JP3273952B2 - How to detect hydrogen gas leakage - Google Patents
How to detect hydrogen gas leakageInfo
- Publication number
- JP3273952B2 JP3273952B2 JP06370291A JP6370291A JP3273952B2 JP 3273952 B2 JP3273952 B2 JP 3273952B2 JP 06370291 A JP06370291 A JP 06370291A JP 6370291 A JP6370291 A JP 6370291A JP 3273952 B2 JP3273952 B2 JP 3273952B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen gas
- paint
- palladium oxide
- gas leakage
- palladium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水素ガスの漏洩を検知
する塗料に関するものであり、安全上水素ガス漏洩の常
時監視が必要な容器、配管等へ利用することができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint for detecting leakage of hydrogen gas, and can be used for containers, pipes and the like which require constant monitoring of hydrogen gas leakage for safety.
【０００２】[0002]
【従来の技術】従来の漏洩検知方法を例示すれば、水素
ガス消費量の監視、水素ガス検知器及びガス洩れ検知
液、更には圧力降下による監視法、磁気探傷法等が提案
され、利用されている。2. Description of the Related Art As conventional leak detection methods, monitoring of hydrogen gas consumption, hydrogen gas detector and gas leak detection liquid, monitoring method by pressure drop, magnetic flaw detection method, etc. have been proposed and used. ing.
【０００３】また、水素の漏洩を検知する検知剤とし
て、酸化パラジウム水化物を含浸させた検知紙が知られ
ている（特公昭５７−５７９７７号公報）。As a detecting agent for detecting the leakage of hydrogen, a detecting paper impregnated with palladium oxide hydrate is known (Japanese Patent Publication No. 57-57977).
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、これら
従来の方法では、漏洩箇所の特定は別の方法で行わなけ
ればならず、常時監視の方法としては作業性の点で不充
分である。However, in these conventional methods, the location of the leak must be specified by another method, and the method of constant monitoring is insufficient in terms of workability.
【０００５】また、酸化パラジウム水化物を単に塗料に
添加したときは、被塗料物の色相によって、あるいは塗
料中の顔料の隠蔽力のために、酸化パラジウムの色相変
化が検出し難いという問題がある。In addition, when hydrated palladium oxide is simply added to a paint, there is a problem that it is difficult to detect a change in the hue of the palladium oxide due to the hue of the object to be coated or the hiding power of the pigment in the paint. .
【０００６】本発明はこれらの問題を解決するために、
水素ガスの漏洩箇所をいち早く特定する、水素ガス漏洩
検知の常時監視用塗料を提供するものである。The present invention has been made to solve these problems.
It is an object of the present invention to provide a paint for constant monitoring of hydrogen gas leak detection, which quickly identifies a hydrogen gas leak location.
【０００７】[0007]
【課題を解決するための手段】本発明は、酸化パラジウ
ム水化物で被覆した微粒子無機粉体を含有することを特
徴とする水素ガス漏洩検知塗料である。SUMMARY OF THE INVENTION The present invention is a hydrogen gas leak detection paint containing fine inorganic powder coated with palladium oxide hydrate.
【０００８】本発明は、酸化パラジウム水化物が水素に
より還元されて黒色のパラジウムを生成する反応を利用
するものである。The present invention utilizes a reaction in which palladium oxide hydrate is reduced by hydrogen to produce black palladium.
【０００９】無機粉体としては、酸化パラジウムの変色
の検知を阻害しない白色ないし淡黄色系の粉体が好まし
い。粒径は１００μ以下、好ましくは１０μ以下、更に
好ましくは５μ以下のものが用いられる。一般に、タル
ク、シリカ、炭酸カルシウム、酸化亜鉛、硫酸バリウ
ム、酸化チタンなどが用いられ、特に酸化チタンが好ま
しい。これら無機粉体に対する酸化パラジウム水化物の
被覆量は、２重量％以上であればよいが、通常２〜１５
重量％程度でよく、好ましくは４〜１５重量％である。As the inorganic powder, a white or pale yellow powder that does not hinder the detection of discoloration of palladium oxide is preferable. Particles having a particle size of 100 μm or less, preferably 10 μm or less, more preferably 5 μm or less are used. Generally, talc, silica, calcium carbonate, zinc oxide, barium sulfate, titanium oxide and the like are used, and titanium oxide is particularly preferable. The coating amount of palladium oxide hydrate on these inorganic powders may be 2% by weight or more, but is usually 2 to 15%.
% By weight, preferably 4 to 15% by weight.
【００１０】酸化パラジウム水化物を生成するパラジウ
ム化合物としては、ＰｄＣｌ2 、ＰｄＣｌ2 ・２ＮａＣ
ｌ、（ＮＨ4 ）2 ＰｄＣｌ4 、Ｐｄ（ＮＯ3 ）2 、Ｐｄ
ＳＯ4 等のパラジウム塩を用いることができ、これら化
合物の水溶液を加水分解させた場合は、容易に酸化パラ
ジウム水化物（水和物）を生成するので、これらの塩を
原料として用いることができる。Palladium compounds that form palladium oxide hydrate include PdCl 2 , PdCl 2 .2NaC
1, (NH 4 ) 2 PdCl 4 , Pd (NO 3 ) 2 , Pd
A palladium salt such as SO 4 can be used, and when an aqueous solution of these compounds is hydrolyzed, a palladium oxide hydrate (hydrate) is easily generated, so that these salts can be used as a raw material. .
【００１１】該パラジウム化合物の水溶液に無機粉体を
懸濁させ、ＮａＯＨを用いて徐々にpHを７．０〜８．０
に調整することにより酸化パラジウム水化物が無機粉体
上に薄膜として生成する。An inorganic powder is suspended in an aqueous solution of the palladium compound, and the pH is gradually adjusted to 7.0 to 8.0 using NaOH.
Thus, palladium oxide hydrate is formed as a thin film on the inorganic powder.
【００１２】こうして得られた酸化パラジウム水化物被
覆無機粉体粒子を用いて塗料を調製するが、塗料成分と
しては、種々のものを用いることができ、塗膜形成材と
しては、セラック、コーパル等の天然樹脂；ロジンエス
テル等の加工樹脂；フェノール樹脂、尿素樹脂、メラミ
ン樹脂、フタル酸樹脂、アクリル樹脂、エポキシ樹脂、
ビニル樹脂等の合成樹脂；アセチルセルロース等のセル
ロース誘導体；塩化ゴム、環化ゴム、合成ゴム等のゴム
誘導体；ポリビニルアルコール、カゼイン、カルボキシ
メチルセルロース等の水溶性化合物等を用いることがで
きる。これらの中でもアクリル樹脂、フタル酸樹脂が好
ましい。A coating is prepared using the palladium oxide hydrate-coated inorganic powder particles thus obtained. Various coating components can be used, and a coating film forming material such as shellac, copal or the like can be used. Natural resin; processed resin such as rosin ester; phenolic resin, urea resin, melamine resin, phthalic acid resin, acrylic resin, epoxy resin,
Synthetic resins such as vinyl resins; cellulose derivatives such as acetylcellulose; rubber derivatives such as chlorinated rubber, cyclized rubber, and synthetic rubber; water-soluble compounds such as polyvinyl alcohol, casein, carboxymethyl cellulose, and the like can be used. Among them, acrylic resin and phthalic acid resin are preferable.
【００１３】また、塗料の分散、塗膜の乾燥、硬化、物
性改良のために公知の各種添加剤、例えば乾燥促進剤、
例えば、ナフテン酸鉛、ナフテン酸マンガン、ナフテン
酸コバルト等；硬化剤；可塑剤、例えば、ジブチルフタ
レート、ヒマシ油等；分散剤、例えば、各種界面活性
剤、レシチン等；乳化剤；防錆剤、例えば、ジンククロ
メート等；皮張り防止剤、例えば、メチルエチルケトオ
キシム、フェノール類等；増粘剤；等を添加することが
できる。また、酸化パラジウムの変色の検知を阻害しな
い範囲で他の顔料を添加することができる。溶剤又は希
釈剤は、ミネラルスピリッツ、キシレン、トルエン等の
塗膜形成に適した公知の溶媒又は分散媒を用いることが
できる。Various additives known in the art for dispersing the paint, drying and curing the coating, and improving the physical properties, such as a drying accelerator,
For example, lead naphthenate, manganese naphthenate, cobalt naphthenate, etc .; hardener; plasticizer, eg, dibutyl phthalate, castor oil, etc .; dispersant, eg, various surfactants, lecithin, etc .; emulsifier; , Zinc chromate and the like; anti-skinning agents such as methyl ethyl ketoxime, phenols and the like; thickeners and the like can be added. Further, other pigments can be added as long as the detection of discoloration of palladium oxide is not hindered. As the solvent or diluent, a known solvent or dispersant suitable for forming a coating film such as mineral spirits, xylene, and toluene can be used.
【００１４】酸化パラジウム水化物で被覆した微粒子無
機粉体の配合量は、塗料中の樹脂固形分に対して通常５
〜７０重量％、好ましくは１０〜６０重量％、特に好ま
しくは２０〜５０重量％である。The compounding amount of the fine inorganic powder coated with palladium oxide hydrate is usually 5 to the solid content of the resin in the paint.
It is from 70 to 70% by weight, preferably from 10 to 60% by weight, particularly preferably from 20 to 50% by weight.
【００１５】[0015]
【発明の効果】本発明の水素ガス漏洩検知塗料は上塗り
塗料として用いられる。これを使用して水素ガスの漏洩
を監視するには、水素ガス漏洩の恐れがある容器、配管
等の所定部に本塗料を塗布しておき、水素ガスの漏洩が
あると、酸化パラジウムと水素ガスとが反応してパラジ
ウム黒が生成、黒色に変色するので、漏洩部の迅速な発
見が可能となる。The paint for detecting hydrogen gas leakage according to the present invention is used as a top coat. In order to monitor the leakage of hydrogen gas by using this, apply this paint to predetermined parts of containers and pipes where there is a risk of hydrogen gas leakage, and if there is leakage of hydrogen gas, palladium oxide and hydrogen The reaction with the gas produces palladium black and changes the color to black, so that a leak can be quickly found.
【００１６】更に漏出水素ガスは塗膜の中を拡散するた
め、漏洩箇所のピンホールを中心に約１０倍程度の範囲
の塗膜を変色させ、微小なピンホールの検出も可能とさ
せる等の効果もある。Further, since the leaked hydrogen gas diffuses in the coating film, the color of the coating film in the range of about 10 times around the pinhole at the leak location is changed to enable detection of minute pinholes. There is also an effect.
【００１７】したがって、長期間に亙り、常時水素ガス
の漏洩を監視することができ、また、酸化パラジウム水
化物は無機粉体に担持されかつ塗料化されているから、
耐久性に優れ、また変色による漏れ箇所の検出が容易で
ある。Therefore, the leakage of hydrogen gas can be constantly monitored over a long period of time, and the palladium oxide hydrate is supported on the inorganic powder and formed into a paint.
It has excellent durability, and it is easy to detect leaks due to discoloration.
【００１８】[0018]
【実施例】以下、実施例によりさらに具体的に本発明を
説明する。The present invention will be described more specifically with reference to the following examples.
【００１９】実施例１ ＰｄＣｌ2 １ｇを溶解した水溶液１４０mlに、酸化チ
タン（粒径０．３μ、ルチル型）１４ｇを懸濁攪拌しな
がら、３０分間で２規定の苛性ソーダ水溶液を滴下しpH
を調整（pH８）して酸化パラジウム水化物を生成させ
た。その後、遠心分離、水洗（繰り返し洗浄、洗浄倍率
１万〜１．５万倍）し、８５℃で乾燥したものを、以下
の塗料組成に基づき配合した。 （組成） フタル酸樹脂ワニス（大豆油と無水フタル酸からなる）３２．０（wt％） ＴｉＯ2 （ＰｄＯ2 ・ＸＨ2 Ｏコート） １３．０ 分散剤 １．０ 乾燥促進剤 ２．４ 皮張り防止剤 ０．４ ミネラルスピリッツ（溶剤） ５１．２ EXAMPLE 1 14 g of titanium oxide (particle size: 0.3 μm, rutile type) was suspended and stirred in 140 ml of an aqueous solution in which 1 g of PdCl 2 was dissolved.
Was adjusted (pH 8) to produce palladium oxide hydrate. Then, it was centrifuged, washed with water (repeated washing, washing magnification 10,000 to 15,000 times), and dried at 85 ° C, and blended based on the following coating composition. (Composition) Phthalic acid resin varnish (composed of soybean oil and phthalic anhydride) 32.0 (wt%) TiO 2 (PdO 2 .XH 2 O coat) 13.0 Dispersant 1.0 Drying accelerator 2.4 leather Anti-tension agent 0.4 Mineral spirits (solvent) 51.2
【００２０】本塗料を容器の漏洩箇所に塗布し、約３ケ
月間放置後、該容器に水素を充填したところ、約３００
μm のピンホール部を中心に約１０倍の３mmの範囲の塗
膜に黒変が観察された。The paint was applied to the leaked part of the container, left for about three months, and then filled with hydrogen.
Blackening was observed in the coating film in a range of 3 mm, which was about 10 times the center of the pinhole portion of μm.
【００２１】実施例２ 塗料配合組成を以下のように変えた以外は実施例１と同
様の方法で実験を行った。 （組成） アクリル酸樹脂ワニス（大成化工製、“ACRIT 8AZ-202"（商品名）） ３４．０（wt％） ＴｉＯ2 （ＰｄＯ2 ・ＸＨ2 Ｏコート） １３．０ 溶剤 ５０．０ 増粘剤 １．０ 実施例１と同様の結果が得られた。Example 2 An experiment was conducted in the same manner as in Example 1 except that the composition of the paint was changed as follows. (Composition) Acrylic resin varnish (manufactured by Taisei Kako, "ACRIT 8AZ-202" (trade name)) 34.0 (wt%) TiO 2 (PdO 2 · XH 2 O coat) 13.0 Solvent 50.0 Thickening Agent 1.0 The same results as in Example 1 were obtained.
【００２２】実施例３〜４ 粉末担体として酸化チタンに変えてタルク（平均粒径２
μ（実施例３））及びシリカ（平均粒径１μ以下（実施
例４））を用いた以外は、実施例１と同様の方法で実験
を行ったところ、実施例１と同様の結果が得られた。Examples 3 and 4 Talc (average particle size 2) was used in place of titanium oxide as a powder carrier.
μ (Example 3)) and silica (average particle size 1 μm or less (Example 4)), and an experiment was conducted in the same manner as in Example 1. As a result, the same results as in Example 1 were obtained. Was done.
【００２３】実施例５ 塗料配合組成を以下のように変えた以外は実施例１と同
様の方法で実験を行った。実施例１と同様の結果が得ら
れた。 （組成） フタル酸樹脂液（実施例１と同じ） １５．０（wt％） メラミン樹脂液（メチロール化メラミンの初期縮合物のブタノール変性物） ２１．０ ＴｉＯ2 （ＰｄＯ2 ・ＸＨ2 Ｏコート） １３．０ 可塑剤 ４．０ 溶剤 ４５．０ 増粘剤 ２．０Example 5 An experiment was conducted in the same manner as in Example 1 except that the composition of the paint was changed as follows. The same results as in Example 1 were obtained. (Composition) Phthalic acid resin liquid (same as in Example 1) 15.0 (wt%) Melamine resin liquid (butanol-modified initial condensate of methylolated melamine) 21.0 TiO 2 (PdO 2 .XH 2 O coat) ) 13.0 Plasticizer 4.0 Solvent 45.0 Thickener 2.0
───────────────────────────────────────────────────── フロントページの続き (72)発明者 堺 松成 愛知県名古屋市緑区大高町字北関山20番 地の１ 中部電力株式会社技術開発本部 電力技術研究所内 (72)発明者 浅野 宗光 愛知県名古屋市緑区大高町字北関山20番 地の１ 中部電力株式会社技術開発本部 電力技術研究所内 (72)発明者 荒山 紀郎 三重県四日市市大治田三丁目３番17号 株式会社 アクトリサーチ内 (72)発明者 清水 忠雄 三重県四日市市大治田三丁目３番17号 株式会社 アクトリサーチ内 (72)発明者 板倉 啓太郎 三重県四日市市大治田三丁目３番17号 株式会社 アクトリサーチ内 (56)参考文献 特開 昭52−129592（ＪＰ，Ａ) 特開 昭54−94097（ＪＰ，Ａ) 特開 昭63−128249（ＪＰ，Ａ) 特開 平３−35138（ＪＰ，Ａ) 実開 昭64−53937（ＪＰ，Ｕ) 特公 昭57−57977（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.7，ＤＢ名) G01M 3/04 C09C 3/06 C09D 5/00 C09D 7/12 G01N 31/22 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Sakai Matsunari 1 at 20 Kitakanyama, Odaka-cho, Midori-ku, Nagoya-shi, Aichi, Japan Electric Power Technology Research Division, Chubu Electric Power Co., Inc. (72) Inventor Munemitsu Asano No. 1 Kitakanyama, Odaka-cho, Midori-ku, Nagoya-shi, Aichi Pref. Electric Power Technology Research Laboratory, Chubu Electric Power Co., Inc. Within Act Research (72) Inventor Tadao Shimizu 3-3-1-17 Ojida, Yokkaichi City, Mie Prefecture Inside Act Research Co., Ltd. (72) Inventor Keitaro 3-3-1, Ojita Yokkaichi City, Mie Prefecture Act Research, Inc. (56) References JP-A-52-129592 (JP, A) JP-A-54-94097 (JP, A) JP-A-63-128249 (JP, A) 3-35138 (JP, A) JitsuHiraku Akira 64-53937 (JP, U) Tokuoyake Akira 57-57977 (JP, B1) (58 ) investigated the field (Int.Cl. 7, DB name) G01M 3/04 C09C 3/06 C09D 5/00 C09D 7/12 G01N 31/22 CA (STN)
Claims (1)
無機粉体を含有する塗料の色相変化を検出することによ
り、水素ガスの漏洩を検知する方法。1. A method for detecting hydrogen gas leakage by detecting a change in hue of a coating material containing fine inorganic powder coated with palladium oxide hydrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06370291A JP3273952B2 (en) | 1991-03-06 | 1991-03-06 | How to detect hydrogen gas leakage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06370291A JP3273952B2 (en) | 1991-03-06 | 1991-03-06 | How to detect hydrogen gas leakage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04279681A JPH04279681A (en) | 1992-10-05 |
| JP3273952B2 true JP3273952B2 (en) | 2002-04-15 |
Family
ID=13236972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06370291A Expired - Fee Related JP3273952B2 (en) | 1991-03-06 | 1991-03-06 | How to detect hydrogen gas leakage |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3273952B2 (en) |
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|---|---|---|---|---|
| JP2006329889A (en) * | 2005-05-27 | 2006-12-07 | Taiyo Kogyo Corp | Evaluating method of decomposition activity of photocatalyst, and sample used for it |
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| WO2018225894A1 (en) * | 2017-06-08 | 2018-12-13 | 하이리움산업(주) | Hydrogen sensor, method for manufacturing hydrogen sensor, and hydrogen-sensing articles |
| KR20180134149A (en) * | 2017-06-08 | 2018-12-18 | 하이리움에너지 주식회사 | Hydrogen-detecting sensor, method of forming the hydrogen-detecting sensor, and hydrogen-detecting miscellaneous goods |
| KR101990120B1 (en) | 2017-06-08 | 2019-06-19 | 하이리움에너지 주식회사 | Hydrogen-detecting sensor, method of forming the hydrogen-detecting sensor, and hydrogen-detecting miscellaneous goods |
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| JPH04279681A (en) | 1992-10-05 |
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