JP2016159225A - Aldehydes remover using ruthenium (fcc) carrier - Google Patents
Aldehydes remover using ruthenium (fcc) carrier Download PDFInfo
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- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title abstract description 7
- 150000001299 aldehydes Chemical class 0.000 title abstract 5
- 239000002245 particle Substances 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 239000010457 zeolite Substances 0.000 claims abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTZYCRSRNSTRGC-LNTINUHCSA-K (z)-4-oxopent-2-en-2-olate;ruthenium(3+) Chemical compound [Ru+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O RTZYCRSRNSTRGC-LNTINUHCSA-K 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 239000003223 protective agent Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical group OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 208000008842 sick building syndrome Diseases 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
Abstract
Description
本発明は、Ｒｕ（ｆｃｃ）担持体を用いたアルデヒド類除去材に関するものである。 The present invention relates to an aldehyde removing material using a Ru (fcc) carrier.
従来より、建物の室内や自動車の車内等でのタバコ臭の主成分であるアセトアルデヒド、あるいは、シックハウス症候群の原因物質として知られているホルムアルデヒド等の除去を目的として、様々な吸着剤の検討がなされている。 Conventionally, various adsorbents have been studied for the purpose of removing acetaldehyde, which is a main component of tobacco odor, in buildings and in automobiles, or formaldehyde, which is known to cause sick house syndrome. ing.
その中でも活性炭は、ＶＯＣ（Volatile Organic Compounds）等を吸着する材料として知られているが、低分子で極性の高い有機物（例えばアセトアルデヒド、ホルムアルデヒド等）を除去することは困難とされている。そこで、上記用途に用いる際は、活性炭にアミン類を担持させて吸着性能を高めることが知られている（特許文献１）。 Among them, activated carbon is known as a material that adsorbs VOC (Volatile Organic Compounds) and the like, but it is difficult to remove organic substances having a low molecular weight and high polarity (for example, acetaldehyde and formaldehyde). Then, when using for the said use, it is known to carry | support an amine on activated carbon and to improve adsorption | suction performance (patent document 1).
しかしながら、上述のアミン類を担持する技術は、担持アミン類の状態が不安定であることから、熱的および経時的な化学変化による失活が起こりやすく、長期的に高い除去性能を保持することは困難であるという問題がある。 However, the above-described technology for supporting amines is unstable in the state of the supported amines, so that it tends to be deactivated due to thermal and chemical changes over time, and maintains high removal performance over the long term. There is a problem that is difficult.
一方、ＶＯＣ除去を目的として、酸化触媒を用いる方法が近年注目されている。前記酸化触媒として、例えば白金を担持した活性炭やアルミナが挙げられる（特許文献２、非特許文献１）。このような白金を担持した酸化触媒は、活性が高く、アルデヒド類の除去にも高い性能を示す。しかし、白金等の貴金属はコストが高く、より安価な触媒または金属の使用が求められているのが現状である。 On the other hand, for the purpose of removing VOCs, a method using an oxidation catalyst has recently attracted attention. Examples of the oxidation catalyst include activated carbon and alumina carrying platinum (Patent Document 2, Non-Patent Document 1). Such an oxidation catalyst supporting platinum has high activity and high performance in removing aldehydes. However, noble metals such as platinum are expensive and currently require the use of cheaper catalysts or metals.
その白金代替として、ルテニウム（Ｒｕ）が用いられるようになってきた。Ｒｕは白金等よりも安価であり、酸化触媒としても活性があることわかっているが、通常、六方最密充填構造（ｈｃｐ）を取るルテニウムの活性を出すには、高温での使用が必要となってくる。 Ruthenium (Ru) has come to be used as an alternative to platinum. Ru is cheaper than platinum and is known to be active as an oxidation catalyst, but normally it needs to be used at a high temperature in order to produce ruthenium having a hexagonal close-packed structure (hcp). It becomes.
本発明は、六方最密充填構造（ｈｃｐ）を取るルテニウム粒子担持体よりも低い温度で、アルデヒド類を効率よく除去できるＲｕ担持体を用いたアルデヒド類除去材の提供を課題として掲げた。 An object of the present invention is to provide a material for removing aldehydes using a Ru carrier that can efficiently remove aldehydes at a temperature lower than that of a ruthenium particle carrier having a hexagonal close-packed structure (hcp).
本発明者らは上記の課題を解決するために鋭意研究した結果、遂に本発明を完成するに到った。すなわち本発明は、以下の通りである。
１．面心立方格子構造を取るＲｕ（ｆｃｃ）粒子と担体とから構成されるＲｕ（ｆｃｃ）担持体を用いたことを特徴とするアルデヒド類除去材。
２．前記担体が、活性炭、活性炭素繊維、アルミナ、シリカ、ゼオライト、複合酸化物および多孔性金属錯体よりなる群から選択される担体である上記１に記載のアルデヒド類除去材。
As a result of intensive studies to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention is as follows.
1. An aldehyde removal material characterized by using a Ru (fcc) carrier comprising Ru (fcc) particles having a face-centered cubic lattice structure and a carrier.
2. 2. The aldehyde removing material according to 1 above, wherein the carrier is a carrier selected from the group consisting of activated carbon, activated carbon fiber, alumina, silica, zeolite, composite oxide and porous metal complex.
本発明によるアルデヒド類除去材は、面心立方格子構造を取るＲｕ（ｆｃｃ）粒子と担体とから構成されるＲｕ（ｆｃｃ）担持体を用いるため、通常、六方最密充填構造（ｈｃｐ）を取るＲｕ（ｈｃｐ）担持体よりも低い温度で、アルデヒド類を効率よく除去することができる。 Since the aldehyde removing material according to the present invention uses a Ru (fcc) carrier composed of Ru (fcc) particles having a face-centered cubic lattice structure and a carrier, it usually has a hexagonal close packed structure (hcp). Aldehydes can be efficiently removed at a temperature lower than that of the Ru (hcp) carrier.
以下、本発明を詳細に説明する。
本発明のアルデヒド類除去材は、面心立方格子構造を取るＲｕ（ｆｃｃ）粒子と担体とから構成されるＲｕ（ｆｃｃ）担持体を用いることを特徴とする。
Hereinafter, the present invention will be described in detail.
The aldehyde removal material of the present invention is characterized by using a Ru (fcc) carrier composed of Ru (fcc) particles having a face-centered cubic lattice structure and a carrier.
ルテニウム粒子は通常、六方最密充填構造（ｈｃｐ）を取る。このＲｕ（ｈｃｐ）粒子では活性を出すための温度が高いが、本発明の面心立方格子構造を取るＲｕ（ｆｃｃ）粒子は、８０℃でも良好なアルデヒド除去率を示す。このＲｕ（ｆｃｃ）粒子は、原料としてトリス（アセチルアセトナト）ルテニウム（ＩＩＩ）を用いることで合成することができる。原料として塩化ルテニウム（ＩＩＩ）等のルテニウム塩を用いた場合は、六方最密充填構造を取るＲｕ（ｈｃｐ）粒子が得られ、面心立方格子構造を取るＲｕ（ｆｃｃ）粒子は得られない。なお、六方最密充填構造（ｈｃｐ）か面心立方格子構造（ｆｃｃ）かは、粉末Ｘ線回折で分析することができる。 Ruthenium particles usually have a hexagonal close packed structure (hcp). The Ru (hcp) particles have a high temperature for activation, but the Ru (fcc) particles having the face-centered cubic lattice structure of the present invention show a good aldehyde removal rate even at 80 ° C. The Ru (fcc) particles can be synthesized by using tris (acetylacetonato) ruthenium (III) as a raw material. When a ruthenium salt such as ruthenium (III) chloride is used as a raw material, Ru (hcp) particles having a hexagonal close-packed structure can be obtained, and Ru (fcc) particles having a face-centered cubic lattice structure cannot be obtained. Whether the hexagonal close-packed structure (hcp) or the face-centered cubic lattice structure (fcc) can be analyzed by powder X-ray diffraction.
本発明に用いられる担体としては、活性炭、活性炭素繊維（ＡＣＦ）、アルミナ、シリカ、ゼオライト、複合酸化物、多孔性金属錯体（Ｐｏｒｏｕｓ Ｃｏｏｒｄｉｎａｔｉｏｎ Ｐｏｌｙｍｅｒｓ、或いは、Ｍｅｔａｌ Ｏｒｇａｎｉｃ Ｆｒａｍｅｗｏｒｋｓとも称される）などが挙げられる。複合酸化物としては、セリウムを含む複合酸化物が好ましく、例えば、セリア−ジルコニア複合酸化物などが挙げられる。 Examples of the carrier used in the present invention include activated carbon, activated carbon fiber (ACF), alumina, silica, zeolite, composite oxide, porous metal complex (also referred to as Porous Coordination Polymers or Metal Organic Frameworks), and the like. It is done. The composite oxide is preferably a composite oxide containing cerium, and examples thereof include ceria-zirconia composite oxide.
Ｒｕ（ｆｃｃ）粒子を担体に担持させる方法としては、所望の特性が得られる手法であれば特に制限はされないが、例えばポリビニルピロリドン（ＰＶＰ）等の保護剤で粒子をコートしながらＲｕ（ｆｃｃ）ナノ粒子の前駆体であるトリス（アセチルアセトナト）ルテニウム（ＩＩＩ）におけるＲｕイオンを還元性溶媒中で還元処理することにより、Ｒｕ（ｆｃｃ）ナノ粒子を先に合成し、後工程でＲｕ（ｆｃｃ）粒子を分散させた溶媒中へ担体を加え、溶媒を蒸発乾固させる蒸発乾固法という方法がある。また、Ｒｕ（ｆｃｃ）ナノ粒子の前駆体であるトリス（アセチルアセトナト）ルテニウム（ＩＩＩ）におけるＲｕイオンとそれを担持する担体を、還元性溶媒中に共存させ、Ｒｕイオンを還元処理する方法もある。還元性溶媒としてはトリエチレングリコールが好ましく、１５０〜２５０℃で数時間加熱して還元することが好ましい。担体が保護剤と親和性が弱い場合を除いては、すべての担体において前者の蒸発乾固法が使用できる。細孔径の小さな担体（例えば活性炭素繊維、多孔性金属錯体等）に関しては、Ｒｕ粒子径よりも細孔径が小さい場合が考えられるので、後者の担体共存下でＲｕイオンを還元処理する方法が好ましい。得られるＲｕ（ｆｃｃ）ナノ粒子は、だいたい３〜５ｎｍとなる。 The method for supporting the Ru (fcc) particles on the carrier is not particularly limited as long as the desired characteristics can be obtained. For example, Ru (fcc) while coating the particles with a protective agent such as polyvinylpyrrolidone (PVP). The Ru (fcc) nanoparticles are synthesized first by reducing the Ru ions in the tris (acetylacetonato) ruthenium (III), which is the precursor of the nanoparticles, in a reducing solvent. There is a method called an evaporation-drying method in which a carrier is added to a solvent in which particles are dispersed and the solvent is evaporated to dryness. Also, there is a method in which Ru ions in Tris (acetylacetonato) ruthenium (III), which is a precursor of Ru (fcc) nanoparticles, coexist in a reducing solvent to reduce Ru ions. is there. The reducing solvent is preferably triethylene glycol, and is preferably reduced by heating at 150 to 250 ° C. for several hours. The former evaporation-drying method can be used for all carriers except when the carrier has a weak affinity with the protective agent. For a carrier having a small pore size (for example, activated carbon fiber, porous metal complex, etc.), the pore size may be smaller than the Ru particle size. Therefore, the method of reducing the Ru ions in the presence of the latter carrier is preferable. . The resulting Ru (fcc) nanoparticles are approximately 3-5 nm.
担体へのＲｕ担持量としては、Ｒｕ粒子が担体に対して０．１〜１０質量％で担持されるように、Ｒｕ粒子の量やＲｕイオンの濃度を調整することが好ましい。より好ましくは１〜５質量％である。１０質量％を超える担持量では、担体に対する金属濃度が高すぎるため、担体に担持はされるが、高分散状態で担持されにくくなるため、好ましくない。 As the amount of Ru supported on the carrier, it is preferable to adjust the amount of Ru particles and the concentration of Ru ions so that Ru particles are supported at 0.1 to 10% by mass with respect to the carrier. More preferably, it is 1-5 mass%. When the loading amount exceeds 10% by mass, the metal concentration with respect to the carrier is too high, and thus the carrier is supported. However, it is difficult to carry the carrier in a highly dispersed state, which is not preferable.
以下、実施例を挙げて本発明をより具体的に説明する。本発明は以下の実施例によって制限を受けるものではなく、前記、後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。なお、実施例および比較例における評価は、以下のようにして行った。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples, and can of course be implemented with appropriate modifications within a range that can be adapted to the above-described gist. Included in the range. In addition, evaluation in an Example and a comparative example was performed as follows.
＜粉末Ｘ線回折測定＞
得られた粒子について、粉末Ｘ線回折装置（ブルカー・エイエックスエス社製「ＮＥＷ Ｄ８ ＡＤＶＡＮＣＥ」を用いて、対称反射法で測定した。測定条件を以下に示す。
１）Ｘ線源：ＣｕＫα（λ＝１．５４１８Å）４０ｋＶ ２００ｍＡ
２）ゴニオメーター：縦型ゴニオメーター
３）検出器：シンチレーションカウンター
４）回折角（２θ）範囲：３〜９０°
５）スキャンステップ：０．０５°
６）積算時間：０．５秒／ステップ
７）スリット：発散スリット＝０．５°、受光スリット＝０．１５ｍｍ、散乱スリット＝０．５°
<Powder X-ray diffraction measurement>
The obtained particles were measured by a symmetric reflection method using a powder X-ray diffractometer (“NEW D8 ADVANCE” manufactured by Bruker AXS Inc. Measurement conditions are shown below.
1) X-ray source: CuKα (λ = 1.5418Å) 40 kV 200 mA
2) Goniometer: Vertical goniometer 3) Detector: Scintillation counter 4) Diffraction angle (2θ) range: 3-90 °
5) Scan step: 0.05 °
6) Integration time: 0.5 sec / step 7) Slit: Diverging slit = 0.5 °, Receiving slit = 0.15 mm, Scattering slit = 0.5 °
＜透過型電子顕微鏡（ＴＥＭ）観察＞
透過型電子顕微鏡（日立製作所製「ＨＴ７７００」、または日本電子社製「ＪＥＭ−２２００ＦＳ」）を用いて、得られたＲｕ粒子を観察した。
<Transmission electron microscope (TEM) observation>
The obtained Ru particles were observed using a transmission electron microscope (“HT7700” manufactured by Hitachi, Ltd. or “JEM-2200FS” manufactured by JEOL Ltd.).
＜アルデヒド類ガス流通系吸着試験＞
Ｒｕ担持体０．２２９ｃｃをカラムに充填し、試験ガスを０．２Ｌ／ｍｉｎで流通させた。試料の入口・出口でのガス濃度を、ホルムアルデメータｈｔＶ（株式会社ジェイエムエス）を用いて測定し、その比から除去率を算出した。具体的には、まず、２５℃雰囲気下で測定を開始し、１時間後、入口・出口でのガス濃度を測定し、除去率を算出した。次に続けて、８０℃雰囲気下に置き、さらに１時間後、入口・出口でのガス濃度を測定し、除去率を算出した。計２時間の測定を行った。評価条件の詳細を以下に示す。
１）測定雰囲気：２５℃または８０℃雰囲気下
２）圧力：常圧
３）試験ガス組成：ホルムアルデヒド濃度３ｐｐｍ（２５℃、５０％ＲＨ空気希釈）
４）空間速度：５７０，０００ｈｒ-1
５）平均粒子径（測定サンプルの粒子サイズ）：３５５〜５００μｍ
<Aldehyde gas flow system adsorption test>
The column was filled with 0.229 cc of Ru support and the test gas was circulated at 0.2 L / min. The gas concentration at the inlet / outlet of the sample was measured using a formal demeter htV (JMS Co., Ltd.), and the removal rate was calculated from the ratio. Specifically, first, measurement was started under an atmosphere of 25 ° C., and after 1 hour, the gas concentration at the inlet / outlet was measured, and the removal rate was calculated. Subsequently, it was placed in an atmosphere at 80 ° C., and after another hour, the gas concentration at the inlet / outlet was measured, and the removal rate was calculated. Measurement was performed for a total of 2 hours. Details of the evaluation conditions are shown below.
1) Measurement atmosphere: 25 ° C. or 80 ° C. atmosphere 2) Pressure: normal pressure 3) Test gas composition: Formaldehyde concentration 3 ppm (25 ° C., 50% RH air dilution)
4) Space velocity: 570,000 hr -1
5) Average particle diameter (particle size of measurement sample): 355 to 500 μm
＜実施例１＞
トリス（アセチルアセトナト）ルテニウム（ＩＩＩ）１．６７３ｇ（４．２ｍｍｏｌ）と保護剤としてのポリビニルピロリドン０．２２２ｇ（２．０ｍｍｏｌ）を還元性溶媒としてのトリエチレングリコール５０ｍｌに入れ、撹拌しながら２００℃で３時間加熱し、面心立方格子構造を取るＲｕ（ｆｃｃ）粒子を合成した。そのＴＥＭ画像を図１、粉末Ｘ線回折チャートを図２に示す。図１のＴＥＭ画像から４．１ｎｍ〜４．６ｎｍ程度の粒子を形成していることが確認できた。また、粉末Ｘ線回折のチャートより、面心立方格子構造を取るＲｕ（ｆｃｃ）粒子が合成されていることが確認できた。
次に上記で合成したＲｕ（ｆｃｃ）粒子１５ｍｇを蒸留水３０ｍｌに分散させ、そこに予め、大気中７００℃で５時間加熱処理したγ−アルミナ１ｇを加え、室温で１日撹拌した。その懸濁液を真空下６０℃で濃縮乾固させ、１質量％Ｒｕ（ｆｃｃ）担持γ−アルミナを得た。プレスによる加圧とふるいによる分級によって、粒径を３５５〜５００μｍに揃えた。その後、アルデヒド類ガス流通系吸着試験を行った。結果を表１に示す。
<Example 1>
1.673 g (4.2 mmol) of tris (acetylacetonato) ruthenium (III) and 0.222 g (2.0 mmol) of polyvinylpyrrolidone as a protective agent were placed in 50 ml of triethylene glycol as a reducing solvent, and the mixture was stirred while stirring. Ru (fcc) particles having a face-centered cubic lattice structure were synthesized by heating at 0 ° C. for 3 hours. The TEM image is shown in FIG. 1, and the powder X-ray diffraction chart is shown in FIG. It was confirmed from the TEM image in FIG. 1 that particles of about 4.1 nm to 4.6 nm were formed. Further, it was confirmed from the powder X-ray diffraction chart that Ru (fcc) particles having a face-centered cubic lattice structure were synthesized.
Next, 15 mg of the Ru (fcc) particles synthesized above were dispersed in 30 ml of distilled water, and 1 g of γ-alumina that had been heat-treated in the atmosphere at 700 ° C. for 5 hours in advance was added thereto, followed by stirring at room temperature for 1 day. The suspension was concentrated to dryness at 60 ° C. under vacuum to obtain 1% by mass Ru (fcc) -carrying γ-alumina. The particle size was adjusted to 355 to 500 μm by pressing with a press and classification by sieving. Thereafter, an aldehyde gas flow system adsorption test was conducted. The results are shown in Table 1.
＜比較例１＞
塩化ルテニウム１．０９８ｇ（４．２ｍｍｏｌ）と保護剤としてのポリビニルピロリドン０．２２２ｇ（２．０ｍｍｏｌ）を還元性溶媒としてのトリエチレングリコール５０ｍｌに入れ、撹拌しながら２００℃で３時間加熱し、六方最密充填構造を取るＲｕ（ｈｃｐ）粒子を合成した。そのＴＥＭ画像を図３、粉末Ｘ線回折チャートを図４に示す。図３のＴＥＭ画像から３．５ｎｍ〜４．５ｎｍ程度の粒子を形成していることが確認できた。また、粉末Ｘ線回折チャートより、六方最密充填構造を取るＲｕ（ｈｃｐ）粒子が合成されていることが確認できた。
次に上記で合成したＲｕ（ｈｃｐ）粒子１５ｍｇを蒸留水３０ｍｌに分散させ、そこに予め、大気中７００℃で５時間加熱処理したγ−アルミナ１ｇを加え、室温で１日撹拌した。その懸濁液を真空下６０℃で濃縮乾固させ、１質量％Ｒｕ（ｈｃｐ）担持γ−アルミナを得た。プレスによる加圧とふるいによる分級によって、粒径を３５５−５００μｍに揃えた。その後、アルデヒド類ガス流通系吸着試験を行った。結果を表１に示す。
<Comparative Example 1>
Ruthenium chloride (1.098 g, 4.2 mmol) and polyvinylpyrrolidone (0.222 g, 2.0 mmol) as a protective agent were placed in 50 ml of triethylene glycol as a reducing solvent and heated at 200 ° C. with stirring for 3 hours. Ru (hcp) particles having a close packed structure were synthesized. The TEM image is shown in FIG. 3, and the powder X-ray diffraction chart is shown in FIG. It was confirmed from the TEM image of FIG. 3 that particles of about 3.5 nm to 4.5 nm were formed. Moreover, it was confirmed from the powder X-ray diffraction chart that Ru (hcp) particles having a hexagonal close-packed structure were synthesized.
Next, 15 mg of the Ru (hcp) particles synthesized above were dispersed in 30 ml of distilled water, and 1 g of γ-alumina that had been heat-treated in the atmosphere at 700 ° C. for 5 hours in advance was added thereto, followed by stirring at room temperature for 1 day. The suspension was concentrated to dryness at 60 ° C. under vacuum to obtain 1% by mass Ru (hcp) -carrying γ-alumina. The particle size was adjusted to 355-500 μm by pressurization and classification by sieving. Thereafter, an aldehyde gas flow system adsorption test was conducted. The results are shown in Table 1.
表１から明らかなように、Ｒｕ（ｆｃｃ）粒子を担持させた担持体を用いた実施例１では、８０℃でのホルムアルデヒド除去率が４４％と高い。比較例１ではより高温にしなければ４０％以上の除去率が達成できないことから、本発明の有用性は明らかである。 As can be seen from Table 1, in Example 1 using a support on which Ru (fcc) particles are supported, the formaldehyde removal rate at 80 ° C. is as high as 44%. In Comparative Example 1, since the removal rate of 40% or more cannot be achieved unless the temperature is increased, the usefulness of the present invention is clear.
本発明のアルデヒド類除去材は、室内や車内のアルデヒド類を除去する効果に優れているので、より快適な空間を提供し、シックハウス症候群等の疾病を減少させることができる。また面心立方格子構造を取るＲｕ（ｆｃｃ）担持体を用いているため、Ｐｔ系触媒より安価であり、産業界に大きく寄与することができると考える。 Since the aldehyde removing material of the present invention is excellent in the effect of removing aldehydes in a room or in a vehicle, it can provide a more comfortable space and reduce diseases such as sick house syndrome. Further, since a Ru (fcc) carrier having a face-centered cubic lattice structure is used, it is cheaper than a Pt-based catalyst and can be considered to contribute greatly to the industry.
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