JP4237853B2 - Corrosion inhibitor and corrosion prevention method for ferrous metals in cooling water system - Google Patents
Corrosion inhibitor and corrosion prevention method for ferrous metals in cooling water system Download PDFInfo
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- JP4237853B2 JP4237853B2 JP34682798A JP34682798A JP4237853B2 JP 4237853 B2 JP4237853 B2 JP 4237853B2 JP 34682798 A JP34682798 A JP 34682798A JP 34682798 A JP34682798 A JP 34682798A JP 4237853 B2 JP4237853 B2 JP 4237853B2
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Description
【0001】
【発明の属する技術分野】
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、及び鉄系金属の腐食防止方法に関する。
【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に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。
【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、従来から亜鉛塩等の重金属塩類や、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使用さ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十分でないため、上記の亜鉛塩やモリブデン酸塩等の重金属化合物と併用するか、或いはポリリン酸塩やケイ酸塩等のスケール生成の原因成分などと併用することにより、防食効果を補うこと(特開昭55−14900号、特開昭63−287600号)が必要とされていた。
【0004】
【発明が解決しようとする課題】
しかしこれらの改良技術でも、環境汚染の問題と防食効果との双方を同時に満足させるには至っていない。
そこで本発明は、冷却水系に用いて毒性が低く且つ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、しかも使用量が少なくても鉄系金属材料に対して優れた防食効果を示す腐食防止剤及び腐食防止方法を提供しようとするものである。
【0005】
【課題を解決するための手段】
本発明の冷却水系における鉄系金属の腐食防止剤は、2−ホスホノブタン−1,2,4−トリカルボン酸及びその塩、1−ヒドロキシエチリデン−1,1−ジホスホン酸及びその塩より選択された少なくとも1種の化合物(成分A)と、トリ−n−ブチル−n−ヘキサデシル−ホスホニウム、トリ−n−ブチル−n−ドデシル−ホスホニウム、テトラキス−ヒドロキシメチル−ホスホニウム及びそれらの塩より選択された少なくとも1種の化合物(成分B)とを、有効成分として含有するものである。
【0006】
かかる本発明の腐食防止剤における成分Bの化合物は、トリ−n−ブチル−n−ヘキサデシル−ホスホニウム、トリ−n−ブチル−n−ドデシル−ホスホニウム、テトラキス−ヒドロキシメチル−ホスホニウム及びそれらの塩より選択された少なくとも1種の化合物であることが好ましく、中でもトリ−n−ブチル−n−ヘキサデシル−ホスホニウムクロリドが特に好ましい。
また本発明の腐食防止剤における成分Aの化合物としては、2−ホスホノブタン−1,2,4−トリカルボン酸又はその塩であることが、特に好ましい。
【0007】
更に本発明の冷却水系における鉄系金属の腐食防止方法は、2−ホスホノブタン−1,2,4−トリカルボン酸及びその塩、1−ヒドロキシエチリデン−1,1−ジホスホン酸及びその塩より選択された少なくとも1種の化合物(成分A)と、トリ−n−ブチル−n−ヘキサデシル−ホスホニウム、トリ−n−ブチル−n−ドデシル−ホスホニウム、テトラキス−ヒドロキシメチル−ホスホニウム及びそれらの塩より選択された少なくとも1種の化合物(成分B)とを、重量比1:100乃至100:1の範囲内且つ有効成分の合計濃度1〜1000mg/Lの範囲内で、水中に存在させることを特徴とするものである。
【0008】
【発明の実施の形態】
本発明の鉄系金属の腐食防止剤の一方の成分Aは、2−ホスホノブタン−1,2,4−トリカルボン酸及びその塩、及び、1−ヒドロキシエチリデン−1,1−ジホスホン酸及びその塩から選択されるが、かかる塩としては、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。そしてまた、本発明の鉄系金属の腐食防止剤の他方の成分Bはホスホニウム化合物であるが、中でもトリ−n−ブチル−n−ヘキサデシル−ホスホニウムクロリドや、トリ−n−ブチル−n−ドデシル−ホスホニウムクロリド、テトラキス−ヒドロキシメチル−ホスホニウムサルフェイトが、特に好ましく用いられる。
【0009】
上記のような成分Aと成分B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、場合により水などの溶剤に溶解した液剤であってもよい。
【0010】
かかる各成分A及び成分Bの使用比率は、重量比で1:100乃至100:1の範囲であってよく、更には1:10乃至30:1、特に1:2乃至5:1の範囲内にあることが好ましい。本発明の鉄系金属の腐食防止剤は、このような範囲内で優れた相乗作用を発揮する。
また、水中における有効成分A及び成分Bの合計濃度は、水と接触する機器の材質にもよるが、1〜1000mg/L の範囲であるのがよく、特に5〜100mg/L の範囲内となるよう添加するのが好ましい。
【0011】
かかる本発明の腐食防止剤は、前記の有効成分の他、例えば亜硝酸、燐酸、珪酸、モリブデン酸、タングステン酸、アルミン酸、硼酸、オキシ酸、アミノ酸、脂肪族有機酸、芳香族カルボン酸、リグニンスルホン酸、或いはこれらの塩などや、タンニン、リグニンなどの鉄用防食剤、或いは、例えば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等のアゾール類、亜鉛塩などの金属防食剤が含有されていてもよい。
【0012】
更に、本発明の腐食防止剤を使用するに当たっては、例えばアクリル酸系重合体、マレイン酸系重合体、メタクリル酸系重合体、スルホン酸系重合体、燐酸系重合体、イタコン酸系重合体、イソブチレン系重合体、あるいはこれらの水溶性塩などのスケール防止剤、例えば5−クロロ−2−メチル−4−イソチアゾリン−3−オン、2−メチル−4−イソチアゾリン−3−オン、1,2−ベンゾイソチアゾリン−3−オン等のイソチアゾロン系化合物、例えばグルタルアルデヒド、フタルアルデヒド等のアルデヒド類、例えば過酸化水素、次亜塩素酸ナトリウム等の無機物類、更にジチオール系化合物、チオシアネート系化合物、ヨーネンポリマー、4級アンモニウム塩系化合物などのスライム防止剤、例えばエチレンジアミン、ジエチレントリアミン等のアミン系化合物、例えばニトリロ三酢酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸等のアミノカルボン酸系化合物、例えばグルコン酸、クエン酸、シュウ酸、ギ酸、酒石酸、フィチン酸、琥珀酸、乳酸等の有機カルボン酸など、各種の水処理剤を併用することができ、場合によっては予め本発明の腐食防止剤にこれらの水処理剤を配合したものを用いてもよい。
【0013】
【実施例】
表1に示す水質を有する試験用水と、腐食防止剤の成分Aの化合物として、2−ホスホノブタン−1,2,4−トリカルボン酸(略号:PBUTCA)及び1−ヒドロキシエチリデン−1,1−ジホスホン酸(略号:HOEDPA)と、成分Aの対照化合物として、ポリマレイン酸(FMC社、ベルクリン200、略号:PMAA)、及びポリアクリル酸(東亜合成社、アロンA−20UK、略号:PACA)と、更に腐食防止剤の成分Bの化合物として、トリ−n−ブチル−n−ヘキサデシル−ホスホニウムクロリド(略号:TBUHDPC )、トリ−n−ブチル−n−ドデシル−ホスホニウムクロリド(略号:TBUDDPC )及びテトラキス−ヒドロキシメチル−ホスホニウムサルフェイト(略号:THOMPS)を、成分Bの対照化合物として、5−クロロ−2−メチル−4−イソチアゾリン−3−オン(略号:CMTAZN)及びメチレンビスチオシアネート(略号:MBTC)とを用意した。
【0014】
【表1】
試験用水の水質
pH 8.0
電気伝導率(μS/cm) 480
カルシウム硬度(CaCO3 mg/L ) 100
マグネシウム硬度(CaCO3 mg/L ) 40
M−アルカリ度(CaCO3 mg/L ) 100
シリカ(SiO2 mg/L ) 60
塩化物イオン(Cl- mg/L ) 72
硫酸イオン(SO4 --mg/L ) 38
【0015】
そして開放容器に入れた試験用水1000mlに、これらの化合物をそれぞれ表2及び表3に示す濃度(mg/L )となるよう添加し、その中に表面積0.33dm2 の研磨鋼板を浸漬して、緩く攪拌しながら35℃で3日間の腐食試験を行った。試験期間中は、それぞれ同じ薬剤濃度の液を1日当たり1000mLの割合で交換補給し、鋼板の腐食減量を測定して腐食度(mg/dm2-D)を算出し、その結果を表2及び表3に併せて示した。
【0016】
【表2】
【0017】
【表3】
【0018】
表2及び表3の結果を見ると、トリ−n−ブチル−n−ヘキサデシル−ホスホニウムクロリド、トリ−n−ブチル−n−ドデシル−ホスホニウムクロリド及びテトラキス−ヒドロキシメチル−ホスホニウムサルフェイトのいずれかと、2−ホスホノブタン−1,2,4−トリカルボン酸及び1−ヒドロキシエチリデン−1,1−ジホスホン酸のいずれかとを組み合わせた本発明の腐食防止剤が、その他の組み合わせが示すような、予想される程度の鉄系金属材料に対する防食性に比べて、明らかに優れた相乗効果を発揮することがわかる。
【0019】
【発明の効果】
本発明の冷却水系における鉄系金属の腐食防止剤は、2−ホスホノブタン−1,2,4−トリカルボン酸及びその塩、1−ヒドロキシエチリデン−1,1−ジホスホン酸及びその塩より選択された少なくとも1種の化合物からなる成分Aと、トリ−n−ブチル−n−ヘキサデシル−ホスホニウム、トリ−n−ブチル−n−ドデシル−ホスホニウム、テトラキス−ヒドロキシメチル−ホスホニウム及びそれらの塩より選択された少なくとも1種の化合物からなる成分Bとを、組み合わせた有効成分を含有してなるものであって、それぞれの成分の相乗効果によって低濃度の使用でも有効に鉄系金属材料の腐食を防止できるうえ、燐含有量が少なく、また重金属類やスケール生成因子を含有しないので、環境汚染を引き起こす恐れがなく、装置の保守管理に関する負担が軽減される効果がある。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a metal corrosion inhibitor used by adding to a water system circulating in equipment composed of iron-based metal, and a method for preventing corrosion of iron-based metal.
[0002]
[Prior art]
Cooling water for air conditioning equipment and industrial cooling water are heated by heat exchange and then sent to a cooling tower, etc., where they are brought into contact with air to evaporate part of the heat. Usually used as water. Such salts in the circulating water are gradually concentrated to a high concentration, causing troubles such as corrosion inside the facilities and piping. Therefore, it is necessary to replenish the water that has decreased by evaporation and to discharge some of the concentrated water from time to time to adjust the salt concentration, and to add anti-corrosion water treatment chemicals. ing.
[0003]
Many devices made of iron-based materials are used for such cooling water-based devices. Conventionally, as a corrosion inhibitor for such iron-based materials, heavy metal salts such as zinc salts, chromates, and phosphoric acids are used. Although compounds have been used, these are not preferable from the viewpoint of environmental pollution. Therefore, in recent years, certain types of phosphonic acids and phosphinocarboxylic acids have been used, but since these compounds are not sufficient in anticorrosive effect, heavy metals such as zinc salts and molybdates described above are used. Supplementing the anticorrosive effect by using in combination with a compound or by using a component causing scale formation such as polyphosphate and silicate (JP 55-14900, JP 63-287600) Was needed.
[0004]
[Problems to be solved by the invention]
However, even these improved technologies have not yet satisfied both the problem of environmental pollution and the anticorrosive effect.
Therefore, the present invention is used in a cooling water system, has low toxicity, does not cause environmental pollution, does not cause scale formation, and exhibits an excellent anticorrosion effect against ferrous metal materials even when the amount used is small. It is an object of the present invention to provide a corrosion inhibitor and a corrosion prevention method.
[0005]
[Means for Solving the Problems]
The corrosion inhibitor for ferrous metals in the cooling water system of the present invention is at least selected from 2-phosphonobutane-1,2,4-tricarboxylic acid and its salt, 1-hydroxyethylidene-1,1-diphosphonic acid and its salt At least one selected from one compound (component A) and tri-n-butyl-n-hexadecyl-phosphonium, tri-n-butyl-n-dodecyl-phosphonium, tetrakis-hydroxymethyl-phosphonium and their salts A seed compound (component B) is contained as an active ingredient.
[0006]
The compound of component B in the corrosion inhibitor of the present invention is selected from tri-n-butyl-n-hexadecyl-phosphonium, tri-n-butyl-n-dodecyl-phosphonium, tetrakis-hydroxymethyl-phosphonium and their salts. At least one compound is preferred, and tri-n-butyl-n-hexadecyl-phosphonium chloride is particularly preferred.
The compound of component A in the corrosion inhibitor of the present invention is particularly preferably 2-phosphonobutane-1,2,4-tricarboxylic acid or a salt thereof.
[0007]
Furthermore, the method for preventing corrosion of ferrous metals in the cooling water system of the present invention was selected from 2-phosphonobutane-1,2,4-tricarboxylic acid and its salt, 1-hydroxyethylidene-1,1-diphosphonic acid and its salt. At least one compound (component A) and at least selected from tri-n-butyl-n-hexadecyl-phosphonium, tri-n-butyl-n-dodecyl-phosphonium, tetrakis-hydroxymethyl-phosphonium and salts thereof One compound (component B) is present in water within a weight ratio of 1: 100 to 100: 1 and within a total concentration of active ingredients of 1 to 1000 mg / L. is there.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
One component A of the iron-based metal corrosion inhibitor of the present invention is composed of 2-phosphonobutane-1,2,4-tricarboxylic acid and a salt thereof, and 1-hydroxyethylidene-1,1-diphosphonic acid and a salt thereof. Although selected, water-soluble salts such as sodium salts, potassium salts, and ammonium salts are preferably used as such salts. The other component B of the iron-based metal corrosion inhibitor of the present invention is a phosphonium compound, among which tri-n-butyl-n-hexadecyl-phosphonium chloride, tri-n-butyl-n-dodecyl- Phosphonium chloride and tetrakis-hydroxymethyl-phosphonium sulfate are particularly preferably used.
[0009]
Component A and Component B as described above can be added separately to the aqueous system to be treated, but are pre-mixed so as to be one agent or combined as separate packages of two or more agents. It can be used as an inhibitor, and in some cases may be a solution dissolved in a solvent such as water.
[0010]
The use ratio of each component A and component B may be in the range of 1: 100 to 100: 1 by weight, more preferably in the range of 1:10 to 30: 1, especially 1: 2 to 5: 1. It is preferable that it exists in. The iron-based metal corrosion inhibitor of the present invention exhibits an excellent synergistic effect within such a range.
In addition, the total concentration of active ingredient A and ingredient B in water depends on the material of the equipment in contact with water, but is preferably in the range of 1 to 1000 mg / L, particularly in the range of 5 to 100 mg / L. It is preferable to add so that it becomes.
[0011]
Such a corrosion inhibitor of the present invention includes, in addition to the above active ingredients, for example, nitrous acid, phosphoric acid, silicic acid, molybdic acid, tungstic acid, aluminate, boric acid, oxyacid, amino acid, aliphatic organic acid, aromatic carboxylic acid, Contains lignin sulfonic acid or salts thereof, iron anticorrosives such as tannin and lignin, or azoles such as tolyltriazole, benzotriazole and mercaptobenzothiazole, and metal anticorrosives such as zinc salts. Also good.
[0012]
Further, in using the corrosion inhibitor of the present invention, for example, acrylic acid polymer, maleic acid polymer, methacrylic acid polymer, sulfonic acid polymer, phosphoric acid polymer, itaconic acid polymer, Scale inhibitors such as isobutylene polymers or their water-soluble salts, such as 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2- Isothiazolone compounds such as benzoisothiazolin-3-one, aldehydes such as glutaraldehyde and phthalaldehyde, inorganic substances such as hydrogen peroxide and sodium hypochlorite, dithiol compounds, thiocyanate compounds, and ionene polymers Anti-slime agents such as quaternary ammonium salt compounds such as ethylenediamine and diethylene Amine compounds such as lyamine, for example, aminocarboxylic acid compounds such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, such as gluconic acid, citric acid, oxalic acid, formic acid, tartaric acid, phytic acid, succinic acid, lactic acid, etc. Various water treatment agents such as organic carboxylic acid can be used in combination, and in some cases, a mixture of these water treatment agents in advance with the corrosion inhibitor of the present invention may be used.
[0013]
【Example】
Test water having the water quality shown in Table 1 and compounds of component A of the corrosion inhibitor include 2-phosphonobutane-1,2,4-tricarboxylic acid (abbreviation: PBUTCA) and 1-hydroxyethylidene-1,1-diphosphonic acid (Abbreviation: HOEDPA), polymaleic acid (FMC, Berglin 200, abbreviation: PMAA) and polyacrylic acid (Toa Gosei Co., Ltd., Aron A-20UK, abbreviation: PACA) as a reference compound for component A, and further corrosion As compounds of component B of the inhibitor, tri-n-butyl-n-hexadecyl-phosphonium chloride (abbreviation: TBUHDPC), tri-n-butyl-n-dodecyl-phosphonium chloride (abbreviation: TBUDDPC) and tetrakis-hydroxymethyl- Phosphonium sulfate (abbreviation: THOMPS) was used as a reference compound for component B as 5-chloro-2-methyl-4-isothiazolyl. 3-one (abbreviation: CMTAZN) and methylene bis thiocyanate (abbreviation: MBTC) and was prepared.
[0014]
[Table 1]
Water quality of test water pH 8.0
Electrical conductivity (μS / cm) 480
Calcium hardness (CaCO 3 mg / L) 100
Magnesium hardness (CaCO 3 mg / L) 40
M-alkalinity (CaCO 3 mg / L) 100
Silica (SiO 2 mg / L) 60
Chloride ion (Cl - mg / L) 72
Sulfate ion (SO 4 - mg / L) 38
[0015]
Then, these compounds are added to 1000 ml of test water in an open container so as to have the concentrations (mg / L) shown in Table 2 and Table 3, respectively, and a polished steel plate having a surface area of 0.33 dm 2 is immersed therein. The corrosion test was conducted at 35 ° C. for 3 days with gentle stirring. During the test period, each solution with the same chemical concentration was replenished at a rate of 1000 mL per day, and the corrosion loss (mg / dm 2 -D) was calculated by measuring the corrosion weight loss of the steel sheet. The results are also shown in Table 3.
[0016]
[Table 2]
[0017]
[Table 3]
[0018]
Looking at the results in Tables 2 and 3, one of tri-n-butyl-n-hexadecyl-phosphonium chloride, tri-n-butyl-n-dodecyl-phosphonium chloride and tetrakis-hydroxymethyl-phosphonium sulfate, -Corrosion inhibitors of the present invention in combination with any of phosphonobutane-1,2,4-tricarboxylic acid and 1-hydroxyethylidene-1,1-diphosphonic acid are as expected as other combinations show It can be seen that it clearly exhibits an excellent synergistic effect compared to the anticorrosive properties for ferrous metal materials.
[0019]
【The invention's effect】
The corrosion inhibitor for ferrous metals in the cooling water system of the present invention is at least selected from 2-phosphonobutane-1,2,4-tricarboxylic acid and its salt, 1-hydroxyethylidene-1,1-diphosphonic acid and its salt a component a consisting of one compound, tri -n- butyl -n- hexadecyl - phosphonium, tri -n- butyl -n- dodecyl - phosphonium tetrakis - hydroxymethyl - at least one selected from the phosphonium and salts thereof Component B, which is composed of various compounds, contains an active ingredient, and the synergistic effect of each component can effectively prevent the corrosion of iron-based metal materials even at low concentrations. Low content and no heavy metals or scale formation factors, so there is no risk of environmental pollution, There is an effect that burden on to protect management is reduced.
Claims (5)
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JP2000169979A JP2000169979A (en) | 2000-06-20 |
JP4237853B2 true JP4237853B2 (en) | 2009-03-11 |
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JP4715987B2 (en) * | 2001-08-22 | 2011-07-06 | 三菱瓦斯化学株式会社 | Water treatment agent |
JP5978711B2 (en) * | 2012-03-29 | 2016-08-24 | 三浦工業株式会社 | Iron corrosion control method |
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