JP2009173490A - Amorphous substance comprising composite of proto-imogolite and phosphoric acid, and adsorbent for desiccant air-conditioning and dew condensation preventing agent using the same - Google Patents
Amorphous substance comprising composite of proto-imogolite and phosphoric acid, and adsorbent for desiccant air-conditioning and dew condensation preventing agent using the same Download PDFInfo
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Abstract
Description
本発明は、次世代の産業を支える重要な基盤技術として、実用化が強く期待されているナノテクノロジーの技術分野において、その特異な形状に起因する微細構造により、高比表面積、高細孔容積、イオン交換能、及び吸着能等に優れた物理化学的な特性を示し、革新的な機能性材料としての応用が期待されている物質に関するものであり、特に、中湿度および高湿度領域において優れた吸着性能を有する吸着剤に関するものである。 The present invention has a high specific surface area, a high pore volume due to the fine structure resulting from its unique shape in the technical field of nanotechnology, which is expected to be put to practical use as an important basic technology supporting the next generation industry. It is related to substances that exhibit excellent physicochemical properties such as ion exchange capacity and adsorption capacity, and are expected to be applied as innovative functional materials, especially in the middle and high humidity ranges. The present invention relates to an adsorbent having high adsorption performance.
ナノサイズのチューブ状アルミニウムケイ酸塩は、例えば、天然において、イモゴライトとして産出するが、このイモゴライトは、土壌中に存在し、主に火山灰由来の土壌に産する。また、天然のイモゴライトは、類縁鉱物であるアロフェンと並んで、土壌における養分や水分の移動及び植物への供給、更に、有害な汚染物質の集積や残留等に対して影響を与えるものである。このチューブ状アルミニウムケイ酸塩は、主な構成元素をケイ素（Ｓｉ）、アルミニウム（Ａｌ）、酸素（Ｏ）及び水素（Ｈ）とし、多数のＳｉ−Ｏ−Ａｌ結合で組み立てられた水和珪酸アルミニウムであって、外径が２．２〜２．８ｎｍ、内径が０．５〜１．２ｎｍ、長さが１０ｎｍ〜数μｍのチューブ状の形態を有し、天然には、火山灰及び軽石等の降下火山噴出物を母材とする土壌に分布している粘土成分である。 Nano-sized tubular aluminum silicate is naturally produced as imogolite, for example, but this imogolite is present in the soil and is mainly produced in soil derived from volcanic ash. Natural imogolite, along with allophane, a related mineral, affects nutrients and moisture in soil, supply to plants, and accumulation and residue of harmful pollutants. This tubular aluminum silicate is composed of silicon (Si), aluminum (Al), oxygen (O) and hydrogen (H) as the main constituent elements, and is a hydrated silicic acid assembled with a number of Si-O-Al bonds. Aluminum having an outer diameter of 2.2 to 2.8 nm, an inner diameter of 0.5 to 1.2 nm, a length of 10 nm to several μm, and naturally has volcanic ash, pumice, etc. It is a clay component distributed in the soil that uses the fall volcano ejecta as a base material.
プロトイモゴライトは、前記イモゴライトの前駆体物質であり、水溶液中に分散したこの前駆体を１００℃程度で加熱することによりイモゴライトとなる、イモゴライト形成過程途中の物質をプロトイモゴライトと呼ぶ。プロトイモゴライトは、イモゴライトの構造に由来する性質を有しているため、２９Ｓｉ固体NMRでは、イモゴライトと同じ−７８ｐｐｍにピークを示し、ケイ素はOH−Ｓｉ−(OＡｌ)3の配位を有している。
プロトイモゴライトは、結晶性のイモゴライトのように比較的長いチューブ状の形態にまでは成長していないが、イモゴライトの構造をそれなりに有しているので、水蒸気吸着特性においてもイモゴライトとプロトイモゴライトとは相対湿度２０％以下における吸着挙動がほぼ同じであり、低湿度領域においてはイモゴライトと同様な吸着剤の性質を有している。
Protoimogolite is a precursor substance of the imogolite, and a substance in the process of forming imogolite that becomes imogolite by heating the precursor dispersed in an aqueous solution at about 100 ° C. is called protomogolite. Protoimogolite has a property derived from the structure of imogolite. Therefore, 29 Si solid-state NMR shows the same peak at −78 ppm as imogolite, and silicon has a coordination of OH—Si— (OAl) 3. ing.
Protoimogolite does not grow into a relatively long tube-like form like crystalline imogolite, but has the structure of imogolite as it is, so in terms of water vapor adsorption characteristics, imogolite and protoimogolite are Adsorption behavior at a relative humidity of 20% or less is substantially the same, and has the same adsorbent properties as imogolite in the low humidity region.
このような、ナノサイズのチューブ状アルミニウムケイ酸塩であるイモゴライト及びその前駆体であるプロトイモゴライトの特異な形状及び物性は、工業的にも有用であると考えられる。すなわち、イモゴライトは、その特異な微細構造に基づいて、各種物質を吸着することができる特性を有することから、例えば、有害汚染物質吸着剤、脱臭剤、さらには二酸化炭素やメタンなどのガス貯蔵剤等としての利用可能性については、従来から言及されている。また、優れた水蒸気吸着性能を有することから、ヒートポンプ熱交換材、結露防止剤、自律的調湿材料などの応用として期待されている。 Such unique shapes and physical properties of imogolite, which is a nano-sized tubular aluminum silicate, and protoimogolite, which is a precursor thereof, are considered to be useful industrially. That is, since imogolite has a characteristic of adsorbing various substances based on its unique fine structure, for example, harmful pollutant adsorbents, deodorizers, and gas storage agents such as carbon dioxide and methane. The availability of such as has been conventionally mentioned. In addition, since it has excellent water vapor adsorption performance, it is expected to be applied as a heat pump heat exchange material, anti-condensation agent, autonomous humidity control material and the like.
特に、デシカント空調では外気から導入される空気中の湿分を取り除くことが目的であるため、夏場の高湿度の空気からでも効率的に湿分を取り除けることが必要とされており、そのためデシカント空調において求められる吸着剤は、一般的に相対湿度が５％程度から６０％における吸着量が多いことであるとされているが、それ以上の高湿度域での吸着量も多いことが望ましい。
さらに、結露防止剤においては、相対湿度９０％以上で水蒸気を多量に吸着し、湿度が低下するとともに脱着する物質が求められている。
そのような背景から中湿度領域あるいは高湿度領域においても水蒸気を吸着できる物質の合成が必要となる。
In particular, desiccant air conditioning is intended to remove moisture in the air introduced from the outside air, so it is necessary to efficiently remove moisture even from high humidity air in summer. In general, it is said that the adsorbent required in 1) has a large amount of adsorption at a relative humidity of about 5% to 60%, but it is also desirable that the amount of adsorption in a higher humidity range be larger.
Further, in the anti-condensation agent, a substance that adsorbs a large amount of water vapor at a relative humidity of 90% or more and desorbs as the humidity decreases is required.
From such a background, it is necessary to synthesize a substance capable of adsorbing water vapor even in a medium humidity region or a high humidity region.
このような中で、チューブ状アルミニウムケイ酸塩の上記特性を有しつつ、中湿度域及び高湿度域においても水蒸気を多量に吸着できる物質を工業的に安価で大量に合成することが求められており、イモゴライト及びプロトイモゴライトの特異な細孔を利用した吸着剤の開発が行なわれてきた。
しかしながら、チューブ状アルミニウムケイ酸塩であるイモゴライトにおいては、そのアスペクト比が約１０００程度と比較的チューブの長さが長いことから、低湿度領域および相対湿度９０％以上の高湿度領域においては高性能な物質であるが（特許文献１参照）、中湿度領域においては吸着量が少ないという欠点があった。
また、非晶質イモゴライトの特異な細孔を利用した吸着剤の開発も行なわれている（特許文献２参照）が、しかしながら、従来の方法では、相対湿度６０％において、３０ｗｔ%の吸着量を有することはできなかった。
さらに、プロトイモゴライトから得られた吸着剤は、相対湿度１０％〜６０％において水蒸気吸着量が２０ｗｔ％以上であって、前述のイモゴライトおよび非晶質イモゴライトから得られる吸着剤に比較して高性能なものであることが知られているが（特許文献３参照）、それでも３０ｗｔ％の吸着量を有することはできなかった。
However, imogolite, which is a tubular aluminum silicate, has a relatively long tube length with an aspect ratio of about 1000, so it has high performance in low humidity areas and high humidity areas with a relative humidity of 90% or more. Although it is a new substance (see Patent Document 1), there is a drawback that the amount of adsorption is small in the middle humidity region.
In addition, an adsorbent using unique pores of amorphous imogolite has been developed (see Patent Document 2). However, in the conventional method, an adsorption amount of 30 wt% is obtained at a relative humidity of 60%. Could not have.
Further, the adsorbent obtained from Protoimogolite has a water vapor adsorption amount of 20 wt% or more at a relative humidity of 10% to 60%, and has a higher performance than the adsorbent obtained from the aforementioned imogolite and amorphous imogolite. However, it was still impossible to have an adsorption amount of 30 wt%.
本発明は、以上のような事情に鑑みてなされたものであって、中湿度領域のみならず高湿度領域においても優れた吸着性能を有する材料、及びその優れた吸着性能を有する吸着剤、特にデシカント空調用吸着剤および結露防止剤を提供することを目的とするものである。 The present invention has been made in view of the circumstances as described above, and is a material having excellent adsorption performance not only in a medium humidity region but also in a high humidity region, and an adsorbent having the excellent adsorption performance, particularly An object of the present invention is to provide an adsorbent for desiccant air conditioning and an anti-condensation agent.
本発明者らは、上記目的を達成すべく検討を重ねた結果、イモゴライト前駆体であるプロトイモゴライトを生成した後に、リン酸を適量添加し加熱することを検討した結果、中湿度領域および高湿度領域において優れた吸着性能を有する、プロトイモゴライトとリン酸の複合化物からなる非晶質物質の合成法を開発することに成功し、本発明を完成するに至った。 As a result of repeated studies to achieve the above-mentioned object, the present inventors have studied the addition of an appropriate amount of phosphoric acid and heating after producing protomogolite as an imogolite precursor. The inventors have succeeded in developing a method for synthesizing an amorphous substance composed of a complex of protomogolite and phosphoric acid having excellent adsorption performance in the region, and have completed the present invention.
すなわち、上記課題を解決するための本発明は、以下のとおりである。
（１）プロトイモゴライトとリン酸の複合化物からなる非晶質物質。
（２）相対湿度１０〜６０％の中湿度領域及び相対湿度６０％以上の高湿度領域において吸着性能を有し、相対湿度６０％における吸着量と相対湿度９５％における吸着量の差が２００ｗｔ％以上であることを特徴とする（１）の非晶質物質。
（３）モノケイ酸水溶液とアルミニウム溶液をＳｉ／Ａｌ比が０．３５〜０．５５となるように混合し、これに酸又はアルカリを添加してｐＨ６〜８に調製し、その後脱塩処理したものに、リン酸を添加した後、加熱することによって得られる、（１）又は（２）の非晶質物質。
（４）上記（１）〜（３）のいずれかの非晶質物質からなる吸着剤。
（５）上記（１）〜（３）のいずれかの非晶質物質からなるデシカント空調用吸着剤。
（６）上記（１）〜（３）のいずれかの非晶質物質からなるデシカント結露防止剤。
That is, the present invention for solving the above-described problems is as follows.
(1) An amorphous substance comprising a complex of prototomogolite and phosphoric acid.
(2) Adsorption performance in a medium humidity region with a relative humidity of 10 to 60% and a high humidity region with a relative humidity of 60% or more, and the difference between the adsorption amount at a relative humidity of 60% and the adsorption amount at a relative humidity of 95% is 200 wt%. The amorphous substance according to (1), which is as described above.
(3) A monosilicic acid aqueous solution and an aluminum solution were mixed so that the Si / Al ratio was 0.35 to 0.55, and an acid or alkali was added thereto to adjust the pH to 6 to 8, followed by desalting. An amorphous substance according to (1) or (2), which is obtained by adding phosphoric acid to a product and heating it.
(4) An adsorbent comprising the amorphous material of any one of (1) to (3) above.
(5) A desiccant air-conditioning adsorbent comprising the amorphous material according to any one of (1) to (3) above.
(6) A desiccant anti-condensation agent comprising the amorphous material according to any one of (1) to (3) above.
本発明により得られる、プロトイモゴライトとリン酸の複合化物からなる非晶質物質は、相対湿度１０〜６０％の中湿度領域及び相対湿度６０％以上の高湿度領域において優れた吸着性能を有し、特に、相対湿度６０％以上における吸着量と相対湿度９５％における吸着量の差が２００ｗｔ％以上であるという優れた吸着性能を有するものであるため、その特性を用いたデシカント空調用吸着剤及び結露防止剤を提供することができ、さらには、有害汚染物質吸着剤、脱臭剤、二酸化炭素やメタンなどのガス貯蔵剤を提供できるという格別の効果が奏される。 The amorphous substance comprising a composite of protomogolite and phosphoric acid obtained by the present invention has excellent adsorption performance in a medium humidity range of 10 to 60% relative humidity and a high humidity range of 60% or more relative humidity. In particular, the adsorbent for desiccant air-conditioning using the characteristics, because it has an excellent adsorption performance that the difference between the adsorption amount at a relative humidity of 60% or more and the adsorption amount at a relative humidity of 95% is 200 wt% or more, and An anti-condensation agent can be provided, and furthermore, a special effect that a harmful pollutant adsorbent, a deodorizing agent, and a gas storage agent such as carbon dioxide and methane can be provided.
次に、本発明について更に詳細に説明する。
本発明におけるプロトイモゴライトは、構成元素をケイ素（Ｓｉ）、アルミニウム（Ａｌ）、酸素（Ｏ）及び水素（Ｈ）とし、多数のＳｉ−Ｏ−Ａｌ結合で組み立てられた水和ケイ酸アルミニウムである。プロトイモゴライトは、１００℃程度で加熱することによりイモゴライトになる前駆体物質を指すが、イモゴライトの一部の構造を有している物質である。
Next, the present invention will be described in more detail.
Protomogolite according to the present invention is a hydrated aluminum silicate that has silicon (Si), aluminum (Al), oxygen (O), and hydrogen (H) as constituent elements and is assembled with a number of Si—O—Al bonds. . Protoimogolite refers to a precursor substance that becomes imogolite when heated at about 100 ° C., and is a substance having a partial structure of imogolite.
このプロトイモゴライトからなるアルミニウムケイ酸塩は、無機ケイ素化合物溶液と無機アルミニウム化合物溶液からなる溶液を混合し、ケイ素とアルミニウムの重合化そして脱塩処理を施した後、加熱熟成により人工的に得ることが可能である。 This aluminum silicate made of Protoimogolite is artificially obtained by mixing the solution made of inorganic silicon compound solution and inorganic aluminum compound solution, polymerizing and desalting the silicon and aluminum, and then heat aging. Is possible.
本発明における、プロトイモゴライトとリン酸の複合化物からなる非晶質物質は、相対湿度６０％において３０ｗｔ％以上の水蒸気を吸着する性能を有するものであり、従来公知のチューブ状アルミニウムケイ酸塩であるイモゴライトや非晶質イモゴライトとは異なる高吸着性物質である。
すなわち、本発明らが鋭意検討を重ねた結果、プロトイモゴライト生成後にリン酸を添加し加熱することにより、プロトイモゴライトとリン酸による複合化を行うことで、従来では得られなかった、相対湿度１０〜６０％の中湿度領域及び相対湿度６０％以上の両領域において優れた吸着性能を有する物質を提供しうる非晶質物質が得られるものであり、特に、相対湿度６０％における吸着量と相対湿度９５％における吸着量との差が２００ｗｔ％以上ある、優れた吸着特性を有するものである。
In the present invention, the amorphous substance composed of a composite of protoimogolite and phosphoric acid has the ability to adsorb 30 wt% or more of water vapor at a relative humidity of 60%, and is a conventionally known tubular aluminum silicate. It is a highly adsorptive substance different from certain imogolites and amorphous imogolites.
That is, as a result of repeated studies by the present inventors, by adding phosphoric acid after heating to protoimogolite and heating it, by combining with protoimogolite and phosphoric acid, a relative humidity of 10 which has not been obtained conventionally is obtained. An amorphous substance capable of providing a substance having excellent adsorption performance in both a medium humidity region of -60% and a relative humidity of 60% or more can be obtained. The difference between the adsorption amount at a humidity of 95% is 200 wt% or more and has excellent adsorption characteristics.
本発明において、プロトイモゴライトの調製には、原料として、通常、無機ケイ素化合物と無機アルミニウム化合物が用いられる。ケイ素源として使用される試剤は、モノケイ酸であればよく、具体的には、オルトケイ酸ナトリウム、メタケイ酸ナトリウム、無定形コロイド状二酸化ケイ素（エアロジル等）等が好適なものとして挙げられる。また、上記ケイ酸塩分子と結合させるアルミニウム源は、アルミニウムイオンであればよく、具体的には、例えば、塩化アルミニウム、硝酸アルミニウムおよびアルミン酸ナトリウム等のアルミニウム化合物が挙げられる。これらのケイ素源及びアルミニウム源は、上記の化合物に限定されるものではなく、それらと同効のものであれば同様に使用することができる。 In the present invention, an inorganic silicon compound and an inorganic aluminum compound are usually used as raw materials for the preparation of protoimogolite. The reagent used as the silicon source may be monosilicate, and specific examples thereof include sodium orthosilicate, sodium metasilicate, amorphous colloidal silicon dioxide (aerosil, etc.) and the like. Moreover, the aluminum source couple | bonded with the said silicate molecule | numerator should just be an aluminum ion, Specifically, aluminum compounds, such as aluminum chloride, aluminum nitrate, and sodium aluminate, are mentioned, for example. These silicon sources and aluminum sources are not limited to the above-mentioned compounds, and can be used in the same manner as long as they have the same effect.
これらの原料を適切な水溶液に溶解させ、所定の濃度の溶液を調製する。本目的を満たす優れた吸着挙動を示すには、ケイ素／アルミニウム比は０．３５〜０．５５となるように混合することが必要である。溶液中のケイ素化合物の濃度は１〜１０００ｍｍｏｌ／Ｌで、アルミニウム化合物の溶液の濃度は１〜１０００ｍｍｏｌ／Ｌであるが、好適な濃度としては１〜１００ｍｍｏｌ／Lのケイ素化合物溶液と、１〜３００ｍｍｏｌ／Lのアルミニウム化合物溶液を混合することが好ましい。これらの比率及び濃度に基づいて、アルミニウム化合物溶液にケイ素化合物溶液を混合し、酸又はアルカリにてｐＨ６〜８に調製して前駆体を形成した後、遠心分離、濾過、膜分離等により、溶液中の共存イオンを取り除き、その後、回収した前駆体を弱酸性〜弱アルカリ性水溶液に分散させたものが、プロトイモゴライトを含む懸濁液である。 These raw materials are dissolved in an appropriate aqueous solution to prepare a solution having a predetermined concentration. In order to exhibit an excellent adsorption behavior that satisfies this purpose, it is necessary to mix so that the silicon / aluminum ratio is 0.35 to 0.55. The concentration of the silicon compound in the solution is 1-1000 mmol / L, and the concentration of the aluminum compound solution is 1-1000 mmol / L. The preferred concentration is 1-100 mmol / L of the silicon compound solution, and 1-300 mmol. It is preferable to mix a / L aluminum compound solution. Based on these ratios and concentrations, a silicon compound solution is mixed with an aluminum compound solution, adjusted to pH 6-8 with acid or alkali to form a precursor, and then subjected to centrifugation, filtration, membrane separation, etc. A suspension containing protoimogolite is obtained by removing coexisting ions therein and then dispersing the recovered precursor in a weakly acidic to weakly alkaline aqueous solution.
このプロトイモゴライトを含む懸濁液に、リン酸を添加し１００℃程度で加熱することにより、プロトイモゴライトとリン酸を複合化することができ、目的の中湿度および高湿度領域において優れた吸着剤を得ることができる。 By adding phosphoric acid to this suspension containing protoimogolite and heating at about 100 ° C., protoimogolite and phosphoric acid can be combined, and the adsorbent is excellent in the intended medium and high humidity ranges. Can be obtained.
次に、本発明を実施例及び比較例に基づいて具体的に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。
（実施例１）
Ｓｉ源として０．０６ｍｏｌ／Ｌのオルトケイ酸ナトリウム水溶液１２５ｍＬと、Ａｌ源として０．１５ｍｏｌ／Ｌの塩化アルミニウム水溶液１２５ｍＬを用いた。塩化アルミニウム水溶液にオルトケイ酸ナトリウム水溶液を加え、約１０分間攪拌を行った。このときのＳｉ／Ａｌ比は０．４０である。攪拌後混合溶液がほぼ透明になったことを確認し、１Nの水酸化ナトリウム水溶液を１ｍＬ／分の速さで滴下し、ｐＨが７．５になるまで添加した。水酸化ナトリウム水溶液の滴下量は２６ｍＬであった。このようにして生成させた前駆体懸濁液を遠心分離にて３回脱塩処理を行った。脱塩処理は遠心分離機を用いて、回転速度３０００ｒｐｍ、時間１０分で行った。脱塩処理後前駆体を純水に分散させ全体で１Ｌとなるようにし、１０分攪拌を行った。さらにこの１Lの前駆体分散溶液を２Lの純水に分散させた後、１Nの塩酸を１５ｍＬ添加し、約1時間攪拌を行い、プロトイモゴライト懸濁液を作成した。
調整した３Ｌのイモゴライト前駆体懸濁液を、５００ｍＬ用テフロン（登録商標）製容器６本に５００ｍＬずつ測り取った。そのうち1本はリン酸を添加しない溶液とし、残りの５本については加熱前の段階で０．５Ｎのリン酸を０．５ｍＬ、１ｍＬ、１．５ｍＬ、２ｍＬ、２．５ｍＬをそれぞれ添加し、９８℃の恒温槽にて1週間加熱を行った。
EXAMPLES Next, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited at all by the following examples.
Example 1
125 mL of 0.06 mol / L sodium orthosilicate aqueous solution was used as the Si source, and 125 mL of 0.15 mol / L aluminum chloride aqueous solution was used as the Al source. A sodium orthosilicate aqueous solution was added to the aluminum chloride aqueous solution and stirred for about 10 minutes. The Si / Al ratio at this time is 0.40. After stirring, it was confirmed that the mixed solution became almost transparent, and a 1N aqueous sodium hydroxide solution was added dropwise at a rate of 1 mL / min and added until the pH reached 7.5. The dropping amount of the sodium hydroxide aqueous solution was 26 mL. The precursor suspension thus produced was subjected to desalting treatment three times by centrifugation. The desalting treatment was performed using a centrifuge at a rotational speed of 3000 rpm and a time of 10 minutes. After the desalting treatment, the precursor was dispersed in pure water so as to be 1 L in total, and stirred for 10 minutes. Further, 1 L of the precursor dispersion was dispersed in 2 L of pure water, 15 mL of 1N hydrochloric acid was added, and the mixture was stirred for about 1 hour to prepare a protoimogolite suspension.
500 mL each of the adjusted 3 L imogolite precursor suspension was measured into 6 500 mL Teflon (registered trademark) containers. One of them is a solution to which phosphoric acid is not added, and the other five are added with 0.5 mL, 1 mL, 1.5 mL, 2 mL, and 2.5 mL of 0.5 N phosphoric acid at the stage before heating, Heating was performed for 1 week in a constant temperature bath at 98 ° C.
評価は６０℃で乾燥させた６試料について、簡便な水蒸気吸着評価を行った。秤量瓶に約０．３ｇの試料を入れ、１００℃の恒温槽にて1時間加熱後秤量を行い、次に２５℃６０％の恒温恒湿槽にて１時間静置させ吸着後秤量を行った。１００℃における乾燥重量を基にして吸着率を求めた結果、吸着率はリン酸添加なしが１７．９ｍａｓｓ％、０．５ｍＬ添加の場合１４．６ｍａｓｓ％、１ｍＬ添加で１３．４ｍａｓｓ％、１．５ｍＬ添加で１９．９ｍａｓｓ％、２ｍＬ添加で２８．５ｍａｓｓ％、２．５ｍＬ添加で２３．７ｍａｓｓ％と、リン酸２ｍＬ添加において最も吸着率が高かった。 The evaluation was performed by simple water vapor adsorption evaluation on 6 samples dried at 60 ° C. About 0.3 g of sample is put in a weighing bottle, heated for 1 hour in a constant temperature bath at 100 ° C., then weighed after standing for 1 hour in a constant temperature and humidity chamber at 25 ° C. and 60%. It was. As a result of obtaining the adsorption rate based on the dry weight at 100 ° C., the adsorption rate was 17.9 mass% without addition of phosphoric acid, 14.6 mass% with addition of 0.5 mL, 13.4 mass% with addition of 1 mL, and 1. The adsorption rate was the highest when 2 mL of phosphoric acid was added, 19.9 mass% when 5 mL was added, 28.5 mass% when 2 mL was added, and 23.7 mass% when 2.5 mL was added.
前記リン酸０．５〜２．５ｍＬ添加で得られた生成物について、Ｘ線回折および原子間力顕微鏡による観察を行った。いずれのリン酸添加量においても同様なX線回折図形および同様な電子間力顕微鏡画像が得られたが、リン酸２．０ｍL添加の生成物を代表とした。図１にリン酸２．０ｍL添加によって得られた生成物の粉末Ｘ線回折図形を示す。図１に見られるように、２θ＝２７°と４０°付近にブロードなピークが見られ、非晶質なアルミニウムケイ酸塩に特徴的なピークが観察された。この結果から実施例１の物質は非晶質物質であることが確認された。
またリン酸２．０ｍL添加によって得られた生成物の原子間力顕微鏡画像を図２に示す。図２に見られるように、実施例１の物質は粒子の形態を有しており、イモゴライトのようなチューブ状の形態を有してないことが確認された。
The product obtained by adding 0.5 to 2.5 mL of phosphoric acid was observed by X-ray diffraction and atomic force microscope. A similar X-ray diffraction pattern and a similar electron force microscope image were obtained at any amount of phosphoric acid added, but the product added with 2.0 mL of phosphoric acid was representative. FIG. 1 shows a powder X-ray diffraction pattern of the product obtained by adding 2.0 mL of phosphoric acid. As seen in FIG. 1, broad peaks were observed around 2θ = 27 ° and 40 °, and peaks characteristic of amorphous aluminum silicate were observed. From this result, it was confirmed that the substance of Example 1 was an amorphous substance.
An atomic force microscope image of the product obtained by adding 2.0 mL of phosphoric acid is shown in FIG. As can be seen in FIG. 2, it was confirmed that the substance of Example 1 had a particle form and did not have a tube-like form like imogolite.
（比較例１：イモゴライトの調製）
チューブ状アルミニウムケイ酸塩（イモゴライト）を以下のようにして得た。
Ｓｉ濃度が６０ｍｍｏｌ／Lになるように純水で希釈したオルトケイ酸ナトリウム水溶液２００ｍｌを調整した後。また、これとは別に塩化アルミニウムを純水に溶解させ、Aｌ濃度が１５０ｍｍｏｌ／L水溶液２００ｍｌを調整した。塩化アルミニウム水溶液にオルトケイ酸ナトリウム水溶液を混合し、マグネティックスターラーで撹拌した。このときのケイ素／アルミニウム比は０．４である。この混合溶液に、１Ｎ水酸化ナトリウム水溶液４４．８ｍｌを滴下しｐHを６とした。この溶液から遠心分離により前駆体を回収し、更に、純水で前駆体を２回遠心分離により洗浄した後、２Lの純水中に分散させた。この前駆体の懸濁液２Lに、１Ｎ塩酸を１０ｍｌ加えｐHを４．２とした後、室温下で１時間攪拌した後、テフロン（登録商標）製の２L密閉容器に移し替え、恒温槽にて１００℃で４日間加熱を行った。こうしてイモゴライトを含む水溶液を得た。冷却後、この水溶液を６０℃で乾燥させた後、孔径０．２μｍのフィルターを用いて洗浄を行った。
(Comparative Example 1: Preparation of imogolite)
Tubular aluminum silicate (imogolite) was obtained as follows.
After adjusting 200 ml of sodium orthosilicate aqueous solution diluted with pure water so that the Si concentration becomes 60 mmol / L. Separately, aluminum chloride was dissolved in pure water to prepare 200 ml of an aqueous solution having an Al concentration of 150 mmol / L. A sodium orthosilicate aqueous solution was mixed with the aluminum chloride aqueous solution and stirred with a magnetic stirrer. The silicon / aluminum ratio at this time is 0.4. To this mixed solution, 44.8 ml of 1N aqueous sodium hydroxide solution was added dropwise to adjust the pH to 6. The precursor was recovered from this solution by centrifugation, and the precursor was washed twice with pure water by centrifugation, and then dispersed in 2 L of pure water. 10 ml of 1N hydrochloric acid was added to 2 L of this precursor suspension to adjust the pH to 4.2, and the mixture was stirred at room temperature for 1 hour, then transferred to a 2 L sealed container made of Teflon (registered trademark), and placed in a thermostatic bath. And heated at 100 ° C. for 4 days. Thus, an aqueous solution containing imogolite was obtained. After cooling, the aqueous solution was dried at 60 ° C. and then washed using a filter having a pore size of 0.2 μm.
得られた生成物について、そのＸ線回折パターンを解析した。
図３に得られた生成物の粉末Ｘ線回折図形を示す。図３からわかるように、得られた生成物は、粉末Ｘ線回折において２θ＝４，９．５，１４，２７，４０°付近にピークを有し、チューブ状アルミニウムケイ酸塩特有のＸ線回折パターンを示した。
About the obtained product, the X-ray-diffraction pattern was analyzed.
FIG. 3 shows a powder X-ray diffraction pattern of the product obtained. As can be seen from FIG. 3, the obtained product has a peak in the vicinity of 2θ = 4, 9.5, 14, 27, and 40 ° in powder X-ray diffraction, and X-rays peculiar to tubular aluminum silicate. A diffraction pattern was shown.
（比較例２：非晶質イモゴライトの調製）
非晶質アルミニウムケイ酸塩（非晶質イモゴライト）を以下のようにして得た。
Ｓｉ濃度が６０ｍｍｏｌ／Lになるように純水で希釈したオルトケイ酸ナトリウム水溶液２００ｍｌを調整した後。また、これとは別に塩化アルミニウムを純水に溶解させ、Aｌ濃度が１５０ｍｍｏｌ／L水溶液２００ｍｌを調整した。塩化アルミニウム水溶液にオルトケイ酸ナトリウム水溶液を混合し、マグネティックスターラーで撹拌した。このときのケイ素／アルミニウム比は０．４である。この混合溶液に、１Ｎ水酸化ナトリウム水溶液４４．８ｍｌを滴下しｐHを６とした。この溶液から遠心分離により前駆体を回収し、更に、純水で前駆体を２回遠心分離により洗浄した後、２Lの純水中に分散させた。この前駆体の懸濁液２Lに、１Ｎ塩酸を２０ｍｌ加えｐHを３．７とした後、室温下で１時間攪拌した後、テフロン（登録商標）製の２L密閉容器に移し替え、恒温槽にて１００℃で２日間加熱を行った。こうして非晶質イモゴライトを含む水溶液を得た。冷却後、この水溶液を60℃で乾燥させた後、孔径０．２μｍのフィルターを用いて洗浄を行った。
(Comparative Example 2: Preparation of amorphous imogolite)
Amorphous aluminum silicate (amorphous imogolite) was obtained as follows.
After adjusting 200 ml of sodium orthosilicate aqueous solution diluted with pure water so that the Si concentration becomes 60 mmol / L. Separately, aluminum chloride was dissolved in pure water to prepare 200 ml of an aqueous solution having an Al concentration of 150 mmol / L. A sodium orthosilicate aqueous solution was mixed with the aluminum chloride aqueous solution and stirred with a magnetic stirrer. The silicon / aluminum ratio at this time is 0.4. To this mixed solution, 44.8 ml of 1N aqueous sodium hydroxide solution was added dropwise to adjust the pH to 6. The precursor was recovered from this solution by centrifugation, and the precursor was washed twice with pure water by centrifugation, and then dispersed in 2 L of pure water. After adding 20 ml of 1N hydrochloric acid to 2 L of this precursor suspension and adjusting the pH to 3.7, the mixture was stirred at room temperature for 1 hour, and then transferred to a 2 L sealed container made of Teflon (registered trademark). And heated at 100 ° C. for 2 days. Thus, an aqueous solution containing amorphous imogolite was obtained. After cooling, the aqueous solution was dried at 60 ° C. and then washed using a filter having a pore size of 0.2 μm.
得られた生成物について、そのＸ線回折パターンを解析した。
図４に得られた生成物の粉末Ｘ線回折図形を示す。図４からわかるように、得られたアルミニウムケイ酸塩は、特定のピークのない非晶質であることを示すＸ線回折パターンを示した。
About the obtained product, the X-ray-diffraction pattern was analyzed.
FIG. 4 shows a powder X-ray diffraction pattern of the product obtained. As can be seen from FIG. 4, the obtained aluminum silicate exhibited an X-ray diffraction pattern indicating that it was amorphous without specific peaks.
（比較例３：プロトイモゴライトの調製）
プロトイモゴライトを以下のようにして得た。
Ｓｉ濃度が６０ｍｍｏｌ／Lになるように純水で希釈したオルトケイ酸ナトリウム水溶液２００ｍｌを調整した後。また、これとは別に塩化アルミニウムを純水に溶解させ、Aｌ濃度が１５０ｍｍｏｌ／L水溶液２００ｍｌを調整した。塩化アルミニウム水溶液にオルトケイ酸ナトリウム水溶液を混合し、マグネティックスターラーで撹拌した。このときのケイ素／アルミニウム比は０．４である。この混合溶液に、１Ｎ水酸化ナトリウム水溶液４４．８ｍｌを滴下しｐHを６とした。この溶液から遠心分離により前駆体を回収し、更に、純水で前駆体を２回遠心分離により洗浄した後、２Lの純水中に分散させた。この前駆体の懸濁液２Lに、１Ｎ塩酸を１０ｍｌ加えｐHを４．２とした後、室温下で１時間攪拌した後、この水溶液を６０℃で６日間乾燥させた。
(Comparative Example 3: Preparation of Protoimogolite)
Protoimogolite was obtained as follows.
After adjusting 200 ml of sodium orthosilicate aqueous solution diluted with pure water so that the Si concentration becomes 60 mmol / L. Separately, aluminum chloride was dissolved in pure water to prepare 200 ml of an aqueous solution having an Al concentration of 150 mmol / L. A sodium orthosilicate aqueous solution was mixed with the aluminum chloride aqueous solution and stirred with a magnetic stirrer. The silicon / aluminum ratio at this time is 0.4. To this mixed solution, 44.8 ml of 1N aqueous sodium hydroxide solution was added dropwise to adjust the pH to 6. The precursor was recovered from this solution by centrifugation, and the precursor was washed twice with pure water by centrifugation, and then dispersed in 2 L of pure water. To 2 L of this precursor suspension, 10 ml of 1N hydrochloric acid was added to adjust the pH to 4.2, followed by stirring at room temperature for 1 hour, and then the aqueous solution was dried at 60 ° C. for 6 days.
得られた生成物について、そのＸ線回折パターンを解析した。
図５に得られた生成物の粉末Ｘ線回折図形を示す。図５からわかるように、得られたアルミニウムケイ酸塩は、特定のピークのない非晶質であることを示すＸ線回折パターンを示した。
About the obtained product, the X-ray-diffraction pattern was analyzed.
FIG. 5 shows a powder X-ray diffraction pattern of the product obtained. As can be seen from FIG. 5, the obtained aluminum silicate exhibited an X-ray diffraction pattern indicating that it was amorphous without a specific peak.
（水蒸気吸着評価）
実施例１において、リン酸の添加量２ｍＬで得られたプロトイモゴライトとりん酸の複合化物からなる非晶質物質、比較例１で得られたイモゴライト、比較例２で得られた非晶質イモゴライト、及び比較例３で得られたプロトイモゴライトについて、日本ベル社製Belsorp１８により測定を行った水蒸気吸着等温線から水蒸気吸着評価を行った。図６に、その結果を示す。図中、◆、◇、▲及び△は、それぞれ、本発明のプロトイモゴライトとリン酸の複合化物からなる非晶質物質、イモゴライト、非晶質イモゴライト、及びプロトイモゴライトの結果を示している。
一般的にデシカント空調における作動範囲は相対湿度１０〜６０％の範囲とされており、図６において、相対湿度１０％における吸着量と相対湿度６０％における吸着量の差は、実施例では３０．２ｗｔ％であるのに対し、比較例１のイモゴライトでは約１３ｗｔ％、比較例２の非晶質イモゴライトでは約７ｗｔ％、比較例３のプロトイモゴライトでは約２２ｗｔ％の増加にとどまっている。
また、本実施例のプロトイモゴライトとリン酸の複合化物からなる非晶質物質は、相対湿度６０％以上の高湿度領域における吸着量は、相対湿度の上昇とともに増加し、相対湿度６０％における吸着量と相対湿度９５％における吸着量の差は、２４７ｗｔ％であるのに対し、イモゴライトでは約５３％、非晶質イモゴライトでは約６ｗｔ％、プロトイモゴライトでは約６５ｗｔ％であった。
以上の結果より、本実施例のプロトイモゴライトとリン酸の複合化物からなる非晶質物質は、相対湿度１０〜６０％の中湿度領域と相対湿度６０％以上の高湿度領域の両方の領域において優れた吸着特性を有し、特に、相対湿度６０％以上における吸着量と相対湿度９５％における吸着量との差が２００ｗｔ％以上であるという、優れた吸着特性を有するものであることが明らかとなった。
(Water vapor adsorption evaluation)
In Example 1, an amorphous substance composed of a composite of protoimogolite and phosphoric acid obtained with an addition amount of phosphoric acid of 2 mL, imogolite obtained in Comparative Example 1, and amorphous imogolite obtained in Comparative Example 2 For the protomolygolite obtained in Comparative Example 3, the water vapor adsorption evaluation was performed from the water vapor adsorption isotherm measured by Belsorp18 manufactured by Nippon Bell Co., Ltd. FIG. 6 shows the result. In the figure, ◆, ◇, ▲, and Δ respectively show the results of the amorphous substance, imogolite, amorphous imogolite, and protomogolite that are a composite of protoimogolite and phosphoric acid of the present invention.
In general, the operating range in the desiccant air conditioning is a range of 10 to 60% relative humidity. In FIG. 6, the difference between the adsorption amount at 10% relative humidity and the adsorption amount at 60% relative humidity is 30. Compared to 2 wt%, the imogolite of Comparative Example 1 increased by about 13 wt%, the amorphous imogolite of Comparative Example 2 increased by about 7 wt%, and the Protoimogolite of Comparative Example 3 increased by about 22 wt%.
In addition, in the amorphous substance composed of a complex of protomogolite and phosphoric acid of this example, the amount of adsorption in a high humidity region where the relative humidity is 60% or more increases with an increase in the relative humidity, and the adsorption at a relative humidity of 60%. The difference between the amount and the amount adsorbed at 95% relative humidity was 247 wt%, whereas imogolite was about 53%, amorphous imogolite was about 6 wt%, and protomogolite was about 65 wt%.
From the above results, the amorphous substance composed of the composite of protoimogolite and phosphoric acid of this example is in both the medium humidity region of relative humidity 10-60% and the high humidity region of relative humidity 60% or more. It is clear that it has excellent adsorption characteristics, in particular, it has excellent adsorption characteristics that the difference between the adsorption amount at a relative humidity of 60% or more and the adsorption amount at a relative humidity of 95% is 200 wt% or more. became.
本発明は、中湿度および高湿度領域において高性能な吸着性を有するプロトイモゴライトとリン酸の複合化物からなる非晶質物質であり、デシカント空調用の除湿剤や結露防止剤のみならず、有害汚染物質吸着剤、脱臭剤、さらには二酸化炭素やメタンなどのガス貯蔵剤を提供するものとして有用である。 The present invention is an amorphous substance composed of a composite of protomogolite and phosphoric acid having high performance adsorbability in medium and high humidity ranges, and is not only dehumidifying and anti-condensing agents for desiccant air conditioning. It is useful for providing pollutant adsorbents, deodorizers, and gas storage agents such as carbon dioxide and methane.
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