JP2016093795A - Modified y-type zeolite dehumidification agent - Google Patents
Modified y-type zeolite dehumidification agent Download PDFInfo
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000010457 zeolite Substances 0.000 title claims abstract description 71
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- 238000007791 dehumidification Methods 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004438 BET method Methods 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 238000005342 ion exchange Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000002274 desiccant Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 description 17
- 239000013078 crystal Substances 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005341 cation exchange Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000003795 desorption Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- -1 aluminum sulfate (modified zeolite Chemical class 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003578 releasing effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000005956 Cosmos caudatus Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 241000705939 Shortia uniflora Species 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Classifications
-
- 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
Abstract
Description
本発明は、Ｙ型ゼオライトの変性物からなる除湿剤に関するものである。 The present invention relates to a dehumidifying agent comprising a modified product of Y-type zeolite.
従来、半導体などの製造装置が収容された各種の工場内や一般家庭では、空気中の水分を一定量に保つために除湿剤が使用されている。このような除湿剤としてはシリカゲルや各種のゼオライトが知られている。 Conventionally, a dehumidifying agent has been used in various factories and general households in which manufacturing apparatuses such as semiconductors are accommodated in order to keep moisture in the air at a constant amount. As such a dehumidifying agent, silica gel and various zeolites are known.
特にゼオライトは、シリカゲルに比して吸湿性に優れており、工業的な用途に広く使用されている。例えば、特許文献１には複数種のゼオライト粒子が分散されている除湿層を備えた除湿ロータが開示されている。
また、特許文献２にはゼオライトを酸処理して非晶質化した変性アルミノケイ酸を乾燥剤として用いることが提案されている。
In particular, zeolite is more hygroscopic than silica gel and is widely used in industrial applications. For example, Patent Document 1 discloses a dehumidification rotor including a dehumidification layer in which a plurality of types of zeolite particles are dispersed.
Patent Document 2 proposes to use a modified aluminosilicic acid that has been made amorphous by acid treatment of zeolite as a desiccant.
しかしながら、特許文献１に開示されているように、ゼオライトをそのまま除湿剤として用いた場合、吸湿後のゼオライトから水分を放出せしめ、再び水分の吸着に再利用するためには、約５００℃程度の高温に加熱することが必要であり、このため一般家庭などでの使用が大きく制限されていた。即ち、再生のための加熱時に火災等を引き起こし易いからである。 However, as disclosed in Patent Document 1, when zeolite is used as a dehumidifying agent as it is, in order to release moisture from the moisture-absorbed zeolite and reuse it again for moisture adsorption, it is about 500 ° C. Heating to a high temperature is necessary, and for this reason, use in general homes has been greatly restricted. That is, it is easy to cause a fire or the like during heating for regeneration.
一方、特許文献２で提案されている変性アルミノケイ酸はゼオライトに比して吸着水分を容易に放出することができるという利点を有しているが、吸湿性能が大きく低下してしまうという問題があり、このため、除湿剤としての使用が実質上困難である。このような処理により得られる、通称ＵＳＹ（Ｕｌｔｒａ Ｓｔａｂｌｅ Ｙ）の製品として、ＣＯＳＭＯ社（韓国）の１０Ｍなどが市販されている。また、一般的にＵＳＹは石油化学系製品用の触媒であるので、比較的高価になる当該のような作業でも工業的に生産する価値が高いが、除湿剤はより安価が求められるため実質的に使用が困難といえる。 On the other hand, the modified aluminosilicic acid proposed in Patent Document 2 has the advantage that adsorbed moisture can be easily released compared to zeolite, but there is a problem that the hygroscopic performance is greatly reduced. For this reason, the use as a dehumidifying agent is substantially difficult. As a product of the so-called USY (Ultra Stable Y) obtained by such treatment, 10M of COSMO (Korea) is commercially available. Further, since USY is generally a catalyst for petrochemical products, it is highly industrially produced even in such operations that are relatively expensive. However, dehumidifiers are substantially less expensive because they are required to be cheaper. It is difficult to use.
更に、特許文献３には、ＦＡＵ型ゼオライトのアルミニウム硫酸塩処理物（ゼオライト変性物）からなる除湿剤が本出願人により提案されている。かかる除湿剤は、水分の吸着性に優れているばかりか、吸着水分の放出を低温で行うことができるという利点を有している。
しかしながら、特許文献３のゼオライト変性物からなる除湿剤においても、吸着水分の低温放出性については更なる向上が求められている。
Further, Patent Document 3 proposes a dehumidifying agent composed of a FAU-type zeolite treated with aluminum sulfate (modified zeolite). Such a dehumidifying agent is not only excellent in moisture adsorptivity, but also has an advantage that adsorption moisture can be released at a low temperature.
However, even in the dehumidifying agent made of the zeolite modified product of Patent Document 3, further improvement is required for the low-temperature release of adsorbed moisture.
従って、本発明の目的は、水分の吸着性に優れ、更に低温での吸着水分の放出性が顕著に改善された除湿剤を提供することにある。 Accordingly, an object of the present invention is to provide a dehumidifying agent that is excellent in moisture adsorbability and has a remarkably improved ability to release adsorbed moisture at low temperatures.
本発明者等は、ゼオライトの吸湿性能について多くの実験を行った結果、Ｙ型ゼオライトの結晶構造を適度に崩壊させることにより、Ｙ型ゼオライトの優れた水分吸着性を損なうことなく、低温での吸着水分の放出性が改善されるという知見を見出し、本発明を完成するに至った。 As a result of conducting many experiments on the hygroscopic performance of the zeolite, the present inventors have appropriately destroyed the crystal structure of the Y-type zeolite, so that the excellent water adsorbability of the Y-type zeolite is not impaired. The inventor has found that the release of adsorbed moisture is improved and has completed the present invention.
本発明によれば、ＳｉＯ２／Ａｌ２Ｏ３（モル比）が４．０より大で且つ５．５以下、Ｎａ／Ａｌモル比が０．２８〜０．７０、結晶度が２０〜９０％、及び水蒸気ＢＥＴ法で測定した親水性比表面積が１０００ｍ２／ｇ以上、水蒸気吸着等温線のＰ／Ｐ０＝０．９以上から求められる全細孔容積が０．３０〜０．４０ｃｍ３／ｇであるＹ型ゼオライトの変性物からなることを特徴とする除湿剤が提供される。 According to the present invention, SiO 2 / Al 2 O 3 (molar ratio) is larger than 4.0 and 5.5 or less, Na / Al molar ratio is 0.28 to 0.70, and crystallinity is 20 to 90. %, And the total pore volume determined from a water vapor adsorption isotherm of not less than 1000 m 2 / g and a water vapor adsorption isotherm of P / P 0 = 0.9 or more is 0.30 to 0.40 cm 3. A dehumidifier comprising a modified product of Y-type zeolite of / g
本発明の除湿剤は、変性に供されるＹ型ゼオライトと同等の全細孔容積を有しており、水蒸気等温線のＰ／Ｐ０＝０．９以上から求められる全細孔容積は０．３０〜０．４０ｃｍ３／ｇであることが好ましい。 The dehumidifying agent of the present invention has a total pore volume equivalent to that of the Y-type zeolite subjected to modification, and the total pore volume obtained from P / P 0 = 0.9 or more of the water vapor isotherm is 0. It is preferable that it is 30-0.40 cm < 3 > / g.
さらに、本発明の除湿剤を構成するＹ型ゼオライト変性物は、Ｙ型ゼオライトをアンモニウムイオン交換した後に焼成することにより得られる。 Furthermore, the modified Y-type zeolite constituting the dehumidifying agent of the present invention can be obtained by calcining the Y-type zeolite after ammonium ion exchange.
また、本発明の除湿剤を担体に担持され除湿用部材が提供され、特に担体は、ハニカム構造であることが好ましい。 In addition, a dehumidifying member is provided by supporting the dehumidifying agent of the present invention on a carrier, and the carrier preferably has a honeycomb structure.
さらに、本発明の除湿剤を使用したヒートポンプやデシカント除湿機が提供される。 Furthermore, the heat pump and desiccant dehumidifier using the dehumidifier of this invention are provided.
本発明の除湿剤は、従来公知のＹ型ゼオライトと同程度の吸湿性能を有しているばかりか、吸着水分の放出性にも優れている。例えば、後述する実施例１に示されているように９０℃×９０分での吸着水分の放出量が１８％程度と極めて多い。即ち、この除湿剤は低温で多量の吸着水分を放出することができるため、吸着水分の放出のために高温に加熱する必要がなく、容易に再生して再利用することができ、特に、一般家庭での使用には最適である。 The dehumidifying agent of the present invention not only has a hygroscopic performance comparable to that of conventionally known Y-type zeolite, but is also excellent in the ability to release adsorbed water. For example, as shown in Example 1 described later, the amount of adsorbed moisture released at 90 ° C. × 90 minutes is as high as about 18%. That is, since this dehumidifier can release a large amount of adsorbed water at low temperature, it does not need to be heated to a high temperature for releasing adsorbed water, and can be easily regenerated and reused. Ideal for home use.
低温での吸着水分放出性が優れているという理由については正確に解明されていないが、本発明者等は、Ｙ型ゼオライトの結晶構造が適度に崩壊されており、水分放出に寄与する細孔部分に変化が持たされているためではないかと考えている。 Although the reason why the adsorptive moisture releasing property at low temperature is excellent has not been clarified accurately, the present inventors have reported that the crystal structure of the Y-type zeolite is appropriately collapsed and pores contributing to moisture release. I think that it is because the part has a change.
即ち、本発明において、除湿剤として用いるＹ型ゼオライトの変性物は、ＳｉＯ２／Ａｌ２Ｏ３（モル比）が４．０より大で且つ５．５以下である。これよりもモル比が低い場合、後述する焼成工程において性能が低下し、望ましい低温再生を発揮することが出来ない。
また、この除湿剤はＮａ／Ａｌモル比が０．２８〜０．７０（特に０．３０〜０．５０）の範囲にある。このことは、この変性物中のＮａがイオン交換されて一部除去されていることを示している。
また、上記Ｙ型ゼオライトの変性物は、結晶度が２０〜９０％（特に４０〜８０％）の範囲にある。このことは、Ｙ型ゼオライトに特有のＸ線回折ピーク強度が消失しない程度に減少し、結晶構造が適度に崩壊し変性されていることを意味する。ところで、このような変性は水溶液中でアンモニウムイオン交換された後、比較的高温での焼成でなされる。即ち、Ｙ型ゼオライトは一般的に耐熱性が高く、イオン交換を行わない場合は８００℃の温度で焼成してもほとんど変性が見られない。また、アンモニウムイオン交換した場合には、５００℃程度の焼成において、結晶構造を破壊しないまま、アンモニウムイオンが分解しアンモニアを放出する（一般的に、この状態を水素Ｙ型ゼオライトと呼ぶ）。
このため、Ｙ型ゼオライトを焼成により変性せしめるためには、前段階で水溶液中でのアンモニウムイオン交換による、一部Ｎａイオンの除去が必要であり、かつ６００〜８００℃程度の高温の焼成が必要なわけである。なお公知のように９００℃程度の焼成を行うと、Ｙ型ゼオライトは相転移を起こし、吸放湿性をほとんど持たない非晶質になってしまう。
こうして、イオン交換と焼成の工程を経たＹ型ゼオライトは、結晶構造の適度な破壊がもたらされることにより、そのＹ型ゼオライトの優れた吸湿性能が維持したまま低温で吸湿した水分を放出できる能力が向上するものと思われる。
Ｙ型ゼオライトの吸湿容量が低下していない証明として、本発明のＹ型ゼオライトの変性物は、水蒸気ＢＥＴ法で測定した親水性比表面積が１０００ｍ２／ｇ以上（特に１０５０〜１３００ｍ２／ｇ）の範囲にあり、かつ水蒸気吸着等温線のＰ／Ｐ０＝０．９以上から求められる全細孔容積が０．３０〜０．４０ｃｍ３／ｇの範囲にある。この親水性比表面積は、窒素吸着の代わりに水蒸気吸着を利用して測定したものであり、この方法により測定された比表面積は、親水性や水分吸着性を示す。即ち、この比表面積が上記範囲内にあることは、このＹ型ゼオライト変性物が、未変性のＹ型ゼオライトと同等レベルの水分吸着性を有していることを示しており、Ｙ型ゼオライトの吸着性能が低下していないことを裏付けられている。
このように、除湿剤として用いる本発明のＹ型ゼオライト変性物は、Ｙ型ゼオライトの細孔構造をある程度維持したまま、水分放出に寄与する細孔部分に変化が持たされていると考えられ、この結果、水分吸着性に優れているばかりか、低温での水分放出性も改善されているわけである。
That is, in the present invention, the modified product of Y-type zeolite used as a dehumidifying agent has a SiO 2 / Al 2 O 3 (molar ratio) larger than 4.0 and not larger than 5.5. When the molar ratio is lower than this, the performance is lowered in the firing step described later, and the desired low-temperature regeneration cannot be exhibited.
The dehumidifying agent has a Na / Al molar ratio in the range of 0.28 to 0.70 (particularly 0.30 to 0.50). This indicates that Na in the denatured product is partially removed by ion exchange.
The modified product of the Y-type zeolite has a crystallinity in the range of 20 to 90% (particularly 40 to 80%). This means that the X-ray diffraction peak intensity peculiar to the Y-type zeolite is reduced to such an extent that it does not disappear, and the crystal structure is appropriately collapsed and modified. By the way, such modification is performed by baking at a relatively high temperature after ammonium ion exchange in an aqueous solution. That is, Y-type zeolite generally has high heat resistance, and when no ion exchange is performed, almost no modification is observed even when calcined at a temperature of 800 ° C. In addition, when ammonium ion exchange is performed, in baking at about 500 ° C., ammonium ions are decomposed and ammonia is released without destroying the crystal structure (this state is generally referred to as hydrogen Y-type zeolite).
For this reason, in order to modify the Y-type zeolite by calcination, it is necessary to remove some Na ions by ammonium ion exchange in an aqueous solution in the previous stage, and calcination at a high temperature of about 600 to 800 ° C. is necessary. That is why. As known in the art, when firing at about 900 ° C., the Y-type zeolite undergoes a phase transition and becomes amorphous with almost no moisture absorption / release properties.
Thus, the Y-type zeolite that has undergone the ion exchange and calcination steps has the ability to release moisture absorbed at low temperatures while maintaining the excellent hygroscopic performance of the Y-type zeolite by bringing about an appropriate destruction of the crystal structure. It seems to improve.
As a proof that the moisture absorption capacity of the Y-type zeolite has not decreased, the modified product of the Y-type zeolite of the present invention has a hydrophilic specific surface area measured by the water vapor BET method of 1000 m 2 / g or more (particularly, 1050 to 1300 m 2 / g). And the total pore volume determined from P / P 0 = 0.9 or more of the water vapor adsorption isotherm is in the range of 0.30 to 0.40 cm 3 / g. This hydrophilic specific surface area is measured by using water vapor adsorption instead of nitrogen adsorption, and the specific surface area measured by this method shows hydrophilicity and moisture adsorption. That is, the fact that this specific surface area is within the above range indicates that this modified Y-type zeolite has a moisture adsorption property equivalent to that of the unmodified Y-type zeolite. It is confirmed that the adsorption performance has not deteriorated.
Thus, it is considered that the modified Y-type zeolite of the present invention used as a dehumidifying agent has a change in the pore portion contributing to moisture release while maintaining the pore structure of the Y-type zeolite to some extent, As a result, not only is water adsorption excellent, but also water release at low temperatures is improved.
＜Ｙ型ゼオライトの変性＞
本発明の除湿剤は、Ｙ型ゼオライトの変性物であるが、この変性物は、Ｙ型ゼオライトを水溶液中でカチオン交換した後、焼成することにより得られる。
<Modification of Y-type zeolite>
The dehumidifying agent of the present invention is a modified product of Y-type zeolite, which can be obtained by calcination after exchanging the Y-type zeolite in an aqueous solution.
Ｙ型ゼオライト；
変性に供されるＹ型ゼオライトとしては、それ自体公知のものの中でも水分吸着性に優れたものが使用される。このようなＹ型ゼオライトは、例えば特許第４５８９０４４号等により所謂Ｎａ−Ｙ型ゼオライトとして公知であるが、その代表的組成等は、以下のとおりである。
ＳｉＯ２／Ａｌ２Ｏ３（モル比）：３．０〜５．５
Ｎａ２Ｏ：１０．０〜１６．０質量％
強熱減量（１０５０℃）：１２．０〜１９．０質量％
親水性比表面積（水蒸気ＢＥＴ法）：１０５０〜１２００ｍ２／ｇ
全細孔容積（水蒸気吸着等温線Ｐ／Ｐ０＝０．９以上）
：０．３０〜０．４０ｃｍ３／ｇ
本発明では、上記のＹ型ゼオライトの中から、ＳｉＯ２／Ａｌ２Ｏ３（モル比）が前述した範囲（４．０より大きく且つ５．０以下）の範囲にあるものを選択し、これを後述するカチオン交換に供する。例えば、酸処理などによってモル比の調整を行った場合には、結晶構造や細孔構造の破壊が生じてしまい、目的とする変性物を得ることができない。
Y-type zeolite;
As the Y-type zeolite subjected to modification, among those known per se, those having excellent water adsorptivity are used. Such a Y-type zeolite is known as a so-called Na-Y-type zeolite by, for example, Japanese Patent No. 4589044, and the typical composition thereof is as follows.
SiO 2 / Al 2 O 3 (molar ratio): 3.0 to 5.5
Na 2 O: from 10.0 to 16.0 wt%
Loss on ignition (1050 ° C.): 12.0 to 19.0% by mass
Hydrophilic specific surface area (water vapor BET method): 1050 to 1200 m 2 / g
Total pore volume (water vapor adsorption isotherm P / P 0 = 0.9 or more)
: 0.30 to 0.40 cm 3 / g
In the present invention, one having the SiO 2 / Al 2 O 3 (molar ratio) in the aforementioned range (greater than 4.0 and less than or equal to 5.0) is selected from the above Y-type zeolites. Is subjected to cation exchange described below. For example, when the molar ratio is adjusted by acid treatment or the like, the crystal structure and the pore structure are destroyed, and the desired modified product cannot be obtained.
カチオン交換；
焼成に先立って行われるカチオン交換は、Ｙ型ゼオライト中のＮａイオンを水溶液中でアンモニウムイオンに交換するものである。即ち、Ｎａ‐Ｙ型ゼオライトは耐熱性に優れているため、これを焼成によって変性するには、焼成温度を著しく高い温度とすることが必要であり、Ｙ型ゼオライトの結晶構造を大きく破壊せずに水分吸着性を維持し得る程度の適度な変性が困難となってしまう。しかるに、Ｎａイオンをアンモニウムイオンに交換しておけば、加熱によってアンモニウムイオンが分解した部分の細孔を後述するようにさらに高温の焼成で容易に変性することが出来るため、Ｙ型ゼオライトの細孔構造を大きく破壊せず、適度に変性することが可能となる。
Cation exchange;
The cation exchange performed prior to calcination is to exchange Na ions in Y-type zeolite with ammonium ions in an aqueous solution. That is, since Na-Y zeolite has excellent heat resistance, in order to modify it by calcination, it is necessary to make the calcination temperature extremely high, and the crystal structure of the Y zeolite is not greatly destroyed. Therefore, it is difficult to moderately modify the water so as to maintain moisture adsorption. However, if Na ions are exchanged for ammonium ions, the pores where ammonium ions are decomposed by heating can be easily modified by firing at a higher temperature as described later. It is possible to modify the structure appropriately without significantly destroying the structure.
このようなカチオン交換は、ＳｉＯ２及びＡｌ２Ｏ３の合計量当りのＮａ２Ｏ含量がＮａ／Ａｌモル比が０．２８〜０．７０、特に０．３０〜０．５０となる程度に行われる。Ｎａイオンが多く残存すると、後述する焼成による適度な変性が困難となってしまう。
また、かかるカチオン交換処理は、塩化アンモニウム等のアンモニウム塩の水溶液を使用し、上述したＹ型ゼオライトと該水溶液とを、室温で撹拌混合すればよいが、６０℃程度に加熱すると反応をより迅速に行うことも可能である。処理時間は、アンモニウム塩の種類や水溶液のアンモニウム塩濃度によっても異なるが、一般に、２〜４０質量％濃度の塩化アンモニウム水溶液を用いた場合で０．５〜２４時間程度である。
Such cation exchange is such that the Na 2 O content per total amount of SiO 2 and Al 2 O 3 is such that the Na / Al molar ratio is 0.28 to 0.70, especially 0.30 to 0.50. Done. If a large amount of Na ions remain, it becomes difficult to moderately modify by firing as will be described later.
In addition, such cation exchange treatment uses an aqueous solution of ammonium salt such as ammonium chloride and the above-described Y-type zeolite and the aqueous solution may be stirred and mixed at room temperature, but the reaction becomes more rapid when heated to about 60 ° C. It is also possible to do this. The treatment time varies depending on the kind of ammonium salt and the ammonium salt concentration of the aqueous solution, but is generally about 0.5 to 24 hours when an aqueous ammonium chloride solution having a concentration of 2 to 40% by mass is used.
焼成；
上記のようにしてカチオン交換処理が行われた後は、ろ過及び水洗を行い、未反応の塩化アンモニウムや生成したＮａ塩を除去した後、焼成を行い、Ｙ型ゼオライトの適度な変性を行う。
Firing;
After the cation exchange treatment is performed as described above, filtration and washing are performed to remove unreacted ammonium chloride and the formed Na salt, followed by calcination to moderately modify the Y-type zeolite.
焼成は、Ｙ型ゼオライトの結晶構造を大きく破壊せずに、細孔構造を適度に変える程度水分吸着性を維持し得る程度に行われるものであり、具体的には、結晶度が２０〜９０％、特に４０〜８０％に低下する程度に焼成が行われる。
なお、本発明において結晶度とは、Ｘ線回折において、標準物質（触媒学会のＪＲＣ−Ｚ−Ｙ４．８）の特定の５つの面指数のピーク強度の和を１００％とし、このピーク強度の和に対する変性ゼオライトのピーク強度の和の相対比である（詳細は、後述の実施例を参照）。
The calcination is performed to such an extent that the water adsorbability can be maintained to such an extent that the pore structure is appropriately changed without greatly destroying the crystal structure of the Y-type zeolite. Specifically, the degree of crystallinity is 20 to 90. %, Especially to the extent that it falls to 40-80%.
In the present invention, the degree of crystallinity means that in X-ray diffraction, the sum of peak intensities of specific five surface indices of a standard substance (JRC-Z-Y4.8 of the Catalytic Society) is defined as 100%, It is the relative ratio of the sum of the peak intensities of the modified zeolite to the sum (for details, see the examples below).
即ち、結晶度が上記範囲よりも大きいと、変性が十分に行われておらず、従ってＹ型ゼオライトの構造がほとんど変化しておらず、このため、低温での水分放出性を向上させるという本発明の目的を達成することができない。また、結晶度が上記範囲よりも小さくなるまで焼成が行われると、Ｙ型ゼオライトの結晶構造が大きく破壊され、非晶質化が進行しすぎてしまい、この結果、水分に対する吸着性及び放出性の何れも大きく損なわれてしまうこととなる。 That is, if the degree of crystallinity is larger than the above range, the modification is not sufficiently performed, and therefore the structure of the Y-type zeolite is hardly changed, so that the water release property at low temperature is improved. The object of the invention cannot be achieved. In addition, if the calcination is performed until the crystallinity is smaller than the above range, the crystal structure of the Y-type zeolite is greatly destroyed, and the amorphization progresses too much. Any of these will be greatly impaired.
上記のような結晶度の範囲にするための適度な焼成は、一般に、６００〜８００℃、特に６５０〜７５０℃程度の焼成温度で行われ、それ自体公知の焼成炉を用いて行われる。焼成時間は、用いる焼成炉の構造や焼成温度によっても異なり、一概に規定することはできないが、一般的には３〜１２時間程度である。例えば、前述したＹ型ゼオライトをカチオン交換せずにそのまま焼成に供した場合、上記のような温度範囲での焼成では結晶度はほとんど低下せず、さらに高温にしなければ変性することができない。 The appropriate firing for achieving the above crystallinity range is generally performed at a firing temperature of about 600 to 800 ° C., particularly about 650 to 750 ° C., and is performed using a known firing furnace. The firing time varies depending on the structure of the firing furnace used and the firing temperature, and cannot generally be defined, but is generally about 3 to 12 hours. For example, when the above-described Y-type zeolite is directly subjected to calcination without cation exchange, the degree of crystallinity is hardly lowered by calcination in the above temperature range and cannot be modified unless the temperature is further increased.
以上のようにして適度な焼成が行われて得られるＹ型ゼオライトの変性物は、適宜、粒度調整を行うことにより、本発明の除湿剤として使用される。 The modified product of Y-type zeolite obtained by performing appropriate firing as described above is used as a dehumidifying agent of the present invention by appropriately adjusting the particle size.
＜除湿剤＞
上記のような適度な焼成によって得られたＹ型ゼオライトの変性物は、ＳｉＯ２／Ａｌ２Ｏ３（モル比）が４．０〜５．５の範囲にあり、出発原料として用いたＹ型ゼオライトと実質的に同じである。即ち、この変性物は、Ｙ型ゼオライトに特有の結晶構造は大きく失われてはおらず、その結晶度は、焼成の項でも説明したように、２０〜９０％、特に４０〜８０％の範囲にある。
<Dehumidifier>
The modified product of Y-type zeolite obtained by appropriate firing as described above has a SiO 2 / Al 2 O 3 (molar ratio) in the range of 4.0 to 5.5, and is Y-type used as a starting material. It is substantially the same as zeolite. That is, this modified product has not lost much crystal structure peculiar to Y-type zeolite, and its crystallinity is in the range of 20 to 90%, particularly 40 to 80%, as explained in the section of calcination. is there.
このように、原料のＹ型ゼオライトの構造が大きく変化していないことから、この変性物の水蒸気ＢＥＴ法で測定した親水性比表面積が１０００ｍ２／ｇ以上、特に１０５０〜１３００ｍ２／ｇの範囲にあり、かつ水蒸気吸着等温線のＰ／Ｐ０＝０．９以上から求められる全細孔容積が０．３０〜０．４０ｃｍ３／ｇにある。即ちこの変性物の親水性比表面積は、変性前のＹ型ゼオライトとほとんど同じであり、このことから、この変性物は、変性前のＹ型ゼオライトと同等レベルの水分吸着性を有していることが判る。 Thus, since the structure of the Y-type zeolite starting material has not changed significantly, hydrophilic specific surface area measured by the water vapor BET method of the modified products 1000 m 2 / g or more, particularly from 1050~1300m 2 / g And the total pore volume determined from P / P 0 = 0.9 or more of the water vapor adsorption isotherm is 0.30 to 0.40 cm 3 / g. That is, the hydrophilic specific surface area of this modified product is almost the same as that of the Y-type zeolite before modification, and therefore, this modified product has the same level of moisture adsorption as the Y-type zeolite before modification. I understand that.
また、このＹ型ゼオライトの変性物は、ナトリウムＹ型ゼオライトのカチオン交換を介して得られたものであることから、Ｎａ／Ａｌモル比が０．２８〜０．７０の範囲にある。 In addition, since the modified product of Y-type zeolite is obtained through cation exchange of sodium Y-type zeolite, the Na / Al molar ratio is in the range of 0.28 to 0.70.
本発明において、上述したＹ型ゼオライト変性物は、一般に、レーザ回折散乱法により測定した中位径（Ｄ５０）が０．５〜３．５μｍの範囲となるように粒度調整されていることが除湿剤として用いる際の成形性や作業性等の点で好ましい。
かかるＹ型ゼオライト変性物からなる除湿剤は、粒状物の使用に供することもできるし、樹脂バインダと混合し、所定の形状に成形して使用に供することもできる。
かかる除湿剤は、水分に対して優れた吸着性を示すばかりか、低温での吸着水分の放出性が向上しており、低温領域での加熱により吸着水分を放出せしめて再生することができる。従って、一般家庭の空調用として好適使用することができ、例えば、特許文献１の除湿ロータなどに設けられている除湿層中に配合して使用することが可能である。或いは、除湿剤を担体に担持して除湿用部材として用いる事もでき、担体はハニカム構造を有していることが好適である。
また、この除湿剤は、水分の吸着及び脱着の何れもが容易に行われるため、空気を利用した蓄熱システム（例えばヒートポンプ）に用いる吸着剤などの用途にも使用することができる。
さらに、この除湿剤は、湿度調節用シートまたは湿度調節壁材として使用することも可能である。
In the present invention, the modified Y-type zeolite described above is generally adjusted in particle size so that the median diameter (D 50 ) measured by a laser diffraction scattering method is in the range of 0.5 to 3.5 μm. It is preferable in terms of formability and workability when used as a dehumidifying agent.
Such a dehumidifying agent made of a modified Y-type zeolite can be used for a granular material, or can be mixed with a resin binder and molded into a predetermined shape for use.
Such a dehumidifying agent not only exhibits excellent adsorptivity to moisture, but also improves the ability to release adsorbed moisture at a low temperature, and can be regenerated by releasing adsorbed moisture by heating in a low temperature region. Therefore, it can be suitably used for air conditioning in general households, and for example, it can be used in a dehumidifying layer provided in the dehumidifying rotor of Patent Document 1. Alternatively, a dehumidifying agent can be carried on a carrier and used as a dehumidifying member, and the carrier preferably has a honeycomb structure.
In addition, the dehumidifying agent can be used for adsorbents used in a heat storage system (for example, a heat pump) using air because both moisture adsorption and desorption are easily performed.
Further, the dehumidifying agent can be used as a humidity adjusting sheet or a humidity adjusting wall material.
本発明の優れた効果を、次の実施例で説明する。
なお、実施例における各種試験は下記の方法で行った。
The superior effect of the present invention is illustrated in the following examples.
In addition, the various tests in an Example were done with the following method.
（１）化学組成；
強熱減量（Ig-Loss）は、試料を１０５０℃で一時間焼成後放冷し減量から定量した。また、他の元素分析については、（株）リガク製Ｒｉｇａｋｕ ＲＩＸ２１００を用い、ターゲットはＲｈ、分析線はＫαで、その他は以下の条件で測定を行った。
なお、試料は１１０℃で３時間乾燥した物を基準とする。
(1) chemical composition;
The ignition loss (Ig-Loss) was quantified from the weight loss after firing the sample at 1050 ° C. for 1 hour and allowing to cool. For other elemental analysis, Rigaku RIX2100 manufactured by Rigaku Corporation was used, the target was Rh, the analytical line was Kα, and the others were measured under the following conditions.
In addition, a sample is based on the thing dried at 110 degreeC for 3 hours.
（２）結晶度
相対湿度９０％に調湿済みのデシケーター中に乾燥試料を入れ、室温下で４８時間以上静置し、水分を飽和量吸着させる。取出した試料を、Ｘ線回折測定する。同一条件で測定した標準物質（触媒学会のＪＲＣ−Ｚ−Ｙ４．８）のＸＲＤにおいて、ＩＣＤＤ３９−１３８０で（３３１）、（４４０）、（５３３）、（６４２）、（５５５）と示される５つの面指数のピーク強度の和を１００％とした時の、測定試料の同一面指数ピーク強度の和の相対比を結晶度とする。
なお、Ｘ線回折測定はリガク社製のｕｌｔｉｍａ４を用いて、Ｃｕ−Ｋαにて下記の条件で測定を行った。
ターゲット：Ｃｕ
フィルター：湾曲結晶グラファイトモノクロメーター
検出器：ＳＣ
電圧：４０ｋＶ
電流：４０ｍＡ
ステップサイズ：０．０２°
計数時間：０．６sec／step
スリット：ＤＳ２／３° ＲＳ０．３ｍｍ ＳＳ２／３°
(2) Crystallinity A dry sample is placed in a desiccator that has been conditioned at a relative humidity of 90%, and is allowed to stand at room temperature for 48 hours or more to adsorb a saturated amount of moisture. The extracted sample is subjected to X-ray diffraction measurement. In the XRD of a standard substance (JRC-Z-Y4.8 of the Catalytic Society) measured under the same conditions, ICDD39-1380 shows (331), (440), (533), (642), (555). The crystallinity is defined as the relative ratio of the sum of the same plane index peak intensities of the measurement sample when the sum of the peak intensity of the two plane indexes is 100%.
In addition, the X-ray-diffraction measurement was performed on the following conditions in Cu-K (alpha) using ultrama4 made from Rigaku Corporation.
Target: Cu
Filter: Curved crystal graphite monochromator Detector: SC
Voltage: 40 kV
Current: 40 mA
Step size: 0.02 °
Counting time: 0.6sec / step
Slit: DS2 / 3 ° RS0.3mm SS2 / 3 °
（３）親水性比表面積
日本ベル社のBelsorp Maxを用いて測定を行った。前処理は、真空条件下で２００℃、３時間の条件で行った。平衡判定時間は３００秒とした。親水性比表面積を測定するに当たり、ＢＥＴ法の適用範囲はＰ/Ｐ０＝０．０１〜０．１とし、解析ソフトBel Masterにより解析した。
(3) Hydrophilic specific surface area It measured using Belsorp Max of Nippon Bell. The pretreatment was performed under vacuum conditions at 200 ° C. for 3 hours. The equilibrium judgment time was 300 seconds. In measuring the hydrophilic specific surface area, the application range of the BET method was set to P / P 0 = 0.01 to 0.1, and analysis was performed with the analysis software Bel Master.
（４）全細孔容積
上記Belsorp Maxの測定の、Ｐ/Ｐ０＝０．９０〜０．９２の範囲における吸着容量から、解析ソフトBel Masterにより全細孔容積を求めた。
(4) Total pore volume From the adsorption capacity in the range of P / P0 = 0.90 to 0.92 in the above measurement of Belsorp Max, the total pore volume was determined by analysis software Bel Master.
（５）吸湿容量の評価
まず、事前に１１０℃で１時間乾燥したシャーレΦ１００ｍｍの質量を測定する（ｗ１）。このシャーレに、約２ｇの除湿剤を測り取り、イオン交換水を１０ｍｌ加えてスラリー化する。このスラリーを、予め１５０℃に温めておいた卓上乾燥機で、２時間前処理乾燥する。乾燥後、シャーレと除湿剤の合計質量（ｗ２）を測定し、硫酸希釈液により、２５℃でＲＨ＝９０％となるように調節したデシケーター内で１６時間かけ飽和吸湿させる。吸湿１６時間後のシャーレと除湿剤の合計質量（ｗ３）を測定し、以下の式により吸着容量（１５０℃乾燥質量基準）を求めた。
吸湿容量[質量％]＝（ｗ３−ｗ２）/（ｗ２−ｗ１）× １００
(5) Evaluation of moisture absorption capacity First, the mass of a petri dish Φ100 mm previously dried at 110 ° C. for 1 hour is measured (w1). About 2 g of dehumidifying agent is measured in this petri dish, and 10 ml of ion exchange water is added to make a slurry. This slurry is pretreated and dried for 2 hours in a desktop dryer preheated to 150 ° C. After drying, the total mass (w2) of the petri dish and the dehumidifying agent is measured, and saturated moisture absorption is performed for 16 hours in a desiccator adjusted to RH = 90% at 25 ° C. with a sulfuric acid diluent. The total mass (w3) of the petri dish and the dehumidifying agent after 16 hours of moisture absorption was measured, and the adsorption capacity (150 ° C. dry mass standard) was determined by the following formula.
Hygroscopic capacity [mass%] = (w3-w2) / (w2-w1) × 100
（６）脱着量の評価
吸湿容量の評価を前処理とする。飽和吸湿したシャーレと除湿剤を、あらかじめ９０℃に温めておいた卓上乾燥機で、９０分間乾燥する。この乾燥したシャーレと除湿剤の合計質量（ｗ４）を測定する。同様に１１０℃、１５０℃の順で同様の操作を繰り返し、それぞれの質量を測定する（ｗ５、ｗ６）。以下の式により、それぞれの温度で、吸湿した水分を放出させた時の脱着量（ＲＨ＝９０％ 吸湿質量基準）を求めた。
脱着量（９０℃）［質量％]＝（ｗ３−ｗ４）／（ｗ３−ｗ１）×１００
脱着量（１１０℃）［質量％]＝（ｗ３−ｗ５）／（ｗ３−ｗ１）×１００
脱着量（１５０℃）［質量％]＝（ｗ３−ｗ６）／（ｗ３−ｗ１）×１００
(6) Evaluation of desorption amount Evaluation of moisture absorption capacity is pre-treatment. The petri dish and the dehumidifying agent that have been saturated and absorbed are dried for 90 minutes with a table dryer preheated to 90 ° C. The total mass (w4) of the dried petri dish and the dehumidifying agent is measured. Similarly, the same operation is repeated in the order of 110 ° C. and 150 ° C., and the respective masses are measured (w5, w6). The desorption amount (RH = 90% hygroscopic mass standard) when moisture absorbed by moisture was released at each temperature was determined by the following formula.
Desorption amount (90 ° C.) [mass%] = (w3-w4) / (w3-w1) × 100
Desorption amount (110 ° C.) [mass%] = (w3-w5) / (w3-w1) × 100
Desorption amount (150 ° C.) [mass%] = (w3-w6) / (w3-w1) × 100
（比較例１）
水澤化学工業株式会社製ナトリウムＹ型ゼオライトであるミズカシーブスＹ−５００（ＳｉＯ２／Ａｌ２Ｏ３＝４.７）を使用した。この結晶度は１１０．１％であった。なお、ミズカシーブスは水澤化学工業株式会社の登録商標である。
(Comparative Example 1)
Mizusuka Sieves Y-500 (SiO 2 / Al 2 O 3 = 4.7), which is a sodium Y-type zeolite manufactured by Mizusawa Chemical Co., Ltd., was used. The crystallinity was 110.1%. Mizuka Sieves is a registered trademark of Mizusawa Chemical Industry Co., Ltd.
（比較例２）
水澤化学工業株式会社製ナトリウムＹ型ゼオライトであるミズカシーブスＹ−４００（ＳｉＯ２／Ａｌ２Ｏ３＝３．８）を使用した。この結晶度は１０４．０％であった。
(Comparative Example 2)
Mizusawa using Mizukashibusu Y-400 is a Chemical Industry Co., Ltd. sodium Y-type zeolite (SiO 2 / Al 2 O 3 = 3.8). The crystallinity was 104.0%.
（実施例１）
（アンモニウムイオン交換工程）
比較例１のＹ型ゼオライト２００ｇ（１１０℃乾燥質量）に対して１８００ｇの水を加えて１０％スラリーとし、２００ｇの塩化アンモニウムを加え、撹拌しながら室温で３時間イオン交換反応を行った。その後、濾過水洗を行った後に１１０℃で一晩乾燥を行った。
（焼成工程）
乾燥品２０ｇを蒸発皿に測り取り、電気炉で７００℃、３時間焼成することで除湿剤を得た。
Example 1
(Ammonium ion exchange process)
1800 g of water was added to 200 g of Y-type zeolite of Comparative Example 1 (110 ° C. dry mass) to make a 10% slurry, 200 g of ammonium chloride was added, and an ion exchange reaction was performed at room temperature for 3 hours with stirring. Then, after performing filtration water washing, it dried at 110 degreeC overnight.
(Baking process)
A dehumidifier was obtained by measuring 20 g of the dried product in an evaporating dish and baking it at 700 ° C. for 3 hours in an electric furnace.
（実施例２）
塩化アンモニウムの量を４５ｇにし、焼成温度を７５０℃とした以外は、実施例１と同様の処理で除湿剤を得た。
(Example 2)
A dehumidifying agent was obtained in the same manner as in Example 1 except that the amount of ammonium chloride was 45 g and the firing temperature was 750 ° C.
（比較例３）
焼成温度を５００℃とした以外は、実施例１と同様の作業で除湿剤を得た。
(Comparative Example 3)
A dehumidifier was obtained in the same manner as in Example 1 except that the firing temperature was 500 ° C.
（比較例４）
市販品であるＣＯＳＭＯ製（韓国）１０Ｍを使用した。
(Comparative Example 4)
Commercially available COSMO (Korea) 10M was used.
（比較例５）
特許文献３の実施例１に従い、除湿剤を得た。
(Comparative Example 5)
A dehumidifying agent was obtained according to Example 1 of Patent Document 3.
（比較例６）
比較例１の代わりに比較例２を用い、焼成温度を６５０℃とした以外は、実施例１と同様の作業で除湿剤を得た。
(Comparative Example 6)
A dehumidifying agent was obtained in the same manner as in Example 1 except that Comparative Example 2 was used instead of Comparative Example 1 and the firing temperature was 650 ° C.
かかる、除湿剤の組成と物性を表２に、吸湿能力と低温での脱着量についての試験結果を表３にそれぞれ示す。 The composition and physical properties of the dehumidifying agent are shown in Table 2, and the test results on the moisture absorption capacity and the desorption amount at low temperature are shown in Table 3, respectively.
Claims (7)
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57100914A (en) * | 1980-10-28 | 1982-06-23 | Grace W R & Co | Manufacture of crystalline alumina zeolite silicate, which is active catalytically |
| JPH06277440A (en) * | 1990-10-24 | 1994-10-04 | Gas Res Inst | Material for drying agent for use in device for cooling and dehumidifying combustion gas |
| US5667560A (en) * | 1993-10-25 | 1997-09-16 | Uop | Process and apparatus for dehumidification and VOC odor remediation |
| US6395070B1 (en) * | 1998-10-06 | 2002-05-28 | Matheson Tri-Gas, Inc. | Methods for removal of impurity metals from gases using low metal zeolites |
| JP2002284520A (en) * | 2001-03-23 | 2002-10-03 | Mizusawa Ind Chem Ltd | Mesoporous silica-alumina gel, moisture conditioning agent, and catalyst carrier |
| JP2003137538A (en) * | 2001-11-01 | 2003-05-14 | Catalysts & Chem Ind Co Ltd | NaY-TYPE ZEOLITE |
| JP2004136269A (en) * | 2002-08-20 | 2004-05-13 | Mitsubishi Chemicals Corp | Adsorbent material for adsorbing type heat pump, adsorbent material for air humidity conditioner, adsorbing type heat pump, and air humidity conditioner |
| JP2004345892A (en) * | 2003-05-21 | 2004-12-09 | National Institute Of Advanced Industrial & Technology | Method for manufacturing tubular structure of aluminum silicate |
| JP2006068623A (en) * | 2004-09-01 | 2006-03-16 | Nichias Corp | Dehumidifier |
| JP2010042996A (en) * | 2009-11-13 | 2010-02-25 | Nichias Corp | Y type zeolite and member for dehumidification using the same |
| JP2012071278A (en) * | 2010-09-29 | 2012-04-12 | Mizusawa Ind Chem Ltd | Dehumidifying agent |
-
2014
- 2014-11-17 JP JP2014232372A patent/JP6373173B2/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57100914A (en) * | 1980-10-28 | 1982-06-23 | Grace W R & Co | Manufacture of crystalline alumina zeolite silicate, which is active catalytically |
| JPH06277440A (en) * | 1990-10-24 | 1994-10-04 | Gas Res Inst | Material for drying agent for use in device for cooling and dehumidifying combustion gas |
| US5667560A (en) * | 1993-10-25 | 1997-09-16 | Uop | Process and apparatus for dehumidification and VOC odor remediation |
| US6395070B1 (en) * | 1998-10-06 | 2002-05-28 | Matheson Tri-Gas, Inc. | Methods for removal of impurity metals from gases using low metal zeolites |
| JP2002284520A (en) * | 2001-03-23 | 2002-10-03 | Mizusawa Ind Chem Ltd | Mesoporous silica-alumina gel, moisture conditioning agent, and catalyst carrier |
| JP2003137538A (en) * | 2001-11-01 | 2003-05-14 | Catalysts & Chem Ind Co Ltd | NaY-TYPE ZEOLITE |
| JP2004136269A (en) * | 2002-08-20 | 2004-05-13 | Mitsubishi Chemicals Corp | Adsorbent material for adsorbing type heat pump, adsorbent material for air humidity conditioner, adsorbing type heat pump, and air humidity conditioner |
| JP2004345892A (en) * | 2003-05-21 | 2004-12-09 | National Institute Of Advanced Industrial & Technology | Method for manufacturing tubular structure of aluminum silicate |
| JP2006068623A (en) * | 2004-09-01 | 2006-03-16 | Nichias Corp | Dehumidifier |
| JP2010042996A (en) * | 2009-11-13 | 2010-02-25 | Nichias Corp | Y type zeolite and member for dehumidification using the same |
| JP2012071278A (en) * | 2010-09-29 | 2012-04-12 | Mizusawa Ind Chem Ltd | Dehumidifying agent |
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