JPH0790640A - Corrosion inhibitor for iron based metal in water system and corrosion inhibiting method - Google Patents
Corrosion inhibitor for iron based metal in water system and corrosion inhibiting methodInfo
- Publication number
- JPH0790640A JPH0790640A JP23001393A JP23001393A JPH0790640A JP H0790640 A JPH0790640 A JP H0790640A JP 23001393 A JP23001393 A JP 23001393A JP 23001393 A JP23001393 A JP 23001393A JP H0790640 A JPH0790640 A JP H0790640A
- Authority
- JP
- Japan
- Prior art keywords
- corrosion
- corrosion inhibitor
- acid derivative
- water
- hydrogen
- 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.)
- Pending
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、鉄系金属で構成された
設備内を循環する水系などに添加して用いられる金属腐
食防止剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal corrosion inhibitor which is used by being added to a water system or the like which circulates in equipment made of ferrous metal.
【０００２】[0002]
【従来の技術】空調設備用の冷却水や産業用における冷
却水などは、熱交換によって温まった後冷却塔などに送
られ、空気と接触させて一部を蒸発することにより熱を
放出し、冷却した後再び冷却水として循環使用されるの
が普通である。このような循環水中の塩類は次第に濃縮
されて高濃度となり、設備や配管内部の腐食などの障害
を引き起こすこととなる。従って、蒸発して減少した水
を補給するとともに濃縮水の一部を時々排出して、塩類
濃度の調整を行なうことが必要であり、また防食用の水
処理用薬剤を添加することが行われている。2. Description of the Related Art Cooling water for air conditioning equipment, cooling water for industrial use, etc. are heated by heat exchange and then sent to a cooling tower or the like, which is brought into contact with air to partly evaporate heat, After cooling, it is usually recycled again as cooling water. Such salts in the circulating water are gradually concentrated to a high concentration, which causes troubles such as corrosion inside the equipment and piping. Therefore, it is necessary to replenish the water that has evaporated and reduced and to discharge a part of the concentrated water from time to time to adjust the salt concentration, and to add anti-corrosion water treatment chemicals. ing.
【０００３】このような冷却水系の装置には鉄系の材料
で製作された機器が多く用いられており、こうした鉄系
材料に対する腐食防止剤として古くからクロム酸塩、亜
鉛塩等の重金属塩類や、燐酸化合物などが使用されてき
たが、これらは環境汚染の点からみて無制限に使用する
ことは好ましくない。そこで近年、ある種のホスフィノ
カルボン酸類をモリブデン酸塩等の防食剤と併用するこ
とが提案されるに至っているが（特開昭５５−１４９０
０号）、満足すべき防食効果は得られていなかった。Equipment made of iron-based materials are often used for such cooling water-based devices, and as corrosion inhibitors for such iron-based materials, heavy metal salts such as chromates and zinc salts have long been used. Although phosphoric acid compounds and the like have been used, it is not preferable to use them without limitation from the viewpoint of environmental pollution. Therefore, in recent years, it has been proposed to use some phosphinocarboxylic acids in combination with an anticorrosive such as molybdate (Japanese Patent Laid-Open No. 55-1490).
No. 0), a satisfactory anticorrosion effect was not obtained.
【０００４】[0004]
【発明が解決しようとする課題】そこで本発明は、毒性
が少なく環境汚染を引き起こすことがなくて、鉄系金属
材料に対して優れた防食効果を示す水系における腐食防
止剤及び腐食防止防止方法を提供しようとするものであ
る。Therefore, the present invention provides a corrosion inhibitor in a water system and a method for preventing corrosion in a water system, which is less toxic and does not cause environmental pollution and exhibits an excellent anticorrosion effect on ferrous metal materials. It is the one we are trying to provide.
【０００５】[0005]
【課題を解決するための手段】上記のような本発明の目
的は、下記の一般式(I) で示されるホスフィン酸誘導体
と、モリブデン酸又はその塩とを有効成分として含有す
る水系における鉄系金属の腐食防止剤によって達成され
る。そして本発明の腐食防止防止方法は、上記のような
本発明の腐食防止剤を水中に有効成分濃度１〜１０００
mg/lで存在させることによって達成される。The object of the present invention as described above is an iron-based aqueous system containing a phosphinic acid derivative represented by the following general formula (I) and molybdic acid or a salt thereof as active ingredients. Achieved by metal corrosion inhibitors. The method for preventing corrosion according to the present invention comprises the corrosion inhibitor according to the present invention as described above in water with an effective ingredient concentration of 1 to 1000.
This is achieved by being present at mg / l.
【０００６】[0006]
【化３】 式中、Ｒは−ＣＯＯＸ′又は−ＣＯＮＨ−Ｃ（ＣＨ3 ）
2 ＣＨ2 ＳＯ3 Ｘ′であり、同一分子中にこれら２種の
基が混在しているものである。またＹは水素、アルカリ
金属原子、−ＳＯ3 Ｘ″又は−ＰＨＯＯＸ″であり、
Ｘ、Ｘ′、Ｘ″は水素又はアルカリ金属原子である。な
おｍ及びｎはそれぞれ０または正の整数であり、ｍ＋ｎ
は１〜１００の整数である。[Chemical 3] In the formula, R is —COOX ′ or —CONH—C (CH 3 ).
2 CH 2 SO 3 X ', which is a mixture of these two groups in the same molecule. The Y is hydrogen, an alkali metal atom, an -SO 3 X "or -PHOOX",
X, X ′, and X ″ are hydrogen or an alkali metal atom. M and n are 0 or a positive integer, and m + n
Is an integer of 1 to 100.
【０００７】本発明の一液型水処理剤に用いられるホス
フィン酸誘導体は、前記の一般式(I) で示されるホスフ
ィン酸誘導体であるが、式中のＲが−ＣＯＯＸ′又は−
ＣＯＮＨ−Ｃ（ＣＨ3 ）2 ＣＨ2 ＳＯ3 Ｘ′であり、同
一分子中にこれら２種の基が混在しているものであるこ
とが必要で、単一種の基のみであっては本発明の効果は
得られない。かかる特殊なホスフィン酸誘導体として
は、例えばＦＭＣ社から罐石生成防止剤としてベルクリ
ン４００の商品名で販売されている薬剤などが好ましく
使用できる。The phosphinic acid derivative used in the one-pack type water treatment agent of the present invention is the phosphinic acid derivative represented by the above-mentioned general formula (I), wherein R in the formula is --COOX 'or-.
CONH-C is a (CH 3) 2 CH 2 SO 3 X ', it is required in which these two groups are mixed in the same molecule, be only a single type of groups present invention Can not be obtained. As such a special phosphinic acid derivative, for example, a drug sold by FMC under the trade name of Berkulin 400 as an anti-tartar formation agent can be preferably used.
【０００８】また本発明において、前記のホスフィン酸
誘導体と併用されるモリブデン酸塩としては、ナトリウ
ム塩、カリウム塩、或いはアンモニウム塩などの水溶性
の塩が好ましく用いられる。In the present invention, the molybdate used in combination with the phosphinic acid derivative is preferably a water-soluble salt such as sodium salt, potassium salt or ammonium salt.
【０００９】上記のホスフィン酸誘導体とモリブデン酸
又はその塩とは、処理対象の水系に対して別々に添加す
ることもできるが、あらかじめ１剤となるように配合す
るか、又は２剤以上の別包装として組み合わせた腐食防
止剤として用いることができ、その場合水などの溶剤に
溶解したものであってもよい。更にかかる本発明の腐食
防止剤は、前記の有効成分の他、スケール防止剤、スラ
イム防止剤、他種金属に対する防食剤などの水処理剤な
どが含有されていてもよい。The above-mentioned phosphinic acid derivative and molybdic acid or a salt thereof can be added separately to the aqueous system to be treated, but they are mixed so as to be one agent in advance, or two or more agents are separately added. It can be used as a corrosion inhibitor combined as a package, in which case it may be dissolved in a solvent such as water. Further, the corrosion inhibitor of the present invention may contain a water treatment agent such as a scale inhibitor, a slime inhibitor, and an anticorrosive agent against other metals in addition to the above-mentioned active ingredients.
【００１０】本発明において、ホスフィン酸誘導体とモ
リブデン酸又はその塩との使用比率は重量比で１：１０
〜１０：１であり、望ましくは３：１〜１：３である。
この範囲内では優れた相乗作用を発揮するが、範囲の外
では低濃度での効果が充分でない。また水に対するこれ
ら薬剤の添加量は、水と接触する機器の材質にもよる
が、通常水中に有効成分として１〜１０００mg/lの濃度
で存在させるのがよく、特に１０〜１００mg/lの範囲内
にあることが好ましい。In the present invention, the weight ratio of the phosphinic acid derivative to molybdic acid or its salt is 1:10.
It is -10: 1, preferably 3: 1 to 1: 3.
An excellent synergistic effect is exhibited within this range, but the effect at low concentrations is insufficient outside the range. The amount of these agents added to water depends on the material of the equipment that comes into contact with water, but it is usually preferable to make them exist in water at a concentration of 1 to 1000 mg / l as an active ingredient, particularly in the range of 10 to 100 mg / l. It is preferable to be within.
【００１１】[0011]
【作用】本発明の腐食防止剤は、前記のホスフィン酸誘
導体とモリブデン酸又はその塩とを有効成分として含有
してなるものであって、燐含有量が少なくて環境汚染を
引き起こす恐れがなく、しかもそれぞれの成分の相乗効
果によって低濃度の使用で有効に鉄系金属材料の腐食を
防止できるものである。The corrosion inhibitor of the present invention contains the above-mentioned phosphinic acid derivative and molybdic acid or a salt thereof as active ingredients, and has a low phosphorus content, which does not cause environmental pollution. Moreover, due to the synergistic effect of the respective components, the corrosion of the iron-based metallic material can be effectively prevented even if it is used at a low concentration.
【００１２】[0012]
（実施例１）ホスフィン酸誘導体として、式(I) の構造
を有していてＲが−ＣＯＯＨと−ＣＯＮＨ−Ｃ（Ｃ
Ｈ3 ）2 ＣＨ2 ＳＯ3 Ｎａとの混在した基で、ｍ＋ｎの
平均値が約１６である化合物Ｐ（ＦＭＣ社、ベルクリン
４００）、式(I) の構造を有していてＲが−ＣＯＯＨで
あり、ｍ＋ｎの平均値が４である化合物Ｑ（ＦＭＣ社、
ベルクリン５００）、及び式(I) の構造を有していてＲ
が−ＣＯＯＨであり、ｍ＋ｎの平均値が約１６である化
合物Ｒ（ＦＭＣ社、ベルスパース１６４）のいずれか
と、モリブデン酸ナトリウム（Ｍ）又は硫酸亜鉛（Ｚ）
とを組み合わせて、表１に示す組成の本発明の薬剤Ａ及
び比較例の薬剤Ｂ〜Ｉを調製した。(Example 1) As a phosphinic acid derivative, it has the structure of formula (I) and R is -COOH and -CONH-C (C
H 3 ) 2 CH 2 SO 3 Na in a mixed group, compound P having an average value of m + n of about 16 (FMC Co., Berlin 400), having the structure of formula (I) and R being —COOH And a compound Q having an average value of m + n of 4 (FMC,
Bellclin 500), and R having the structure of formula (I)
Is -COOH, and one of the compound R (FMC Corp., Velspers 164) having an average value of m + n of about 16, sodium molybdate (M) or zinc sulfate (Z).
In combination, the agents A of the present invention and the agents B to I of the comparative examples having the compositions shown in Table 1 were prepared.
【００１３】[0013]
【表１】 [Table 1]
【００１４】次に、つくば市水道水にこれらの薬剤Ａ〜
Ｇをそれぞれ表２に示す濃度となるよう添加して試験水
を調製し、開放容器に１０００mlを入れて表面積０．２
７dm 2 の鋼片を浸漬し、長さ５０mmの攪拌子を用いて３
００rpm で攪拌を継続しながら３５℃で７日間腐食試験
を行った。鋼片の腐食減量から腐食度(mdd) を算出し
て、その結果を表２に示した。Next, these chemicals A to
Add G to the concentration shown in Table 2 and add test water.
Prepare 1000 ml in an open container and add 0.2
7 dm 2Immerse the steel piece in 3 and use a stirrer with a length of 50 mm for 3
Corrosion test for 7 days at 35 ° C with continuous stirring at 00 rpm
I went. The corrosion rate (mdd) was calculated from the corrosion weight loss of the billet.
The results are shown in Table 2.
【００１５】[0015]
【表２】 [Table 2]
【００１６】この結果から、本発明の腐食防止剤が鉄系
金属材料に対して優れた防食性を示し、明らかな相乗効
果を発揮するのに対して、類似構造のホスフィン酸誘導
体化合物Ｑ又はＲを用いた薬剤では通常予想される程度
の防食性を示すのみで、特に相乗効果が認められないこ
とがわかる。From these results, the corrosion inhibitor of the present invention exhibits excellent anticorrosion properties for iron-based metallic materials and exhibits a clear synergistic effect, while the phosphinic acid derivative compound Q or R having a similar structure is obtained. It can be seen that the drug using the agent shows only the normally expected anticorrosion property and no synergistic effect is observed.
【００１７】（実施例２）化合物Ｐとモリブデン酸ナト
リウム（Ｍ）とを表３に示すような配合比に従って水に
溶解して本発明の腐食防止剤Ｊ〜Ｌを調製した。これら
の薬剤Ｊ〜Ｌについて、実施例１と同様の方法により鋼
片の腐食試験を行ない、その結果を表３に併せて示し
た。Example 2 Compounds P and sodium molybdate (M) were dissolved in water according to the compounding ratios shown in Table 3 to prepare the corrosion inhibitors J to L of the present invention. Corrosion tests of steel pieces were performed on these agents J to L by the same method as in Example 1, and the results are also shown in Table 3.
【００１８】[0018]
【表３】 [Table 3]
【００１９】（実施例３）実施例１の本発明の腐食防止
剤Ａをつくば市水道水に対してそれぞれ有効成分濃度が
表４に示す値となるように添加して試験水を調製し、実
施例１と同様の方法により防食性を試験した。その結果
を表４に併せて示す。この結果をみると、本発明の腐食
防止剤は広い濃度範囲で優れた防食効果を示すことがわ
かる。(Example 3) The corrosion inhibitor A of the present invention of Example 1 was added to the tap water of Tsukuba City so that the concentration of each active ingredient was the value shown in Table 4, to prepare test water. The corrosion resistance was tested by the same method as in Example 1. The results are also shown in Table 4. From these results, it can be seen that the corrosion inhibitor of the present invention exhibits an excellent anticorrosion effect in a wide concentration range.
【００２０】[0020]
【表４】 [Table 4]
【００２１】[0021]
【発明の効果】本発明の鉄系金属の腐食防止剤は、燐の
含有量が少ないので環境汚染の心配がなく、またスケー
ル生成の原因となる珪酸塩などを併用せずに低濃度で効
果的に金属防食ができ、経済的であるという利点があ
る。INDUSTRIAL APPLICABILITY The corrosion inhibitor for iron-based metals of the present invention has a low phosphorus content, so there is no fear of environmental pollution, and it is effective at low concentrations without the combined use of silicates, which cause scale formation. The advantage is that metal corrosion can be achieved and it is economical.
Claims (2)
酸誘導体と、モリブデン酸又はその塩とを有効成分とし
て含有する水系における鉄系金属の腐食防止剤。 【化１】 式中、Ｒは−ＣＯＯＸ′又は−ＣＯＮＨ−Ｃ（ＣＨ3 ）
2 ＣＨ2 ＳＯ3 Ｘ′であり、同一分子中にこれら２種の
基が混在しているものである。またＹは水素、アルカリ
金属原子、−ＳＯ3 Ｘ″又は−ＰＨＯＯＸ″であり、
Ｘ、Ｘ′、Ｘ″は水素又はアルカリ金属原子である。な
おｍ及びｎはそれぞれ０または正の整数であり、ｍ＋ｎ
は１〜１００の整数である。1. A corrosion inhibitor for ferrous metals in an aqueous system, which comprises a phosphinic acid derivative represented by the following general formula (I) and molybdic acid or a salt thereof as active ingredients. [Chemical 1] In the formula, R is —COOX ′ or —CONH—C (CH 3 ).
2 CH 2 SO 3 X ', which is a mixture of these two groups in the same molecule. The Y is hydrogen, an alkali metal atom, an -SO 3 X "or -PHOOX",
X, X ′, and X ″ are hydrogen or an alkali metal atom. M and n are 0 or a positive integer, and m + n
Is an integer of 1 to 100.
酸誘導体とモリブデン酸又はその塩とを、１：１０〜１
０：１の重量比で、水中に有効成分濃度１〜１０００mg
/lで存在させることを特徴とする水系における鉄系金属
の腐食防止方法。 【化２】 式中、Ｒは−ＣＯＯＸ′又は−ＣＯＮＨ−Ｃ（ＣＨ3 ）
2 ＣＨ2 ＳＯ3 Ｘ′であり、同一分子中にこれら２種の
基が混在しているものである。またＹは水素、アルカリ
金属原子、−ＳＯ3 Ｘ″又は−ＰＨＯＯＸ″であり、
Ｘ、Ｘ′、Ｘ″は水素又はアルカリ金属原子である。な
おｍ及びｎはそれぞれ０または正の整数であり、ｍ＋ｎ
は１〜１００の整数である。2. A phosphinic acid derivative represented by the following general formula (I) and molybdic acid or a salt thereof: 1:10 to 1
Active ingredient concentration 1-1000 mg in water at a weight ratio of 0: 1
A method for preventing corrosion of ferrous metals in a water system, characterized in that it is present at a ratio of 1 / l. [Chemical 2] In the formula, R is —COOX ′ or —CONH—C (CH 3 ).
2 CH 2 SO 3 X ', which is a mixture of these two groups in the same molecule. The Y is hydrogen, an alkali metal atom, an -SO 3 X "or -PHOOX",
X, X ′, and X ″ are hydrogen or an alkali metal atom. M and n are 0 or a positive integer, and m + n
Is an integer of 1 to 100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23001393A JPH0790640A (en) | 1993-09-16 | 1993-09-16 | Corrosion inhibitor for iron based metal in water system and corrosion inhibiting method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23001393A JPH0790640A (en) | 1993-09-16 | 1993-09-16 | Corrosion inhibitor for iron based metal in water system and corrosion inhibiting method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0790640A true JPH0790640A (en) | 1995-04-04 |
Family
ID=16901222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23001393A Pending JPH0790640A (en) | 1993-09-16 | 1993-09-16 | Corrosion inhibitor for iron based metal in water system and corrosion inhibiting method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0790640A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63194799A (en) * | 1987-02-05 | 1988-08-11 | Hakutou Kagaku Kk | Multipurpose multifunctional water treating agent |
-
1993
- 1993-09-16 JP JP23001393A patent/JPH0790640A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63194799A (en) * | 1987-02-05 | 1988-08-11 | Hakutou Kagaku Kk | Multipurpose multifunctional water treating agent |
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