RU2776180C1 - Cha-containing zeolite jmz-1 and methods for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a CHA-containing zeolite JMZ-1 containing a structure-directing agent (SDA) in the frame structure and to a calcined zeolite (JMZ-1C). The invention also relates to methods for producing JMZ-1 and JMZ-1C and methods for applying the calcined zeolite JMZ-1C as a catalyst. Described is a zeolite for purifying spent gas with a CHA-type frame structure, wherein the zeolite constitutes an aluminosilicate with a silicon oxide and aluminium oxide ratio (SAR) from 10 to 50, wherein the zeolite has a characteristic X-ray powder diffraction pattern before the removal of the template agent by calcination, containing at least the following diffraction peaks (in degrees 2θ (± 0.2), wherein relative intensity values are specified in parentheses) at the positions: 9.55 (VS), 16.27 (VS), 20.99 (VS), 24.65 (M) and 31.22 (M), wherein the zeolite has characteristic X-ray diffractometry data after the removal of the template agent by calcination, containing at least the following peaks (in degrees 2θ, wherein relative intensity values are specified in parentheses) at the positions: 9.59 (VS), 13.03 (M), 16.21 (W), 17.99 (W), 20.83 (M–S), 23.31 (W), 25.24 (W), 26.22 (W), 30.98 (M–W) and 31.43 (W) ±0.2, where the relative intensity is based on the strongest line of the X-ray diffraction pattern, assigned a value of 100, and is defined as (W) [weak]: below 20; (M) [medium]: in the range of 20 to 40; (S) [strong]: in the range of 40 to 60 and (VS) [very strong]: above 60; and wherein the template agent contains trimethyl(cyclohexylmethyl) ammonium cations.

EFFECT: metal-containing JMZ-1C has an increased SCR activity compared to CHA-structure zeolites with the same metal content and comparable silicon dioxide and aluminium oxide ratios (SAR).

20 cl, 3 ex, 9 tbl, 12 dwg

Description

Scope of the invention

The present invention relates to CHA-containing zeolite JMZ-1 containing structure-forming agent (SDA) in the framework structure, and calcined zeolite (JMZ-1C). The present invention also relates to methods for producing JMZ-1 and JMZ-1C and methods for using JMZ-1C calcined zeolite as a catalyst.

Prerequisites for the creation of the invention

Zeolites are crystalline materials built from repeating TO ₄ tetrahedral unit cells, where T is most commonly Si, Al, or P (or combinations of tetrahedral unit cells). These unit cells form bonds with each other to form frameworks having regular intracrystalline cavities and/or channels with molecular dimensions. Aluminosilicates contain Si and Al as T. Various types of synthetic zeolites have been synthesized, each with a unique framework based on the particular configuration of its tetrahedral unit cells. The International Zeolite Association (IZA) has assigned each topological type a unique three-letter code (eg CHA) according to the IUPAC nomenclature (http://www.iza-structure.org/databases/).

Zeolites have many industrial applications, and zeolites with certain framework structures, such as CHA, are known to be effective catalysts for cleaning flue gas in industrial applications, including internal combustion engines, gas turbines, coal-fired power plants, and the like. In one example, the content of oxides of nitrogen (NO _x ) in the exhaust gas can be controlled by a so-called selective catalytic reduction (SCR) process in which NO _x compounds in the exhaust gas are brought into contact with a reducing agent in the presence of a zeolite catalyst.

Synthetic topology-type CHA zeolites prepared as aluminosilicate compositions are prepared using structure forming agents (SDA), also referred to as "templates" or "template agents". SDA agents used in the preparation of CHA-type aluminosilicate materials are typically complex organic molecules that organize or arrange the molecular shape and structure of the zeolite framework. In general, SDA can be thought of as the shape around which zeolite crystals form. After crystal formation, SDA agents are removed from the internal structure of the crystals, leaving a molecularly porous aluminosilicate backbone.

In typical synthesis methods, solid zeolite crystals are precipitated from a reaction mixture that contains framework-forming reagents (eg, a source of silicon and a source of aluminum), a source of hydroxide ions (eg, NaOH), and SDA. To achieve the desired crystallization, such synthesis methods are usually implemented within a few days (depending on factors such as crystallization temperature). After crystallization is completed, the solid precipitate containing zeolite crystals is separated from the mother liquor, which is disposed of. This disposal mother liquor contains unused SDA, which often decomposes due to harsh reaction conditions, and unreacted silica.

US Pat. No. 4,544,538 relates to crystalline zeolite SSZ-13, obtained from organic nitrogen-containing cations, which are derived from 1-adamantamine, 3-quinuclidinol and 2-exoaminonorbornane. SSZ-13 has a chabazite crystal structure. Characteristic X-ray diffraction (XRD) lines of unfired SSZ-13 zeolites with an organic template component present are shown in Table 1 of US Pat. No. 4,544,538 and shown below in Table 1.

Table 1

2θ d(A) 100 I/Io 2θ d(A) 100 I/Io 9.57 9.24 61 22.72 3.91 eight 14.06 6.30 21 25.01 3.56 69 16.23 5.46 80 26.30 3.589 eighteen 17.82 4.98 24 31.00 2.885 47 20.87 4.26 100 31.29 2.859 21 22.14 4.01 9

Characteristic X-ray diffraction (XRD) lines of calcined SSZ-13 zeolites from which the organic template component has been removed are shown in Table 2 of US Pat. No. 4,544,538 and are shown in Table 2 below.

table 2

2θ d(A) 100 I/Io 2θ d(A) 100 I/Io 9.62 9.19 100 23.36 3.808 6 13.04 6.79 32 25.23 3,530 eighteen 16.22 5.46 eighteen 26.26 3.394 eleven 17.99 4.93 16 31.02 2,883 27 20.87 4.26 fifty 31.44 2,846 13

US Pat. No. 9,636,667 relates to a process for preparing a CHA-type zeolite material containing YO ₂ and X ₂ O ₃ , wherein the process comprises the steps of: (1) providing a mixture containing one or more sources of YO ₂ , one or more sources of X ₂ O ₃ and one or more compounds containing a tetraalkylammonium cation R ¹ R ² R ³ R ⁴ N ⁺ as a structurant; (2) crystallizing the mixture obtained in step (1) to obtain a CHA-type zeolite material; where Y is a tetravalent element and X is a trivalent element, where R ¹ , R ² and R ³ are independently alkyl, where R ⁴ is cycloalkyl, and where the mixture obtained in step (1) does not contain any or a significant amount of a source of Z ₂ O ₅ where Z is P, as well as zeolite materials that can be obtained in accordance with the method of the invention, and their use. Characteristic lines of X-ray diffraction (XRD) zeolite material with a framework structure type CHA contain at least the following reflections are shown in table 3 of US patent No. 9,636,667.

Table 3

Bragg angle 2θ/°
[CuK(α1)] Intensity (%) 9.44–9.88 29–92 16.03–16.55 32–79 17.81–18.13 12–42 20.62–21.30 100 25.02–25.42 25–70 30.83–31.43 39–73

There is a need to develop new zeolites having the basic structure of known zeolites, minor changes in the structure of which can affect one or more of the catalytic properties of the zeolite. In some instances, although minor changes in structure may not be apparent using commonly used analytical techniques, it is possible to improve the catalytic activity of a structurally modified zeolite compared to closely related analogous zeolites. Surprising improvements in the catalytic activity of such structurally modified zeolites can bring engine exhaust gas compositions into compliance with various regulatory requirements.

Statement of the Invention

In the first aspect of the invention, a JMZ-1 zeolite with a CHA-type framework structure is provided, where the zeolite has a composition with a molar ratio: SiO ₂ : (n)Y ₂ O ₃ , where Y = Al, Fe, B or Ga and n = 0–0 ,1, wherein (a) the X-ray powder diffraction pattern prior to removal of the template agent by calcination contains at least the following diffraction peaks (in degrees 2θ (±0.2), with relative intensities in parentheses) at positions: 9.55 (VS) , 16.27 (VS), 20.99 (VS), 24.65 (M), and 31.22 (M) ± 0.2, and (b) the X-ray diffraction data after removal of the template agent by calcination contain at least the following peaks (in degrees 2θ, with relative intensities in brackets) at positions: 9.59 (VS), 13.03 (M), 16.21 (W), 17.99 (W), 20.83 (M –S), 23.31 (W), 25.24 (W), 26.22 (W), 30.98 (M–W), and 31.43 (W) ± 0.2, where relative intensity is based on the strongest line of the X-ray diffraction pattern, which is assigned a value of 100, and is defined as (W) [weak]: less than 20; (M) [medium]: in the range of 20-40; (S) [strong]: in the range of 40–60; and (VS) [very strong]: more than 60.

Also proposed is a composition containing JMZ-1 zeolite with a framework structure of the CHA type and a structure-forming agent (SDA), where SDA is inside the framework structure, and the specified zeolite has a composition with a molar ratio: SiO ₂ : (n)Y ₂ O ₃ , where Y = Al, Fe, B or Ga and n = 0–0.1, and its characteristic X-ray powder diffraction pattern contains peaks at the 2-theta positions 9.55 (VS), 16.27 (VS), 20.99 (VS) , 24.65 (M) and 31.22 (M) ± 0.2, with relative intensity values given in brackets.

In a second aspect of the invention, there is provided a calcined zeolite (JMZ-1C) containing a framework structure comprising a framework structure of the CHA type having a composition with a molar ratio of: SiO ₂ : (n)Y ₂ O ₃ where Y = Al, Fe, B or Ga and n = 0–0.1, and its characteristic X-ray powder diffraction pattern contains peaks at the 2-theta positions 9.59 (VS), 13.03 (M), 16.21 (W), 17.99 (W), 20.83 (M–S), 23.31 (W), 25.24 (W), 26.22 (W), 30.98 (M–W) and 31.43 (W) ± 0.2, with relative intensity values indicated in parentheses.

In a third aspect of the invention, a composition is provided containing a mixture of water, a source of silica, a source of alumina, a base, an alkali metal cation, and trimethyl(cyclohexylmethyl)ammonium cations, the composition having a molar composition ratio of:

SiO ₂ / Al ₂ O ₃ 10–100 OH ^- / SiO ₂ 0.05–1 R/ _SiO2 0.05–0.5 Alkali metal cation / SiO ₂ 0.1–1.0 H ₂ O / SiO ₂ 5–80

where R is SDA, preferably trimethyl(cyclohexylmethyl) ammonium cations. This composition can be used to produce the zeolite of the first or second aspects of the present invention.

In a fourth second aspect of the present invention, there is provided a composition comprising a calcined zeolite of the second aspect of the present invention and one or more of a filler, a binder, a stabilizer, and a rheology modifier.

In a fifth second aspect of the present invention, a catalyst article is provided comprising: (a) a composition of the fourth aspect of the present invention; and (b) a monolithic substrate, on which is applied or in the structure of which the specified composition is included.

In a sixth aspect of the present invention, a system is provided comprising an engine that produces NOx, a catalyst article containing JMZ-1C or a metal-containing JMZ-1C, a conduit for directing flowing exhaust gas from the engine to the catalyst article, and a source of nitrogen decompound located before the catalyst article.

In a seventh aspect of the present invention, there is provided a method for generating JMZ-1, comprising:

a. forming a reaction mixture containing: (i) at least one source of alumina, (ii) at least one source of silicon dioxide, and (iii) a structurant (SDA) containing a trimethyl(cyclohexylmethyl)ammonium cation,

b. heating the reaction mixture and forming zeolite crystals having a CHA framework structure and a structurant, and a mother liquor, and

c. recovering at least a portion of the zeolite crystals from the mother liquor.

In the eighth aspect of the present invention, there is provided a method for producing calcined zeolite (JMZ-1C) of the second aspect of the present invention by calcining JMZ-1.

In a ninth aspect of the present invention, there is provided a method for purifying exhaust gas from an engine by bringing the exhaust gas into contact with JMZ-1C or JMZ-1C impregnated metal.

In a tenth aspect of the present invention, JMZ-1C or metal-containing JMZ-1C can stimulate the formation of methylamines in the reaction of methanol and ammonia and the conversion of methanol to lower olefins, in particular ethylene and propylene.

In an eleventh aspect of the present invention, the catalyst article for converting low molecular weight oxygenates to an olefin-rich hydrocarbon stream may comprise JMZ-1C or metal-containing JMZ-1C, wherein the JMZ-1C or metal-containing JMZ-1C is located on the support and/or within the structure.

Brief description of graphic materials

On FIG. 1 shows the X-ray diffraction pattern (XRD) of the sample
JMZ-1 obtained in example 1.

On FIG. 2 is a scanning electron microscopy (SEM) micrograph of the JMZ-1 sample obtained in Example 2.

On FIG. 3 is an X-ray diffraction pattern (XRD) of the calcined JMZ-1 (JMZ-1C) sample prepared in Example 2.

On FIG. 4 is a graph of % NOx conversion using fresh 3% Cu-containing CHA zeolites.

On FIG. 5 is a graph of N ₂ O concentration in exhaust gas passing over fresh 3% Cu-containing CHA zeolites.

On FIG. 6 is a graph of % NH ₃ conversion using fresh 3% Cu-containing CHA zeolites.

On FIG. 7 is a graph of % NOx conversion using 3% Cu-containing CHA zeolites hydrothermally aged at 900°C for 1 hour.

On FIG. 8 is a plot of N ₂ O concentration in exhaust gas passing over 3% Cu-containing CHA zeolites hydrothermally aged at 900 °C for 1 hour.

On FIG. 9 is a graph of % NH ₃ conversion using 3% Cu-containing CHA zeolites hydrothermally aged at 900°C for 1 hour.

On FIG. 10 is a graph of % NOx conversion using 3% Cu-containing CHA zeolites hydrothermally aged at 900°C for 3 hours.

On FIG. 11 is a plot of N ₂ O concentration in exhaust gas passing over 3% Cu-containing CHA zeolites hydrothermally aged at 900 °C for 3 hours.

On FIG. 12 is a graph of % NH ₃ conversion using 3% Cu-containing CHA zeolites hydrothermally aged at 900°C for 3 hours.

Detailed description of the invention

In the present description and the appended claims, the singular forms include references to the plural, unless the context clearly requires otherwise. Thus, for example, the reference to "catalyst" includes a mixture of two or more catalytic converters, etc.

Where a range or ranges are specified for various numeric elements, the specified range or ranges may include values unless otherwise specified.

As used herein, the term “zeolite” means a molecular sieve containing at least one tetravalent T atom or mixture of tetravalent T atoms (e.g., silicon, germanium, or mixtures thereof) and at least one trivalent T atom or mixtures of trivalent T -atoms (eg aluminum, boron, gallium, vanadium, iron or mixtures thereof). As used herein, the zeolites are preferably aluminosilicates whose framework structure consists of alumina and silicon oxide (ie, repeating tetrahedral unit cells of SiO ₄ and AlO ₄ ). The zeolite may contain within the backbones, pores and/or channels formed by the framework structure, cationic inorganic materials, including metals, and cationic or neutral organic particles (including structure-forming agents). It is believed that calcined zeolites do not contain structure-forming agents.

As used herein, the term "CHA" refers to the topological type of CHA recognized by the structure committee of the International Zeolite Association (IZA), and the term "CHA-zeolite" means an aluminosilicate in which the main crystalline phase is CHA. Other crystalline phases may also be present, but the main crystalline phase contains at least about 90 wt.% CHA, preferably at least about 95 wt.% CHA, and even more preferably at least about 97 or at least about 99 wt.% CHA. Preferably, the CHA molecular sieve is substantially free of other crystalline phases and is not an intergrowth of two or more types of framework structures. The term "substantially free" in relation to other crystalline phases means that the molecular sieve contains at least 99 wt.% CHA, where the weight percentage is based on the weight of the framework and does not include exchange metals.

The term "inside the framework structure" means that the material is located within one or more of the skeletons, pores and/or channels formed by the framework structure, but is not located within the framework that forms the structure of the zeolite.

The term "within the cores, pores and/or channels formed by the framework structure" means that the material (structure-forming agent, SDA) is located within one or more cores, pores and/or channels formed by the framework structure, but is not present in the framework structure of the zeolite.

The term "zeolite containing extralattice metal" refers to a zeolite in which the metal is on the surface and/or within the core and/or pores of the zeolite. It does not apply to zeolites in which the metal is in a framework that forms the zeolite.

The term "does not contain" means that the material in question "does not contain" any impurity, which may be present only in trace amounts, usually less than 1 wt.%, preferably less than 0.5 wt.%, more preferably <0.1 wt%.

The term "substantially free" means that the material in question does not contain a significant amount of said material. That is, the material in question is not present in an amount that could affect the basic physical and/or chemical properties of the material, in particular the ability of the material to selectively reduce or retain NOx. In some embodiments, the content of the material in question is less than 3 wt.%, preferably less than 1 wt.%, more preferably less than 0.5 wt.%, and even more preferably less than 0.1 wt.%.

In some embodiments, an alkali metal source, such as sodium, is not intentionally added to the synthesis mixture in order to ensure that the material is present in the mixture. The phrase "substantially free of alkali metals" or "free of alkali metals" in this document means that the alkali metal is not intentionally added to the synthesis mixture as an ingredient. The term "substantially alkali-free" or "alkali-free" catalyst as used herein essentially means that the catalyst material contains a negligible level of alkali metal relative to the intended catalytic activity. In some embodiments, the implementation of the JMZ-1 or JMZ-1C zeolite contains less than about 0.1 wt.% and preferably less than about 0.01 wt.% alkali metal, such as sodium or potassium.

In a first aspect of the present invention, a zeolite (JMZ-1) is provided, and having a CHA-type framework structure, wherein the zeolite has a composition with a molar ratio of: SiO ₂ : (n)Y ₂ O ₃ , where Y = Al, Fe, B or Ga and n = 0–0.1, wherein (a) the X-ray powder diffraction pattern prior to removal of the template agent by calcination contains at least the following diffraction peaks (in degrees 2θ (±0.2), with relative intensities in parentheses) at positions: 9 .55 (VS), 16.27 (VS), 20.99 (VS), 24.65 (M), and 31.22 (M) ± 0.2, and (b) X-ray diffraction data after template agent removal by calcination contain at least the following peaks (in degrees 2θ, with relative intensities in brackets) at positions: 9.59 (VS), 13.03 (M), 16.21 (W), 17.99 (W), 20.83 (M–S), 23.31 (W), 25.24 (W), 26.22 (W), 30.98 (M–W) and 31.43 (W) ± 0.2, where the relative intensity is based on the strongest line of the X-ray diffraction pattern, which is assigned the value 100, and defined as (W) [weak]: less than 20; (M) [medium]: in the range of 20-40; (S) [strong]: in the range of 40–60; and (VS) [very strong]: more than 60.

The characteristic X-ray powder diffraction pattern of the zeolite of the first aspect of the present invention may further contain peaks at the 2-theta positions of 13.15 (W), 13.91 (W), 17.50 (W), 19.18 (W), 21.95 ( W), 22.87 (W), 23.34 (W), 26.49 (W), 28.05 (W) and 30.43 (W) ± 0.2, with relative intensity values indicated in brackets.

On FIG. 1 shows an X-ray powder diffraction (XRD) pattern of JMZ-1. Feature lines are presented in Table 4, where primary feature lines are denoted by *.

Table 4. Characteristic lines of the X-ray powder diffraction (XRD) zeolite JMZ-1 immediately after production (containing the template).

degrees
2θ ^(a) I/io Relative value of I/Io degrees
2θ ^(a) I/io Relative
I/Io value 9.55 100 VS 22.87 16 W 13.15 fourteen W 23.34 eight W 13.91 eleven W 24.65 29 M 16.27 73 VS 26.49 13 W 17.50 fifteen W 28.05 5 W 19.18 eight W 30.40 fourteen W 20.99 99 VS 31.22 33 M 21.95 eight W

(a) = ±0.2

The relative intensity is based on the strongest line of the X-ray diffraction pattern, which is assigned a value of 100. W (weak): less than 20; M (medium): 20-40; S (strong): 40-60; and VS (very strong): more than 60.

The characteristic X-ray powder diffraction pattern of the zeolite of the first aspect of the present invention may further contain peaks at the 2-theta positions of 13.15 (W), 13.91 (W), 17.50 (W), 19.18 (W), 21.95 ( W), 22.87 (W), 23.34 (W), 28.05 (W), and 30.40 (W) ± 0.2, with relative intensity values given in brackets.

X-ray powder diffraction patterns were obtained using standard techniques. The radiation was a doublet CuKα radiation, and a spectrometer with a scintillation counter with a chart pen recorder was used for registration. Peak heights I and their positions in degrees 2θ, where θ is the Bragg angle, were read from the paper tape of the spectrometer. From these measured values, the relative intensity values 100 I/I ₀ can be calculated, where I ₀ is the intensity of the strongest line or peak and d is the interplanar spacing in angstroms corresponding to the detected lines. The X-ray diffraction pattern from Table 4 is typical for all types of compositions of the JMZ-1 family (containing the template). Slight variations in line values in the diffraction patterns shown in the tables or figures may also be the result of variations in the organic compound used in the preparation and variations in the silica to alumina molar ratio between samples. Despite these slight variations, the basic crystal structures in the as-prepared and fired state remain essentially unchanged.

The characteristic lines (degrees, 2θ, and relative intensity) of the zeolite described in US Pat. No. 9,636,667 are presented in Table 5 along with the corresponding peaks of the JMZ-1 zeolite in the as-prepared state containing structure-forming agents (SDA).

Table 5

JMZ-1 US 9,636,667 Degrees, 2θ I/io
% Degrees, 2θ I/io
% 9.55 100 9.44–9.88 29–92 16.27 73 16.03–16.55 32–79 < 2 17.81–18.13 12–42 20.99 100 20.62–21.30 100 < 2 25.02–25.42 25–70 31.22 33 30.83–31.43 39–73

JMZ-1 is novel compared to the zeolites described in U.S. Patent No. 9,636,667, which requires that the X-ray diffraction pattern (XRD) has six peaks in the above ranges and that they have intensities compared to the peak with the (2θ) position at range of 20.62-21.30 degrees, with this peak being the highest and having a relative intensity of 100. JMZ-1 differs from the zeolites described in US Pat. No. 9,636,667 in the following features:

JMZ-1 has no peak (intensity < 2% of maximum intensity) in the ranges 17.81–18.1 and 25.02–25.42;

JMZ-1 has a position (2θ) peak in the range of 9.44-9.88 degrees, but the relative intensity of the JMZ-1 peak is 100, which exceeds the range of 29-92 required for US Pat. No. 9,636,667 zeolites; and

JMZ-1 has a position (2θ) peak in the 30.83-31.43 degree range, but the relative peak intensity of JMZ-1 is 33, which is less than the 39-73 range required for US Pat. No. 9,636,667 zeolites.

Thus, the X-ray diffraction pattern (XRD) of JMZ-1 differs from the X-ray diffraction pattern (XRD) of US Pat. No. 9,636,667 zeolites.

This zeolite may be an aluminosilicate (Y=Al).

If the zeolite is an aluminosilicate, it may have a silica to alumina ratio (SAR) of about 10 to about 50, preferably 15-30, more preferably 20-25.

The structurant may contain trimethyl(cyclohexylmethyl) ammonium cations.

The JMZ-1 zeolite has a crystal structure and has a CHA framework, and this framework contains tetravalent silicon oxide, trivalent aluminum oxide, and trimethyl(cyclohexylmethyl)ammonium cation is embedded in its crystal structure, and the zeolite crystals are anhydrous and do not contain substituted or unsubstituted anions 5 ,4-azonium; and ammonium anions having substituents selected from polycyclic bridged compounds, cycloaryls, heterocyclic compounds, cycloalkyls other than cyclohexylmethyl, and C2-C4 alkyls. The composition may contain a zeolite including these elements.

The zeolite framework may be free or substantially free of: (i) transition metals, including antimony, bismuth, chromium, cobalt, copper, iron, manganese, molybdenum, nickel, niobium, tin, titanium, tungsten, vanadium, zinc, and zirconium; (ii) noble metals, including platinum group metals (PGMs) such as indium, palladium, platinum, rhodium and ruthenium, and precious metals such as gold and silver; and (iii) rare earth metals such as cerium, erbium, europium, lanthanum, neodymium, praseodymium, terbium, ytterbium and yttrium.

The zeolites of the present invention are not silicon aluminophosphates (SAPO) and therefore do not contain significant amounts of phosphorus in their framework. Thus, zeolite frameworks do not contain phosphorus in the form of a regular repeating unit cell and/or do not contain phosphorus in an amount capable of influencing the basic physical and/or chemical properties of the material, in particular, the ability of the material to selectively reduce NO _x concentration over a wide temperature range. . The content of phosphorus in the frame may be less than about 1 wt.%, preferably less than 0.1 wt.%, most preferably less than 0.01 wt.% based on the total weight of the zeolite.

The CHA topological type zeolite of the present invention may contain low levels of iron. The iron may be present in the tetrahedral position of the framework and/or in the form of cationic particles. The amount of iron contained in the tetrahedral position of the framework and/or in the form of cationic particles after synthesis is usually less than about 0.1 wt.%.

Also proposed is a composition containing JMZ-1 zeolite with a framework structure of the CHA type and a structure-forming agent (SDA), where SDA is inside the framework structure, and the specified zeolite has a composition with a molar ratio: SiO ₂ : (n)Y ₂ O ₃ , where Y = Al, Fe, B or Ga and n = 0–0.1, and its characteristic X-ray powder diffraction pattern contains peaks at the 2-theta positions 9.55 (VS), 16.27 (VS), 20.99 (VS) , 24.65 (M) and 31.22 (M) ± 0.2, with relative intensity values given in brackets.

In a second aspect of the invention, a zeolite (JMZ-1C) with a CHA-type framework structure is provided, having a composition with a molar ratio: SiO ₂ : (n)Y ₂ O ₃ , where Y = Al, Fe, B or Ga and n = 0–0 ,1, and its characteristic X-ray powder diffraction pattern contains peaks at the 2-theta positions 9.59 (VS), 13.03 (M), 16.21 (W), 17.99 (W), 20.83 (M– S), 23.31 (W), 25.24 (W), 26.22 (W), 30.98 (M–W) and 31.43 (W) ± 0.2, with relative values in brackets intensity, while the specified zeolite does not contain structure-forming agent (SDA). Said zeolite is preferably a calcined zeolite.

JMZ-1C is novel compared to the zeolites described in US Pat. No. 9,636,667, which require that the X-ray diffraction pattern (XRD) has six peaks in the above ranges and that they have intensities compared to the peak with the (2θ) position at range of 20.62-21.30 degrees, with this peak being the highest and having a relative intensity of 100. Feature lines (position, 2θ, degrees, and relative intensity) of the zeolite described in US Pat. No. 9,636,667 are presented in Table 6 together with corresponding peaks of zeolite JMZ-1C.

Table 6

JMZ-1C US 9,636,667 degrees
2θ I/io
% degrees
2θ I/io
% 9.59 100 9.44–9.88 29–92 16.21 16 16.03–16.55 32–79 17.99 12 17.81–18.13 12–42 20.83 41 20.62–21.30 100 25.24 12 25.02–25.42 25–70 30.98 19 30.83–31.43 39–73

JMZ-1C differs from the zeolites described in US Pat. No. 9,636,667 in the following ways:

For JMZ-1C zeolite, the position (2θ) of the maximum intensity peak is 9.59 degrees, and for the zeolite of US Pat. No. 9,636,667, the position (2θ) of the maximum intensity peak is 20.62-21.30 degrees.

JMZ-1C has a position (2θ) peak in the range of 9.44-9.88 degrees, but the relative intensity of the JMZ-1 peak is 100, which exceeds the range of 29-92 required for US Pat. No. 9,636,667 zeolites.

JMZ-1C has a position (2θ) peak in the range of 16.03-16.55 degrees, but the relative intensity of the JMZ-1 peak is 16, which is less than the 32-79 range required for US Pat. No. 9,636,667 zeolites.

JMZ-1C has a peak at a (2θ) position in the range of 20.62-21.30 degrees, but the relative peak intensity of JMZ-1 is 41, which is less than 100, i.e., the peak intensity that is required for the zeolites of US Patent No. 9,636,667 .

JMZ-1C has a position (2θ) peak in the range of 25.02-25.42 degrees, but the relative peak intensity of JMZ-1 is 12, which is less than the 25-70 range required for US Pat. No. 9,636,667 zeolites.

JMZ-1C has a position (2θ) peak in the range of 30.83-31.43 degrees, but the relative peak intensity of JMZ-1 is 19, which is less than the 39-73 range required for US Pat. No. 9,636,667 zeolites.

Thus, the X-ray diffraction pattern (XRD) of JMZ-1C differs from the X-ray diffraction pattern (XRD) of US Pat. No. 9,636,667 zeolites.

The JMZ-1C zeolite may be an aluminosilicate. (Y = Al.)

JMZ-1C may preferably contain ions of one or more catalytic metals, which are introduced into the cavities, channels and/or pores of the zeolite by ion exchange or otherwise by impregnation. Examples of metals that can be introduced via ion exchange or impregnation after zeolite synthesis include: (i) transition metals including antimony, bismuth, chromium, cobalt, copper, iron, manganese, molybdenum, nickel, niobium, tin, titanium, tungsten, vanadium, zinc and zirconium; (ii) noble metals, including platinum group metals (PGMs) such as indium, palladium, platinum, rhodium and ruthenium, and precious metals such as gold and silver; (iii) alkaline earth metals such as barium, beryllium, calcium, magnesium and strontium; and (iv) rare earth metals such as cerium, erbium, europium, lanthanum, neodymium, praseodymium, terbium, ytterbium and yttrium. Preferred transition metals introduced after synthesis by ion exchange are selected from the group consisting of cobalt, copper, iron, manganese, nickel and mixtures thereof.

Particularly preferred exchange metals include copper and iron, especially in combination with calcium and/or cerium, and especially if the transition metals (T _M ) and alkali metals ( _AM ) are present in a T _M : A _M molar ratio of about 15:1 to about 1:1, e.g., about 10:1 to about 2:1, about 10:1 to about 3:1, or about 6:1 to about 4:1.

The transition metal may be present in an amount of from about 0.1 to about 10 wt.%, for example, from about 0.5 to about 5 wt.%, from about 0.1 to about 1.0 wt.%, from about 2, 5 to about 3.5 wt.% and from about 4.5 to about 5.5 wt.%, and the mass percentage is indicated based on the total weight of the zeolite material.

Zeolite JMZ-1C can be used as a catalyst in certain applications. Dried JMZ-1 crystals are preferably fired, but can also be used without firing. Zeolite JMZ-1C, preferably calcined (calcined), can be used without metal introduction by ion exchange after synthesis or with metal introduction by ion exchange after synthesis, preferably with metal introduction by ion exchange after synthesis.

In some aspects of the present invention, a JMZ-1C containing catalyst is provided that is free or substantially free of any exchangeable metals, in particular metals introduced after synthesis via ion exchange or impregnation.

The metals introduced after synthesis can be added to the molecular sieve by any known method such as ion exchange, impregnation, isomorphic substitution, and the like.

These exchangeable metal cations are different from the metals that make up the molecular framework of the zeolite, and thus, metal exchange zeolites are different from metal-substituted zeolites.

The catalytic properties of the calcined zeolite (JMZ-1C) containing an exchange metal such as copper differ from those of other CHA structured zeolites having a comparable SAR after hydrothermal aging. A comparable SAR ratio is a SAR value that is within two units, preferably within three units, more preferably within four units. As shown in Example 3 below, the catalytic activity of a calcined zeolite (JMZ-1C) containing an exchange metal such as copper and hydrothermal aging at 900°C for 3 hours can provide one or more of:

a. at least 10% higher NOx conversion at a temperature in the range of about 175°C to about 225°C compared to a CHA catalyst having a comparable SAR ratio (SAR = 22-25); and

b. at least 20% higher NH ₃ conversion at a temperature in the range of about 165°C to about 225°C compared to a CHA catalyst having a comparable SAR ratio (SAR = 22-25).

After hydrothermal aging at 900°C for three hours, JMZ-1C containing 3% Cu introduced by impregnation can provide increased NOx reduction, especially at temperatures below 225°C, compared to chabazites containing 3% Cu and having a comparable SAR ratio (SAR = 22–25). After being hydrothermally aged at 900°C for three hours, JMZ-1C containing 3% Cu introduced by impregnation can provide improved NH ₃ conversion, especially at temperatures from 165°C to 225°C compared to zeolite with the structure CHA containing 3% Cu and having a comparable SAR ratio.

In a third aspect of the invention, a composition is provided containing a mixture of water, a source of silica, a source of alumina, a base, an alkali metal cation, and trimethyl(cyclohexylmethyl)ammonium cations, the composition having a molar composition ratio of:

SiO ₂ / Al ₂ O ₃ 10–100 OH ^- / SiO ₂ 0.05–1 R/ _SiO2 0.05–0.5 Alkali metal cation / SiO ₂ 0.1–1.0 H ₂ O / SiO ₂ 5–80

where R is SDA, preferably trimethyl(cyclohexylmethyl) ammonium cations.

Preferably the composition has a molar composition ratio:

SiO ₂ / Al ₂ O ₃ 15–70 OH ^- / SiO ₂ 0.1–0.7 R/ _SiO2 0.05–0.2 Alkali metal cation / SiO ₂ 0.15–0.65 H ₂ O / SiO ₂ 10–6

The composition may be a solution, a colloidal dispersion (colloidal sol), a gel or a paste, with a gel being the preferred option.

In a fourth aspect of the present invention, there is provided a composition comprising the calcined zeolite of the second aspect of the present invention and one or more of a filler, a binder, a stabilizer, and a rheology modifier.

The calcined zeolite may contain an extralattice transition metal or noble metal. The extralattice transition metal may be selected from the group consisting of Co, Cu, Fe, Mn, Mo, Nb, Ni, Ta, V, and W. Preferably, the extralattice transition metal is Cu or Fe.

The extralattice noble metal may be selected from Ag, Au, Ir, Os, Pd, Pt, Rh, or Ru.

The calcined zeolite may contain from about 0.1% to about 5% by weight of a transition metal or noble metal.

The calcined zeolite may contain from about 0.1% to about 5% by weight of ionic copper.

The calcined zeolite may further contain Ca, Ce, or a combination of Ca and Ce.

The catalysts of the present invention are particularly applicable to heterogeneous catalytic reaction systems (ie, in which a solid catalyst is contacted with a gaseous reactant). To increase contact surface area, mechanical stability and/or fluid flow characteristics, catalysts may be located on a support, preferably on a porous support, and/or within the support. The porous oxide coating containing the catalyst can be applied to an inert substrate such as corrugated metal plate or honeycomb cordierite brick. In an alternative embodiment, the catalyst is mixed together with other components such as fillers, binders and reinforcing agents into an extrudable paste which is then extruded through an extruder die to form a honeycomb brick. Accordingly, the catalytic article may comprise a CHA catalyst as described herein supported on and/or incorporated into a support.

In some aspects of the present invention, a porous oxide catalytic coating is provided. The porous oxide coating containing the JMZ-1C calcined zeolite described herein is preferably a solution, suspension or slurry. Suitable coatings include surface coatings, partial penetration coatings, full penetration coatings, or any combination thereof.

The porous oxide coating may also include non-catalytic components such as fillers, binders, stabilizers, rheology modifiers, and other additives, including one or more of alumina, silica, non-zeolitic aluminosilicate, titanium oxide, zirconium oxide, cerium oxide. The catalyst composition may contain pore-forming agents such as graphite, cellulose, starch, polyacrylate, and polyethylene, and the like. These additional components do not necessarily catalyze the desired reaction, but they do increase the performance of the catalyst material, for example, by increasing its operating temperature range, increasing the contact surface area ^of the catalyst, increasing the adhesion ^of the catalyst to the ^substrate , and the like. , >1.7 g/in ³ or >2.00 g/in ³ and preferably <3.5 g/in ³ eg <2.5 g/in ³ . The porous oxide coating may be applied to the substrate at a load of about 0.8 to 1.0 g/in ³ , 1.0 to 1.5 g/in ³ , or 1.5 to 2.5 g/in ³ .

In a fifth aspect of the present invention, there is provided a catalyst article comprising: (a) a composition of the fourth aspect of the present invention; and (b) a monolithic substrate, on which is applied or in the structure of which the specified composition is included.

Two of the most common substrate structures on which a catalyst can be applied are the honeycomb substrate and the plate. Preferred types of substrates, especially for automotive applications, include flow-through monoliths and flow wall monoliths. The flow monoliths have a so-called honeycomb geometry that contains a plurality of adjacent parallel channels open at both ends and substantially extending from the inlet surface to the outlet surface of the substrate and providing a high surface area to volume ratio. Flow wall monoliths are similar to flow wall monoliths except that the ends of the channels in the flow wall monoliths are alternatively plugged to force gas flow through the porous walls which act as filters.

For certain applications, the honeycomb flow monolith preferably has a high honeycomb density, such as about 600 to about 800 honeycombs per square inch, and/or an average inner wall thickness of about 0.18 to about 0.35 mm, preferably about 0.20 up to about 0.25 mm. For some other applications, the honeycomb flow monolith preferably has a low honeycomb density, from about 150 to about 600 honeycombs per square inch, more preferably from about 200 to about 400 honeycombs per square inch. Preferably, the honeycomb monolith is porous.

Other materials that can be used as a substrate besides cordierite, silicon carbide, silicon nitride, ceramic, and metal include aluminum nitride, silicon nitride, aluminum titanate, α-aluminum oxide, mullite, such as acicular mullite, pollucite, such as Al ₂ OsZFe, Al ₂ O ₃ /Ni or B ₄ CZFe or composites containing segments of any two or more of them. Preferred materials include cordierite, silicon carbide and alumina titanate.

Plate type catalysts have lower pressure drops and are less prone to clogging and fouling than honeycomb type catalysts, which is an advantage in high efficiency stationary applications, but plate configurations can be much larger and more expensive. The honeycomb configuration is typically smaller than the plate configuration, which is an advantage in automotive applications, but has higher pressure drops and clogs more easily. The plate substrate may be constructed from metal, preferably corrugated metal.

The catalytic article can be manufactured by the method described herein. The catalytic article can be produced by a method which includes the steps of depositing a metal-containing calcined zeolite (JMZ-1C), preferably in the form of a porous oxide coating, on a support in the form of a layer before or after at least one additional layer of another composition, such as an ammonia oxidation catalyst. , an oxidation catalyst, a reduction catalyst, a scavenging component or an NO _x storage component, for exhaust gas purification. One or more catalyst layers on the support, including the CHA catalyst layer, are arranged in successive layers. As used herein, the term "in-line" in relation to supported catalyst layers means that each layer is in contact with adjacent layer(s) and that the catalyst layers are generally stacked on top of each other on the support.

The CHA catalyst may be disposed on the support as a first layer or zone, and another composition such as an oxidation catalyst, reduction catalyst, scavenging component, or NOx storage component may be disposed on the support as a second layer or zone. As used herein, the terms "first layer" and "second layer" are used to describe the relative positions of the catalyst layers in a catalyst article relative to the normal direction of travel of exhaust gases through and/or over the catalyst article. Under normal exhaust gas flow conditions, the exhaust gas contacts the first layer before coming into contact with the second layer. The second layer may be applied to the inert substrate as a bottom layer, and the first layer is a top layer that is applied over the second layer in a series of successive sublayers.

Before coming into contact with the second layer, the exhaust gas may enter (and hence contact with) the first layer and then return through the first layer to exit the catalyst component.

The first layer may be a first zone located on the upstream part of the substrate, and the second layer may be located on the substrate in the form of a second zone, and the second zone is located downstream of the first zone.

The catalytic article can be produced by a method which includes the steps of applying JMZ-1C to a substrate, preferably as a porous oxide coating, as the first zone and then applying at least one additional exhaust gas treatment composition to the substrate as the second zone. , wherein at least a portion of the first zone is located downstream of the second zone. In an alternative embodiment, the CHA catalyst composition may be applied to the support in a second zone downstream of the first zone containing the additional composition. Examples of additional compositions include oxidation catalysts, reduction catalysts, scavenging components (eg for sulphur, water, etc.) or NOx storage components.

To reduce the space occupied by the exhaust system, the individual components of the exhaust system may be configured to perform more than one function. For example, depositing an SCR catalyst on a flow wall filter substrate to form the SCRF, rather than on a flow substrate, reduces the overall size of the exhaust gas treatment system by having one substrate perform two functions, namely: catalytic reduction NO _x concentration in the exhaust gas; and mechanical removal of soot from the exhaust gas. This is the preferred use of calcined zeolite due to the stability of calcined zeolite after hydrothermal aging. The substrate may be a flow wall filter having a honeycomb structure or a partial flow filter. Flow wall filters are similar to honeycomb flow substrates in that they contain a plurality of contiguous parallel channels. However, the channels of the honeycomb flow substrates are open at both ends, while the channels of the flow wall substrates are plugged at one end, with the channels being plugged at opposite ends of adjacent channels in an alternating manner. Closing the ends of the channels in an alternating manner prevents the flow of gas entering through the inlet surface of the substrate directly through the channel and its outlet on the opposite side. Instead, the exhaust gas enters the front surface of the substrate and passes through about half of the channels, after which it passes under pressure through the walls of the channels, enters the second half of the channels and exits through the rear surface of the substrate.

The substrate wall has a porosity and pore size that is permeable to gases but, as the gas passes through the wall, traps most of the particulate matter, such as soot, from the gas. The preferred flow wall substrates are high efficiency filters. Flow wall filters useful in the present invention preferably have an efficiency of at least 70%, at least about 75%, at least about 80%, or at least about 90%. The efficiency may be from about 75% to about 99%, from about 75% to about 90%, from about 80% to about 90%, or from about 85% to about 95%. In this case, efficiency refers to soot and other particles of similar size, as well as concentrations of particulate matter that are typically present in conventional diesel engine exhaust gas. For example, the size of particulate matter in the exhaust gas of a diesel engine may be in the range of 0.05 µm to 2.5 µm. Thus, efficiency may be based on this range or some sub-range, such as 0.1 to 0.25 µm, 0.25 to 1.25 µm, or 1.25 to 2.5 µm.

Porosity is a measure of the percentage of free pore space in a porous substrate and is related to the back pressure in the exhaust system: in general, the lower the porosity, the higher the back pressure. The porous substrate preferably has a porosity of about 30% to about 80%, such as about 40% to about 75%, about 40% to about 65%, or about 50% to about 60%.

Pore interconnectivity, measured as a percentage of the total pore volume of the substrate, is the degree to which pores, voids, and/or channels are connected to each other to form continuous paths through the porous substrate, i.e., from inlet surface to outlet surface. The opposite measure of pore interconnectivity is the sum of the volume of closed pores and the volume of pores that have a channel extending to only one of the surfaces of the substrate. Preferably, the porous substrate has a pore interconnection volume of at least about 30%, more preferably at least about 40%.

The average pore size of the porous substrate is also of great importance in terms of filtration. The average pore size can be determined by any suitable means, including mercury porosimetry. The average pore size of the porous substrate must be high enough to help provide low back pressure, while still providing sufficient performance due to the properties of the substrate itself, by promoting a layer of carbon on the surface of the substrate, or by a combination of both factors. Preferred porous substrates have an average pore size of about 10 to about 40 microns, such as about 20 to about 30 microns, about 10 to about 25 microns, about 10 to about 20 microns, about 20 to about 25 microns, about 10 to about 15 microns; and about 15 to about 20 microns.

Generally, the preparation of an extruded solid, such as a honeycomb flow filter or a flow wall filter containing a JMZ-1C catalyst, involves mixing JMZ-1C, a binder, optionally an organic viscosity enhancing compound, into a homogeneous paste, which is then added to the binder/ the matrix component or its precursor, and optionally one or more of the stabilized cerium oxide and inorganic fibers. The mixture is compacted in a mixing or kneading apparatus or extruder. The blends contain organic additives such as binders, pore formers, plasticizers, surfactants, lubricants, dispersants as processing aids to improve wetting and hence a uniform batch. The resulting plastic material is then cast, in particular using an extrusion press or an extruder containing an extrusion die, and the resulting castings are dried and fired. Organic additives are "burned out" during the firing process of the extruded solid. The catalytically active calcined zeolite JMZ-1C can also be applied as a porous oxide coating to the extruded solid in one or more sublayers that are located on the surface or completely or partially penetrate the extruded solid.

The binder/matrix component is preferably selected from the group consisting of cordierite, nitrides, carbides, borides, intermetallics, lithium aluminosilicate, spinel, optionally doped alumina, silica source, titanium dioxide, zirconia, titania-zirconia, zirconia , zircon, and mixtures of any two or more of them. The paste may optionally contain reinforcing inorganic fibers selected from the group consisting of carbon fibers, glass fibers, metal fibers, boron fibers, alumina fibers, quartz fibers, aluminosilicate fibers, silicon carbide fibers, potassium titanate fibers, aluminum borate fibers, and ceramic fibers. fibers.

The alumina binder/matrix component is preferably γ-alumina, but may be any other transition modification of alumina, i.e. α-alumina, β-alumina, χ-alumina, η-alumina, ρ- alumina, κ-alumina, θ-alumina, δ-alumina, mixed lanthanum oxide and β-alumina; and mixtures of any two or more of such transitional alumina modifications. To increase the thermal stability of alumina, it is preferable to alloy it with at least one element other than aluminum. Suitable additives for doping alumina include silicon, zirconium, barium, lanthanides, and mixtures of any two or more of these. Suitable lanthanide-based dopants include La, Ce, Nd, Pr, Gd, and mixtures of any two or more of these.

Preferably JMZ-1C (calcined zeolite) is distributed throughout and preferably uniformly throughout the entire extruded catalyst body.

If any of the extruded solids described above are manufactured as a flow wall filter, the porosity of the flow wall filter may be 30-80%, such as 40-70%. Porosity, pore volume and pore radius can be measured, for example, by mercury intrusion porosimetry.

In a sixth aspect of the present invention, a system is provided comprising an engine that produces NOx, a catalyst article containing JMZ-1C or metal-containing JMZ-1C, a conduit for directing flowing exhaust gas from the engine to the catalyst article, and a source of nitrogen-containing reductant located upstream of the catalytic products. This system makes it possible to clean the exhaust gas resulting from the combustion process, for example, in an internal combustion engine (automobile or stationary), gas turbine and coal-fired or oil-fired power plants. Such systems include a catalyst article comprising JMZ-1C, a zeolite of the second aspect of the present invention, and at least one additional exhaust gas purification component, wherein the catalyst article and at least one additional component are configured to function as a coherent manufacturing unit.

The system may include an engine that produces NOx, a catalyst article containing JMZ-1C or metal-containing JMZ-1C, a conduit for directing flowing exhaust gas from the engine to the catalyst article, and a source of nitrogen decompound located upstream of the catalyst article. The system may include a controller for dosing a nitrogen-containing reductant into the flowing exhaust gas only if it is determined that the JMZ-1C or metal-containing JMZ-1C is capable of catalyzing NO _x reduction with the desired or better efficiency over a certain temperature range, for example, at temperatures above 100 °C, above 150°C or above 175°C. Dosing of the nitrogen-containing reductant can be carried out in such a way that the exhaust gas entering the SCR catalyst contains from 60% to 200% of the theoretical ammonia calculated for the ratio NH ₃ / NO 1 : 1 and the ratio NH ₃ / NO ₂ 4 : 3 .

The system may include an oxidation catalyst (eg, diesel oxidation catalyst, DOC) for oxidizing nitrogen monoxide in the exhaust gas to nitrogen dioxide, which may be located upstream of the dosing point of the nitrogen-containing reductant into the exhaust gas. In some aspects, the oxidation catalyst is configured to exit the gas stream entering the zeolite SCR catalyst and having a NO : NO ₂ volume ratio of from about 4:1 to about 1:3, for example, at an exhaust gas temperature at the inlet of the oxidation catalyst of 250° C to 450°C. The oxidation catalyst may include at least one platinum group metal (or some combination thereof), such as platinum, palladium, or rhodium supported on a flow-through monolithic support. The at least one platinum group metal may be platinum, palladium, or a combination of platinum and palladium. The platinum group metal can be deposited on a high surface area porous oxide coating component such as alumina, a zeolite such as aluminosilicate zeolite, silica, non-zeolitic aluminosilicate, cerium oxide, zirconium oxide, titanium oxide, or a mixed or composite oxide. containing both cerium oxide and zirconium oxide.

A suitable filter support may be placed between the oxidation catalyst and the SCR catalyst. The filter substrates may be selected from any of those mentioned above, such as flow wall filters. If the filter is catalyzed, for example, with an oxidation catalyst of the type described above, it is preferred that the dosing point of the nitrogen reducing agent is located between the filter and the zeolite catalyst. In an alternative embodiment, if the filter is not catalyzed, means for dosing nitrogen-containing reductant may be located between the oxidation catalyst and the filter.

The catalytic article may comprise an ammonia slip catalyst located downstream of the selective catalytic reduction (SCR) catalyst. The ammonia slip catalyst may oxidize at least a portion of any nitrogen containing reductant that is not consumed in the selective catalytic reduction process. The ammonia slip catalyst may be located on the outlet side of the flow wall filter and the SCR catalyst may be located on the upstream side of the filter. The ammonia slip catalyst may be located at the downstream end of the flow support, and the SCR catalyst may be located at the upstream end of the flow support. This means that the ammonia slip catalyst and the SCR catalyst are placed on separate blocks in the exhaust system. Such separate units may be placed next to each other and be in contact with each other or be separated from each other by a certain distance, provided that they are in fluid communication with each other and provided that the SCR catalyst unit is located upstream of the block with ammonia slip catalytic converter.

In a seventh aspect of the present invention, there is provided a method for generating JMZ-1, comprising:

a. forming a reaction mixture containing: (i) at least one source of alumina, (ii) at least one source of silicon dioxide, and (iii) a structurant (SDA) containing a trimethyl(cyclohexylmethyl)ammonium cation,

b. heating the reaction mixture and forming zeolite crystals containing a CHA framework structure and a structurant and a mother liquor, and

c. recovering at least a portion of the zeolite crystals from the mother liquor.

The zeolite crystals are preferably separated from the subsequent mother liquor by any conventional means such as filtration.

The reaction mixture for the JMZ-1 synthesis process typically contains at least one source of silica, at least one source of alumina, at least one SDA suitable for forming JMZ-1, and at least one source of hydroxide ions. However, it should be understood that the synthesis method described herein is not necessarily limited to aluminosilicates, but can also be applied to the synthesis of other molecular sieves having a CHA structure, such as borosilicates, titanosilicates, vanadosilicates, and the like. in the case of an effective replacement of aluminum with B, Fe, Ti, or V, respectively. Thus, more generally, the reaction mixture from which the molecular sieves are crystallized contains at least one active source of a tetravalent element oxide or a mixture of oxides of tetravalent elements (e.g., silicon oxide, germanium oxide, or mixtures thereof) and at least one oxide of a trivalent element. element or a mixture of oxides of trivalent elements (for example, alumina, boron oxide, gallium oxide, iron oxide, vanadium oxide or mixtures thereof). In the reaction mixture, an aluminosilicate zeolite of the FAU topological type can also be used as a source of aluminum.

Suitable silica sources include, without limitation, fumed silica, silicates, precipitated silica, colloidal silica, silica gels, zeolites such as zeolite Y and/or zeolite X, and silica hydroxides and alkoxides. Those sources of silica are preferred which provide a high relative yield. Typical sources of alumina are also well known and include aluminates, alumina, other zeolites such as FAU zeolite, alumina colloids, boehmites, pseudoboehmites, aluminum hydroxides, aluminum salts such as aluminum sulfate and aluminum chloride, aluminum hydroxides and alkoxides, gels aluminum oxide.

Typically, a source of hydroxide ions is used in the reaction mixture, such as an alkali metal hydroxide and/or an alkaline earth metal hydroxide, including sodium, potassium, lithium, cesium, rubidium, calcium and magnesium hydroxide. However, this component may be omitted as long as equivalent basicity is maintained. A structurant (SDA) can be used to produce the hydroxide ion. Thus, ion exchange, for example, of a halide ion for a hydroxide ion, may be advantageous in order to reduce or eliminate the required amount of alkali metal hydroxide. The alkali metal cation or alkaline earth metal cation may be part of the synthesized crystalline oxide material, which will balance the charges of the valence electrons in it.

The reaction mixture may further contain an alkali metal. The alkali metal is preferably sodium, potassium, or a combination thereof.

Salts, in particular alkali metal halides such as sodium chloride, can also be added to the reaction mixture or formed in the reaction mixture.

Preferably, the reaction mixture is free or substantially free of one or more of fluorine, fluorine compounds, and fluoride ions (fluoride).

The structurant (SDA), preferably the trimethyl(cyclohexylmethyl)ammonium cation, may be associated with an anion selected from the group consisting of fluoride, chloride, bromide, iodide, hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, carbonate and bicarbonate. Preferably the structurant (SDA) is an iodide anion or a hydroxide anion, more preferably a hydroxide anion.

The reaction mixture may further contain from about 0.1 to about 10 wt.% seed crystals, and the seed crystals contain a crystalline molecular sieve having a CHA framework structure.

The seed crystals may contain from 1 to 40 wt.% impurities of at least one crystalline molecular sieve.

The reaction mixture contains a mixture of water, a source of silicon dioxide, a source of alumina, a base, an alkali metal cation and trimethyl(cyclohexylmethyl) ammonium cations, and the composition has a molar composition ratio:

SiO ₂ / Al ₂ O ₃ 10–100 OH ^- / SiO ₂ 0.05–1 R/ _SiO2 0.05–0.5 Alkali metal cation / SiO ₂ 0.1–1.0 H ₂ O / SiO ₂ 5–80

where R is SDA, preferably trimethyl(cyclohexylmethyl) ammonium cations.

Preferably the reaction mixture has a molar composition ratio:

SiO ₂ / Al ₂ O ₃ 15–70 OH ^- / SiO ₂ 0.1–0.7 R/ _SiO2 0.05–0.2 Alkali metal cation / SiO ₂ 0.15–0.65 H ₂ O / SiO ₂ 10–6

The reaction mixture may be a solution, a colloidal dispersion (colloidal sol), a gel or a paste, with a gel being the preferred form.

Preferably, the overall silica yield of the process is at least about 60%, such as at least about 70%, at least about 80%. Preferably, the overall SDA yield of the process is at least about 40%, such as at least about 60%, at least about 80%, at least about 90%, at least about 40% to about 90%, about 40% to about 60%, about 60% to about 80%, about 80% to about 90%, about 90% to about 95%, or about 95% to about 99%.

Reaction temperatures, mixing times and rates, and other process parameters that are suitable for traditional methods for synthesizing CHA structures are also generally suitable for the present invention. Typically, the reaction mixture is kept at an elevated temperature until JMZ-1 crystals form. Hydrothermal crystallization is typically carried out under autogenous pressure at a temperature of from about 75 to about 220°C, for example from about 120 to 160°C, for several hours, for example from about 0.1 to about 20 days and preferably from about 0 .25 to about 3 days. The zeolite is preferably obtained by stirring or mixing.

At the stage of hydrothermal crystallization, nucleation of JMZ-1 crystals from the reaction mixture can occur spontaneously. The use of JMZ-1 crystals or other CHA topology crystals as seed material can be advantageous in terms of reducing the time required for complete crystallization. When used as a seed, JMZ-1 crystals can be added in an amount of 0.1 to 10% by weight of the silica used in the reaction mixture.

After the formation of JMZ-1 crystals, the solid product is separated from the reaction mixture by standard separation methods such as filtration. The JMZ-1 crystals are washed with water and then dried for several seconds to several minutes (for example, 5 seconds to 10 minutes for instant drying) or several hours (for example, about 4 to about 24 hours for oven drying at from 75 to about 150 °C) to obtain synthesized JMZ-1 crystals having a CHA topological framework structure and a structure forming agent (SDA) inside the crystals. The drying step can be carried out at atmospheric pressure or under vacuum.

It should be understood that the sequence of steps described above, as well as each of the time periods and temperatures mentioned above, are given by way of example only and are subject to change.

Crystals of zeolite JMZ-1 obtained in accordance with this method may be homogeneous, contain little or no twins and/or contain many twins, or may form agglomerates.

JMZ-1 crystals prepared according to the methods described herein may have an average crystallite size of about 0.01 to about 5 microns, such as about 0.5 to about 5 microns, about 0.1 to about 1 µm and from about 1 to about 5 µm. Large crystals can be ground using a jet mill or other grinding method by colliding particles with each other to an average size of from about 1.0 to about 1.5 microns to facilitate the application of the catalyst-containing slurry to a support, such as a flow-through monolithic support.

JMZ-1 synthesized by the methods described herein preferably has a silica to alumina ratio (SAR) in the range of about 8 to about 50, inclusive, about 10 to about 35, or about 15 to about 25. The SAR ratio may be selectively achieved based on the composition of the initial mixture for synthesis and/or adjustment of other process variables. The ratio of silicon oxide and alumina in zeolites can be determined by the traditional method of analysis. This ratio is considered as close as possible to the ratio in the rigid atomic framework of the zeolite crystal and does not apply to silicon or aluminum contained in the binder (for use in catalysts) or in cationic or other form within the channels.

Zeolites synthesized by the present process may include one or more extralattice alkali and/or alkaline earth metals. These metals are usually introduced into the reaction mixture along with a source of hydroxide ions. Examples of such metals include one or more of barium, calcium, cesium, lithium, magnesium, potassium, rubidium, sodium, and strontium.

In general, it is desirable to remove the alkali metal cation by ion exchange and replace it with hydrogen, ammonium ion, or any desired metal ion. Accordingly, the zeolites of the present invention may be a sodium form zeolite, a potassium form zeolite, or a combination of Na and K forms, and the like, or may be a hydrogen form zeolite, an ammonium form zeolite, or a metal-substituted zeolite. Typical ion exchange methods involve bringing the synthetic zeolite into contact with a solution containing a salt of the desired substituting cation or cations. Although a wide range of salts can be used, the most preferred are chlorides and other halides, nitrates, sulfates and carbonates. Typical ion exchange methods are widely known in the art. The ion exchange occurs after synthesis and can be carried out either before or after the calcination of the zeolite. After bringing into contact with a salt solution of the desired replacement cation, the zeolite is usually washed with water and dried at temperatures in the range from 65°C to about 315°C, typically from 80°C to 150°C. After washing, the zeolite can be calcined under an inert gas atmosphere and/or in air at temperatures ranging from about 315°C to 850°C for periods of time ranging from 1 to 48 hours or more to obtain a catalytically active and stable zeolite.

In an eighth aspect of the present invention, there is provided a process for producing JMZ-1C by calcining (roasting) JMZ-1. As used herein, the term "calcining", "calcining" or "calcining" means heating a material in the presence of air or oxygen. This definition is consistent with the IUPAC definition of calcination. (IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by: A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). Revised XML online: http://goldbook.iupac. org (2006-), prepared by: M. Nic, J. Jirat, B. Kosata, updated by A. Jenkins, ISBN 0-9678550-9-8, doi:10.1351/goldbook.) promoting the exchange of metal ions in the zeolite, as well as to enhance the adhesion of the zeolite to the substrate. The temperature used in the calcination depends on the components contained in the material to be calcined, and generally ranges from about 300°C to about 900°C, and the duration of the calcination is about 1-8 hours. In some cases, the calcination can be performed at temperatures up to about 1200°C. In applications involving the processes described herein, calcination is generally performed at temperatures from about 400°C to about 700°C for about 1 to 8 hours, preferably at temperatures from about 400°C to about 650°C in for about 1-4 hours.

In a ninth aspect of the present invention, methods are provided for purifying exhaust gas from an engine by contacting the exhaust gas with a catalyzed zeolite of the second aspect of the present invention (JMZ-1C or metal impregnated JMZ-1C).

The method for reducing the NO _X compounds contained in the gas and/or oxidizing the NH ₃ includes bringing the gas into contact with JMZ-1C or metal-containing JMZ-1C for a time sufficient to reduce the level of NO _x compounds in the gas. The methods of the present invention may include one or more of the following steps. (a) accumulation and/or combustion of soot that is in contact with the inlet of the catalytic filter; (b) introducing a nitrogen-containing reducing agent into the exhaust gas stream prior to bringing it into contact with the catalytic filter, preferably without intermediate catalytic steps involving NO _x and reducing agent treatment; (c) forming NH ₃ over a NO _x adsorption catalyst or lean NO _x trap, and preferably using such NH ₃ as a reducing agent in a downstream SCR reaction; (d) contacting the exhaust gas stream with DOC to oxidize the soluble organic fraction (SOF) based on hydrocarbons and/or carbon monoxide to CO ₂ and/or oxidize NO to NO ₂ , which in turn can be used to oxidize solid particles in the particulate filter; and/or reducing the amount of particulate matter (PM) in the exhaust gas; (e) contacting the exhaust gas with one or more SCR flow catalyst devices in the presence of a reducing agent to reduce the NO _X concentration in the exhaust gas; and (f) contacting the exhaust gas with an ammonia slip catalyst, preferably downstream of the SCR catalyst, to oxidize most or all of the ammonia before venting the exhaust gas to atmosphere or passing the exhaust gas through a recirculation loop before being fed/re-supplied to the engine .

JMZ-1C or metal-containing JMZ-1C can promote the reaction of a reducing agent, preferably ammonia, with oxides of nitrogen to selectively form elemental nitrogen (N ₂ ) and water (H ₂ O). Thus, the catalyst may be formulated to favor the reduction of nitrogen oxides with the reducing agent (ie, may be an SCR catalyst). Examples of such reducing agents include hydrocarbons (eg C3-C6 hydrocarbons) and nitrogen containing reducing agents such as ammonia and ammonium hydrazine, or any suitable ammonia precursor such as urea ((NH ₂ ) ₂ CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate.

The nitrogen-based reductant, in particular NH ₃ , for use in the SCR process can be wholly or at least partially provided by a NO _X Adsorption Catalyst (NAC), a Low NO _X Trap (LNT), or a NO _X Storage/Recovery Catalyst (NSRC) located upstream of the SCR catalyst, such as the SCR catalyst of the present invention, located on the filter with flow walls. The NAC components used in the present invention include a catalytic combination of a base material (such as an alkali metal, an alkaline earth metal, or a rare earth metal, including alkali metal oxides, alkaline earth metal oxides, and combinations thereof) and a precious metal (such as platinum) and optionally a catalyst component restoration such as rhodium. Specific types of base materials used in NAC include cesium oxide, potassium oxide, magnesium oxide, sodium oxide, calcium oxide, strontium oxide, barium oxide, and combinations thereof. The precious metal is preferably present in an amount of from about 10 to about 200 g/ft ³ , for example from 20 to 60 g/ft ³ . In an alternative embodiment, the catalyst precious metal has an average concentration that can be from about 40 to about 100 g/ft ³ .

During periodic rich mode regeneration cycles, NH ₃ can form over the NO _x adsorption catalyst. An SCR catalyst located downstream of the NO _x adsorption catalyst can improve the overall efficiency of reducing the NO _x concentration in the system. In a combined system, the SCR catalyst is able to store NH ₃ liberated from the NAC catalyst during intermittent rich mode regeneration cycles, and the stored NH ₃ is used to selectively reduce some or all of the NO _x oxides that pass through the NAC catalyst under normal operating conditions in poor mode.

This exhaust gas purification method can be applied to exhaust gas produced from a combustion process, such as in an internal combustion engine (automobile or stationary), gas turbine, and coal-fired or oil-fired power plants. This method can also be used to treat gases generated in industrial processes such as oil refining, refinery heating and boiler installations, furnaces, chemical processing industries, coke ovens, municipal solid waste treatment plants and waste incinerators, etc. . The method can be used to clean exhaust gas from an automobile lean internal combustion engine, such as a diesel engine, a lean gasoline engine, or an engine powered by liquid petroleum gas or natural gas.

The exhaust gas purification method may include bringing the combustion exhaust gas containing NO _x and/or NH ₃ into contact with the catalytic article of the fifth aspect of the invention to selectively reduce at least a portion of NO _x to N ₂ and H ₂ O and/or oxidize at least least part of NH ₃ .

The calcined zeolite of the second aspect of the present invention (JMZ-1C or metal-containing JMZ-1C) can also promote ammonia oxidation. Preferably the JMZ-1C contains one or more metal ions, such as copper or iron, which are incorporated into the JMZ-1C by impregnation. The catalyst may be formulated to favor oxygen oxidation of ammonia, in particular ammonia at a concentration typically found downstream of an SCR catalyst (e.g., an ammonia oxidation catalyst (AMOX) such as an ammonia slip catalyst (ASC)). The CHA structure catalyst can be positioned as a top layer deposited on top of an oxidizing bottom layer, where the bottom layer contains a platinum group metal (PGM) containing catalyst or a non-PGM containing catalyst. Preferably, the catalyst component in the lower layer is located on a high surface area carrier including, but not limited to, alumina.

The SCR and AMOX steps may be performed sequentially, with both processes using a catalyst containing the CHA catalyst described herein, with the SCR process occurring before the AMOX process. For example, the SCR catalyst composition may be located on the inlet side of the filter, and the AMOX catalyst composition may be located on the outlet side of the filter.

Accordingly, a method is provided for reducing NO _x compounds contained in a gas or oxidizing NH ₃ , which includes contacting the gas with a catalyst composition described herein to catalytically reduce NO _x compounds for a time sufficient to reduce the level of NO _x compounds. and/or NH ₃ in gas.

The SCR and/or AMOX process can be carried out at a temperature of at least 100°C, preferably at a temperature of from about 150°C to about 750°C, more preferably from about 175 to about 550°C, even more preferably from 175 to 400°C. C.

Under certain conditions, the temperature range may be from 450 to 900°C, preferably from 500 to 750°C, more preferably from 500 to 650°C, even more preferably from 450 to 550°C. Temperatures above 450 °C can in particular be used for treating exhaust gases from heavy and light diesel engines having exhaust systems containing (optionally catalyzed) diesel particulate filters that are actively regenerated, for example by injecting hydrocarbons into an exhaust system upstream of the filter, wherein the zeolite catalyst for use in the present invention is located downstream of the filter.

In a tenth aspect of the present invention, JMZ-1C or metal-containing JMZ-1C can stimulate the formation of methylamines in the reaction of methanol and ammonia and the conversion of methanol to lower olefins, in particular ethylene and propylene.

A process for converting an oxygenate, such as methanol, to an olefin (MTO) by contacting methanol with JMZ-1C or metal-containing JMZ-1C, as described above herein. The reaction process for converting oxygenate to olefin (OTO) is well known to those skilled in the art. In particular, in the OTO reaction process, the oxygenate is contacted with a molecular sieve catalyst composition under conditions effective to convert at least a portion of the oxygenate to light olefins. If the methanol is an oxygenate, this process is generally referred to as the methanol-to-olefins (MTO) reaction process. Methanol is a particularly preferred oxygenate for the synthesis of ethylene and/or propylene.

The process for converting an oxygenate feed to a light olefin product includes: a) providing an oxygenate feed containing a significant portion of methanol; b) providing a catalyst composition containing JMZ-1C or metal-containing JMZ-1C and optionally a basic metal oxide co-catalyst; and c) contacting the oxygenate feedstock with the catalyst composition under conditions sufficient to convert at least a portion of the oxygenate feedstock to a light olefin product.

An oxygenate feedstock, in particular a composition that is a mixture of alcohols and contains methanol and ethanol, is a suitable feedstock for various catalytic processes, in particular for oxygenate-to-olefin (OTO) reaction processes, in which the catalyst composition, as a rule, contains a primary oxide catalyst containing at least two of Al, Si and P (for example, if the primary oxide catalyst contains Al and Si, it is an aluminosilicate molecular sieve, preferably a high silica aluminosilicate molecular sieve), and preferably a basic cocatalyst on based on a metal oxide, can be used to convert an oxygenate feed to a light olefin product, for example containing ethylene and/or propylene, preferably including ethylene. The olefins can then be recovered and used in further processing, for example in the production of polyolefins such as polyethylene and/or polypropylene, olefin oligomers, olefin copolymers, mixtures thereof and/or compounds thereof.

One or more additional components may be included in the feed to the OTO reaction system. For example, the feedstock sent to the OTO reaction system, in addition to methanol and ethanol, may optionally contain one or more compounds with aliphatic functional groups, such as alcohols, amines, carbonyl compounds, such as aldehydes, ketones and carboxylic acids, ethers, halides, mercaptans, sulfides, and the like; and mixtures thereof. The aliphatic functional group of such compounds typically contains 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, most preferably 1 to 4 carbon atoms.

Non-limiting examples of compounds with aliphatic functional groups include alcohols such as methanol, ethanol, n-propanol, isopropanol and the like, alkyl mercaptans such as methyl mercaptan and ethyl mercaptan, alkyl sulfides such as methyl sulfide, alkyl amines such as methylamine, alkyl ethers such as DME, diethyl ether and methyl ethyl ether, alkyl halides such as methyl chloride and ethyl chloride, alkyl ketones such as dimethyl ketone, alkyl aldehydes such as formaldehyde and acetaldehyde, and various organic acids such as formic acid and acetic acid.

The various feedstocks described above are predominantly converted to one or more olefins. The olefins or olefin monomers derived from the feedstock typically contain 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and most preferably are ethylene and/or propylene. Non-limiting examples of olefin monomers include ethylene, propylene, butene-1, pentene-1,4-methylpentene-1, hexene-1, octene-1 and decene-1, preferably ethylene, propylene, butene-1, pentene -1,4-methylpentene-1, hexene-1, octene-1 and their isomers. Other olefin monomers may include, without limitation, unsaturated monomers, diolefins having from 4 to 18 carbon atoms, conjugated or unconjugated dienes, polyenes, vinyl monomers, and cyclic olefins.

In an eleventh aspect of the present invention, a catalyst article for converting low molecular weight oxygenates to an olefin-rich hydrocarbon stream may comprise JMZ-1C or metal-containing JMZ-1C, wherein the JMZ-1C or metal-containing JMZ-1C is located on the support and/or within the structure.

A catalytic article for converting low molecular weight oxygenates to an aromatics-rich hydrocarbon stream may contain JMZ-1C or metal-containing JMZ-1C, where JMZ-1C or metal-containing JMZ-1C are located on the substrate and/or within the structure.

The catalyst may be included in or mixed with other additive materials. Such an additive is generally referred to as a catalyst or catalyst composition, which is part of the mixture. Preferably, the additive materials are substantially inert to conversion reactions using dialkyl ethers (eg, dimethyl ether) and/or alkanols (eg, methanol, ethanol, etc.).

One or more other materials may be blended with the JMZ-1C or the metal containing JMZ-1C, in particular materials that are resistant to the temperatures and other conditions used in organic conversion processes. Such materials may include catalytically active and inactive materials and synthetic or natural zeolites, as well as inorganic materials such as clays, silica and/or other metal oxides such as alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels, including mixtures of silica and metal oxides. The use of a catalytically active material may contribute to changing the degree of conversion and/or selectivity of the catalyst in the conversion of the oxygenate. Inactive materials can suitably serve as diluents to control the degree of conversion in the process, which allows you to get products in an economical and orderly manner without the use of other means of controlling the reaction rate. These materials can be incorporated into natural clays, such as bentonite and kaolin, to improve the crush strength of the catalyst under industrial conditions. Materials (eg, clays, oxides, etc.) can act as catalyst binders. It may be desirable to provide a catalyst having high crush strength, since in a commercial application it may be desirable to prevent the catalyst from breaking down into powdered materials.

Clays of natural origin that may be used may include, but are not limited to, the montmorillonite and the kaolin family, where said family includes subbentonites and kaolins, well known as Dixie, McNamee, Georgia, and Florida clays, or others in which the major mineral component is halloysite, kaolinite, dikite, nakrite or anauxite. These clays can be used in the raw state, as mined, or first subjected to calcination, acid treatment, or chemical modification. Other suitable binders may include, without limitation, inorganic oxides such as silica, titanium dioxide, beryllium oxide, alumina, and mixtures thereof.

In addition to the above materials, JMZ-1C or metal containing JMZ-1C can be incorporated into composites with porous matrix material such as silica-alumina, silica-magnesium oxide, silica-zirconium oxide, silica-thorium oxide, silica -beryllium oxide and silicon oxide-titanium oxide, as well as in ternary compositions such as silicon oxide-aluminum oxide-thorium oxide, silicon oxide-aluminum oxide-zirconium oxide, silicon oxide-aluminum oxide-magnesium oxide and silicon oxide-magnesium oxide - zirconium oxide.

The relative proportions of JMZ-1C or metal-containing JMZ-1C and the inorganic oxide matrix can vary widely. For example, the mixture may have a zeolite content in the range of from about 1 to about 90 wt.% and most typically, in particular, when preparing a composite in the form of granules, in the range of from about 2 to about 80 wt.% based on the weight of the composite.

The present invention also relates to products C2, C3, C4 and C5 obtained in the processes of OTO or MTO using JMZ-1C or metal-containing JMZ-1C as a catalyst or co-catalyst.

EXAMPLES

SDA (template) trimethyl(cyclohexylmethyl)ammonium cation (CAS accession number 30833-81-9) was prepared using well-known procedures described in the literature (e.g., C. C. Price, E. L. Eliel and R. J. Convery, J. Org. Chem., 1957, 22, 347).

Example 1. Synthesis of pure phase of zeolite JMZ-1

A reactive gel having a molar composition of:

60 SiO ₂ : 2.22 Al ₂ O ₃ : 6 K ₂ O : 10 Template : 9 K ₂ SO ₄ : 3000 H ₂ O

was prepared by weighing the individual reagents into a 45 ml PTFE cup containing a PTFE magnetic stirrer bar. The reagents used and the order in which they are added are described below:

a) Demineralized water,

b) colloidal silicon dioxide,

c) Potassium hydroxide,

d) aluminum sulfate,

e) Potassium sulfate

f) Template - trimethyl (cyclohexylmethyl) ammonium iodide.

The CHA framework seeds (about 5 wt % solid silica used as reagent) were added to the mixture. After adding all the reagents, the mixture was thoroughly homogenized for 15 minutes using an acoustic stirrer. The PTFE cup was placed in an external stainless steel vessel, hermetically sealed, then placed in an oven, heated to a temperature of 180 °C with rotation at a frequency of 30 rpm, after which the reactants in the mixture reacted. After 6 days of exposure at a temperature of 180°C, the furnace was cooled, the reactor was opened, and the resulting material was centrifuged, decanted, and demineralized water was added to it. After initial mixing with water and removal of water, the procedure was repeated 3 more times (4 washes in total), after which the resulting product was dried overnight at a temperature of 110°C. The dried product was then analyzed by X-ray powder diffractometry (XRD). The product contained a pure JMZ-1 zeolite phase. An X-ray powder diffraction (XRD) pattern is shown in FIG. 1, and the lines on the XRD diffractogram are presented in Table 7.

Table 7. Characteristic lines of the X-ray powder diffraction (XRD) zeolite JMZ-1 immediately after production (containing the template).

degrees
2θ I/io Relative value
I/io degrees
2θ I/io Relative value
I/io 9.55 100 VS 22.87 16 W 13.15 fourteen W 23.34 eight W 13.91 eleven W 24.65 29 M 16.27 73 VS 26.49 13 W 17.50 fifteen W 28.05 5 W 19.18 eight W 30.40 fourteen W 20.99 99 VS 31.22 33 M 21.95 eight W

Table 8 shows a comparison of X-ray powder diffraction (XRD) characteristic lines of zeolite JMZ-1 with characteristic lines of SSZ-13 (SDA agent with CHA structure) according to table 1 of US patent No. 4,544,538.

Table 8. Characteristic lines of the X-ray powder diffraction (XRD) zeolite JMZ-1 (containing template) in comparison with unfired SSZ-13 (containing template).

JMZ-1 SSZ-13 degrees
2θ I/io Relative value
I/io degrees
2θ I/io Relative value
I/io 9.55 100 VS 9.57 61 VS 13.15 fourteen W 13.91 eleven W 14.06 21 M 16.27 73 VS 16.23 80 VS 17.50 fifteen W 17.82 24 M 19.18 eight W 20.99 99 VS 20.87 100 VS 21.95 eight W 22.14 9 W 22.87 16 W 22.72 eight W 23.34 eight W 24.65 29 M 25.01 69 VS 26.49 fourteen W 26.30 eighteen W 28.05 5 W 30.40 fourteen W 31.00 47 31.22 33 M 31.29 21 S

This comparison shows that although both JMZ-1 and SSZ-13 are template-containing zeolites with a CHA structure, the structures of the two materials are different.

Example 2 Synthesis of Zeolite JMZ-1 to Evaluate Catalytic Properties

A reactive gel having a molar composition of:

60 SiO ₂ : 2.22 Al ₂ O ₃ : 5.5 K ₂ O : 10 Template : 9 K ₂ SO ₄ : 3000 H ₂ O

was prepared by weighing the individual reagents into a 45 ml PTFE coated cup containing a PTFE magnetic bar. The reagents used and the order in which they are added are described below:

a) Demineralized water,

b) colloidal silicon dioxide,

c) Potassium hydroxide,

d) aluminum sulfate,

e) Potassium sulfate

f) Template - trimethyl (cyclohexylmethyl) ammonium iodide.

The reaction mixture was homogenized as described in example 1, then the reaction was carried out for 6 days at a temperature of 180°C and a reactor speed of 30 rpm.

The product was processed as described in example 1, then analyzed by X-ray powder diffractometry (XRD). The product contained a pure JMZ-1 zeolite phase, the X-ray powder diffraction pattern of which was very similar to that described in Example 1. XRF analysis showed that the silica to alumina ratio (SAR) of the product was 23.4. The SEM image of the product is shown in FIG. 2.

The zeolite (JMZ-1) was activated by air calcination immediately after preparation. The sample was heated to a temperature of 110°C at a rate of 2°C/min, then heated to a temperature of 450°C at a rate of 5°C/min and kept at a temperature of 450°C for 16 hours. Then the material was heated to a temperature of 550°C at a rate of 5°C/min and kept at a temperature of 550°C for 16 hours. Sample JMZ-1C was cooled to room temperature and then subjected to ion exchange in a 1 M ammonium chloride solution using 10 ml solution per gram of calcined zeolite. Ion exchange was carried out at room temperature for 1 hour. Stirring was then stopped, the ion-exchanged zeolite was centrifuged and the clear supernatant decanted. This ion exchange procedure was repeated, then the zeolite was centrifuged, washed (with decantation of the supernatant) and dried. The obtained zeolite in the NH4 form was converted into the hydrogen form by calcination in air by heating to a temperature of 150°C at a rate of 2 °C/min and holding at a temperature of 150°C for 10 hours, followed by heating to a temperature of 450°C at a rate of 5 °C/min and a final hold at 450°C for 16 hours.

The product after activation was characterized by the XRD pattern shown in FIG. 3 and interplanar spacings and intensity values shown in Table 9 below.

Table 9. Characteristic XRD peaks of the activated product

degrees
2θ I/io Relative
intensity degrees
2θ I/io Relative
intensity 9.59 100 VS 23.31 5 W 13.03 29 M 25.24 12 W 16.21 16 W 26.22 9 VS 17.99 12 W 30.98 19 M 20.83 41 M–S 31.43 9 M

Example 3 NH ₃ Selective Catalytic Reduction (SCR) Catalyst Test

The calcined JMZ-1 product described in Example 2, JMZ-1C, was impregnated with copper at a load of 3 wt.% using the required amount of copper (II) acetate monohydrate (Alfa Aesar) dissolved in demineralized water. The impregnated sample was dried overnight at 105°C and then calcined in air at 500°C for 2 hours.

Catalyst powder samples were granulated and then aged in a stream of 4.5% H ₂ O in air. The samples were heated at a rate of 10°C/min to a temperature of 900°C. After holding at 900 °C for 1 or 3 hours, the samples were cooled in a vapor-air mixture until the temperature reached < 200 °C, then air was passed through the samples only until they were cooled to about room temperature.

Samples of granular catalyst powders were tested in a device in which a gas containing 500 ppm NOx (NO only), 550 ppm NH ₃ , 10% O ₂ , 10% H ₂ O with the remainder of N ₂ flows through the catalyst at a space velocity of 60 K (390 l/g cat/h). The temperature was increased (linearly) from 150 to 500°C at a rate of 5°C/min.

On FIG. 4-12 show the activity profiles of fresh and aged NOx conversion catalysts at temperatures from about 150°C to about 550°C, where FIG. 4-6 show profiles of fresh samples, FIG. 7–9 show the profiles of specimens hydrothermally aged at 900°C for 1 hour, and Figs. Figures 10–12 show profiles of specimens hydrothermally aged at 900°C for 3 hours. The activity of the fresh and one hour aged JMZ-1C catalysts was similar to that of either of the two CHA zeolites with SAP ratios of 22 and 25, while the activities of the 3 hour aged catalysts were different, with the JMZ-1C catalysts essentially provide higher NOx conversions. On FIG. 10 shows that the NOx conversion of the JMZ-1C catalysts was at least 10% higher over the temperature range of about 175°C to about 225°C compared to a CHA catalyst having an SAR ratio of 22 and about 20% higher over a temperature range of about 175°C to about 225°C compared to a CHA catalyst having a SAR ratio of 25.

The concentration of N ₂ O in the gas passing through the fresh and aged catalysts at temperatures from about 150°C to about 550°C is shown in FIG. 6, 9 and 22 (fresh, aged for 1 hour and aged for 3 hours, respectively). The gas entering the apparatus contained 500 ppm. NOx calculated as NO only. N ₂ O levels in the gas after passing through the JMZ-1C catalysts were comparable to levels after passing through two types of zeolites with a CHA structure and SAP ratios of 22 and 25.

On FIG. 11 shows the activity profiles of NH ₃ conversion catalysts hydrothermally aged for 3 hours at 900°C at temperatures from about 150°C to about 550°C. At temperatures from about 165°C to about 225°C, the JMZ-1C catalysts provided an increase in NH ₃ conversion compared to two zeolites with a CHA structure and SAP ratios of 22 and 25. For example, at a temperature of about 175°C, the maximum conversion The NH ₃ with each of the two CHA zeolites with SAR ratios of 22 and 25 was about 30%, while the JMZ-1C catalysts provided conversions of about 38 and 64%, which were about 27% and 113% higher. the highest NH ₃ conversion with each of the two CHA zeolites with SAP ratios of 22 and 25.

Claims (25)

1. An exhaust gas purification zeolite with a CHA type framework structure, wherein the zeolite is an aluminosilicate having a silica to alumina ratio (SAR) of 10 to 50, the zeolite having a characteristic X-ray powder diffraction pattern prior to removal of the template agent by calcination, comprising at least least the following diffraction peaks (in degrees 2θ (±0.2), with relative intensities in parentheses) at positions: 9.55 (VS), 16.27 (VS), 20.99 (VS), 24.65 (M) and 31.22 (M), and wherein the zeolite has characteristic X-ray diffraction data after removal of the template agent by calcination, containing at least the following peaks (in degrees 2θ, with relative intensities in parentheses) at positions: 9.59 (VS), 13.03 (M), 16.21 (W), 17.99 (W), 20.83 (M–S), 23.31 (W), 25.24 (W), 26, 22 (W), 30.98 (M–W), and 31.43 (W) ±0.2, where the relative intensity is based on the strongest line of the X-ray diffraction pattern, which assigned a value of 100, and defined as (W) [weak]: less than 20; (M) [medium]: in the range of 20-40; (S) [strong]: in the range of 40–60 and (VS) [very strong]: over 60; and wherein the template agent contains trimethyl(cyclohexylmethyl) ammonium cations. 2. An exhaust gas purification composition comprising a zeolite with a CHA-type framework structure and a structure-forming agent (SDA), the SDA being inside the framework structure, the zeolite being an aluminosilicate having a silica to alumina ratio (SAR) of 10 to 50, and its characteristic X-ray powder diffraction pattern contains peaks at the 2-theta positions 9.55 (VS), 16.27 (VS), 20.99 (VS), 24.65 (M), and 31.22 (M) ±0, 2, with relative intensity values indicated in brackets, where the relative intensity is based on the strongest line of the X-ray diffraction pattern, which is assigned a value of 100, and is defined as (W) [weak]: less than 20; (M) [medium]: in the range of 20-40; (S) [strong]: in the range of 40-60 and (VS) [very strong]: more than 60, and SDA contains trimethyl(cyclohexylmethyl)ammonium cations. 3. The composition of claim 2, wherein the characteristic X-ray powder diffraction pattern further comprises peaks at the 2-theta positions 13.15 (W), 13.91 (W), 17.50 (W), 19.18 (W), 21.95 (W), 22.87 (W), 23.34 (W), 28.05 (W) and 30.40 (W) ±0.2, with relative intensity values indicated in brackets. 4. Composition according to claim 2 or 3, wherein the zeolite has a silica to alumina ratio (SAR) of 15-30, preferably 20-25. 5. Composition according to any one of paragraphs. 2–4, in which the structurant (SDA) is a trimethyl(cyclohexylmethyl) ammonium cation. 6. An exhaust gas purification composition comprising zeolite crystals having a CHA framework structure, in which the zeolite crystals have a framework structure containing tetravalent silicon oxide, trivalent aluminum oxide, and a trimethyl(cyclohexylmethyl)ammonium cation is embedded in their crystal structure, wherein the zeolite crystals are anhydrous and free of substituted or unsubstituted 5,4-azonium anions and ammonium anions having substituents selected from polycyclic bridged compounds, cycloaryls, heterocyclic compounds, cycloalkyls other than cyclohexylmethyl, and C ₂ -C ₄ alkyls. 7. An exhaust gas purification zeolite comprising a framework structure including a CHA-type framework structure, wherein the zeolite is an aluminosilicate having a silica to alumina ratio (SAR) of 10 to 50, and its characteristic X-ray powder diffraction pattern contains peaks at the 2 positions -theta 9.59 (VS), 13.03 (M), 16.21 (W), 17.99 (W), 20.83 (M–S), 23.31 (W), 25.24 ( W), 26.22 (W), 30.98 (M–W) and 31.43 (W) ±0.2, with relative intensity values indicated in parentheses, while the specified zeolite does not contain a structure-forming agent (SDA). 8. A zeolite according to claim 7 containing an extralattice transition metal or noble metal. 9. The zeolite according to claim 7, containing from about 0.1 to about 5 wt.% transition metal or noble metal. 10. Composition for cleaning exhaust gas containing zeolite according to one of paragraphs. 7-9 and one or more of filler, binder, stabilizer and rheology modifier. 11. Catalytic product for exhaust gas purification, containing: (a) the composition according to claim 10 and (b) a monolithic substrate on which is applied or in which the specified catalyst composition is included. 12. An exhaust gas treatment system comprising an engine that produces _NOx , a catalyst article according to claim 11, a conduit for directing flowing exhaust gas from the engine to the catalyst article, and a source of nitrogen decompound located upstream of the catalyst article. 13. An exhaust gas cleaning composition containing a mixture of water, a source of silicon dioxide, a source of alumina, a base, an alkali metal cation and trimethyl(cyclohexylmethyl) ammonium cations, the composition having a molar composition ratio: SiO ₂ /Al ₂ O ₃ 10–100 OH ^- /SiO ₂ 0.05–1 R/ _SiO2 0.05–0.5 Alkali metal/SiO ₂ cation 0.1–1.0 _H2O / _SiO2 5–80 where R is SDA, preferably trimethyl(cyclohexylmethyl) ammonium cations. 14. The method of synthesizing the composition according to paragraphs. 2-6, including: a) forming a reaction mixture containing: (i) at least one source of alumina, (ii) at least one source of silicon dioxide, and (iii) a structurant (SDA) containing a trimethyl(cyclohexylmethyl) cation ) ammonium; and b) heating the reaction mixture and forming a composition containing zeolite crystals having a CHA framework structure and a structurant, and a mother liquor, and c) recovering at least a portion of the zeolite crystals from the mother liquor. 15. The method according to p. 14, in which the reaction mixture is a gel having a molar composition ratio: SiO ₂ /Al ₂ O ₃ 10–100 OH ^- /SiO ₂ 0.05–1 R/ _SiO2 0.05–0.5 Alkali metal/SiO ₂ cation 0.1–1.0 _H2O / _SiO2 5–80 where R is SDA. 16. The method according to claim 14 or 15, further comprising calcining the zeolite crystals. 17. Composition for cleaning exhaust gas, obtained or obtained by the methods according to paragraphs 14-16. 18. The method of forming a zeolite according to one of paragraphs. 7-9, including the calcination of the zeolite according to claim 1 or the composition according to one of claims. 2–6. 19. A method for cleaning exhaust gas from an engine by bringing the exhaust gas into contact with a zeolite according to one of paragraphs. 7–9. 20. An exhaust gas purification method, comprising: (a) bringing combustion exhaust gas containing NO _x and/or NH ₃ into contact with a catalyst article according to claim 11 and (b) selective reduction of at least part of NO _x to N ₂ and H ₂ O and/or oxidation of at least part of NH ₃ .

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