WO2014038690A1 - Sel de silicoaluminophosphate et catalyseur de réduction d'oxydes d'azote comprenant celui-ci - Google Patents

Sel de silicoaluminophosphate et catalyseur de réduction d'oxydes d'azote comprenant celui-ci Download PDF

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WO2014038690A1
WO2014038690A1 PCT/JP2013/074238 JP2013074238W WO2014038690A1 WO 2014038690 A1 WO2014038690 A1 WO 2014038690A1 JP 2013074238 W JP2013074238 W JP 2013074238W WO 2014038690 A1 WO2014038690 A1 WO 2014038690A1
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sapo
solid acid
amount
less
nitrogen oxide
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PCT/JP2013/074238
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English (en)
Japanese (ja)
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岡庭　宏
敬助 徳永
英和 青山
良和 永井
満明 吉光
平野　茂
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東ソー株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • 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 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.
  • 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.
  • 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.
  • 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].
  • SAPO-47 having an average crystal grain size of less than 5 ⁇ m and a Si / Al molar ratio of less than 0.23.
  • SAPO-47 as described in [1] above, wherein the solid acid amount is 0.5 mmol / g or more.
  • 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.
  • the SAPO-47 according to any one of [1] to [3], wherein an alkaline earth metal is supported.
  • 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.
  • a mixture having the following composition is crystallized.
  • 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.
  • 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.
  • 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.
  • 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.
  • a nitrogen oxide reduction catalyst it can be used as a more suitable catalyst.
  • 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.
  • 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 ⁇ m) 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.
  • 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).
  • 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).
  • 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.
  • the SAPO-47 of the present invention has an average crystal grain size of less than 5 ⁇ m, preferably 4.5 ⁇ m or less, and more preferably 4 ⁇ m or less.
  • SAPO-47 having low catalytic activity is obtained.
  • the average crystal grain size is 5 ⁇ m or more, the operability (handling) when applied to a catalyst carrier such as a honeycomb is deteriorated.
  • the average crystal grain size may be 0.5 ⁇ m or more, further 1 ⁇ m or more, and further 3 ⁇ m or more.
  • the average crystal grain size in SAPO-47 of the present invention is the average of the primary particle sizes.
  • 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.
  • the catalytic activity is the performance as a catalyst.
  • the surface area of SAPO-47 of the present invention may be such that a catalytic reaction occurs.
  • 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.
  • the molar ratio of Si / Al is 0.23 or more, the crystal structure becomes unstable.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • NH 3 -TPD method a method having the following three steps can be exemplified.
  • an inert gas can be circulated through the silicoaluminophosphate at a treatment temperature of 400 to 600 ° C.
  • 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.
  • the temperature can be raised to about 100 ° C. to 700 ° C. while circulating an inert gas through the silicoaluminophosphate.
  • 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.
  • the solid acid is confirmed and quantified, it is necessary to separate both of them.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the SAPO-47 of the present invention may be SAPO-47 on which a metal and an alkaline earth metal are supported.
  • 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.
  • 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.
  • 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.
  • 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”).
  • SAPO-47 can be crystallized without using a compound containing butylamine as an essential component.
  • the production method of the present invention will be described in detail.
  • the manufacturing method of this invention has a crystallization process which crystallizes the mixture containing alkylethylenediamine.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the composition of silicon, phosphorus, aluminum, water and SDA in the mixture is preferably the following composition.
  • each ratio in the said composition is molar ratio
  • SDA is said alkylethylenediamine.
  • 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.
  • 2P / 2Al is preferably 0.7 or more, more preferably 0.8 or more, in terms of molar ratio.
  • 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.
  • Si / 2Al is 0.1 or more
  • SAPO-47 having a larger amount of solid acid is easily obtained.
  • Si / 2Al is 1.2 or less, further 0.8 or less, SAPO-47 can be easily obtained in a shorter crystallization time.
  • H 2 O / 2Al is preferably 5 or more and more preferably 15 or more in terms of molar ratio.
  • 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.
  • the mixture preferably contains a seed crystal.
  • 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. .
  • the crystallization time is easily shortened.
  • 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.
  • 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.
  • the type of seed crystal is preferably silicoaluminophosphate, more preferably silicoaluminophosphate having a chabazite structure, and even more preferably SAPO-34.
  • the seed crystal preferably has an average particle size of 3 ⁇ m or less, more preferably 1.5 ⁇ m, and still more preferably 1 ⁇ m or less.
  • the average grain size of the seed crystals is 3 ⁇ m or less, the crystal grain size of SAPO-47 obtained is difficult to increase.
  • the average particle size of the seed crystal there is no lower limit of the average particle size of the seed crystal, but for example, if it is 0.1 ⁇ m or more, and further 0.5 ⁇ m or more, the seed crystal is less likely to aggregate, so the effect of mixing the seed crystal tends to be easily obtained.
  • a mixture having the following composition can be exemplified.
  • each ratio in each of the above compositions is a molar ratio
  • SDA is tetraethylethylenediamine
  • 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.
  • 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.
  • SAPO-47 having the average crystal grain size and Si / Al molar ratio of the present invention is obtained by crystallizing the mixture.
  • 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.
  • 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.
  • any one process of a baking process or a re-washing process In the manufacturing method of this invention, you may have at least any one process of a baking process or a re-washing process.
  • the SAPO-47 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.
  • 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.
  • the SAPO-47 In the re-washing step, the SAPO-47 after drying is washed again.
  • the metal derived from the raw material such as the alkali metal may remain on the surface or pores of SAPO-47.
  • 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.
  • 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.
  • 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.
  • the SAPO-47 used for metal loading is preferably either proton type (H + type) SAPO-47 or ammonia type (NH 4 + type) SAPO-47.
  • the metal loading on SAPO-47 tends to be performed more efficiently.
  • crystallization of SAPO-47 may be performed at 400 ° C. or higher in the atmosphere.
  • 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.
  • any supporting method can be selected.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Copper-supported SAPO-47 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.
  • 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.
  • the copper-supported SAPO-47 has a nitrogen oxide reduction rate at 500 ° C. of 70% or more, and more preferably 80% or more.
  • the copper-supported SAPO-47 has a nitrogen oxide reduction rate at 300 ° C. of 70% or more, and further 80% or more.
  • copper-supported SAPO-47 has a high nitrogen oxide reduction rate even at a high temperature and a low temperature of about 300 ° C.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • SAPO-47 is SAPO-47 on which copper and alkaline earth metal are supported (hereinafter referred to as “copper-alkaline earth metal supported SAPO”).
  • 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.
  • 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)
  • the nitrogen oxide reduction rate of the SCR catalyst There is no generalized or standardized condition for the method for evaluating the nitrogen oxide reduction rate of the SCR catalyst.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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”).
  • the present adsorbing / desorbing agent a water vapor adsorbing and desorbing agent for discharging water vapor is used outside the system.
  • water vapor water
  • 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.
  • adsorption / desorption such adsorption and desorption of water vapor (hereinafter referred to as “adsorption / desorption”) is repeated.
  • 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).
  • 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.
  • 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 adsorption / desorption agent may be a water vapor adsorption / desorption agent containing SAPO-47 on which an alkaline earth metal is supported.
  • 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.
  • 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.
  • 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 ⁇ m, preferably 4.5 ⁇ m or less, and more preferably 4 ⁇ m or less.
  • the average crystal grain size may be 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, and even more preferably 3 ⁇ m 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.
  • 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.
  • 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.
  • a binder or molding aid 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.
  • 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.
  • the BET specific surface area of the sample was measured by nitrogen adsorption by the BET multipoint method.
  • 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).
  • ICP method inductively coupled plasma emission spectrometry
  • 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.
  • 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.
  • ammonia was adsorbed on 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.
  • 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.
  • 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.
  • 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.
  • TEEDA tetraethylethylenediamine
  • 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 ⁇ m obtained by the same method as in Reference Example 1 was used as a seed crystal.
  • 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 ⁇ m, and a BET specific surface area of 636 m 2 / g.
  • 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.
  • 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.
  • 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 ⁇ m obtained by the same method as in Reference Example 1 was used as a seed crystal.
  • 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 ⁇ m.
  • 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.
  • 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 thereto and mixed to obtain a reaction mixture.
  • SAPO-34 having an average crystal grain size of 0.8 ⁇ m obtained by the same method as in Reference Example 1 was used as a seed crystal.
  • 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 ⁇ m, and a BET specific surface area of 594 m 2. / G.
  • 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 ⁇ m 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.
  • 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 ⁇ m, and a BET specific surface area of 637 m 2 / g. there were.
  • 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 ⁇ m obtained by the same method as in Reference Example 1 was used as a seed crystal.
  • 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 ⁇ m, and a BET specific surface area of 616 m 2 / g.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m 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.
  • 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 ⁇ m, and a BET specific surface area of 672 m 2 / g. there were.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m, and a BET specific surface area of 579 m 2 / g. .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m.
  • 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.
  • 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.
  • 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. .
  • 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.
  • Example 11 The nitrogen oxide reduction rate at 500 ° C. in Example 11 was twice or more that in Reference Example 2.
  • 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.
  • 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.
  • 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.
  • 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.
  • TEEDA tetraethylethylenediamine
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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
  • 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.
  • 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
  • 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.
  • 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 ⁇ m. 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
  • ICP inductively coupled plasma emission spectrometer
  • 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.
  • 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.
  • the calcium-supported SAPO-47 of this experimental example hardly deteriorates the water vapor adsorption / desorption characteristics even after repeated hydration treatment.
  • 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.
  • 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.

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Abstract

La présente invention a pour objet de fournir un SAPO-47 qui permet d'obtenir un catalyseur présentant une activité catalytique élevée, en particulier une activité catalytique élevée à de faibles températures, et son procédé de production. Ce SAPO-47 présente une taille moyenne des particules cristallines inférieure à 5 μm et un rapport molaire Si/Al inférieur à 0,23. De plus, dans le SAPO-47, la quantité d'acide solide après traitement par hydratation par rapport à la quantité d'acide solide avant traitement par hydratation est de préférence supérieure ou égale à 40 %. Ce SAPO-47 peut être produit par l'intermédiaire d'un procédé de production comprenant un processus de cristallisation dans lequel est cristallisé un mélange comprenant une alkyléthylènediamine.
PCT/JP2013/074238 2012-09-10 2013-09-09 Sel de silicoaluminophosphate et catalyseur de réduction d'oxydes d'azote comprenant celui-ci WO2014038690A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001503389A (ja) * 1996-11-13 2001-03-13 シェブロン ケミカル カンパニー エルエルシー オレフィン異性化法
CN1830783A (zh) * 2006-03-23 2006-09-13 南开大学 硅磷酸铝分子筛的合成方法
WO2011092521A1 (fr) * 2010-02-01 2011-08-04 Johnson Matthey Plc Filtre de réduction catalytique sélective (rcs) extrudé

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001503389A (ja) * 1996-11-13 2001-03-13 シェブロン ケミカル カンパニー エルエルシー オレフィン異性化法
CN1830783A (zh) * 2006-03-23 2006-09-13 南开大学 硅磷酸铝分子筛的合成方法
WO2011092521A1 (fr) * 2010-02-01 2011-08-04 Johnson Matthey Plc Filtre de réduction catalytique sélective (rcs) extrudé

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
E. DUMITRIU ET AL.: "Synthesis optimization of chabasite-like SAPO-47 in the presence of sec- butylamine", MICROPOROUS AND MESOPOROUS MATERIALS, vol. 31, 1999, pages 187 - 193 *

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