JPS58224185A - Corrosion inhibitive lithium bromide composition - Google Patents
Corrosion inhibitive lithium bromide compositionInfo
- Publication number
- JPS58224185A JPS58224185A JP10673582A JP10673582A JPS58224185A JP S58224185 A JPS58224185 A JP S58224185A JP 10673582 A JP10673582 A JP 10673582A JP 10673582 A JP10673582 A JP 10673582A JP S58224185 A JPS58224185 A JP S58224185A
- Authority
- JP
- Japan
- Prior art keywords
- lithium bromide
- lithium
- acid
- soln
- alkali metal
- 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
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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/187—Mixtures of inorganic inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Sorption Type Refrigeration Machines (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は水酸化リチウム含有臭化リチウム水溶液組成物
、特に吸収式冷凍機等に用いられる水酸化リチウム含有
臭化リチウム水溶液の金属腐蝕性を効果的に抑止する添
加物と水酸化リチウム含有臭化リチウム水溶液とよりな
る新規な腐蝕抑止性臭化リチウム組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides an additive that effectively inhibits metal corrosion of lithium bromide aqueous solution compositions containing lithium hydroxide, particularly lithium bromide aqueous solutions containing lithium hydroxide used in absorption refrigerators, etc. and a lithium bromide aqueous solution containing lithium hydroxide.
臭化リチウム水溶液は軟鋼、銅、黄銅等に対する腐蝕性
を持つことは良く知られており、これら金属材料が吸収
式冷凍機に用いられ、その吸収液として臭化リチウム水
溶液が使用される場合はその腐蝕抑止剤として各種のも
のが提案され、そのうちいくつかのものは実際の使用に
供されている。It is well known that lithium bromide aqueous solution is corrosive to mild steel, copper, brass, etc., and when these metal materials are used in absorption refrigerators and lithium bromide aqueous solution is used as the absorption liquid, Various types of corrosion inhibitors have been proposed, some of which are in actual use.
例えばモリブデン酸リチウム、クロム酸リチウム、硝酸
リチウム等の硝酸塩、リン酸リチウム、ホウ酸リチウム
、過塩素酸リチウム、タングステン酸リチウム、バナジ
ン酸リチウム、チオシアン酸すチウム、ケイ弗化リチウ
ム、亜硝酸リチウム、ジフェニルグアニジン、メルカプ
トベンゾチアゾール、ベンゾトリアゾール、ベンゾトリ
アゾールとモリブデン酸塩、アルカノールアミンもしく
け硝酸塩との混合物の他、水酸化リチウムとモリブデン
酸リチウム、クロム酸リチウム、硝酸リチウムとの混合
物等が例挙される。For example, nitrates such as lithium molybdate, lithium chromate, lithium nitrate, lithium phosphate, lithium borate, lithium perchlorate, lithium tungstate, lithium vanadate, lithium thiocyanate, lithium silicofluoride, lithium nitrite, Examples include diphenylguanidine, mercaptobenzothiazole, benzotriazole, mixtures of benzotriazole with molybdates, alkanolamines, and nitrates, as well as mixtures of lithium hydroxide with lithium molybdate, lithium chromate, and lithium nitrate. Ru.
しかし従来のこれらの添加剤は臭化リチウム水溶液の全
面腐蝕防止の点では効果があるものの、種々の欠点を有
している。例えば、クロム酸塩、モリブデン酸塩、硝酸
塩、亜硝酸リチウム等はそれ自体還元されて消耗がはげ
しいので管理が煩雑であり、ベンゾトリアゾールは臭化
リチウム水溶液への溶解性に難があり、ベンゾ） ＩＪ
アゾール又はその誘導体とモリブデン酸塩と水酸化リチ
ウムとの混合物を添加した場合は、高温での防蝕性に欠
ける。水酸化リチウム単独の添加も防蝕性は不充分であ
る。However, although these conventional additives are effective in preventing general corrosion of lithium bromide aqueous solutions, they have various drawbacks. For example, chromates, molybdates, nitrates, lithium nitrite, etc. are themselves reduced and are rapidly consumed, making their management complicated, and benzotriazole has difficulty in solubility in lithium bromide aqueous solutions (benzotriazole). I.J.
When a mixture of azole or its derivative, molybdate and lithium hydroxide is added, corrosion protection at high temperatures is lacking. Addition of lithium hydroxide alone also provides insufficient corrosion protection.
本発明者等はこれらの欠点を解決すべく検討した結果、
水酸化リチウム含有臭化リチウム水溶液とクロム酸のア
ルカリ金属塩と硝酸のアルカリ金属塩もしくは亜硝酸の
アルカリ金属塩とからなる組成物が全面腐蝕防止効果を
飛躍的に向上させること、更に水酸化リチウム含有臭化
リチウム水溶液に対して前記クロム酸のアルカリ金属塩
が０００１〜１重Ｍ優、硝酸のアルカリ金属塩が０．０
１〜０１重量％、亜硝酸のアルカリ金属塩が０００１〜
００５重量係である場合が特に秀れていることを見出し
本発明を完成した。As a result of the inventors' studies to solve these drawbacks,
A composition comprising a lithium bromide aqueous solution containing lithium hydroxide, an alkali metal salt of chromic acid, an alkali metal salt of nitric acid, or an alkali metal salt of nitrous acid dramatically improves the overall corrosion prevention effect, and furthermore, lithium hydroxide. The alkali metal salt of chromic acid is 0001 to 1 M, and the alkali metal salt of nitric acid is 0.0 to the aqueous solution of lithium bromide.
1 to 01% by weight, 0001 to 001% by weight of alkali metal salt of nitrous acid
The present invention was completed based on the discovery that the weight ratio of 005 is particularly excellent.
以下、本発明を更に詳しく説明する。The present invention will be explained in more detail below.
本発明に係る組成物を構成する水酸化リチウム含有臭化
リチウム水溶液は通常用いられている５３ないし５５重
量多臭化リチウム水溶液に水酸化リチウムが加えられ０
．０１〜０３重量％の水酸化リチウム濃度に調整される
。The lithium bromide aqueous solution containing lithium hydroxide constituting the composition of the present invention is obtained by adding lithium hydroxide to a commonly used 53 to 55 weight lithium polybromide aqueous solution.
．． The lithium hydroxide concentration is adjusted to 0.01-0.03% by weight.
また、他の構成成分のクロム酸のアルカリ金属塩は少な
くとも常温ないし４０℃近辺で水酸化リチウム含有臭化
リチウム水溶液に溶解性があるので吸収液の商品として
の流通時の取り扱い易さの点で便利である。In addition, since the alkali metal salt of chromic acid, which is another component, is soluble in the lithium bromide aqueous solution containing lithium hydroxide at least at room temperature to around 40°C, it is easy to handle when distributing the absorption liquid as a product. It's convenient.
クロム酸のアルカリ金属塩の濃度は特に限定されるもの
ではないが、水酸化リチウム含有臭化リチウム水溶液に
対して微ｌｉｔに過ぎては効果は期待できなく少なくと
も０００１重量係であることが好ましい。また逆に多す
ぎる場合は隙間腐蝕を促進する傾向にあり、１重１％を
越えないことが好ましい。The concentration of the alkali metal salt of chromic acid is not particularly limited, but if the concentration is too small for the lithium bromide aqueous solution containing lithium hydroxide, no effect can be expected, so it is preferably at least 0001% by weight. On the other hand, if it is too large, it tends to promote crevice corrosion, so it is preferable that the content does not exceed 1% by weight.
更に他の構成成分としての硝酸のアルカリ金属塩もしく
は亜硝酸のアルカリ金属塩は共に特にナトリウム塩、カ
リウム塩がその使いやすさの点で秀れている。 また濃
度については、水酸化リチウム含有臭化リチウム水溶液
に対して、硝酸塩の場合 ００１重量％以下、亜硝酸塩
の場合 ０．００１重量％以下では効果が薄く、硝酸塩
の場合０１重泄チ、亜硝酸塩の場合０．０５重附チを越
えると、共に隙間腐蝕を逆に促進する傾向にある。Furthermore, among the alkali metal salts of nitric acid and alkali metal salts of nitrous acid as other constituents, sodium salts and potassium salts are particularly excellent in terms of their ease of use. Regarding the concentration, the effect is weak at 0.001% by weight or less for nitrates and 0.001% by weight or less for nitrites, and 0.01% by weight or less for nitrites, and 0.01% by weight or less for nitrites. If the weight exceeds 0.05, crevice corrosion tends to be accelerated.
各構成成分の夫々の好ましい範囲は−に記の通りアああ
が、腐ゎユ□効よ。点ア特い効ノｑ範、。The preferable ranges of each component are as described in -. Point A is particularly effective.
クロム酸のアルカリ金属塩は０．０１〜０５重量係硝酸
のアルカリ金属塩は００１〜０．０６重量係、亜硝酸の
アルカリ金属塩は０．００２〜０．０２ｍＨｉ係である
。The alkali metal salt of chromic acid has a weight ratio of 0.01 to 0.05 mHi, the alkali metal salt of nitric acid has a weight ratio of 0.01 to 0.06 mHi, and the alkali metal salt of nitrous acid has a weight ratio of 0.002 to 0.02 mHi.
本発明における水酸化リチウム含有の効果が臭化リチウ
ムのみの場合に比べて秀れていることは従来から知られ
ている通りであるが、本発明においては前記のごとく臭
化リチウム５３〜５５重量係、水酸化リチウム０．０１
〜０．３重量係からなる水溶液が用いられている。It has been known that the effect of containing lithium hydroxide in the present invention is superior to that of lithium bromide alone, but in the present invention, as mentioned above, lithium bromide has a weight of 53 to 55%. Lithium hydroxide 0.01
An aqueous solution consisting of ~0.3% by weight is used.
次に本発明に係る組成物を用いた実施例について説明す
る。Next, examples using the composition according to the present invention will be described.
実施例 １〜１０、比較例 １〜４
実施の効果は、腐蝕減量及び隙間腐蝕の有無の測定によ
り判断した。Examples 1 to 10 and Comparative Examples 1 to 4 The effects of the implementation were determined by measuring the corrosion weight loss and the presence or absence of crevice corrosion.
これらの具体的測定方法について説明する。These specific measurement methods will be explained.
腐蝕減量は水酸化リチウムを０．１重蹴係、臭化リチウ
ムを５５重ｆｆｉ％含有する水溶液にクロム酸及び硝酸
もしくは亜硝酸の夫々のアルカリ金属塩を添力化だ水溶
液を水蒸気コンデンサ４９加熱用フラスコに入れ（たて
） ５．０ ＣＤ１Ｘ （よこ）３．Ｏｃｍｘ（厚み）
ｏ２ｃｍの２３．２ｇの５Ｓ４１材で、吊り下げ用孔を
持つイ板をエメリー紙でよく研磨し、且つ脱脂処理をし
た２枚を隔離して吊り下げ、１０００時間の煮沸処理を
し、その重量減により判断した。Corrosion loss is determined by adding chromic acid and alkali metal salts of nitric acid or nitrous acid to an aqueous solution containing 0.1% lithium hydroxide and 55% lithium bromide.Heat the aqueous solution with a steam condenser 49. 5.0 CD1X (horizontal) 3. Ocmx (thickness)
A board made of 23.2 g of 5S41 material with a diameter of 02 cm and a hanging hole was well polished with emery paper and degreased.The two sheets were separated and hung, boiled for 1000 hours, and the weight was determined. Judgment was made based on the decrease.
また隙間腐蝕の発生の有無は、前記腐蝕減量測定に供し
たものと同組成の水溶液を、同様のフラスコ中に入れ、
（たて）３００刀×（よこ） ２．０ ｃｍ×（厚み）
０．２ ｃｍの５Ｓ４１材平板でエメリー紙でよく研
磨し、脱脂処理をしたものにシリコーンゴム製輪ゴム（
巾０．５Ｃｍ１折り径１． ｓ ｃｍ ）をよこ方向に
２本掛けたものを浸漬し１０００時間煮沸処理をして後
、輪ゴムで被覆されていた部分の表面腐蝕の発生の有無
により判定した。In addition, the presence or absence of crevice corrosion can be determined by placing an aqueous solution with the same composition as that used for the corrosion weight loss measurement in the same flask.
(vertical) 300 swords x (horizontal) 2.0 cm x (thickness)
A silicone rubber band (
Width 0.5cm 1 fold diameter 1. s cm) hung in the horizontal direction was immersed and boiled for 1000 hours, and then judged by the presence or absence of surface corrosion in the area covered with the rubber band.
第１表には水溶液組成と、測定した本発明の効果を示し
た。Table 1 shows the aqueous solution composition and the measured effects of the present invention.
１を
第１表
（＊１）実施例では５５重量％ＬｉＢｒ水溶液にＬｉＯ
Ｈを０１重量％添加した水溶液に対する添加量。1 in Table 1 (*1) In the example, LiO was added to a 55% by weight LiBr aqueous solution.
Amount added to an aqueous solution containing 0.1% by weight of H.
比較例では５５重量％ＬｉＢｒ水溶液に対する添加量。In the comparative example, the amount added to a 55% by weight LiBr aqueous solution.
以上の結果から明らかなごとく本発明の組成物は臭化リ
チウム水溶液の防蝕性に非常に効果的であることがわか
る。As is clear from the above results, the composition of the present invention is highly effective in preventing corrosion of lithium bromide aqueous solutions.
特許出願人 昭和電工株式会社 代理人 弁理士菊地精−Patent applicant: Showa Denko Co., Ltd. Agent: Patent attorney Sei Kikuchi
Claims (3)
酸のアルカリ金属塩と硝酸のアルカリ金属塩もしくは亜
硝酸のアルカリ金属塩とからなることを特徴とする腐蝕
抑止性臭化リチウム組成物(1) A corrosion-inhibiting lithium bromide composition comprising a lithium bromide aqueous solution containing lithium hydroxide, an alkali metal salt of chromic acid, an alkali metal salt of nitric acid, or an alkali metal salt of nitrous acid.
含有臭化リチウム水溶液に対して０．００１〜１重量係
である特許請求の範囲第１項記載の腐蝕抑止性臭化リチ
ウム組成物(2) The corrosion-inhibiting lithium bromide composition according to claim 1, wherein the alkali metal salt of chromic acid is present in an amount of 0.001 to 1% by weight relative to the lithium bromide aqueous solution containing lithium hydroxide.
リチウム水溶液に対して００１〜０１重量係である特許
請求の範囲第１もしくは第２項記載の腐蝕抑止性臭化リ
チウム組成物（４）亜硝酸のアルカリ金属塩が水酸化リ
チウム含有臭化リチウム水溶液に対して０．００１〜０
０５重量％である特許請求の範囲第１もしくは第２項記
載の腐蝕抑止性臭化リチウム組成物(3) The corrosion-inhibiting lithium bromide composition (4) according to claim 1 or 2, wherein the alkali metal salt of nitric acid has a weight ratio of 001 to 01 with respect to the lithium bromide aqueous solution containing lithium hydroxide. The alkali metal salt of nitrous acid is 0.001 to 0 relative to the lithium bromide aqueous solution containing lithium hydroxide.
05% by weight of the corrosion inhibiting lithium bromide composition according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10673582A JPS58224185A (en) | 1982-06-23 | 1982-06-23 | Corrosion inhibitive lithium bromide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10673582A JPS58224185A (en) | 1982-06-23 | 1982-06-23 | Corrosion inhibitive lithium bromide composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58224185A true JPS58224185A (en) | 1983-12-26 |
Family
ID=14441182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10673582A Pending JPS58224185A (en) | 1982-06-23 | 1982-06-23 | Corrosion inhibitive lithium bromide composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58224185A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01174588A (en) * | 1987-12-28 | 1989-07-11 | Yazaki Corp | Aqueous solution composition |
| US6004476A (en) * | 1997-07-26 | 1999-12-21 | Fmc Corporation | Corrosion inhibiting solutions and processes for refrigeration systems comprising heteropoly complex anions of transition metal elements additional additives |
| US6004475A (en) * | 1996-06-27 | 1999-12-21 | Fmc Corporation | Corrosion inhibiting solutions for refrigeration systems comprising heteropoly complex anions of transition metal elements |
| US6620341B1 (en) | 1999-12-23 | 2003-09-16 | Fmc Corporation | Corrosion inhibitors for use in oil and gas wells and similar applications |
| US6758988B1 (en) | 1999-09-07 | 2004-07-06 | Fmc Corporation | Corrosion inhibiting solutions for absorption systems |
-
1982
- 1982-06-23 JP JP10673582A patent/JPS58224185A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01174588A (en) * | 1987-12-28 | 1989-07-11 | Yazaki Corp | Aqueous solution composition |
| US6004475A (en) * | 1996-06-27 | 1999-12-21 | Fmc Corporation | Corrosion inhibiting solutions for refrigeration systems comprising heteropoly complex anions of transition metal elements |
| US6004476A (en) * | 1997-07-26 | 1999-12-21 | Fmc Corporation | Corrosion inhibiting solutions and processes for refrigeration systems comprising heteropoly complex anions of transition metal elements additional additives |
| US6758988B1 (en) | 1999-09-07 | 2004-07-06 | Fmc Corporation | Corrosion inhibiting solutions for absorption systems |
| US7410596B2 (en) | 1999-09-07 | 2008-08-12 | Rocky Research | Corrosion inhibiting solutions for absorption systems |
| US6620341B1 (en) | 1999-12-23 | 2003-09-16 | Fmc Corporation | Corrosion inhibitors for use in oil and gas wells and similar applications |
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