JP2002292398A - Inhibitor composition for scale containing calcium and method for preventing scale containing calcium in water system - Google Patents
Inhibitor composition for scale containing calcium and method for preventing scale containing calcium in water systemInfo
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- JP2002292398A JP2002292398A JP2001098697A JP2001098697A JP2002292398A JP 2002292398 A JP2002292398 A JP 2002292398A JP 2001098697 A JP2001098697 A JP 2001098697A JP 2001098697 A JP2001098697 A JP 2001098697A JP 2002292398 A JP2002292398 A JP 2002292398A
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- calcium
- scale
- containing calcium
- salt
- scale containing
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Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、相乗効果を奏する
2種類のホスホン酸を必須成分として含有するカルシウ
ム系スケールの防止剤組成物および上記組成物によるカ
ルシウム系スケースの防止方法に関する。さらに詳しく
は、カルシウム硬度300mg/立以上、または/およ
びpHが9.6以上の水系においてもカルシウム系スケ
ールの発生を防止するのに有用な組成物およびカルシウ
ム系スケールの防止方法に関する。The present invention relates to a calcium-based scale inhibitor composition containing two kinds of phosphonic acids having a synergistic effect as essential components, and a method for preventing calcium-based skein by the above composition. More specifically, the present invention relates to a composition useful for preventing the occurrence of calcium-based scale even in an aqueous system having a calcium hardness of 300 mg / stand or more and / or a pH of 9.6 or more, and a method for preventing calcium-based scale.
【0002】[0002]
【従来の技術】各種工業水系において、水中の硬度成分
と溶存炭酸塩によって生じる炭酸カルシウムを主とする
カルシウム系スケールが発生し、様々な障害をもたらす
ことが広く知られており、この発生を防止またはできる
だけ抑制することが望まれている。このため従来から上
記水系に添加してカルシウム系スケールの発生を防止ま
たは抑制する薬剤が種々提案されており、中でも有機ホ
スホン酸類が広く知られている(例えば特開昭64−7
7693号公報参照)。しかしこれらホスホン酸類が効
果を発揮し得る水質には上限があって、カルシウム硬度
が非常に高い水系やpHが高い水系では薬剤の適用限界
を越え、例え添加量を増やしても多大なスケール障害を
もたらす場合が少なくない。特に湿式排煙脱硫工程水や
製紙工業の脱墨工程水などでは水質変動が激しく、カル
シウム硬度とpHが高いために安定したスケール防止効
果を発揮する薬剤が望まれている。水質変動の要因を例
えば脱墨工程において挙げると、 脱墨しようとする古紙原料から持ち込まれるカルシウ
ム成分の量によって、水系のカルシウム硬度が変動する 高濃度のパルプスラリーを希釈するために使用する水
が循環使用されるため、循環回数の多寡によりカルシウ
ム硬度およびpHが変動する 漂白工程におけるアルカリ添加量により、脱墨工程の
pHが変動することが考えられる。 こうした変動要因をホスホン酸類の水質上限以下に制御
することは該プロセスの性質から実質的に不可能であっ
て、特にこうした水系では適用水質範囲の広いスケール
防止方法が望まれている。2. Description of the Related Art In various industrial water systems, it is widely known that calcium-based scales mainly composed of calcium carbonate generated by hardness components and dissolved carbonates in water are generated and cause various obstacles. Or it is desired to suppress as much as possible. For this reason, various agents which are added to the above aqueous system to prevent or suppress the generation of calcium scale have been proposed, and among them, organic phosphonic acids are widely known (for example, JP-A-64-7).
No. 7693). However, there is an upper limit to the water quality at which these phosphonic acids can exert their effects, and in aqueous systems with very high calcium hardness or high pH, the drug's application limit is exceeded, and even if the added amount is increased, a large scale obstacle is caused. Often it brings. In particular, the water quality of the flue gas desulfurization process water or the deinking process water of the paper industry is highly fluctuating, and the calcium hardness and the pH are high. Factors of water quality fluctuations, for example, in the deinking process, are as follows: The amount of calcium component brought in from the waste paper raw material to be deinked varies the calcium hardness of the water system. Since it is used in circulation, the calcium hardness and pH fluctuate depending on the number of circulations. It is practically impossible to control such fluctuation factors below the upper limit of the water quality of the phosphonic acid due to the nature of the process. In particular, in such a water system, a scale prevention method having a wide range of applicable water quality is desired.
【0003】[0003]
【発明が解決しようとする課題】こうした課題を解決す
る目的で、例えば有機ホスホン酸類とアクリル酸系もし
くはマレイン酸系共重合体、およびクエン酸からなるカ
ルシウム系スケール防止剤(特開平5−4096号公
報)が提案されているが、高い添加濃度が必要である
上、カルシウム硬度が高く、且つpHが高い水系での効
果が良くないという問題点がある。In order to solve these problems, for example, a calcium-based scale inhibitor comprising an organic phosphonic acid and an acrylic or maleic acid copolymer, and citric acid (Japanese Patent Laid-Open No. 5-4096) However, there is a problem that a high addition concentration is required, and the effect in an aqueous system having a high calcium hardness and a high pH is not good.
【0004】本発明は上記の状況下になされたものであ
り、特に高硬度の水系や高pHの水系においても優れた
スケール防止効果を発現することができる適用範囲の広
いカルシウム系スケールの防止剤組成物およびカルシウ
ム系スケールの防止方法を提供するものである。The present invention has been made under the above-mentioned circumstances, and particularly, a calcium-based scale inhibitor which can exert an excellent scale-preventing effect even in a water system having a high hardness or a water system having a high pH. The present invention provides a composition and a method for preventing calcium-based scale.
【0005】[0005]
【課題を解決するための手段】本発明のカルシウム系ス
ケールの防止剤組成物は、1−ヒドロキシエチリデン−
1,1−ジホスホン酸またはその塩と、2−ホスホノブ
タン−1,2,4−トリカルボン酸またはその塩との配
合割合が1:9〜9:1であることを特徴とする。ま
た、本発明の水系でのカルシウム系スケールの防止方法
は、カルシウム硬度が炭酸カルシウムとして300mg
/立以上、M−アルカリ度が300mg/立以上、また
は/およびpHが9.6以上の水系、あるいは水質変動
により上記条件となる水系に対して、1−ヒドロキシエ
チリデン−1,1−ジホスホン酸またはその塩と、2−
ホスホノブタン−1,2,4−トリカルボン酸またはそ
の塩との配合割合が1:9〜9:1である組成物を添加
することを特徴とする。そして、その水系は製紙工業の
脱墨工程であることが好ましい。The calcium-based scale inhibitor composition of the present invention comprises 1-hydroxyethylidene-
The compounding ratio of 1,1-diphosphonic acid or a salt thereof and 2-phosphonobutane-1,2,4-tricarboxylic acid or a salt thereof is 1: 9 to 9: 1. Further, the method for preventing calcium-based scale in an aqueous system according to the present invention has a calcium hardness of 300 mg as calcium carbonate.
1-hydroxyethylidene-1,1-diphosphonic acid for aqueous systems having an M-alkaliness of 300 mg / stand or higher, and / or a pH of 9.6 or higher, or water systems having the above conditions due to fluctuations in water quality. Or a salt thereof, and 2-
It is characterized by adding a composition having a blending ratio of 1: 9 to 9: 1 with phosphonobutane-1,2,4-tricarboxylic acid or a salt thereof. And the aqueous system is preferably a deinking process of the paper industry.
【0006】[0006]
【発明の実施の形態】本発明のカルシウム系スケールの
防止剤組成物は、1−ヒドロキシエチリデン−1,1−
ジホスホン酸(以下HEDPとも記す。)またはその塩
と、2−ホスホノブタン−1,2,4−トリカルボン酸
(以下PBTCとも記す。)またはその塩とを必須成分
として配合して1剤としたものであり、HEDPとPB
TCの配合比は1:9〜9:1が好ましく、1:3〜
3:1がさらに好ましい。尚、ホスホン酸塩としてはナ
トリウム塩、カリウム塩等のアルカリ金属塩、アンモニ
ウム塩等である。BEST MODE FOR CARRYING OUT THE INVENTION The calcium-based scale inhibitor composition of the present invention comprises 1-hydroxyethylidene-1,1-
Diphosphonic acid (hereinafter also referred to as HEDP) or a salt thereof and 2-phosphonobutane-1,2,4-tricarboxylic acid (hereinafter also referred to as PBTC) or a salt thereof are blended as essential components to form one agent. Yes, HEDP and PB
The compounding ratio of TC is preferably from 1: 9 to 9: 1, and from 1: 3 to
3: 1 is more preferred. Incidentally, examples of the phosphonate include alkali metal salts such as sodium salt and potassium salt, and ammonium salts.
【0007】本発明の前記組成物は、HEDPまたはそ
の塩や、PBTCまたはその塩の単独での使用に比べ相
乗効果によって低添加量で効果を発揮する。さらに水質
変動が大きい条件下であってもカルシウム系スケールの
生成を抑制し得る。そして、本発明の相乗効果が奏され
る限り、ポリマー類、有機酸類、キレート剤類、本発明
のHEDP、PBTC以外の各種ホスホン酸類等の他の
任意の成分を配合したり、併用しても差し支えない。こ
のようにさらに配合する任意の成分としては例えば、ポ
リマーとしてアクリル酸と2−ヒドロキシー3−アリル
オキシー1−プロパンスルホン酸との共重合体およびそ
の塩、有機酸類としてクエン酸、リンゴ酸、グルコン酸
およびそのアルカリ金属塩、キレート剤類としてエチレ
ンジアミン四酢酸およびそのアルカリ金属塩、その他の
ホスホン酸類としてエチレンジアミンテトラメチレンホ
スホン酸およびその塩が挙げられる。[0007] The composition of the present invention exerts an effect at a low addition amount due to a synergistic effect as compared with the use of HEDP or a salt thereof or PBTC or a salt thereof alone. Further, even under the condition where the water quality fluctuates greatly, the formation of calcium-based scale can be suppressed. And, as long as the synergistic effect of the present invention is exerted, any other components such as polymers, organic acids, chelating agents, HEDP and various phosphonic acids other than PBTC of the present invention may be blended or used together. No problem. Examples of optional components to be further blended in this way include, for example, a copolymer of acrylic acid and 2-hydroxy-3-allyloxy-1-propanesulfonic acid and a salt thereof as a polymer, and citric acid, malic acid, and gluconic acid as organic acids. And its alkali metal salts, chelating agents such as ethylenediaminetetraacetic acid and its alkali metal salts, and other phosphonic acids such as ethylenediaminetetramethylenephosphonic acid and its salts.
【0008】本発明の水系でのカルシウム系スケールの
防止方法は、前記組成物をスケール障害が発生する工程
の前段階に添加することが望ましい。本発明の前記組成
物が効果を発揮する水中濃度は水質条件に依存するた
め、特に制限されないが、通常は水中濃度0.1mg/
立から数十mg/立の少量で足りる。また添加方法とし
ても特に制限はなく、添加は間欠的でもよいし、連続的
でもよいが、スケールが発生する場所の前段階に添加す
ることが望ましい。[0008] In the method for preventing calcium-based scale in an aqueous system according to the present invention, it is desirable that the above-mentioned composition is added at a stage prior to the step of causing scale hindrance. The concentration of water in which the composition of the present invention exerts its effect is not particularly limited because it depends on the water quality conditions.
A small amount of several tens mg / stand is sufficient. The method of addition is not particularly limited, and the addition may be intermittent or continuous, but it is desirable to add it before the place where the scale occurs.
【0009】〔本発明による組成物(実施例)と、本発
明によらない組成物(比較例)との性能の比較試験〕試
験片を懸垂した炭酸カルシウムの過飽和水溶液に、上記
実施例、比較例の各組成物を個々に添加し、その後の水
質変化と、試験片へのスケール付着速度によって性能を
比較した。用いた試験片は、30×50mm、厚さ1m
mのSUS304製であり、試験前にトルエンによる脱
脂処理を行った。具体的には、純水をベースとして塩化
カルシウム水溶液を添加し、所定のカルシウム濃度に調
製したあと、上記実施例、比較例の各組成物を添加し、
続いて炭酸水素ナトリウム溶液を添加してアルカリ度を
調製し、最後に水酸化ナトリウム溶液を添加してpHを
調整した。この炭酸カルシウム過飽和水溶液を40℃の
恒温水槽に移し、マグネチックスターラーで1時間攪拌
し、攪拌後、検液を0.22μmのフィルターで濾過
し、濾液のカルシウム硬度をJIS0101の方法によ
って測定した。スケール付着速度は試験片を過飽和水溶
液に一定時間浸漬し、浸漬後に取り出して1N塩酸水溶
液に浸漬し、試験片に付着した炭酸カルシウムスケール
を溶解し、溶解後のカルシウム硬度を上記と同様に測定
し、この測定結果から換算してスケール付着量を求め
た。スケールの付着速度はこのスケール付着量と試験片
の表面積、試験期間から次式によって求めた。 スケール付着速度=スケール付着量(g)/試験期間
(日)/試験片の表面積(m2)[Comparison test of the performance of the composition according to the present invention (example) and the composition not according to the present invention (comparative example)] The above-mentioned examples were compared with a supersaturated aqueous solution of calcium carbonate in which a test piece was suspended. Each composition of the example was individually added, and the performance was compared based on the change in water quality thereafter and the rate of scale adhesion to the test piece. The test piece used was 30 × 50 mm, thickness 1 m
m of SUS304, and subjected to a degreasing treatment with toluene before the test. Specifically, after adding a calcium chloride aqueous solution based on pure water and adjusting to a predetermined calcium concentration, the above Examples, each composition of the comparative example was added,
Subsequently, a sodium bicarbonate solution was added to adjust the alkalinity, and finally, a sodium hydroxide solution was added to adjust the pH. This supersaturated aqueous solution of calcium carbonate was transferred to a constant temperature water bath at 40 ° C., and stirred for 1 hour with a magnetic stirrer. After the stirring, the test solution was filtered with a 0.22 μm filter, and the calcium hardness of the filtrate was measured according to JIS0101. The scale adhesion speed is determined by immersing the test piece in a supersaturated aqueous solution for a certain period of time, taking out after immersion, immersing in a 1N hydrochloric acid aqueous solution, dissolving the calcium carbonate scale attached to the test piece, and measuring the calcium hardness after dissolution in the same manner as above. The scale adhesion amount was determined by converting the measurement results. The scale deposition rate was determined by the following equation from the scale deposition amount, the surface area of the test piece, and the test period. Scale deposition rate = scale deposition amount (g) / test period (days) / surface area of test piece (m 2 )
【0010】試験条件および試験結果をまとめて表−1
に示す。Table 1 summarizes the test conditions and test results.
Shown in
【0011】[0011]
【表1】 [Table 1]
【0012】〈相乗効果および高pHにおける効果〉H
EDP単独処理では比較例1、2および比較例6、7に
示すようにカルシウム硬度300mg/立において、p
Hが9.8を越えると添加濃度を高めても防止効果を得
ることが困難である。PBTC単独処理においても比較
例3、4および比較例8〜10に示すように、これも上
記と同様である。これに対して、本発明の組成物は実施
例1、2および8、9から明らかな通り、高pHでも優
れたスケール防止効果を示し、pH10.6においてさ
え低添加濃度で効果があり、単独添加の比較例と比較す
ると相乗効果が認められた。そこでHEDPとPBTC
の配合割合を変えてその効果を比較したところ(実施例
3〜7)、pH条件が極めて過酷な試験条件であったp
H10.6においてさえ、1:9〜9:1という広い範
囲で相乗効果が認められた。<Synergy and Effect at High pH> H
In the EDP alone treatment, as shown in Comparative Examples 1 and 2 and Comparative Examples 6 and 7, at a calcium hardness of 300 mg / standing, p
If H exceeds 9.8, it is difficult to obtain a preventive effect even when the concentration of addition is increased. The same applies to the PBTC-only treatment, as shown in Comparative Examples 3 and 4 and Comparative Examples 8 to 10. In contrast, the compositions of the present invention, as is apparent from Examples 1, 2 and 8, 9 show an excellent scale-inhibiting effect even at a high pH, and are effective even at a pH of 10.6 even at a low added concentration. A synergistic effect was observed as compared with the comparative example of addition. So HEDP and PBTC
(Examples 3 to 7), the effect of pH was changed under extremely severe test conditions.
Even at H10.6, a synergistic effect was observed over a wide range from 1: 9 to 9: 1.
【0013】〈高カルシウム硬度における効果〉カルシ
ウム硬度が高い条件におけるスケール防止効果を調べる
目的から、カルシウム硬度900mgCaCO3/立、
M−アルカリ度900mgCaCO3/立、pH9.6
の条件で試験した結果、合計添加濃度が6mg/立とい
う低濃度においてもほとんどスケール付着がない効果を
示した(実施例10)。<Effect at High Calcium Hardness> For the purpose of examining the scale prevention effect under the condition of high calcium hardness, calcium hardness is 900 mgCaCO 3 / standing,
M-alkalinity 900mgCaCO 3 / standing, pH 9.6
As a result of the test under the conditions (1) and (2), even when the total concentration was as low as 6 mg / stand, there was almost no scale adhesion (Example 10).
【0014】〈本発明によるカルシウム系スケールの防
止方法の実施例〉新聞古紙と雑誌古紙の混合物を原料と
する某製紙工場の脱墨工程において、フローテーターの
後工程にある過酸化水素漂白塔出口からシックナーに至
る工程でスケール障害があった。すなわち過酸化水素漂
白塔スラリーに対して20mg/立となるようにスラリ
ー希釈水にHEDP塩を連続添加していたにも拘わら
ず、過酸化水素漂白塔以降の配管およびシックナーにス
ケールが発生し、パルプスラリーの流量が低下したり、
シックナーが閉塞して処理不能になる障害があった。こ
のため定期的に脱墨工程の運転を止めて酸洗浄をしてい
たが、度々不定期に洗浄をしなければならない状況であ
った。シックナーの絞り水の水質を測定したところ、次
に示すように高pHの系であった。 カルシム硬度 :290mgCaCO3/立 M−アルカリ度:630mgCaCO3/立 pH :10.9 温度 :35℃ この系に対し、本発明のHEDPとPBTCの配合比率
が1:1の実施例の組成物を合計有効成分として20m
g/立を同じ要領で連続添加した。この結果、シックナ
ーにおける目詰まりは著しく減少し、定期洗浄までの期
間中に突発的な洗浄をする必要がなくなった。また、定
期的運転停止時に観察した配管内のスケール付着量も著
しく低下していた。シックナーの絞り水が連続的に流れ
るシックナー下部の貯槽に、前述の比較試験で用いたの
と同じ試験片を浸漬してスケール付着速度を測定したと
ころ、HEDP単独処理時のスケール付着速度が70g
/m2/日であったのに対し、本発明によるHEDP/
PBTCの併用処理では3g/m2/日であった。この
処理効果によって脱墨工程は洗浄のための不定期の運転
停止がなく、安定な操業が可能になった。<Embodiment of a method for preventing calcium-based scale according to the present invention> In a deinking process of a paper mill using a mixture of used newspaper and used magazine paper as a raw material, an outlet of a hydrogen peroxide bleaching tower is provided after a flotator. There was scale obstacle in the process from to thickener. That is, despite the continuous addition of the HEDP salt to the slurry dilution water at a concentration of 20 mg / stand with respect to the hydrogen peroxide bleaching tower slurry, scale was generated in the piping and the thickener after the hydrogen peroxide bleaching tower, If the flow rate of pulp slurry decreases,
There was a problem that the thickener was blocked and could not be processed. For this reason, the operation of the deinking process was periodically stopped to perform the acid cleaning, but the cleaning had to be performed at irregular intervals. When the quality of the squeeze water of the thickener was measured, it was a high pH system as shown below. Calcium hardness: 290 mg CaCO 3 / standing M-alkalinity: 630 mg CaCO 3 / standing pH: 10.9 Temperature: 35 ° C. To this system, the composition of the example of the present invention in which the mixing ratio of HEDP to PBTC is 1: 1 was used. 20m as total active ingredient
g / stand were continuously added in the same manner. As a result, clogging in the thickener is significantly reduced, and there is no need for abrupt cleaning during the period up to regular cleaning. In addition, the scale adhesion amount in the pipe observed during the periodical shutdown was significantly reduced. When the same test piece as that used in the above-mentioned comparative test was immersed in the storage tank under the thickener in which the squeezing water of the thickener continuously flows, and the scale adhesion speed was measured, the scale adhesion speed when HEDP alone was treated was 70 g.
/ M 2 / day, whereas the HEDP /
The combined treatment with PBTC yielded 3 g / m 2 / day. Due to this treatment effect, the deinking process did not have an irregular shutdown for cleaning, and a stable operation became possible.
【0015】[0015]
【発明の効果】請求項1により、高硬度のカルシウム硬
度または/および高pHの水系に対して、少ない添加量
でカルシウム系スケールの発生を防止する組成物を提供
することができる。又、請求項2により、高硬度のカル
シウム硬度または/および高pHの水系に少量、添加
し、カルシウム系スケールの発生を大幅に抑制し、水系
の運転を安定に行うことができる。According to the first aspect of the present invention, it is possible to provide a composition capable of preventing the generation of a calcium-based scale with a small amount of addition to a high-hardness calcium hardness and / or a high-pH aqueous system. According to the second aspect, a small amount is added to a high hardness calcium hardness and / or a high pH water system to greatly suppress the generation of a calcium scale and to stably operate the water system.
Claims (3)
ホスホン酸またはその塩と、2−ホスホノブタン−1,
2,4−トリカルボン酸またはその塩との配合割合が
1:9〜9:1であることを特徴とするカルシウム系ス
ケールの防止剤組成物。(1) 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof, and 2-phosphonobutane-1,
An inhibitor composition for a calcium-based scale, wherein the compounding ratio with 2,4-tricarboxylic acid or a salt thereof is 1: 9 to 9: 1.
300mg/立以上、M−アルカリ度が300mg/立
以上、または/およびpHが9.6以上の水系、あるい
は水質変動により上記条件となる水系に対して、1−ヒ
ドロキシエチリデン−1,1−ジホスホン酸またはその
塩と、2−ホスホノブタン−1,2,4−トリカルボン
酸またはその塩との配合割合が1:9〜9:1である組
成物を添加することを特徴とするカルシウム系スケール
の防止方法。2. An aqueous system having a calcium hardness of at least 300 mg / m 2 as calcium carbonate, an M-alkalinity of at least 300 mg / m 2, and / or a pH of 9.6 or more, or an aqueous system having the above conditions due to fluctuations in water quality. , 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof and 2-phosphonobutane-1,2,4-tricarboxylic acid or a salt thereof in a ratio of 1: 9 to 9: 1. A method for preventing calcium-based scale.
2に記載のカルシウム系スケールの防止方法。3. The method according to claim 2, wherein the aqueous system is a deinking process of the paper industry.
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JP2007277769A (en) * | 2006-04-10 | 2007-10-25 | Hakuto Co Ltd | Cleanser for paper/pulp manufacturing process and cleansing method for paper/pulp manufacturing process system |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5720985B2 (en) * | 1973-05-22 | 1982-05-04 | ||
JPS58199877A (en) * | 1982-05-03 | 1983-11-21 | ナルコ・ケミカル・カンパニ− | Composition and method of preventing corrosion of ferrous metal |
JPS63258697A (en) * | 1987-04-16 | 1988-10-26 | Hakutou Kagaku Kk | Corrosion inhibitor also for suppressing scale of metals in aqueous system |
JPH0994598A (en) * | 1995-09-29 | 1997-04-08 | Kurita Water Ind Ltd | Corrosionproof and scale-proof method of open circulating cooling water system |
JPH10323696A (en) * | 1997-05-23 | 1998-12-08 | Kurita Water Ind Ltd | Antiscaling agent and scale-preventing method |
-
2001
- 2001-03-30 JP JP2001098697A patent/JP3945178B2/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5720985B2 (en) * | 1973-05-22 | 1982-05-04 | ||
JPS58199877A (en) * | 1982-05-03 | 1983-11-21 | ナルコ・ケミカル・カンパニ− | Composition and method of preventing corrosion of ferrous metal |
JPS63258697A (en) * | 1987-04-16 | 1988-10-26 | Hakutou Kagaku Kk | Corrosion inhibitor also for suppressing scale of metals in aqueous system |
JPH0994598A (en) * | 1995-09-29 | 1997-04-08 | Kurita Water Ind Ltd | Corrosionproof and scale-proof method of open circulating cooling water system |
JPH10323696A (en) * | 1997-05-23 | 1998-12-08 | Kurita Water Ind Ltd | Antiscaling agent and scale-preventing method |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007277769A (en) * | 2006-04-10 | 2007-10-25 | Hakuto Co Ltd | Cleanser for paper/pulp manufacturing process and cleansing method for paper/pulp manufacturing process system |
JP4520424B2 (en) * | 2006-04-10 | 2010-08-04 | 伯東株式会社 | Cleaning method for paper and pulp manufacturing process |
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