JP2556656B2 - Method for preventing corrosion of ferrous metal in cooling water system and corrosion inhibitor for ferrous metal in cooling water system - Google Patents
Method for preventing corrosion of ferrous metal in cooling water system and corrosion inhibitor for ferrous metal in cooling water systemInfo
- Publication number
- JP2556656B2 JP2556656B2 JP5193297A JP19329793A JP2556656B2 JP 2556656 B2 JP2556656 B2 JP 2556656B2 JP 5193297 A JP5193297 A JP 5193297A JP 19329793 A JP19329793 A JP 19329793A JP 2556656 B2 JP2556656 B2 JP 2556656B2
- Authority
- JP
- Japan
- Prior art keywords
- cooling water
- water system
- corrosion
- corrosion inhibitor
- ferrous metal
- 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 - Lifetime
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
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亜鉛塩等の重金
属塩や、クロム酸塩、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、ある種のホスホン酸類
やホスフィノカルボン酸類などが用いられるようになっ
てきているが、これらの化合物はいずれも防食効果が弱
いために、亜鉛塩やモリブデン酸塩等の重金属塩、或い
はポリ燐酸塩、珪酸塩等のスケール生成の原因成分など
を併用しないと充分な防食効果が得られず、更に効果的
な腐食防止剤が求められていた。Equipment made of iron-based materials is often used for such cooling water-based devices, and as a corrosion inhibitor for such iron-based materials, heavy metal salts such as zinc salts and chromates 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, some phosphonic acids and phosphinocarboxylic acids have come to be used, but since these compounds all have weak anticorrosion effects, heavy metal salts such as zinc salts and molybdate salts, or A sufficient anticorrosion effect cannot be obtained unless a causative component of scale formation such as polyphosphate or silicate is used, and a more effective corrosion inhibitor has been demanded.
【０００４】[0004]
【発明が解決しようとする課題】そこで本発明は、毒性
が少なくて環境汚染を引き起こすことがなく、またスケ
ール生成の恐れもなく、しかも鉄系材料に対して高い防
食効果を示す腐食防止方法を提供することを目的とし
た。Therefore, the present invention provides a method for preventing corrosion, which is less toxic, does not cause environmental pollution, has no fear of scale formation, and has a high anticorrosive effect on iron-based materials. Aimed 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、オキシカルボン酸とを１：１０〜１０：１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
によって達成される。そしてかかる本発明の腐食防止方
法は、一般式(I) で示されるホスフィン酸誘導体と、オ
キシカルボン酸とを有効成分として含有する腐食防止剤
を用いることによって更に容易に実施することができ
る。The object of the present invention as described above is to provide a phosphinic acid derivative represented by the following general formula (I) and an oxycarboxylic acid in a weight ratio of 1:10 to 10: 1. It is achieved by a method for preventing corrosion of ferrous metals in an aqueous system, characterized in that the active ingredient is present in water at a concentration of 1 to 1000 mg / l. The corrosion prevention method of the present invention can be more easily carried out by using a corrosion inhibitor containing a phosphinic acid derivative represented by the general formula (I) and an oxycarboxylic acid as active ingredients.
【０００６】[0006]
【化３】 式中、Ｒは−ＣＯＯＸ′又は−ＣＯＮＨ−Ｃ（ＣＨ3 ）
2 ＣＨ2 ＳＯ3 Ｘ′であり、同一分子中でこれら２種の
基が混在している。またＹは水素、−ＳＯ3 Ｘ″及び−
ＰＨＯＯＸ″から選ばれ、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。Embedded image In the formula, R is —COOX ′ or —CONH—C (CH 3 ).
A 2 CH 2 SO 3 X ', in the same molecule these two groups are mixed. The Y is hydrogen, -SO 3 X "and -
PHOOX ″, where X, X ′, X ″ are hydrogen or an alkali metal atom. Note that m and n are each 0 or a positive integer, and m + n is an integer of 1 to 100.
【０００７】[0007]
【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オキシカルボン酸としては、クエン
酸、酒石酸、リンゴ酸、グルコン酸などが挙げられる
が、なかでもクエン酸が好ましく用いられる。In the present invention, examples of the oxycarboxylic acid used in combination with the phosphinic acid derivative include citric acid, tartaric acid, malic acid and gluconic acid. Of these, citric acid is preferably used.
【０００９】上記のホスフィン酸誘導体とオキシカルボ
ン酸とは、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 oxycarboxylic acid can be added separately to the aqueous system to be treated, but they may be added in advance so as to form one agent, or
Alternatively, it can be used as a corrosion inhibitor by combining two or more agents in separate packages, and in that 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オ
キシカルボン酸との使用比率は、重量比で１：１０〜１
０：１の範囲内にあることが好ましく、この範囲で優れ
た相乗作用を発揮する。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 use ratio of the phosphinic acid derivative and the oxycarboxylic acid is 1:10 to 1 by weight.
It is preferably in the range of 0: 1, and excellent synergism is exhibited in this 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, and particularly in the range of 10 to 100 mg / l. Is preferred.
【００１１】[0011]
【作用】本発明の腐食防止剤は、前記のホスフィン酸誘
導体と前記のオキシカルボン酸とを配合してなるもので
あって重金属塩を含まず、また燐含有量も少ないので環
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使用量が少なくても有効に鉄系金属
材料の腐食を防止する。The corrosion inhibitor of the present invention is a mixture of the above phosphinic acid derivative and the above oxycarboxylic acid, contains no heavy metal salt, and contains a small amount of phosphorus, which may cause environmental pollution. Moreover, the synergistic effect of each component effectively prevents the corrosion of the iron-based metallic material even when the amount used is small.
【００１２】[0012]
【実施例】ホスフィン酸誘導体として、式(I) の構造を
有していてｍ＋ｎの平均値が約１６である化合物Ｐ（Ｆ
ＭＣ社、ベルクリン４００）５重量部と、オキシカルボ
ン酸としてクエン酸Ｃ、酒石酸Ｔ、リンゴ酸Ｍ、及びグ
ルコン酸Ｇのいずれか１０重量部とを純水に溶解し、４
８％の水酸化カリウム水溶液を用いてｐＨ７に調整した
のち、更に純水を加えて合計１００重量部として、表１
に示すような組合せを持つ腐食防止剤＃１〜＃４を調製
した。Example As a phosphinic acid derivative, the structure of formula (I)
A compound P (F having an average value of m + n of about 16)
MC Company, Bellclin 400) 5 parts by weight and Oxycarb
Citric acid C as phosphate, tartaric T, malic acid M, and the one 10 parts by weight of gluconic acid G was dissolved in pure water, 4
After adjusting the pH to 7 using an 8% aqueous potassium hydroxide solution, pure water was further added to bring the total to 100 parts by weight.
Corrosion inhibitors # 1 to # 4 having the combinations shown in Table 1 were prepared.
【００１３】[0013]
【００１４】次に、つくば市水道水１０００mlにこれら
の薬剤＃１〜＃４の０．１ｇを添加してそれぞれ試験水
を調製し、開放容器に入れて表面積０．２７dm2 の鋼片
を浸漬し、長さ５０mmの攪拌子を用いて３００rpm 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（mg／dm2 ・日）を算出し、そ
の結果を表１に示した。Next, 0.1 g of these chemicals # 1 to # 4 was added to 1000 ml of tap water in Tsukuba City to prepare test water, which was placed in an open container and a steel piece having a surface area of 0.27 dm 2 was dipped. Then, a corrosion test was carried out at 35 ° C. for 7 days while continuing stirring at 300 rpm using a stirrer having a length of 50 mm. The corrosion degree (mg / dm 2 · day) was calculated from the corrosion weight loss of the steel slab, and the results are shown in Table 1.
【００１５】また比較試験としてつくば市水道水１００
０mlにホスフィン酸誘導体化合物Ｐ又はオキシカルボン
酸Ｃ、Ｔ、Ｍ、Ｇをそれぞれ１０又は２０mgとなるよう
に添加し、１mol/l の水酸化カリウム水溶液を用いてｐ
Ｈ７に調整して試験水を調製し、上記と同様にして腐食
試験を行って腐食度を算出し、その結果を表１に併せて
示した。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、明らかに相乗効果を
発揮することがわかる。As a comparative test, 100 tap water in Tsukuba City
The phosphinic acid derivative compound P or the oxycarboxylic acid C, T, M and G was added to 0 ml so as to be 10 or 20 mg respectively, and p was added using a 1 mol / l potassium hydroxide aqueous solution.
The test water was prepared by adjusting to H7, and the corrosion test was performed in the same manner as above to calculate the corrosion degree, and the results are also shown in Table 1. From these results, it can be seen that the corrosion inhibitor of the present invention exhibits excellent anticorrosion properties with respect to iron-based metallic materials and exhibits a clear synergistic effect.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【発明の効果】本発明の鉄系金属の腐食防止剤は、重金
属塩類を含まずまた燐の含有量も少ないので、毒性が少
なくて環境汚染の心配がなく、またスケール生成の原因
となる塩類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 does not contain heavy metal salts and contains a small amount of phosphorus, and therefore has low toxicity.
Not without the worry of environmental pollution, also effectively can metal corrosion protection at low concentrations without a combination of such salts cause of scale formation, there is an advantage that it is economical.
Claims (4)
酸誘導体と、オキシカルボン酸とを１：１０〜１０：１
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冷却水系における鉄系金属の
腐食防止方法。 【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。またＹは水素、−ＳＯ3 Ｘ″及び−
ＰＨＯＯＸ″から選ばれ、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 phosphinic acid derivative represented by the following general formula (I) and an oxycarboxylic acid: 1:10 to 10: 1
The method for preventing corrosion of ferrous metals in a cooling water system, characterized in that the active ingredient concentration is 1 to 1000 mg / l in water at a weight ratio of 1. Embedded image In the formula, R is —COOX ′ or —CONH—C (CH 3 ).
A 2 CH 2 SO 3 X ', these two groups are mixed in the same molecule. The Y is hydrogen, -SO 3 X "and -
PHOOX ″, where X, X ′, X ″ are hydrogen or an alkali metal atom. Note that m and n are each 0 or a positive integer, and m + n is an integer of 1 to 100.
酸誘導体と、オキシカルボン酸とを有効成分として含有
する冷却水系における鉄系金属の腐食防止剤。 【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。またＹは水素、−ＳＯ3 Ｘ″及び−
ＰＨＯＯＸ″から選ばれ、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 corrosion inhibitor for a ferrous metal in a cooling water system, comprising a phosphinic acid derivative represented by the following general formula (I) and an oxycarboxylic acid as active ingredients. Embedded image In the formula, R is —COOX ′ or —CONH—C (CH 3 ).
A 2 CH 2 SO 3 X ', these two groups are mixed in the same molecule. The Y is hydrogen, -SO 3 X "and -
PHOOX ″, where X, X ′, X ″ are hydrogen or an alkali metal atom. Note that m and n are each 0 or a positive integer, and m + n is an integer of 1 to 100.
求項２に記載の腐食防止剤。3. The contract wherein the oxycarboxylic acid is citric acid.
Corrosion inhibitor according to Motomeko 2.
との重量配合比が１：１０〜１０：１である、請求項２
又は３に記載の腐食防止剤。4. A ratio by weight of phosphinic acid derivatives and hydroxycarboxylic acid is 1: 10 to 10: 1, claim 2
Or the corrosion inhibitor according to 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5193297A JP2556656B2 (en) | 1993-08-04 | 1993-08-04 | Method for preventing corrosion of ferrous metal in cooling water system and corrosion inhibitor for ferrous metal in cooling water system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5193297A JP2556656B2 (en) | 1993-08-04 | 1993-08-04 | Method for preventing corrosion of ferrous metal in cooling water system and corrosion inhibitor for ferrous metal in cooling water system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0748685A JPH0748685A (en) | 1995-02-21 |
| JP2556656B2 true JP2556656B2 (en) | 1996-11-20 |
Family
ID=16305577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5193297A Expired - Lifetime JP2556656B2 (en) | 1993-08-04 | 1993-08-04 | Method for preventing corrosion of ferrous metal in cooling water system and corrosion inhibitor for ferrous metal in cooling water system |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2556656B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4895330A (en) * | 1972-03-17 | 1973-12-07 | ||
| EP0009080B1 (en) * | 1978-07-19 | 1982-06-23 | Ciba-Geigy Ag | Corrosion inhibitors; compositions for protecting ferrous metals and the protected metals |
| JP2608550B2 (en) * | 1986-10-17 | 1997-05-07 | 株式会社 片山化学工業研究所 | Corrosion protection method for soft water boiler |
-
1993
- 1993-08-04 JP JP5193297A patent/JP2556656B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0748685A (en) | 1995-02-21 |
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