JP3362434B2 - Pitting corrosion inhibitor for copper - Google Patents
Pitting corrosion inhibitor for copperInfo
- Publication number
- JP3362434B2 JP3362434B2 JP07796993A JP7796993A JP3362434B2 JP 3362434 B2 JP3362434 B2 JP 3362434B2 JP 07796993 A JP07796993 A JP 07796993A JP 7796993 A JP7796993 A JP 7796993A JP 3362434 B2 JP3362434 B2 JP 3362434B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- pitting
- corrosion
- corrosion inhibitor
- inhibitor
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/167—Phosphorus-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は銅用孔食防止剤に係り、
特に、銅管等の銅材質部材の孔食発生の前段階としての
自然電位上昇を抑制し、孔食の発生を有効に防止する銅
用孔食防止剤に関する。
【０００２】
【従来の技術】冷却水系等の各種水系に使用される銅又
は銅合金よりなる配管、その他の部材では、銅（又は銅
合金）の腐食ないしは腐食による孔食が大きな問題とな
っている。これら銅材質配管等の孔食は、一般に、その
自然電位が１９０ｍＶ以上になると発生するとされてい
る。
【０００３】従来、銅材質の腐食防止のために、水系に
腐食防止剤を添加する方法が多く採用されており、腐食
防止剤としてはトリルトリアゾール、ベンゾトリアゾー
ル、メルカプトベンゾチアゾールが主に用いられてい
る。
【０００４】
【発明が解決しようとする課題】しかしながら、従来の
トリルトリアゾール、ベンゾトリアゾール、メルカプト
ベンゾチアゾールよりなる腐食防止剤では、腐食を十分
に防止し得ない場合があった。特に、地下水を補給水と
する蓄熱冷温水系では、これらの腐食防止剤を用いて
も、銅材質の腐食ないし孔食が発生し易い。
【０００５】本発明は上記従来の問題点を解決し、銅材
質の腐食を、少ない薬剤使用量にて長期にわたり確実に
防止することができる蓄熱水系用の銅用孔食防止剤を提
供することを目的とする。
【０００６】
【課題を解決するための手段】本発明の蓄熱水系用の銅
用孔食防止剤は、銅材質部材の自然電位上昇を抑制する
ことによって孔食の発生を防止する蓄熱水系用の銅用孔
食防止剤であって、テトラキス（ヒドロキシメチル）ホ
スホニウム硫酸塩を含むことを特徴とする。
【０００７】以下に本発明を詳細に説明する。
【０００８】本発明の蓄熱水系用の銅用孔食防止剤にお
いて、有効成分として用いるテトラキス（ヒドロキシメ
チル）ホスホニウム硫酸塩は下記構造式で示されるもの
である。
【０００９】
【化１】
【００１０】このようなテトラキス（ヒドロキシメチ
ル）ホスホニウム硫酸塩を含む本発明の銅用孔食防止剤
は、被処理対象である蓄熱水系に対して１〜５００ｍｇ
／ｌの添加で良好な自然電位上昇抑制作用が発揮され、
孔食は有効に防止される。
【００１１】なお、本発明の銅用孔食防止剤の被処理対
象水系への投入回数はその被処理対象系によっても異な
るが、本発明の銅用孔食防止剤は長期効果持続性に優れ
ることから、３〜６カ月に１回の投入添加で十分な効果
が得られる。また、銅材質部材の自然電位を測定し、そ
の自然電位に基いて投入を制御することもできる。具体
的には銅管の自然電位が１５０ｍＶを超えた場合には、
本発明の銅用孔食防止剤を投入添加するようにすれば良
い。
【００１２】
【作用】本発明に係るテトラキス（ヒドロキシメチル）
ホスホニウム硫酸塩は、従来の防食剤では効果が得られ
なかった蓄熱水系に対しても、極めて良好な電位上昇抑
制効果、即ち、孔食防止効果が得られ、少量の薬剤使用
量にて、長期にわたり銅材質の孔食を確実に防止するこ
とができる。
【００１３】
【実施例】以下に実施例及び比較例を挙げて、本発明を
より具体的に説明するが、本発明はその要旨を超えない
限り、以下の実施例に限定されるものではない。
【００１４】比較例１
表１に示す水質の地下水を、図１に示す試験装置で通水
し、自然電位及び腐食の進行を調べた。
【００１５】なお、図１において、１は水槽、２は流量
計、３はりん脱酸銅管（直径１６ｍｍ、長さ５００ｍ
ｍ、肉厚０．５ｍｍ）、４は電位差計、５はＡｇ／Ａｇ
Ｃｌ比較電極、Ｐはポンプ、Ｖ１，Ｖ２はバルブ、６，
７，８は配管であり、水槽１内の水はポンプＰにより、
配管６、流量計２、配管７、りん脱酸銅管３及び配管８
を経て室温にて０．１ｍ／ｓの流速で、１２時間通水、
１２時間停止の周期で循環させ、銅管の自然電位の経日
変化を調べた。
【００１６】
【表１】【００１７】その結果、表２に示す如く、試験開始後経
時的に銅管の自然電位が上昇し、２０日後には自然電位
は銅管の孔食発生電位と言われている１９０ｍＶ（飽和
Ａｇ／ＡｇＣｌ電極）以上に達し、孔食が進行した。
【００１８】また、１２０日後に銅管を半割りにしたと
ころ、内面に一面に緑青が発生していた。
【００１９】実施例１、比較例２
水槽内に表２に示す薬剤を表２に示す割合で添加したこ
と以外は比較例１と同様に通水試験を行なって、自然電
位の経日変化を調べ、結果を表２に示した。
【００２０】また、１２０日後の銅管内面の状態を調べ
たところ、実施例１では緑青の発生は全く見られなかっ
たが、比較例２では緑青が発生していた。
【００２１】以上の結果から、本発明の銅用孔食防止剤
によれば自然電位の上昇は抑制され、孔食は確実に防止
されることが明らかである。
【００２２】これに対して、従来の腐食防止剤であるト
リルトリアゾールを用いた比較例２では、腐食防止剤を
用いない比較例１の結果と殆ど変わらず、効果が全くな
い。
【００２３】
【表２】【００２４】
【発明の効果】以上詳述した通り、本発明の銅用孔食防
止剤によれば、蓄熱水系において、少ない薬剤使用量に
て、長期間、腐食ないし孔食に到る銅材質の電位上昇を
抑制し、銅材質の腐食ないし孔食を有効に防止すること
ができる。このため、銅管等の孔食による貫通、漏水事
故を確実に防止することが可能とされる。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pitting corrosion inhibitor for copper,
In particular, to suppress the spontaneous potential increase as a pre-stage of pitting corrosion of the copper material member of a copper pipe or the like, to copper for pitting corrosion inhibitor to effectively prevent the occurrence of pitting. [0002] In piping and other members made of copper or copper alloy used in various water systems such as a cooling water system, corrosion of copper (or copper alloy) or pitting corrosion due to corrosion becomes a serious problem. I have. It is generally considered that pitting corrosion of copper pipes or the like occurs when the natural potential becomes 190 mV or more. Hitherto, in order to prevent corrosion of copper materials, a method of adding a corrosion inhibitor to an aqueous system has been often adopted. As the corrosion inhibitor, tolyltriazole, benzotriazole, and mercaptobenzothiazole are mainly used. I have. [0004] However, in some cases, conventional corrosion inhibitors comprising tolyltriazole, benzotriazole, and mercaptobenzothiazole cannot sufficiently prevent corrosion. In particular, in a thermal storage cold / hot water system using groundwater as makeup water, even if these corrosion inhibitors are used, corrosion or pitting of the copper material is likely to occur. The present invention has been made to solve the above-mentioned conventional problems, and to provide a copper pitting corrosion inhibitor for a heat storage water system, which can reliably prevent corrosion of copper material for a long period of time with a small amount of chemicals. With the goal. SUMMARY OF THE INVENTION The pitting corrosion inhibitor for copper for a heat storage water system of the present invention suppresses an increase in the natural potential of a copper material member.
Hole for copper for heat storage water system to prevent pitting corrosion
An anticorrosive, comprising tetrakis (hydroxymethyl) phosphonium sulfate. Hereinafter, the present invention will be described in detail. The tetrakis (hydroxymethyl) phosphonium sulfate used as an active ingredient in the copper pitting inhibitor for a heat storage water system of the present invention is represented by the following structural formula. [0009] [0010] The pitting corrosion inhibitor for copper of the present invention containing such a tetrakis (hydroxymethyl) phosphonium sulfate is used in an amount of 1 to 500 mg based on the heat storage water system to be treated.
/ L is effective in suppressing the increase in spontaneous potential.
Pitting is effectively prevented. [0011] Incidentally, the input number to be processed aqueous copper for pitting inhibitor of the present invention varies depending on the object to be processed based, but for copper pitting inhibitor of the present invention is excellent in long-term effects lasting Therefore, a sufficient effect can be obtained by adding once every 3 to 6 months. In addition, it is also possible to measure the natural potential of the copper material member and control the injection based on the natural potential. Specifically, when the natural potential of the copper tube exceeds 150 mV,
The pitting corrosion inhibitor for copper of the present invention may be added and added. The tetrakis (hydroxymethyl) according to the present invention
Phosphonium sulfate also has a very good potential rise suppressing effect, that is, a pitting prevention effect, even for a heat storage water system, which was not effective with a conventional anticorrosive, and has a long term The pitting corrosion of the copper material can be reliably prevented over a long period of time. The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. . Comparative Example 1 Groundwater having the quality shown in Table 1 was passed through a test apparatus shown in FIG. 1 to examine the natural potential and the progress of corrosion. In FIG. 1, 1 is a water tank, 2 is a flow meter, and 3 is a phosphor deoxidized copper tube (diameter 16 mm, length 500 m).
m, wall thickness 0.5 mm), 4 is a potentiometer, 5 is Ag / Ag
Cl reference electrode, P is a pump, V 1 and V 2 are valves, 6,
7 and 8 are pipes, and the water in the water tank 1 is pumped by a pump P.
Pipe 6, flow meter 2, pipe 7, phosphorus deoxidized copper pipe 3, and pipe 8
At room temperature at a flow rate of 0.1 m / s for 12 hours,
Circulation was carried out in a cycle of a 12-hour stop, and the daily change of the self-potential of the copper tube was examined. [Table 1] As a result, as shown in Table 2, the spontaneous potential of the copper tube increased with time after the start of the test, and after 20 days, the spontaneous potential was 190 mV (saturated Ag), which is called the pitting potential of the copper tube. / AgCl electrode) or more, and pitting corrosion has progressed. When the copper tube was cut in half after 120 days, patina appeared on the entire inner surface. Example 1 and Comparative Example 2 A water flow test was performed in the same manner as in Comparative Example 1 except that the chemicals shown in Table 2 were added to the water tank at the ratios shown in Table 2, and the change in natural potential over time was measured. Investigation and the results are shown in Table 2. When the state of the inner surface of the copper tube was examined 120 days later, no patina was observed in Example 1 but patina was observed in Comparative Example 2. From the above results, the increase in natural potential, according to the copper for pitting inhibitor of the present invention is suppressed, pitting it is clear to be reliably prevented. On the other hand, in Comparative Example 2 using tolyltriazole, which is a conventional corrosion inhibitor, there is almost no difference from the result of Comparative Example 1 in which no corrosion inhibitor is used, and there is no effect at all. [Table 2] [0024] As described above in detail, according to the copper for pitting inhibitor of the present invention, the heat storage water system, with a small drug amount, long term, copper material leading to corrosion or pitting Of the copper material can be effectively prevented from corroding or pitting. For this reason, it is possible to reliably prevent penetration and water leakage accidents due to pitting of the copper pipe or the like.
【図面の簡単な説明】
【図１】実施例及び比較例で用いた通水試験装置を示す
系統図である。
【符号の説明】
１ 水槽
２ 流量計
３ りん脱酸銅管
４ 電位差計
５ Ａｇ／ＡｇＣｌ比較電極BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a system diagram showing a water flow test device used in Examples and Comparative Examples. [Description of Signs] 1 Water tank 2 Flow meter 3 Phosphorus deoxidized copper tube 4 Potentiometer 5 Ag / AgCl reference electrode
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−285082（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23F 11/00 - 11/18 C02F 5/08 ＷＰＩ（ＤＩＡＬＯＧ)──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-2-285082 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C23F 11/00-11/18 C02F 5 / 08 WPI (DIALOG)
Claims (1)
とによって孔食の発生を防止する蓄熱水系用の銅用孔食
防止剤であって、テトラキス（ヒドロキシメチル）ホス
ホニウム硫酸塩を含むことを特徴とする蓄熱水系用の銅
用孔食防止剤。(57) [Claims] [Claim 1] Suppressing a rise in the natural potential of a copper material member.
Pitting for copper for heat storage water systems to prevent pitting from occurring
A inhibitor, tetrakis for copper pitting inhibitor for heat storage water system comprising (hydroxymethyl) phosphonium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07796993A JP3362434B2 (en) | 1993-04-05 | 1993-04-05 | Pitting corrosion inhibitor for copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07796993A JP3362434B2 (en) | 1993-04-05 | 1993-04-05 | Pitting corrosion inhibitor for copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06287776A JPH06287776A (en) | 1994-10-11 |
| JP3362434B2 true JP3362434B2 (en) | 2003-01-07 |
Family
ID=13648760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07796993A Expired - Fee Related JP3362434B2 (en) | 1993-04-05 | 1993-04-05 | Pitting corrosion inhibitor for copper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3362434B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4921001B2 (en) * | 2006-03-15 | 2012-04-18 | アクアス株式会社 | How to remove patina |
-
1993
- 1993-04-05 JP JP07796993A patent/JP3362434B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06287776A (en) | 1994-10-11 |
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