JP5092219B2 - Aluminophosphate-carrying adsorption element and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous homogeneous dispersion (coating liquid) having good dispersion stability and suitable for producing an adsorbent element, etc., to provide the adsorbent element scarcely causing deterioration in adhesion strength of an adsorbent material to a carrier due to a repetition of adsorption and desorption, and to provide a method for producing the same. <P>SOLUTION: This aqueous dispersion of the aluminophosphates comprises an aqueous dispersion formed by dispersing at least the aluminophosphates and an organic binder in water, wherein the aqueous dispersion contains at least one kind of anionic surfactant. The adsorbent element supporting the aluminophosphates has at least the aluminophosphates, the organic binder, and the anionic surfactant on the carrier. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

The present invention relates to A luminometer phosphate compound carrying adsorption element and a manufacturing method thereof. Particularly suitable for production of an aluminophosphate-carrying adsorbing element for use in heat pumps, cold storage systems, and humidity control air conditioners using water adsorption / desorption on adsorbents, aluminophosphates-carrying adsorbing element, and method for producing the same It is about.

  Conventionally, an apparatus for adsorbing organic solvent vapor from a gas such as air containing organic solvent vapor by supporting a hydrophobic zeolite on a carrier is known. For example, if a slurry containing an organic emulsion binder is used as a binder to be blended with zeolite (ordinary zeolite or aluminosilicate), the zeolite content of the slurry can be increased, so that the efficiency of the zeolite impregnation step is increased, and the gel of the binder itself Therefore, the viscosity of the slurry can be kept within the proper range over a long period of time, and there is almost no change in pH due to the blending of the binder, so that the slurry can maintain a pH suitable for storage of the zeolite. It is known that the crystal structure can be maintained (see Patent Document 1). However, this patent document does not describe that the slurry contains a surfactant and an aqueous dispersion of aluminophosphates. Further, in this patent document, when used as an adsorbing element, all of the organic binder is removed by baking at a high temperature, and there is no description about the adsorbing performance of the adsorbing element in which zeolite is held by the organic binder.

In addition, adsorbents consisting of silicone resin and zeolite powder are coated on the substrate as an adsorbent that adsorbs volatile organic compounds, etc. efficiently, can be desorbed easily and quickly, and is excellent in workability. An adsorbent material that has been subjected to a baking process is known (Patent Document 2).
On the other hand, adsorption heat pumps that use adsorption and desorption of water to and from adsorbents, cold storage systems, and methods for conditioning humidity in living spaces have been proposed, and if aluminophosphate-based zeolite is used as the adsorbent, the temperature is high. It is known that operation is possible even if the temperature difference between the heat source and the low-temperature heat source is small, and that the adsorbent can be regenerated at a low temperature (Patent Documents 3 to 5).
JP 2002-95964 A JP 2001-321425 A JP 2002-372332 A JP 2004-132690 A JP 2004-136269 A

As described above, the aluminophosphate zeolites described in Patent Documents 3 to 5 are practically advantageous because they can be regenerated at low temperatures. In order to apply such a zeolite to an adsorbing element, it is usually necessary to use it in a state where the adsorbent is held with an organic binder in order to obtain sufficient adhesive strength. According to our study, when the organic emulsion binder described in Patent Document 1 is used, for example, when trying to support the carrier in the same manner as a conventionally known aluminosilicate, the gelation of the slurry is remarkable, It has been found that the adhesion between the carrier layer and the carrier may be poor, or that the adhesive strength may decrease or the adsorption capacity may decrease with repeated adsorption and desorption. In the case of Patent Document 2, the adsorption element obtained by using not an aqueous dispersion but also using a silicone resin or the like is increased in proportion to the absorption rate under actual use conditions. It has been found that there arises a problem that the desorption rate is greatly reduced.

An object of the present invention is to provide a small suction device and a manufacturing method thereof of reduction in adhesive strength to the support of the adsorbent caused by the repetition of adsorption desorption.
Furthermore, an adsorption element having a large adsorption amount in the operating temperature range of the adsorption element (usually 100 ° C. or less), a high adsorption / desorption speed, a small change in adsorption characteristics due to repeated adsorption / desorption, and an excellent adsorption element and its It is to provide a manufacturing method.

As a result of intensive studies to solve the above problems, the present inventors have found that an aqueous dispersion in which at least aluminophosphates and an organic binder are dispersed in water contains a specific ionic surfactant. The inventors have found that the object is achieved, and have reached the present invention.
That is, the gist of the present invention is an aqueous dispersion in which at least an aluminophosphate and an organic binder are dispersed in water, wherein the aluminophosphate contains at least one anionic surfactant. The aqueous dispersion and the aqueous dispersion for adsorption elements.

The gist of the present invention is a method for producing an aluminophosphates-supporting adsorbing element comprising a step of attaching an aqueous dispersion to a carrier and drying, wherein the aqueous dispersion comprises at least an aluminophosphate and (meth) One or two selected from acrylic resin, (meth) acrylic / styrene copolymer resin, ethylene / vinyl acetate copolymer resin, silica modified acrylic copolymer resin, silicone acrylic copolymer resin and urethane modified ethylene / vinyl acetate copolymer resin An aqueous dispersion in which an organic binder composed of more than one species is dispersed in water, which contains at least one kind of anionic surfactant, the aluminophosphates-supporting adsorbing element, Aluminof used for at least one of heat pump, cold storage heat system and humidity control air conditioner using water adsorption / desorption It consists in the production method of the aluminophosphate compound carrying adsorption element which is a Sufeto carrying adsorption element.
Another gist lies in an aluminophosphate-supported adsorbing element manufactured by this method .

  The aqueous dispersion of aluminophosphates of the present invention has good dispersibility of aluminophosphates and little precipitation of aluminophosphates due to storage. In addition, the adsorbing element obtained by using this has a good adsorbing amount characteristic (adsorbing amount) with little decrease in the adhesive strength of the adsorbing material to the carrier due to repeated adsorption and desorption.

<Aluminophosphates>
The aluminophosphates used in the present invention (hereinafter sometimes abbreviated as ALPOs) are crystalline aluminophosphates defined by IZA (International Zeolite Association).
In the crystalline aluminophosphate, atoms constituting the skeletal structure are aluminum and phosphorus, and a part thereof may be substituted with other atoms. Among them, I) aluminum is a heteroatom (Me1: where Me1 belongs to the third or fourth period of the periodic table, and from elements of Group 2A, Group 7A, Group 8, Group 1B, Group 2B, Group 3B (except for Al) Show at least one element selected
The ) Me-aluminophosphate partially substituted with), II) Me-aluminophosphate with phosphorus substituted with a heteroatom (Me2; where Me2 is a group 4B element belonging to the third or fourth period of the periodic table), Alternatively, III) Me-aluminophosphate in which both aluminum and phosphorus are substituted with heteroatoms (Me1 and Me2 respectively) is preferable from the viewpoint of adsorption characteristics.
Here, the constituent ratio (molar ratio) of Me, Al and P constituting the skeleton structure is usually a molar ratio of the following formulas 1-1 to 3-1, preferably the following formulas 1-2 to 3-2. If x is smaller than the above range, the amount of adsorption in the region where the adsorbate pressure is low tends to be small or the synthesis tends to be difficult, and if it is larger than the above range, impurities tend to be mixed during synthesis. Further, if y and z are out of the above ranges, synthesis is difficult.

0 ≦ x ≦ 0.3… 1-1
(X represents the molar ratio of Me to the total of Me, Al, and P)
0.2 ≦ y ≦ 0.6… 2-1
(Y represents the molar ratio of Al to the total of Me, Al, and P)
0.3 ≦ z ≦ 0.6… 3-1
(Z represents the molar ratio of P to the sum of Me, Al, and P)
0.01 ≦ x ≦ 0.3… 1-2
(X represents the molar ratio of Me to the total of Me, Al, and P)
0.3 ≦ y ≦ 0.5… 2-2
(Y represents the molar ratio of Al to the total of Me, Al, and P)
0.4 ≦ z ≦ 0.5 ... 3-2
(Z represents the molar ratio of P to the sum of Me, Al, and P)
Me may be contained alone or in combination of two or more. Preferable Me (Me1, Me2) is an element belonging to the third and fourth periods of the periodic table. Me1 preferably has an ionic radius of 3 to 0.8 nm in a divalent state, and more preferably has an ionic radius of 0.4 to 7 nm in a divalent and tetracoordinate state. Among these, at least one element selected from Fe, Co, Mg, and Zn is preferable from the viewpoint of ease of synthesis and adsorption characteristics, and Fe is particularly preferable. Me2 is a group 4B element belonging to the third or fourth period of the periodic table, and is preferably Si.

Further, aluminophosphate compounds of the present invention, the framework density (FD) is usually, 13T / nm ³ or more 20T / nm ³ or less, preferably, 13.5T / nm ³ or more, more preferably 14T / Nm ³ or more, while 19 T / nm ³ or less is preferred. Here, T / nm ³ means T atoms (number of elements constituting a skeleton other than oxygen per 1 nm ^{3 of} zeolite) present per unit volume nm ³ , and is a unit indicating framework density: FD. is there. If the amount is less than the above range, the structure tends to be unstable and the durability is lowered. On the other hand, if the range is exceeded, the adsorption capacity tends to be small and the adsorbent tends not to be used.

The aluminophosphates of the present invention have a structure defined by the International Zeolite Association (IZA) and are AEI, AEL, AET, AFI, AFN, AFR, AFS, AFT, AFX, ATO, ATS, CHA , ERI, LEV, and VFI. Among these, AEI, AEL, AFI, CHA, and LEV are preferable, and AFI and CHA are particularly preferable from the viewpoint of adsorption characteristics and durability.

The ALPOs can be used alone or in combination of two or more.

<Organic binder>
The organic binder of the present invention is not particularly limited, but is preferably a polymer having a vinyl monomer as a polymerization component. Among them, a polymer containing at least a vinyl monomer having a Q value (measurement of resonance stabilization) of 0.03 or more as a polymerization component. It is preferably a coalescence. The organic binder functions as an adhesive to the carrier of ALPOs in the adsorption element described later.

Here, the Q value of the vinyl monomer is a measure of resonance stabilization, and its numerical value is described in J. Brandrup et al., Polymer Handbook, Interscience (1974).
Examples of vinyl monomers having a Q value of 0.03 or more and their Q values are as follows. Styrene (1), vinyl chloride (0.044), vinylidene chloride (0.22), methyl methacrylate (0.74), methyl acrylate (0.42), methyl vinyl ketone (0.69), acrylonitrile (0 .60), isoprene (3.33), butadiene (2.39), acrylamide (0.23), vinylidene acid (20.13), methyl vinyl sulfide (0.32). Of these, those having a Q value of 0.1 or more and 10 or less are preferred, and those of 0.2 or more and 1 or less are particularly preferred. The organic binder of the present invention may be a homopolymer or copolymer of monomers having a Q value in the above range. Specifically, the organic binder is, for example, one selected from (meth) acrylic resins, (meth) acrylic / styrene copolymer resins, styrene / butadiene copolymer resins, and styrene / acrylonitrile copolymer resins. Or 2 or more types are mentioned. Among these, (meth) acrylic resins and (meth) acrylic / styrene copolymer resins are particularly preferable because of the stability of the aqueous dispersion and the heat resistance of the adsorption element obtained using the same.

The organic binder of the present invention is a copolymer of vinyl monomer and silicone having a Q value in the above range or a modified product thereof, or a copolymer of vinyl monomer and urethane monomer having a Q value in the above range, or Modified products are also preferred. Examples of such organic binders include silica-modified acrylic copolymers and silicone acrylic copolymers.
Examples of the Q value smaller than the above range include vinyl acetate (0.026), ethylene (0.015), propylene (0.002) and the like. When the organic binder contains a vinyl monomer satisfying the Q value as a (co) polymerization component, the heat resistance tends to be improved.

<Anionic surfactant>
The anionic surfactant according to the present invention is not particularly limited, and examples thereof include the following as lipophilic groups, hydrophilic groups and counter cations constituting them:
Lipophilic group: linear alkyl, branched alkyl, multi-chain type, alkylbenzene, alkylnaphthalene, polyoxypropylene, perfluoroalkyl, polysiloxane and the like.
Hydrophilic groups: 1) fatty acid, 2) sulfuric acid ester such as sodium polyoxyethylene alkyl ether sulfate, 3) sulfonic acid ester such as alkylbenzene sulfonic acid, alkyl diphenyl ether disulfonic acid, 4) sulfosuccinic acid ester, 5) phosphoric acid ester and the like.
Counter cation: alkali metal ion, alkaline earth metal ion, ammonium and the like.

The reason why the aqueous dispersion of an aluminophosphates becomes a slurry suitable for loading by containing an anionic surfactant is not sufficiently clear, but is stabilized by the aluminophosphate particles and the anionic surfactant. It is presumed that electrostatic repulsion is increased and aggregation of the aluminophosphate particles is prevented by the interaction with the emulsion particles or the interaction between the aluminophosphate particles and the anionic surfactant.
In addition, in the case of an aluminosilicate such as Y-type zeolite or a commonly used adsorbent such as silica, a relatively stable slurry can be obtained regardless of the type of surfactant, but in the case of aluminophosphates, If the emulsion containing the anionic surfactant of the present invention is not used, problems such as significant sedimentation of the slurry occur. For this reason, as shown above, the method of the present invention can prevent aggregation of the specific surface state of aluminophosphates, which is different from other aluminosilicates such as zeolite. Conceivable.

  The anionic surfactant may be contained in an organic binder emulsion or may be added to a slurry obtained by mixing an aluminophosphate and an organic binder emulsion. It is preferably contained as an emulsifier.

<Aluminophosphate aqueous dispersion>
The aluminophosphates aqueous dispersion of the present invention is an aqueous dispersion in which at least aluminophosphates, an anionic surfactant and an organic binder are dispersed in water.
The content of ALPOs in the aqueous dispersion of the present invention is usually 10 to 60% by weight, preferably 20 to 50% by weight.
When the content of the ALPO is within the above range, the support can be efficiently impregnated with the ALPO. In the present invention, the organic binder functions as an adhesive. However, since the content of zeolite in the slurry can be increased, the zeolite can be efficiently impregnated.

The weight average particle diameter of the ALPOs is not particularly limited, but usually 0.5 to 15 μm is used. In order to improve dispersibility, 0.5 to 0 μm is preferable, and 0.5 to 8 μm is particularly preferable.
In addition to the above, the aqueous dispersion may contain a nonionic surfactant, a cationic surfactant, an anti-settling agent, and a viscosity modifier as necessary. The content of these additives is not particularly limited, but is 0 to 10% by weight, preferably 0.1 to 5% by weight. When there are too many additives, there exists a tendency for adhesiveness to deteriorate.

The aqueous dispersion of the present invention usually contains 1 to 20% by weight, preferably 3 to 15% by weight, of an organic binder (in terms of solid content when the organic binder is an emulsion). It is preferable that the blending amount of the organic binder is within the above range because the fixing property and impregnation property of the ALPOs to the carrier are good.
Moreover, the ratio of the organic binder with respect to ALPO is 1-100 weight% normally, Preferably, it is 5-20 weight%. If the amount is too small, the adhesive strength is insufficient. If the amount is too large, the amount of adsorption tends to decrease.

The content of the anionic surfactant is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight. If the amount is too small, the stability of the aqueous dispersion (slurry) tends to deteriorate, and if too large, the adhesiveness tends to deteriorate.
The aqueous dispersion of the present invention has a pH of usually 4 to 9, preferably 5 to 8, and more preferably 5.5 to 7.8. When the pH is within this range, the crystal structure of the ALPOs does not collapse, and the quality as a zeolite-supporting slurry can be maintained over a long period of time.

<Adsorption element>
The adsorbing element of the present invention is an aluminophosphates-supporting adsorbing element having ALPOs, an organic binder, and an anionic surfactant on a carrier.
As the shape of the carrier supporting the ALPO, a flat plate shape, a fin shape, a honeycomb shape, or the like is used. Examples of the material of the carrier include metals such as aluminum, copper, and stainless steel in the case of a flat plate and fin, and ceramic paper is used in addition to the metal in the honeycomb. ALPOs are supported on a carrier using an organic binder as an adhesive.
The amount of ALPO supported on the carrier is not particularly limited, but is usually about 1 mg / cm ² or more and 50 mg / cm ² or less.

<Manufacture of adsorption element>
The method for producing the adsorption element of the present invention is not particularly limited as long as the element to be produced satisfies the above configuration, but the aqueous dispersion of the present invention is applied to a carrier or the carrier is immersed in the aqueous dispersion. It is manufactured by drying after attaching by a technique such as the above. The drying conditions are not particularly limited, but the drying temperature is usually 50 to 140 ° C, preferably 90 to 140 ° C, and the drying time is usually 5 minutes to 100 hours, preferably 10 minutes to 120 minutes. is there. Although the atmosphere is not particularly limited, it is usually in the air, dry air, inert atmosphere, or reduced pressure. When the reaction is performed under atmospheric pressure, it is preferable to circulate or circulate the gas. It is preferable that the drying conditions are within the above range because the organic matter does not burn and the drying efficiency is improved. If the drying temperature is too low or the drying time is too short, the adhesive strength tends to decrease. Conversely, if the drying temperature is too high or the drying time is too long, the adsorbent is coated with an organic binder and the adsorption speed decreases. Tend.

  The adsorption element of the present invention can be used as an adsorption element for an adsorption heat pump, a desiccant air conditioner or the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
<Aluminophosphates used in Examples and Comparative Examples>
ALPO-A:
According to JP 2004-136269 A, Example 1, iron aluminophosphate (FAPO) was synthesized.

To a mixture of 38.4 g of water and 17.6 g of 85% phosphoric acid, 9.5 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added and stirred. This was stirred for 3 hours, and an aqueous solution prepared by dissolving 6.78 g of ferrous sulfate heptahydrate in 36.6 g of water was added thereto, and further 10.8 g of triethylamine was mixed and stirred for 3 hours. The starting reactant was obtained.
0.32FeSO ₄ : 0.92Al ₂ O ₃ : P ₂ O ₅ : 1.4 Triethylamine: 60H ₂ O

The above starting reaction product was charged into a 200 cc stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and allowed to react at 200 ° C. for 12 hours in a stationary state. After the reaction, the reaction mixture was cooled, the supernatant was removed by decantation, and the precipitate was collected. The precipitate was washed three times with water, filtered, dried at 120 ° C., and then pulverized to an average particle size of 3 μm by a dry method. A 3 g sample containing the template thus obtained was collected, placed in a vertical quartz fired tube, heated to 550 ° C. at 1 ° C./min in an air stream of 200 ml / min, and kept at 550 ° C. for 6 hours. Firing was performed. When the XRD of the crystalline iron aluminophosphate thus obtained was measured, it was a so-called FAPO-5 of AFI type. In addition, when elemental analysis was conducted by ICP analysis after heating and dissolving in an aqueous hydrochloric acid solution, the composition ratio (molar ratio) of each component to the total of aluminum, phosphorus and iron in the skeleton structure was 4.0% for iron and aluminum for It was 46.7% and phosphorus was 49.3%.
ALPO-B:
Silicoaluminophosphate (SAPO) was synthesized according to Japanese Unexamined Patent Publication No. 2003-183020 and Example 2.

87.1 g of 85% phosphoric acid was added to 180 g of water, and 57.2 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. This was designated as liquid A. Separately from the liquid A, a liquid in which 5.04 g of fumed silica (Aerosil 200), 36.6 g of morpholine, and 240 g of water were mixed was prepared. This was slowly added to solution A. Further, 47.0 g of triethylamine was added and stirred for 3 hours to obtain an aqueous gel having the following composition.
0.2SiO ₂ : Al ₂ O ₃ : 0.9P ₂ O ₅ : 1 morpholine: 1.1 triethylamine: 60H ₂ O
The mixture thus obtained was charged into a 1 l stainless steel autoclave containing a fluororesin inner cylinder and reacted at 190 ° C. for 60 hours while stirring at 100 rpm. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. When the XRD of the zeolite thus obtained was measured, it was a CHA structure. Thereafter, the template was removed by baking in an air stream in the same manner as in Example 1 except that the powder was pulverized in a dry manner to an average particle size of 7 μm and the baking temperature was 560 ° C. Zeolite was heated and dissolved in an aqueous hydrochloric acid solution, and elemental analysis was performed by ICP analysis. As a result, the composition ratio (molar ratio) of each component with respect to the total of silicon, aluminum, and phosphorus was 7.9% for silicon, 48.7% for aluminum, and 43.3% for phosphorus.

<Organic binder emulsion used in Examples and Comparative Examples>
Organic binder emulsion type: Trade name (surfactant ionicity, emulsion resin type, solid content) is as follows. Rikabond is manufactured by Chuo Rika Kogyo Co., Ltd.
Organic Emulsion A: Trade name Rikabond ES-232 (anion, acrylic / styrene copolymer, solid content 51 wt%)
Organic emulsion B: trade name Rikabond ET-19 (anion, silica-modified acrylic copolymer, solid content 38 wt%)
Organic Emulsion C: Trade name Rikabond ES-106 (anion, silicone acrylic copolymer, solid content 51 wt%)
Organic emulsion D: Trade name Rikabond CR-100A (anion, modified vinyl copolymer, solid content 44%)
Organic Emulsion E: Trade name Rikabond FK-480N (anion, acrylic / styrene copolymer, solid content 40 wt%)
Organic Emulsion F: Trade name Rikabond BA-53 (anion, urethane-modified ethylene / vinyl acetate copolymer, solid content 57 wt%)
Organic Emulsion G: Trade name Rikabond BA-58 (anion, urethane-modified ethylene / vinyl acetate copolymer, solid content 57 wt%)
Organic Emulsion H: Trade name Rikabond BE-814 (anion, ethylene vinyl acetate copolymer, solid content 55 wt%)
Organic Emulsion I: Trade Name Rikabond BE-800HQ (Nonion, Ethylene Vinyl Acetate Copolymer, Solid Content 55wt%)
Organic emulsion J: Trade name Rikabond BC-331 (nonion, vinyl acetate / acrylic copolymer, solid content 47 wt%)
Organic Emulsion K: Trade Name Rikabond AW-71L (Weak Cation, Vinyl Acetate / Acrylic Copolymer, Solid Content 46t%)
Organic Emulsion L: Trade Name Rikabond BA-321L (Nonion, urethane-modified ethylene / vinyl acetate copolymer, solid content 59%)

Example 1
An adsorption element carrying ALPO-A as an aluminophosphate on an aluminum plate was produced as follows.
To 77.7 parts of water, 9.8 parts of organic emulsion A: trade name Rikabond ES-232 (manufactured by Chuo Rika Kogyo Co., Ltd., anionic, acrylic / styrene copolymer solid content 51 wt%) was added and stirred. Subsequently, 50 parts of ALPO-A having an average particle diameter of 3 microns was added. By stirring, an aluminophosphate aqueous dispersion (slurry) was obtained. The sum of ALPO and the solid content of the organic binder is 40% by weight. The solid content weight ratio between ALPO and the organic binder is 10: 1. The slurry was allowed to stand for 15 hours, but the slurry was kept uniform without settling. Next, the slurry was applied on an aluminum plate, moisture was removed at 40 ° C., and then a drying process was performed at 120 ° C. for 30 minutes to obtain an adsorbing element. The loading amount of ALPO-A is 8 mg / cm ² .

The amount of adsorption was measured as follows.
Adsorption process: Water vapor of 47.4 kPa and an adsorbing element were brought into contact with each other at 90 ° C. for 40 seconds to adsorb the water vapor.
Desorption process: Water vapor pressure was 0.9 kPa at 90 ° C. for 40 seconds, and water vapor was desorbed from the adsorption element.

When the cycle of the adsorption step-desorption step was repeated 100 times, the average water vapor adsorption amount (g) per 1 g of ALPOs per one time was defined as the adsorption amount.
Even after repeated adsorption and desorption, ALPO peeling from the plate was not observed, and the adhesion durability was good. The results of slurry stability and adsorption amount are shown in Table 1.

Examples 2-3
An aluminophosphate aqueous dispersion was obtained in the same manner as in Example 1 except that organic emulsions B, C and D were used in place of organic emulsion A as the organic binder. The solid content concentration is the same as in Example 1. The results are shown in Table 1.
Examples 4-5
Aluminophosphate aqueous dispersion as in Example 1 except that organic emulsion E, F, G instead of organic emulsion A as the organic binder and ALPO-B instead of ALPO-A as the aluminophosphate were used. A liquid was obtained. The solid content concentration is the same as in Example 1. The results are shown in Table 1.

Comparative Example 1
An adsorbing element was produced according to Example 1 except that no organic binder was used. The results are shown in Table 1. Most ALPO peeled off the aluminum plate.
Comparative Example 2
An aluminophosphate aqueous dispersion was obtained in the same manner as in Example 1 except that organic emulsion I was used instead of organic emulsion A as the organic binder. The solid content concentration is the same as in Example 1. The results are shown in Table 1. A slurry using a known vinyl acetate emulsion for the ALPO system has a high sedimentation property and poor handling, and has a low adsorption amount and adhesion durability.

Comparative Examples 3-5
In the same manner as in Example 1, except for using organic emulsions J, K, and L instead of organic emulsion A as organic binder and ALPO-B instead of ALPO-A as aluminophosphates, an aluminophosphate aqueous dispersion A liquid was obtained. The solid content concentration is the same as in Example 1. The results are shown in Table 1.
Comparative Example 6
An adsorbing element was produced according to Example 4 except that no organic binder was used. The results are shown in Table 1. Most ALPO peeled off the aluminum plate.

* 1 Slurry stability was determined by visually observing the degree of sedimentation 15 hours after preparing an aqueous dispersion. ○: No settling, x: Settling.
* 2 The adhesion durability was determined by observing the state of application on the aluminum plate after measuring the amount of adsorption. ○: no peeling, x: peeling

Discussion of Results: When Example 6 (organic emulsion F), Example 7 (organic emulsion G) and Comparative Example 5 (organic emulsion L) are compared, both of these are surfactants and urethane-modified ethylene / vinyl acetate copolymer. Although it is an organic emulsion containing a coalescence, according to IR measurement results, it is confirmed that the spectral patterns of F, G and L are the same, and the basic structure of the copolymer is the same. know. Therefore, it was verified that the difference in the effects of slurry stability and adhesion durability originated from the difference in the ionic species of the surfactant (anion or other).

Claims (9)

A method for producing an aluminophosphate-supporting adsorbing element comprising a step of attaching an aqueous dispersion to a carrier and drying the carrier,
The aqueous dispersion contains at least aluminophosphates, (meth) acrylic resin, (meth) acrylic / styrene copolymer resin, ethylene / vinyl acetate copolymer resin, silica-modified acrylic copolymer resin, silicone acrylic copolymer resin, and One or two or more organic binders selected from urethane-modified ethylene / vinyl acetate copolymer resins are dispersed in water and contain at least one kind of anionic surfactant. Yes,
The aluminophosphate-carrying adsorbing element is an aluminophosphate-carrying adsorbing element used in at least one of a heat pump, a cold storage heat system, and a humidity control air conditioner using adsorption / desorption of water to and from an adsorbent. A method for producing an aluminophosphate-supporting adsorbing element.   The alumino according to claim 1, wherein the organic binder comprises one or more selected from a silica-modified acrylic copolymer resin, a silicone acrylic copolymer resin, and a urethane-modified ethylene / vinyl acetate copolymer resin. A method for producing a phosphate-supporting adsorbing element.   3. The method for producing an aluminophosphate-supporting adsorbing element according to claim 1, wherein the organic binder is an emulsion.   The method for producing an aluminophosphates-supporting adsorbing element according to any one of claims 1 to 3, wherein the carrier is metal or ceramic paper. The aluminophosphate has a framework density (FD) of 14 T / nm ³ or more and 20 T / nm ³ or less (where T / nm ³ is a T atom existing per unit volume nm ³ (per 1 nm ^{3 of} zeolite). 5. The method for producing an aluminophosphates-supported adsorbing element according to claim 1, wherein the number of elements constituting a skeleton other than oxygen).   6. The method for producing an aluminophosphate-carrying adsorbing element according to any one of claims 1 to 5, wherein the structure of the aluminophosphate is AFI or CHA.   The method for producing an aluminophosphate-supporting adsorbing element according to claim 1 or 6, wherein the drying temperature is from 50C to 140C.   The method for producing an aluminophosphate-supporting adsorbing element according to any one of claims 1 to 7, wherein the aluminophosphate is contained in an amount of 10 to 60% by weight.   An aluminophosphates-supporting adsorbing element manufactured by the method for manufacturing an aluminophosphates-supporting adsorbing element according to any one of claims 1 to 8.