ° C. or lower with respect to the area of the TPR spectrum at 100 ° C. or higher and 800 ° C. or lower. CHA-type zeolite having an area ratio of 0.05 or more and 0.60 or less. The CHA-type zeolite of the present embodiment is a CHA-type zeolite containing copper, and may be regarded as a copper-containing CHA-type zeolite.

The copper content of the CHA-type zeolite of the present embodiment is more than 0% by mass, preferably 2.0% by mass or more. When the copper content is more than 0% by mass, that is, when copper is contained, the CHA-type zeolite of the present embodiment can be expected to exhibit excellent catalytic activity as an NH ₃ -SCR (Selective Catalytic Reduction) catalyst. Moreover, the copper content of the CHA-type zeolite of the present embodiment is preferably 6.0% by mass or less, 5.0% by mass or less, or 4.0% by mass or less. If the copper content exceeds 6.0% by mass, copper that does not contribute to the NH ₃ -SCR reaction may reduce catalytic activity.

The copper content in the present embodiment is a value determined by the same method as the copper content in the CHA-type zeolite obtained by the production method of the present embodiment described above.

The copper contained in the CHA-type zeolite of the present embodiment is preferably supported. That is, the copper contained in the CHA-type zeolite of the present embodiment is preferably contained as atoms other than T atoms, and more preferably contained in at least one of the surface and pores of the CHA-type zeolite. preferable.

The CHA-type zeolite of the present embodiment has a TPR spectrum area at 450 ° C. or higher and 800 ° C. or lower (hereinafter referred to as " H-spectral area”) (hereinafter also referred to as “spectral area ratio”) is 0.05 or more and 0.60 or less.

Areas of the TPR spectra below 450° C. correspond to divalent copper (Cu ²⁺ ) and areas of the TPR spectra above 450° C. correspond to monovalent copper (Cu ⁺ ). Therefore, the spectral area ratio is one of the indices indicating the proportion of monovalent copper in the copper contained in the CHA-type zeolite. The CHA-type zeolite of the present embodiment contains monovalent copper, and the coexistence of monovalent copper and divalent copper in this ratio results in high reactivity in the NH ₃ —SCR reaction and NH ₃ — It becomes easier to achieve both durability as an SCR catalyst. The CHA-type zeolite of the present embodiment preferably has a spectral area ratio of 0.07 or more, 0.08 or more, or 0.15 or more, and preferably 0.50 or less or 0.45 or less, and further 0.30 or less.

In this embodiment, the A-spectrum area, H-spectrum area and spectral area ratio can be calculated from the TPR spectrum obtained by hydrogen-temperature programmed reduction (H ₂ -TPR) measurement under the following conditions.

Pretreatment: Gas type Helium
Gas flow rate 50mL/min
Processing temperature 300°C
Treatment time 0.5 hours H ₂ -TPR: Gas species Argon, hydrogen
Gas flow rate Argon: 28.5 mL/min
Hydrogen: 1.5 mL/min
Heating rate 10°C/min
Measurement temperature 100℃～800℃
H ₂ -TPR can be measured using a general catalyst evaluation device (for example, device name: BELCATII, manufactured by MicrotracBEL).

A-spectrum area (mmol/g) and H-spectrum area (mmol/g) are 100 per unit mass [g] of copper-containing CHA-type zeolite from the TPR spectrum obtained by the above-mentioned H ₂ -TPR measurement. C. to 800.degree. C. and an integral value of the TPR spectrum from 450.degree. C. to 800.degree.

The CHA-type zeolite subjected to H ₂ -TPR measurement is CHA-type zeolite (described later) that does not substantially contain SDA, and is preferably heat-treated CHA-type zeolite.

The molar ratio of silica to alumina (SiO ₂ /Al ₂ O ₃ ratio) of the CHA-type zeolite of the present embodiment is 8 or more, 10 or more, 13 or more, or 16 or more, and 24 or less, 22 or less, or 20 Any of the following is acceptable.

The molar ratio of copper to alumina in the CHA-type zeolite of the present embodiment (hereinafter also referred to as “Cu/Al ₂ O ₃ ratio”) is greater than 0 and is 0.20 or more or 0.40 or more, and It may be 1.00 or less, 0.90 or less, 0.80 or less, or 0.60 or less.

The CHA-type zeolite of the present embodiment may contain SDA, and the SDA/SiO ratio may be 0 or more, more than 0, or 0.001 or more, and may be 0.15 or less and 0.10 or less. Or it can be exemplified that it is 0.09 or less. The CHA-type zeolite of the present embodiment preferably contains substantially no SDA, and the SDA/SiO ₂ ratio is 0.05 or less, 0.02 or less, or It is preferably 0.01 or less.

In the CHA-type zeolite of the present embodiment, the upper and lower limits of the SiO ₂ /Al ₂ O ₃ ratio, other compositions, and the spectrum area ratio may be any combinations described above.

EXAMPLES The present embodiment will be described below with reference to examples. However, this embodiment is not limited to these.
(zeolite structure)
A powder X-ray diffractometer (device name: Ultima IV, manufactured by Rigaku Corporation) was used to perform XRD measurement on the sample. The measurement conditions are as follows.

Accelerating current/voltage: 40mA/40kV
Radiation source: CuKα ray (λ = 1.5405 Å)
Measurement mode: Continuous scan
Scan condition: 40°/min
Measurement range: 2θ = 3° to 43°
Divergence longitudinal limiting slit: 10mm
Divergence/Entrance Slit: 1°
Light receiving slit: open
Receiving solar slit: 5°
Detector: Semiconductor detector (D/teX Ultra)
Filter: Ni filter The obtained XRD pattern was analyzed using analysis software attached to the device (software name: Smart Lab Studio II, manufactured by Rigaku Corporation) under the following conditions.

Fitting conditions: automatic, refine background
Dispersive pseudo-Voigt function (peak shape)
Background removal method: Fitting method
Kα2 removal method: Kα1/Kα2 ratio = 0.497
Smoothing method: B-Spline curve
Smoothing conditions: Second derivative method, σ cut value = 3, χ threshold = 1.5
The zeolite structure was identified by comparing the analyzed XRD pattern with a reference pattern.
(composition analysis)
A composition analysis of the sample was performed using a general inductively coupled plasma emission spectrometer (device name: OPTIMA7300DV, manufactured by PERKIN ELMER). A sample was dissolved in a mixed solution of hydrofluoric acid and nitric acid to prepare a measurement solution. The resulting measurement solution was used to analyze the composition of the sample.
(yield)
The yield was obtained from the following formula.

Yield (% by mass) = W _Cry /W _Raw x 100
W _Cry and W _Raw in the above equations were calculated using mass ratios of Si and Al determined by composition analysis.
(Copper content)
The copper content was obtained from the following formula.

Copper content (% by mass) = (W _Cu /W _Cry-Cu ) x 100
W _Cry-Cu and W _Cu in the above formula were calculated using the mass ratios of Si, Al and Cu determined by composition analysis.

(TPR spectrum)
H ₂ -TPR measurement was performed using a general catalyst evaluation apparatus (apparatus name: BELCATII, manufactured by MicrotracBEL).
The pretreatment and H ₂ -TPR conditions are shown below.

Sample amount: 0.2 g
Pretreatment: Gas type Helium
Gas flow rate 50mL/min
Processing temperature 300°C
Treatment time 0.5 hours H ₂ -TPR: Gas species Argon, hydrogen
Gas flow rate Argon: 28.5 mL/min
Hydrogen: 1.5 mL/min
Heating rate 10°C/min
Measurement temperature 100℃～800℃
The integrated value (mmol) of the TPR spectrum at 100° C. or higher and 800° C. or lower and the integrated value (mmol) of the TPR spectrum at 450° C. or higher and 800° C. or lower obtained from the measurement results of H ₂ -TPR were The H-spectrum area and the A-spectrum area were calculated by dividing by (0.2 g). A spectral area ratio was obtained from the obtained values.

Example 1
N,N,N-dimethylethylcyclohexylammonium bromide (hereinafter also referred to as "DMECHBr"), copper sulfate, TEPA, 48% aqueous sodium hydroxide solution, pure water, and amorphous aluminosilicate (SiO ₂ /Al ₂ O ₃ ratio = 20.5) to obtain a raw material composition with the following molar composition:

_SiO2 / _Al2O3 ratio ₌ 20.5
DMECHBr/ _SiO2 ratio = 0.12
TEPA/ _SiO2 ratio = 0.06
Cu/ _SiO2 ratio = 0.04
Na/ _SiO2 ratio = 0.16
_H2O / _SiO2 ratio = 20
TACHOH/TACH ⁺ ratio = 0.00
After mixing SSZ-13 (CHA-type zeolite) with the obtained raw material composition so that the seed crystal content is 1.0% by mass, 50 g of the raw material composition is filled in an 80 mL sealed container, The vessel was rotated at 55 rpm and reacted at 160° C. for 72 hours. The resulting crystallized product was subjected to solid-liquid separation, washed with deionized water, and then dried overnight at 110° C. in air. The crystallized product is copper-containing CHA-type zeolite (copper-supported CHA-type zeolite), and has a SiO ₂ /Al ₂ O ₃ ratio of 20.4, a Cu/Al ₂ O ₃ ratio of 0.59, and a copper content of 2.0. 7% by weight, and an SDA/SiO ₂ ratio of 0.10. Moreover, the yield was 99.5%.

Example 2
In addition to DMECHBr, N,N,N-dimethylethylcyclohexylammonium hydroxide (hereinafter also referred to as "DMECHOH") was used, and except for using a raw material composition having the following molar composition A crystallized product was obtained in the same manner as in Example 1.

_SiO2 / _Al2O3 ratio ₌ 20.5
DMECHBr/ _SiO2 ratio = 0.09
DMECHOH/ _SiO2 ratio = 0.03
TEPA/ _SiO2 ratio = 0.06
Cu/ _SiO2 ratio = 0.04
Na/ _SiO2 ratio = 0.16
_H2O / _SiO2 ratio = 20
TACHOH/TACH ⁺ ratio = 0.25
The crystallized product is a copper-containing CHA-type zeolite (copper-supported CHA-type zeolite), and has a SiO ₂ /Al ₂ O ₃ ratio of 20.1, a Cu/Al ₂ O ₃ ratio of 0.72, and a copper content of 3.0. 3% by weight, and an SDA/SiO ₂ ratio of 0.097. Moreover, the yield was 98.2%.

Example 3
DMECHBr, copper sulfate, EDPTA, 48% aqueous sodium hydroxide solution, pure water, and amorphous aluminosilicate (SiO ₂ /Al ₂ O ₃ ratio = 17.8), and the following molar composition A crystallized product was obtained in the same manner as in Example 1, except that the raw material composition having

_SiO2 / _Al2O3 ratio ₌ 17.8
DMECHBr/ _SiO2 ratio = 0.12
EDPTA/ _SiO2 ratio = 0.06
Cu/ _SiO2 ratio = 0.04
Na/ _SiO2 ratio = 0.20
_H2O / _SiO2 ratio = 18
TACHOH/TACH ⁺ ratio = 0.00
The crystallized product is a copper-containing CHA-type zeolite (copper-supported CHA-type zeolite), and has a SiO ₂ /Al ₂ O ₃ ratio of 17.6, a Cu/Al ₂ O ₃ ratio of 0.51, and a copper content of 2.0. 8% by weight, and an SDA/SiO ₂ ratio of 0.080. Moreover, the yield was 98.9%.

Example 4
Crystals were formed in the same manner as in Example 1 except that amorphous aluminosilicate (SiO ₂ /Al ₂ O ₃ ratio = 20.1) was used and a raw material composition having the following molar composition was used. I got a monster.

_SiO2 / _Al2O3 ratio ₌ 20.1
DMECHOH/ _SiO2 ratio = 0.03
DMECHBr/ _SiO2 ratio = 0.12
Na/ _SiO2 ratio = 0.16
_H2O / _SiO2 ratio = 18
TACHOH/TACH ⁺ ratio = 0.00
The crystallized product is a copper-containing CHA-type zeolite (copper-supported CHA-type zeolite), and has a SiO ₂ /Al ₂ O ₃ ratio of 19.8, a Cu/Al ₂ O ₃ ratio of 0.59, and a copper content of 2.0. 8% by weight, and an SDA/SiO ₂ ratio of 0.098. Moreover, the yield was 98.4%.

Examples 5-8
The copper-containing CHA-type zeolites obtained in Examples 1 to 4 were calcined in the air at 600° C. for 4 hours to obtain the calcined copper-containing CHA-type zeolites, and the copper-containing CHA-type zeolites of Examples 5 to 8, respectively. bottom. The SDA/ _SiO2 ratios are 0.006 (Example 5), 0.005 (Example 6), 0.010 (Example 7) and 0.006 (Example 8), respectively, and _{the SiO2} / Al ₂ O ₃ ratio, Cu/Al ₂ O ₃ ratio and copper content were the same as before firing.

Comparative example 1
A crystallized product was obtained in the same manner as in Example 2, except that a raw material composition having the following molar composition was used.

_SiO2 / _Al2O3 ratio ₌ 20.5
DMECHBr/ _SiO2 ratio = 0.03
DMECHOH/ _SiO2 ratio = 0.09
TEPA/ _SiO2 ratio = 0.06
Cu/ _SiO2 ratio = 0.04
Na/ _SiO2 ratio = 0.16
_H2O / _SiO2 ratio = 20
TACHOH/TACH ⁺ ratio = 0.75
The obtained crystallized product was MOR-type zeolite.

Comparative example 2
Crystallization was performed in the same manner as in Example 1, except that DMECHBr was not used and a raw material composition having the following molar composition was used.

_SiO2 / _Al2O3 ratio ₌ 20.5
TEPA/ _SiO2 ratio = 0.06
Cu/ _SiO2 ratio = 0.04
Na/ _SiO2 ratio = 0.16
_H2O / _SiO2 ratio = 20
In this comparative example, the raw material composition was not crystallized and the product was amorphous.

From Comparative Example 1, it was confirmed that MOR-type zeolite was crystallized and CHA-type zeolite was not obtained when a raw material composition having a high TACHOH/TACH ⁺ ratio was used. Moreover, from Comparative Example 1, it was confirmed that CHA-type zeolite was not crystallized even when DMECH salt was not used as SDA.

Comparative example 3
Crystallization was performed in the same manner as in Example 1 except that the composition ratio of the raw material composition was changed to obtain a raw material composition having the following molar composition.

_SiO2 / _Al2O3 ratio ₌ 20.5
DMECHBr/ _SiO2 ratio = 0.12
TEPA/ _SiO2 ratio = 0.06
Cu/ _SiO2 ratio = 0.04
Na/ _SiO2 ratio = 0.08
_H2O / _SiO2 ratio = 20
TACHOH/TACH ⁺ ratio = 0.00
Since this comparative example had a Na/SiO ₂ ratio of less than 0.10, the raw material composition did not crystallize and the product was amorphous.

Comparative example 4
A crystallized product was obtained in the same manner as in Example 1, except that a raw material composition having the following molar composition was used.

_SiO2 / _Al2O3 ratio ₌ 20.5
DMECHBr/ _SiO2 ratio = 0.12
TEPA/ _SiO2 ratio = 0.06
Cu/ _SiO2 ratio = 0.04
Na/ _SiO2 ratio = 0.24
_H2O / _SiO2 ratio = 20
TACHOH/TACH ⁺ ratio = 0.00
The obtained crystallized product was MOR-type zeolite.

From this, it was confirmed that even with a raw material composition containing DMECH ^{3 +} , copper-containing CHA-type zeolite does not crystallize when the Na/SiO ₂ ratio exceeds the range of the CHA manufacturing method.

Comparative example 5
A CHA-type zeolite was produced based on the preferred synthesis range described in Table 1 of Japanese Patent No. 6791758. That is, TMAdAOH, copper sulfate, TEPA, fumed silica, and aluminum hydroxide were used to mix raw material compositions having the following molar compositions to obtain raw material compositions having the following molar compositions.

_SiO2 / _Al2O3 ratio ₌ 34.0
TMAdAOH/ _SiO2 ratio = 0.50
TEPA/ _SiO2 ratio = 0.03
Cu/ _SiO2 ratio = 0.03
Na/ _SiO2 ratio = 0.00
_H2O / _SiO2 ratio = 20
After mixing SSZ-13 (CHA-type zeolite) with the obtained raw material composition so that the seed crystal content is 1.0% by mass, 50 g of the raw material composition is filled in an 800 mL sealed container, The vessel was rotated at 55 rpm and reacted at 145° C. for 144 hours. The resulting crystallized product was subjected to solid-liquid separation, washed with deionized water, and then dried overnight at 110° C. in air. The crystallized product is a copper-containing CHA-type zeolite, has a SiO ₂ /Al ₂ O ₃ ratio of 29.4, a Cu/Al ₂ O ₃ ratio of 1.13, a copper content of 3.7% by mass, and SDA/ The _SiO2 ratio was 0.008. Moreover, the yield was 86.5%.

The resulting CHA-type zeolite was calcined in air at 600° C. for 4 hours to obtain a calcined copper-containing CHA-type zeolite, which was used as the zeolite of this comparative example.

The calcined copper-containing CHA-type zeolites obtained in Examples 5 to 8 and Comparative Example 5 were pretreated and subjected to H ₂ -TPR measurement. The results of the H ₂ -TPR measurements are shown in the table below. The TPR spectrum of the copper-containing CHA-type zeolite of Example 8 is shown in FIG.

Ｈ_２－ＴＰＲの結果より、実施例５乃至８はスペクトル面積比が０．０５以上０．６０以下であるのに対し、比較例５はスペクトル面積比が０であることが確認できた。

From the results of H ₂ -TPR, it was confirmed that Examples 5 to 8 had a spectral area ratio of 0.05 or more and 0.60 or less, while Comparative Example 5 had a spectral area ratio of 0.

Claims (6)

A structure directing agent source containing at least N,N,N-trialkylcyclohexylammonium cations, a polyamine source, a copper source, an alumina source, a silica source, a sodium source and water, wherein the molar ratio of silica to alumina is 24 or less. , the molar ratio of sodium to silica is 0.10 or more and 0.23 or less, and the molar ratio of the N,N,N-trialkylcyclohexylammonium cation hydroxide to the N,N,N-trialkylcyclohexylammonium cation A method for producing a CHA-type zeolite, comprising the step of crystallizing a composition having a is 0.7 or less to obtain a crystallized product. The manufacturing method according to claim 1, wherein the composition comprises at least amorphous aluminosilicate. The production method according to claim 1 or 2, wherein the polyamine source is at least one of tetraethylenepentamine and N,N'-bis(3-aminopropyl)ethylenediamine. The production method according to claim 1 or 2, wherein said N,N,N-trialkylcyclohexylammonium cation is N,N,N-dimethylethylcyclohexylammonium cation. The copper content of the CHA-type zeolite is more than 0% by mass and 6.0% by mass or less, and the ratio of the area of the TPR spectrum at 450 ° C. or higher and 800 ° C. or lower to the area of the TPR spectrum at 100 ° C. or higher and 800 ° C. or lower. is 0.05 or more and 0.60 or less. The copper content is more than 0% by mass and 6.0% by mass or less, and the ratio of the area of the TPR spectrum at 450°C to 800°C to the area of the TPR spectrum at 100°C to 800°C is 0.05 or more. A CHA-type zeolite of 0.60 or less.

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