JP2014196228A - Water vapor adsorbing and desorbing agent including silicoaluminophosphate salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water vapor adsorbing and desorbing agent which exhibits large amounts of water vapor adsorption and desorption when used as a water component removal system.SOLUTION: A water vapor adsorbing and desorbing agent contains SAPO-47 represented by the general formula (1) defined by (SiAlP)O, where x is the mole fraction of Si and satisfies 0.05≤x≤0.20, y is the mole fraction of Al and satisfies 0.40≤y≤0.55, and z is the mole fraction of P and satisfies 0.40≤z≤0.50, and x+y+z=1 is satisfied.

Description

  The present invention relates to a water vapor adsorption / desorption agent containing silicoaluminophosphate. The water vapor adsorption / desorption agent according to the present invention relates to a water vapor adsorption / desorption agent suitable for an adsorption heat pump system, a desiccant air conditioning system, a humidity adjusting wall agent, a humidity adjusting sheet and the like.

  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, after water vapor (water) is adsorbed to the water vapor adsorbent / desorbent at an adsorption temperature of 25 ° C. to 40 ° C., it is heated to a desorption temperature of 60 ° C. to 100 ° C. 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 (Patent Documents). 1 to 2).

  Patent Document 1 reports a water vapor adsorption / desorption 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.

  Patent Document 2 discloses an adsorption / desorption agent made 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.

JP 2003-340236 A JP 2007-181795 A

  The water vapor adsorption / desorption agents proposed so far have not been sufficient in the amount of water vapor adsorption / desorption.

  The present invention solves the above problems and provides a water vapor adsorbing and desorbing agent that is made of silicoaluminophosphate and is useful for adsorption heat pump systems, desiccant air conditioning systems, humidity adjusting walls, humidity adjusting sheets, and the like. That is, an object of the present invention is to provide a water vapor adsorption / desorption agent having a high water vapor adsorption / desorption amount when used as a moisture removal system.

  The present inventor examined the crystal structure and water vapor adsorption / desorption characteristics of silicoaluminophosphate. As a result, it was found that SAPO-47 has a high water vapor adsorption amount and high durability against repeated water vapor adsorption and desorption, and the present invention has been completed.

  That is, the present invention is a water vapor adsorbing / desorbing agent containing SAPO-47, and further a water vapor adsorbing / desorbing 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.)

  Hereinafter, the water vapor adsorbing and desorbing agent of the present invention will be described.

  The water vapor adsorption / desorption agent of the present invention is a water vapor adsorption / desorption agent containing SAPO-47. The water vapor adsorption / desorption agent of the present invention may contain SAPO-47, and may be a water vapor adsorption / desorption agent made of 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.

  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-type structure, but the crystal system is triclinic SAPO-34 and a silicoaluminophosphate different from SAPO-47. is there.

  The SAPO-34 X-ray diffraction pattern is published on the following IZA website. URL http: // www. isa-online. org / synthesis / Recipes / XRD / SAPO-34. html (search date September 6, 2012).

  Furthermore, the water vapor adsorption / desorption agent of the present invention is preferably a water vapor adsorption / desorption agent containing SAPO-47 whose solid acid amount after hydration treatment is 40% or more with respect to the solid acid amount before hydration treatment. If the amount of solid acid after hydration treatment relative to the amount of solid acid before hydration treatment (hereinafter referred to as “solid acid retention rate”) is 40% or more, water vapor adsorption / desorption is repeated even if water vapor adsorption / desorption is repeated. It becomes a water vapor adsorbing and desorbing agent with little decrease in the amount. 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.

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 the solid acid.

Examples of the NH ₃ -TPD method include a method having the following three steps.

1) Pretreatment process to remove gas and moisture adsorbed on silicoaluminophosphate 2) Ammonia adsorption process to adsorb ammonia on silicoaluminophosphate, and 3) Ammonia adsorbed on silicoaluminophosphate , Ammonia desorption process to desorb from there

  An example of the pretreatment step is to circulate an inert gas through the silicoaluminophosphate at a treatment temperature of 400 to 600 ° C. Moreover, as an ammonia adsorption | suction process, it can exemplify that the impossible gas containing 1-20 volume% ammonia is distribute | circulated to silicoaluminophosphate at the process temperature of 100-150 degreeC. 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 step, 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 from the peak of ammonia desorbed at a temperature of 250 to 450 ° C., and the amount of ammonia corresponding to the peak is quantified and regarded as the amount of solid acid.

  Moreover, as a hydration process, SAPO-47 can be left still and processed for 1 hour or more and 60 days or less in the saturated water vapor | steam atmosphere of 60 degreeC or more and 100 degrees C or less, for example.

  Furthermore, the water vapor adsorption / desorption agent of the present invention 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 a treatment (hereinafter referred to as “cycle hydration treatment”) that has been subjected to multiple hydration treatments is easily suppressed. .

  Here, as the cycle hydration treatment, for example, after the treatment for allowing the water vapor adsorbent / desorbent 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, A treatment for allowing the water vapor adsorbent / desorbent to stand for 1 hour or more and 60 days or less in a dry atmosphere (ie, an atmosphere having a water content of 0.05% by volume or less) at 1 ° C. or less is defined as 1 cycle. Repeating 10 times or more and 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 contained in the water vapor adsorption / desorption agent 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. 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.

  Note that the average crystal grain size in SAPO-47 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 particle size in the present invention is obtained by averaging secondary particles formed by aggregation of primary particles, so-called aggregate particles, or SAPO-47 of the present invention, This is different from the average particle diameter of the aggregated particles obtained by pulverizing this.

As BET specific surface area of the SAPO-47, for example, 500 meters ² / g or more include the following 800 m ² / g.

  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 of the present invention has a Si / Al molar ratio of less than 0.23, preferably 0.2 or less. 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, 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, more preferably 0.75 or more, further 0.8 or more, or even 0.85 or more. Can do. On the other hand, as the maximum value of the proportion of phosphorus contained in SAPO-47, 0.9 or less can be exemplified by the molar ratio of P / Al.

  The water vapor adsorption / desorption agent of the present invention 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 water vapor adsorbing and desorbing agent of the present invention 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 and a molding aid may be mixed with the water vapor adsorbing / desorbing agent of the present invention 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.

  The method for producing the water vapor adsorption / desorption agent of the present invention will be described below.

  The water vapor adsorbing / desorbing agent of the present invention is obtained by obtaining SAPO-47 and making it into an arbitrary form.

  SAPO-47 contained in the moisture adsorption / desorption agent of the present invention can be obtained by a production method having a crystallization step of crystallizing a mixture containing alkylethylenediamine.

  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.

  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. Preferably, it is an ethyl group.

Examples of preferable alkylethylenediamine in the crystallization step include at least one selected from the group of tetraethylethylenediamine, triethylethylenediamine, and tetramethylethylenediamine, more preferably tetraethylethylenediamine. Tetraethylethylenediamine is represented by the molecular formula C ₁₀ H ₂₄ N ₂ , which is also referred to as N, N, N ′, N′-tetraethylethane-1,2-diamine, ethylenebis (diethylamine) or the like. It is.

In the crystallization step, a mixture containing alkylethylenediamine as an organic mineralizer and containing a silicon (Si) source, a phosphorus (P) source, an aluminum (Al) source and water (H ₂ O) may be crystallized. preferable.

  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, sulfuric acid Mention may be made of at least one solid aluminum compound selected from the group of aluminum and sodium aluminate, organoaluminum compounds such as aluminum isopropoxide, and mixtures thereof.

  Furthermore, a compound containing two or more selected from the group of silicon, phosphorus and aluminum can also be used as a raw material. Examples of such compounds include aluminophosphoric acid gels and silicoaluminophosphoric acid gels.

  The mixture is obtained by mixing these raw materials with water and alkylethylenediamine as an organic mineralizer. Arbitrary methods can be used for mixing raw materials and the like when obtaining the mixture. For example, each raw material, water, and organic mineralizer 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 alkylethylenediamine in the mixture is preferably the following composition.

P ₂ O ₅ / Al ₂ O ₃ 0.7 or more and 1.5 or less SiO ₂ / Al ₂ O ₃ 0.1 or more and 1.2 or less H ₂ O / Al ₂ O ₃ 5 or more and 100 or less Alkylethylenediamine / Al ₂ O ₃ 0.5 or more and 5 or less In addition, each ratio in the said composition is molar ratio.

As for the ratio of phosphorus and aluminum in the mixture, P ₂ O ₅ / Al ₂ O ₃ is preferably 0.7 or more and more preferably 0.8 or more in terms of molar ratio. When P ₂ O ₅ / Al ₂ O ₃ is 0.7 or more, the yield of SAPO-47 obtained tends to increase. On the other hand, if P ₂ O ₅ / Al ₂ O ₃ is 1.5 or less, and 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 SiO ₂ / Al ₂ O ₃ is 0.1 or more and more preferably 0.2 or more in terms of molar ratio. When SiO ₂ / Al ₂ O ₃ is 0.1 or more, SAPO-47 having a larger amount of solid acid is easily obtained. On the other hand, if SiO ₂ / Al ₂ O ₃ is 1.2 or less, and 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 / Al ₂ O ₃ is preferably 5 or more and more preferably 15 or more in terms of molar ratio. When H ₂ O / Al ₂ O ₃ is 5 or more, the resulting mixture is rich in fluidity. Thereby, it becomes easy to become a mixture excellent in operability. It is preferred _H 2 O / _Al 2 _{O 3} in the mixture is _small, H 2 O / _Al 2 _{O 3} is 100 or less, if more than 70 or less, a mixture having a fluidity suitable for crystallization Become. Furthermore, when H ₂ O / Al ₂ O ₃ is 50 or less, crystallization can be performed at a higher concentration, which tends to be advantageous in industrial production.

As for the ratio of alkylethylenediamine and aluminum in the mixture, alkylethylenediamine / Al ₂ O ₃ is preferably 0.5 or more and more preferably 1 or more in terms of molar ratio. This makes it easier to obtain SAPO-47 with a large amount of solid acid. More alkylethylenediamines / _Al 2 _{O 3} is large, the amount of the solid acid is greater SAPO-47 can be easily obtained. Alkylethylenediamines / _Al 2 _{O 3} is 5 or less, more than 3, or even if more than 1.5, the solid acid-intensive SAPO-47 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 wt% or more of seed crystals, more preferably contains 0.1 wt% or more, further preferably contains 0.5 wt% or more, and even more preferably contains 1 wt% 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 crystal grain size of SAPO-47 obtained tends to be uniform. If the crystal grain size of the obtained SAPO-47 becomes uniform, the seed crystal content in the mixture is arbitrary. Therefore, as an upper limit of seed crystal content, 10 weight% or less, Furthermore, 5 weight% or less can be mentioned, for example.

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 the seed crystal.

  Furthermore, the type of seed crystal is preferably silicoaluminophosphate, more preferably silicoaluminophosphate having a chabazite structure, and SAPO-34 is even more preferable.

  In the crystallization step, the seed crystal preferably has an average particle size of 5 μm or less, more preferably 1.5 μm or less, and even more preferably 1 μm or less. When the average grain size of the seed crystals is 5 μm or less, the crystal grain size of SAPO-47 obtained is difficult to increase. There is no lower limit of the average particle diameter of the seed crystal, but for example, when it is 0.1 μm or more, and further 0.5 μm or more, the seed crystal is less likely to aggregate, and the effect of mixing the seed crystal tends to be easily obtained. There is.

  As a preferable mixture for obtaining SAPO-47, a mixture having the following composition can be exemplified.

P ₂ O ₅ / Al ₂ O ₃ 0.7 or more and 1.5 or less SiO ₂ / Al ₂ O ₃ 0.1 or more and 1.2 or less H ₂ O / Al ₂ O ₃ 5 or more and 100 or less Alkylethylenediamine / Al ₂ O ₃ 0.5 or more and 5 or less Seed crystal addition amount 0.05 wt% or more and 10 wt% or less

  In addition, each ratio in the said composition is molar ratio, and a seed crystal is a 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, and further 80 hours or less. The higher the crystallization temperature, the shorter the crystallization time. Although there is no restriction | limiting in the upper limit of crystallization temperature, It is preferable that it is 220 degrees C or less. In the crystallization step, it is preferable to crystallize the mixture while stirring. Thereby, the crystal grain diameter of SAPO-47 obtained tends to become more uniform.

  In the manufacturing method of this invention, you may have a washing | cleaning process and a drying process further.

  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. Thereby, SDA taken into SAPO-47 at the time of crystallization can be removed. 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 higher and 800 ° C. or lower in the atmosphere or in an oxidizing atmosphere such as oxygen gas.

  In the rewashing step, the SAPO-47 after drying is rewashed. When SAPO-47 is crystallized using a raw material containing an alkali metal or the like, a metal derived from the raw material such as an 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 only 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 method for producing SAPO-47 contained in the water vapor adsorbing and desorbing agent of the present invention may have an alkaline earth metal supporting step of supporting alkaline earth metal on SAPO-47.

  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.

In the alkaline earth metal loading step, SAPO-47 to be used for alkaline earth metal loading is either proton type (H ⁺ type) SAPO-47 or ammonia type (NH ₄ ⁺ type) SAPO-47. Is preferred. Thereby, it exists in the tendency which can carry | support the metal to SAPO-47 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 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.

  If an alkaline earth metal is supported in the alkaline earth metal supporting step, an arbitrary method can be selected as the supporting method. Examples of the loading method include an ion exchange method, an impregnation loading method, an evaporation to dryness method, a precipitation loading method, and a physical mixing method, and the amount of alkaline earth metal supported on SAPO-47 is easy to control. The supporting method is preferably either an impregnation supporting method or an evaporation to dryness method.

  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 with respect to the weight of SAPO-47 may be 2.5% or less, further 2% or less, or 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 water vapor adsorption / desorption agent containing SAPO-47 of the present invention has a high water vapor adsorption / desorption amount, and is useful for adsorption heat pump systems, desiccant air conditioning systems, humidity adjusting wall agents, humidity adjusting sheets and the like. Can be used as

  Furthermore, the water vapor adsorption / desorption agent of the present invention 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 water removal system.

It is a figure which shows the water vapor | steam adsorption isotherm measured at 25 degreeC of the silicoaluminophosphate obtained in 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 example 1. FIG. 2 is a comparison diagram of an X-ray diffraction pattern of a reference example and an X-ray diffraction pattern of Example 1 (in the figure, the solid line is Example 1 and the broken line is a reference example). Reference X-ray diffraction pattern of SAPO-34 published by IZA. (Source: <URL http://www.iza-online.org/synthesis/Recipes/XRD/SAPO-34.html>

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to this.

(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 and pulverized, and then sized to 20 to 30 mesh. 0.1 g of the sized sample was weighed and filled into a fixed bed normal pressure flow type 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 circulated 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 that was not adsorbed on the sample was removed from the reaction tube.

  Thereafter, the temperature of the sample was increased from 100 ° C. to 700 ° C. at a temperature increase 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 desorption peak having a peak top at a desorption temperature of 100 ° C. or higher and lower than 250 ° C. is a peak derived from desorption of ammonia physically adsorbed on a sample (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 (0.25 mL of 10 vol% ammonia-helium mixed gas) with a known ammonia amount (mmol) 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)

(X-ray diffraction measurement)
Using a general X-ray diffractometer (trade name: MXP-3, manufactured by Mac Science), X-ray diffraction measurement of the sample was performed. A CuKα ray (λ = 1.5405 mm) is used as the radiation source, the measurement mode is step scan, the scan condition is 0.04 ° per second, the measurement time is 3 seconds, and the measurement range is 2 ° to 4 ° to 44 °. Measured with

  The sample was identified by comparing the obtained X-ray diffraction pattern with the X-ray diffraction pattern of SAPO-47 described in Non-Patent Document 1. That is, it has an X-ray diffraction peak of maximum intensity at 2θ = 24.8 ± 0.2 °, 2θ = 16.0 ± 0.2, 24.8 ± 0.2 °, and 30.7 ± 0.2. 3 medium intensity X-ray diffraction peaks at 2 ° and 2θ = 17.7 ± 0.2, 21.9 ± 0.2 °, 25.9 ± 0.2 ° and 31.0 ± 0. Identified as SAPO-47 by having four small intensity X-ray diffraction peaks at 2 °.

(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
Under these conditions, a water vapor adsorption isotherm was obtained, 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.

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 baking (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.

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.

  Moreover, 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 by the same method 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 0.72 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).

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.

  Moreover, 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 by the same method 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, 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).

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.

Moreover, 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 by the same method 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 0.76 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).

Example 5
SAPO-47 was obtained in the same manner as in 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 by dry weight, and then 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-supported 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 and 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, while the sample was kept at 75 ° C., the sample was left standing in an air atmosphere having a dew point of −40 ° C. (water content 0.05% by volume or less). 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. Accordingly, it was confirmed that the calcium-supporting SAPO-47 of this example hardly deteriorates the water vapor adsorption / desorption characteristics even when it is repeatedly hydrated.

Example 6
SAPO-47 was obtained in the same manner as in 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 by dry weight, and then 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-supported 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).

Example 7
SAPO-47 was obtained in the same manner as in 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 by dry weight, and then 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-supported 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 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 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 (FIG. 4) of SAPO-34 published by IZA, 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 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 Example 1 in FIG. 1, Comparative Example 1 had a small amount of water vapor adsorption at a relative pressure of 0.05 to 0.30. The silicoaluminophosphate of Example 1 has a higher solid acid retention before and after the hydration treatment, and is superior in water resistance of the crystal skeleton.

  The water vapor adsorbing and desorbing agent of the present invention can be used as a water vapor adsorbing and desorbing agent such as an adsorption heat pump system, a desiccant air conditioning system, a humidity adjusting wall agent, and a humidity adjusting sheet.

Claims (6)

The 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 and x + y + z = 1.)   The water vapor adsorption / desorption agent according to claim 1, wherein the solid acid amount after hydration treatment is 40% or more with respect to the solid acid amount before hydration treatment.   The water vapor adsorbing and desorbing agent according to claim 1 or 2, comprising SAPO-47 on which an alkaline earth metal is supported.   4. The water vapor adsorption / desorption agent according to claim 3, wherein the alkaline earth metal is at least one selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). .   The water vapor adsorption / desorption agent according to claim 3 or 4, wherein the alkaline earth metal is calcium. 6. The water vapor adsorbing and desorbing agent according to claim 1, comprising SPO-47 obtained by a production method having a crystallization step of crystallizing a mixture represented by the following composition.
P ₂ O ₅ / Al ₂ O ₃ (molar ratio) 0.7 or more and 1.5 or less SiO ₂ / Al ₂ O ₃ (molar ratio) 0.1 or more and 1.2 or less H ₂ O / Al ₂ O ₃ (mole) Ratio) 5 or more and 100 or less Alkylethylenediamine / Al ₂ O ₃ (molar ratio) 0.5 or more and 5 or less

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