JPH01212779A - Method for preventing corrosion of heat exchanger tube - Google Patents
Method for preventing corrosion of heat exchanger tubeInfo
- Publication number
- JPH01212779A JPH01212779A JP3785188A JP3785188A JPH01212779A JP H01212779 A JPH01212779 A JP H01212779A JP 3785188 A JP3785188 A JP 3785188A JP 3785188 A JP3785188 A JP 3785188A JP H01212779 A JPH01212779 A JP H01212779A
- Authority
- JP
- Japan
- Prior art keywords
- heat exchanger
- seawater
- exchanger tube
- chelate
- ppm
- 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
- 238000005260 corrosion Methods 0.000 title claims abstract description 21
- 230000007797 corrosion Effects 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 14
- 239000013535 sea water Substances 0.000 claims abstract description 23
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 15
- 239000013522 chelant Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims description 13
- 239000005416 organic matter Substances 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 21
- 235000014413 iron hydroxide Nutrition 0.000 abstract description 15
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract description 15
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000011253 protective coating Substances 0.000 abstract 2
- 238000004299 exfoliation Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910006299 γ-FeOOH Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、熱交換器用伝熱管の防食方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for preventing corrosion of heat exchanger tubes.
［従来の技術］
各種熱交換器用伝熱管には、銅合金管が多用されている
。また、海水を冷却水とする熱交換器においては、この
銅合金伝熱管の防食方法の１つとして、冷却海水中へ第
一鉄イオンを注入して水酸化鉄の保護皮膜を形成する方
法が広く採用されている。[Prior Art] Copper alloy tubes are often used as heat exchanger tubes for various heat exchangers. In addition, in heat exchangers that use seawater as cooling water, one method for preventing corrosion of copper alloy heat transfer tubes is to inject ferrous ions into the cooling seawater to form a protective film of iron hydroxide. Widely adopted.
［発明が解決しようとする課題］
しかしながら、生物汚染防止の目的で海水の塩素処理が
実施されている場合とか、例えば、石油化学工業等にお
いて第一鉄イオン注入点から熱交換器迄の距離が長い場
合等においては、第一鉄イオンを注入しても保護皮膜の
形成が十分でないことがある。このため、従来の防食方
法では、上述の分野において、腐食を十分に防止するこ
とができないという難点がある。[Problem to be solved by the invention] However, in cases where seawater is chlorinated for the purpose of preventing biological pollution, or for example in the petrochemical industry, where the distance from the ferrous ion injection point to the heat exchanger is In cases where the length is long, the formation of a protective film may not be sufficient even if ferrous ions are implanted. Therefore, conventional corrosion prevention methods have the disadvantage that they cannot sufficiently prevent corrosion in the above-mentioned fields.
本発明はかかる問題点に鑑みてなされたものであって、
海水の塩素処理が実施されている場合又は遠距離注入等
の場合においても、第一鉄イオンの注入により有効な保
護皮膜を形成することができる熱交換器管の防食方法を
提供することを目的とする。The present invention has been made in view of such problems, and includes:
The purpose of the present invention is to provide a corrosion prevention method for heat exchanger tubes that can form an effective protective film by implanting ferrous ions even when chlorination of seawater is being carried out or in the case of long-distance injection. shall be.
［課題を解決するための手段］
本発明に係る熱交換器管の防食方法は、第一鉄イオンを
０．０１乃至１０ｐｐｍ 、 Ｆ ｅとキレートを形成
する有機物を０．０１乃至１０ｐｐｍだけ添加した海水
を銅合金製熱交換器管内に通流させて熱交換器管内面に
保護皮膜を形成することを特徴とする。[Means for Solving the Problems] The method for preventing corrosion of heat exchanger tubes according to the present invention includes adding 0.01 to 10 ppm of ferrous ions and 0.01 to 10 ppm of an organic substance that forms a chelate with Fe. It is characterized by forming a protective film on the inner surface of the heat exchanger tube by flowing seawater through the copper alloy heat exchanger tube.
［作用］
本発明においては、第一鉄イオンを０．０１乃至１０ｐ
ｐｍの濃度で注入するから、熱交換器管内面に水酸化鉄
皮膜が形成され、管内面を防食する。また、同時にＦｅ
とキレートを形成する有機物を０．０１乃至１０ｐｐｍ
の濃度で添加するから、水酸化鉄のコロイド粒子が、付
着力が弱い懸濁物となることが抑制される。[Function] In the present invention, ferrous ions are added at 0.01 to 10p.
Since it is injected at a concentration of pm, an iron hydroxide film is formed on the inner surface of the heat exchanger tubes, which protects the inner surfaces of the tubes from corrosion. At the same time, Fe
0.01 to 10 ppm of organic substances that form chelates with
Since the iron hydroxide colloid particles are added at a concentration of , the colloidal particles of iron hydroxide are prevented from forming a suspension with weak adhesion.
従って、塩素処理海水中でも、また遠距離注入において
も、防食上十分な厚さの水酸化鉄皮膜が形成される。Therefore, even in chlorinated seawater and in long-distance injection, an iron hydroxide film with a sufficient thickness for corrosion protection is formed.
［実施例］
以下、本発明の実施例について具体的に説明する。本実
施例においては、銅合金製熱交換器用伝熱管の内面に、
第一鉄イオン（Ｆｅ ”）を帆０１乃至１０ｐｐｍ添
加すると共に、Ｆｅとキレートを形成する有機物を０．
０１乃至・１０ｐｐｍ添加した海水を通流させる。これ
により、伝熱管内面に水酸化鉄の皮膜が形成される。[Examples] Examples of the present invention will be specifically described below. In this example, on the inner surface of the copper alloy heat exchanger tube,
Ferrous ions (Fe'') are added at 0.1 to 10 ppm, and organic substances that form chelates with Fe are added at 0.00 to 10 ppm.
01 to 10 ppm of seawater is passed through the tube. As a result, a film of iron hydroxide is formed on the inner surface of the heat exchanger tube.
第一鉄イオンの注入により管内面に水酸化鉄皮膜が形成
される機構については、次のように考えられる。海水中
に注入された第一鉄イオン（Ｆｅ２＋）は極めて短時間
のうちに酸化を受けてγ−ＦｅＯＯＨになる。このγ−
ＦｅＯＯＨはコロイド粒子となり、時間の経過につれて
コロイド粒子が成長して大きくなり、やがては懸濁物と
なる。The mechanism by which an iron hydroxide film is formed on the inner surface of a tube due to the implantation of ferrous ions is thought to be as follows. Ferrous ions (Fe2+) injected into seawater are oxidized to γ-FeOOH in an extremely short period of time. This γ-
FeOOH becomes colloidal particles, and as time passes, the colloidal particles grow and become larger, eventually becoming a suspension.
水酸化鉄皮膜はこのγ−Ｆ ｅ ＯＯＨのコロイド粒子
が静電的な力によって管壁に付着したものである。The iron hydroxide film is formed by colloidal particles of γ-Fe OOH attached to the tube wall by electrostatic force.
ところが、塩素処理海水中では塩素による酸化によって
、また、遠距離注入では時間の経過によって、γ−Ｆｅ
ＯＯＨのコロイド粒子が付着力が弱い懸濁物となってし
まう。このため、管内面への水酸化鉄皮膜の生成が不十
分となる。However, in chlorinated seawater, γ-Fe is lost due to oxidation due to chlorine, and over time during long-distance injection.
The colloidal particles of OOH become a suspension with weak adhesion. For this reason, the formation of the iron hydroxide film on the inner surface of the tube becomes insufficient.
本願発明者等がこのような塩素による酸化又は経時変化
による影響を防止すべく種々検討した結果、冷却海水中
のＦｅ ２＋濃度を０．０１乃至１０ｐｐｍとし、同時
にＦｅとキレートを形成することができる有機物を０．
０１乃至１０ｐｐｍの濃度範囲で冷却海水に添加するこ
とによって、上記環境下においても水酸化鉄皮膜を十分
に生成することができることを見い出した。つまり、Ｆ
ｅとキレートを形成することができる有機物をｏ、ｏｉ
乃至１０ｐｐｍ＋たけ海水に添加することによって、付
着力が弱い懸濁物の生成が防止され、管内面に十分に厚
い水酸化鉄皮膜が生成される。As a result of various studies conducted by the inventors of the present application in order to prevent the effects of oxidation caused by chlorine or changes over time, it was possible to set the Fe 2+ concentration in the cooling seawater to 0.01 to 10 ppm and form a chelate with Fe at the same time. Organic matter 0.
It has been found that by adding it to cooling seawater in a concentration range of 0.01 to 10 ppm, an iron hydroxide film can be sufficiently produced even under the above environment. In other words, F
Organic substances that can form chelates with e are o and oi.
By adding 10 ppm to 10 ppm+ to seawater, the formation of suspensions with weak adhesion is prevented and a sufficiently thick iron hydroxide film is formed on the inner surface of the tube.
第一鉄イオンＦｅ ２＋の濃度を帆０１乃至１０ｐｐ
ｍと限定した理由は、このＦｅ ２＋濃度が０．０１ｐ
ｐｍ未満では防食に必要な水酸化鉄皮膜を形成すること
ができない。また、Ｆｅ ２＋濃度が１０ｐｐｍを超え
ると、水酸化鉄皮膜が厚くなり過ぎ、皮膜の内部応力で
容易に剥離してしまうようになる。このような理由から
、Ｆｅ ２＋濃度を上記範囲に限定したものである。Adjust the concentration of ferrous ion Fe 2+ from 01 to 10 pp.
The reason why it is limited to m is that this Fe 2+ concentration is 0.01p
If it is less than pm, the iron hydroxide film required for corrosion protection cannot be formed. Furthermore, when the Fe 2+ concentration exceeds 10 ppm, the iron hydroxide coating becomes too thick and easily peels off due to the internal stress of the coating. For these reasons, the Fe 2+ concentration is limited to the above range.
一方、Ｆｅとキレートを形成することができる有機物の
濃度を０．０１乃至１０ｐｐｍと限定した理由は、有機
物濃度が０．０１ｐｐｍ未満では水酸化鉄皮膜形成の改
善効果が得られないこと、また、１０ｐｐｍを超えて添
加してもその効果は飽和してしまい、無駄であるだけで
なく、水質汚染の原因ともなる。このため、有機物の濃
度範囲を０．０１乃至１０ｐｐｍとした。On the other hand, the reason why the concentration of organic matter that can form a chelate with Fe is limited to 0.01 to 10 ppm is that if the concentration of organic matter is less than 0.01 ppm, the effect of improving iron hydroxide film formation cannot be obtained. Even if it is added in an amount exceeding 10 ppm, the effect will be saturated, which is not only wasteful but also causes water pollution. For this reason, the concentration range of organic matter was set to 0.01 to 10 ppm.
Ｆｅとキレートを形成することができる有機物としては
、カルボン酸又はアミン等がある。その中でもカルボン
酸を用いた場合は、防食性が更に一層優れた保護皮膜を
得ることができる。これは、カルボン酸中のカルボキシ
ル基とＦｅとの給合力が強いためである。また、このカ
ルボン酸としては、クエン酸又は酢酸等があるが、分子
内に２個以上のカルボキシル基を有する錯式カルボン酸
を使用することにより、更に一層防食性が優れた保護皮
膜を得ることができる。これは、Ｆｅが２個のカルボキ
シル基とキレート結合を形成することにより、さらに安
定したキレート化合物を形成することかできるためであ
る。Examples of organic substances that can form a chelate with Fe include carboxylic acids and amines. Among them, when carboxylic acid is used, a protective film with even more excellent corrosion resistance can be obtained. This is because the bonding force between the carboxyl group in the carboxylic acid and Fe is strong. In addition, examples of this carboxylic acid include citric acid and acetic acid, but by using a complex carboxylic acid having two or more carboxyl groups in the molecule, a protective film with even better corrosion resistance can be obtained. Can be done. This is because Fe can form a more stable chelate compound by forming a chelate bond with two carboxyl groups.
次に、供試管として、外径が２５．４ｍｍ、厚さが１゜
２４１、長さが１０００ｍ＋ａのアルミニウム黄銅管を
使用して、本発明の実施例方法により保護皮膜を形成し
その防食性能を試験した結果について説明する。Next, using an aluminum brass tube with an outer diameter of 25.4 mm, a thickness of 1°241, and a length of 1000 m+a as a test tube, a protective film was formed by the method of the embodiment of the present invention, and its anticorrosion performance was evaluated. The results of the test will be explained.
残留塩素の０．ｌｐｐｍの塩素処理を実施した清浄海水
を使用し、管内流速が２ｍ／秒となるようにした。Residual chlorine: 0. Clean seawater treated with lppm of chlorine was used, and the flow velocity in the pipe was set to 2 m/sec.
また、硫酸第一鉄の注入点から供試管までの距離は２０
０ｍとし、通水時間は、硫酸第１鉄の総量が同じになる
ようにした。In addition, the distance from the injection point of ferrous sulfate to the test tube is 20
0 m, and the water flow time was such that the total amount of ferrous sulfate was the same.
海水中の有機物とＦｅ ２＋濃度を下記第１表に示す
。なお、第１表には有機物を添加しない場合、その有機
物の濃度が低い場合、又はＦｅ ２＋濃度が所定範囲
から外れる場合の比較例も掲載した。The organic matter and Fe 2+ concentrations in seawater are shown in Table 1 below. Note that Table 1 also lists comparative examples in which no organic substance was added, the concentration of the organic substance was low, or the Fe 2+ concentration was outside the predetermined range.
各実施例及び比較例方法にて形成された保護皮膜の防食
性能を評価するため次の試験をおこなった。The following tests were conducted to evaluate the anticorrosion performance of the protective films formed by the methods of each example and comparative example.
（ａ）保護皮膜の生成状況 半裁し、目視により皮膜の生成状況を観察した。(a) Formation status of protective film The film was cut in half and the state of film formation was visually observed.
（ｂ）Ｆｅ付着量
保護皮膜を塩酸で溶解し、原子吸光分析により被膜中の
Ｆｅ量を求めた。(b) Amount of Fe deposited The protective film was dissolved in hydrochloric acid, and the amount of Fe in the film was determined by atomic absorption spectrometry.
（Ｃ）ジェット試験
供試管を半裁した試料に対し、清浄海水の高流速ジェッ
トを試料面に垂直に当てて、その部分の腐食深さを測定
した。試験は２０日間継続した。(C) Jet test A high-velocity jet of clean seawater was applied perpendicularly to the sample surface of a sample of the test tube cut in half, and the corrosion depth of that portion was measured. The test lasted 20 days.
（ｄ）通水試験
高流速（５ｍ／秒）の清浄海水を２ケ月間通水し、潰食
による試料の減肉量を測定した。(d) Water flow test Clean seawater was passed through the sample at a high flow rate (5 m/sec) for 2 months, and the amount of thinning of the sample due to erosion was measured.
これらの試験の結果を前記第１表に併せて示した。The results of these tests are also shown in Table 1 above.
この第１表から明らかなように、本発明の実施例方法に
より形成した保護皮膜は剥離することがなく防食性が優
れたものであり、その結果、ジェット試験・通水試験で
の腐食程度が極めて軽度である。As is clear from Table 1, the protective film formed by the example method of the present invention does not peel off and has excellent corrosion resistance, and as a result, the degree of corrosion in the jet test and water flow test was low. Very mild.
一方、比較例方法により形成した保護皮膜は、防食性能
が十分でなく、腐食の程度が大きい。On the other hand, the protective film formed by the method of the comparative example did not have sufficient anticorrosion performance and suffered a large degree of corrosion.
［発明の効果］
以上説明したように、本発明に係る熱交換器管の防食方
法によれば、０．０１乃至１０ｐｐｍの第一鉄イオンの
外に、Ｆｅとキレートを形成する有機物を０．０１乃至
１０ｐｐｍだけ添加した海水を熱交換器管内に通流させ
るから、海水の塩素処理が実施されている熱交換器の場
合又は第一鉄イオン注入点から熱交換器迄の距離が長い
場合等においても十分に高い防食効果を得ることができ
る。[Effects of the Invention] As explained above, according to the method for preventing corrosion of heat exchanger tubes according to the present invention, in addition to 0.01 to 10 ppm of ferrous ions, 0.01 to 10 ppm of organic matter that forms a chelate with Fe is added. Since seawater added at 0.01 to 10 ppm is passed through the heat exchanger tubes, this may be the case if the heat exchanger is undergoing chlorination of seawater or if the distance from the ferrous ion injection point to the heat exchanger is long. A sufficiently high anti-corrosion effect can be obtained even in this case.
Claims (3)
キレートを形成する有機物を０．０１乃至１０ｐｐｍだ
け添加した海水を銅合金製熱交換器管内に通流させて熱
交換器管内面に保護皮膜を形成することを特徴とする熱
交換器管の防食方法。(1) Seawater to which 0.01 to 10 ppm of ferrous ions and 0.01 to 10 ppm of organic matter that forms a chelate with Fe is added is passed through a copper alloy heat exchanger tube to coat the inner surface of the heat exchanger tube. A method for preventing corrosion of heat exchanger tubes, characterized by forming a protective film.
請求項１に記載の熱交換器管の防食方法。(2) The method for preventing corrosion of heat exchanger tubes according to claim 1, wherein the organic substance is a carboxylic acid.
を有する錯式カルボン酸であることを特徴とする請求項
２に記載の熱交換器管の防食方法。(3) The method for preventing corrosion of a heat exchanger tube according to claim 2, wherein the organic substance is a complex carboxylic acid having two or more carboxyl groups in the molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3785188A JPH01212779A (en) | 1988-02-20 | 1988-02-20 | Method for preventing corrosion of heat exchanger tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3785188A JPH01212779A (en) | 1988-02-20 | 1988-02-20 | Method for preventing corrosion of heat exchanger tube |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01212779A true JPH01212779A (en) | 1989-08-25 |
Family
ID=12509040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3785188A Pending JPH01212779A (en) | 1988-02-20 | 1988-02-20 | Method for preventing corrosion of heat exchanger tube |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01212779A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008546910A (en) * | 2005-06-24 | 2008-12-25 | ハネウェル・インターナショナル・インコーポレーテッド | Method for inhibiting corrosion on brazed metal surfaces, and coolants and additives for use therein |
| US9023235B2 (en) | 2012-09-07 | 2015-05-05 | Prestone Products Corporation | Heat transfer fluid additive composition |
-
1988
- 1988-02-20 JP JP3785188A patent/JPH01212779A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008546910A (en) * | 2005-06-24 | 2008-12-25 | ハネウェル・インターナショナル・インコーポレーテッド | Method for inhibiting corrosion on brazed metal surfaces, and coolants and additives for use therein |
| US9660277B2 (en) | 2005-06-24 | 2017-05-23 | Prestone Products Corporation | Methods for inhibiting corrosion in brazed metal surfaces and coolants and additives for use therein |
| US9023235B2 (en) | 2012-09-07 | 2015-05-05 | Prestone Products Corporation | Heat transfer fluid additive composition |
| US9598624B2 (en) | 2012-09-07 | 2017-03-21 | Prestone Products Corporation | Heat transfer fluid additive composition |
| US10017678B2 (en) | 2012-09-07 | 2018-07-10 | Prestone Products Corporation | Heat transfer fluid additive composition |
| US10119058B2 (en) | 2012-09-07 | 2018-11-06 | Prestone Products Corporation | Heat transfer fluid additive composition |
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