JPH0353080A - Method for preventing corrosion of inside of copper alloy tube - Google Patents
Method for preventing corrosion of inside of copper alloy tubeInfo
- Publication number
- JPH0353080A JPH0353080A JP18599389A JP18599389A JPH0353080A JP H0353080 A JPH0353080 A JP H0353080A JP 18599389 A JP18599389 A JP 18599389A JP 18599389 A JP18599389 A JP 18599389A JP H0353080 A JPH0353080 A JP H0353080A
- Authority
- JP
- Japan
- Prior art keywords
- ferrous sulfate
- iron
- soln
- carboxylic acid
- tube
- 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
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000005260 corrosion Methods 0.000 title claims abstract description 8
- 230000007797 corrosion Effects 0.000 title claims abstract description 8
- 230000003405 preventing effect Effects 0.000 title claims abstract description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 19
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 19
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 19
- -1 carboxylic acid ions Chemical class 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 22
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 49
- 229910052742 iron Inorganic materials 0.000 abstract description 24
- 239000013535 sea water Substances 0.000 abstract description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 3
- 238000011033 desalting Methods 0.000 abstract 1
- 238000005536 corrosion prevention Methods 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は銅又は銅合金の防食方法に関し、更に詳しくは
、船舶、化学プラント、発電プラント等の海水利用熱交
換器、復水器などの銅又は銅合金管内面の防食方法に関
する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for preventing corrosion of copper or copper alloys, and more specifically, to a method for preventing corrosion of copper or copper alloys, and more specifically, for use in seawater heat exchangers, condensers, etc. for ships, chemical plants, power plants, etc. This invention relates to a corrosion prevention method for the inner surface of copper or copper alloy pipes.
現在、各種プラントの海水利用熱交換器、復水器類の銅
合金管の防食対策としては、冷却海水中に微量の鉄イオ
ンを注入することによって行われ、鉄イオン注入方法と
しては、硫酸ｉ−鉄溶液を注入する方法と本発明者らが
先に提案した硫酸第一鉄溶液中にカルボン酸イオンを共
存させた溶液を注入する方法（特願昭６１〜２９１５９
６号）がある。後者は、鉄イオンの急激なコロイド化を
抑制し、鉄被膜の付着量をコントロールするものである
。鉄イオン注入による防食は海水中に注入された第一鉄
イ才ン（１’Ｅ！” ）が酸化物状態、コロイド状態と
なり管内面に鉄被膜を形筬することによる。Currently, corrosion prevention measures for copper alloy pipes in seawater heat exchangers and condensers in various plants are carried out by injecting a small amount of iron ions into cooling seawater. - A method of injecting an iron solution and a method of injecting a solution in which carboxylic acid ions coexist in a ferrous sulfate solution proposed by the present inventors (Japanese Patent Application No. 61-29159)
No. 6). The latter suppresses rapid colloidalization of iron ions and controls the amount of iron coating deposited. Corrosion prevention by iron ion implantation is due to the fact that ferrous iron (1'E!'') injected into seawater becomes an oxide state and a colloid state, forming an iron coating on the inner surface of the pipe.
第３図は本発明者らが先に提案した硫酸第一鉄溶液中に
カルボン酸イオンを共存させた溶液を注入する方法（特
願昭６１−２９１５９６号）による鉄被膜付着量の分布
を示した図である。注入条件は、
（イ）銅合金管内の海水流速・
２ ｍ／ｓｅｃ
（口）海水温度・・・・・２０℃
（ハ）銅合金管形状・・３４ｍｍφＸ６０ｍ（二）注入
濃度及び時間・・Ｆｅとして１． ＯＰＰＭＸ４０Ｈｒ
（ホ）クエン酸添加量・・硫酸第一鉄（ＦｅＳＯ．・７
Ｈ２０） ５重量に
対し、１重量
である。Figure 3 shows the distribution of the amount of iron coating deposited by the method previously proposed by the present inventors, in which a solution containing carboxylic acid ions is injected into a ferrous sulfate solution (Japanese Patent Application No. 61-291596). This is a diagram. The injection conditions are: (a) Seawater flow rate in the copper alloy pipe: 2 m/sec (port) Seawater temperature: 20°C (c) Copper alloy pipe shape: 34mmφ x 60m (ii) Injection concentration and time: Fe As 1. OPPMX40Hr (e) Amount of citric acid added...ferrous sulfate (FeSO.・7
H20) It is 1 weight per 5 weight.
第３図において、０〜６０ｍまで鉄付着量の積分値は約
２０ｇとなるが、注入した鉄量は、約２６０ｇであり、
付着効率がｌＯ％以下と低い。In Fig. 3, the integral value of the amount of iron deposited from 0 to 60 m is about 20 g, but the amount of iron injected is about 260 g.
The adhesion efficiency is low at 10% or less.
本発明は上記技術水準に鑑み、従来法の鉄量の付着効率
の低さを改善した銅合金管内の防食方法を提供しようと
するものである。In view of the above-mentioned state of the art, the present invention aims to provide a method for preventing corrosion inside a copper alloy pipe, which improves the low iron adhesion efficiency of the conventional method.
このため、本発明者らは鉄量の付着効率の向上を図るた
め、鋭意研究を行った結果、まず硫酸第一鉄溶液のみの
注入を数時間行い、その後カルボン酸イオンを添加した
溶液を数１０時間注入することにより、付着効率が向上
し、かつ、付着量の分布もカルボン酸イオン添加法（特
願昭６１−２９１５９６号）単独の場合より均一性があ
ることを見い出し、本発明を完或するに至った。Therefore, in order to improve the adhesion efficiency of iron, the present inventors conducted intensive research and found that first, a ferrous sulfate solution alone was injected for several hours, and then a solution containing carboxylic acid ions was injected for several hours. It was discovered that by implanting for 10 hours, the adhesion efficiency was improved and the distribution of the adhesion amount was more uniform than when using only the carboxylic acid ion addition method (Japanese Patent Application No. 61-291596), and completed the present invention. It came to a certain point.
すなわち、本発明は硫酸第一鉄溶液の注入を１０時間以
内にわたって行い、その後硫酸第一鉄溶液にカルボン酸
を溶解し、硫酸第一鉄溶液中にカルボン酸イオンを共存
させた溶液を注入する銅合金管内面の防食方法である。That is, in the present invention, a ferrous sulfate solution is injected for up to 10 hours, then a carboxylic acid is dissolved in the ferrous sulfate solution, and a solution in which carboxylic acid ions are coexisting in the ferrous sulfate solution is injected. This is a corrosion prevention method for the inner surface of copper alloy pipes.
第１図は本発明の一実施例における試験装置のフロー図
である。FIG. 1 is a flow diagram of a test apparatus in an embodiment of the present invention.
海水タンク１に汲み上げられた海水２を、海水ボンブ３
で塩化ビニール管４を経て銅合金管５へ供給する。６は
硫酸第一鉄溶液槽であり、硫酸第一鉄溶液槽６内の硫酸
第一鉄溶液７を定量ポンブ８でビニールホース９を経て
塩化ビニール管４の末端に注入する。Seawater 2 pumped into seawater tank 1 is transferred to seawater bomb 3.
It is supplied to a copper alloy pipe 5 via a vinyl chloride pipe 4. 6 is a ferrous sulfate solution tank, and the ferrous sulfate solution 7 in the ferrous sulfate solution tank 6 is injected into the end of the vinyl chloride pipe 4 through a vinyl hose 9 using a metering pump 8.
（イ）銅合金管内の海水流速・・２ｍ ／ ｓｅｃ（ロ
）海水温度・・・・ ・・・２０℃（ハ）銅合金管形状
・・３４ｍｍφ×６０ｍ（二）注入条件
■硫酸第一鉄溶液の注入
Ｆｅとして１．ＯＰＰＭｘ ６ Ｈｒ
■カルボン酸イオンを共存させた溶液の注入
Ｆｅとして１．ＯＰＰＭｘ １ ８ Ｈｒカルボン酸と
してクエン酸を用い、硫
酸第一鉄（ＦＥ！Ｓｏ４−７Ｈ２０） ５重量に対し、
１重量の比率で添加。(a) Seawater flow rate in the copper alloy pipe: 2m/sec (b) Seawater temperature: 20°C (c) Copper alloy pipe shape: 34mmφ x 60m (ii) Injection conditions ■ Ferrous sulfate 1. As injection of solution Fe. OPPMx 6 Hr ■As injection of Fe in a solution containing carboxylic acid ions 1. OPPMx 1 8 Hr Using citric acid as the carboxylic acid, for 5 weight of ferrous sulfate (FE!So4-7H20),
Added at a ratio of 1 part by weight.
第２図に前記条件下での鉄被膜付着量の分布を示した。FIG. 2 shows the distribution of the amount of iron coating deposited under the above conditions.
第２図において実＃１Ａが本発明方法によるもの、破
線Ｂは第３図に示した特願昭６１−２９１５９６号によ
る場合の結果であり、注入時間が４０Ｈｒと長い。In FIG. 2, actual #1A is the result obtained by the method of the present invention, and broken line B is the result obtained by the method of Japanese Patent Application No. 61-291596 shown in FIG. 3, and the injection time is as long as 40 hours.
第２図において、本発明方法による０〜６０ｍまでの鉄
付着量の積分値は約３０ｇ１注入した鉄量は約１６０ｇ
であり、付着効率は約■９％であり、従来の約２倍にア
ップした。In Fig. 2, the integral value of the amount of iron deposited from 0 to 60 m by the method of the present invention is approximately 30 g, and the amount of iron injected is approximately 160 g.
The adhesion efficiency was approximately ■9%, which is approximately twice as high as that of the conventional method.
また、鉄付着量の分布も従来技術より均一であることが
判る。It is also seen that the distribution of the amount of iron deposited is more uniform than in the prior art.
さらに、本発明方法により鉄被膜を形戊させた銅合金管
に約６ケ月間海水を通水後、管内面を調査したところ腐
食の発生はなく防食効果は良妊であった。Furthermore, after passing seawater through a copper alloy tube with an iron coating formed by the method of the present invention for about 6 months, the inner surface of the tube was examined, and no corrosion occurred and the anticorrosion effect was good.
なお、硫酸第一鉄溶液のみの注入を１０時間以上長く行
うとカルボン酸イオンを共存させた溶液を注入した後の
鉄被膜に密着性が劣り、剥離しやすくなることが判り、
鉄被膜の付着量、密着性の面から硫酸第一鉄溶液のみの
注入は１０時間以下とする必要がある。Furthermore, it has been found that if the injection of ferrous sulfate solution alone is continued for more than 10 hours, the adhesion of the iron coating after injection of the solution containing carboxylic acid ions will be poor and it will easily peel off.
In view of the amount of adhesion and adhesion of the iron coating, it is necessary to inject only the ferrous sulfate solution for 10 hours or less.
海水淡水化装置の熱放出部のように電熱管長が長く、か
つ、短期処理が要求される熱交換器類の防食対策として
極めて有効である。It is extremely effective as a corrosion prevention measure for heat exchangers that have long electric heating tubes and require short-term treatment, such as the heat release section of seawater desalination equipment.
第１図は本発明実施例における試験装置のフロー図。第
２図は本発明実施例の鉄付着量の分布と従来の方法によ
る鉄付着量の分布を合わせて示す図表、第３図は従来の
方法による鉄付着量の分布を示す図表である。
第２図
調合金管侵（ｍ）
第３図
調合缶管長
（ＴｒＬ）FIG. 1 is a flow diagram of a test apparatus in an embodiment of the present invention. FIG. 2 is a chart showing the distribution of the amount of iron deposited according to the embodiment of the present invention and the distribution of the amount of iron deposited according to the conventional method, and FIG. 3 is a chart showing the distribution of the amount of iron deposited according to the conventional method. Figure 2: Alloy pipe length (m) Figure 3: Mixing can pipe length (TrL)
Claims (1)
硫酸第一鉄溶液にカルボン酸イオンを共存させた溶液を
注入することを特徴とする銅合金管内面の防食方法。After injection of ferrous solution of sulfuric acid over a period of 10 hours,
A method for preventing corrosion on the inner surface of a copper alloy pipe, which is characterized by injecting a solution containing carboxylic acid ions in a ferrous sulfate solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18599389A JPH0353080A (en) | 1989-07-20 | 1989-07-20 | Method for preventing corrosion of inside of copper alloy tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18599389A JPH0353080A (en) | 1989-07-20 | 1989-07-20 | Method for preventing corrosion of inside of copper alloy tube |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0353080A true JPH0353080A (en) | 1991-03-07 |
Family
ID=16180490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18599389A Pending JPH0353080A (en) | 1989-07-20 | 1989-07-20 | Method for preventing corrosion of inside of copper alloy tube |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0353080A (en) |
-
1989
- 1989-07-20 JP JP18599389A patent/JPH0353080A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112779543A (en) | Organic acid cleaning agent and preparation method thereof | |
| CN107365922A (en) | Full intelligent ground descaling device | |
| CN107338368A (en) | A kind of complete intelligent antiscaling, descaling alloy and preparation method thereof | |
| CN107324449A (en) | Complete intelligent scale prevention device on heavy caliber pipeline | |
| CN107512784A (en) | A kind of corrosion inhibiting and descaling agent for organic alcohols refrigerating system and preparation method thereof | |
| Weisstuch et al. | An electrochemical study of heteropoly molybdates as cooling water corrosion inhibitors | |
| JPH0353080A (en) | Method for preventing corrosion of inside of copper alloy tube | |
| JPS621856A (en) | Corrosion resistant copper-base member and its manufacture | |
| TW200532055A (en) | Corrosion inhibition method | |
| JPS63145788A (en) | Anticorrosive | |
| EP0081612B1 (en) | Heat pipe | |
| RU94042402A (en) | Method of water treatment and a chemical for inhibition of corrosion and deposit formation | |
| JPS63121681A (en) | Method for preventing corrosion of copper alloy pipe | |
| JPH01212780A (en) | Method for preventing corrosion of copper alloy tube | |
| JP2919765B2 (en) | Underwater corrosion inhibitor | |
| CN109030338A (en) | A kind of method of electro-catalysis chemical attack original austenite grain | |
| JPH02227193A (en) | Method for preventing generation of rust and/or scale in water channel | |
| CN112501624A (en) | Prefilming agent for acid-washed industrial circulating water pipeline | |
| CN111560617A (en) | Preparation method and use method of novel circulating water cleaning pre-filming agent | |
| JPH08158076A (en) | Anticorrosive for copper alloy | |
| JPH0293084A (en) | Anticorrosive injector | |
| TH22161A (en) | Improvements related to drinking water dispensers | |
| JPH06306697A (en) | Highly efficient method for reducing trivalent fe ion in iron based electroplating solution | |
| Sutiman et al. | The influence of water concentration on the corrosion of low alloy steels in the system methanol-ethylene glycol-formic acid | |
| JPS605670B2 (en) | Chemical conversion treatment method for zinc and zinc alloys |