WO2014038690A1 - Silicoaluminophosphate salt and nitrogen oxide reduction catalyst including same - Google Patents

Abstract

The objective of the present invention is to provide a SAPO-47 which gives a catalyst with a high catalytic activity, especially a high catalytic activity at low temperatures, and a method for producing the same. This SAPO-47 has an average crystal particle size of less than 5 μm and a Si/Al molar ratio of less than 0.23. Additionally, in the SAPO-47, the amount of solid acid after a hydration treatment with respect to the amount of solid acid before a hydration treatment is preferably 40% or more. This SAPO-47 can be produced by a production method that has a crystallization process where a mixture including alkylethylenediamine is crystallized.

Description

Silicoaluminophosphate and nitrogen oxide reduction catalyst containing the same

The present invention relates to SAPO-47, which is a kind of silicoaluminophosphate, and a nitrogen oxide reduction catalyst containing the same. More specifically, the present invention relates to SAPO-47 that gives a catalyst having high catalytic activity at low temperatures, a nitrogen oxide reduction catalyst containing the same, and a nitrogen oxide reduction method using the same.

SAPO-47 is a silicoaluminophosphate having a chabazite structure (Non-Patent Document 1), and its synthesis has been reported so far (for example, Non-Patent Documents 2 and 3).
Non-Patent Document 2 discloses SAPO-47 having a composition of Si: Al: P = 0.112: 0.481: 0.407 obtained by crystallization of a mixture containing methylbutylamine. It has been reported.
Non-Patent Document 3 crystallizes a gel containing secondary butylamine and composed of 1.0Al ₂ O ₃ : 1.0P ₂ O ₃ : 3.0 secondary butylamine: 0.6SiO ₂ : 70H ₂ O. SAPO-47 obtained by doing so and a mixture of SAPO-47 and SAPO-5 are disclosed.
However, SAPO-34, which is also a silicoaluminophosphate having a chabazite structure, is used as a catalyst, whereas SAPO-47 has not been reported to be used as a catalyst. There was no SAPO-47 suitable for.

Collection of Simulated XRD Powder Patterns For Zeolites, Fifth Revised Edition 2007, 114-115 Journal of Physical Chemistry, 1989, 93, 6516-6520 Microporous and Mesoporous materials 1999, 31, 187-193

SAPO-47 disclosed in Non-Patent Documents 2 and 3 has a large particle size and is difficult to use for catalyst applications. In addition, these SAPO-47s could not be used as practical catalysts because of their low catalytic properties, so-called catalytic activity.
In addition, in order to produce SAPO-47 of Non-Patent Documents 1 to 3, it was essential to use an organic structure directing agent containing butylamine. However, since butylamine has a low boiling point and easily volatilizes, its handling is difficult. Nevertheless, SAPO-47 could not be obtained using other organic structure directing agents.
An object of the present invention is to solve these problems and to provide SAPO-47 and a method for producing the same that provide a catalyst having a high catalytic activity, particularly a high catalytic activity at a low temperature.

In view of the above problems, the present inventors have intensively studied. As a result, it has been found that SAPO-47 in which the crystal grain size and Si / Al are controlled becomes SAPO-47 which gives a catalyst having a high catalytic activity, particularly at a low temperature. Furthermore, it has been found that such SAPO-47 provides a catalyst exhibiting a high nitrogen oxide reduction rate even when used at a low temperature, and the present invention has been completed.
That is, the gist of the present invention is the following [1] to [13].

[1] SAPO-47 having an average crystal grain size of less than 5 μm and a Si / Al molar ratio of less than 0.23.
[2] SAPO-47 as described in [1] above, wherein the solid acid amount is 0.5 mmol / g or more.
[3] SAPO-47 as described in [1] or [2] above, wherein the solid acid amount after hydration treatment is 40% or more with respect to the solid acid amount before hydration treatment.
[4] The SAPO-47 according to any one of [1] to [3], wherein an alkaline earth metal is supported.
[5] SAPO-47 as described in [4] above, wherein the alkaline earth metal is calcium.
[6] SAPO-47 according to any one of [1] to [5] above, wherein at least one selected from the group consisting of Group VIIIB elements, Group IB elements, and Group VIIB elements in the periodic table is supported.
[7] SAPO-47 as described in [6] above, wherein at least one selected from the group of Group VIIIB elements, Group IB elements and Group VIIB elements of the periodic table is copper.
[8] The method for producing SAPO-47 according to any one of [1] to [7] above, further comprising a crystallization step of crystallizing a mixture containing alkylethylenediamine.
[9] The method for producing SAPO-47 as described in [8] above, wherein in the crystallization step, a mixture having the following composition is crystallized.
2P / 2Al 0.7 or more, 1.5 or less Si / 2Al 0.1 or more, 1.2 or less H ₂ O / 2Al 5 or more, 100 or less Alkylethylenediamine / 2Al 0.5 or more, 5 or less (however, the above composition Each ratio in is a molar ratio.)
[10] The method for producing SAPO-47 as described in [8] or [9] above, wherein in the crystallization step, the alkylethylenediamine is tetraalkylethylenediamine.
[11] The method for producing SAPO-47 according to any one of the above [8] to [10], comprising a metal supporting step of supporting a metal on SAPO-47.
[12] A nitrogen oxide reduction catalyst comprising SAPO-47 according to any one of [1] to [7].
[13] A method for reducing nitrogen oxides using the nitrogen oxide reduction catalyst according to [12].

According to the present invention, it is possible to provide SAPO-47 which gives a catalyst having a high catalytic activity, particularly at a low temperature. Furthermore, according to the present invention, SAPO-47 can be provided in which the decrease in the amount of solid acid is small even after the treatment for exposing it to a moisture-containing atmosphere for a certain period of time.
The SAPO-47 of the present invention can be used as a catalyst, further as a nitrogen oxide reduction catalyst, and further as an SCR catalyst. In particular, the SAPO-47 of the present invention supporting copper can be used as a catalyst having a high nitrogen oxide reduction rate, particularly a high nitrogen oxide reduction rate at a low temperature. Furthermore, the SAPO-47 of the present invention is used as a nitrogen oxide reduction catalyst having a high nitrogen oxide reduction rate at a low temperature even after hydration, such as a nitrogen oxide reduction catalyst excellent in so-called low temperature activity. be able to.
In addition, SAPO-47 loaded with copper and alkaline earth metal, and SAPO-47 loaded with copper and calcium are used in environments where there are large changes in atmosphere such as temperature and humidity, such as SCR catalysts for automobile exhaust gas. As a nitrogen oxide reduction catalyst, it can be used as a more suitable catalyst.
Furthermore, the method for producing SAPO-47 of the present invention can provide a novel method for producing SAPO-47 that does not contain butylamine as an essential component.
Furthermore, the water vapor adsorbing and desorbing agent containing SAPO-47 of the present invention has a high water vapor adsorbing and desorbing amount, and is useful for adsorption heat pump systems, desiccant air conditioning systems, humidity adjusting wall agents, humidity adjusting sheets, and the like. It can be used as a water vapor adsorption / desorption agent.
Furthermore, such a water vapor adsorption / desorption agent can be used as a water vapor adsorption / desorption agent having a high water vapor adsorption / desorption amount when used as a water vapor adsorption / desorption agent in a moisture removal system.

FIG. 2 is an SEM observation diagram (in the figure: scale is 10 μm) showing SAPO-47 obtained in Example 1. FIG. 3 is a graph showing a powder X-ray diffraction pattern of SAPO-47 obtained in Example 1. FIG. 2 is a comparison diagram of the X-ray diffraction pattern of Reference Example 1 and the powder X-ray diffraction pattern of Example 1 (in the figure, the solid line is Example 1 and the broken line is Reference Example 1). It is a reference powder X-ray diffraction pattern of SAPO-34 published by IZA. (Reference source: <URL http://www.iza-online.org/synthesis/Recipes/XRD/SAPO-34.html> It is a figure which shows the water vapor | steam adsorption isotherm measured at 25 degreeC of the silicoaluminophosphate obtained in Experimental example 1. FIG. It is a figure which shows the water vapor | steam adsorption isotherm measured at 25 degreeC of the silicoaluminophosphate obtained in the comparative experiment example 1. FIG. FIG. 4 is a comparison diagram between the X-ray diffraction pattern of Reference Example 1 and the X-ray diffraction pattern of Experimental Example 1 (in the figure, the solid line is Experimental Example 1 and the broken line is Reference Example 1).

Hereinafter, the SAPO-47 of the present invention will be described in detail.
The present invention relates to SAPO-47. SAPO-47 is an 8-membered silicoaluminophosphate having a chabazite structure.
Silicoaluminophosphate is a zeolite-related substance having silicon (Si), aluminum (Al), phosphorus (P) and oxygen (O) as the main components of its skeleton. The composition of silicoaluminophosphate can be generally expressed by the following formula (1).

_{(Si x Al y P z)} O 2 (1)

(However, 0.05 <x ≦ 0.2, 0.45 ≦ y ≦ 0.55, 0.4 ≦ z ≦ 0.45, and x + y + z = 1)

An eight-membered ring having a chabazite structure is a structure that becomes a CHA type when expressed by the IUPAC structure code defined by the Structure Commission of the International Zeolite Society (IZA).
Furthermore, the crystal system of SAPO-47 is hexagonal. Thus, for example, silicoaluminophosphate is an 8-membered ring having a chabazite structure, but its crystal system is triclinic SAPO-34 and silicoaluminophosphate different from SAPO-47. is there.

The X-ray diffraction pattern of SAPO-34 is VERIFIED SYNTHESES OF ZEOLITIC MATERIALS H. Robson, Editor K.K. P. Lillerud, XRD Patterns Second Revised Edition (2001) P.M. 131, or published on the following IZA website. URL http: // www. isa-online. org / synthesis / Recipes / XRD / SAPO-34. html (search date September 6, 2012).

The SAPO-47 of the present invention has an average crystal grain size of less than 5 μm, preferably 4.5 μm or less, and more preferably 4 μm or less. When the average crystal grain size is 5 μm or more, SAPO-47 having low catalytic activity is obtained. In addition, when the average crystal grain size is 5 μm or more, the operability (handling) when applied to a catalyst carrier such as a honeycomb is deteriorated. On the other hand, from the viewpoint of balancing the catalytic activity and the operability, the average crystal grain size may be 0.5 μm or more, further 1 μm or more, and further 3 μm or more.
The average crystal grain size in SAPO-47 of the present invention is the average of the primary particle sizes. Further, the primary particle is an independent minimum unit particle that is confirmed by observation with a scanning electron microscope. Therefore, the average crystal grain size in the present invention is a secondary particle formed by agglomerating primary particles, that is, a particle obtained by averaging the particle size of so-called agglomerated particles, or molding SAPO-47 of the present invention, This is different from the average particle diameter of the aggregated particles obtained by pulverizing this.

Here, the catalytic activity is the performance as a catalyst. For example, the oxidation characteristics when the SAPO-47 of the present invention is used as a solid acid catalyst, or the nitrogen oxidation when this is used as a nitrogen oxide reduction catalyst. Such as product reduction properties.
The surface area of SAPO-47 of the present invention may be such that a catalytic reaction occurs. Examples of the BET specific surface area of the SAPO-47 of the present invention include 500 m ² / g or more and 800 m ² / g or less.
The SAPO-47 of the present invention has many pores. Therefore, there is almost no correlation between the size of the BET specific surface area and the size of the average particle diameter.

SAPO-47 of the present invention has a Si / Al molar ratio of less than 0.23 and preferably 0.2 or less. When the molar ratio of Si / Al is 0.23 or more, the crystal structure becomes unstable. As a result, when such SAPO-47 is used as a catalyst, the catalytic activity tends to decrease. Therefore, the SAPO-47 of the present invention may have a Si / Al molar ratio of 0.18 or less, more preferably 0.16 or less, and even more preferably 0.15 or less. On the other hand, when the Si / Al molar ratio is 0.01 or more, further 0.1 or more, the SAPO-47 of the present invention tends to exhibit higher catalytic activity.

If SAPO-47 of the present invention satisfies the above Si / Al molar ratio, the proportion of phosphorus contained therein can be set to an arbitrary value. The proportion of phosphorus contained in the SAPO-47 of the present invention is, for example, P / Al in a molar ratio of 0.7 or more, further 0.75 or more, further 0.8 or more, or even 0.85 or more. Can be mentioned. On the other hand, examples of the maximum value of the proportion of phosphorus contained in the SAPO-47 of the present invention include 0.9 or less in terms of the molar ratio of P / Al.
The SAPO-47 of the present invention has little change in the amount of solid acid even after a treatment (hereinafter referred to as “hydration treatment”) in which the SAPO-47 is exposed to a moisture-containing atmosphere for a certain period of time. Is preferred. Accordingly, when the SAPO-47 of the present invention is used as a catalyst or a catalyst containing the same, the catalyst activity hardly changes.

Here, the “solid acid” is an index for evaluating the catalytic activity of silicoaluminophosphate.
The solid acid can be confirmed and quantified by a general NH ₃ -TPD method. The solid acid has a property of adsorbing ammonia (NH ₃ ). The NH ₃ -TPD method is a measurement method using this property, in which ammonia is adsorbed and desorbed from silicoaluminophosphate, and the ammonia desorbed from silicoaluminate in a specific temperature range is confirmed and quantified, This is a measurement method for confirming and quantifying this as a solid acid.
As the NH ₃ -TPD method, a method having the following three steps can be exemplified.

1) a pretreatment process for removing gas or moisture adsorbed on silicoaluminophosphate,
2) Ammonia adsorption process for adsorbing ammonia on silicoaluminophosphate, and 3) Ammonia desorption process for desorbing ammonia adsorbed on silicoaluminophosphate therefrom

As the pretreatment step, an inert gas can be circulated through the silicoaluminophosphate at a treatment temperature of 400 to 600 ° C. Further, as the ammonia adsorption step, it is possible to exemplify that an inert gas containing 1 to 20% by volume of ammonia is circulated through the silicoaluminophosphate at a treatment temperature of 100 to 150 ° C. Further, as the ammonia desorption step, the temperature can be raised to about 100 ° C. to 700 ° C. while circulating an inert gas through the silicoaluminophosphate.

In the ammonia desorption process, the solid acid can be confirmed and quantified by confirming and quantifying the desorbed ammonia. The ammonia adsorbed on the silicoaluminophosphate includes ammonia that is physically adsorbed and ammonia that is adsorbed by a solid acid. When the solid acid is confirmed and quantified, it is necessary to separate both of them. For example, the presence of a solid acid can be confirmed with an ammonia peak desorbed at a temperature of 250 to 450 ° C., and the amount of ammonia corresponding to the peak is quantified, and this is regarded as the solid acid amount.

The SAPO-47 of the present invention preferably has a solid acid amount after hydration treatment (hereinafter referred to as “solid acid retention ratio”) of 40% or more with respect to the solid acid amount before hydration treatment, preferably 50% or more. Is more preferably 65% or more, and even more preferably 70% or more. If the solid acid retention rate is within this range, even when the SAPO-47 of the present invention is used in the state of being exposed to the atmosphere and further to the atmosphere containing a large amount of water vapor, the change in the catalytic activity is small. The catalyst exhibits stable catalytic activity. On the other hand, the amount of solid acid tends to decrease by hydrating SAPO-47. Therefore, the solid acid retention rate is usually 100% or less, and further 90% or less.
Here, there is no generalized or standardized condition for the hydration treatment. As the hydration treatment, for example, SAPO-47 can be left standing for 1 hour or more and 60 days or less in a saturated water vapor atmosphere of 60 ° C. or higher and 100 ° C. or lower.

SAPO-47 of the present invention preferably has a high solid acid amount. Since the amount of the solid acid is high, the SAPO-47 of the present invention becomes a catalyst having a high catalytic activity. Therefore, the solid acid amount of SAPO-47 of the present invention is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, and further preferably 0.7 mmol / g or more. . When the solid acid amount is 0.5 mmol / g or more, the SAPO-47 of the present invention tends to be a catalyst having a higher catalytic activity. As the amount of solid acid increases, the catalytic activity tends to increase. On the other hand, if the amount of solid acid is too large, the crystal structure tends to become unstable. Therefore, the amount of solid acid is 1.6 mmol / g or less, further 1.2 mmol / g or less, or even 1.1 mmol / g or less, or even 0.9 mmol / g or less, so that the SAPO of the present invention can be used. -47 tends to have a high catalytic activity and a stable crystal structure.

SAPO-47 of the present invention preferably has a solid acid amount within the above range at least before the hydration treatment, and more preferably the solid acid amount before and after the hydration treatment. However, as described above, the amount of solid acid tends to decrease by hydrating SAPO-47. Therefore, the amount of solid acid after the hydration treatment is, for example, 0.2 mmol / g or more, further 0.25 mmol / g or more, further 0.3 mmol / g or more, or further 0.4 mmol / g or more, Furthermore, it should just be 0.5 mmol / g or more, and also should just be 0.55 mmol / g or more. If the amount of solid acid is within this range after hydration treatment, even when SAPO-47 of the present invention is used in an atmosphere where the crystal structure of SAPO-47 is easily broken, such as in a water vapor atmosphere, This is a stable catalyst having high catalytic activity.

The SAPO-47 of the present invention may be SAPO-47 on which an alkaline earth metal is supported. Since the alkaline earth metal is supported on the SAPO-47 of the present invention, the decrease in the amount of solid acid after the treatment after multiple hydration treatments (hereinafter referred to as “cycle hydration treatment”) is suppressed. It becomes easy to be done.
Here, as the cycle hydration treatment, for example, after SAPO-47 is allowed to stand in a saturated water vapor atmosphere of 60 ° C. or higher and 100 ° C. or lower for 1 hour or longer and 60 days or shorter, 60 ° C. or higher and 200 ° C. A treatment in which SAPO-47 is allowed to stand for 1 hour or more and 60 days or less in the following dry atmosphere (that is, in an atmosphere having a water content of 0.05% by volume or less) is defined as one cycle. Repeating 50 times or less.

The alkaline earth metal is preferably at least one selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba), and more preferably calcium.
When the alkaline earth metal is calcium, the calcium loading is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and even more preferably 0.4% by weight or more. If the amount of calcium supported is within this range, the decrease in the amount of solid acid after the cycle hydration treatment is more easily suppressed. Further, if the calcium content is 2.5% by weight or less, further 2% by weight or less, and further 1.5% by weight or less, an effect of suppressing a sufficient decrease in the amount of solid acid can be obtained. In addition, when alkaline-earth metal is other than calcium, the content should just be a quantity comparable as the amount of substances (mol) corresponding to said calcium content (weight%).

SAPO-47 of the present invention may be SAPO-47 on which a metal is supported. The metal supported on SAPO-47 of the present invention is preferably at least one selected from the group consisting of Group VIIIB elements, Group IB elements and Group VIIB elements of the periodic table, and includes platinum (Pt) and palladium (Pd). More preferably, it is at least one selected from the group consisting of rhodium (Rh), iron (Fe), copper (Cu), cobalt (Co), manganese (Mn) and indium (In). Even more preferably, substantially only copper is preferred. When these metals are supported on the SAPO-47 of the present invention, when they are used as a catalyst, they tend to be a catalyst having a particularly high catalytic activity. For example, the SAPO-47 of the present invention is a SAPO-47 on which copper is supported, so that it becomes a nitrogen oxide reduction catalyst exhibiting a high nitrogen oxide reduction rate.

The amount of the metal supported is arbitrary. For example, the weight of the supported metal is 0.5% by weight or more, further 1% by weight or more, or even 1% by weight of the SAPO-47 of the present invention. It can be mentioned that it is 2% by weight or more, and further 1.5% by weight or more. On the other hand, if the amount of the metal supported is 5% by weight or less, and further 3% by weight or less, the effect of improving the catalytic activity by the metal support is easily obtained.

Further, the SAPO-47 of the present invention may be SAPO-47 on which a metal and an alkaline earth metal are supported. As a result, the SAPO-47 of the present invention is a catalyst exhibiting a high nitrogen oxide reduction rate after being repeatedly exposed to an atmosphere containing moisture, and further after being repeatedly exposed to an atmosphere containing moisture, at 200 ° C. or less. Becomes a catalyst exhibiting a high nitrogen oxide reduction rate.
In the case of SAPO-47 on which a metal and an alkaline earth metal are supported, the preferred metal and alkaline earth metal may be the above alkaline earth metal and the above metal, respectively. These supported amounts may be the above-mentioned alkaline earth metal supported amount and the above metal supported amount, respectively.

Next, a method for producing SAPO-47 of the present invention will be described.
The production method of the present invention is a method for producing SAPO-47, characterized by having a crystallization step of crystallizing a mixture containing alkylethylenediamine.
In the SAPPO-47 production method reported so far, it has been essential to crystallize using a compound containing butylamine as an organic structure directing agent (hereinafter referred to as “SDA”). In contrast, in the production method of the present invention, SAPO-47 can be crystallized without using a compound containing butylamine as an essential component.

Hereinafter, the production method of the present invention will be described in detail.
In the manufacturing method of this invention, it has a crystallization process which crystallizes the mixture containing alkylethylenediamine. Thereby, SAPO-47 having the average crystal grain size and the Si / Al molar ratio of the present invention is obtained.
The alkylethylenediamine is preferably at least one selected from the group of dialkylethylenediamine, trialkylethylenediamine and tetraalkylethylenediamine, more preferably at least one of trialkylethylenediamine or tetraalkylethylenediamine, and tetraalkyl More preferably, it is ethylenediamine, and it is substantially preferable that it is only tetraalkylethylenediamine.
The alkyl group contained in the alkylethylenediamine is preferably at least one selected from the group of a methyl group, an ethyl group, a propyl group, and a butyl group, and more preferably any one or more of a methyl group or an ethyl group. An ethyl group is preferred and even more preferred.

As a more preferable alkylethylenediamine in the crystallization step, at least one selected from the group of tetraethylethylenediamine, triethylethylenediamine and tetramethylethylenediamine, more preferably tetraethylethylenediamine can be exemplified. Tetraethylethylenediamine is represented by a molecular formula of C ₁₀ H ₂₄ N ₂ , which is an alkyl called N, N, N ′, N′-tetraethylethane-1,2-diamine, ethylenebis (diethylamine), or the like. Ethylenediamine.

In the crystallization step, it is preferable to crystallize a mixture containing alkylethylenediamine as SDA and containing a silicon (Si) source, a phosphorus (P) source, an aluminum (Al) source and water (H ₂ O).
The raw materials for the silicon source, phosphorus source and aluminum source can be selected arbitrarily. The following can be illustrated as these raw materials.
As the silicon source, at least one water-soluble silicon compound consisting of colloidal silica, silica sol and water glass, or at least one kind consisting of silicon compound dispersed in a solvent, amorphous silica, fumed silica and sodium silicate. And solid silicon compounds, organosilicon compounds such as ethyl orthosilicate, and mixtures thereof.

Examples of the phosphorus source include one or more water-soluble phosphorus compounds of orthophosphoric acid and phosphorous acid, one or more solid phosphorus compounds of condensed phosphoric acid such as pyrophosphoric acid and calcium phosphate, and mixtures thereof. be able to.
As an aluminum source, at least one water-soluble aluminum compound selected from the group consisting of aluminum sulfate solution, sodium aluminate solution and alumina sol, or an aluminum compound dispersed in a solvent, amorphous alumina, pseudoboehmite, boehmite, aluminum hydroxide, Mention may be made of at least one solid aluminum compound selected from the group of aluminum sulfate and sodium aluminate, organic aluminum compounds such as aluminum isopropoxide, and mixtures thereof.

Furthermore, a compound containing two or more selected from the group consisting of silicon, phosphorus and aluminum can also be used as a raw material. Examples of such compounds include aluminophosphate gel and silicoaluminophosphate gel.

A mixture is obtained by mixing these raw materials with water and SDA. Arbitrary methods can be used for mixing raw materials and the like when obtaining the mixture. For example, each raw material, water, and SDA may be mixed one by one in order, or two or more raw materials may be mixed simultaneously.
You may adjust pH of the obtained mixture as needed. When adjusting the pH of the mixture, for example, an acid such as hydrochloric acid, sulfuric acid or hydrofluoric acid, or an alkali such as sodium hydroxide, potassium hydroxide or ammonium hydroxide may be mixed into the mixture.

In the crystallization step, the composition of silicon, phosphorus, aluminum, water and SDA in the mixture is preferably the following composition.

2P / 2Al 0.7 or more, 1.5 or less Si / 2Al 0.1 or more, 1.2 or less H ₂ O / 2Al 5 or more, 100 or less SDA / 2Al 0.5 or more, 5 or less

In addition, each ratio in the said composition is molar ratio, SDA is said alkylethylenediamine. Moreover, each component in the said composition can also be described as an oxide. That is, in the above composition, 2P / 2Al is P ₂ O ₅ / Al ₂ O ₃ , Si / 2Al is SiO ₂ / Al ₂ O ₃ , H ₂ O / 2Al is H ₂ O / Al ₂ O ₃ , SDA / 2Al can be expressed as SDA / Al ₂ O ₃ , respectively.

As for the ratio of phosphorus and aluminum in the mixture, 2P / 2Al is preferably 0.7 or more, more preferably 0.8 or more, in terms of molar ratio. When 2P / 2Al is 0.7 or more, the yield of SAPO-47 obtained tends to increase. On the other hand, if 2P / 2Al is 1.5 or less, further 1.2 or less, SAPO-47 can be easily obtained in a shorter crystallization time.
The ratio of silicon and aluminum in the mixture is preferably such that Si / 2Al is 0.1 or more and more preferably 0.2 or more in terms of molar ratio. When Si / 2Al is 0.1 or more, SAPO-47 having a larger amount of solid acid is easily obtained. On the other hand, if Si / 2Al is 1.2 or less, further 0.8 or less, SAPO-47 can be easily obtained in a shorter crystallization time.

As for the ratio of water and aluminum in the mixture, H ₂ O / 2Al is preferably 5 or more and more preferably 15 or more in terms of molar ratio. When H ₂ O / 2Al is 5 or more, the resulting mixture is rich in fluidity. Thereby, it becomes easy to become a mixture excellent in operability. The H ₂ O / 2Al in the mixture is preferably small, but if the H ₂ O / 2Al is 100 or less, more preferably 70 or less, the mixture has fluidity suitable for crystallization. Furthermore, since H ₂ O / 2Al is 50 or less, crystallization can be performed at a higher concentration, which is advantageous in industrial production.

The ratio of SDA and aluminum in the mixture is preferably 0.5 or more, more preferably 1 or more in terms of molar ratio. This makes it easier to obtain SAPO-47 with a higher amount of solid acid. The larger SDA / 2Al, the easier it is to obtain SAPO-47 with a higher amount of solid acid. If SDA / 2Al is 5 or less, further 3 or less, or even 1.5 or less, SAPO-47 having a large amount of solid acid is more easily obtained.

In the crystallization step, the mixture preferably contains a seed crystal. When the mixture contains seed crystals, SAPO-47 can be easily obtained in a short crystallization time.
The mixture preferably contains 0.05% by weight or more of seed crystals, more preferably 0.1% by weight or more, still more preferably 0.5% by weight or more, and even more preferably 1% by weight or more. . When the mixture contains 0.05% by weight or more of seed crystals, the crystallization time is easily shortened. In addition, when the mixture contains seed crystals, the SAPO-47 obtained has a uniform crystal grain size. If the crystal grain size of the obtained SAPO-47 becomes uniform, the seed crystal content in the mixture is arbitrary. Therefore, examples of the upper limit of the seed crystal content include 10% by weight or less, and further 5% by weight or less.
The content (% by weight) of seed crystals contained in the mixture is based on the total weight when silicon, phosphorus and aluminum in the mixture are regarded as SiO ₂ , P ₂ O ₅ and Al ₂ O ₃ , respectively. It is the ratio of the weight of seed crystals.

Furthermore, the type of seed crystal is preferably silicoaluminophosphate, more preferably silicoaluminophosphate having a chabazite structure, and even more preferably SAPO-34.
In the crystallization step, the seed crystal preferably has an average particle size of 3 μm or less, more preferably 1.5 μm, and still more preferably 1 μm or less. When the average grain size of the seed crystals is 3 μm or less, the crystal grain size of SAPO-47 obtained is difficult to increase. There is no lower limit of the average particle size of the seed crystal, but for example, if it is 0.1 μm or more, and further 0.5 μm or more, the seed crystal is less likely to aggregate, so the effect of mixing the seed crystal tends to be easily obtained. There is.
As a preferable mixture for obtaining SAPO-47 of the present invention, a mixture having the following composition can be exemplified.

2P / 2Al 0.7 or more, 1.5 or less Si / 2Al 0.1 or more, 1.2 or less H ₂ O / 2Al 5 or more, 100 or less SDA / 2Al 0.5 or more, 5 or less Seed crystal addition amount 0. 05 wt% or more, 10 wt% or less

Furthermore, a mixture having the following composition can be exemplified.

2P / 2Al 0.9 or more, 1.1 or less Si / 2Al 0.3 or more, 1.1 or less H ₂ O / 2Al 15 or more, 50 or less SDA / 2Al 0.5 or more, 1.5 or less Seed crystal 0. 1% to 5% by weight

In addition, each ratio in each of the above compositions is a molar ratio, SDA is tetraethylethylenediamine, and the seed crystal is silicoaluminophosphate.

The production method of the present invention has a crystallization step of crystallizing the mixture. If the mixture is crystallized, the crystallization method can be appropriately selected. A preferred crystallization method is hydrothermal treatment of the mixture. Hydrothermal treatment may be performed by placing the mixture in a sealed pressure resistant container and heating the mixture.
The crystallization temperature is preferably 130 ° C. or higher, and more preferably 150 ° C. or higher. When the crystallization temperature is 130 ° C. or higher, SAPO-47 is crystallized in a relatively short crystallization time, for example, 100 hours or less, further 80 hours or less. The higher the crystallization temperature, the shorter the crystallization time. However, for example, if the crystallization temperature is 220 ° C. or lower, further 200 ° C. or lower, SAPO-47 is easily crystallized even if the crystallization time is 5 hours or more, and further 50 hours or more.
In the crystallization step, it is preferable to crystallize the mixture while stirring. As a result, the crystal grain size of SAPO-47 obtained tends to be more uniform.

In the manufacturing method of this invention, you may have a washing | cleaning process and a drying process further.
In the production method of the present invention, SAPO-47 having the average crystal grain size and Si / Al molar ratio of the present invention is obtained by crystallizing the mixture.
In the washing step, the SAPO-47 after crystallization is separated from the liquid phase by any solid-liquid separation method such as filtration, decantation or centrifugation. The SAPO-47 after solid-liquid separation may be washed with water as appropriate.
In the drying step, the SAPO-47 after filtration is dried. Examples of the drying method include a method of drying at 90 ° C. or higher and 120 ° C. or lower for 5 hours or longer in the air.

In the manufacturing method of this invention, you may have at least any one process of a baking process or a re-washing process.
In the firing step, the SAPO-47 after drying is fired. As a result, SDA taken into SAPO-47 during crystallization can be removed. By removing SDA from SAPO-47, the resulting SAPO-47 tends to exhibit higher catalytic activity when using it of the present invention in applications such as catalysts.
In the baking step, any baking method can be applied as long as SDA can be removed from SAPO-47. Examples of such a firing method include firing at a firing temperature of 400 ° C. or more and 800 ° C. or less in the atmosphere or in an oxidizing atmosphere such as oxygen gas.

In the re-washing step, the SAPO-47 after drying is washed again. When SAPO-47 is crystallized using a material containing an alkali metal or the like as a raw material, the metal derived from the raw material such as the alkali metal may remain on the surface or pores of SAPO-47.
In the re-cleaning step, any cleaning method can be applied as long as the metal derived from the raw material remaining in SAPO-47 can be removed therefrom. Examples of such re-cleaning methods include acid cleaning and ion exchange.
Said baking process and re-washing process can be performed as needed. Therefore, you may perform any one of only a baking process or only a re-washing process. Moreover, when performing both a baking process and a re-washing process, you may perform any of these order first.

The production method of the present invention may have a metal supporting step of supporting a metal on SAPO-47. By supporting the metal, when the obtained SAPO-47 is used for various catalyst applications, its catalytic properties such as its catalytic activity are likely to be particularly high.
Examples of the metal supported on SAPO-47 include at least one selected from the group consisting of Group VIIIB elements, Group IB elements, and Group VIIB elements in the periodic table. Platinum (Pt), palladium (Pd), rhodium It is preferably at least one selected from the group of (Rh), iron (Fe), copper (Cu), cobalt (Co), manganese (Mn) and indium (In), more preferably copper. Substantially only copper is preferred. For example, when copper is supported on SAPO-47, that is, copper-supported SAPO-47 is used as a nitrogen oxide reduction catalyst, a particularly high nitrogen oxide reduction rate is likely to be exhibited.

In the metal loading step, the SAPO-47 used for metal loading is preferably either proton type (H ⁺ type) SAPO-47 or ammonia type (NH ₄ ⁺ type) SAPO-47. As a result, the metal loading on SAPO-47 tends to be performed more efficiently.
In order to make SAPO-47 into proton type (H ⁺ type) SAPO-47, for example, crystallization of SAPO-47 may be performed at 400 ° C. or higher in the atmosphere. In order to change SAPO-47 to ammonia type (NH ₄ ⁺ type) SAPO-47, for example, ion exchange of SAPO-47 after crystallization with an aqueous ammonium chloride solution can be mentioned.
The raw material used for metal loading is any one selected from the group consisting of nitrates, sulfates, acetates, chlorides, complex salts, oxides and complex oxides containing metals to be supported on SAPO-47, and mixtures thereof. be able to.

If a metal is supported in the metal supporting step, any supporting method can be selected. Examples of the supporting method include an ion exchange method, an impregnation supporting method, an evaporation to dryness method, a precipitation supporting method, or a physical mixing method, and the amount of metal supported on SAPO-47 can be easily controlled. Is preferably either the impregnation support method or the evaporation to dryness method.
The amount of the metal supported is arbitrary, but for example, the weight of the supported metal is 0.5% by weight or more, further 1% by weight or more, and further 1.2% by weight with respect to the weight of SAPO-47. As mentioned above, it can be mentioned that metal is supported on SAPO-47 so as to be 1.5% by weight or more. On the other hand, if the metal is supported on SAPO-47 so that the amount of the metal supported is 5% by weight or less, further 3% by weight or less, the catalytic activity due to the metal support tends to be easily obtained.
Further, the metal supporting step may be a metal supporting step in which an alkaline earth metal is supported on SAPO-47 together with or in place of the above metal.

The alkaline earth metal element is preferably at least one selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba), and more preferably calcium.
The alkaline earth metal raw material is selected from the group consisting of nitrates, sulfates, acetates, chlorides, complex salts, oxides and complex oxides containing alkaline earth metals to be supported on SAPO-47, and these Mixtures can be used, preferably nitrates or acetates.
What is necessary is just to use the quantity used as the target carrying amount for these alkaline-earth metal raw materials. For example, when the alkaline earth metal is calcium, the amount of calcium relative to the weight of SAPO-47 is 0.1% by weight or more, further 0.2% by weight or more, and further 0.4% by weight or more. Can be mentioned. On the other hand, the amount of calcium relative to the weight of SAPO-47 may be 2.5% or less, further 2% or less, and even 1.5% or less. When the alkaline earth metal is other than calcium, the alkaline earth metal in the raw material of the alkaline earth metal has an amount equivalent to the amount of substance (mol) corresponding to the above calcium amount (% by weight). That is, the raw material may be used.

The SAPO-47 of the present invention can be used as a catalyst. Further, the SAPO-47 on which copper of the present invention is supported, and the SAPO-47 on which copper and alkaline earth metal of the present invention are supported are a nitrogen oxide reduction catalyst or an SCR catalyst (hereinafter, these are combined). It can be used as “nitrogen oxide reduction catalyst”. Thereby, a nitrogen oxide reduction catalyst having a high nitrogen oxide reduction rate at a low temperature can be provided.
When SAPO-47 of the present invention on which copper is supported (hereinafter referred to as “copper-supported SAPO-47”) is used as a nitrogen oxide reduction catalyst, etc., nitrogen when used at a high temperature of 500 ° C. or higher The oxide reduction rate increases. In addition to this, the copper-supported SAPO-47 becomes a nitrogen oxide reduction catalyst or the like having a high nitrogen oxide reduction rate even when it is used at a low temperature of less than 500 ° C. or even 300 ° C. or less.
For example, the copper-supported SAPO-47 has a nitrogen oxide reduction rate at 500 ° C. of 70% or more, and more preferably 80% or more. In addition, the copper-supported SAPO-47 has a nitrogen oxide reduction rate at 300 ° C. of 70% or more, and further 80% or more.

As described above, copper-supported SAPO-47 has a high nitrogen oxide reduction rate even at a high temperature and a low temperature of about 300 ° C. In addition, the copper-supported SAPO-47 has a high nitrogen oxide reduction rate even when used at a particularly low temperature, for example, 200 ° C. or lower, and even 150 ° C. or lower. It becomes a product reduction catalyst. For example, copper-supported SAPO-47 has a nitrogen oxide reduction rate at 150 ° C. of more than 60%, and more than 65%.
Further, it is preferable that the copper-supported SAPO-47 has little change in the nitrogen oxide reduction rate even after the hydration treatment. It is more preferable that the change is small, and even after the hydration treatment, it is more preferable that the change in the nitrogen oxide reduction rate at a low temperature of 200 ° C. or less is small. As a result, the copper-supported SAPO-47 becomes a nitrogen oxide reduction catalyst or the like that can stably reduce and remove nitrogen oxides even after long-term use.

Therefore, the nitrogen oxide reduction rate after hydration treatment (hereinafter referred to as “NOx reduction maintenance rate”) relative to the nitrogen oxide reduction rate before hydration treatment is preferably 80% or more, and 90% or more. It is more preferable that In particular, the NOx reduction maintenance rate at a low temperature, for example, the NOx reduction maintenance rate at 300 ° C. is more preferably 80% or more, and the NOx reduction maintenance rate at 150 ° C. is still more preferably 80% or more.
In order to have higher nitrogen oxide reduction characteristics and to prolong the catalyst life, SAPO-47 is SAPO-47 on which copper and alkaline earth metal are supported (hereinafter referred to as “copper-alkaline earth metal supported SAPO”). -47 "), and SAPO-47 loaded with copper and calcium (hereinafter referred to as" copper-calcium loaded SAPO-47 ") is more preferable. Copper-alkaline earth metal-supported SAPO-47 has a high nitrogen oxide reduction rate, especially at low temperatures, even after being repeatedly exposed to a water-containing atmosphere as in cyclic hydration. Indicates the rate. Therefore, copper-alkaline earth metal-supported SAPO-47, and further copper-calcium-supported SAPO-47, is a nitrogen oxide reduction agent used in environments with large changes in atmosphere such as temperature and humidity, such as SCR catalyst for automobile exhaust gas. It becomes more suitable as a catalyst.

Here, the nitrogen oxide reduction rate refers to the concentration of nitrogen oxides in the processing gas before the contact when the processing gas containing nitrogen oxides is brought into contact with the nitrogen oxide reduction catalyst or the like. This is the concentration of nitrogen oxides in the reduced process gas. This can be obtained by the following equation (2).

Nitrogen oxide reduction rate (%)
= {1- (nitrogen oxide concentration in the processing gas after contact / nitrogen oxide concentration in the processing gas before contact)} × 100 (2)

There is no generalized or standardized condition for the method for evaluating the nitrogen oxide reduction rate of the SCR catalyst. As an evaluation method of the nitrogen oxide reduction rate of the SCR catalyst, for example, the method shown in the examples, or a gas mixture containing nitrogen oxide and ammonia in a volume ratio of 1: 1 is circulated through the catalyst. As a result, the nitrogen oxide in the mixed gas is reduced, the concentration of nitrogen oxide in the mixed gas before and after circulation is measured, and the above formula (2) is obtained.
In the case of this SCR catalytic reaction, ammonia is used as a reducing agent. Therefore, the nitrogen oxide reduction rate in this case is a value of the nitrogen oxide reduction rate as a so-called ammonia SCR catalyst.
As described above, since SAPO-47 of the present invention has high catalytic activity, the catalyst comprising SAPO-47 of the present invention and the catalyst comprising the same are used as, for example, nitrogen oxide reduction catalyst, factory exhaust gas, automobile exhaust gas, etc. Can be used in various exhaust gas treatment systems.

Further, at least one of SAPO-47 and SAPO-47 on which an alkaline earth metal is supported can be used as a water vapor adsorbing / desorbing agent containing the same (hereinafter referred to as “the present adsorbing / desorbing agent”).
In systems such as an adsorption heat pump system and a desiccant air conditioning system, a water vapor adsorbing and desorbing agent for discharging water vapor is used outside the system. In this system, water vapor (water) is adsorbed on the water vapor adsorbing / desorbing agent at an adsorption temperature of 25 ° C. to 40 ° C., and then heated to a desorption temperature of 60 ° C. to 100 ° C. The water adsorbed on the water vapor adsorbing / desorbing agent is desorbed by heating, whereby the water vapor adsorbing / desorbing agent is dried. The dried water vapor adsorbing / desorbing agent is cooled to the adsorption temperature and used again for water adsorption. In this system, such adsorption and desorption of water vapor (hereinafter referred to as “adsorption / desorption”) is repeated. As a water vapor adsorption / desorption agent used in such a system, an adsorbent having a large amount of water vapor adsorption / desorption in the temperature range from the adsorption temperature to the desorption temperature is desired, and various adsorbents have been proposed.

Japanese Laid-Open Patent Publication No. 2003-340236 reports a water vapor adsorbing and desorbing agent for an adsorption heat pump containing a zeolite-related substance. The zeolite-related material was a zeolite-related material containing aluminum, phosphorus and silicon in the skeleton structure and having a structure code of CHA. The water vapor adsorption / desorption agent containing the zeolite-related substance has a water adsorption amount change of 0.15 when the relative vapor pressure is changed by 0.15 in the range of the relative vapor pressure of 0.05 to 0.30 on the water vapor adsorption isotherm. It had a relative vapor pressure range of 18 g / g or more.
Japanese Patent Application Laid-Open No. 2007-181795 discloses an adsorption / desorption agent composed of a zeolite-related substance containing at least Al and P as elements constituting the skeleton and containing Mg or Si. The zeolite-related substance has a one-dimensional structure in which pores have a diameter of 3.8 to 7.1 angstroms, and the crystal structure is an ATS structure, ATN structure, AWW structure, LTL structure, or SAS structure. It had any crystal structure.
The water vapor adsorption / desorption agents proposed so far have not been sufficient in the amount of water vapor adsorption / desorption.

The present adsorbent / desorbent solves the above-mentioned problems and is made of silicoaluminophosphate, and provides a water vapor adsorbent / desorbent useful for adsorption heat pump systems, desiccant air conditioning systems, humidity control walls, humidity control sheets, etc. be able to. That is, the present adsorption / desorption agent can provide a water vapor adsorption / desorption agent having a high water vapor adsorption / desorption amount when used as a moisture removal system.
The present adsorption / desorption agent is a water vapor adsorption / desorption agent containing SAPO-47, and further, is a water vapor adsorption / desorption agent containing SAPO-47 represented by the following general formula (1).

_{(Si x Al y P z)} O 2 (1)

(Where x is the molar fraction of Si: 0.05 ≦ x ≦ 0.20, y is the molar fraction of Al: 0.40 ≦ y ≦ 0.55, z is the molar fraction of P: 0.00. 40 ≦ z ≦ 0.50, x + y + z = 1, x is 0.05 ≦ x ≦ 0.20, y is 0.40 ≦ y ≦ 0.55, z is 0.4 ≦ z ≦ 0.45, x + y + z = 1 is preferred.)

The present adsorption / desorption agent is a water vapor adsorption / desorption agent containing SAPO-47. The present adsorbent / desorbent only needs to contain SAPO-47, and may be a water vapor adsorbent / desorbent composed of SAPO-47.
Further, the adsorption / desorption agent is preferably a water vapor adsorption / desorption agent containing SAPO-47 having a solid acid retention rate of 40% or more. When the solid acid retention rate is 40% or more, even if the adsorption / desorption of water vapor is repeated, the water vapor adsorption / desorption agent is reduced little. The solid acid can be considered as one of the active sites for water vapor adsorption. The higher the solid acid retention rate, the higher the stability of the crystal skeleton and the easier it is to maintain the active site of water vapor adsorption before and after the hydration treatment. Since the solid acid retention rate is high, it becomes a water vapor adsorption / desorption agent with little decrease in the amount of water vapor adsorption / desorption. From this point of view, the solid acid retention rate is preferably 40% or more, more preferably 50% or more, still more preferably 65% or more, and even more preferably 70% or more. On the other hand, the amount of solid acid tends to decrease by hydration. Therefore, the solid acid retention rate is usually 100% or less, and further 90% or less.

Further, the adsorption / desorption agent may be a water vapor adsorption / desorption agent containing SAPO-47 on which an alkaline earth metal is supported. By supporting an alkaline earth metal on SAPO-47, a decrease in the amount of solid acid after the cycle hydration treatment is easily suppressed.
The alkaline earth metal is preferably at least one selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba), and more preferably calcium.
When the alkaline earth metal is calcium, the calcium loading is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and even more preferably 0.4% by weight or more. If the amount of calcium supported is within this range, the decrease in the amount of solid acid after the cycle hydration treatment is more easily suppressed. Further, if the calcium content is 2.5% by weight or less, further 2% by weight or less, and further 1.5% by weight or less, an effect of suppressing a sufficient decrease in the amount of solid acid can be obtained. In addition, when alkaline-earth metal is other than calcium, the content should just be a quantity comparable as the amount of substances (mol) corresponding to said calcium content (weight%).

SAPO-47 contained in the present adsorption / desorption agent has an average crystal grain size of less than 5 μm, preferably 4.5 μm or less, and more preferably 4 μm or less. The average crystal grain size may be 0.5 μm or more, more preferably 1 μm or more, and even more preferably 3 μm or more.
Examples of the BET specific surface area of SAPO-47 include 500 m ² / g or more and 800 m ² / g or less.
Note that SAPO-47 has many pores. Therefore, there is almost no correlation between the size of the BET specific surface area and the size of the average particle diameter.

The SAPO-47 contained in the adsorption / desorption agent may have a Si / Al molar ratio of 0.27 or less, more preferably less than 0.23, and may be 0.2 or less. SAPO-47 may have a Si / Al molar ratio of 0.18 or less, more preferably 0.16 or less, and even more preferably 0.15 or less. On the other hand, the Si / Al molar ratio may be 0.01 or more, and further 0.1 or more.
The proportion of phosphorus contained in SAPO-47 is, for example, P / Al in a molar ratio of 0.7 or more, further 0.75 or more, further 0.8 or more, or even 0.85 or more. Can do. On the other hand, the maximum value of the proportion of phosphorus contained in SAPO-47 can be exemplified by 0.9 or less in the P / Al molar ratio.
This adsorption / desorption agent can be in any form. For example, it may be used as a powder, or may be used as a coating or a molded body. When used as a coating, the present adsorbent / desorbent may be used as a powder slurry and coated on a substrate such as a honeycomb rotor.

When used as a molded body, a binder or molding aid may be mixed with the present adsorption / desorption agent and used as a granular molded body. Furthermore, it may be integrally formed with other materials, or may be formed into a sheet by mixing with paper or resin.
This adsorbent / desorbent can be produced, for example, by obtaining SAPO-47 by the above-described production method and making it into an arbitrary form.

Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

(Measurement of average crystal grain size)
A general scanning electron microscope (trade name: JSM-6390LV, manufactured by JEOL Ltd.) was used, and the sample was observed with a scanning electron microscope (hereinafter referred to as “SEM”). The magnification of SEM observation was 10,000 times. From the SEM image of the sample obtained by SEM observation, 100 crystal particles were randomly selected and their sizes were measured. The average value of the measured values obtained was determined and used as the average crystal grain size of the sample.

(X-ray diffraction measurement)
A general X-ray diffractometer (trade name: MXP-3, manufactured by Mac Science Co., Ltd.) was used to measure the X-ray diffraction of the sample. A CuKα ray (λ = 1.5405 mm) is used as the radiation source, the measurement mode is step scan, the scan condition is step 0.04 °, the measurement time is 3 seconds, and the measurement range is 2 ° to 44 °. Measured with
The sample was identified by comparing the obtained powder X-ray diffraction pattern with the powder X-ray diffraction pattern of SAPO-47 described in Non-Patent Document 1. That is, it has a powder X-ray diffraction peak of maximum intensity at 2θ = 20.6 ± 0.2 °, 2θ = 16.0 ± 0.2, 24.8 ± 0.2 °, and 30.7 ± 0. Having 3 medium intensity powder X-ray diffraction peaks of 2 °, and 2θ = 17.7 ± 0.2, 21.9 ± 0.2 °, 25.9 ± 0.2 ° and 31.0 It was identified as SAPO-47 by having four small intensity powder X-ray diffraction peaks of ± 0.2 °.

(Measurement of BET specific surface area)
The BET specific surface area of the sample was measured by nitrogen adsorption by the BET multipoint method. A gas adsorption specific surface area measuring device (trade name: Omni Soap, manufactured by Beckman Coulter, Inc.) was used as the measuring device. Prior to the measurement, vacuum evacuation was performed by heating at 330 ° C. for 4 hours. The measurement was performed at a relative pressure (P / P ₀ ) = 0.05 to 0.15.

(Analysis of composition)
The composition analysis was performed by inductively coupled plasma emission spectrometry (ICP method). That is, the sample was dissolved in a mixed solution of hydrofluoric acid and nitric acid to prepare a measurement solution. The composition of the sample was analyzed by measuring the obtained measurement solution using a general inductively coupled plasma emission spectrometer (trade name: OPTIMA 3000 DV, manufactured by PERKIN ELMER).

(Measurement of solid acid amount)
The solid acid amount of the sample was measured by the NH ₃ -TPD method shown below.
Prior to measurement, the sample was pressure-molded, pulverized, and sized to 20-30 mesh. 0.1 g of the sized sample was weighed and charged into a fixed-bed atmospheric pressure reaction tube (hereinafter simply referred to as “reaction tube”).
This was heated to 500 ° C. while flowing helium gas through the reaction tube filled with the sample. Thereby, the sample and helium gas were brought into contact. After holding at 500 ° C. for 1 hour, the reaction tube filled with the sample was cooled to 100 ° C.

After cooling, while maintaining the temperature of the reaction tube filled with the sample at 100 ° C., an ammonia-helium mixed gas containing 10% by volume of ammonia was allowed to flow therethrough at a flow rate of 60 mL / min for 1 hour. As a result, ammonia was adsorbed on the sample. After ammonia adsorption to the sample, the ammonia-helium mixed gas was stopped, and instead, helium gas was allowed to flow at 60 mL / min for 1 hour. Thereby, ammonia gas remaining in the atmosphere of the reaction tube, that is, ammonia not adsorbed on the sample was removed from the reaction tube.
Thereafter, the sample was heated from 100 ° C. to 700 ° C. at a rate of 10 ° C./min while flowing helium gas at a flow rate of 60 mL / min. Thereby, ammonia adsorbed on the sample was desorbed from the sample. Ammonia desorbed from the sample was continuously quantified by a gas chromatograph equipped with a thermal conductivity detector (TCD), thereby obtaining a desorption spectrum of ammonia.

In the obtained desorption spectrum, a peak derived from desorption of ammonia by physically adsorbing a desorption peak having a peak top at a desorption temperature of 100 ° C. or higher and lower than 250 ° C. (hereinafter referred to as “physical adsorption peak”). The desorption peak having a peak top at a desorption temperature of 250 ° C. or higher and 450 ° C. or lower was regarded as a peak derived from the solid acid of the sample (hereinafter referred to as “solid acid peak”).
The peak area of the solid acid peak in the desorption spectrum was determined, and the NH ₃ -TPD peak of a gas with a known ammonia amount (mmol) (0.25 mL of 10 vol% ammonia-helium mixed gas) was measured in advance. The ratio with the area was determined. Thus, the ammonia desorption amount (mmol) corresponding to the solid acid peak was determined, and the solid acid amount of the sample was determined by the following equation.

Sample solid acid content (mmol / g)
= Ammonia desorption amount corresponding to the solid acid peak (mmol) / SAPO-47 mass (g)

(Measurement method of nitrogen oxide reduction rate)
Prior to measurement, the sample was pressure-molded, pulverized, and then sized to 12 to 20 mesh. The nitrogen oxide reduction rate of the sample after sizing was measured by the ammonia SCR method shown below.
A 1.5 mL sample was weighed and filled into a reaction tube. Then, the process gas which consists of the following compositions containing nitrogen oxide was distribute | circulated to the said reaction tube at each temperature of 150 degreeC, 300 degreeC, and 500 degreeC. The other conditions were measured at a processing gas flow rate of 1.5 L / min and a space velocity (SV) of 60,000 hr ⁻¹ .

Process gas composition NO 200ppm
NH ₃ 200ppm
O ₂ 10% by volume
H ₂ O 3% by volume
Remaining N ₂

The nitrogen oxide concentration (ppm) in the treatment gas after the catalyst flow is determined with respect to the nitrogen oxide concentration (200 ppm) in the treatment gas passed through the reaction tube, and the nitrogen oxide reduction rate is calculated according to the above equation (2). Asked.

(Cycle hydration treatment)
Prior to the treatment, the sample was pressure-molded, pulverized, and sized to 12 to 20 mesh. 4 g of the sample after the sizing was weighed, and while being kept at 75 ° C., the sample was exposed to a water-containing atmosphere containing 35% by volume of water. After 1 hour, the sample was kept in an air atmosphere at a dew point of −40 ° C. (water content 0.05% by volume or less) while maintaining the sample at 75 ° C. The two treatments were set as one cycle, and the cycle was repeated 40 times to obtain cycle hydration treatment.

Example 1
(Manufacture of SAPO-47)
30.8 g of pure water, 9.8 g of 85% phosphoric acid aqueous solution (special grade reagent, manufactured by Kishida Chemical), 3.3 g of 30% colloidal silica (ST-N30, manufactured by Nissan Chemical), 98% tetraethylethylenediamine (hereinafter referred to as “TEEDA”) 7.5 g of a special grade reagent (manufactured by ALDRICH) and 5.7 g of 77% pseudo boehmite (Pural SB, manufactured by Sasol) were mixed.
Furthermore, the weight of the seed crystal is 1.0% by weight with respect to the total weight when silicon, aluminum and phosphorus in the obtained mixture are regarded as SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ , respectively. Then, seed crystals were added thereto and mixed to obtain a reaction mixture. SAPO-34 having an average crystal grain size of 0.8 μm obtained by the same method as in Reference Example 1 was used as a seed crystal.

2P / 2Al = 1.0
Si / 2Al = 0.4
H ₂ O / 2Al = 50
TEEDA / 2Al = 1.0
1.0% by weight of seed crystals

This reaction mixture was put in an 80 mL stainless steel sealed pressure vessel and kept at 180 ° C. for 62 hours while stirring by rotating at 55 rpm around the horizontal axis. Thereafter, the product was filtered, washed with water, and dried overnight at 110 ° C. to obtain silicoaluminophosphate.
Further, the X-ray diffraction pattern of the obtained silicoaluminophosphate showed a powder X-ray diffraction pattern equivalent to that of Non-Patent Document 1, and it was found that the silicoaluminophosphate was SAPO-47.
The SAPO-47 composition has a Si / Al molar ratio of 0.15 and a P / Al molar ratio of 0.89, an average crystal grain size of 3.2 μm, and a BET specific surface area of 636 m ² / g.

(Hydration treatment)
The obtained SAPO-47 was calcined at 600 ° C. for 2 hours. As a result, the organic structure directing agent was removed to obtain a proton type (H ⁺ type) SAPO-47. After baking, SAPO-47 was weighed in a 0.5 g petri dish, and placed in a desiccator containing pure water at the bottom, and then the desiccator was sealed. By placing the desiccator in a dryer maintained at 80 ° C., SAPO-47 was placed in an atmosphere of saturated water vapor concentration (291 g / m ³ ) at 80 ° C. SAPO-47 was hydrated by standing in the atmosphere for 8 days.

(Measurement of solid acid amount)
The amount of solid acid of each of SAPO-47 after calcination (that is, SAPO-47 before hydration treatment) and SAPO-47 after hydration treatment was measured. As a result, the solid acid amount of SAPO-47 after calcination was 0.72 mmol / g, the solid acid amount of SAPO-47 after hydration was 0.53 mmol / g, and the solid acid retention rate was 73%. Met.
The evaluation results of SAPO-47 of this example are shown in Table 1, the results of SEM observation are shown in FIG. 1, and the X-ray diffraction pattern is shown in FIG.

Example 2
(Manufacture of SAPO-47)
30.7 g of pure water, 7.9 g of 85% phosphoric acid aqueous solution, 5.0 g of 30% colloidal silica, 7.6 g of 98% TEEDA, and 5.7 g of 77% pseudoboehmite were mixed.
Furthermore, the weight of the seed crystal is 1.0% by weight with respect to the total weight when silicon, aluminum and phosphorus in the obtained mixture are regarded as SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ , respectively. Then, seed crystals were added thereto and mixed to obtain a reaction mixture. SAPO-34 having an average crystal grain size of 0.8 μm obtained by the same method as in Reference Example 1 was used as a seed crystal.

2P / 2Al = 0.8
Si / 2Al = 0.6
H ₂ O / 2Al = 50
TEEDA / 2Al = 1.0
1.0% by weight of seed crystals

This reaction mixture was put in an 80 mL stainless steel sealed pressure vessel and kept at 180 ° C. for 63 hours while stirring by rotating at 55 rpm around the horizontal axis. Thereafter, the product was filtered, washed with water, and dried overnight at 110 ° C. to obtain silicoaluminophosphate.
Further, the X-ray diffraction pattern of the obtained silicoaluminophosphate showed a powder X-ray diffraction pattern equivalent to that of Non-Patent Document 1, and it was found that the silicoaluminophosphate was SAPO-47.
The SAPO-47 had a Si / Al molar ratio of 0.16 and a P / Al molar ratio of 0.87, and an average crystal grain size of 3.2 μm.

(Measurement of solid acid amount)
SAPO-47 was calcined and hydrated in the same manner as in Example 1, and the amount of the solid acid was measured. As a result, the solid acid amount of SAPO-47 after calcination was 0.80 mmol / g, the solid acid amount of SAPO-47 after hydration was 0.59 mmol / g, and the solid acid retention rate was 74%. Met.
The evaluation results of SAPO-47 of this example are shown in Table 1.

Example 3
(Manufacture of SAPO-47)
Pure water 26.6 g, 85% phosphoric acid aqueous solution 9.5 g, 30% colloidal silica 8.09 g, 98% TEEDA 7.3 g, and 77% pseudo boehmite 5.5 g were mixed.
Furthermore, the weight of the seed crystal is 1.0% by weight with respect to the total weight when silicon, aluminum and phosphorus in the obtained mixture are regarded as SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ , respectively. Then, seed crystals were added thereto and mixed to obtain a reaction mixture. SAPO-34 having an average crystal grain size of 0.8 μm obtained by the same method as in Reference Example 1 was used as a seed crystal.

2P / 2Al = 1.0
Si / 2Al = 1.0
H ₂ O / 2Al = 50.0
TEEDA / 2Al = 1.0
1.0% by weight of seed crystals

The reaction mixture was placed in an 80 mL stainless steel sealed pressure vessel and held at 180 ° C. for 62 hours while rotating at 55 rpm around the horizontal axis. Thereafter, the product was filtered, washed with water, and dried overnight at 110 ° C. to obtain silicoaluminophosphate.
Further, the X-ray diffraction pattern of the obtained silicoaluminophosphate showed a powder X-ray diffraction pattern equivalent to that of Non-Patent Document 1, and it was found that the silicoaluminophosphate was SAPO-47.
The SAPO-47 has a Si / Al molar ratio of 0.20 and a P / Al molar ratio of 0.87, an average crystal grain size of 3.4 μm, and a BET specific surface area of 594 m ^2. / G.

(Measurement of solid acid amount)
SAPO-47 was calcined and hydrated in the same manner as in Example 1, and the amount of the solid acid was measured. As a result, the solid acid amount of SAPO-47 after calcination was 1.08 mmol / g, the solid acid amount of SAPO-47 after hydration was 0.75 mmol / g, and the solid acid retention rate was 69%. Met.
The evaluation results of SAPO-47 of this example are shown in Table 1.

Example 4
(Manufacture of SAPO-47)
66.3 g of pure water, 20.7 g of 85% phosphoric acid aqueous solution, 5.3 g of 30% colloidal silica, 15.8 g of 98% TEEDA, and 11.9 g of 77% pseudoboehmite were mixed.
Then, the weight of the seed crystal is 1.0% by weight based on the total weight when silicon, aluminum and phosphorus in the obtained mixture are regarded as SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ , respectively. The reaction mixture was obtained by adding and mixing seed crystals to the mixture. SAPO-34 having an average crystal grain size of 0.8 μm obtained by the same method as in Reference Example 1 was used as a seed crystal.
The composition of the obtained reaction mixture was as follows.

2P / 2Al = 1.0
Si / 2Al = 0.3
H ₂ O / 2Al = 50
TEEDA / 2Al = 1.0
1.0% by weight of seed crystals

This reaction mixture was put into a 200 mL stainless steel sealed pressure vessel and kept at 175 ° C. for 20 hours while rotating at 55 rpm around the horizontal axis. Thereafter, the product was filtered, washed with water, and dried overnight at 110 ° C. to obtain silicoaluminophosphate.
After hydrothermal treatment, the product was recovered by filtration, washed with water, and dried at 110 ° C. overnight to obtain silicoaluminophosphate.
The obtained silicoaluminophosphate showed a powder X-ray diffraction pattern equivalent to that of Non-Patent Document 1, and the silicoaluminophosphate was found to be SAPO-47. The SAPO-47 has a Si / Al molar ratio of 0.12, a P / Al molar ratio of 0.88, an average crystal grain size of 3.1 μm, and a BET specific surface area of 637 m ² / g. there were.

(Measurement of solid acid amount)
SAPO-47 was calcined and hydrated in the same manner as in Example 1, and the amount of the solid acid was measured. As a result, the solid acid amount of SAPO-47 after calcination was 0.68 mmol / g, the solid acid amount of SAPO-47 after hydration was 0.50 mmol / g, and the solid acid retention rate was 72%. Met.
The evaluation results of SAPO-47 of this example are shown in Table 1.

Example 5
(Manufacture of SAPO-47)
1930 g of pure water, 619 g of 85% phosphoric acid aqueous solution, 210 g of 30% colloidal silica, 484 g of 98% TEEDA, and 357 g of 77% pseudoboehmite were mixed.
Furthermore, the weight of the seed crystal is 1.0% by weight with respect to the total weight when silicon, aluminum and phosphorus in the obtained mixture are regarded as SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ , respectively. Then, seed crystals were added thereto and mixed to obtain a reaction mixture. SAPO-34 having an average crystal grain size of 0.8 μm obtained by the same method as in Reference Example 1 was used as a seed crystal.

2P / 2Al = 1.0
Si / 2Al = 0.4
H ₂ O / 2Al = 50.0
TEEDA / 2Al = 1.0
1.0% by weight of seed crystals

The reaction mixture was placed in a 4000 mL stainless steel sealed pressure vessel and held at 175 ° C. for 17 hours with stirring at 273 rpm. Thereafter, the product was filtered, washed with water, and dried overnight at 110 ° C. to obtain silicoaluminophosphate.
Further, the X-ray diffraction pattern of the obtained silicoaluminophosphate showed a powder X-ray diffraction pattern equivalent to that of Non-Patent Document 1, and it was found that the silicoaluminophosphate was SAPO-47.
The SAPO-47 composition has a Si / Al molar ratio of 0.15, a P / Al molar ratio of 0.87, an average crystal grain size of 3.2 μm, and a BET specific surface area of 616 m ² / g.

(Measurement of solid acid amount)
In the same manner as in Example 1, SAPO-47 was calcined and hydrated, and the amount of solid acid was measured. As a result, the solid acid amount of SAPO-47 after calcination was 0.76 mmol / g, the solid acid amount of SAPO-47 after hydration was 0.58 mmol / g, and the solid acid retention rate was 76%. Met.
The evaluation results of SAPO-47 of this example are shown in Table 1.

Example 6
(Production of calcium-supporting SAPO-47)
SAPO-47 was obtained in the same manner as in Example 5, and this was calcined to obtain proton-type SAPO-47. On the other hand, 0.19 g of calcium nitrate tetrahydrate (manufactured by Kishida Chemical Co., Ltd., special grade reagent) was dissolved in 2.53 g of pure water to obtain an aqueous calcium nitrate solution. The aqueous calcium nitrate solution was dropped into 7.0 g of SAPO-47, and then kneaded for 10 minutes.
The kneaded sample was dried at 110 ° C. overnight and then calcined in air at 550 ° C. for 2 hours to obtain calcium-supporting SAPO-47. The calcium content was 0.46% by weight.

(Measurement of solid acid amount)
In the same manner as in Example 1, calcium-containing SAPO-47 was calcined and hydrated, and the amount of solid acid was measured.
The solid acid amount of calcium-containing SAPO-47 is 0.71 mmol / g, the solid acid amount of SAPO-47 after hydration treatment is 0.53 mmol / g, and the solid acid retention rate after hydration treatment is 75. %Met.
The evaluation results of the calcium-containing SAPO-47 of this example are shown in Table 1.

Example 7
(Production of calcium-supporting SAPO-47)
Calcium-supported SAPO-47 was obtained in the same manner as in Example 6 except that a calcium nitrate aqueous solution obtained by dissolving 0.31 g of calcium nitrate tetrahydrate in 2.49 g of pure water was used. The calcium content was 0.76% by weight.

(Measurement of solid acid amount)
In the same manner as in Example 1, calcium-containing SAPO-47 was calcined and hydrated, and the amount of solid acid was measured.
The solid acid amount of calcium-containing SAPO-47 is 0.69 mmol / g, and the solid acid amount of SAPO-47 after hydration treatment is 0.53 mmol / g, and the solid acid retention rate after hydration treatment is 77. %Met.
Table 1 shows the evaluation results of the calcium-supporting SAPO-47 of this example.

Example 8
(Production of calcium-supporting SAPO-47)
Calcium-supported SAPO-47 was obtained in the same manner as in Example 6 except that a calcium nitrate aqueous solution obtained by dissolving 0.57 g of calcium nitrate tetrahydrate in 2.41 g of pure water was used. The amount of calcium supported was 1.4% by weight.

(Measurement of solid acid amount)
In the same manner as in Example 1, calcium-supported SAPO-47 was calcined and hydrated, and the amount of solid acid was measured.
The solid acid amount of calcium-supporting SAPO-47 is 0.64 mmol / g, and the solid acid amount of SAPO-47 after hydration treatment is 0.51 mmol / g, and the solid acid retention rate after hydration treatment is 79. %Met.
Table 1 shows the evaluation results of the calcium-supporting SAPO-47 of this example.

Comparative Example 1
29.3 g of pure water, 9.7 g of 85% phosphoric acid aqueous solution, 4.9 g of 30% colloidal silica, 98% normal methyl normal butylamine (hereinafter referred to as “MBA”; special grade reagent, manufactured by ALDRICH) 7.5 g, 77% 5.6 g of pseudo boehmite was mixed.
Furthermore, the weight of the seed crystal is 1.5% by weight based on the total weight when silicon, aluminum and phosphorus in the obtained mixture are regarded as SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ , respectively. Then, seed crystals were added thereto and mixed to obtain a reaction mixture. SAPO-34 having an average crystal grain size of 0.8 μm obtained by the same method as in Reference Example 1 was used as a seed crystal.
The composition of the obtained reaction mixture was as follows.

2P / 2Al = 1.0
Si / 2Al = 0.6
H ₂ O / 2Al = 50
MBA / 2Al = 2.0
1.0% by weight of seed crystals

The obtained reaction mixture was put into an 80 mL stainless steel sealed pressure resistant vessel, hydrothermally treated by holding at 180 ° C. for 62 hours while rotating at 55 rpm around the horizontal axis, and the reaction mixture was crystallized.
After hydrothermal treatment, the product was recovered by filtration, washed with water, and dried at 110 ° C. overnight to obtain silicoaluminophosphate.
The obtained silicoaluminophosphate showed a powder X-ray diffraction pattern equivalent to that of Non-Patent Document 1, and the silicoaluminophosphate was found to be SAPO-47. The SAPO-47 has a Si / Al molar ratio of 0.26, a P / Al molar ratio of 0.73, an average crystal grain size of 3.2 μm, and a BET specific surface area of 672 m ² / g. there were.

(Measurement of solid acid amount)
SAPO-47 was calcined and hydrated in the same manner as in Example 1, and the amount of the solid acid was measured. As a result, the solid acid amount of SAPO-47 after calcination was 1.74 mmol / g, the solid acid amount of SAPO-47 after hydration treatment was 0 mmol / g, and the solid acid retention rate was 0%. It was.
The evaluation results of SAPO-47 of this comparative example are shown in Table 1.

Reference example 1
7.6 g of pure water, 8.0 g of 85% phosphoric acid aqueous solution, 3.8 g of 30% colloidal silica, 35% tetraethylammonium hydroxide (hereinafter referred to as “TEAOH”; special grade reagent, manufactured by ALDRICH) 32.9 g, 77 % Pseudo boehmite (5.2 g) was mixed to prepare a reaction mixture having the following composition.
The composition of the obtained reaction mixture was as follows.

2P / 2Al = 0.9
Si / 2Al = 0.5
H ₂ O / 2Al = 50
TEAOH / 2Al = 2.0

The reaction mixture was placed in an 80 mL stainless steel sealed pressure vessel, heated at 55 rpm around the horizontal axis, heated from 20 ° C. to 200 ° C. over 2 hours, stopped in rotation and allowed to stand at 200 ° C. Hold for 92 hours. Thereafter, the product was filtered, washed with water, and dried overnight at 110 ° C. to obtain silicoaluminophosphate.
The obtained silicoaluminophosphate has 2θ = 17.7 ± 0.2 °, 21.9 ± 0.2 °, 24.8 ± 0.2 °, 31.0 ± 0. It did not have a 2 ° X-ray diffraction peak. On the other hand, X-ray diffraction peaks that SAPO-47 does not have are X-rays of 2θ = 18.2 ± 0.2 °, 25.3 ± 0.2 °, 31.4 ± 0.2 °. It had a diffraction peak. A comparison between the X-ray diffraction pattern of the silicoaluminophosphate and the SAPO-47 X-ray diffraction pattern of Example 1 is shown in FIG.

As a result of comparing the XRD diffraction pattern of the silicoaluminophosphate with the reference X-ray diffraction pattern of SAPO-34 published by IZA (FIG. 4), it was found that the silicoaluminophosphate was SAPO-34. It was.
The SAPO-34 had a Si / Al atomic ratio of 0.25, a P / Al atomic ratio of 0.79, an average crystal grain size of 0.8 μm, and a BET specific surface area of 579 m ² / g. .

(Measurement of solid acid amount)
In the same manner as in Example 1, SAPO-34 was calcined and hydrated, and the amount of solid acid was measured. As a result, the solid acid amount of SAPO-34 after calcination was 1.08 mmol / g, the solid acid amount of SAPO-34 after hydration was 0.42 mmol / g, and the solid acid retention rate was 39%. Met.
The evaluation results of SAPO-34 of this reference example are shown in Table 1.

Compared to SAPO-47 (Comparative Example 1) obtained by using methylbutylamine as SDA, SAPO-47 of the present invention was confirmed to have a higher solid acid retention rate. Furthermore, SAPO-47 of Examples 1 to 8 not only has a high solid acid of 0.5 mmol / g or more, more preferably 0.7 mmol / g or more even after hydration treatment, but also maintains its solid acid. The rate was 65% or more, and further 70% or more, and it was confirmed that the SAPO-47 was more stable than the conventional SAPO-47 (Comparative Example 1).
Further, it was confirmed that the calcium-supported SAPO-47 has a solid acid retention rate equal to or higher than that of SAPO-47 not supporting calcium.

The post-baking SAPO-47 of Examples 5 to 8 were respectively pressure-molded, pulverized, and then sized to 12 to 20 mesh. 4 g of the sample after the sizing was weighed, and while being kept at 75 ° C., the sample was exposed to a water-containing atmosphere containing 35% by volume of water. After 1 hour, the sample was kept in an air atmosphere at a dew point of −40 ° C. (water content 0.05% by volume or less) while maintaining the sample at 75 ° C. The two treatments were defined as one cycle. About the sample after repeating the said cycle 20 times, the solid acid amount was measured by the method similar to Example 1. FIG. The results are shown in Table 2.

In Examples 6 to 8, the solid acid amount of 75% or more before the repeated hydration treatment was maintained even after the repeated hydration treatment. From this, it was confirmed that the calcium-supported SAPO-47 suppressed the decrease in the amount of solid acid even after repeated hydration treatment.

(Measurement of nitrogen oxide reduction rate)
Example 9
SAPO-47 obtained in Example 1 was calcined at 600 ° C. for 2 hours. After baking, the sample was weighed in an amount of 7.5 g with a solid content weight excluding moisture, and 3.36 g of an aqueous copper nitrate solution was added dropwise thereto, and then kneaded in a mortar for 10 minutes. As the copper nitrate aqueous solution, a solution obtained by dissolving 0.46 g of copper nitrate trihydrate (primary reagent, manufactured by Kishida Chemical Co., Ltd.) in 2.9 g of pure water was used.
The kneaded sample was dried at 110 ° C. overnight and then calcined in the atmosphere at 500 ° C. for 1 hour to obtain a copper-supported SAPO-47. The obtained copper-supported SAPO-47 had a copper loading of 1.6% by weight.
The nitrogen oxide reduction rate of the copper-supported SAPO-47 after calcination (that is, copper-supported SAPO-47 before hydration treatment) was measured. The results are shown in Table 3.

Example 10
Example except that 0.37 g of copper nitrate trihydrate dissolved in 2.9 g of pure water was used as the copper nitrate aqueous solution and that 3.27 g of the copper nitrate aqueous solution was added dropwise to the calcined sample. Under the same conditions as in Example 9, copper-supported SAPO-47 was obtained from SAPO-47 of Example 1. The copper loading of the obtained copper loading SAPO-47 was 1.3% by weight.
The nitrogen oxide reduction rate of the copper-supported SAPO-47 after calcination (that is, copper-supported SAPO-47 before hydration treatment) was measured. The results are shown in Table 3.

Comparative Example 2
Copper-supported SAPO-47 was obtained in the same manner as in Example 9, except that SAPO-47 obtained in Comparative Example 1 was used. The obtained copper-supported SAPO-47 had a copper load of 1.6% by weight.
The nitrogen oxide reduction rate of the copper-supported SAPO-47 after calcination (that is, copper-supported SAPO-47 before hydration treatment) was measured. The results are shown in Table 3.

Reference example 2
Copper-supported SAPO-34 was obtained in the same manner as in Example 9 except that SAPO-34 obtained in Reference Example 1 was used. The obtained copper-supported SAPO-34 had a copper support amount of 1.6% by weight. Regarding the copper-supported SAPO-34 after firing (that is, the copper-supported SAPO-34 before hydration treatment), the nitrogen oxide The reduction rate was measured. The results are shown in Table 3.

The nitrogen oxide reduction rate at 500 ° C. is as high as 80% or more. Under high temperatures, SAPO-47 of the present invention has catalytic activity comparable to SAPO-34, which has been put into practical use as a nitrogen oxide reduction catalyst. It was confirmed that it had.
The nitrogen oxide reduction rate at 300 ° C. is as high as 85% or more. Under low temperature, SAPO-47 of the present invention is equal to or more than SAPO-34 which is practically used as a nitrogen oxide reduction catalyst. It was confirmed that the catalyst had the catalytic activity.
Further, the nitrogen oxide reduction rate of SAPO-47 of the present invention at 150 ° C. exceeded 60%. Thus, at a low temperature of 200 ° C. or less, the catalyst activity is higher than that of SAPO-34 which is practically used as a nitrogen oxide reduction catalyst as well as copper-supported SAPO-47 obtained by using MBA. I found it.

Next, some of the copper-supported samples obtained in Examples 9 and 10, Comparative Example 2, and Reference Example 2 were taken out. The copper-supported sample was hydrated in the same manner as in Example 1 except that the standing period was 20 days. With respect to the copper-supported sample after the hydration treatment, the nitrogen oxide reduction rate at 150 ° C. was measured. Moreover, the NOx reduction maintenance rate was calculated | required from the measurement result in the copper carrying sample after baking (namely, the copper carrying sample before a hydration process), and the said measurement result. The results are shown in Table 4.

Hydration treatment reduced the nitrogen oxide reduction rate of any copper-loaded sample. However, the nitrogen oxide reduction rate of the copper-supported SAPO-47 of Example 9 and Example 10 after the hydration treatment is maintained at 60% or more, and a high NOx reduction maintenance rate of 80% or more, further 90% or more. Had. In addition, it was found that the copper-supported SAPO-47 of this example had a high nitrogen oxide reduction property with a nitrogen oxide reduction rate of 150% or higher at 150 ° C. even after hydration.
Thus, it was found that SAPO-47 of the present invention has a NOx reduction maintenance rate of 80% or more, which is higher than that of Reference Example SAPO-34 at low temperatures.
As a result, it was confirmed that SAPO-47 of the present invention has a high nitrogen oxide reduction rate at a low temperature and exhibits stable catalytic activity.

Example 11
SAPO-47 was obtained in the same manner as in Example 5. The SAPO-47 composition had a Si / Al molar ratio of 0.14, a P / Al molar ratio of 0.87, and an average crystal grain size of 3.2 μm.
The obtained SAPO-47 was calcined at 600 ° C. for 2 hours to obtain a proton (H ⁺ ) type.
After baking, SAPO-47 was weighed in a solid weight weight excluding moisture of 7.5 g, and a copper nitrate aqueous solution (3.36 g) was added dropwise thereto, and then kneaded in a mortar for 10 minutes. The copper nitrate aqueous solution used was prepared by dissolving 0.46 g of copper nitrate trihydrate in 2.9 g of pure water.
The kneaded sample was dried at 110 ° C. overnight and then calcined in the atmosphere at 500 ° C. for 1 hour to obtain a copper-supported SAPO-47 of this example. The obtained copper-supported SAPO-47 had a copper loading of 1.6% by weight.
The obtained copper-supported SAPO-47 was subjected to a cycle hydration treatment, and then the nitrogen oxide reduction rate was measured. The results are shown in Table 5.

Example 12
According to the same method as in Example 11, except that a mixed aqueous solution of copper nitrate and calcium nitrate in which 0.46 g of copper nitrate trihydrate and 0.11 g of calcium nitrate tetrahydrate were dissolved in 2.9 g of pure water was used. A copper-calcium-supporting SAPO-47 of this example was obtained.
The obtained copper-calcium supported SAPO-47 had a copper loading of 1.6% by weight and a calcium loading of 0.26% by weight.
The obtained copper-calcium supported SAPO-47 was subjected to a cycle hydration treatment, and then the nitrogen oxide reduction rate was measured. The results are shown in Table 5.

Example 13
This example was prepared in the same manner as in Example 11 except that a mixed aqueous solution of copper nitrate and calcium nitrate in which 0.46 g of copper nitrate trihydrate and 0.20 g of calcium nitrate were dissolved in 2.9 g of pure water was used. Of copper-calcium supported SAPO-47 was obtained.
The obtained copper-calcium supported SAPO-47 had a copper loading of 1.6% by weight and a calcium loading of 0.44% by weight.
The obtained copper-calcium supported SAPO-47 was subjected to a cycle hydration treatment, and then the nitrogen oxide reduction rate was measured. The results are shown in Table 5.

From these results, it was found that SAPO-47 of the present invention has a higher nitrogen oxide reduction rate than SAPO-34, particularly a high nitrogen oxide reduction rate in a low temperature range of 150 ° C. or lower. .
Furthermore, after subjecting the samples of Examples 11 to 13 and Reference Example 2 to cycle hydration treatment, a treatment in which air containing 10% by weight of water vapor was circulated at 900 ° C. for 1 hour (hereinafter referred to as “endurance treatment”). "). The nitrogen oxide reduction rate was measured for each sample after the durability treatment. The results are shown in Table 6.

The nitrogen oxide reduction rate at 500 ° C. in Example 11 was twice or more that in Reference Example 2. Thus, even when repeatedly exposed to an atmosphere containing moisture, the SAPO-47 of the present invention has a nitrogen oxide reduction characteristic superior to that of the conventional SAPO-34 even in a high temperature range. confirmed. Furthermore, compared with Reference Example 2, Example 11 had a nitrogen oxide reduction rate of 300 ° C. or lower and a nitrogen oxide reduction rate at 150 ° C. of 4 times or higher. It was confirmed that the SAPO-47 of the present invention maintained nitrogen oxide reduction characteristics superior to those of the conventional SAPO-34, particularly in the low temperature range.
Further, the copper-calcium supported SAPO-47 exhibited a high nitrogen oxide reduction rate of 1.5 times or more, and further 1.9 times or more of the copper supported SAPO-47 at any temperature.

Next, SAPO-47 was evaluated as a water vapor adsorption / desorption agent by the following experimental example.
(Evaluation of water vapor adsorption amount)
Prior to the measurement, the sample was pressure-molded, pulverized, and sized to 20-30 mesh, and pretreated at 350 ° C. for 2 hours. After the pretreatment, the water vapor adsorption amount was evaluated under the following conditions.

Apparatus: Magnetic floating balance (manufactured by Nippon Bell Co., Ltd.)
Adsorption temperature: 25 ° C
Air constant temperature: 80 ° C
Initial introduction pressure: 5 kPa

The water vapor adsorption isotherm was obtained under the above conditions, and the water vapor adsorption amount at a relative pressure of 0.05 to 0.30 was determined from this. The water vapor adsorption amount was determined as the water vapor adsorption amount (g / 100 g) with respect to 100 g of the sample.

Experimental example 1
(Manufacture of SAPO-47)
29.3 g of pure water, 9.7 g of 85% phosphoric acid aqueous solution (special grade reagent, manufactured by Kishida Chemical), 4.9 g of 30% colloidal silica (ST-N30, manufactured by Nissan Chemical), 98% tetraethylethylenediamine (hereinafter referred to as “TEEDA”) 7.4 g of a special grade reagent (produced by ALDRICH) and 5.6 g of 77% pseudo boehmite (Pural SB, produced by Sasol) were mixed.
Then, the weight of the seed crystal is 1.0% by weight based on the total weight when silicon, aluminum and phosphorus in the obtained mixture are regarded as SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ , respectively. Seed crystals were added to and mixed with the reaction mixture to obtain a reaction mixture. The seed crystal used was obtained by pulverizing crystalline silicoaluminophosphate with a ball mill for 1 hour.
The composition of the obtained reaction mixture was as follows.

P ₂ O ₅ / Al ₂ O ₃ (molar ratio) = 1.0
SiO ₂ / Al ₂ O ₃ (molar ratio) = 0.6
H ₂ O / Al ₂ O ₃ (molar ratio) = 50
TEEDA / Al ₂ O ₃ (molar ratio) = 1.0
Addition amount of seed crystal = 1.0% by weight

The resulting reaction mixture was placed in an 80 mL stainless steel sealed pressure vessel. The pressure vessel was hydrothermally treated by holding at 180 ° C. for 62 hours while stirring by rotating at 55 rpm around the horizontal axis to crystallize the reaction mixture.
After hydrothermal treatment, the product was collected by filtration, washed with water, and dried at 110 ° C. overnight to obtain silicoaluminophosphate.
The obtained silicoaluminophosphate showed a powder X-ray diffraction pattern equivalent to that of Non-Patent Document 1, and the silicoaluminophosphate was found to be SAPO-47. The product after drying was subjected to composition analysis using an inductively coupled plasma emission spectrometer (ICP), and had the following composition in terms of oxide.
(Si _0.124 Al _0.468 P _0.407 ) O ₂

(Hydration treatment)
The obtained SAPO-47 was calcined at 600 ° C. for 2 hours. As a result, SDA was removed to obtain proton-type (H ⁺ -type) SAPO-47. After baking, SAPO-47 was weighed in a 0.5 g petri dish, and placed in a desiccator containing pure water at the bottom, and then the desiccator was sealed. By placing the desiccator in a dryer maintained at 80 ° C., SAPO-47 was placed in an atmosphere of saturated water vapor concentration (291 g / m ³ ) at 80 ° C. SAPO-47 was hydrated by standing in the atmosphere for 8 days.

(Measurement of solid acid amount)
The solid acid amounts of SAPO-47 after firing (that is, SAPO-47 before hydration treatment) and SAPO-47 after hydration treatment were measured. As a result, the solid acid amount of SAPO-47 after calcination was 0.74 mmol / g, and the solid acid amount of SAPO-47 after hydration treatment was 0.56 mmol / g. The maintenance rate was 76%.
(Evaluation of water vapor adsorption amount)
From the water vapor adsorption isotherm, the water vapor adsorption amount at a relative pressure of 0.05 to 0.30 was 23.2 (g / 100 g). The water vapor adsorption isotherm measured at 25 ° C. is shown in FIG.

Experimental example 2
30.8 g of pure water, 9.8 g of 85% phosphoric acid aqueous solution, 3.3 g of 30% colloidal silica, 7.5 g of 98% TEEDA, and 5.7 g of 77% pseudoboehmite were mixed.
Furthermore, the weight of the seed crystal is 1.0% by weight with respect to the total weight when silicon, aluminum and phosphorus in the obtained mixture are regarded as SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ , respectively. Seed crystals were added to this mixture and mixed to obtain a reaction mixture. The seed crystal used was obtained by pulverizing crystalline silicoaluminophosphate with a ball mill for 1 hour.
The composition of the obtained reaction mixture was as follows.

P ₂ O ₅ / Al ₂ O ₃ (molar ratio) = 1.0
SiO ₂ / Al ₂ O ₃ (molar ratio) = 0.4
H ₂ O / Al ₂ O ₃ (molar ratio) = 50
TEEDA / Al ₂ O ₃ (molar ratio) = 1.0
Addition amount of seed crystal = 1.0% by weight

This reaction mixture was put into an 80 mL stainless steel sealed pressure vessel and kept at 180 ° C. for 62 hours while stirring by rotating at 55 rpm around the horizontal axis. Thereafter, the product was filtered, washed with water, and dried overnight at 110 ° C. to obtain silicoaluminophosphate.
Further, the X-ray diffraction pattern of the obtained silicoaluminophosphate showed a powder X-ray diffraction pattern equivalent to that of Non-Patent Document 1, and it was found that the silicoaluminophosphate was SAPO-47. The product after drying was subjected to composition analysis using an inductively coupled plasma emission spectrometer (ICP), and had the following composition in terms of oxide.
(Si _0.076 Al _0.489 P _0.435 ) O ₂

(Measurement of solid acid amount)
SAPO-47 was calcined and hydrated in the same manner as in Experimental Example 1, and the amount of the solid acid was measured. As a result, the solid acid amount of SAPO-47 after calcination was 0.72 mmol / g, and the solid acid amount of SAPO-47 after hydration treatment was 0.53 mmol / g. The maintenance rate was 73%.
(Evaluation of water vapor adsorption amount)
From the water vapor adsorption isotherm, the water vapor adsorption amount at a relative pressure of 0.05 to 0.30 was 25.4 (g / 100 g).

Experimental example 3
66.3 g of pure water, 20.7 g of 85% phosphoric acid aqueous solution, 5.3 g of 30% colloidal silica, 15.8 g of 98% TEEDA, and 11.9 g of 77% pseudoboehmite were mixed.
Furthermore, the weight of the seed crystal is 1.0% by weight with respect to the total weight when silicon, aluminum and phosphorus in the obtained mixture are regarded as SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ , respectively. Seed crystals were added to this mixture and mixed to obtain a reaction mixture. The seed crystal used was obtained by pulverizing crystalline silicoaluminophosphate with a ball mill for 1 hour.
The composition of the obtained reaction mixture was as follows.

P ₂ O ₅ / Al ₂ O ₃ (molar ratio) = 1.0
SiO ₂ / Al ₂ O ₃ (molar ratio) = 0.3
H ₂ O / Al ₂ O ₃ (molar ratio) = 50
TEEDA / Al ₂ O ₃ (molar ratio) = 1.0
Addition amount of seed crystal = 1.0% by weight

The reaction mixture was placed in a 200 mL stainless steel sealed pressure vessel and kept at 175 ° C. for 20 hours while stirring by rotating at 55 rpm around the horizontal axis. Thereafter, the product was filtered, washed with water, and dried overnight at 110 ° C. to obtain silicoaluminophosphate.
Further, the X-ray diffraction pattern of the obtained silicoaluminophosphate showed a powder X-ray diffraction pattern equivalent to that of Non-Patent Document 1, and it was found that the silicoaluminophosphate was SAPO-47. The product after drying was subjected to composition analysis using an inductively coupled plasma emission spectrometer (ICP), and had the following composition in terms of oxide.
(Si _0.062 Al _0.499 P _0.439 ) O ₂

(Measurement of solid acid amount)
SAPO-47 was calcined and hydrated in the same manner as in Experimental Example 1, and the amount of the solid acid was measured. As a result, the solid acid amount of SAPO-47 after calcination was 0.68 mmol / g, and the solid acid amount of SAPO-47 after hydration treatment was 0.50 mmol / g. The maintenance rate was 73%.
(Evaluation of water vapor adsorption amount)
From the water vapor adsorption isotherm, the water vapor adsorption amount at a relative pressure of 0.05 to 0.30 was 26.6 (g / 100 g).

Experimental Example 4
1930 g of pure water, 619 g of 85% phosphoric acid aqueous solution, 210 g of 30% colloidal silica, 484 g of 98% TEEDA, and 357 g of 77% pseudoboehmite were mixed.
Furthermore, the weight of the seed crystal is 1.0% by weight with respect to the total weight when silicon, aluminum and phosphorus in the obtained mixture are regarded as SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ , respectively. Seed crystals were added to this mixture and mixed to obtain a reaction mixture. The seed crystal used was obtained by pulverizing crystalline silicoaluminophosphate with a ball mill for 1 hour.
The composition of the obtained reaction mixture was as follows.

P ₂ O ₅ / Al ₂ O ₃ (molar ratio) = 1.0
SiO ₂ / Al ₂ O ₃ (molar ratio) = 0.4
H ₂ O / Al ₂ O ₃ (molar ratio) = 50
TEEDA / Al ₂ O ₃ (molar ratio) = 1.0
Addition amount of seed crystal = 1.0% by weight

This reaction mixture was placed in a 4000 mL stainless steel sealed pressure resistant vessel and kept at 175 ° C. for 17 hours while stirring at 273 rpm. Thereafter, the product was filtered, washed with water, and dried overnight at 110 ° C. to obtain silicoaluminophosphate.
Further, the X-ray diffraction pattern of the obtained silicoaluminophosphate showed a powder X-ray diffraction pattern equivalent to that of Non-Patent Document 1, and it was found that the silicoaluminophosphate was SAPO-47. The BET surface area was 616 m ² / g and the average particle size was 3.2 μm. The product after drying was subjected to composition analysis using an inductively coupled plasma emission spectrometer (ICP), and had the following composition in terms of oxide.
(Si _0.072 Al _0.496 P _0.432 ) O ₂

(Measurement of solid acid amount)
SAPO-47 was calcined and hydrated in the same manner as in Experimental Example 1, and the amount of the solid acid was measured. As a result, the solid acid amount of SAPO-47 after calcination was 0.76 mmol / g, and the solid acid amount of SAPO-47 after hydration treatment was 0.58 mmol / g. The maintenance rate was 71%.
(Evaluation of water vapor adsorption amount)
From the water vapor adsorption isotherm, the water vapor adsorption amount at a relative pressure of 0.05 to 0.30 was 20.8 (g / 100 g).

Experimental Example 5
SAPO-47 was obtained in the same manner as in Experimental Example 4, and calcined at 600 ° C. for 2 hours. Further, a calcium nitrate solution in which 0.19 g of calcium nitrate tetrahydrate (Kishida Chemical Co., Ltd .: reagent grade) was dissolved in 2.53 g of pure water was obtained. A calcium nitrate solution was added dropwise to 7.0 g of the baked SAPO-47 in a dry weight, and this was kneaded in a mortar for 10 minutes.
The kneaded sample was dried at 110 ° C. overnight and then calcined in air at 550 ° C. for 2 hours to obtain calcium-supporting SAPO-47. The amount of calcium supported was 0.46% by weight.

(Evaluation of water vapor adsorption amount)
From the water vapor adsorption isotherm of calcium-supporting SAPO-47, the water vapor adsorption amount at a relative pressure of 0.05 to 0.30 was 23.5 (g / 100 g).

(Cycle hydration treatment)
Calcium-supported SAPO-47 was pressure-molded, pulverized, and then sized to 12 to 20 mesh. 4 g of the sample after the sizing was weighed, and while being kept at 75 ° C., the sample was exposed to a water-containing atmosphere containing 35% by volume of water. After 1 hour, the sample was kept in an air atmosphere at a dew point of −40 ° C. (water content 0.05% by volume or less) while maintaining the sample at 75 ° C. The two treatments were set as one cycle, and the cycle was repeated 40 times to obtain cycle hydration treatment.
After the cycle hydration treatment, the water vapor adsorption amount was evaluated. From the water vapor adsorption isotherm, the water vapor adsorption amount at a relative pressure of 0.05 to 0.30 was 23.1 (g / 100 g), and there was almost no decrease in the water vapor adsorption amount before and after cycle hydration. As a result, it was confirmed that the calcium-supported SAPO-47 of this experimental example hardly deteriorates the water vapor adsorption / desorption characteristics even after repeated hydration treatment.

Experimental Example 6
SAPO-47 was obtained in the same manner as in Experimental Example 4, and calcined at 600 ° C. for 2 hours. Further, a calcium nitrate solution in which 0.31 g of calcium nitrate tetrahydrate was dissolved in 2.49 g of pure water was obtained. A calcium nitrate solution was added dropwise to 7.0 g of the baked SAPO-47 in a dry weight, and this was kneaded in a mortar for 10 minutes.
The kneaded sample was dried at 110 ° C. overnight and then calcined in air at 550 ° C. for 2 hours to obtain calcium-supporting SAPO-47. The amount of calcium supported was 0.7% by weight.
(Evaluation of water vapor adsorption amount)
From the water vapor adsorption isotherm of calcium-supporting SAPO-47, the water vapor adsorption amount at a relative pressure of 0.05 to 0.30 was 22.1 (g / 100 g).

Experimental Example 7
SAPO-47 was obtained in the same manner as in Experimental Example 4, and calcined at 600 ° C. for 2 hours. Further, a calcium nitrate solution in which 0.57 g of calcium nitrate tetrahydrate was dissolved in 2.41 g of pure water was obtained. A calcium nitrate solution was added dropwise to 7.0 g of the baked SAPO-47 in a dry weight, and this was kneaded in a mortar for 10 minutes.
The kneaded sample was dried at 110 ° C. overnight and then calcined in air at 550 ° C. for 2 hours to obtain calcium-supporting SAPO-47. The amount of calcium supported was 1.4% by weight.
(Evaluation of water vapor adsorption amount)
From the water vapor adsorption isotherm of calcium-supporting SAPO-47, the water vapor adsorption amount at a relative pressure of 0.05 to 0.30 was 20.1 (g / 100 g).

Comparative Experiment Example 1
244 g of pure water, 279 g of 85% phosphoric acid aqueous solution (Kishida Chemical: Special Grade Reagent), 135 g of 30% colloidal silica (Nissan Chemical: ST-N30), 1159 g of 35% tetraethylammonium hydroxide (Alpha Acer), 77% pseudoboehmite (Sasol) : Pural SB) 183 g was mixed to prepare a reaction mixture having the following composition.

P ₂ O ₅ / Al ₂ O ₃ (molar ratio) = 0.88
SiO ₂ / Al ₂ O ₃ (molar ratio) = 0.5
H ₂ O / Al ₂ O ₃ (molar ratio) = 50
TEAOH / Al ₂ O ₃ (molar ratio) = 2.0

(TEAOH represents tetraethylammonium hydroxide used as an organic mineralizer.)

The reaction mixture was placed in a 4000 mL stainless steel sealed pressure vessel and held at 200 ° C. for 92 hours with stirring at 270 rpm.
The product was filtered, washed with water, and dried at 110 ° C. overnight to obtain silicoaluminophosphate.
The obtained silicoaluminophosphate has 2θ = 17.7 ± 0.2 °, 21.9 ± 0.2 °, 24.8 ± 0.2 °, 31.0 ± 0. It did not have a 2 ° X-ray diffraction peak. On the other hand, X-ray diffraction peaks that SAPO-47 does not have are X-rays of 2θ = 18.2 ± 0.2 °, 25.3 ± 0.2 °, 31.4 ± 0.2 °. It had a diffraction peak. A comparison between the X-ray diffraction pattern of the silicoaluminophosphate and the SAPO-47 X-ray diffraction pattern of Experimental Example 1 is shown in FIG.
As a result of comparing the XRD diffraction pattern of the silicoaluminophosphate with the reference X-ray diffraction pattern of SAPO-34 published by IZA (FIG. 4), it was found that the silicoaluminophosphate was SAPO-34. It was.
The product after drying was subjected to composition analysis using an inductively coupled plasma emission spectrometer (ICP), and had the following composition in terms of oxide.
(Si _0.12 Al _0.49 P _0.39 ) O ₂

(Measurement of solid acid amount)
SAPO-34 was calcined and hydrated by the same method as in Experimental Example 1, and the amount of the solid acid was measured. As a result, the solid acid amount of SAPO-34 after calcination was 1.06 mmol / g, and the solid acid amount of SAPO-34 after hydration treatment was 0.42 mmol / g. The maintenance rate was 40%.
(Evaluation of water vapor adsorption amount)
From the water vapor adsorption isotherm, the water vapor adsorption amount at a relative pressure of 0.05 to 0.30 was 15.6 (g / 100 g), which was a low adsorption amount. The water vapor adsorption isotherm measured at 25 ° C. is shown in FIG.
Compared with the water vapor adsorption isotherm of Experimental Example 1 in FIG. 5, the water vapor adsorption amount at a relative pressure of 0.05 to 0.30 was small. The silicoaluminophosphate of Experimental Example 1 has a higher solid acid retention rate before and after the hydration treatment and is superior in water resistance of the crystal skeleton.

Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
Japanese Patent Application No. 2012-198616 filed on September 10, 2012, Japanese Patent Application No. 2012-253368 filed on November 19, 2012, Japanese Patent Application filed on October 31, 2012 The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2013-045658 filed on March 7, 2013 and Japanese Patent Application No. 2012-240853 are incorporated herein by reference. It is incorporated as disclosure of the specification.

Claims (13)

SAPO-47 having an average crystal grain size of less than 5 μm and a Si / Al molar ratio of less than 0.23. The SAPO-47 according to claim 1, wherein the solid acid amount is 0.5 mmol / g or more. The SAPO-47 according to claim 1 or 2, wherein the solid acid amount after hydration treatment is 40% or more with respect to the solid acid amount before hydration treatment. The SAPO-47 according to any one of claims 1 to 3, wherein an alkaline earth metal is supported. The SAPO-47 according to claim 4, wherein the alkaline earth metal is calcium. The SAPO-47 according to any one of claims 1 to 5, wherein at least one selected from the group consisting of group VIIIB elements, group IB elements and group VIIB elements of the periodic table is supported. The SAPO-47 according to claim 6, wherein at least one selected from the group consisting of group VIIIB elements, group IB elements and group VIIB elements of the periodic table is copper. The method for producing SAPO-47 according to any one of claims 1 to 7, further comprising a crystallization step of crystallizing a mixture containing alkylethylenediamine. The method for producing SAPO-47 according to claim 8, wherein in the crystallization step, a mixture having the following composition is crystallized.
2P / 2Al 0.7 or more, 1.5 or less Si / 2Al 0.1 or more, 1.2 or less H ₂ O / 2Al 5 or more, 100 or less Alkylethylenediamine / 2Al 0.5 or more, 5 or less (however, the above composition Each ratio in is a molar ratio.) The method for producing SAPO-47 according to claim 8 or 9, wherein in the crystallization step, the alkylethylenediamine is tetraalkylethylenediamine. The method for producing SAPO-47 according to any one of claims 8 to 10, further comprising a metal supporting step of supporting metal on SAPO-47. A nitrogen oxide reduction catalyst comprising SAPO-47 according to any one of claims 1 to 7. A method for reducing nitrogen oxides using the nitrogen oxide reduction catalyst according to claim 12.

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