JPS61272392A - Patina remover - Google Patents
Patina removerInfo
- Publication number
- JPS61272392A JPS61272392A JP60115054A JP11505485A JPS61272392A JP S61272392 A JPS61272392 A JP S61272392A JP 60115054 A JP60115054 A JP 60115054A JP 11505485 A JP11505485 A JP 11505485A JP S61272392 A JPS61272392 A JP S61272392A
- Authority
- JP
- Japan
- Prior art keywords
- patina
- copper
- hydrazine
- remover
- corrosion
- 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.)
- Granted
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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Detergent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は緑青除去剤に係り、特に銅及び銅合金の地金を
侵すことなく緑青のみを選択的かつ効果的に除去し、銅
基材の腐食を防止することができる緑青除去剤に関する
。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a patina removal agent, and in particular, it selectively and effectively removes only patina without attacking copper and copper alloy base metals, and removes patina from copper base materials. Concerning a patina remover that can prevent corrosion of.
［従来の技術］
熱交換器等の系内の銅基材を有する機器は、長期間使用
すると孔食等の腐食が起こり、これは時間の経過と共に
進行し、装置に重大な欠陥を与え安定運転を阻害する原
因となる。[Prior Art] When equipment with a copper base material in the system, such as a heat exchanger, is used for a long period of time, corrosion such as pitting corrosion occurs, and this progresses over time, causing serious defects in the equipment and making it unstable. This may cause problems with driving.
従来、基材表面に生成する酸化銅を含む腐食生成物を除
去する方法としては塩酸あるいはスルファミン醜を用い
た酸洗浄が行われている。Conventionally, acid cleaning using hydrochloric acid or sulfamine has been used as a method for removing corrosion products containing copper oxide generated on the surface of a substrate.
［発明が解決しようとする問題点］
しかしながら、酸洗浄では洗浄廃液がｐＨ１〜４の強酸
性溶液であることから、
■ 銅地金に対して腐食性を有するため、機器の腐食損
傷を生じる危険があり、長時間の洗浄はできない。[Problems to be solved by the invention] However, in acid cleaning, the cleaning waste liquid is a strongly acidic solution with a pH of 1 to 4. ■ It is corrosive to copper metal, so there is a risk of corrosion damage to the equipment. It cannot be washed for a long time.
■ 洗浄により溶出した銅イオンが、鉄表面に電着し、
新たな二次腐食が生じる。■ Copper ions eluted during cleaning are electrodeposited on the iron surface,
New secondary corrosion occurs.
■ 洗浄後、十分に水洗し、酸を洗い流さなければなら
ない、酸が残存した場合、その場所から孔食等が生じる
おそれがある。■ After cleaning, it is necessary to thoroughly rinse with water to wash away the acid. If acid remains, there is a risk of pitting corrosion etc. occurring from that location.
等の問題点があり、従来においては、いずれの方法によ
っても銅の腐食生成物を効果的に除去することはできな
かった。Due to these problems, it has not been possible to effectively remove copper corrosion products by any of the conventional methods.
ところで、従来、腐食防止を目的として緑青を除去する
という考え方はなされておらず、緑青専用の洗浄除去剤
は提案されていない。By the way, conventionally, there has been no concept of removing patina for the purpose of corrosion prevention, and no cleaning and removal agent specifically for patina has been proposed.
なお特公昭４７−４１２３０号公報には、銅表面の洗浄
に際してヒドラジンを用いることが開示されている。し
かしながら、同号公報に記載の発明は銅表面の銅又は酸
化銅をも除去するものである。しかも、洗浄剤には酸も
必須成分とされており、スケールとしての酸化銅のみな
らず防食のために生成している銅表面の酸化銅層をも除
去してしまうことがら銅基材表面が著しく活性化される
こととなる。その上、洗浄後、酸が残留した場合、これ
が腐食の原因となる可能性もある。このため、特公昭４
７−４１２３０号公報に記載の洗浄剤は、緑青の選択除
去には不適である。Note that Japanese Patent Publication No. 47-41230 discloses the use of hydrazine for cleaning copper surfaces. However, the invention described in the same publication also removes copper or copper oxide on the copper surface. In addition, acid is considered an essential component of cleaning agents, which removes not only the copper oxide scale, but also the copper oxide layer that is formed on the copper surface for corrosion prevention, so the surface of the copper base material is It will be significantly activated. Moreover, if any acid remains after cleaning, this can also cause corrosion. For this reason, the special public
The cleaning agent described in JP 7-41230 is not suitable for selectively removing patina.
［問題点を解決するための手段］
本発明は上記従来の問題点を解決し、銅の腐食を効果的
に防止し得る薬剤を提供するものであって、ヒドラジン
を含むことを特徴とする。[Means for Solving the Problems] The present invention solves the above-mentioned conventional problems and provides an agent capable of effectively preventing corrosion of copper, which is characterized by containing hydrazine.
本発明は、緑青（Ｃｕ ４ （ＯＨ） ｓ Ｓ ０４
、Ｃｕｔ （ＯＨ）ｓ ＣＯ３）と孔食とが不可分の
関係にあり、銅基材に緑青が存在するとその下層におい
て銅の孔食が進行することに注目し、緑青を洗浄除去す
ることにより孔食の発生、進行を防止しようとするもの
である。The present invention provides green-blue (Cu 4 (OH) s S 04
, Cut (OH)s CO3) and pitting corrosion are inseparable, and when patina is present in the copper base material, copper pitting corrosion progresses in the underlying layer. This is an attempt to prevent the occurrence and progression of eclipses.
本発明において、処理対象とする銅表面に生成している
酸化銅防食膜を保護し、緑青の選択的除去効果を向上さ
せるために、１＆青除去剤はヒドラジンとともに銅用防
食剤を含有していることが好ましい。In the present invention, in order to protect the copper oxide anticorrosive film formed on the copper surface to be treated and improve the selective removal effect of patina, the 1&blue remover contains a copper anticorrosive agent together with hydrazine. Preferably.
銅用防食剤としては、ベンゾチアゾール、メルカプトベ
ンゾチアゾール、ベンゾトリアゾール。Corrosion inhibitors for copper include benzothiazole, mercaptobenzothiazole, and benzotriazole.
トリルトリアゾール等が挙げられ、その含有量はヒドラ
ジンに対する重量比で０．０５Ｗ−１％程度とするのが
好ましい。Examples include tolyltriazole, and the content thereof is preferably about 0.05W-1% in weight ratio to hydrazine.
このような本発明の緑青除去剤は、緑青の発生した箇所
に効果的に使用可能であるが、例えば、一般的な冷却水
プラントの調熱交換器、ターボ冷凍機、吸収式冷凍機の
調熱交換器チューブ、その韻調建材等の洗浄に極めて有
効である。The patina removal agent of the present invention can be effectively used in places where patina has occurred, but it can be used, for example, in heat adjustment exchangers, turbo chillers, and absorption chillers of general cooling water plants. Extremely effective for cleaning heat exchanger tubes, their construction materials, etc.
以下に本発明の緑青除去剤による処理方法について説明
する。The treatment method using the patina removing agent of the present invention will be explained below.
本発明の緑青除去剤により緑青を洗浄除去する方法とし
ては、
■ 本発明の緑青除去剤を必要に応じて水等で希釈して
洗浄液を調製し、洗浄液を容器に入れ、洗浄対象部材を
そのままあるいは分解して浸漬する（バッチ方式）、こ
の場合、必要に応じて洗浄液を攪拌する。The method for cleaning and removing patina with the patina remover of the present invention is as follows: (1) Prepare a cleaning solution by diluting the patina remover of the present invention with water etc. as necessary, put the cleaning solution in a container, and leave the member to be cleaned as it is. Alternatively, it is disassembled and immersed (batch method). In this case, the cleaning solution is stirred as necessary.
■ 洗浄対象の機器の運転を中止し、調製した洗浄液を
対象部に循環供給する（バッチ方式）。■ Stop the operation of the equipment to be cleaned and circulate and supply the prepared cleaning solution to the target area (batch method).
■ 運転中において、循環Ｘ中に本発明の緑青除去剤を
所定量添加して循環させる（Ｏ３ＲＲ（Ｏｎ Ｓｔ
ｒｅａｍ Ｒｕ５ｔ Ｒｅｍｏ −ｖｅｒ）方式、
この方式は熱交換器等の処理に適し、運転しながら緑青
を除去し、除去された緑青はブロー木と共に系外に排出
される。）の方法が挙げられる。なお、処理温度はいず
れも１５〜３０℃の室温が適当である。■ During operation, a predetermined amount of the patina remover of the present invention is added to circulation X and circulated (O3RR (On St
ream Ru5t Remo-ver) method,
This method is suitable for treating heat exchangers, etc., and removes patina during operation, and the removed patina is discharged from the system together with the blown wood. ) method can be mentioned. Note that room temperature of 15 to 30°C is appropriate for the treatment temperature.
これらの方法のうち、特に■の０５ＲＲ方式によれば、
運転中に所定量の緑青除去剤を添加するだけで良いため
、任意の頻度で処理することができ、使用量も比較的少
量で良く、洗浄回数を多くすることも可能である。Among these methods, especially according to the 05RR method (■),
Since it is only necessary to add a predetermined amount of the patina remover during operation, the treatment can be performed at any frequency, the amount used can be relatively small, and the number of cleanings can be increased.
本発明の緑青除去剤は上記バッチ方式あるいは０３ＲＲ
方式のいずれの処理方法においても、処理系内のヒドラ
ジンの初期濃度が５０ＰＰｍ以上であることが好ましい
、洗浄開始時の系内の初期ヒドラジン濃度が５０ｐｐｍ
未満であると、緑青除去効果が低くなる。ヒドラジン濃
度は５０ｐｐｍ以上であれば、良好な洗浄効果を発揮し
得る。ただし、あまりに高濃度となると、処理対象基材
に悪影響を及ぼす可能性もあるので、処理系内のヒドラ
ジン濃度は３％程度以下とするのが好ましい。The patina remover of the present invention can be used in the above-mentioned batch method or in the 03RR method.
In any of the treatment methods, it is preferable that the initial concentration of hydrazine in the treatment system is 50 ppm or more, and the initial concentration of hydrazine in the system at the start of cleaning is 50 ppm.
If it is less than that, the patina removal effect will be low. If the hydrazine concentration is 50 ppm or more, a good cleaning effect can be exhibited. However, if the concentration is too high, it may have an adverse effect on the substrate to be treated, so the concentration of hydrazine in the treatment system is preferably about 3% or less.
従って、本発明の緑青除去剤は、処理系内のヒドラジン
濃度を上記範囲に保つことができるような量でヒドラジ
ンを含有していることが好ましい。Therefore, the patina removal agent of the present invention preferably contains hydrazine in an amount that allows the hydrazine concentration in the treatment system to be maintained within the above range.
［作用］
ヒドラジンの作用により、緑青を還元溶解、あるいはキ
レート溶解し、極めて効率良く除去することができる。[Action] Due to the action of hydrazine, patina can be reductively dissolved or chelate-dissolved and removed very efficiently.
しかも、ヒドラジンは銅又は鉄に対する腐食性を有さな
いため、二次腐食等の問題は解決される。Moreover, since hydrazine does not have corrosivity to copper or iron, problems such as secondary corrosion are solved.
［発明の実施例］
以下に実施例及び参考例を挙げて本発明を更に具体的に
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。[Examples of the Invention] The present invention will be described in more detail below with reference to Examples and Reference Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.
実施例１
水道水に表１に示す量のヒドラジンを添加した洗浄液を
調製し、各々ｔｆＬ容のビーカーに採り、２０℃恒温槽
内に静置した。ビーカー内にはスターラーを入れ常時緩
速攪拌を行った。この洗浄液中に緑青が付着している９
、５ｍｍφ、長さ７５０の試供鋼チューブを懸垂させ
、それぞれ１時間洗浄した後、チューブを抜き出し、洗
浄液中の金銅量を測定した。また、洗浄後の銅チューブ
の外観を観察し、残留具合を調べた。Example 1 A cleaning solution was prepared by adding hydrazine in the amount shown in Table 1 to tap water, and each solution was placed in a tfL beaker and left standing in a constant temperature bath at 20°C. A stirrer was placed in the beaker and constant slow stirring was performed. There is a patina attached to this cleaning solution9
Sample steel tubes with a diameter of 5 mm and a length of 750 mm were suspended, and after each was washed for 1 hour, the tubes were taken out and the amount of gold and copper in the cleaning solution was measured. In addition, the appearance of the copper tube after cleaning was observed and the amount of residue was examined.
結果を表１に示す。The results are shown in Table 1.
表 １
※ 肉眼観察
Ａ・・・完全に除去
Ｂ・・・部分的に残留
Ｃ・・・残留
実施例２
実施例１において、ヒドラジン８０ｐｐｍ及びメルカプ
トベンゾチアゾールｌｏｐｐｍを添加した洗浄液を用い
たこと以外は、同様の洗浄操作を行ない、洗浄後の洗浄
液中の金銅量の測定及び銅チューブの外観の観察を行っ
た。その結果、洗浄液中の金銅量は４．６ｐｐｍであり
、また洗浄後の銅チューブには緑青は全く見られず、極
めて良好な洗浄効果が発揮されたことが認められた。Table 1 * Visual observation A...Completely removed B...Partially retained C...Remained Example 2 Except for using a cleaning solution containing 80 ppm of hydrazine and loppm of mercaptobenzothiazole in Example 1. A similar cleaning operation was performed, and the amount of gold and copper in the cleaning solution after cleaning was measured and the appearance of the copper tube was observed. As a result, the amount of gold-copper in the cleaning solution was 4.6 ppm, and no patina was observed on the copper tube after cleaning, indicating that an extremely good cleaning effect was exhibited.
実施例３
吸収式冷凍機の吸収器に用いられた、部分的に緑青が発
生している銅チューブについて本発明剤による洗浄を行
った。Example 3 A copper tube used in an absorber of an absorption refrigerator, which had partially developed patina, was cleaned with the agent of the present invention.
即ち、冷凍機の運転を継続しながら、吸収器循環水に、
ヒドラジン８４ｐｐｍを添加して、吸収器に送った。な
お吸収器の入日の温度は２７℃、出口温度は３２℃であ
った。２４時間後、楯環水中のヒドラジン濃度は０．８
ｐｐｍに低下していた。In other words, while the refrigerator continues to operate, the absorber circulating water is
84 ppm of hydrazine was added and sent to the absorber. The temperature of the absorber at sunset was 27°C, and the temperature at the outlet was 32°C. After 24 hours, the hydrazine concentration in the shield water was 0.8.
ppm.
洗浄後、開缶し、銅チューブを半割りにして内壁を観察
したところ、緑青は完全に除去され、壁面は酸化銅の光
沢を放っていた。After cleaning, the can was opened, the copper tube was cut in half, and the inner wall was observed. The patina was completely removed, and the wall surface had a copper oxide luster.
実施例４
ターボ冷凍機の蒸発器に用いられた、はぼ全面に緑青が
発生している銅チューブについて、本発明剤による洗浄
を行った。即ち、冷凍機の運転を停止し、蒸発器にバイ
パスラインを仮設し、Ｎ２Ｈ４１，８％を添加して、バ
ッチ洗浄を実施した。Example 4 A copper tube used in an evaporator of a centrifugal refrigerator, which had patina on its entire surface, was cleaned with the agent of the present invention. That is, the operation of the refrigerator was stopped, a bypass line was temporarily installed in the evaporator, and 1.8% N2H4 was added to perform batch cleaning.
２時間の洗浄の後、銅チューブを抜管半割りにして、内
壁を観察したところ、緑青は完全に除去され、壁面は酸
化銅の光沢を放っていた。After 2 hours of cleaning, the copper tube was removed and cut in half, and the inner wall was observed. The patina was completely removed and the wall surface had a copper oxide luster.
参考例１
実施例１において、ヒドラジン８０ｐｐｍ及び塩酸５％
を添加した洗浄液を用いたこと以外は全く同様にして供
試鋼チューブの洗浄を行い、洗浄後の洗浄液中の金銅量
の測定及び銅チューブの外観の観察を行った。その結果
、洗浄液中の全銅駿は５００ｐｐｍであり、チューブ外
観は酸化銅の色は見られず、純銅の光沢を有していた。Reference Example 1 In Example 1, hydrazine 80 ppm and hydrochloric acid 5%
The test steel tubes were cleaned in exactly the same manner except that a cleaning solution containing . As a result, the total copper content in the cleaning solution was 500 ppm, and the outer appearance of the tube showed no copper oxide color and had the luster of pure copper.
本例より、酸を用いた場合には、緑青だけでなく基材自
体も洗い出す可使性があり、基材に悪影響を与えること
があることが明らかである。From this example, it is clear that when an acid is used, there is a possibility of washing out not only the patina but also the base material itself, which may have an adverse effect on the base material.
［効果］
以上詳述した通り、本発明の緑青除去剤は、ヒドラジン
を含むものであって、
■ 緑青のみを選択的かつ効果的に除去することができ
る。[Effects] As detailed above, the patina removing agent of the present invention contains hydrazine, and (1) can selectively and effectively remove only patina.
■ 除去された緑青は、ヒドラジンの作用−により鉄表
面に電着することはない。このため、二次腐食は防止さ
れる。■ The removed patina will not be electrodeposited on the iron surface due to the action of hydrazine. Therefore, secondary corrosion is prevented.
■ 酸化銅の防食被膜を除去することはない。■ The copper oxide anti-corrosion coating is not removed.
従って、酸洗浄の如く、本発明の緑青除去剤による処理
で基材が活性化されることはなく、極めて良好な状態に
基材を保持できる。Therefore, unlike acid washing, the substrate is not activated by the treatment with the patina removing agent of the present invention, and the substrate can be maintained in an extremely good condition.
■ 銅及び鉄に対する腐食性がない、従って、長時間の
除去処理も問題がない、また、処理模本剤が残留しても
腐食の原因になることはないため、処理後の水洗を軽減
することも可能である。■ It is not corrosive to copper and iron, so there is no problem with long-term removal treatment, and even if the treatment simulator remains, it will not cause corrosion, reducing the need for washing with water after treatment. It is also possible.
■ 熱交換器等を処理する場合１本発明の緑青除去剤は
運転に悪影響を与えることがないため、運転中に循環水
に添加して使用することができ、処理操作が容易である
。(2) When treating heat exchangers, etc. 1 The patina removal agent of the present invention does not adversely affect operation, so it can be added to circulating water during operation, and treatment operations are easy.
等の利点を有する。It has the following advantages.
従って、本発明の緑青除去剤によれば、緑青の除去を短
時間で極めて良好に行うことができ、これにより基材の
孔食等の腐食を防止することが可能となる。Therefore, according to the patina removal agent of the present invention, patina can be removed extremely well in a short period of time, thereby making it possible to prevent corrosion such as pitting corrosion of the base material.
代理人 弁理士 重 野 剛
１ 事件の表示
昭和６０年特許願第１１５０５４号
２ 発明の名称
緑青除去剤
３ 補正をする者
事件との関係 特許出願人
名称 （１０６）栗田工業株式会社４ 代理人
住 所 東京都港区赤坂４丁目８番１９号〒１０７
赤坂表町ビル５０２号
６ 補正の対象
７ 補正の内容
（１） 明細書第３頁下から４ないし３行に「緑青（Ｃ
ｕ ４ （ＯＨ） ｓ Ｓ ０４、Ｃｕ４（ＯＨ）＊Ｃ
０３）ＪとあるのをｒＩ＆責（塩基性炭酸銅Ｃｕ ＣＯ
３・Ｃｕ （ＯＨ） ２ 、水酸化銅Ｃｕ（ＯＨ）２．
硝酸銅Ｃｕ（Ｎｏｖ）２．塩基性硝酸銅Ｃｕ （ＮＯ３
）２ ”Ｃｕ （ＯＨ）２．ビロリン酸銅ＣｕＰ２Ｏフ
、リン酸第２銅Ｃｕ ３（ＰＯ４）２． リン酸水素
′ｗ４Ｃｕ ＨＰ Ｏ４、塩基性硫酸銅Ｃｕ５Ｏ４ｅ
３Ｃｕ （ＯＨ）２など）１と訂正する。Agent Patent attorney Tsuyoshi Shigeno 1 Indication of the case Patent Application No. 115054 of 1985 2 Name of the invention Patina remover 3 Relationship with the case of the person making the amendment Name of the patent applicant (106) Kurita Industries Co., Ltd. 4 Agent residence Address: 4-8-19 Akasaka, Minato-ku, Tokyo 107
Akasaka Omotemachi Building No. 502 6 Target of amendment 7 Contents of amendment (1) In the 4th or 3rd line from the bottom of page 3 of the specification, there is a “patina (C
u 4 (OH) s S 04, Cu4 (OH) *C
03) What is J is rI&response (basic copper carbonate Cu CO
3.Cu(OH)2, copper hydroxide Cu(OH)2.
Copper nitrate Cu (Nov)2. Basic copper nitrate Cu (NO3
) 2 "Cu (OH) 2. Copper birophosphate CuP2O, cupric phosphate Cu 3 (PO4) 2. Hydrogen phosphate 'w4Cu HP O4, basic copper sulfate Cu5O4e
3Cu (OH)2, etc.) Correct it to 1.
（２） 同第４頁第１１行にｒｏ、０５ＷＮ１％」とあ
るのをｒｏ、ｏｓ〜２０％」と訂正する。(2) On page 4, line 11, the text "ro, 05WN1%" is corrected to "ro, os ~ 20%."
以 上that's all
Claims (2)
とする特許請求の範囲第１項に記載の緑青除去剤。(2) The patina remover according to claim 1, wherein the patina remover contains a copper anticorrosive agent.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60115054A JPS61272392A (en) | 1985-05-28 | 1985-05-28 | Patina remover |
| KR1019870700060A KR930004559B1 (en) | 1985-05-28 | 1986-05-20 | Method for removal of patina |
| GB8724359A GB2196991B (en) | 1985-05-28 | 1986-05-20 | Method for removal of patina |
| PCT/JP1986/000257 WO1986007099A1 (en) | 1985-05-28 | 1986-05-20 | Patina remover, process for its preparation, and method for removing patina |
| BR8607125A BR8607125A (en) | 1985-05-28 | 1986-05-20 | PATINA REMOVER, PROCESS FOR ITS PRODUCTION, AND PROCESS FOR PATINA REMOVAL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60115054A JPS61272392A (en) | 1985-05-28 | 1985-05-28 | Patina remover |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61272392A true JPS61272392A (en) | 1986-12-02 |
| JPS6345474B2 JPS6345474B2 (en) | 1988-09-09 |
Family
ID=14653034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60115054A Granted JPS61272392A (en) | 1985-05-28 | 1985-05-28 | Patina remover |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS61272392A (en) |
| KR (1) | KR930004559B1 (en) |
| BR (1) | BR8607125A (en) |
| GB (1) | GB2196991B (en) |
| WO (1) | WO1986007099A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007332396A (en) * | 2006-06-12 | 2007-12-27 | Toshiba Mitsubishi-Electric Industrial System Corp | Descaling method |
| JP2012012698A (en) * | 2010-05-31 | 2012-01-19 | Nalco Japan Kk | Verdigris inhibitor and verdigris inhibition method |
| JP2016204677A (en) * | 2015-04-15 | 2016-12-08 | 栗田工業株式会社 | Patina inhibition agent and patina inhibition method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8511344D0 (en) * | 1985-05-03 | 1985-06-12 | Ici Plc | Heterocyclic compounds |
| KR100619181B1 (en) * | 2004-11-10 | 2006-09-07 | 한국지질자원연구원 | Anti-oxidant process of copper powder by using tannic acid in conjunctions with hydrazine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50109873A (en) * | 1974-02-08 | 1975-08-29 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS498778B1 (en) * | 1970-04-08 | 1974-02-28 | ||
| JPS507203B2 (en) * | 1972-01-19 | 1975-03-24 | ||
| JPS5540245A (en) * | 1978-09-13 | 1980-03-21 | Mitsubishi Heavy Ind Ltd | Clean-up method of thermal power plant |
| FR2522522A1 (en) * | 1982-01-27 | 1983-09-09 | Leuna Werke Veb | PROCESS FOR IMPROVING THE INITIAL ACTIVITY OF ACTIVATED HYDRAZINE |
| GB2139206B (en) * | 1983-04-22 | 1986-10-29 | Leuna Werke Veb | Preventing corrosion |
| FR2540854A1 (en) * | 1983-04-22 | 1984-08-17 | Leuna Werke Veb | Process for removing oxygen dissolved in water |
| US4556492A (en) * | 1983-12-16 | 1985-12-03 | Ecolochem, Inc. | Deoxygenation process |
| ZA872662B (en) * | 1986-04-28 | 1987-10-02 | W.R. Grace & Company | Control of corrosion in aqueous systems |
-
1985
- 1985-05-28 JP JP60115054A patent/JPS61272392A/en active Granted
-
1986
- 1986-05-20 KR KR1019870700060A patent/KR930004559B1/en not_active IP Right Cessation
- 1986-05-20 BR BR8607125A patent/BR8607125A/en not_active IP Right Cessation
- 1986-05-20 WO PCT/JP1986/000257 patent/WO1986007099A1/en unknown
- 1986-05-20 GB GB8724359A patent/GB2196991B/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50109873A (en) * | 1974-02-08 | 1975-08-29 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007332396A (en) * | 2006-06-12 | 2007-12-27 | Toshiba Mitsubishi-Electric Industrial System Corp | Descaling method |
| JP2012012698A (en) * | 2010-05-31 | 2012-01-19 | Nalco Japan Kk | Verdigris inhibitor and verdigris inhibition method |
| JP2016204677A (en) * | 2015-04-15 | 2016-12-08 | 栗田工業株式会社 | Patina inhibition agent and patina inhibition method |
Also Published As
| Publication number | Publication date |
|---|---|
| BR8607125A (en) | 1988-02-23 |
| KR930004559B1 (en) | 1993-06-01 |
| KR880700102A (en) | 1988-02-15 |
| JPS6345474B2 (en) | 1988-09-09 |
| WO1986007099A1 (en) | 1986-12-04 |
| GB8724359D0 (en) | 1987-11-18 |
| GB2196991B (en) | 1990-03-28 |
| GB2196991A (en) | 1988-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3072502A (en) | Process for removing copper-containing iron oxide scale from metal surfaces | |
| US4452643A (en) | Method of removing copper and copper oxide from a ferrous metal surface | |
| US4789406A (en) | Method and compositions for penetrating and removing accumulated corrosion products and deposits from metal surfaces | |
| US4045253A (en) | Passivating metal surfaces | |
| US4025359A (en) | Inhibited acid composition for cleaning water systems | |
| US4111830A (en) | Method of inhibiting corrosion | |
| JPS61272392A (en) | Patina remover | |
| US3507795A (en) | Composition for removal of copper and copper oxide scales from boilers | |
| US3692583A (en) | Desmutting etched aluminum alloys | |
| US4586961A (en) | Methods and compositions for removing copper and copper oxides from surfaces | |
| US4861386A (en) | Enhanced cleaning procedure for copper alloy equipment | |
| JP2007270222A (en) | Scale detergent and scale removing method | |
| JPH05255874A (en) | Pickling promoter, pickling solution composition containing the same promoter and method for promoting metal pickling using the same composition | |
| JPH02305982A (en) | Higher-alkylbenzotriazole as novel corrosion inhibitor of copper and copper alloy | |
| JPS605888A (en) | Chemical washing method of iron oxide scale | |
| STREICHER | Synergistic inhibition of ferric ion corrosion during chemical cleaning of metal surfaces | |
| US2209291A (en) | Rust removing composition | |
| JP5842293B2 (en) | Anti-paining agent and anti-paining method | |
| ES2708173T3 (en) | Formulation of metal loss inhibitor and processes | |
| JPH0142357B2 (en) | ||
| JPS602389B2 (en) | Chemical cleaning method for steel parts | |
| JPS6086286A (en) | Water treating chemical agent | |
| JP2007119803A (en) | Method for cleaning inside face of copper tube or copper alloy tube | |
| JP4190260B2 (en) | Surface treatment method for lead-containing copper alloy and water contact member made of copper alloy | |
| JP2003041387A (en) | Method for removing silica-base scale |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |