JP2020065997A - Aqueous ammonia treatment using ammonia decomposition catalyst in dark place liquid - Google Patents
Aqueous ammonia treatment using ammonia decomposition catalyst in dark place liquid Download PDFInfo
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- JP2020065997A JP2020065997A JP2018213311A JP2018213311A JP2020065997A JP 2020065997 A JP2020065997 A JP 2020065997A JP 2018213311 A JP2018213311 A JP 2018213311A JP 2018213311 A JP2018213311 A JP 2018213311A JP 2020065997 A JP2020065997 A JP 2020065997A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000007788 liquid Substances 0.000 title claims abstract description 48
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 title abstract description 36
- 238000000354 decomposition reaction Methods 0.000 title description 17
- -1 four elements of W Chemical class 0.000 claims abstract description 31
- 150000003658 tungsten compounds Chemical class 0.000 claims abstract description 19
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 33
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000908 ammonium hydroxide Substances 0.000 abstract description 9
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 description 45
- 239000002245 particle Substances 0.000 description 42
- 235000011114 ammonium hydroxide Nutrition 0.000 description 34
- 239000013078 crystal Substances 0.000 description 26
- 239000011521 glass Substances 0.000 description 24
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 18
- 239000007789 gas Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
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- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 15
- 238000005259 measurement Methods 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
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- 239000002184 metal Substances 0.000 description 10
- 229910000365 copper sulfate Inorganic materials 0.000 description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 9
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
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- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- 239000004743 Polypropylene Substances 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
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- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、液中において暗所、室温においてアンモニア水を分解する触媒効果を有する材料又はそれを用いた部材に関するものである。The present invention relates to a material having a catalytic effect of decomposing ammonia water in a liquid in a dark place at room temperature, or a member using the material.
光のある環境においてアンモニアを分解する触媒として、国内では酸化チタンが光触媒として今から２０年ほど前に研究が活発に行われていた。酸化チタンは紫外線領域にのみに反応するために、太陽光に対しては水を分解するほどに分子の分解を行うことが出来る。価電子帯の真空順位が低く、電子を取り出す際に必要とするエネルギーが大きく、しかもバンドギャップが大きいため、約３ｅＶ程度の励起エネルギーが必要とされていた。光の波長では３８０ｎｍ程度以下に相当する。このために人の視覚が認識できる光の波長域４００〜７００ｎｍでは光触媒性能を持っていなかった。この酸化チタンは水溶液中においても紫外線領域であればアンモニアを分解することが出来る。Titanium oxide was used as a photocatalyst in Japan as a catalyst for decomposing ammonia in a light environment, and research was actively conducted about 20 years ago. Since titanium oxide reacts only in the ultraviolet region, it can be decomposed into molecules as much as water is decomposed against sunlight. Since the vacuum order of the valence band is low, the energy required for extracting electrons is large, and the band gap is large, an excitation energy of about 3 eV has been required. The wavelength of light corresponds to about 380 nm or less. For this reason, it has no photocatalytic performance in the wavelength range of 400 to 700 nm of light that can be recognized by human eyes. This titanium oxide can decompose ammonia even in an aqueous solution in the ultraviolet range.
昨今、室内の光源が半導体のＬＥＤとなり、紫外線を持たない可視光のみと光源となっていることから、従来型の光触媒である酸化チタンではＬＥＤの光源では十分な光触媒性能が得られていない。酸化チタンの改良として窒素雰囲気中で熱処理、またはプラズマ雰囲気でＮドープを行う方法や、または酸化チタンを合成する際に予めＮｂ等の元素を添加してＮｂドープの酸化チタンを合成する方法が検討されてきた。In recent years, since the indoor light source is a semiconductor LED and only visible light without ultraviolet rays is used as a light source, conventional titanium oxide, which is a photocatalyst, does not have sufficient photocatalytic performance with an LED light source. As a modification of titanium oxide, a method of performing heat treatment in a nitrogen atmosphere or N-doping in a plasma atmosphere, or a method of synthesizing titanium oxide by adding an element such as Nb in advance to synthesize Nb-doped titanium oxide is examined. It has been.
酸化チタンの分子分解の酸化力は価電子帯が深い位置にあり、電子が伝導体に励起された後のホールが非常に強い電子吸引力となり、接触した分子から電子を奪う結果、分子が酸化されて分解する。したがって、一つの研究の流れとしては常に伝導体にある電子を他に移動させることや、元々触媒性のあるような金属や酸化物を酸化チタン表面に部分的に形成して光触媒性能が改善される報告も多数ある。具体的にはＰｄ、Ｒｕ、Ｐｔ、Ｎｉ等を酸化チタン表面に形成することが一般的である。The oxidation power of the molecular decomposition of titanium oxide is such that the valence band is at a deep position, and the holes after the electrons are excited by the conductor have a very strong electron-attracting force. Be disassembled. Therefore, one research trend is to always move electrons in the conductor to another, and to partially improve the photocatalytic performance by partially forming an originally catalytic metal or oxide on the titanium oxide surface. There are also many reports. Specifically, it is general to form Pd, Ru, Pt, Ni or the like on the titanium oxide surface.
酸化チタンは以前より毒性が心配されてきた経緯がある。そこで、酸化チタンの代替としてバンドギャップが酸化チタンよりも小さく、且つ価電子帯の位置が酸化チタンのように深い位置にあるものが探索されてきた。このような開発経緯の中で酸化タングステンが着目された。酸化タングステンは酸化チタンよりもややバンドギャップが小さめであり、２．８ｅＶ程度のものである。この結果、可視光領域の青色の波長にも吸収を持つ特性があり、可視光応答型の光触媒性能を持っている。酸化タングステンも酸化チタンと同様にＰｄ、Ｒｕ、Ｐｔ、Ｎｉ等を表面に形成することにより触媒性能が改善される。Titanium oxide has historically been concerned about its toxicity. Therefore, as an alternative to titanium oxide, a material having a band gap smaller than that of titanium oxide and a valence band position as deep as titanium oxide has been searched for. Tungsten oxide has attracted attention in the context of such development. The band gap of tungsten oxide is slightly smaller than that of titanium oxide, and is about 2.8 eV. As a result, it has a characteristic of absorbing blue wavelengths in the visible light region as well, and has a visible light responsive photocatalytic performance. Similar to titanium oxide, tungsten oxide also has improved catalytic performance by forming Pd, Ru, Pt, Ni or the like on the surface.
しかしながら、これらの光触媒は暗所において液中にあるアンモニアを分解するということが出来ないため、アンモニアにより汚染された水の浄化方法として、オゾンによる酸化処理やバイオ処理による除去が主体となっていた。However, since these photocatalysts cannot decompose ammonia in the liquid in a dark place, as a purification method of water contaminated by ammonia, removal by ozone oxidation treatment or biotreatment was the main method. .
一般的に用いられる光触媒として酸化チタンや酸化タングステンの場合、光触媒は光の照射状態では液中においてもアンモニアを分解することが出来るが、暗所において液中にあるアンモニアを分解する効果がないという致命的な問題があった。In the case of titanium oxide or tungsten oxide as a commonly used photocatalyst, the photocatalyst can decompose ammonia even in liquid under irradiation of light, but it is not effective in decomposing ammonia in liquid in the dark. There was a fatal problem.
Ｗ，Ｈ，Ｎ，Ｏの四元素を含むことからなるタングステン化合物が暗所の液相中において液中に含まれるアンモニアやアンモニア化合物を分解する触媒として効果があることを発見した。このようなタングステン化合物において、液中に溶存するアンモニアの分解効果を改善する組成として、少なくともＡｕ，Ｐｔ，Ｐｄ，Ａｇ，Ｎｉ，Ｃｕ，Ｎａ，Ｋ，Ｌｉ，Ｃｓの中から１種以上をドープ、または被着させたものからなるタングステン化合物にすることにより可能であることが分かった。このタングステン化合物からなる触媒は光の無い条件で温度が２０から４０℃の範囲においてアンモニア水を分解しアンモニアを減少させることが可能であることを発見した。例えば触媒量として１０ｍｇ均一に担持させた１０ｃｍ角のガラス板を用いて１００ｐｐｍのアンモニア水１００ｃｃの液を入れた容器に浸漬した際に２４時間後のアンモニア水の濃度を大きく減少させることが出来ることを確認した。It has been discovered that a tungsten compound containing four elements of W, H, N and O is effective as a catalyst for decomposing ammonia and ammonia compounds contained in the liquid in the liquid phase in the dark. In such a tungsten compound, at least one of Au, Pt, Pd, Ag, Ni, Cu, Na, K, Li and Cs is doped as a composition for improving the decomposition effect of ammonia dissolved in the liquid. It has been found that this is possible by using a tungsten compound consisting of the above or the deposited one. It was discovered that this catalyst composed of a tungsten compound can decompose ammonia water and reduce ammonia in the temperature range of 20 to 40 ° C. in the absence of light. For example, it is possible to greatly reduce the concentration of ammonia water after 24 hours when it is immersed in a container containing 100 ppm of ammonia water of 100 cc using a glass plate of 10 cm square uniformly supporting 10 mg as a catalyst amount. It was confirmed.
具体的には、上記のタングステン化合物として、（ＮＨ３）ｘ−ｙ・Ｍｙ・ｍＷＯ３・ｒＨ２Ｏ（ｘ−ｙ＞０、ｙ≧０、ｍ＞０、ｒ≧０）、Ｍｙ・ｍＷＯ３・ｒＨ２Ｏ（ｙ＞０、ｍ＞０、ｒ≧０）、（ＮＨ４）２（ｘ−ｙ）・Ｍ２ｙ・（ＷＯ４）ｚ・ｒＨ２Ｏ（ｘ−ｙ＞０、ｙ≧０、ｚ＞０、ｒ≧０）、またはＭｙ・（ＷＯ４）ｚ・ｒＨ２Ｏ（ｙ＞０、ｚ＞０、ｒ≧０）、（ＮＨ４）２（ｘ−ｙ）・Ｍ２ｙ・（ＷＯ４）ｚ・（ＷＯ３）ｑ・ｒＨ２Ｏ（ｘ−ｙ＞０、ｙ≧０、ｚ＞０、ｑ＞０、ｒ≧０）、Ｍｙ・（ＷＯ４）ｚ・（ＷＯ３）ｑ・ｒＨ２Ｏ（ｙ＞０、ｚ＞０、ｑ＞０、ｒ≧０）（Ｍ：Ｌｉ、Ｎａ、Ｋ、Ｃｓ、Ｒｂ）が挙げられる。Specifically, as the tungsten compounds, (NH 3) x-y · M y · mWO 3 · rH 2 O (x-y> 0, y ≧ 0, m> 0, r ≧ 0), M y · mWO 3 · rH 2 O ( y> 0, m> 0, r ≧ 0), (NH 4) 2 (x-y) · M 2y · (WO 4) z · rH 2 O (x-y> 0 , y ≧ 0, z> 0 , r ≧ 0), or M y · (WO 4) z · rH 2 O (y> 0, z> 0, r ≧ 0), (NH 4) 2 (x-y ) · M 2y · (WO 4 ) z · (WO 3) q · rH 2 O (x-y> 0, y ≧ 0, z> 0, q> 0, r ≧ 0), M y · (WO 4 ) Z · (WO 3 ) q · rH 2 O (y> 0, z> 0, q> 0, r ≧ 0) (M: Li, Na, K, Cs, Rb).
前記のタングステン化合物から構成される触媒はそれぞれの化合物単体でも効果はあるが、前記の化合物の中から、少なくとも一種以上を含んだものからなるタングステン化合物触媒が暗所において、液中にあるアンモニアまたは水酸化アンモニウムを分解する触媒機能を持つ。Although the catalyst composed of the above-mentioned tungsten compound is effective even if each compound alone, the tungsten compound catalyst composed of one containing at least one or more of the above compounds is used in a dark place with ammonia in the liquid or It has a catalytic function to decompose ammonium hydroxide.
本発明の触媒材料を用いることにより光がない条件で液中にあるアンモニア、水酸化アンモニウムを分解する性能を有するために、従来浄水に問題となっていた水処理用途として浄水中に溶存するアンモニアや水酸化アンモニウムを分解する処理に有効である。Ammonia dissolved in purified water as a water treatment application which has been a problem in conventional purified water because it has the ability to decompose ammonia and ammonium hydroxide in the liquid in the absence of light by using the catalyst material of the present invention. It is effective in the treatment of decomposing ammonium hydroxide.
酸化タングステンを作る過程でパラタングステン酸アンモニウムを用いて水溶液中で加熱しながら分解反応を行った際に、塩酸添加した場合において無色透明の液体が形成された。この液体に含まれる化合物は様々な試験から液温が２０℃にした状態においても、光の無い暗所において液体中のアンモニアや水酸化アンモニウムを分解する触媒性能を持つことが分かった。この成分を分析した結果、Ｗ，Ｈ，Ｎ，Ｏの四元素を含むことからなるタングステン化合物であることが分かった。具体的にはタングステン酸アンモニウム化合物であることが分かり、パラタングステン酸アンモニウムに近い組成比を持つものであった。この方法で作製されたタングステン化合物はＸ線結晶構造解析装置を用いて評価した結果、主に（ＮＨ４）６・Ｈ２（Ｗ３Ｏ１０）４・２０Ｈ２Ｏ、５（ＮＨ４）２Ｏ・１２ＷＯ３・１１Ｈ２Ｏ、５（ＮＨ４）２Ｏ・１２ＷＯ３・７Ｈ２Ｏ、（ＮＨ４）１０・Ｗ１２Ｏ４１・５Ｈ２Ｏ、もしくは（ＮＨ４）１０・Ｈ２Ｗ１２Ｏ４２・４Ｈ２Ｏに示されるようなアンモニアを含んだ含水結晶であった。この結晶にアルカリ系の水酸化物を添加することによりアンモニウムイオンサイトは例えばナトリウムイオンのようなアルカリ金属イオンと容易に置換反応が働いて、タングステン酸アルカリ金属塩の形態を容易に合成することが可能である。また、市販されているパラタングステン酸アンモニウムも同様にアルカリ金属イオンでアンモニアイオンを置換することにより同様な効果がある。A colorless transparent liquid was formed when hydrochloric acid was added when the decomposition reaction was performed while heating in an aqueous solution using ammonium paratungstate during the process of making tungsten oxide. From various tests, it was found from various tests that the compound contained in this liquid has a catalytic property of decomposing ammonia and ammonium hydroxide in the liquid in a dark place without light even when the liquid temperature is 20 ° C. As a result of analyzing this component, it was found to be a tungsten compound containing four elements of W, H, N and O. Specifically, it was found to be an ammonium tungstate compound, and had a composition ratio close to that of ammonium paratungstate. The tungsten compound produced by this method was evaluated using an X-ray crystal structure analyzer. As a result, mainly (NH 4 ) 6 · H 2 (W 3 O 10 ) 4 · 20H 2 O, 5 (NH 4 ) 2 O · 12WO 3 · 11H 2 O , 5 (NH 4) 2 O · 12WO 3 · 7H 2 O, (NH 4) 10 · W 12 O 41 · 5H 2 O or (NH 4), 10 · H 2 W 12 O 42 · 4H were 2 O in ammonia laden hydrous crystalline as shown. By adding an alkaline hydroxide to this crystal, the ammonium ion site easily undergoes a substitution reaction with an alkali metal ion such as sodium ion, so that a form of an alkali metal tungstate can be easily synthesized. It is possible. Further, commercially available ammonium paratungstate also has similar effects by substituting ammonia ions with alkali metal ions.
上記の触媒性能を持つタングステン化合物を具体的に示すと、例えばＮＨ４Ｗ３Ｏ９，Ｎａ２ＷＯ４，Ｎａ２Ｗ２Ｏ７，Ｎａ０．７４ＷＯ３，Ｎａ０．５４ＷＯ３，ＨＮａ５Ｗ６Ｏ２１（Ｈ２Ｏ）１０，Ｎａ５Ｗ６Ｏ２１（Ｈ２Ｏ）１３，Ｎａ２（ＷＯ４）（Ｈ２Ｏ）２，Ｈ２Ｋ１０Ｗ１２Ｏ４２（Ｈ２Ｏ）７．５，Ｈ２Ｋ８Ｗ１２Ｏ４０（Ｈ２Ｏ）１４，Ｈ５Ｋ９Ｗ１２Ｏ４０（Ｈ２Ｏ）１２，Ｋ２Ｗ２Ｏ３（Ｏ２）４（Ｈ２Ｏ）４，Ｎａ２（ＷＯ４）（Ｈ２Ｏ）２，Ｈ４Ｒｂ６Ｗ１２Ｏ４０（Ｈ２Ｏ）４，Ｌｉ１．４４Ｗ４Ｏ１２，Ｌｉ２Ｗ２Ｏ７，Ｌｉ２（ＷＯ４）の組成、もしくは結晶構造を持つものが例として挙げられる。このような化合物においてＮａを一部Ｌｉに置換したり、Ｋを一部Ｌｉに置換したり、ＲｂをＮａに一部置換したりすることも可能であり、置換元素や量に限定されるものではなく、主たる組成比に近いものか、または主たる組成比に近く、且つ上記化合物を構成する結晶構造があれば良い。また少量であれば二価や三価の金属元素で置換が可能であり、本特性を維持する、または改善することも可能である。更に酸素欠損が１ａｔ％以下の少量であれば問題はない。Specific examples of the tungsten compound having the above catalytic performance include, for example, NH 4 W 3 O 9 , Na 2 WO 4 , Na 2 W 2 O 7 , Na 0.74 WO 3 , Na 0.54 WO 3 , HNa. 5 W 6 O 21 (H 2 O) 10 , Na 5 W 6 O 21 (H 2 O) 13 , Na 2 (WO 4 ) (H 2 O) 2 , H 2 K 10 W 12 O 42 (H 2 O ) 7.5, H 2 K 8 W 12 O 40 (H 2 O) 14, H 5 K 9 W 12 O 40 (H 2 O) 12, K 2 W 2 O 3 (O 2) 4 (H 2 O ) 4 , Na 2 (WO 4 ) (H 2 O) 2 , H 4 Rb 6 W 12 O 40 (H 2 O) 4 , Li 1.44 W 4 O 12 , Li 2 W 2 O 7 , Li 2 ( Examples thereof include those having a composition of WO 4 ) or a crystal structure. In such a compound, it is possible to partially replace Na with Li, partially replace K with Li, or partially replace Rb with Na, and the elements and amounts are limited. However, it is sufficient if the crystal structure is close to the main composition ratio, or close to the main composition ratio, and has a crystal structure that constitutes the compound. Further, if it is a small amount, it can be replaced with a divalent or trivalent metal element, and this characteristic can be maintained or improved. Further, if the oxygen deficiency is a small amount of 1 at% or less, there is no problem.
上記に記載した本発明のタングステン化合物の一般的な組成表現式としては、（ＮＨ３）ｘ−ｙ・Ｍｙ・ｍＷＯ３・ｒＨ２Ｏ（ｘ−ｙ＞０、ｙ≧０、ｍ＞０，ｒ≧０）、Ｍｙ・ｍＷＯ３・ｒＨ２Ｏ（ｙ＞０、ｍ＞０、ｒ≧０）、（ＮＨ４）２（ｘ−ｙ）・Ｍ２ｙ・（ＷＯ４）ｚ・ｒＨ２Ｏ（ｘ−ｙ＞０、ｙ≧０、ｚ＞０、ｒ≧０）またはＭｙ・（ＷＯ４）ｚ・ｒＨ２Ｏ（ｙ＞０，ｚ＞０，ｒ≧０），（ＮＨ４）２（ｘ−ｙ）・Ｍ２ｙ・（ＷＯ４）ｚ・（ＷＯ３）ｑ・ｒＨ２Ｏ（ｘ−ｙ＞０、ｙ≧０、ｚ＞０、ｑ＞０、ｒ≧０）、Ｍｙ・（ＷＯ４）ｚ・（ＷＯ３）ｑ・ｒＨ２Ｏ（ｙ＞０、ｚ＞０、ｑ＞０、ｒ≧０）（Ｍ：Ｌｉ、Ｎａ、Ｋ、Ｃｓ、Ｒｂ）が組成として表現されるものである。以下の表現式でＭと記載されたものはＬｉ、Ｎａ、Ｋ、Ｃｓ、Ｒｂの中から少なくとも１種以上を含んだものとして表現している。この表現式では基本的にはＷ原子にＯが八面体配位した構造にアンモニウムイオンやアルカリ金属イオンを含んだ結晶構造、または非晶質の形態となっている。 この化合物のタングステンの価数はプラス６価に近いことがＸＰＳの結果から確認できている。一例としてＬｉ２ＷＯ４におけるＷの価数を検討するため、ＷＯ３単体を比較例として用いてＷとＯの結合エネルギーをＸ線光電子分光装置（ＪＥＯＬ製ＪＰＳ−９２００Ｓ）で測定した。この結果を図１に示した。この結果よりＷＯ３とほぼ同一の結合エネルギーを持っていることが分かった。（ＮＨ４）０．２５ＷＯ３，Ｎａ０．７４ＷＯ３，Ｎａ０．５４ＷＯ３のようにＷの価数が６価より５価に近くなるものもある。これらの化合物も本発明のものと同等の効果をもっている。The general composition expression of the tungsten compound of the present invention described above, (NH 3) x-y · M y · mWO 3 · rH 2 O (x-y> 0, y ≧ 0, m> 0 , r ≧ 0), M y · mWO 3 · rH 2 O (y> 0, m> 0, r ≧ 0), (NH 4) 2 (x-y) · M 2y · (WO 4) z · rH 2 O (x-y> 0 , y ≧ 0, z> 0, r ≧ 0) or M y · (WO 4) z · rH 2 O (y> 0, z> 0, r ≧ 0), (NH 4) 2 (x-y) · M 2y · (WO 4) z · (WO 3) q · rH 2 O (x-y> 0, y ≧ 0, z> 0, q> 0, r ≧ 0) , M y · (WO 4) z · (WO 3) q · rH 2 O (y> 0, z> 0, q> 0, r ≧ 0) (M: Li, Na, K, Cs, Rb) is It is expressed as a composition. Those expressed as M in the following expression are expressed as containing at least one or more of Li, Na, K, Cs, and Rb. This expression basically has a crystal structure in which an ammonium ion or an alkali metal ion is contained in a structure in which O is octahedrally coordinated with a W atom, or an amorphous form. It has been confirmed from the XPS results that the valence of tungsten in this compound is close to plus 6. As an example, in order to investigate the valence of W in Li 2 WO 4, the binding energy of W and O was measured by an X-ray photoelectron spectrometer (JPS-9200S manufactured by JEOL) using WO 3 alone as a comparative example. The result is shown in FIG. From these results, it was found that they have almost the same binding energy as WO 3 . (NH 4 ) 0.25 WO 3 , Na 0.74 WO 3 , and Na 0.54 WO 3 may have a valence of W closer to 5 than 6 rather than 6. These compounds also have the same effects as those of the present invention.
表現した化学式の具体的な化合物を一例として示す。以下の表現式で示した化合物は単純にＨ２Ｏをないものも含んだものとして表現している。これは加熱温度により部分的に脱水化する現象もあるためである。この際、触媒として水分子として結晶中に含まれる場合とヒドロキシ基とプロトンが結晶中に含まれる場合があり、どちらも結晶構造は全く異なるが、本発明では結晶構造に限定されるものではないので、どちらか一方であるか、または非晶質でも良い。以下に示す一例は非常に単純な組成比のもので記したが、本実施例で用いた化合物例として示したものでは化学式量はもっと大きいものとなっているものが多い。A specific compound of the expressed chemical formula is shown as an example. The compounds represented by the following formulas are simply expressed as including compounds without H 2 O. This is because there is also a phenomenon of partial dehydration depending on the heating temperature. In this case, the catalyst may be contained in the crystal as a water molecule or may be contained in the crystal as a hydroxy group, and the crystal structure of both is completely different, but the present invention is not limited to the crystal structure. Therefore, it may be either one or amorphous. Although one example shown below is described with a very simple composition ratio, in many of the examples of compounds used in this example, the chemical formula amount is much larger.
例えば（ＮＨ３）ｘ−ｙ・Ｍｙ・ｍＷＯ３・ｒＨ２Ｏ（ｘ−ｙ＞０、ｙ≧０、ｍ＞０、ｒ≧０）において、ｘ＝０．７４、ｙ＝０．６、ｍ＝１、ｒ＝０とすると場合には、例えばＭをＮａにした例で表現するとＮａ０．７４ＷＯ３においてＮａが一部アンモニアに置き換えられた（ＮＨ３）０．１４Ｎａ０．６０ＷＯ３を示す。In example (NH 3) x-y · M y · mWO 3 · rH 2 O (x-y> 0, y ≧ 0, m> 0, r ≧ 0), x = 0.74, y = 0.6 , M = 1, r = 0, for example, when M is Na, for example, Na 0.74 WO 3 is partially replaced with ammonia (NH 3 ) 0.14 Na 0. 60 WO 3 is shown.
次に例えばＭをＮａにした例で表現するとＭｙ・ｍＷＯ３・ｒＨ２Ｏ（ｙ＞０、ｍ＞０、ｒ≧０）においてはｙ＝０．７４、ｍ＝１、ｒ＝０としてＮａ０．７４ＷＯ３を示す。主にＷＯ３の結晶中にＮａを電気的に注入したエレクトロクロミック材料で使われるものに類似する。Next example is expressed in the examples in which the M in Na M y · mWO 3 · rH 2 O (y> 0, m> 0, r ≧ 0) in the y = 0.74, as m = 1, r = 0 It shows Na 0.74 WO 3 . It is mainly similar to that used in electrochromic materials in which Na is electrically injected into the crystal of WO 3 .
また、（ＮＨ４）２（ｘ−ｙ）・Ｍ２ｙ・（ＷＯ４）ｚ・ｒＨ２Ｏ（ｘ−ｙ＞０、ｙ≧０、ｚ＞０、ｒ≧０）においては、例えばＭをＮａにした例で表現すると単純にｙ＝０、ｘ＝２、ｒ＝０とすると（ＮＨ４）２ＷＯ４となり、これは（ＮＨ３）２ＷＯ３Ｈ２Ｏと同一である。しかしながら、水分子として結晶中に含まれる場合とヒドロキシ基とプロトンで結晶中に含まれる場合があり、どちらも結晶構造は全く異なるが、本発明では結晶構造に限定されるものではないので、どちらか一方であるか、または非晶質でも良い。一例は非常に単純な組成比のもので記したが、本実施例で用いた化合物例として示したものでは化学式量はもっと大きいものとなっているものが多い。Further, in (NH 4 ) 2 (x−y ) · M 2 y · (WO 4 ) z · rH 2 O (x−y> 0, y ≧ 0, z> 0, r ≧ 0), for example, M is Expressed in the example of Na, if y = 0, x = 2, and r = 0, it becomes (NH 4 ) 2 WO 4 , which is the same as (NH 3 ) 2 WO 3 H 2 O. However, it may be contained in the crystal as a water molecule or may be contained in the crystal with a hydroxy group and a proton, and the crystal structures of both are completely different, but the present invention is not limited to the crystal structure. It may be either one or amorphous. One example is described with a very simple composition ratio, but in many of the examples of compounds used in this example, the chemical formula amount is much larger.
またはＭｙ・（ＷＯ４）ｚ・ｒＨ２Ｏ（ｙ＞０、ｚ＞０、ｒ≧０）はｙ＝２、ｚ＝１、ｒ＝０であればＭをＮａとするとＮａ２ＷＯ４となる。これはＮａ２ＯＷＯ３と同様であり、Ｗの価数は６価になるものである。本実施例で効果を示した。Or, if M y · (WO 4 ) z · rH 2 O (y> 0, z> 0, r ≧ 0) is y = 2, z = 1, and r = 0, and M is Na, Na 2 WO 4 Becomes This is the same as Na 2 OWO 3, and the valence of W is hexavalent. The effect is shown in this embodiment.
（ＮＨ４）２（ｘ−ｙ）・Ｍ２ｙ・（ＷＯ４）ｚ・（ＷＯ３）ｑ・ｒＨ２Ｏ（ｘ−ｙ＞０、ｙ≧０、ｚ＞０、ｑ＞０、ｒ≧０）において、ｘ＝１、ｙ＝０、ｚ＝１、ｑ＝１、ｒ＝０とすると場合には（ＮＨ４）２ＷＯ４ＷＯ３となり、別の表現にすると（ＮＨ４）２・Ｏ・（ＷＯ３）２となるものである。一般式ではＮＨ４の一部をアルカリ金属イオンに置き換えたものを示した。 (NH 4) 2 (x- y) · M 2y · (WO 4) z · (WO 3) q · rH 2 O (x-y> 0, y ≧ 0, z> 0, q> 0, r ≧ 0), if x = 1, y = 0, z = 1, q = 1, r = 0, it becomes (NH 4 ) 2 WO 4 WO 3 , and in another expression, (NH 4 ) 2 O. (WO 3 ) 2 . In the general formula, a part of NH 4 is replaced with an alkali metal ion.
Ｍｙ・（ＷＯ４）ｚ・（ＷＯ３）ｑ・ｒＨ２Ｏ（ｙ＞０、ｚ＞０、ｑ＞０、ｒ≧０）において、ｙ＝２、ｚ＝１、ｑ＝１、ｒ＝０としＭをＮａとするとＮａ２・（ＷＯ４）・（ＷＯ３）となり、別の表現にするとＮａ２・Ｏ・（ＷＯ３）２となるものである。In M y · (WO 4 ) z · (WO 3 ) q · rH 2 O (y> 0, z> 0, q> 0, r ≧ 0), y = 2, z = 1, q = 1, r = 0 and M is Na, Na 2 · (WO 4 ) · (WO 3 ), and another expression is Na 2 · O · (WO 3 ) 2 .
ここではアルカリ金属イオンだけで表記しているが、他の金属イオンとして例えば２０ａｔ％以下であれば置換しても良い。具体的にはＮａ２ＷＯ４であればＮａをＣａ、Ｚｎ、Ｍｇ、Ｎｉ、Ａｇ等のアルカリ金属イオン以外の他の金属イオンで置換しても量によっては触媒効果が下がるが、金属イオンを選ぶことにより触媒性能は改善される。前述の表現式で表される化合物において同様である。Although only the alkali metal ions are shown here, other metal ions may be substituted as long as they are, for example, 20 at% or less. Specifically, in the case of Na 2 WO 4 , even if Na is replaced with another metal ion other than alkali metal ions such as Ca, Zn, Mg, Ni, and Ag, the catalytic effect is lowered depending on the amount, but the metal ion is changed. The choice improves catalyst performance. The same applies to the compound represented by the above expression.
前述のように本発明のタングステン化合物の粒子としてはサイズが小さいことが良く、結晶または非晶質状態でも良い。形態としてはこれらの触媒物質を溶媒に添加しスプレーで塗布した状態において充分な触媒効果を持っている。特に本発明のタングステン化合物においてタングステン元素を他の金属元素として１０ａｔ％もしくは１％以下の少量置換でも同様な触媒効果が得られる。また粒子表面にＰｔ、Ｒｕ，Ａｇ、Ｐｄを添加することにより触媒性能を著しく改善できる。As described above, the particles of the tungsten compound of the present invention are preferably small in size, and may be in a crystalline or amorphous state. As a form, these catalyst substances have a sufficient catalytic effect in a state where they are added to a solvent and applied by spraying. Particularly, in the tungsten compound of the present invention, a similar catalytic effect can be obtained by substituting a small amount of 10 at% or 1% or less with another metal element of tungsten. Further, by adding Pt, Ru, Ag or Pd to the surface of the particles, the catalytic performance can be remarkably improved.
特に本発明のタングステン化合物において主成分のタングステン元素をＺｎ、Ｓｎ、Ｃａ，Ｓｒ，Ｍｇ、Ｆｅ、Ｃｒ、Ｃｏ、Ｂｉ，Ｎｉ、Ｃｕ、Ｎｄ、Ｌａ、Ｓｍ等、アルカリ金属、アルカリ土類金属元素、Ｌａ系元素、遷移金属元素を上限として１０ａｔ％、好ましくは１ａｔ％以下の少量置換でも同様な触媒効果が得られる。また粒子表面にＰｔ、Ｒｕ、Ａｇ、Ｐｄの中から一種以上を被着させることにより触媒性能を著しく改善できる。量としては５０００ｐｐｍ程度、もしくは１０００ｐｐｍ程度以下でも良いが、少なくとも１０ｐｐｍ以上であることが望ましい。In particular, in the tungsten compound of the present invention, the main element of the tungsten element is Zn, Sn, Ca, Sr, Mg, Fe, Cr, Co, Bi, Ni, Cu, Nd, La, Sm, etc., alkali metal, alkaline earth metal element. A similar catalytic effect can be obtained by substituting a small amount of 10 at%, preferably 1 at% or less, with the La, La, and transition metal elements being the upper limits. Further, the catalytic performance can be remarkably improved by depositing one or more of Pt, Ru, Ag and Pd on the particle surface. The amount may be about 5000 ppm, or about 1000 ppm or less, but it is preferably at least 10 ppm or more.
本発明の触媒化合物の結晶構造解析に株式会社リガク製 Ｍｕｌｔｉ Ｆｌｅｘを使用した。タングステン化合物のＸＲＤによる結晶構造解析で得られたデータを図２、図３、図４に示した。図２は（ＮＨ４）６・Ｈ２（Ｗ３Ｏ１０）４・２０Ｈ２Ｏのものに近い結晶構造持つものである。図４は５（ＮＨ４）２Ｏ・１２ＷＯ３・１１Ｈ２Ｏのものと一致した。図２の化合物に関しては液相中で非常に小さい粒子が得られ、株式会社日立ハイテクノロジーズ社製透過電子顕微鏡（Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ：ＴＥＭ）Ｈ−７５６０を用いてＴＥＭ観察を行った結果を図５に示した。MultiFlex manufactured by Rigaku Corporation was used for crystal structure analysis of the catalyst compound of the present invention. The data obtained by the crystal structure analysis of the tungsten compound by XRD are shown in FIGS. 2, 3 and 4. FIG. 2 has a crystal structure close to that of (NH 4 ) 6 .H 2 (W 3 O 10 ) 4 / 20H 2 O. Figure 4 is consistent with the 5 (NH 4) the 2 O · 12WO 3 · 11H 2 O as. With respect to the compound of FIG. 2, very small particles were obtained in the liquid phase, and the result of TEM observation using a transmission electron microscope (TEM) H-7560 manufactured by Hitachi High-Technologies Corporation was used. It was shown to.
また、アンモニウムサイトをアルカリ金属元素イオンで置換したものを用いて同様に結晶構造解析を行った。この際に用いたタングステン酸アンモニウム化合物としては図２に示した結晶構造のナノ粒子を用いた。この化合物のアンモニウムイオンサイトをＮａイオンで置換した化合物のＸＲＤ結果を図６に示した。この結果からＮａイオンでアンモニウムイオンを置換することにより、Ｎａ２ＷＯ４とＮａ２ＷＯ４・２Ｈ２Ｏからなる化合物になっていることが分かった。ここに示したタングステン酸アンモニウム化合物にＮａイオンでアンモニウムイオンを置換する方法として、Ｎａ，Ｌｉ、Ｋ、Ｃｓ等からなるアルカリ性溶液に入れて置換反応させるだけでも良い。Further, the crystal structure analysis was similarly performed using the one in which the ammonium site was replaced with the alkali metal element ion. As the ammonium tungstate compound used at this time, nanoparticles having the crystal structure shown in FIG. 2 were used. The XRD result of the compound in which the ammonium ion site of this compound was replaced with Na ion is shown in FIG. By replacing the ammonium ions with Na ions from this result, it was discovered that a compound consisting of Na 2 WO 4 and Na 2 WO 4 · 2H 2 O . As a method for substituting the ammonium tungstate compound for ammonium ion with Na ion, the substitution reaction may be performed only by placing it in an alkaline solution composed of Na, Li, K, Cs or the like.
このような化合物において、化合物粉の粉砕法もしくは出発原料の液相での析出条件を変えることによりサイズを調整することが出来る。例えばこれらの材料は溶解度が低いために塩酸等により多少溶解させた後に温度を下げて析出させることでも良い。この粉のサイズが１ｍｍ〜１００μ程度では触媒性能は良く得られない。本発明の場合、少なくとも０．２μ以下であることが望まれる。または平均粒径が１μ以下において、５０ｎｍ以下の粒子の重量が１０％以上あることにより同様に触媒性能が著しく示される。The size of such a compound can be adjusted by changing the method of pulverizing the compound powder or changing the deposition conditions of the starting material in the liquid phase. For example, since these materials have low solubilities, they may be dissolved with hydrochloric acid or the like to some extent, and then the temperature may be lowered to cause precipitation. If the size of the powder is about 1 mm to 100 μ, good catalytic performance cannot be obtained. In the case of the present invention, at least 0.2 μ or less is desired. Alternatively, when the average particle size is 1 μm or less, the weight of particles having a particle size of 50 nm or less is 10% or more, and similarly, the catalytic performance is remarkably exhibited.
本発明の化合物を用いて、触媒として用いる際にはスプレーや刷毛塗りにより被着させたいものに化合物を付ける際に本化合物を有機溶剤や水に混ぜ込み、塗料化することにより被着させやすくなる。この塗料に接着力を持たせるために有機系バインダーや無機系バインダーを添加しても良い。例えばシロキサン化合物の有機無機ハイブリッド樹脂を用いることや無機ポリマーを用いることでも良い。また、粘土系材料や石膏素材、コンクリート素材等も用いることができ、バインダーの組成や結晶系に限定されるものではない。When using the compound of the present invention as a catalyst, it is easy to deposit by mixing the compound with an organic solvent or water when applying the compound to what you want to apply by spraying or brush coating, and forming a paint Become. An organic binder or an inorganic binder may be added in order to impart adhesive force to this paint. For example, an organic-inorganic hybrid resin of a siloxane compound or an inorganic polymer may be used. Clay-based materials, gypsum materials, concrete materials and the like can also be used, and the composition of the binder and the crystal system are not limited.
上記の塗料を形成する場合、タングステン化合物の粒子サイズが１０ｎｍ程度にすることにより水に分散させた状態では固形分濃度が３０％でも無色透明の水溶液を形成できるが、固形分濃度が１０％以上で保存すると水溶液中に結晶粒子の析出が多く見られるようになる。したがって結晶粒子の析出を防ぐためには固形分濃度が１０％より少ない方が良く、望ましくは５％以下であることが良い。When the above paint is formed, a colorless transparent aqueous solution can be formed even if the solid content concentration is 30% when the tungsten compound has a particle size of about 10 nm and is dispersed in water, but the solid content concentration is 10% or more. When it is stored in, the precipitation of crystal particles will be more frequently seen in the aqueous solution. Therefore, in order to prevent the precipitation of crystal particles, the solid content concentration is preferably less than 10%, more preferably 5% or less.
触媒塗料を形成して触媒を触媒固形分として被着体に塗布する量としては少なくとも１ｃｍ２当たりに０．００１ｇでも良いが、更に少なくした場合、例えば０．０１μｇ程度以下では十分な効果は見られない。この被着体を液中に入れることにより、液中に溶存するアンモニアや水酸化アンモニウムを分解し、それらを減少させることが出来る。The amount of the catalyst coating formed to apply the catalyst as a catalyst solid content to the adherend may be 0.001 g per at least 1 cm 2, but when it is further reduced, for example, about 0.01 μg or less, a sufficient effect is not seen. I can't. By putting this adherend in the liquid, it is possible to decompose ammonia and ammonium hydroxide dissolved in the liquid and reduce them.
アンモニアを含んだ液として、特に水に限定されるものではなく、非水系溶媒のメタノール、エタノールやイソプロパノール、ジメチルケトン、メチルエチルケトン、エチレングリコール、ポリエチレングリコールでも良い。非水系溶媒の中において極性の弱いような、ヘキサンやベンゼン、スチレン、オレイン酸等の溶媒においても同様な効果があり、この場合にはアンモニアのような極性化合物の液体をエマルジョン的な状態にしても同様にアンモニアを除去できる効果がある。The liquid containing ammonia is not particularly limited to water, but may be a non-aqueous solvent such as methanol, ethanol or isopropanol, dimethyl ketone, methyl ethyl ketone, ethylene glycol or polyethylene glycol. The same effect can be obtained in solvents such as hexane, benzene, styrene, and oleic acid, which have weak polarity in non-aqueous solvents. In this case, a polar compound liquid such as ammonia is made into an emulsion state. Also has the effect of similarly removing ammonia.
窒素化合物として、アンモニアだけに限定されるものではなく、脂肪族第一アミン、脂肪族第二アミン、脂肪族第三アミン、脂肪族不飽和アミン、脂環式アミン、芳香族アミン等にも効果がある。例えばメチルアミン、エチルアミン、プロピルアミン、ジエチルアミン、ジメチルアミン、トリメチルアミン、トリエチルアミン、アリルアミン、ジアリルアミン、アニリン、メチルアニリン等が挙げられる。その他として、ホルムアルデヒド、アセトアルデヒド、ノネナール等アルデヒド系化合物、酢酸、イソ吉草酸等カルボン酸系化合物、硫化水素、メチルメルカプタン島硫黄含有化合物等にも効果がある。The nitrogen compound is not limited to ammonia, but is also effective for aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, aliphatic unsaturated amines, alicyclic amines, aromatic amines, etc. There is. Examples thereof include methylamine, ethylamine, propylamine, diethylamine, dimethylamine, trimethylamine, triethylamine, allylamine, diallylamine, aniline and methylaniline. In addition, it is also effective for aldehyde compounds such as formaldehyde, acetaldehyde, nonenal, carboxylic acid compounds such as acetic acid and isovaleric acid, hydrogen sulfide and sulfur compounds containing methylmercaptan island.
上記の被着体としては以下のものが挙げられる。生地の繊維、板、ビーズ、多孔質体、多孔質粒子、ハニカム構造体、不織布、織布、ガラス構造体の表面、金属構造物の表面、プラスチック構造体の表面等に付着させて、アンモニアや水酸化アンモニウムが含まれる液体と接触させることにより、アンモニアや水酸化アンモニウムを分解し液中にあるこれらのアンモニアや水酸化アンモニウムを減少させるが出来る。Examples of the adherend include the following. By attaching it to the fibers, plates, beads, porous bodies, porous particles, honeycomb structures, non-woven fabrics, woven fabrics, surfaces of glass structures, surfaces of metal structures, surfaces of plastic structures, etc. By contacting with a liquid containing ammonium hydroxide, ammonia or ammonium hydroxide can be decomposed and the amount of ammonia or ammonium hydroxide in the liquid can be reduced.
被着体に触媒を担持させる場合、用いるバインダーとして、例えば非有機溶媒としてアクリル樹脂系やウレタン系、アクリル−スチレン共重合体の水系エマルジョンを用いても良く、一般的な有機溶媒系のバインダーを用いることでも良い。例えばフッ素樹脂系バインダーを用いても良い。これらのバインダーを用いて触媒性能を有するために、バインダーが硬化する際に硬化した樹脂中に触媒粒子が塗料液中にある触媒粒子のサイズを大きくならない、または凝集しないようにする。例えば平均粒径が５〜１０ｎｍのものが一次粒子のサイズ、または凝集粒子のサイズが１００ｎｍより大きくならないように、好ましくは５０ｎｍ以下にすることが望ましい。When the catalyst is supported on the adherend, as the binder to be used, for example, an acrylic resin-based or urethane-based non-organic solvent, an aqueous emulsion of an acrylic-styrene copolymer may be used, and a general organic solvent-based binder is used. You can also use it. For example, a fluororesin-based binder may be used. In order to have catalytic performance by using these binders, the catalyst particles in the resin cured when the binder is cured do not increase the size of the catalyst particles in the coating liquid or aggregate. For example, the average particle size of 5 to 10 nm is preferably 50 nm or less so that the size of primary particles or the size of aggregated particles does not exceed 100 nm.
本発明のタングステン酸アンモニウム化合物として、主成分が（ＮＨ４）６・Ｈ２（Ｗ３Ｏ１０）４・２０Ｈ２Ｏを用いた。用いた粉はＸ線解析装置により結晶構造の解析を行った。この結果を図２に示した。この結果より主成分が（ＮＨ４）６・Ｈ２（Ｗ３Ｏ１０）４・２０Ｈ２Ｏであった。この粉を１０ｇ秤量し５００ｃｃのビーカに入れて、次に大きさ０．１ｍｍφのジルコニアビーズを１ｋｇ入れた後に純水２００ｇを添加してプロペラ型の攪拌機を攪拌速度３００ｒｐｍで１２０時間処理を行って粉砕した。この時の粒度分布は図７に示すものとなった。粒度分布の測定はＨＯＲＩＢＡ製ＬＡ−９５０で行った。平均粒径は０．１７μｍとなった。As the ammonium tungstate compound of the present invention, the main component was (NH 4 ) 6 · H 2 (W 3 O 10 ) 4 · 20H 2 O. The crystal structure of the powder used was analyzed by an X-ray analyzer. The result is shown in FIG. The results from the main component was (NH 4) 6 · H 2 (W 3 O 10) is 4 · 20H 2 O. 10 g of this powder was weighed and put in a 500 cc beaker, then 1 kg of zirconia beads having a size of 0.1 mmφ was added, 200 g of pure water was added, and a propeller-type stirrer was treated for 120 hours at a stirring speed of 300 rpm. Crushed. The particle size distribution at this time is shown in FIG. The particle size distribution was measured with LA-950 manufactured by HORIBA. The average particle size was 0.17 μm.
次に前述の平均粒径０．１７μｍのタングステン酸アンモニウム化合物（ＮＨ４）６・Ｈ２（Ｗ３Ｏ１０）４・２０Ｈ２Ｏを純水に添加して固形分１％濃度にした水溶液１リットルにタングステン酸アンモニウム化合物に対して３００ｐｐｍになるようにＰｄＣｌ５を添加して１２時間攪拌した。これにバインダー剤（新中村化学工業製 ＮＫバインダー Ｒ−５ＨＮ）を固形分として触媒量の３倍量になるように添加して攪拌装置で１時間攪拌して均一にした。この液を用いて厚さ１．５ｍｍ程度のポリプロピレン製透明プラスチック板 幅６ｃｍ長さ１６ｃｍに全面の裏表にスプレーで塗布した。この時の乾燥後の重量は０．３ｇとなっており、塗膜の単位面積当たりの重量は１．５ｍｇ／ｃｍ２となった。これを図８に示すような９００ｍＬのガラス瓶に入れて、完全に光を遮蔽する金属製の箱に入れ、且つ温度を２０℃になるように制御してアルモニア水の分解を調べた。アンモニア水を入れた時の雰囲気は大気中のために大気の窒素や酸素濃度が含まれている。分解特性を調べる際に液中のアンモニア成分と気相中のアンモニア成分の平衡状態が密閉系では成立するために気相中のアンモニア濃度を評価した。液相中のアンモニア濃度が減少すると気相中のアンモニア濃度が減少する。この相関関係から気相中のアンモニア濃度を測定することにより、間接的に液相中のアンモニア濃度を評価した。この実施例では、ガラス瓶の中にアンモニア水の濃度が１００ｐｐｍになるようにしたアンモニア水を２００ｃｃ入れ、触媒を付着したポリプロピレン製透明プラスチック板を液に全体が漬かるように折り曲げて入れた。比較サンプルとして触媒を担持しないポリプロピレン製透明プラスチック板を用いて同様にセットした。アンモニア水から発生するアンモニアガスをガステック検知器 ＧＶ‐１００Ｓを用いて、検知管は型番９１Ｌで測定濃度範囲０．１〜４０ｐｐｍのものを用いた。初期の濃度と２４時間経過後のアンモニア濃度を調べた。この結果を表１に示した。表中の数値として測定精度を考慮して小数点二桁目は四捨五入のものとした。表中には分かりやすいように初期濃度を１として規格化して、触媒担持のプラスチック板と触媒担持の無いプラスチック板を用いたものを比較した。この表１から分かるように触媒を担持しないプラスチック板を用いたものでは、全く初期濃度から変化しないことが分かる。触媒を担持したものはアンモニアが減少していることが分かった。この結果から、触媒を担持したプラスチック板は液中のアンモニアを分解していることが分かった。Next, an aqueous solution 1 was prepared by adding the above-mentioned ammonium tungstate compound (NH 4 ) 6 · H 2 (W 3 O 10 ) 4 / 20H 2 O having an average particle size of 0.17 μm to pure water to have a solid content of 1%. PdCl 5 was added to liter so as to be 300 ppm with respect to the ammonium tungstate compound, and the mixture was stirred for 12 hours. A binder agent (NK binder R-5HN manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to the mixture as a solid content in an amount 3 times the catalyst amount, and the mixture was stirred for 1 hour with a stirrer to make it uniform. Using this solution, a transparent plastic plate made of polypropylene having a thickness of about 1.5 mm having a width of 6 cm and a length of 16 cm was sprayed on the front and back surfaces. The weight after drying at this time was 0.3 g, and the weight per unit area of the coating film was 1.5 mg / cm 2 . This was placed in a 900 mL glass bottle as shown in FIG. 8, placed in a metal box that completely shields light, and the temperature was controlled to 20 ° C. to investigate the decomposition of armonia water. Since the atmosphere when the ammonia water is put is in the atmosphere, it contains nitrogen and oxygen concentrations in the atmosphere. When investigating the decomposition characteristics, the ammonia concentration in the gas phase was evaluated because the equilibrium state of the ammonia component in the liquid and the ammonia component in the gas phase is established in the closed system. When the ammonia concentration in the liquid phase decreases, the ammonia concentration in the gas phase decreases. The ammonia concentration in the liquid phase was indirectly evaluated by measuring the ammonia concentration in the gas phase from this correlation. In this example, 200 cc of ammonia water having a concentration of 100 ppm of ammonia water was placed in a glass bottle, and a polypropylene transparent plastic plate to which a catalyst was attached was bent and placed so that the whole was immersed in the liquid. As a comparative sample, a polypropylene transparent plastic plate that does not carry a catalyst was used and set in the same manner. The gas tech detector GV-100S was used for the ammonia gas generated from the ammonia water, and the detection tube used was a model number 91L with a measurement concentration range of 0.1 to 40 ppm. The initial concentration and the ammonia concentration after 24 hours were examined. The results are shown in Table 1. As the numerical values in the table, the second decimal point is rounded off in consideration of measurement accuracy. In the table, the initial concentration was standardized to be 1 for the sake of clarity, and a comparison was made between a catalyst-supported plastic plate and a catalyst-free plastic plate. As can be seen from Table 1, in the case of using the plastic plate on which the catalyst is not supported, there is no change from the initial concentration. It was found that ammonia was reduced in the catalyst-supported one. From these results, it was found that the catalyst-supported plastic plate decomposed ammonia in the liquid.
この触媒担持したプラスチック板のサンプルを用いてトリメチルアミンの分解を調べた。試験条件は実施例１と同様にした。この結果を表２に示した。表中には初期濃度で規格化した数値で示した。この表２から分かるように触媒担持品はトリメチルアミンが減少していることが分かる。また、比較例として示した触媒を担持しないものでは数値は変わらないことが分かった。この結果から、アミン系のトリメチルアミンも分解することが分かった。Degradation of trimethylamine was examined using this sample of a plastic plate carrying the catalyst. The test conditions were the same as in Example 1. The results are shown in Table 2. In the table, the values standardized with the initial concentration are shown. As can be seen from Table 2, trimethylamine is reduced in the catalyst-supported product. It was also found that the values shown in Comparative Examples that do not carry the catalyst do not change the numerical values. From this result, it was found that the amine-based trimethylamine was also decomposed.
この触媒担持したプラスチック板のサンプルを用いてトリメチルアミンの分解を調べた。試験条件は実施例１において水にアンモニアを溶かしたアンモニア水系においてトリメチルアミンをエチレングリコールに溶かした系に変え、その他の条件は同様にした。この結果を表３に示した。表中には初期濃度で規格化した数値で示した。この表３から分かるように触媒担持品はトリメチルアミンが減少していることが分かる。また、比較例として示した触媒を担持しないものでは数値は変わらないことが分かった。この結果から、アミン系のトリメチルアミンも分解することが分かった。Degradation of trimethylamine was examined using this sample of a plastic plate carrying the catalyst. The test conditions were changed to the system in which trimethylamine was dissolved in ethylene glycol in the ammonia water system in which ammonia was dissolved in water in Example 1, and the other conditions were the same. The results are shown in Table 3. In the table, the values standardized with the initial concentration are shown. As can be seen from Table 3, trimethylamine is reduced in the catalyst-supported product. It was also found that the values shown in Comparative Examples that do not carry the catalyst do not change the numerical values. From this result, it was found that the amine-based trimethylamine was also decomposed.
本発明のタングステン酸ナトリウム化合物が主成分である粉を用いた。Ｘ線解析装置により結晶構造の解析を行った。この結果を図６に示した。この結果より主成分がＮａ２ＷＯ４であり、副成分としてＮａ２ＷＯ４・２Ｈ２Ｏであった。また、この粉の組成を粉砕していない状態のＳＥＭ観察像を図９に示した。更にＳＥＭ−ＥＤＸにて組成分析を行ったデータを示した。図１０にはＥＤＸのピークデータを示し、図１１にピーク値から算出された元素の量を示している。生データのために、試料台に使っている金属アルミ円盤からのアルミニウムのピークやサンプルを試料台に固定するために使用している導電性テープからの炭素や酸素も検出されているので、正確な組成は定量していないが、主成分がＮａとＷから成り立っていることは確認された。Ｎａ量が多く見られるのは余剰のＮａ２ＯやＮａ２ＣＯ３が乾燥過程で粉の表面に析出されるためである。この結果とＸＲＤの結果より化合物の主成分はＮａ２ＷＯ４に近いことが示された。この粉を１０ｇ秤量し５００ｃｃのビーカに入れて、次に大きさ０．０５ｍｍφのジルコニアビーズを１ｋｇ入れた後に純水２００ｇを添加してプロペラ型の攪拌機を攪拌速度３００ｒｐｍで１２０時間処理を行って粉砕した。この平均粒径は０．１２μｍとなった。このスラリーに純水を添加して固形分１％濃度にした水溶液１リットルにタングステン酸ナトリウム化合物に対して３００ｐｐｍになるようにＰｄＣｌ５を添加して１２時間攪拌した。これにバインダー剤（ＤＩＣ製 セラネート ＷＨＷ−８２２）を固形分として触媒量の２倍量になるように添加して攪拌装置で１時間攪拌して均一にした。作製した触媒塗料を用いて厚さ１ｍｍ程度のポリエステル繊維からなる生地 幅１０ｃｍ、長さ１０ｃｍに全面の裏表にスプレーで塗布した。この時の触媒としての担持量は０．５ｇとなるように塗布してり、塗膜の単位面積当たりの重量は５ｍｇ／ｃｍ２となった。これを図８に示すようなガラス瓶に入れて、２０℃の液体温度、雰囲気にして光の無い条件において、液中のアンモニアの分解を調べた。この際、ガラス瓶の中の液中のアンモニア濃度が１００ｐｐｍになるようにしたアンモニア水を２００ｇ添加した。この液に硫酸銅１０ｍｇを添加して銅アンモニア錯体を形成させて青色に着色させた。液中のアンモニアの量は硫酸銅１０ｍｇを添加して色の変化からアンモニアの残留状態を確認し、且つ液と気相の平衡状態にあることを用いてガラス瓶の中の気相中のアンモニアをガステック検知器 ＧＶ‐１００Ｓを用いて評価した。検知管は型番３Ｌで測定濃度範囲０．５〜７８ｐｐｍのものを用いた。初期の濃度と４８時間経過後のアンモニア濃度を調べた。この結果を表４に示した。表中の数値として測定精度を考慮して小数点二桁目は四捨五入のものとした。表中には分かりやすいように初期濃度を１として規格化して、触媒担持のポリエステル繊維と触媒担持の無いポリエステル繊維を用いたものを比較した。この表４から分かるように触媒を担持しないポリエステル繊維を用いたものでは、全く初期濃度から変化しないことが分かる。触媒を担持したものはアンモニアが減少しているため、触媒を担持したポリエステル繊維は液中のアンモニアを分解していることが分かった。また、表５に銅アンモニア錯体から着色する液体の状態を示した。硫酸銅を添加しているため、初期はアンモニアによる銅のアンモニア錯体により青緑色に着色していたが、触媒担持したものでは色が薄くなっていた。これは銅のアンモニア錯体を形成するアンモニアが減少していることによる錯体の色の濃さが無くなっていることによるため、直接、液中のアンモニアが減少していることを示す。A powder containing the sodium tungstate compound of the present invention as a main component was used. The crystal structure was analyzed by an X-ray analyzer. The result is shown in FIG. Main component This result is Na 2 WO 4, were Na 2 WO 4 · 2H 2 O as an auxiliary component. Further, an SEM observation image in a state where the composition of this powder is not crushed is shown in FIG. Furthermore, the data which carried out the composition analysis by SEM-EDX were shown. FIG. 10 shows EDX peak data, and FIG. 11 shows the amounts of elements calculated from the peak values. For raw data, the peaks of aluminum from the metal-aluminum disk used for the sample stage and carbon and oxygen from the conductive tape used to fix the sample to the sample stage are also detected, so it is accurate. Although the composition was not quantified, it was confirmed that the main components consist of Na and W. A large amount of Na is seen because excess Na 2 O and Na 2 CO 3 are deposited on the surface of the powder during the drying process. From this result and the XRD result, it was shown that the main component of the compound was close to Na 2 WO 4 . 10 g of this powder was weighed and put in a 500 cc beaker, then 1 kg of zirconia beads having a size of 0.05 mmφ was added, 200 g of pure water was added, and a propeller-type stirrer was treated for 120 hours at a stirring speed of 300 rpm. Crushed. This average particle diameter was 0.12 μm. Pure water was added to this slurry to 1 liter of an aqueous solution having a solid content of 1%, and PdCl 5 was added so that the concentration was 300 ppm with respect to the sodium tungstate compound, and the mixture was stirred for 12 hours. To this, a binder agent (Celanate WHW-822 manufactured by DIC) was added as a solid content so as to be twice the amount of the catalyst, and stirred for 1 hour with a stirrer to make it uniform. Using the prepared catalyst paint, a cloth made of polyester fiber having a thickness of about 1 mm was applied on the entire front and back sides by spraying to have a width of 10 cm and a length of 10 cm. At this time, the amount of the catalyst supported was 0.5 g, and the weight of the coating film per unit area was 5 mg / cm 2 . This was put in a glass bottle as shown in FIG. 8, and the decomposition of ammonia in the liquid was examined under the conditions of a liquid temperature of 20 ° C. and an atmosphere without light. At this time, 200 g of ammonia water in which the concentration of ammonia in the liquid in the glass bottle was 100 ppm was added. 10 mg of copper sulfate was added to this solution to form a copper ammonia complex, which was colored blue. Regarding the amount of ammonia in the liquid, 10 mg of copper sulfate was added to confirm the residual state of ammonia from the color change, and the fact that the liquid and vapor phase were in equilibrium was used to remove ammonia in the vapor phase in the glass bottle. Evaluation was performed using a GAS-TEC detector GV-100S. A detector tube having a model number of 3 L and a measurement concentration range of 0.5 to 78 ppm was used. The initial concentration and the ammonia concentration after 48 hours were examined. The results are shown in Table 4. As the numerical values in the table, the second decimal point is rounded off in consideration of measurement accuracy. In the table, for the sake of clarity, the initial concentration was standardized as 1, and the polyester fibers with and without the catalyst were compared for comparison. As can be seen from Table 4, in the case of using the polyester fiber not supporting the catalyst, there is no change from the initial concentration. It was found that the polyester fiber supporting the catalyst decomposes the ammonia in the liquid because the catalyst supporting the catalyst has a reduced amount of ammonia. Further, Table 5 shows the state of the liquid colored from the copper ammonia complex. Since copper sulfate was added, it was initially colored blue-blue by the ammonia complex of copper with ammonia, but the catalyst-supported one had a faint color. This indicates that the ammonia in the liquid is directly reduced because the color strength of the complex is lost due to the reduction of ammonia forming the ammonia complex of copper.
実施例４において、Ｎａの代わりにアルカリ金属元素のＬｉ、Ｋ、Ｃｓに置換した化合物としてＬｉ２ＷＯ４，Ｃｓ２ＷＯ４，Ｋ２ＷＯ４、Ｌｉ１．５Ｋ０．５ＷＯ４，Ｎａ１．７Ｋ０．３ＷＯ４，Ｃｓ１Ｎａ１ＷＯ４を用いて同様に実験を行った。この結果は実施例４と同様にアンモニアの分解が確認できた。In Example 4, Li 2 WO 4 , Cs 2 WO 4 , K 2 WO 4 , Li 1.5 K 0.5 WO 4 , Na as compounds in which alkali metal elements Li, K, and Cs were substituted in place of Na The same experiment was performed using 1.7 K 0.3 WO 4 and Cs 1 Na 1 WO 4 . As a result, decomposition of ammonia was confirmed as in Example 4.
（ＮＨ４）６・Ｈ２（Ｗ３Ｏ１０）４・２０Ｈ２Ｏを３００℃１時間で焼成して（ＮＨ３）０．２５ＷＯ３ を作製した。この粉を１０ｇ秤量し５００ｃｃのビーカに入れて、次に大きさ０．１ｍｍφのジルコニアビーズを１ｋｇ入れた後に純水２００ｇを添加した。この後、水酸化ナトリウムを０．１ｇ添加して、１時間ほど攪拌しアンモニアサイトをナトリウムイオンに部分的に置換した。この攪拌過程で容器からアンモニア臭が得られた。更に塩化白金酸Ｈ２（ＰｔＣｌ６）を（ＮＨ３）０．２５ＷＯ３に対して５００ｐｐｍになるように添加した後、ヒドラジンを０．１ｃｃ添加した。この後、プロペラ型の攪拌機を攪拌速度３００ｒｐｍで粉砕時間を変えて平均粒径を２５００ｎｍから５０ｎｍ程度まで粉砕し、バインダー（荒川化学製 ユリア―ノＷ６００）を固形分として触媒量の３倍重量になるように添加して１時間攪拌した。作製した平均粒径の異なる粒子の触媒塗料を用いて、厚さ１ｍｍ程度の綿生地 幅１０ｃｍ長さ１０ｃｍに全面の裏表にスプレーで塗布した。塗布後８０℃にて１時間乾燥した。乾燥後の重量は０．８ｇになるように固定した。塗膜の単位面積当たりの重量は８ｍｇ／ｃｍ２となった。これを図８に示すような９００ｍＬのガラス瓶に入れて、完全に光を遮蔽する金属製の箱に入れ、且つ温度を２０℃になるように制御してアルモニア水の分解を調べた。アンモニア水を入れた時の雰囲気は大気中のために大気の窒素や酸素濃度が含まれている。分解特性を調べる際に液中のアンモニア成分と気相中のアンモニア成分の平衡状態が密閉系では成立するために気相中のアンモニア濃度を評価した。この際、初期にガラス瓶の中にアンモニア水の濃度が１００ｐｐｍになるようにしたアンモニア水を２００ｃｃ入れ、触媒を担持した綿生地を液に全体が漬かるように折り曲げて入れた。アンモニア水から発生するアンモニアガスをガステック検知器 ＧＶ‐１００Ｓを用いて、検知管は型番９１Ｌで測定濃度範囲０．１〜４０ｐｐｍのものを用いた。初期の濃度と２４時間経過後のアンモニア濃度を調べた。この結果を表６に示した。表中の数値として測定精度を考慮して小数点二桁目は四捨五入のものとした。表中には分かりやすいように初期濃度を１として規格化して、触媒担持の綿生地を用いたものを比較した。この結果を表６に示した。表中のアンモニア濃度の単位は初期値のアンモニア濃度を用いて規格化したために、初期値を１とした。この表６から平均粒径が小さい程、アンモニアの濃度が低減していることが分かる。平均粒子サイズは０．２μｍが望ましく、好ましくは０．１μｍ以下が良いことが分かった。Was produced (NH 4) 6 · H 2 (W 3 O 10) of 4 · 20H 2 O was baked at 300 ° C. 1 hour (NH 3) 0.25 WO 3. 10 g of this powder was weighed and placed in a 500 cc beaker, then 1 kg of zirconia beads having a size of 0.1 mmφ was placed therein, and then 200 g of pure water was added. Then, 0.1 g of sodium hydroxide was added and stirred for about 1 hour to partially replace the ammonia site with sodium ion. Ammonia odor was obtained from the container during this stirring process. Further, chloroplatinic acid H2 (PtCl6) was added so as to have a concentration of 500 ppm with respect to (NH 3 ) 0.25 WO 3 , and then 0.1 cc of hydrazine was added. After that, a propeller type stirrer was crushed at a stirring speed of 300 rpm and the crushing time was changed to crush the average particle diameter from 2500 nm to about 50 nm, and the binder (Ariakawa Chemical Co., Ltd., urea-no W600) was added as solid content to 3 times the catalyst amount by weight. And added for 1 hour. Using the prepared catalyst paints having different average particle diameters, a cotton cloth having a thickness of about 1 mm, a width of 10 cm, and a length of 10 cm was sprayed on the front and back surfaces. After coating, it was dried at 80 ° C. for 1 hour. The weight after drying was fixed to 0.8 g. The weight per unit area of the coating film was 8 mg / cm 2 . This was placed in a 900 mL glass bottle as shown in FIG. 8, placed in a metal box that completely shields light, and the temperature was controlled to 20 ° C. to investigate the decomposition of armonia water. Since the atmosphere when the ammonia water is put is in the atmosphere, it contains nitrogen and oxygen concentrations in the atmosphere. When investigating the decomposition characteristics, the ammonia concentration in the gas phase was evaluated because the equilibrium state of the ammonia component in the liquid and the ammonia component in the gas phase is established in the closed system. At this time, 200 cc of ammonia water adjusted to have an ammonia water concentration of 100 ppm was initially put in a glass bottle, and a cotton fabric carrying a catalyst was bent and put so that the whole was soaked in the liquid. The gas tech detector GV-100S was used for the ammonia gas generated from the ammonia water, and the detection tube used was a model number 91L with a measurement concentration range of 0.1 to 40 ppm. The initial concentration and the ammonia concentration after 24 hours were examined. The results are shown in Table 6. As the numerical values in the table, the second decimal point is rounded off in consideration of measurement accuracy. In the table, the initial concentration was standardized to be 1 so as to be easily understood, and those using the catalyst-supported cotton fabric were compared. The results are shown in Table 6. Since the unit of the ammonia concentration in the table is standardized by using the initial value of the ammonia concentration, the initial value is set to 1. It can be seen from Table 6 that the smaller the average particle size, the lower the concentration of ammonia. It has been found that the average particle size is desirably 0.2 μm, preferably 0.1 μm or less.
実施例６で作製した平均粒径の異なるものにおいて、平均粒径１．２５μｍのものと平均粒径０．０５μｍ（５０ｎｍ）のものの混合比を変えて固形分濃度１％の触媒塗料を作製し、固形分の全重量において、混ぜた平均粒径が０．０５μｍの重量％と触媒性能を調べた。この際、触媒塗料中の固形分濃度は固定値の１％と固定した。条件はガスをアンモニアからトリメチルアミンに変えて、その他の条件は実施例６と同一にして行った。トリメチルアミンの濃度はガステック検知器 ＧＶ‐１００Ｓを用いて、検知管は型番３Ｌで測定濃度範囲０．５〜７８ｐｐｍのもので評価した。この結果を表７に示した。表中の数値として測定精度を考慮して小数点二桁目は四捨五入のものとした。表中には分かりやすいように初期濃度を１として規格化して、触媒担持の綿生地を用いたものを比較した。この結果から、触媒性を持たせるには全体的な平均粒径が１μｍ程度のものにおいても、平均粒径が０．０５μｍの粉が少なくとも１０重量％含まれていることが好ましいことが分かった。この際、前記の二つの混合する粒子において平均粒径が１μｍ程度のサイズを大小に変えても平均粒径が０．０５μｍの重量％が１０重量％含まれている、好ましくは３０重量％以上含まれていると触媒効果が大きいことが分かった。したがって、全体の粉の重量において平均粒径が０．０５μｍの重量％が１０重量％以上であること、３０重量％以上含まれているが好ましい。In the catalysts having different average particle diameters prepared in Example 6, the mixture ratio of the average particle diameter of 1.25 μm and the average particle diameter of 0.05 μm (50 nm) was changed to prepare a catalyst paint having a solid content concentration of 1%. In addition, the catalyst performance was examined with respect to the total weight of the solid content and the weight percentage of the mixed average particle diameter of 0.05 μm. At this time, the solid content concentration in the catalyst coating was fixed at 1% of the fixed value. The conditions were that the gas was changed from ammonia to trimethylamine, and other conditions were the same as in Example 6. The concentration of trimethylamine was evaluated by using Gastec detector GV-100S with a detector tube having a model number of 3 L and a measurement concentration range of 0.5 to 78 ppm. The results are shown in Table 7. As the numerical values in the table, the second decimal point is rounded off in consideration of measurement accuracy. In the table, the initial concentration was standardized to be 1 so as to be easily understood, and those using the catalyst-supported cotton fabric were compared. From this result, it was found that it is preferable that at least 10% by weight of powder having an average particle diameter of 0.05 μm is contained in order to impart catalytic properties even if the overall average particle diameter is about 1 μm. . At this time, even if the size of the average particle size of the two mixed particles is changed to about 1 μm, 10% by weight of the average particle size of 0.05 μm is contained, preferably 30% by weight or more. It was found that the catalytic effect was large when it was included. Therefore, it is preferable that the weight of the whole powder is such that the weight% of the average particle diameter of 0.05 μm is 10% by weight or more, and the content of 30% by weight or more is contained.
本発明の化合物として５（ＮＨ４）２Ｏ・１２ＷＯ３・１１Ｈ２Ｏを用いて試験を行った。この粉を１０ｇ秤量し５００ＣＣのビーカに入れて、次に大きさ０．０３ｍｍφのジルコニアビーズを１ｋｇ入れた後に純水２００ｇを添加した。この後、プロペラ型の攪拌機を攪拌速度３００ｒｐｍで平均粒径を５０ｎｍ程度まで粉砕した。粉砕後、水酸化セシウムを０．２ｇ添加して１時間攪拌した。この攪拌過程で容器からアンモニア臭が得られた。この後、塩化パラジウムを５（ＮＨ４）２Ｏ・１２ＷＯ３・１１Ｈ２Ｏに対して５００ｐｐｍになるように添加した後、ヒドラジンを０．１ＣＣ添加し１２時間攪拌した。更にこの液にバインダー（荒川化学製 ユリア―ノＷ６００）を固形分として触媒量の３倍重量になるように添加して１時間攪拌し均一化した触媒塗料を作製した。作製した触媒塗料を用いて厚さ０．８ｍｍ程度のガラス板幅６ｃｍ 長さ１０ｃｍに全面の裏表にスプレーで塗布した。塗布後８０℃にて１時間乾燥した。この際に乾燥後の触媒担持量は０．３ｇになるように固定した。これは塗膜の単位面積当たりの触媒重量は ５ｍｇ／ｃｍ２となっている。これを図８に示すような９００ｍＬのガラス瓶に入れて、完全に光を遮蔽する金属製の箱に入れ、且つ温度を２０℃になるように制御してアルモニア水の分解を調べた。アンモニア水を入れた時の雰囲気は大気中のために大気の窒素や酸素濃度が含まれている。分解特性を調べる際に液中のアンモニア成分と気相中のアンモニア成分の平衡状態が密閉系では成立するために気相中のアンモニア濃度を評価した。この際、初期にガラス瓶の中にアンモニア水の濃度が１００ｐｐｍになるようにしたアンモニア水を２００ｃｃ入れ、この液に硫酸銅１０ｍｇを添加して銅アンモニア錯体を形成させて青色に着色させた。液中のアンモニアの量は硫酸銅１０ｍｇを添加して色の変化からアンモニアの残留状態を確認した。触媒を担持したガラス板を液に全体が漬かるように入れた。アンモニア水から発生するアンモニアガスをガステック検知器 ＧＶ‐１００Ｓを用いて、検知管は型番９１Ｌで測定濃度範囲０．１〜４０ｐｐｍのものを用いた。初期の濃度と２４時間経過後のアンモニア濃度を調べた。比較例としてガラス板に触媒を担持しないものを用いた。この結果を表８に示した。表中の数値として測定精度を考慮して小数点二桁目は四捨五入のものとした。表中には分かりやすいように初期濃度を１として規格化して比較した。この結果を表８に示した。表９に色の変化を調べた結果を示す。この結果から、アンモニアが触媒により分解していることが分かった。Test 5 (NH 4) using 2 O · 12WO 3 · 11H 2 O as a compound of the present invention was performed. 10 g of this powder was weighed and placed in a 500 CC beaker, then 1 kg of zirconia beads having a size of 0.03 mmφ was placed therein, and then 200 g of pure water was added. Then, a propeller-type stirrer was crushed at a stirring speed of 300 rpm to an average particle size of about 50 nm. After crushing, 0.2 g of cesium hydroxide was added and stirred for 1 hour. Ammonia odor was obtained from the container during this stirring process. Then, after addition of palladium chloride 5 (NH 4) so as to 500ppm with respect 2 O · 12WO 3 · 11H 2 O, hydrazine was stirred 0.1CC added 12 hours. Further, a binder (Uriano W600 manufactured by Arakawa Chemical Co., Ltd.) was added to this solution as a solid content so as to be 3 times the weight of the catalyst amount, and stirred for 1 hour to prepare a uniform catalyst coating. A glass plate having a thickness of about 0.8 mm and a width of 6 cm and a length of 10 cm was spray-coated on the entire front and back surfaces using the produced catalyst coating material. After coating, it was dried at 80 ° C. for 1 hour. At this time, the amount of catalyst supported after drying was fixed to 0.3 g. This has a catalyst weight per unit area of the coating film of 5 mg / cm 2 . This was placed in a 900 mL glass bottle as shown in FIG. 8, placed in a metal box that completely shields light, and the temperature was controlled to 20 ° C. to investigate the decomposition of armonia water. Since the atmosphere when the ammonia water is put is in the atmosphere, it contains nitrogen and oxygen concentrations in the atmosphere. When investigating the decomposition characteristics, the ammonia concentration in the gas phase was evaluated because the equilibrium state of the ammonia component in the liquid and the ammonia component in the gas phase is established in the closed system. At this time, 200 cc of ammonia water having an ammonia water concentration of 100 ppm was initially put in a glass bottle, and 10 mg of copper sulfate was added to this solution to form a copper-ammonia complex, which was colored blue. Regarding the amount of ammonia in the liquid, 10 mg of copper sulfate was added and the residual state of ammonia was confirmed from the color change. The glass plate supporting the catalyst was put into the liquid so that the whole was soaked. The gas tech detector GV-100S was used for the ammonia gas generated from the ammonia water, and the detection tube used was a model number 91L with a measurement concentration range of 0.1 to 40 ppm. The initial concentration and the ammonia concentration after 24 hours were examined. As a comparative example, a glass plate without a catalyst was used. The results are shown in Table 8. As the numerical values in the table, the second decimal point is rounded off in consideration of measurement accuracy. In the table, the initial concentration was set to 1 and standardized for easy understanding. The results are shown in Table 8. Table 9 shows the results of examining the change in color. From this result, it was found that ammonia was decomposed by the catalyst.
本発明のタングステン酸アンモニウム化合物として、主成分が（ＮＨ４）６・Ｈ２（Ｗ３Ｏ１０）４・２０Ｈ２Ｏを用いて、３００℃１時間の大気中での焼成を行った。この粉をＸ線解析装置により結晶構造の解析を行った。この結果を図１２に示した。この結果より主成分が（ＮＨ４）０．２５ＷＯ３、ＷＯ３であった。この粉を１０ｇ秤量し５００ｃｃのビーカに入れて、次に大きさ０．０５ｍｍφのジルコニアビーズを１ｋｇ入れた後に純水２００ｇを添加してプロペラ型の攪拌機を攪拌速度３００ｒｐｍで１２０時間処理を行って粉砕した。この時の粒度分布は図１３に示すものとなった。粒度分布の測定はＨＯＲＩＢＡ製ＬＡ−９５０で行った。平均粒径は０．０９μｍとなった。このスラリーを用いて固形分濃度を１％にした液を５０ｃｃ作製した。更にこの液にバインダー（荒川化学製 ユリア―ノＷ６００）を固形分として触媒量の３倍重量になるように添加して１時間攪拌し均一化した触媒塗料を作製した。この触媒塗料を用いて厚さ０．３ｍｍ程度のＳＵＳ３０４の金属板幅１０ｃｍ 長さ１０ｃｍに全面の裏表にスプレーで塗布した。塗布後８０℃にて１時間乾燥した。この際に乾燥後の触媒担持量は０．６ｇになるように固定した。これは塗膜の単位面積当たりの触媒重量は ６ｍｇ／ｃｍ２となっている。これを図８に示すような９００ｍＬのガラス瓶に入れて、完全に光を遮蔽する金属製の箱に入れ、且つ温度を２０℃になるように制御してアルモニア水の分解を調べた。アンモニア水を入れた時の雰囲気は大気中のために大気の窒素や酸素濃度が含まれている。分解特性を調べる際に液中のアンモニア成分と気相中のアンモニア成分の平衡状態が密閉系では成立するために気相中のアンモニア濃度を評価した。この際、初期にガラス瓶の中にアンモニア水の濃度が１００ｐｐｍになるようにしたアンモニア水を２００ｃｃ入れ、この液に硫酸銅１０ｍｇを添加して銅アンモニア錯体を形成させて青色に着色させた。液中のアンモニアの量は硫酸銅１０ｍｇを添加して色の変化からアンモニアの残留状態を確認した。触媒を担持したガラス板を液に全体が漬かるように入れた。アンモニア水から発生するアンモニアガスをガステック検知器 ＧＶ‐１００Ｓを用いて、検知管は型番９１Ｌで測定濃度範囲０．１〜４０ｐｐｍのものを用いた。初期の濃度と２４時間経過後のアンモニア濃度を調べた。比較例としてガラス板に触媒を担持しないものを用いた。この結果を表１０に示した。表１１に色の変化を調べた結果を示す。表中の数値として測定精度を考慮して小数点二桁目は四捨五入のものとした。表中には分かりやすいように初期濃度を１として規格化して比較した。この結果から、アンモニアが触媒により分解していることが分かった。As the ammonium tungstate compound of the present invention, the main component was (NH 4 ) 6 · H 2 (W 3 O 10 ) 4 · 20H 2 O, and firing was performed in the air at 300 ° C for 1 hour. The crystal structure of this powder was analyzed by an X-ray analyzer. The result is shown in FIG. From these results, the main components were (NH 4 ) 0.25 WO 3 and WO 3 . 10 g of this powder was weighed and put in a 500 cc beaker, then 1 kg of zirconia beads having a size of 0.05 mmφ was added, 200 g of pure water was added, and a propeller-type stirrer was treated for 120 hours at a stirring speed of 300 rpm. Crushed. The particle size distribution at this time is shown in FIG. The particle size distribution was measured with LA-950 manufactured by HORIBA. The average particle size was 0.09 μm. Using this slurry, 50 cc of a liquid having a solid content of 1% was prepared. Further, a binder (Uriano W600 manufactured by Arakawa Chemical Co., Ltd.) was added to this solution as a solid content so as to be 3 times the weight of the catalyst amount, and stirred for 1 hour to prepare a uniform catalyst coating. Using this catalyst paint, a metal plate of SUS304 having a thickness of about 0.3 mm was applied by spraying on the front and back of the entire surface to a width of 10 cm and a length of 10 cm. After coating, it was dried at 80 ° C. for 1 hour. At this time, the amount of catalyst supported after drying was fixed to be 0.6 g. This has a catalyst weight per unit area of the coating film of 6 mg / cm 2 . This was placed in a 900 mL glass bottle as shown in FIG. 8, placed in a metal box that completely shields light, and the temperature was controlled to 20 ° C. to investigate the decomposition of armonia water. Since the atmosphere when the ammonia water is put is in the atmosphere, it contains nitrogen and oxygen concentrations in the atmosphere. When investigating the decomposition characteristics, the ammonia concentration in the gas phase was evaluated because the equilibrium state of the ammonia component in the liquid and the ammonia component in the gas phase is established in the closed system. At this time, 200 cc of ammonia water having an ammonia water concentration of 100 ppm was initially put in a glass bottle, and 10 mg of copper sulfate was added to this solution to form a copper-ammonia complex, which was colored blue. Regarding the amount of ammonia in the liquid, 10 mg of copper sulfate was added and the residual state of ammonia was confirmed from the color change. The glass plate supporting the catalyst was put into the liquid so that the whole was soaked. The gas tech detector GV-100S was used for the ammonia gas generated from the ammonia water, and the detection tube used was a model number 91L with a measurement concentration range of 0.1 to 40 ppm. The initial concentration and the ammonia concentration after 24 hours were examined. As a comparative example, a glass plate without a catalyst was used. The results are shown in Table 10. Table 11 shows the results of examining the change in color. As the numerical values in the table, the second decimal point is rounded off in consideration of measurement accuracy. In the table, the initial concentration was set to 1 and standardized for easy understanding. From this result, it was found that ammonia was decomposed by the catalyst.
（ＮＨ４）６・Ｈ２（Ｗ３Ｏ１０）４・２０Ｈ２Ｏを３００℃１時間で焼成して（ＮＨ３）０．２５ＷＯ３ を作製した。この粉を１０ｇ秤量し５００ｃｃのビーカに入れて、次に大きさ０．１ｍｍφのジルコニアビーズを１ｋｇ入れた後に純水２００ｇを添加した。この後、水酸化ナトリウムを０．１ｇ添加して、１時間ほど攪拌しアンモニアサイトをナトリウムイオンに部分的に置換した。この攪拌過程で容器からアンモニア臭が得られた。更に塩化白金酸Ｈ２（ＰｔＣｌ６）を（ＮＨ３）０．２５ＷＯ３に対して５００ｐｐｍになるように添加した後、ヒドラジンを０．１ＣＣ添加した。この後、プロペラ型の攪拌機を攪拌速度３００ｒｐｍで粉砕時間を変えて平均粒径を５０ｎｍ程度まで粉砕し、バインダー（荒川化学製 ユリア―ノＷ６００）を固形分として触媒量の３倍重量になるように添加して１時間攪拌した。作製した触媒塗料を用いて、厚さ１ｍｍ程度の綿生地 幅１０ｃｍ長さ１０ｃｍに全面の裏表にスプレーで塗布した。塗布後８０℃にて１時間乾燥した。乾燥後の触媒担持重量を０．０５〜５ｇになるように変えて作製した。担持触媒量は０．０５〜５ｍｇ／ｃｍ２になっている。これを図８に示すような９００ｍＬのガラス瓶に入れて、完全に光を遮蔽する金属製の箱に入れ、且つ温度を２０℃になるように制御してアルモニア水の分解を調べた。アンモニア水を入れた時の雰囲気は大気中のために大気の窒素や酸素濃度が含まれている。分解特性を調べる際に液中のアンモニア成分と気相中のアンモニア成分の平衡状態が密閉系では成立するために気相中のアンモニア濃度を評価した。この際、初期にガラス瓶の中にアンモニア水の濃度が１００ｐｐｍになるようにしたアンモニア水を２００ＣＣ入れ、この液に硫酸銅１０ｍｇを添加して銅アンモニア錯体を形成させて青色に着色させた。液中のアンモニアの量は硫酸銅１０ｍｇを添加して色の変化からアンモニアの残留状態を確認した。触媒を担持したガラス板を液に全体が漬かるように入れた。アンモニア水から発生するアンモニアガスをガステック検知器 ＧＶ‐１００Ｓを用いて、検知管は型番９１Ｌで測定濃度範囲０．１〜４０ｐｐｍのものを用いた。初期の濃度と２４時間経過後のアンモニア濃度を調べた。この結果を表１２に示した。表中の数値として測定精度を考慮して小数点二桁目は四捨五入のものとした。表中には分かりやすいように初期濃度を１として規格化して比較した。この結果から、触媒担持量としては０．２ｍｇ／ｃｍ２％以上、望ましくは０．５ｍｇ／ｃｍ２以上であることが良いことが分かった。Was produced (NH 4) 6 · H 2 (W 3 O 10) of 4 · 20H 2 O was baked at 300 ° C. 1 hour (NH 3) 0.25 WO 3. 10 g of this powder was weighed and placed in a 500 cc beaker, then 1 kg of zirconia beads having a size of 0.1 mmφ was placed therein, and then 200 g of pure water was added. Then, 0.1 g of sodium hydroxide was added and stirred for about 1 hour to partially replace the ammonia site with sodium ion. Ammonia odor was obtained from the container during this stirring process. Further, chloroplatinic acid H2 (PtCl6) was added so as to be 500 ppm with respect to (NH 3 ) 0.25 WO 3 , and then 0.1 CC of hydrazine was added. After that, a propeller stirrer was crushed at a stirring speed of 300 rpm and the crushing time was changed to crush the particles to an average particle size of about 50 nm, and the binder (Ariakawa Chemical Co., Ltd., urea-no W600) was used as a solid content to be 3 times the catalyst weight. And stirred for 1 hour. Using the prepared catalyst paint, a cotton cloth having a thickness of about 1 mm and having a width of 10 cm and a length of 10 cm was sprayed on the entire front and back surfaces. After coating, it was dried at 80 ° C. for 1 hour. It was produced by changing the weight of the catalyst supported after drying to be 0.05 to 5 g. The amount of supported catalyst is 0.05 to 5 mg / cm 2 . This was placed in a 900 mL glass bottle as shown in FIG. 8, placed in a metal box that completely shields light, and the temperature was controlled to 20 ° C. to examine the decomposition of armonia water. Since the atmosphere when the ammonia water is put is in the atmosphere, it contains nitrogen and oxygen concentrations in the atmosphere. When investigating the decomposition characteristics, the ammonia concentration in the gas phase was evaluated because the equilibrium state of the ammonia component in the liquid and the ammonia component in the gas phase is established in the closed system. At this time, 200 CC of ammonia water having an ammonia water concentration of 100 ppm was initially put in a glass bottle, and 10 mg of copper sulfate was added to this solution to form a copper-ammonia complex, which was colored blue. Regarding the amount of ammonia in the liquid, 10 mg of copper sulfate was added and the residual state of ammonia was confirmed from the color change. The glass plate supporting the catalyst was put into the liquid so that the whole was soaked. The gas tech detector GV-100S was used for the ammonia gas generated from the ammonia water, and the detection tube used was a model number 91L with a measurement concentration range of 0.1 to 40 ppm. The initial concentration and the ammonia concentration after 24 hours were examined. The results are shown in Table 12. As the numerical values in the table, the second decimal point is rounded off in consideration of measurement accuracy. In the table, the initial concentration was set to 1 and standardized for easy understanding. From this result, it was found that the catalyst loading amount is preferably 0.2 mg / cm 2 % or more, and more preferably 0.5 mg / cm 2 or more.
本発明の化合物は室温において、光がない条件において液中にあるアンモニアを分解する優れた触媒性能を有している。これは一般的な取水に存在しているアンモニアを分解し除去する材料や装置や廃液に含まれるアンモニアを除去する部品や装置、システムとして用いることが出来る。The compound of the present invention has an excellent catalytic performance for decomposing ammonia in a liquid at room temperature in the absence of light. It can be used as a material or device for decomposing and removing ammonia present in general water intake, or as a component, device, or system for removing ammonia contained in waste liquid.
１ サンプルを入れるガラス瓶（ガラス瓶の蓋の内側にＰＥフィルムで封止）
２ 触媒を担持したプラスチック板1 Glass bottle containing the sample (sealed with PE film inside the glass bottle lid)
2 Plastic plate supporting catalyst
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