chabazite-type zeolite, method for producing chabazite-type zeolite, nox reducing removal catalyst,

专利摘要:
CHABAZITE TYPE ZEOLITE, METHOD TO PRODUCE CHABAZITE TYPE ZEOLITE, NOx REDUCING REMOVAL CATALYST, AND, NOx REDUCING REMOVAL METHOD. an average particle size of at least 1.09 µm and not more than 8.0 µm. The chabazite-type zeolite of the present invention has remarkable durability and heat resistance and, moreover, the copper-loaded chabazite-type zeolite increased the percentage of NOx reduction at low temperatures compared to the prior-art copper-loaded zeolite
公开号:BR112013015583B1
申请号:R112013015583-3
申请日:2011-12-22
公开日:2020-11-10
发明作者:Ko Ariga；Hidekazu Aoyama；Yuuki Ito
申请人:Tosoh Corporation；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to a chabazite-type zeolite with large crystals, and to its production method.
[002] The present invention relates to a new chabazite-type zeolite loaded with copper. It also refers to a NOx reducing removal catalyst including chabazite-type zeolite with a higher NOx reduction rate at low temperature than conventional copper-loaded zeolite-type catalysts.
[003] It also refers to a method to reduce NOx contained in a gas stream in the presence of oxygen using the NOx reducing removal catalyst.
[004] Priority is claimed for Japanese patent application no. 2010-285496, filed on December 22, 1010, and Japanese patent application no. 2011-064882 filed on March 23, 2011, the content of which is incorporated herein by reference. BACKGROUND OF THE INVENTION
[005] Chabazite-type zeolite is a zeolite that has a configured three-dimensional pore structure, built from 8-membered oxygen rings of 3.8 x 3.8 angstroms, and is designated and classified with the structure type code of CHA, as zeolite identified by the detailed crystalline structure, by the International Zeolite Association (Non-patent document 1).
[006] Chabazite-type zeolite is known as a naturally occurring zeolite, and typically has the composition of Ca62 + [SÍ24Ali2O72] (non-patent document 2). As examples of synthetic zeolite, chabazite-type zeolite with a SiO2 / AI2O3 molar ratio of 3.45-4.9 has been described as zeolite D in patent document 1, and as zeolite R in patent document 2. As a typical method of synthesis, the method in which a chabazite-type zeolite is crystallized from type Y zeolite as a raw material under hydrothermal conditions is described in patent document 3.
[007] In patent document 4 and patent document 5, the so-called high silica chabazite zeolite with a molar ratio SiO2 / AI2O3 of 5-50 which is designated as SSZ-13 and its synthesis method are described.
[008] In patent document 6, a chabazite-type zeolite with a SiO2 / AI2O3 molar ratio of 20-50 and a crystal diameter of 0.5 pm or less is described as SSZ-62.
[009] In addition, the possibility of synthesizing a chabazite-type zeolite with a SÍO2 / AI2O3 molar ratio of 50 or more is described respectively in patent document 7 and non-patent document 3 in relation to the method for producing it with fluorine, and in patent document 8 with respect to the fluoride-free method.
[0010] In recent years, a chabazite-type zeolite loaded with copper has particularly attracted attention as a catalyst for selective NOx reduction in automotive exhaust gas.
[0011] As an example of copper-loaded chabazite zeolite, a catalyst-loading copper has been described in SSZ-62 (patent document 6), as well as a copper-charged catalyst, where the molar ratio SÍO2 / AI2O3 is greater than approximately 15, and the atomic ratio of copper to aluminum is in a range greater than approximately 0.25 (patent document 9).
[0012] In addition, patent document 10 discloses a catalyst consisting of chabazite-type zeolite in which the SiO2 / AI2O3 molar ratio is 15-50, and the average particle size is 1.5 pm or more.
[0013] A chabazite zeolite has also been described that has a SiO2 / AI2O3 molar ratio less than 15, and which can be used as a NOx removal catalyst (patent document 11). In addition, in patent document 11, it is shown that chabazite-type zeolite with SiO2 / AI2O3 molar ratio less than 10 is desirable for use in the thermal condition at 700 ° C.
[0014] However, these chabazite-type zeolite catalysts still have insufficient NOx reduction rates in the low temperature region after the durability treatment in a high temperature vapor atmosphere (also referred to as “hydrothermal durability treatment”). Consequently, a higher performing NOx-reducing catalyst is desirable.
[0015] Thus, chabazite-type zeolites are expected to be used in a variety of applications, particularly as an adsorbent or a catalyst support. However, for industrial use, it must have sufficient ion exchange capacity and solid acidity, as well as durability for an adsorbent or catalysis support. For example, for use in an adsorption-desorption process involving a thermal regeneration step, zeolites need not decline in adsorption performance, even when heated repeatedly, or zeolite catalysts used in exhaust gas purification must have thermal durability in order to retain catalytic performance at high temperature. In addition, for use in catalysts and adsorbents, the particle size distribution of zeolites has to be in the appropriate range, because zeolites are used in the form of an extruded product or a product coated on an alveolar substrate. Consequently, a previously unobtainable chabazite-type zeolite is required which has better durability and heat resistance, which has a high rate of NOx reduction in a low temperature region after the hydrothermal durability treatment, and which also has a size distribution controlled particle. REFERENCES OF THE PREVIOUS TECHNIQUE
[0016] PATENT DOCUMENTS Patent document 1: English patent no. 868,846 Patent document 2: U.S. patent no. 3,030,181 Patent document 3: U.S. patent no. 4,503,024 Patent document 4: U.S. patent no. 4,544,538 Patent document 5: U.S. patent no. 4,665,110 Patent document 7: Japanese translation published in. 2007-534582 of the international PCT application Patent Document 8: Japanese translation published in. 2008-512744 of the international PCT application Patent Document 9: Japanese translation published in. 2010-519038 of the international PCT application Patent document 10: unexamined Japanese patent application, first publication no. 2010-168269 Patent document 11: U.S. patent 2011 / 020204A1
[0017] NON-PATENT DOCUMENTS Non-patent document 1: Atlas of Zeolite Framework Types, Revised Fifth Edition, p. 96 (2001) Non-patent document 2: Nature, Vol. 181, p. 1974 (1958) Non-patent document 3: Chem. Commun, p. 1881 (1998). DESCRIPTION OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION
[0018] The purpose of the present invention is to provide a chabazite-like zeolite as a base material for catalytic support or adsorbents that has a high content of Al in terms of the number of ion exchange sites or amount of solid acid, and which has a high level of durability and heat resistance, as well as a method to produce it. In addition, the present invention provides a new copper-loaded chabazite-type zeolite. Furthermore, compared to conventional copper-loaded chabazite zeolite catalysts, it provides a NOx reducing removal catalyst containing copper-loaded zeolite that has a high NOx reduction rate in the low temperature region, as well as a method for reducing NOx removal using the catalyst. MEANS TO SOLVE THE PROBLEMS
[0019] The present inventors have conducted diligent research concerning the improvement of the durability and heat resistance of chabazite-type zeolites, and a method for producing the zeolites. As a result, they observed that chabazite-type zeolite with a molar ratio SiO2 / AI2O3 less than 15, which is suitable for a catalyst, adsorbent or ion exchange agent, and an average particle size of 1.0 pm to 8, Pm has a high level of durability and heat resistance and additionally they have found a method and produced the new chabazite-type zeolite of the present invention. The invention has been completed.
[0020] The present invention has the following aspects.
[0021] (1) A chabazite-like zeolite in which the zeolite has a SiO2 / AI2O3 molar ratio less than 15, and an average particle size is 1.0 pm to 8.0 pm.
[0022] (2) Chabazite-type zeolite according to (1) above, in which the average particle size is from 1.0 pm to 5.0 pm.
[0023] (3) Chabazite-type zeolite according to both (1) and (2) above, wherein the zeolite has a particle size of 90% based on the volume of 15.09 pm or less.
[0024] (4) A method for producing a chabazite-type zeolite according to any one of (1) to (3) above, comprising crystallizing a raw material composition in which a molar ratio of structure targeting agent / SiCh in the raw material composition, it satisfies 0.05 <(structure targeting agent) / SiO2 <0.13, and which the molar ratio of water / SiChna raw material composition satisfies 5 <H2O / SiO2 <30 in the presence of at least two types of cations selected from the group consisting of Na +, K +, Rb +, Cs + and NH4 +.
[0025] (5) The method for producing the chabazite-type zeolite according to (4) above wherein the structure targeting agent includes at least one element selected from the group consisting of a hydroxide, halide, carbonate, methyl carbonate and sulfate, which includes N, N, N-trialkylated ammonium as a cation, as well as a hydroxide, halide, carbonate, methyl carbonate and sulfate which includes N, N, N-trimethylbenzyl ammonium ion, N-alkyl-3 ion -quinuclidinol, or N, N, N-trialkylexoamino norbornane as a cation.
[0026] (6) The method for producing the chabazite-type zeolite according to (5) above, wherein the targeting agent of the structure includes at least one element selected from the group consisting of N, N, N-trimethylated methyl hydroxide ammonium, N, N, N-trimethyladamantyl ammonium halide, N, N, N-trimethyladamatyl ammonium carbonate, N, N, N-trimethyladamatyl ammonium carbonate and N, N, N-trimethyladamatyl ammonium sulfate.
[0027] (7) A chabazite-like zeolite, in which the zeolite has a molar ratio SiO2 / AI2O3 less than 15, an average particle size of 1.0 pm to 8.0 pm, and is charged with copper.
[0028] (8) The chabazite-type zeolite according to (7) above, in which the average particle size is from 1.0 pm to 5.0 pm.
[0029] (9) Chabazite-type zeolite according to both (7) and (8) above, in which zeolite has a particle size of 90% based on a volume of 15.0 pm or less.
[0030] (10) Chabazite-type zeolite according to any one of (7) to (9) above, in which the atomic copper / aluminum ratio is 0.10 to 1.00.
[0031] (11) Chabazite-type zeolite according to any of (7) to (10) above, in which zeolite ion exchange sites are occupied by copper and / or protons (H +).
[0032] (12) Chabazite-type zeolite according to any of (7) to (11) above, wherein the crystalline structure of the zeolite is SSZ-13.
[0033] (13) A NOx reducing removal catalyst, including chabazite zeolite according to any of (7) to (12) above.
[0034] (14) NOx reducing removal catalyst according to (13) above, in which the NOx reduction rate at 150 ° C after the hydrothermal durability treatment is 52% or more.
[0035] (15) A NOx reducing removal method, which uses the NOx reducing removal catalyst according to (13) or (14) above. EFFECTS OF THE INVENTION
[0036] The chabazite-type zeolite of the present invention has a composition that is suitable as a base material to support catalyst or adsorbents, and has a high level of durability and heat resistance. The particle size distribution of the chabazite-type zeolite of the present invention is also controlled to be useful for practical application. In addition, chabazite-type zeolite with a high level of durability and heat resistance can be produced under conditions where the amount of expensive organic structure targeting agent used is small. In addition, a NOx reducing removal catalyst including copper-loaded chabazite zeolite of the present invention exhibits high catalytic activity, even after durability hydrothermal treatment. BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Fig. 1 is a scanning electron microscope photograph (hereinafter referred to as “SEM”) of zeolite 1.
[0038] Fig. 2 is a SEM photograph of zeolite 3.
[0039] Fig. 3 is a SEM photograph of zeolite 5.
[0040] Fig. 4 is a SEM photograph of zeolite 9.
[0041] Fig. 5 is a SEM photograph of zeolite 10.
[0042] Fig. 6 is a photograph of comparative zeolite 1.
[0043] Fig. 7 is a SEM photograph of comparative zeolite 2.
[0044] Fig. 8 is a SEM photograph of comparative zeolite 3.
[0045] Fig. 9 is a SEM photograph of comparative zeolite 5.
[0046] Fig. 10 is a SEM photograph of comparative zeolite 10.
[0047] Fig. 11 is a SEM photograph of the copper-loaded zeolite obtained in example 21. MODE FOR CARRYING OUT THE INVENTION
[0048] The chabazite-type zeolite of the present invention is described
[0049] The chabazite-type zeolite of the present invention is a high silica chabazite with a SiO2 / AI2O3 molar ratio less than 15. The SiO2 / AI2O3 molar ratio is preferably 10 or more, but less than 15. In the case where the ratio molar SiO2 / AI2O3 is 15 or greater, adequate durability and heat resistance for an absorber or catalyst support may be obtained, but the ion exchange capacity or solid acidity required for some applications may be insufficient.
[0050] The heat resistance of the chabazite-type zeolite of the present invention is evaluated by the residual crystallinity rate after the hydrothermal durability treatment. The durability of chabazite-type zeolite with copper is evaluated by the NOx reduction rate, also after the hydrothermal durability treatment. Furthermore, the hydrothermal durability treatment was carried out for 1 hour at a temperature of 900 ° C at a spatial speed of 6,000 h-1 under an air flow containing 10% by volume of water vapor. The performance of a NOx reduction catalyst is generally assessed by the performance after the hydrothermal durability treatment. There is no particular standardized method with respect to hydrothermal durability treatment. Therefore, the hydrothermal durability treatment conditions of the chabazite-type zeolite of the present invention are within the range of conditions that are generally used as hydrothermal durability treatment conditions for NOx reduction catalyst, and there is nothing particularly special about these conditions. .
[0051] The average particle size of the chabazite-type zeolite of the present invention is 1.0 pm to 8.0 pm. The size of the crystal smaller than 1.0 pm previously described, tends to decrease the durability and resistance to heat, in the case of using it for adsorbents or catalyst supports. On the other hand, if the average particle size exceeds 8.0 pm, clogging or detachment tends to occur when the zeolite is coated on an alveolar substrate, and is a factor in the deterioration of the compressive strength when used for molded products.
[0052] The chabazite-like zeolite crystalline particles of the present invention have the characteristics that most are dispersed as rhombohedral or cubic particles, and that they have a crystalline particle shape that allows rhombohedrons to be clearly observed. Consequently, the average particle size of the chabazite-type zeolite of the present invention is evaluated by the sizes of the independently dispersed crystalline particle. In the previously reported chabazite-type zeolites, there is formation of aggregate particles consisting of multiple crystalline particles with undefined interparticle outlines because of the growth of aggregation, which differs from the particle shape of the chabazite-type zeolite of the present invention. From the point of view of the industrial manufacturing technique of synthetic zeolite and its use in adsorbents or catalysts, the average particle size of the chabazite-type zeolite of the present invention is preferably from 1.0 pm to 5.0 pm.
[0053] Average particle size of the chabazite-type zeolite of the present invention means average particle size based on SEM observation. Here, mean particle size based on SEM observation is the particle size (primary particle size) of observation images obtained by scanning electron microscope (SEM) and is an average value of the sizes of the respective existing chabazite zeolite particles. in an optional magnification field of view where 50 or more primary particles can be observed.
[0054] Regarding the average particle size of the chabazite-type zeolite of the present invention, even with chabazite-type zeolite which has an average particle size that does not fall in the range of 1.0 pm to 8.0 pm, when measured by a method other than the measurement method for average particle size based on SEM observation, if it is from 1.0 pm to 8.0 pm by measuring by the method based on SEM observation, it falls within the average particle size range chabazite-type zeolite of the present invention.
[0055] The average particle size based on SEM observation can, for example, be evaluated by an arithmetic average of particle sizes obtained by conducting measurement in an optional direction of 50 or more crystalline particles randomly selected in one or more fields of view of observation photographed at an increase of 5,000 times. If the shape and number of crystalline particles can be clearly observed, there are no particular limitations regarding the conditions for observation by SEM.
[0056] In the chabazite-type zeolite of the present invention, 90% of the particle size is preferably 15.0 pm or less, and more preferably 10.0 pm or less. Although the aforementioned average particle size is for primary particles based on SEM observation, 90% of the particle size signifies a particle size of these aggregated particles.
[0057] The particle size distribution of the chabazite-type zeolite of the present invention can be evaluated by measuring the particle size distribution (volumetric distribution) by laser scattering and diffraction method. The particle size distribution by laser diffraction and dispersion method can be quantified with satisfactory reproducibility by conducting measurement after the treatment that disperses zeolite in water, and that makes the dispersed state of the crystalline particles uniform by means of an ultrasonic homogenizer. When the 90% particle size exceeds 15.0 pm, it is difficult to obtain dispersed crystalline particles dispersed with the average particle size from 1.0 pm to 8.0 pm which is a characteristic feature of the chabazite-type zeolite of the present invention. Furthermore, clogging or detachment tends to occur when the zeolite is coated on an alveolar substrate, which is a factor in the deterioration of the compressive strength when used for molded products.
[0058] Next, a method for producing the chabazite-type zeolite of the present invention is described.
[0059] The raw material for chabazite-type zeolite of the present invention consists of a silica source, an aluminum source, an alkali source, a structure targeting agent (hereinafter referred to as "SDA") and water. It is also acceptable to add components that have a crystallization-promoting effect such as seed crystal.
[0060] As the source of silica, one can use, for example, colloidal silica, amorphous silica, sodium silicate, tetraethyl orthosilicate, aluminosilicate gel and the like.
[0061] As a source of alumina, one can use, for example, aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum chloride, aluminum silicate gel, metallic aluminum and the like. It is preferable to use silica sources and alumina sources that have a shape that allows sufficiently uniform mixing with other raw materials.
[0062] As a source of alkali, one can use, for example, various salts, such as hydroxides, halides, sulfates, nitrates and carbonates of solid, potassium, rubidium, cesium and arnonium, alkaline components in aluminates and silicates, alkaline components in aluminosilicate gel and the like.
[0063] Like SDA, one can use at least one element selected from the group consisting of a hydroxide, halide, carbonate, methyl carbonate, and sulfate that includes N, N, N-trimethylated methyl arnone as a cation, as well as a hydroxide, halide, carbonate, methyl carbonate, and sulfate that includes N, N, N-trimethylbenzyl arnium ion, N-alkyl-3-quinuclidinol ion, or N, N, N-trialkylexoamino norbornane as a cation.
[0064] As the SDA, it is preferable to use at least one element selected from the group consisting of N, N, N-trimethyladamantyl arnone hydroxide (hereinafter abbreviated as TMADAOH), N, N, N-trimethyladamantyl arnone, carbonate of N, N, N-trimethylated mannan arnoneum, methyl carbonate of N, N, N-trimethylated mannan arnoneum, and sulfate of N, N, N-trimethylated mannan arnonium.
The chabazite-type zeolite of the present invention can be produced with an SDA / SiCh molar ratio of at least 0.05, but less than 0.13, and an H2O / SiO2 molar ratio of at least 5 but less than 30.
[0066] With an SDA / SiO2 molar ratio of 0.13 or more, only chabazite-type zeolite with an average crystalline particle size less than 1.5 pm can be obtained as hitherto. In addition, as SDA is expensive, an SDA / SiO2 molar ratio of 0.13 or more has no economic reason. On the other hand, with an SDA / SiO2 molar ratio less than 0.05, crystallization of chabazite-type zeolite is insufficient. Consequently, the heat resistance of the obtained chabazite-type zeolite is insufficient because of the generation of by-products (impurities) or low crystallinity.
[0067] When the H2O / SiO2 molar ratio is 30 or more, the yield is reduced and the process is then uneconomical. On the other hand, in the case of less than 5, due to the elimination of the fluidity of the raw material composition caused by the increase in its viscosity, it is difficult to produce industrially. In addition, however, by-products (impurities, residual unreacted material) tend to be generated.
[0068] The SiO2 / AI2O3 molar ratio of the chabazite-like zeolite raw material composition of the present invention is preferably 50 or less. When SiO2 / AI2O3 exceeds 50, it becomes uneconomical or difficult to synthesize chabazite-type zeolite with a SiO2 / AI2O3 molar ratio less than 15.
The OH / SiO2 molar ratio which is an index of the amount of hydroxyl ion is preferably at least 0.1 but less than 0.9. It is most preferably 0.15 to 0.5. When less than 0.1, it is difficult for the zeolite to crystallize, and when the OH / SiO2 molar ratio is 0.9 or more, it is difficult to obtain chabazite-type zeolite having the SiO2 / AI2O3 molar ratio and particle size of the present invention, because the dissolution of the silica component is accelerated.
[0070] When the chabazite-type zeolite of the present invention is produced, crystallization is conducted in the presence of at least two types of cations selected from the group consisting of Na +, K +, Rb +, Cs + and NHA as cations having mineralizing effect. In the case where such cations are not contained, the crystallization progression insufficiently proceeds to an SDA / SiO2 molar ratio less than 0.13, and by-products (impurity crystals) are generated. Furthermore, it is difficult to obtain chabazite-type zeolite with the average particle size of 1.0 pm to 8.0 pm of the present invention. When only such a cation is contained, crystallization is insufficient, or zeolite with the average particle size of the present invention is difficult to obtain.
[0071] The chabazite-type zeolite of the present invention can be produced by crystallizing a raw material composition consisting of water, a silica raw material, an alumina raw material, an alkaline component and an SDA for a period of sufficient time in a sealed pressure vessel at any desired temperature of 100 ° C to 200 ° C. During crystallization, the composition of the raw material could be under static conditions, but it should preferably be under stirring and mixing conditions.
[0072] After the crystallization is finished, the resulting matter is cooled sufficiently, subjected to solid-liquid separation, washed with a sufficient amount of pure water and dried at any desired temperature of 100 ° C to 150 ° C to obtain the zeolite chabazite type of the present invention.
[0073] The obtained chabazite-type zeolite can be used without change as an adsorbent, catalysis support, or ion exchange material. In addition, the chabazite-type zeolite obtained can also be used after removing SDA and / or alkali metal contained in the fine pores as needed. The removal treatment of SDA and / or alkali metal can adopt a liquid phase treatment that uses a chemical solution containing a component to decompose an SDA component or an acid solution, an exchange treatment that uses resin or the like, or a treatment of thermal decomposition, or it can adopt a combination of these treatments. In addition, one can also use a method in which conversion to type H or type NH4 is performed using the ion exchange capacity of zeolite, and this method can adopt conventional techniques.
[0074] Next, a description will be made of the new copper-loaded chabazite-type zeolite of the present invention, and of a catalyst including such zeolite.
[0075] Chabazite-type zeolite is known as zeolite which is used in NOx reduction catalysts, and particularly in selective catalytic reduction catalysts referred to as SCR catalysts (SCR is an abbreviation of “selective catalytic reduction”) that uses ammonia as an agent reducer.
[0076] The new copper-loaded chabazite-type zeolite of the present invention is chabazite-type zeolite with a SiO2 / AI2O3 molar ratio less than 15, and is a copper-loaded chabazite-type zeolite with an average particle size of 1.0 pm at 8.0 pm.
[0077] The new copper-loaded chabazite-type zeolite of the present invention has excellent catalytic activity when used as an SCR catalyst because of the interaction of chabazite-type zeolite and copper.
[0078] In this specification, catalytic activity means a rate of NOx reduction with respect to the copper-loaded chabazite zeolite of the present invention. The atomic ratio of charged copper to aluminum (copper / aluminum) is preferably in the range of 0.10 to 1.00. The lower limit of the atomic ratio (copper / aluminum) is preferably 0.15 or more, and more preferably 0.2 or more. The upper limit of the atomic ratio (copper / aluminum) is preferably 0.6 or less, and more preferably 0.4 or less. When the copper / aluminum atomic ratio exceeds 1.00, the catalytic activity decreases noticeably because of the hydrothermal durability treatment.
[0079] The ion exchange sites of the new copper-loaded chabazite-type zeolite of the present invention are preferably occupied by copper and / or protons (H +). The rate of NOx reduction is further increased by having the ion exchange sites other than the ion exchange sites occupied by copper occupied with protons alone.
The SiO2 / AI2O3 molar ratio is less than 15, preferably at least 10, but less than 15, more preferably 10 to 14.8, and even more preferably 11 to 14.8.
[0081] When the MIO2 / AI2O3 molar ratio is less than 15, the number of ion exchange sites (catalytically active points) is increased, compared with conventional chabazite-type zeolite with a MIO2 / AI2O3 molar ratio (for example, zeolite type chabazite with a SiO2 / AI2O3 molar ratio of 15-50). Hereby, excellent catalytic activity can be achieved when using the new copper-loaded chabazite zeolite of the present invention as an SCR catalyst.
[0082] The average particle size of the new copper-loaded chabazite-type zeolite of the present invention is 1.0 pm to 8.0 pm.
[0083] Having an average particle size of 1.0 pm or more, preferably 1.2 pm or more, more preferably 1.5 pm or more, and even more preferably 2.0 pm or more, the zeolite type chabazite of the present invention became zeolite with enhanced heat resistance. As a result, compared to chabazite-type zeolites loaded with conventional copper, not only is the NOx reduction rate higher in a high temperature region of 400 ° C or more and preferably from 400 ° C to 600 ° C after the hydrothermal treatment of durability, but also the rate of NOx reduction is higher in a low temperature region of 100 ° C to 250 ° C, preferably from 100 ° C to 200 ° C, and more preferably from 150 ° C to 200 ° C after treatment hydrothermal for durability. The causes of the highest rate of NOx reduction in the low-temperature region mentioned above are not necessarily clear. However, because the average particle size increases in this range, the rate of NOx reduction in the chabazite-type zeolite of the present invention in the low temperature region tends to increase.
[0084] The NOx reduction rate of the copper-loaded chabazite zeolite of the present invention is 52% or more at 150 ° C, and more preferably 54% or more at 150 ° C after the hydrothermal durability treatment. Even in cases where the rate of NOx reduction at temperatures other than 150 ° C is not 52% or more, copper-laden zeolite that has a reduction rate of 52% or more at 150 ° C falls within the range of NOx reduction rate that has the copper-loaded chabazite zeolite of the present invention.
[0085] On the other hand, if the average particle size becomes too large, the handling capacity decreases when used as a catalyst. Therefore, the average particle size of the chabazite-type zeolite of the present invention is 8.0 pm or less, preferably 5.0 pm or less, and more preferably 3.5 pm or less.
[0086] The average particle size in the present invention is that of primary particles that are aggregated by crystallites. Consequently, it differs from that of particles (so called secondary particles) aggregated by the primary particles.
The copper-loaded chabazite-type zeolite of the present invention preferably has 90% of the particle size of 15.0 pm or less, and 10.0 pm or less is more preferable. The particle size distribution in the present invention can be assessed by measuring the particle size distribution (volumetric distribution) by laser scattering and diffraction method. The particle size distribution by the laser diffraction and dispersion method can be quantified with satisfactory reproducibility by conducting measurement after treatment in which zeolite is dispersed in water, and the dispersed state of the crystalline particles is uniformized by an ultrasonic homogenizer. When 90% of the particle size exceeds 15.0 pm, it is difficult to obtain crystalline particles dispersed with the average particle size from 1.0 pm to 8.0 pm which is the characteristic feature of the chabazite-type zeolite of the present invention. Furthermore, clogging or detachment tends to occur when the zeolite is coated on a honeycomb substrate, which is a fact of deteriorating compressive strength when used for molded products.
[0088] A figurative requirement of the zeolites of the present invention is that they have a chabazite structure. Among these, chabazite-type zeolite with the crystalline structure that belongs to SSZ-13 is particularly preferable. The reason for this is that it is possible to provide adequate durability to the zeolite because it has a crystalline structure that belongs to SSZ-13 in which the molar ratio SÍO2 / AI2O3 is 5 or more
[0089] Next, the production method and the use method of the new copper-loaded chabazite zeolite of the present invention are described.
[0090] There are no particular limitations with respect to the production method of the new copper-loaded zeolite-type zeolite of the present invention. For example, production can be conducted by producing chabazite-type zeolite, converting it to type H and subsequently using it to load copper.
[0091] The new copper-loaded chabazite-type zeolite of the present invention is preferably produced by carrying copper in the chabazite-type zeolite obtained by the aforementioned production method. It is particularly preferable to produce by loading copper into the chabazite-type zeolite. Through this, it is possible to obtain chabazite-type zeolite in which the ionic adsorption sites are occupied by copper and / or protons (H +).
[0092] If copper can be loaded into the zeolite, there are no particular limitations regarding the charging method. Regarding the copper-loaded method, a method such as ion exchange, impregnation, evaporation to dryness, precipitation, physical mixing and replacement of the structure can be adopted.
[0093] As for the raw materials used in loading copper, both soluble and insoluble materials such as nitrates, sulfates, acetates, chlorides, complex salts, oxides and compound oxides that include copper can be used.
[0094] As a method for loading copper into chabazite-type zeolite, one can mention a method in which copper is charged by ion exchange using copper acetate monohydrate in a proportion of 0.2 times equivalent or more and 5.0 times equivalent or less with respect to the chabazite-type zeolite of the present invention.
[0095] Regarding the number of copper equivalents employed, when copper is loaded into chabazite-type zeolite, an equivalent amount of 0.5 in terms of the atomic ratio (Cu / Al) of copper that includes raw materials used in the loading of copper to aluminum in chabazite-type zeolite was considered 1 time equivalent.
[0096] The new copper-loaded chabazite zeolite of the present invention can be used as a catalyst incorporated in an exhaust gas treatment system. In addition, it can also be used as a catalyst that performs reductive removal of NOx contained in a gas stream in the presence of oxygen, a so-called NOx reduction catalyst.
[0097] In particular, the new copper-loaded chabazite-type zeolite of the present invention can be used as a so-called NOx reduction catalyst with excellent low temperature activity; that is, as a catalyst that, even after the hydrothermal treatment of durability, not only has a high rate of NOx reduction in a high temperature region of 400 ° C or more, and preferably from 400 ° C to 600 ° C, but it also has a high NOx reduction rate in a low temperature region of 100 ° C to 250 ° C, preferably from 100 ° C to 200 ° C, and more preferably from 150 ° C to 200 ° C. In the present invention, the rate of NOx reduction in the high temperature region after the hydrothermal durability treatment is evaluated in terms of the NOx reduction rate at 500 ° C, and the NOx reduction rate in the low temperature region after the hydrothermal durability treatment is evaluated by the NOx reduction rate at 150 ° C.
[0098] The low temperature activity as an SCR catalyst of the new copper-loaded chabazite zeolite of the present invention can be evaluated by measuring the NOx reduction rate at a low temperature of 100 ° C to 250 ° C, preferably from 100 ° C to 200 ° C, and more preferably 150 ° C to 200 ° C after the aforementioned hydrothermal durability treatment.
[0099] A NOx reduction catalyst consisting of the chabazite-type zeolite of the present invention can be used by mixing and molding it with binders such as silica, alumina and clay minerals. As clay minerals used for molding, one can list kaolin, atapulgite, montmorillonite, bentonite, allophane and sepiolite. It can also be used for coating with washing on a honeycomb substrate made of cordierite or metal.
[00100] Reductive removal of NOx from the exhaust gas can be done by placing the aforementioned exhaust gas in contact with a catalyst consisting of the aforementioned chabazite-type zeolite. With respect to NOx which is reductively removed by the chabazite-type zeolite of the present invention, there is, for example, nitrogen monoxide, dioxide and nitrogen, dinitrogen trioxide, dinitrogen tetraoxide, dinitrogen monoxide and mixtures thereof. Nitrogen monoxide, nitrogen dioxide and dinitrogen monoxide are preferable. There are no particular limitations with respect to the NOx concentration of the exhaust gas that is treatable by the present invention.
[00101] It is also effective in cases where components other than NOx are contained in the aforementioned exhaust gas, and hydrocarbon, carbon monoxide, carbon dioxide, hydrogen, nitrogen, sulfur oxides and water can also be contained. Specifically, with the NOx reducing removal method of the present invention, NOx can be reductively removed, for example, from a wide variety of exhaust gases from diesel cars, gasoline cars, boilers, gas turbines and so on.
[00102] The NOx reducing removal method of the present invention reductively removes NOx in the presence of a reducing agent. Reducing agents such as hydrocarbon, carbon monoxide and hydrogen that are contained in the aforementioned exhaust gas can be used, and it is also acceptable to coexist with suitable reducing agents by adding them to the exhaust gas as necessary. There is no particular limitation regarding the reducing agents that can be added to the exhaust gas, and for example, ammonia, urea, organic amines, hydrocarbons, alcohols, ketones, carbon monoxide and hydrogen can be mentioned. In order to further increase the efficiency of reducing NOx removal, ammonia, urea and organic amines which have a high reaction selectivity are preferable. There is no particular limitation regarding the method of adding these reducing agents, and a method can be adopted in which the reducing components are directly added in the gaseous form, a method in which they are blasted in the liquid form of an aqueous solution, and aerated , a method in which spray pyrolysis is conducted, and the like. The additive amounts of these reducing agents can optionally be set to allow sufficient NOx reducing removal.
[00103] With respect to the NOx reducing removal method of the present invention, there is no particular limitation with respect to the spatial velocity while the exhaust gas and a catalyst composed of the chabazite-type zeolite of the present invention are in contact, but a spatial velocity of 500-500,000 h-1 on a volumetric basis is preferable, and 2,000- 300,000 h-1 is more preferable. (Examples)
[00104] The present invention is specifically described below by means of examples and comparative examples. However, the present invention is not limited by these examples. Example 1 (production of zeolite 1)
[00105] To 13.9g of a 25% aqueous solution of N, N, N-trimethylated ammonium ammonium (hereinafter referred to as "25% aqueous TMADAOH solution") 31.4 g of pure water, 2.5 g of a 48% aqueous solution of potassium hydroxide and 9.0 g of amorphous aluminosilicate gel prepared from sodium silicate and aluminum sulphate, and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.048 A12O3: 0.124 TMADAOH: 0.054 Na2O: 0.081 K2O: 18 H2O.
[00106] This raw material composition was sealed in an 80 cc stainless steel autoclave and heated for 72 hours at 150 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was a pure chabazite zeolite, that is, a single chabazite zeolite phase. The SiOVAECb molar ratio of this chabazite-type zeolite was 14.9. With respect to this chabazite-type zeolite, 150 images of crystal particles were selected at random from three fields of view photographed at an increase of 5,000 times per SEM, and the particle size (hereinafter referred to as “SEM particle size”) obtained as the arithmetic mean of the respective particle sizes was 1.54 pm. Pure water was added to the chabazite-type zeolite to prepare a slurry of 1% solids content, and measurement of particle size distribution (volumetric distribution) was conducted by laser diffraction and dispersion method after conducting the ultrasonic dispersion treatment. for 2 minutes. As a result, with respect to the obtained chabazite-type zeolite, the 10% particle size was 1.54 pm, the 50% particle size was 2.36 pm, and the 90% particle size was 3.39 pm. This chabazite-type zeolite was considered zeolite 1.
[00107] Table 1 below shows a comparison of the X-ray diffraction pattern of chabazite-type zeolite (US patent 4,544,538) and the X-ray diffraction pattern of the product obtained in example 1. Table 1
Example 2 (production of zeolite 2)
[00108] 11.1 g of a 25% aqueous TMADAOH solution, 35.2 g of pure water, 1.2 g of a 48% aqueous potassium hydroxide solution, and 9.6 g of amorphous aluminum silicate gel prepared at from sodium silicate and aluminum sulphate were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.063 AI2O3: 0.098 TMADAOH: 0.065 Na2O: 0.036 K2O: 18 H2O.
[00109] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 48 hours at 170 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The SiO2 / Al2O3 molar ratio of this chabazite-type zeolite was 14.2.
[00110] This chabazite-type zeolite was subjected to observation by SEM and measurement of particle size distribution in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 1.03 pm, the 10% particle size was 1.54 pm, the 50% particle size was 3.94 pm, and the 90% particle size was 7.14 pm. This chabazite-type zeolite was considered zeolite 2. Example 3 (production of zeolite 3)
[00111] 9.3 g of a 25% aqueous TMADAOH solution, 36.2 g of pure water, 0.4 g of a 48% aqueous sodium hydroxide solution, 2.0 g of an aqueous potassium hydroxide solution 48%, and 9.2 g of amorphous aluminum silicate gel subjected to Na removal treatment were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.065 A12O3: 0.081 TMADAOH: 0.02 Na2O: 0.063 K2O: 18H2O.
[00112] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 70 hours at 150 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The SiO2 / Al2O3 molar ratio of this chabazite-type zeolite was 14.4. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 1.90 pm, the 10% particle size was 2.76 pm, 50% particle size was 5.37 pm, and 90% particle size was 9.07 pm. This chabazite-type zeolite was considered zeolite 3. Example 4 (production of zeolite 4)
[00113] 9.3 g of a 25% aqueous TMADAOH solution, 36.2 g of pure water, 0.9 g of a 48% aqueous sodium hydroxide solution, 1.4 g of an aqueous potassium hydroxide solution 48%, and 9.3 g of amorphous aluminum silicate gel were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.076 AI2O3: 0.081 TMADAOH: 0.042 Na2O: 0.042 K2O: 18 H2O.
[00114] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 70 hours at 170 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite zeolite, i.e., a single chabazite zeolite phase. The SiO ^ AEOs molar ratio of this chabazite-type zeolite was 12.5. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 1.59 pm, the 10% particle size was 2.98 pm, 50% particle size was 7.90 pm, and 90% particle size was 20.7 pm. This chabazite-type zeolite was considered zeolite 4. Example 5 (production of zeolite 5)
[00115] A product was obtained by the same method as in Example 4, except that the SiO ^ AECh molar ratio of the raw material composition was changed.
[00116] Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite zeolite, that is, a single chabazite zeolite phase. The molar ratio SiO2 / AI2O3 of this chabazite-type zeolite was 14.4. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 2.23 pm, the 10% particle size was 4.65 pm, 50% particle size was 9.22 pm, and 90% particle size was 16.7 pm. This chabazite-type zeolite was considered zeolite 5. Example 6 (production of zeolite 6)
[00117] A product was obtained by the same method as in Example 3, except that the crystallization temperature was adjusted to 170 ° C.
[00118] Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite zeolite, that is, a single chabazite zeolite phase. The molar ratio SiO2 / AI2O3 of this chabazite-type zeolite was 14.4. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 2.67 pm, the 10% particle size was 4.18 pm, 50% particle size was 9.16 pm, and 90% particle size was 17.9 pm. This chabazite-type zeolite was considered zeolite 6. Example 7 (production of zeolite 7)
[00119] A product was obtained by the same method as in Example 3, except that the crystallization temperature was adjusted to 180 ° C.
[00120] Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite zeolite, that is, a single chabazite zeolite phase. The molar ratio SiO2 / AI2O3 of this chabazite-type zeolite was 14.8. This chabazite-type zeolite was subjected to SEM observation and measurement of particle size distribution in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 3.50 pm, the 10% particle size was 5.95 pm, 50% particle size was 10.7 pm, and 90% particle size was 19.0 pm. This chabazite-type zeolite was considered zeolite 7. Example 8 (production of zeolite 8)
[00121] 589 g of a 25% TMADAOH aqueous solution, 2,270 g of pure water, 27 g of a 48% aqueous sodium hydroxide solution, 127 g of a 48% aqueous potassium hydroxide solution, and 582 g of gel amorphous aluminum silicate were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.072 AI2O3: 0.081 TMADAOH: 0.021 Na2O: 0.063 K2O: 18 H2O.
[00122] This raw material composition was sealed in a 4 L stainless steel autoclave, and heated for 91 hours at 150 ° C under direct stirring. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The SiO2 / Al2O3 molar ratio of this chabazite-type zeolite was 13.4. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 2.34 pm, the 10% particle size was 2.69 pm, 50% particle size was 6.38 pm, and 90% particle size was 9.96 pm. This chabazite-type zeolite was considered zeolite 8. Example 9 (production of zeolite 9)
[00123] 8.3 g of a 25% aqueous TMADAOH solution, 37.0 g of pure water, 0.9 g of a 48% aqueous sodium hydroxide solution, 1.4 g of an aqueous potassium hydroxide solution 48%, and 9.4 g of amorphous aluminum silicate gel were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.076 AI2O3: 0.082 TMADAOH: 0.043 Na2O: 0.043 K2O: 18 H2O.
[00124] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 70 hours at 150 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The molar ratio SiO2 / AI2O3 of this chabazite-type zeolite was 12.1. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 1.12 pm, the 10% particle size was 2.54 pm, 50% particle size was 4.26 pm, and 90% particle size was 8.04 pm. This chabazite-type zeolite was considered zeolite 9. Example 10 (production of zeolite 10)
[00125] 7.5 g of TMADAOH 25% aqueous solution, 37.0 g of pure water, 1.0 g of 48% aqueous sodium hydroxide solution, 1.4 g of aqueous potassium hydroxide solution 48%, and 9.3 g of amorphous aluminum silicate gel were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.072 AI2O3: 0.065 TMADAOH: 0.044 Na2O: 0.044 K2O: 18 H2O.
[00126] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 70 hours at 150 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The molar ratio SiO2 / AI2O3 of this chabazite-type zeolite was 13.3. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same manner as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 1.50 pm, 0 10% particle size was 2.74 pm, 50% particle size was 5.56 pm, and 90% particle size was 9.96 pm. This chabazite-type zeolite was considered zeolite 10. Example 11 (production of zeolite 11)
[00127] A product was obtained by the same method as in Example 10, except that the SiO2 / AI2O3 molar ratio of the raw material composition was changed to 12, and the crystallization temperature was changed to 160 ° C.
[00128] Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite zeolite, that is, a single chabazite zeolite phase. The SiO2 / Al2Os molar ratio of this chabazite-type zeolite was 12.2. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 1.41 pm, the 10% particle size was 3.23 pm, 50% particle size was 5.84 pm, and 90% particle size was 24.5 pm. This chabazite-type zeolite was considered zeolite 11. Example 12 (production of zeolite 12)
[00129] 6.9 g of a 25% aqueous TMADAOH solution, 38.2 g of pure water, 1.0 g of a 48% aqueous sodium hydroxide solution, 1.5 g of an aqueous potassium hydroxide solution 48%, and 9.4 g of amorphous aluminum silicate gel were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.082 AI2O3: 0.060 TMADAOH: 0.046 Na2O: 0.046 K2O: 18 H2O.
[00130] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 70 hours at 150 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, washed with a sufficient amount of pure water, and dried at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The SiO2 / Al2O3 molar ratio of this chabazite-type zeolite was 11.8. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 1.45 pm, the 10% particle size was 3.11 pm, 50% particle size was 5.64 pm, and 90% particle size was 38.2 pm. This chabazite-type zeolite was considered zeolite 12. Comparative example 1 (production of comparative zeolite 1)
[00131] Referring to the method described in Example 2 of U.S. Patent 4,544,538, chabazite-type zeolite was produced as follows.
[00132] 14.7 g of aqueous sodium silicate solution No. 3 (SiO2: 29.3%, Na2O: 9.2%), 19.6 g of an aqueous solution of N, N, N-trimethylated ammonium ammonium 20% (hereinafter referred to as “TMADABr”), and 2.1 g of pure water were mixed together to prepare an aqueous solution (the aqueous solution obtained was considered “aqueous solution A”). Then, 1.4 g of aqueous aluminum sulfate solution (AI2O3: 8.0%) and 2.0 g of 48% aqueous sodium hydroxide solution were added to 17.1 g of pure water to prepare a aqueous solution (the aqueous solution obtained was considered “aqueous solution B”). Aqueous solution B was added to aqueous solution A, and the solution was stirred until the solution was homogeneous to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.016 AI2O3: 0.20 TMADABr: 0.47 Na2Ü: 36 H2O.
[00133] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 144 hours at 140 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The molar ratio SiO2 / AI2O3 of this chabazite-type zeolite was 8.9. This chabazite zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite zeolite, the SEM particle size was 8.78 pm, the 10% particle size was 8.06 pm, 50% particle size was 14.46 pm, and 90% particle size was 32.66 pm. This chabazite-type zeolite was considered a comparative zeolite 1. Comparative example 2 (production of comparative zeolite 2)
[00134] Referring to the method described in Example 7 of U.S. Patent 4,544,538, chabazite-type zeolite was produced as follows.
[00135] 14.9 g of Aqueous sodium silicate solution No. 3, 12.8 g of a 20% TMADABr aqueous solution, and 7.9 g of pure water were mixed together to prepare an aqueous solution (the solution obtained was considered “aqueous solution A2”). Then, 3.3 g of aqueous aluminum sulfate solution and 2.1 g of 48% aqueous sodium hydroxide solution were added to 16.0 g of pure water to prepare an aqueous solution (the aqueous solution obtained was considered “B2 aqueous solution”). Aqueous solution B2 was added to the aqueous solution A2, and the solution was stirred until the solution became homogeneous to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.036 AI2O3: 0.13 TMADABr: 0.47 Na2O: 36 H2O.
[00136] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 144 hours at 140 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the concept obtained was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The SiO2 / Al2Os molar ratio of this chabazite-type zeolite was 10.7. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same manner as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 0.62 pm, the 10% particle size was 0.65 pm, 50% particle size was 1.04 pm, and 90% particle size was 1.55 pm. This chabazite-type zeolite was considered a comparative zeolite 2. Comparative example 3 (production of comparative zeolite 3)
[00137] Chabazite-type zeolite was produced by the same method as Comparative Example 2, except that the molar ratio SiO2 / AI2O3 of the raw material composition was changed.
[00138] 15.1 g of aqueous sodium silicate solution No. 3, 13.0 g of a 20% TMADABr aqueous solution, and 8.0 g of pure water were mixed together to prepare an aqueous solution (the solution obtained was considered “A3 aqueous solution”). Then, 0.6 g of aqueous aluminum sulfate solution and 2.1 g of 48% aqueous sodium hydroxide solution were added to 18.2 g of pure water to prepare an aqueous solution (the aqueous solution obtained was considered “aqueous solution B3”). Aqueous solution B3 was added to the aqueous solution A3, and the solution was stirred until the solution was homogeneous to obtain a raw material composition. The composition of the raw material composition was SiCE: 0.007 AI2O3: 0.13 TMADABr: 0.47 Na2O: 36 H2O.
[00139] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 144 hours at 140 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the concept obtained was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The molar ratio SiO2 / AI2O3 of this chabazite-type zeolite was 9.9. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same manner as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 14.04 pm, the 10% particle size was 18.42 pm, 50% particle size was 47.48 pm, and 90% particle size was 86.32 pm. This chabazite-type zeolite was considered a comparative zeolite 3. Comparative example 4 (production of comparative zeolite 4)
[00140] Referring to the method described in U.S. patent 4,665,110, chabazite-type zeolite was produced as follows.
[00141] 17.9 g of a 13% TMADAOH aqueous solution, 27.2 g of pure water, 0.9 g of a 48% aqueous sodium hydroxide solution, 0.29 g of aluminum hydroxide, and 3, 7 g of amorphous silica powder (manufactured by Tosoh Silica Corporation; trade name: Nipsil VN-3) were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.036 A12O3: 0.20 TMADAOH: 0.10 Na2O: 44 H2O.
[00142] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 158 hours at 150 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The SiOVAhCh molar ratio of this chabazite-type zeolite was 22.3. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 0.48 pm, the 10% particle size was 0.71 pm, 50% particle size was 1.25 pm, and 90% particle size was 2.64 pm. This chabazite-type zeolite was considered a comparative zeolite 4. Comparative example 5 (production of comparative zeolite 5)
[00143] Chabazite-type zeolite was produced by the same method as Comparative Example 4, except that the SiO2 / Al2O3 molar ratio of the raw material composition was changed.
[00144] Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite zeolite, that is, a single chabazite zeolite phase. The SiO2 / Al2O3 molar ratio of this chabazite-type zeolite was 13.8. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same manner as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 0.36 pm, the 10% particle size was 0.35 pm, 50% particle size was 0.59 pm, and 90% particle size was 8.21 pm. This chabazite-type zeolite was considered a comparative zeolite 5. Comparative example 6 (production of comparative zeolite 6)
[00145] 9.2 g of a 25% aqueous TMADAOH solution, 35.3 g of pure water, 3.4 g of a 48% aqueous potassium hydroxide solution, and 9.2 g of amorphous aluminum silicate gel that were subjected to Na removal treatment were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.076 AI2O3: 0.081 TMADAOH: 0.106 K2O: 18 H2O.
[00146] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 70 hours at 150 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powdered X-ray diffraction, the product was a mixture of chabazite and merlionite. Comparative example 7 (production of comparative zeolite 7)
[00147] 9.4 g of a 25% aqueous TMADAOH solution, 36.1 g of pure water, 2.2 g of a 48% aqueous potassium hydroxide solution, and 9.3 g of amorphous aluminum silicate gel that were subjected to Na removal treatment were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.082 Al2Os: 0.081 TMADAOH: 0.070 K2O: 18 H2O.
[00148] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 70 hours at 150 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The molar ratio SiO2 / AI2O3 of this chabazite-type zeolite was 12.0. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 0.89 pm, the 10% particle size was 2.90 pm, 50% particle size was 5.97 pm, and 90% particle size was 10.9 pm. This chabazite-type zeolite was considered a comparative zeolite 7. Comparative example 8 (production of comparative zeolite 8)
[00149] Referring to the method described in Japanese unexamined patent application, first publication No. 2010-168269, chabazite-type zeolite was produced as follows.
[00150] 11.2 g of a 25% TMADAOH aqueous solution, 35.1 g of pure water, 1.4 g of a 48% aqueous potassium hydroxide solution, and 9.4 g of amorphous aluminum silicate gel were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.050 A12O3: 0.098 TMADAOH: 0.058 Na2O: 0.044 K2O: 18 H2O.
[00151] This raw material composition was sealed in an 80 cc stainless steel autoclave, and heated for 70 hours at 150 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The molar ratio SiO2 / AI2O3 of this chabazite-type zeolite was 17.9. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the SEM particle size was 1.50 pm, the 10% particle size was 1.66 pm, 50% particle size was 3.31 pm, and 90% particle size was 5.70 pm. This chabazite-type zeolite was considered a comparative zeolite 8. Comparative example 9 (production of comparative zeolite 9)
[00152] Referring to the method described in U.S. Patent 4,503,024, chabazite-type zeolite was produced as follows.
[00153] To 128.6 g of pure water, 16.1 g of 48% aqueous potassium hydroxide solution and 15.3 g of type Y zeolite (manufactured by Tosoh Corporation, trademark: HSZ-320HOA) were added, and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiCE: 0.18 AI2O3: 0.06 Na2O: 0.39 K2O: 43 H2O.
[00154] This raw material composition was sealed in a 200 cc stainless steel autoclave, and heated for 96 hours at 95 ° C while kept stationary. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite zeolite, that is, a single chabazite zeolite phase. The molar ratio SiO2 / AI2O3 of this chabazite-type zeolite was 4.5. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same manner as in example 1. As a result of SEM observation, it was clear that this chabazite-type zeolite consisted of fine particle aggregates of less than 0 , 5 pm. Consequently, SEM particle size measurement was not conducted. The 10% particle size was 4.90 pm, the 50% particle size was 7.47 pm, and the 90% particle size was 21.8 pm. This chabazite-type zeolite was considered a comparative zeolite 9. Comparative example 10 (production of comparative zeolite 10)
[00155] Referring to the method described in U.S. Patent 2011 / 020204A1, chabazite-type zeolite was produced as follows.
[00156] 125.2 g of pure water, 19.6 g of 48% aqueous potassium hydroxide solution, and 15.2 g of type Y zeolite (manufactured by Tosoh Corporation, registered trademark: HSZ-320HOA) were added together and the ingredients were sufficiently mixed to obtain a raw material composition. The composition of the raw material composition was SiO2: 0.18 A12O3: 0.06 Na2O: 0.48 K2O: 43 H2O.
[00157] This raw material composition was sealed in a 200 cc stainless steel autoclave, and heated for 96 hours at 95 ° C while rotation was conducted at 55 rpm. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a product. Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite-type zeolite, that is, a single chabazite-type zeolite phase. The SiCE / AECh molar ratio of this chabazite-type zeolite was 4.4. This chabazite-type zeolite was subjected to SEM observation and particle size distribution measurement in the same manner as in example 1. As a result of SEM observation, it was clear that this chabazite-type zeolite consisted of fine particle aggregates of less than 0 , 5 gm. Consequently, SEM particle size measurement was not conducted. With respect to this chabazite-type zeolite, the 10% particle size was 4.77 pm, the 50% particle size was 7.32 pm, and the 90% particle size was 22.0 pm. This chabazite-type zeolite was considered a comparative zeolite 10.
[00158] The raw material and product compositions of Examples 1-12 and Comparative Examples 1-10 are shown in Table 2 below. In addition, Table 3 shows the molar ratio SiO2 / AI2O3, the particle sizes obtained by measuring the particle size distribution, and the particle sizes quantified by SEM photographs relevant to the products. Table 2
Table 3

Example 13 (hydrothermal resistance test)
[00159] After calcination of the dry powders of Zeolite 10 and comparative Zeolite 5 for 2 hours at 600 ° C during air flow, each powder was molded in a press and then ground to obtain a regulated powder in a 12-20 mesh. A fixed bed flow reaction tube of ordinary pressure was filled with 3 mL of zeolite, and treated for 1 hour at 900 ° C under circulation at 300 mL / min of air containing 10 volume% moisture. The heat resistance of zeolite was evaluated in terms of crystallinity after hydrothermal treatment of durability. Crystallinity was computed as a peak intensity ratio by measuring powder X-ray diffraction, and using the state before hydrothermal treatment of durability as 100 at the diffraction peak of d = 4.25 shown in Table 1. Table 4 shows crystallinity (%) after each hydrothermal durability treatment. It is shown that the chabazite-type zeolite of the present invention has a greater retention of crystallinity, and better heat resistance than conventional chabazite-type zeolite. Table 4

[00160] The following examples show examples and comparative examples of chabazite-type zeolites loaded with copper between the aforementioned chabazite-type zeolites.
[00161] All measurements were performed using the method shown below. (Method for measuring average particle size)
[00162] Measurement of average particle size was conducted by SEM observation in the same manner as in example 1. Selection of 150 crystal particle images was conducted randomly from SEM photographs of three fields of view photographed at an increase of 5,000 times, and the respective particle sizes were averaged to obtain the particle size (hereinafter referred to as “SEM particle size”). (Method to calculate atomic ratio of copper to aluminum by the ICP composition analysis method)
[00163] A 500 ml measuring flask was loaded with 10 ml of 60% nitric acid and 10 ml of hydrofluoric acid, and alignment with the commercial lime was conducted by adding pure water to prepare the cleaning solution. 30 mg of chabazite-type zeolite was placed in a 100 mL measuring flask, and alignment with commercial lime was conducted by adding the prepared cleaning solution - this was used as the ICP analysis solution.
[00164] The molar concentration of Cu obtained by conducting ICP composition analysis was divided by the molar concentration of Al to obtain the atomic ratio of copper to aluminum. (Method to measure the NOx reduction rate (%))
[00165] Measurement of the NOx reduction rate (%) was conducted in the case where gas came into contact at a prescribed temperature under the following conditions. SCR catalysts are generally evaluated using gas that contains an ammonia and NOx reducing agent that must be reduced to 1: 1. The NOx reduction conditions used in the present invention do not include any particular special conditions, and fall within the range of the general conditions used to assess the NOx reducibility of ordinary SCR catalysts.
[00166] NOx reduction conditions adopted for the evaluation of the present invention: Composition of treated gas: NO 200 ppm NH3 200 ppm O2 10 volume% H2O 3 volume% N2 balance Flow of treated gas: 1.5 liters / minute Spatial speed: 60,000 h'1
[00167] Regarding the measurement procedure, chabazite loaded with copper was molded in a press, after which spraying was carried out, and granulation was conducted up to a 12-20 mesh. Each of the granulated zeolites was subjected to a hydrothermal durability treatment by the same method as in Example 13. A fixed-bed flow reaction tube of ordinary pressure was filled with 1.5 ml of copper loaded chabazite after the durability hydrothermal treatment. The evaluation was carried out of regular NOx removal activity at an optional temperature of 150 ° C to 500 ° C while gas from the above-mentioned composition was circulated at 1,500 mL / min in a catalytic layer.
[00168] The NOx removal activity is expressed by the following formula. Formula 1 XNOX - {([NOx] input - [NOx] output) / [NOx] input} X 100
[00169] Here, XNOX indicates the NOx reducing rate (%), [NOx] input indicates the NOx concentration of the gas that is introduced, and [NOx] output indicates the NOx concentration of the gas that is discharged. Example 14 (manufacture of chabazite-type zeolite and copper loading)
[00170] As a structure targeting agent, an aqueous solution of N, N, N-trimethylated mannyl arnonium 25.1% was used. 39.4 g of this structure targeting agent, 87.1 g of pure water, 8.52 g of a 48% aqueous potassium hydroxide solution, 1.97 g of a 48% aqueous sodium hydroxide solution, and 103.1 g of amorphous aluminosilicate gel prepared from sodium silicate and aluminum sulfate were sufficiently mixed together to obtain a raw material composition. This raw material composition was SiO2: 0.065 AI2O3: 0.08 TMADAOH: 0.04 Na2O: 0.13 K2O: 18 H2O.
[00171] This raw material composition was placed in a stainless steel autoclave, and heated for 70 hours at 170 ° C. The product after heating was subjected to solid-liquid separation, the obtained solid phase was washed with a sufficient amount of pure water, and drying was carried out at 110 ° C to obtain a solid product. As a result of the fluorescent X-ray analysis of the obtained solid product, the molar ratio SiO2 / AI2O3 was determined to be 14.4.
[00172] The zeolite X-ray diffraction pattern is shown in Table 5 below. Table 5

[00173] This X-ray diffraction pattern was identical to the X-ray diffraction pattern in Table 1 of the unexamined Japanese patent application, first publication number 2010-168269. Consequently, it was certified that this zeolite was chabazite-type zeolite. The SEM particle size of this chabazite-type zeolite was 2.67 pm. The measurement of the particle size distribution was conducted in the same way as in example 1. As a result, with respect to this chabazite-type zeolite, the 10% particle size was 4.18 pm, the 50% particle size was 9 , 16 pm, and the 90% particle size was 17.9 pm.
[00174] After converting this chabazite-type zeolite into NHA-type chabazite-type zeolite by exchanging NHA, it was heated for one hour at 500 ° C to obtain type H + chabazite-type zeolite. (Copper loading)
[00175] After the injection of 0.95 g of copper acetate monohydrate in 80 g of pure water, stirring was carried out for 10 minutes at 200 rpm to prepare an aqueous solution of copper acetate. 5.45 g of the aforementioned type H + chabazite zeolite (weight at one hour drying at 600 ° C; hereinafter referred to as “dry base”) were injected into this aqueous copper acetate solution, and stirring was conducted for 2 hours at 30 ° C at 200 rpm, after which solid-liquid separation was conducted. The solid phase obtained by the solid-liquid separation was washed with 400 g of pure warm water, and was dried overnight at 110 ° C to produce a catalyst. As a result of the analysis of ICP composition of the obtained catalyst, the atomic ratio of copper to aluminum was 0.30, and the molar ratio SiO2 / AI2O3 was 14.5. (Hydrothermal durability treatment)
[00176] Hydrothermal durability treatment was conducted by the same method as in Example 13. Dry powder of the obtained catalyst was molded under pressure, after which it was ground, and granulated in a 12-20 mesh. A fixed bed flow reaction tube of ordinary pressure was filled with 3 mL of granulated zeolite, and treated for one hour at 900 ° C while air still circulating containing 10% volume of moisture at 300 mL / min. (Measurement of the NOx reduction rate (%))
[00177] Performed by the method described above. The catalyst NOx reduction rate was measured by adding a feed gas mixture made up of 200 ppm NO, 200 ppm NH3, 10% O2, 3% H2O, and with the equilibrium consisting of N2 in a fixed bed flow reaction of ordinary pressure containing the catalyst that has been subjected to hydrothermal durability treatment. Reaction was conducted at a spatial speed of 60,000 hour-1 over a temperature range of 150 ° C to 500 ° C. The NOx reduction rate was computed by dividing the NO concentration that was reductively removed after passing over the catalytic layer by the NOx concentration in the feed gas. Example 15 (production of chabazite-type zeolite and copper loading)
[00178] Chabazite-type zeolite was produced by the same method as Example 14, except that the raw material composition was heated for 70 hours at 150 ° C.
[00179] Based on powder X-ray diffraction and fluorescent X-ray analysis, the product was pure chabazite zeolite, that is, a single phase of chabazite zeolite. The molar ratio SiO2 / AI2O3 of this chabazite-type zeolite was determined to be 14.4. The SEM particle size of this chabazite-type zeolite was 1.90 pm. By conducting the particle size distribution measurement in the same way as in example 1, the 10% particle size of this chabazite-type zeolite was 2.76 pm, its 50% particle size was 5.37 pm, and its particle size 90% particle was 9.07 pm.
[00180] After the conversion of this chabazite-type zeolite into NHC-type chabazite zeolite by exchanging NHC, it was heated for one hour at 500 ° C to obtain chabazite-type z + type H +. (Copper loading)
[00181] After the injection of 2.84 g of copper acetate monohydrate in 80 g of pure water, stirring was conducted for 10 minutes at 200 rpm to prepare an aqueous solution of copper acetate. 5.45 g of the above mentioned type H + chabazite zeolite (dry base) were injected into this aqueous copper acetate solution, and stirring was conducted for 2 hours at 30 ° C at 200 rpm, after which solid-liquid separation was conducted. The solid phase obtained by the solid-liquid separation was washed with 400 g of pure warm water, and was dried overnight at 110 ° C to produce a catalyst. As a result of the analysis of the ICP composition of the obtained catalyst, the atomic ratio of copper to aluminum was 0.28, and the molar ratio SiO2 / AI2O3 was 14.5. (Hydrothermal durability treatment and measurement of the NOx reduction rate (%))
[00182] Then, by the same method that was briefly described in example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate was measured. Example 16 (copper loading)
[00183] A catalyst was produced by the same method as Example 14, except that 0.52 g of copper acetate monohydrate and 5.00 g of chabazite type H + zeolite were used during the loading of copper. As a result of the analysis of ICP composition of the obtained catalyst, the atomic ratio of copper to aluminum was 0.25.
[00184] Then, by the same method as in Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. Example 17 (copper loading)
[00185] A catalyst was produced by the same method as in Example 15, except that an aqueous solution of copper acetate prepared with half (1.42 g) of the amount of copper acetate monohydrate was used. As a result of the analysis of the ICP composition of the obtained catalyst, the atomic ratio of copper to aluminum was 0.32.
[00186] Then, by the same method as in Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. Example 18 (copper loading)
[00187] A catalyst was produced in the same way as in example 15, except that Zeolite 7 (Example 7) was used as the zeolite loaded with copper.
[00188] Dry powder of zeolite 7 was calcined for 2 hours at 600 ° C with air flow. Ion exchange treatment was carried out by feeding an aqueous solution obtained by dissolving an excessive amount of arnonium chloride for aluminum content in the zeolite. After the ion exchange treatment, solid-liquid separation was conducted, the obtained solid phase was washed with a sufficient amount of pure water, and drying was conducted at 110 ° C. The obtained dry powder was subjected to fluorescent X-ray analysis, and it was confirmed that Na or K were removed to the lower limit of detection of fluorescent X-ray analysis (Na2Ü, K2O <0.01% by weight). This NHC chabazite zeolite was calcined for 1 hour at 500 ° C to obtain H + chabazite zeolite.
[00189] After feeding 0.95 g of copper acetate monohydrate in 80 g of pure water, stirring was conducted for 10 minutes at 200 rpm to produce an aqueous solution of copper acetate. 5.45 g (dry basis) of the above mentioned type H + chabazite zeolite were fed into the aqueous copper acetate solution, and stirring was carried out for 2 hours at 30 ° C at 200 rpm to perform solid-liquid separation by Nutsche. The solid phase obtained by solid-liquid separation was washed with 400 g of pure warm water, and dried overnight at 110 ° C to produce a catalyst. As a result of the ICP composition analysis of the obtained catalyst, the atomic ratio of copper to aluminum was 0.24.
[00190] Then, by the same method as in Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. Example 19 (copper loading)
[00191] A catalyst was produced in the same way as in example 18, except that an aqueous solution of copper acetate prepared with 1.5 times (1.42 g) of the amount of copper acetate monohydrate was used. As a result of the analysis of ICP composition of the obtained catalyst, the atomic ratio of copper to aluminum was 0.29.
[00192] Then, by the same method as in Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. Example 20 (copper loading)
[00193] A catalyst was produced in the same way as in example 19, except that Zeolite 8 (Example 8) was used as the zeolite charged with copper. As a result of the analysis of the ICP composition of the obtained catalyst, the atomic ratio of copper to aluminum was 0.30.
[00194] Then, by the same method as Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. Example 21 (copper loading)
[00195] A catalyst was produced in the same way as in example 19, except that Zeolite 10 (Example 10) was used as the zeolite charged with copper. As a result of the ICP composition analysis of the obtained catalyst, the atomic ratio of copper to aluminum was 0.24.
[00196] Then, by the same method as in Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. Comparative example 11 (production of chabazite-type zeolite and copper loading)
[00197] As zeolite loaded with copper, zeolite was synthesized by the method recorded in US 4,665,110.
[00198] X-ray diffraction patterns and X-ray diffraction images of the synthetic product obtained were identical to the X-ray diffraction patterns recorded in US 4,544,538. Consequently, it has been confirmed that this zeolite is chabazite-type zeolite.
[00199] With respect to this chabazite-type zeolite, the SEM particle size was 0.48 pm, and the molar ratio SiO2 / AI2O3 was 22.3. Thus, with respect to the chabazite-type zeolite of Comparative Example 1, it was observed that not only the SEM particle size is small, but also that the SiO2 / AI2O3 molar ratio is large, compared to the chabazite-type zeolites of Examples 14 and 15.
[00200] After undergoing the exchange of NHA with respect to this chabazite-type zeolite, it was heated for 1 hour at 500 ° C to produce chabazite-type zeolite type H +. (Copper loading)
[00201] After feeding 2.6 g of copper acetate monohydrate in 100 g of pure water, stirring was conducted for 10 minutes at 200 rpm to produce an aqueous solution of copper acetate. 10.71 g (dry basis) of the above mentioned type H + chabazite zeolite were fed into the aqueous copper acetate solution, and stirring was carried out for 2 hours at 30 ° C at 200 rpm to perform solid-liquid separation. The solid phase obtained by the solid-liquid separation was washed with 400 g of pure warm water, and dried overnight at 110 ° C to produce a catalyst. As a result of the analysis of ICP composition of the obtained catalyst, the atomic ratio of copper to aluminum was 0.37, and the molar ratio SiO2 / AI2O3 was 22.6. (Hydrothermal durability treatment and measurement of the NOx reduction rate (%))
[00202] Then, by the same method as Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. Comparative example 12 (production of chabazite-type zeolite and copper loading)
[00203] A catalyst was produced by the same method as Comparative Example 11, except that 6.0 g of copper acetate monohydrate was fed into 200 g of pure water, after which stirring was conducted for 10 minutes at 200 rpm to produce a aqueous copper acetate solution.
[00204] Regarding the chabazite-type zeolite obtained, the SEM particle size was 0.48 pm, and the molar ratio SiO2 / AI2O3 was 22.3. Thus, with respect to the chabazite-type zeolite of Comparative Example 2, it was observed that not only the SEM particle size is small, but also that the SiO2 / AI2O3 molar ratio is large compared to the chabazite-type zeolites of Examples 14 and 15.
[00205] After undergoing the NHU exchange with respect to this chabazite type zeolite, it was heated for 1 hour at 500 ° C to produce chabazite type H + type zeolite. A copper-loaded catalyst was obtained using the same method as Comparative Example 1. As a result of the ICP composition analysis of the obtained catalyst, the atomic ratio of copper to aluminum was 0.41, and the molar ratio SiO2 / AI2O3 was 22, 6. (Hydrothermal durability treatment and measurement of the NOx reduction rate (%))
[00206] Then, by the same method as in Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. Comparative example 13 (copper loading)
[00207] A catalyst was produced in the same way as in example 18, except that comparative Zeolite 8 (Comparative example 8) was used as the copper charged zeolite.
[00208] Dry powder of comparative zeolite 8 was calcined for 2 hours at 600 ° C with air flow. Ion exchange treatment was conducted by feeding an aqueous solution obtained by dissolving an excessive amount of ammonium chloride for aluminum content in the zeolite. Solid-liquid separation was subsequently carried out, washing was carried out with a sufficient amount of pure water, and drying was carried out at 110 ° C. The obtained dry powder was subjected to fluorescent X-ray analysis, and it was confirmed that Na or K were removed up to the lower limit of detection of fluorescent X-ray analysis (Na2Ü, K2O <0.01% by weight). This NH4 + chabazite type zeolite was calcined for 1 hour at 500 ° C to obtain H + type chabazite type zeolite.
[00209] After feeding 1.54 g of copper acetate monohydrate in 200 g of pure water, stirring was conducted for 10 minutes at 200 rpm to produce an aqueous solution of copper acetate. 18.6 g (dry basis) of the above mentioned type H + chabazite zeolite were fed into the aqueous copper acetate solution, and stirring was conducted for 2 hours at 30 ° C at 200 rpm to perform solid-liquid separation. The solid phase obtained by the solid-liquid separation was washed with 800 g of pure warm water, and dried overnight at 110 ° C to produce a catalyst. As a result of the ICP composition analysis of the obtained catalyst, the atomic ratio of copper to aluminum was 0.24.
[00210] Then, by the same method as in Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. Comparative example 14 (copper loading)
[00211] A catalyst was produced in the same way as in comparative example 13, except that an aqueous solution of copper acetate prepared with 3 times the amount of copper acetate monohydrate was used. As a result of the analysis of the ICP composition of the obtained catalyst, the atomic ratio of copper to aluminum was 0.30. Then, by the same method as in Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. [00212] Comparative example 15 (copper loading) [00213] A catalyst was produced in the same way as in comparative example 13, except that an aqueous copper acetate solution prepared with 10 times the amount of copper acetate monohydrate was used, and the temperature at which the stirring was conducted after feeding the chabazite-type zeolite type H + into the aqueous copper acetate solution was 60 ° C. As a result of the analysis of the ICP composition of the obtained catalyst, the atomic ratio of copper to aluminum was 1.02.
[00212] Comparative example 15 (copper loading)
[00213] A catalyst was produced in the same way as in comparative example 13, except that an aqueous solution of copper acetate prepared with 10 times the amount of copper acetate monohydrate was used, and the temperature at which stirring was carried out after feeding of chabazite type H + zeolite in the aqueous copper acetate solution was 60 ° C. As a result of the analysis of the ICP composition of the obtained catalyst, the atomic ratio of copper to aluminum was 1.02.
[00214] Then, by the same method as in Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. Comparative example 16 (copper loading)
[00215] Referring to the method described in example 1 of U.S. patent 2011 / 020204A1, a catalyst was produced using comparative zeolite 10 (Comparative example 10) as the copper charged zeolite.
[00216] A slurry was obtained by adding 11 g of dry powder of comparative zeolite 10 to an aqueous solution obtained by dissolving 89 g of ammonium nitrate in 165 g of pure water. This slurry was stirred for 1 hour at 80 ° C, and ion exchange was carried out between zeolite and chabazite type NH / zeolite. Subsequently, solid-liquid separation was conducted, and the obtained solid phase was washed with a sufficient amount of pure water. After repeating this ion exchange treatment three times, drying was carried out at 110 ° C. Fluorescent X-ray analysis of the obtained dry powder was conducted, and it was confirmed that Na or K was removed to the lower limit of detection of fluorescent X-ray analysis (Na2Ü, FUO <0.01% by weight). This NHA chabazite-type zeolite was calcined for 4 hours at 540 ° C to obtain H + type chabazite-type zeolite.
[00217] An aqueous solution of copper sulphate was produced by dissolving 1.02 g of copper sulphate pentahydrate in 50 g of pure water. 3.5 g of the aforementioned type H + chabazite zeolite were added to the aqueous copper sulfate solution, and stirring was carried out for 1 hour at 70 ° C. Subsequently, the solid phase obtained by the solid-liquid separation was washed with 500 g of pure water, and dried overnight at 110 ° C to produce a catalyst. As a result of the analysis of the ICP composition of the obtained catalyst, the atomic ratio of copper to aluminum was 0.19.
[00218] Then, by the same method as in Example 14, the catalyst was molded under pressure, granulated, and subjected to hydrothermal durability treatment, after which the NOx reduction rate (%) was measured. Example 19 (copper loading)
[00219] Table 6 shows the SEM compositions and particle size of the copper loaded chabazites of Examples 14-21 and Comparative Examples 11-16, as well as their NOx removal rates (%) at 150 ° C and 500 ° C after durability hydrothermal treatment. It is shown that the chabazite-type zeolite of the present invention has greater NOx-reducing activity and better hydrothermal durability than conventional chabazite-type zeolite. Table 6


[00220] The present invention has been explained in detail with reference to specific examples, but it will be obvious to those skilled in the art that a variety of modifications and revisions can be added in a scope that does not escape the intent of the present invention. INDUSTRIAL APPLICABILITY
[00221] As the chabazite-type zeolite of the present invention has high durability and heat resistance, it can be conveniently used as a selective catalytic reduction catalyst for NOx in automobile exhaust gas.

权利要求:
Claims (15)
[0001]
1. Chabazite-type zeolite, characterized by the fact that said zeolite has a molar ratio SiO2 / AI2O3 of 10 or greater and less than 15 and an average particle size of 1.0 pm to 8.0 pm.
[0002]
2. Chabazite-type zeolite according to claim 1, characterized by the fact that said average particle size is from 1.0 pm to 5.0 pm.
[0003]
Chabazite-type zeolite according to claim 1 or 2, characterized in that said zeolite has a particle size of 90% based on the volume of 15.0 pm or less.
[0004]
4. Method for producing chabazite-type zeolite as defined in any one of claims 1 to 3, characterized in that it comprises crystallizing a raw material composition in which the molar ratio of a structure targeting agent / SiCE in the composition of raw material satisfies: 0.05 <(structure targeting agent) / SiCE <0.13 and in which the water / SiCE molar ratio in the raw material composition satisfies: 5 <H2O / SiO2 <30 in the presence of hair at least two types of cations selected from the group consisting of Na +, K +, Rb +, Cs + and NHÇ.
[0005]
5. Method for producing chabazite-type zeolite according to claim 4, characterized in that the structure targeting agent comprises at least one element selected from the group consisting of a hydroxide, halide, carbonate, methyl carbonate, and sulfate which comprises N, N, N-trialkylated methyl ammonium as a cation, as well as a hydroxide, halide, carbonate, methyl carbonate, and sulfate which comprises N, N, N-trimethylbenzyl ammonium ion, N-alkyl-3- ion quinuclidinol, or N, N, N-trialkylexoaminonorbornane as a cation.
[0006]
6. Method for producing chabazite-type zeolite according to claim 5, characterized in that the structure targeting agent comprises at least one element selected from the group consisting of N, N, N-trimethylated mannyl arnium hydroxide, N, N, N-trimethylated mannan arnonium, N, N, N-trimethylated mannan arnonium carbonate, N, N, N-trimethylated mannan arnonium carbonate, and N, N, N-trimethylated mannan arnonium sulfate.
[0007]
7. Chabazite-type zeolite, characterized by the fact that said zeolite has a SiO2 / AI2O3 molar ratio of 10 or greater and less than 15, an average particle size of 1.0 pm to 8.0 pm and is charged with copper .
[0008]
Chabazite-type zeolite according to claim 7, characterized in that the said average particle size is from 1.0 pm to 5.0 pm.
[0009]
Chabazite-type zeolite according to claim 7 or 8, characterized in that said zeolite has a particle size of 90% based on the volume of 15.0 pm or less.
[0010]
10. Chabazite-type zeolite according to any of claims 7 to 9, characterized by the fact that the atomic copper / aluminum ratio of said zeolite is 0.10 to 1.00.
[0011]
11. Chabazite-type zeolite according to any of claims 7 to 10, characterized by the fact that ion exchange sites in said zeolite are occupied by copper and / or protons (H +).
[0012]
Chabazite-type zeolite according to any one of claims 7 to 11, characterized in that the crystalline structure of said zeolite is SSZ-13.
[0013]
13. NOx reducing removal catalyst, characterized by the fact that it comprises chabazite-type zeolite as defined in any of claims 7 to 12.
[0014]
14. NOx reducing removal catalyst according to claim 13, characterized in that the NOx reduction rate at 150 ° C after the hydrothermal durability treatment is 52% or more.
[0015]
15. Method for reducing NOx removal, characterized by the fact that it uses the NOx reducing removal catalyst as defined in claim 13 or 14.

类似技术:

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公开号 | 公开日 | 专利标题

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BR112013015583B1|2020-11-10|chabazite-type zeolite, method for producing chabazite-type zeolite, nox reducing removal catalyst, and, nox reducing removal method

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同族专利:

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CN103328385A|2013-09-25|

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CN110316743A|2019-10-11|

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MX356439B|2018-05-29|

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WO2012086753A1|2012-06-28|

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CA2822788C|2018-11-13|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-06-11| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-07-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-10| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2010-285496|2010-12-22|

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JP2010285496|2010-12-22|

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JP2011-064882|2011-03-23|

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