JPS58189379A - Anticorrosive for calcium chloride brine - Google Patents
Anticorrosive for calcium chloride brineInfo
- Publication number
- JPS58189379A JPS58189379A JP7183382A JP7183382A JPS58189379A JP S58189379 A JPS58189379 A JP S58189379A JP 7183382 A JP7183382 A JP 7183382A JP 7183382 A JP7183382 A JP 7183382A JP S58189379 A JPS58189379 A JP S58189379A
- Authority
- JP
- Japan
- Prior art keywords
- lignin
- calcium chloride
- tannin
- acid
- brine
- 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
- 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
- C23F11/10—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 organic inhibitors
- C23F11/12—Oxygen-containing compounds
- C23F11/122—Alcohols; Aldehydes; Ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
この発明は、塩化カルシウムプライン用防食剤に関する
。さらに詳しくは、塩化カルシウムプライン使用系の各
種金属ことに鉄系金属の腐食抑制に優れた効果を発揮す
る防食剤Ｖｃｌｌする。DETAILED DESCRIPTION OF THE INVENTION This invention relates to an anticorrosive agent for calcium chloride prine. More specifically, Vcll is an anticorrosive agent that exhibits excellent corrosion inhibition effects on various metals, including iron-based metals, using calcium chloride prine.
塩化カルシウムブライン祉、各種製造工場において、原
料、中間品または製品を冷却したり保冷するのに使用す
る冷凍機の冷媒として広く用いらし、一般に１５〜３５
重量％の塩化カルシウム水溶液が用いられる。しかしこ
の水溶液は一般冷却水に比して腐食性を減少させること
が著しく困難であるため、通常、一般冷却水に有効な防
食剤をそのまま適用しても良好な防食効果を得ることは
困難であった。例えば特許１！１Ｉ５３−１３１７９号
には重合リン酸とケイ酸ナトリウムを用いた例が記載さ
れているが、これらの化合物は塩化カルシウムプライン
に対する溶解性が低いので溶解しうるような低濃度では
期待した効果を得にくい。また特開昭５３−１４１１３
７号には亜鉛塩を用いた方法が記載されているが、亜鉛
塩単独では溶解性が低いのでこれも溶解しうる低濃度で
は期待した効果が得られない。Calcium chloride brine is widely used in various manufacturing factories as a refrigerant in refrigerators used to cool and keep raw materials, intermediate products, or products cold, and generally has a concentration of 15 to 35
% by weight aqueous calcium chloride solution is used. However, it is extremely difficult to reduce the corrosivity of this aqueous solution compared to general cooling water, so it is usually difficult to obtain a good corrosion protection effect even if an effective corrosion inhibitor is applied to general cooling water as is. there were. For example, Patent No. 1!1I53-13179 describes an example using polymerized phosphoric acid and sodium silicate, but these compounds have low solubility in calcium chloride prine, so it is not expected at low concentrations that they can be dissolved. It is difficult to obtain the desired effect. Also, JP-A-53-14113
No. 7 describes a method using zinc salt, but since zinc salt alone has low solubility, the expected effect cannot be obtained at a low concentration where zinc salt can also be dissolved.
このように塩化カルシウムプライン系においては、通常
−膜冷却水系等で使用される金属の防食対策が色々講じ
られているものの満足な結果が得られていない。As described above, in calcium chloride prine systems, although various measures have been taken to prevent corrosion of metals used in normal membrane cooling water systems, etc., satisfactory results have not been obtained.
この発明はかような問題点を解消すべくなされたもので
める。この発明の発明者らは、芳香族系化合物を該プラ
イン系に適用する点に想階し、鋭意研究を行なった結果
、タンニン類やリグニン類が塩化カルシウムプライン中
の鉄系金属の腐食抑制に優れた効果を発揮する事実を見
出しこの発明に到達した。This invention has been made to solve these problems. The inventors of this invention envisioned the application of aromatic compounds to the prine system, and as a result of intensive research, they found that tannins and lignins are effective in inhibiting corrosion of iron-based metals in calcium chloride prine. This invention was achieved by discovering the fact that it exhibits excellent effects.
この発明の発明者らの知るところ、この発明のタンニン
紙やリグニン類は、一般冷却水のごとき塩類の少ない系
において若干防食作用を有することは知られているが、
この発明の対象である塩化カルシウムプラインのごとき
腐食抑−」の困難な特殊な系において優れた防食効果を
発揮することは全く知られていない。As far as the inventors of this invention know, the tanned paper and lignins of this invention are known to have a slight anticorrosion effect in systems with low salt content, such as general cooling water.
It is completely unknown that it exhibits an excellent corrosion-preventing effect in special systems where it is difficult to inhibit corrosion, such as calcium chloride prine, which is the subject of this invention.
か゛くしてこの発明によれば、タンニン紙又はリグニン
類を有効成分として含有することを特徴とする塩化カル
シウムプライン用防食剤が提供される。Thus, according to the present invention, there is provided an anticorrosive agent for calcium chloride prine, which is characterized by containing tannin paper or lignins as an active ingredient.
この発明のタンニン類やリグニ／＠とは槁物体等の天然
物中に存在し抽出により得られる高分子物質である。こ
れらは抽出工程によシ若干変成されたものであってもよ
く、抽出後変成させたものであってもよい。The tannins and lignin of this invention are polymeric substances that exist in natural products such as tannins and can be obtained by extraction. These may be slightly denatured during the extraction process, or may be denatured after extraction.
一上記タン二／類としてはピロガロールタンニン、カテ
フールタンニン、加水分解性タンニン、縮合孕タンニン
等のいずれに分類されつるものでも使用でき、所謂タン
ニン綾と呼ばれるものも使用できる。。一方、リグニン
類としては、酸リグニン、酸化銅アンモニアリグニン、
過ヨウ素峻リグニン、アルカリリグニン、リグニンスル
ホン酸、チオリグニン、クロルリグニン、ブラウンス天
然リグニン、ブジョルクマンリグニン、ジオキサンリグ
ニン、ハイドロトロピックリグニン、アルコールリグニ
ン、フェノールリグニン、酢酸リグニン等が挙げられる
。As the above-mentioned tannins, any tannins classified as pyrogallol tannins, catefyl tannins, hydrolyzable tannins, condensed tannins, etc. can be used, and so-called tannins can also be used. . On the other hand, lignins include acid lignin, cuprammonium oxide lignin,
Examples include periodic lignin, alkaline lignin, lignin sulfonic acid, thiolignin, chlorlignin, Brown's natural lignin, Bujolkman lignin, dioxane lignin, hydrotropic lignin, alcohol lignin, phenol lignin, acetic acid lignin, and the like.
この発明の上記有効成分は通常、水に溶解した液剤か、
そのままの粉剤の形釣で用いるのが適当である。The above-mentioned active ingredient of this invention is usually a liquid solution dissolved in water,
It is appropriate to use it as a powder for shape fishing.
かような防食剤全使用するに当って、その添加量は防食
対象すなわち塩化カルシウムプラインの各種条件や製剤
中の有効成分含量によって左右されるため％に限定され
るものではないが、通常、経済性も考慮して塩化カルシ
クムプラインに対して有効成分の量が２０〜５０００
ｐｐｍ 、好ましくは１００〜３０００ ｐｐｍ 、よ
り好ましくは５００〜３０００ｐｐｍとなるように添加
されるのが適当である。When using all such anticorrosive agents, the amount added depends on the various conditions of the target to be protected, that is, the calcium chloride line, and the active ingredient content in the preparation, so it is not limited to a percentage, but it is usually economical. Considering the nature of the active ingredients, the amount of active ingredients is 20 to 5,000 compared to calcium chloride purine.
It is appropriate to add it in an amount of ppm, preferably 100 to 3000 ppm, more preferably 500 to 3000 ppm.
なお、この発明の防食剤の添加と共に塩化カルシウムプ
ラインのｐＨｆアルカリ側ＶＣ調整することが防食効果
の上昇の点で好ましい。この際のプラインのｐＨは７以
上、・通常７〜１０とするのが適当であり、８〜ｌＯと
するのが好ましい。ただしプライン自体のｐＨが１０ｔ
″越える場合にはｐＨｍ’Ｍは不要である。In addition, it is preferable to adjust the pH and alkali side VC of the calcium chloride prine together with the addition of the anticorrosive agent of the present invention in order to increase the anticorrosive effect. At this time, the pH of the prine is suitably 7 or more, usually 7 to 10, preferably 8 to 1O. However, the pH of the prine itself is 10t.
'', pHm'M is not necessary.
従って、−好ましい観点から、この発明はりゲニン魅父
はタンニン類を塩化カルシウムブライン中に添加すると
共に該ブライ／のｐＨを７以上、こと［７〜ｌＯに必要
に応じて調整することからなる塩化カルシウムプライ／
系の防食方法ｔ−４Ｎ供する。Therefore, - from a preferred point of view, the present invention provides a chlorinated acid extract consisting of adding tannins to a calcium chloride brine and optionally adjusting the pH of the brine to 7 or higher, preferably 7 to 1O. Calcium ply/
Corrosion prevention method t-4N is provided.
上記塩化カルシウムブラインのｐＨ１ｉ整は、−水酸化
ナトリウム、水酸化カリタム、水酸化カルシウム等の水
綾化物や脚素数１〜６のフルシノールアミン類、アルキ
ルアミン類、アルキレンポリアミン組等の水溶性アミン
類をプライ／に添加することにより行うのが過当である
が、これ以外にアンモニア、ヒドラジン、塩基性塩等の
水溶性で塩基性を示すものであれば使用可能である。The pH1i adjustment of the calcium chloride brine is as follows: - Water hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc., and water-soluble amines such as flucinolamines having a leg prime number of 1 to 6, alkylamines, alkylene polyamines, etc. It is appropriate to carry out this by adding a substance like the above to the ply, but other substances that are water-soluble and show basicity such as ammonia, hydrazine, and basic salts can also be used.
もちろん上記ｐＨ［製剤は、この発明の有効成分又は製
剤と混合して添加してもよく、別々に添加してもよい。Of course, the above-mentioned pH [preparation] may be added as a mixture with the active ingredient or preparation of the present invention, or may be added separately.
通常、ｐｐｍ製剤をも含めた製剤として用いるのが簡便
で好ましい。かような製剤例を以下に示す。Generally, it is convenient and preferable to use a formulation including a ppm formulation. Examples of such formulations are shown below.
製剤例１
タンニン酸 ６７］１（量部水酸化カリウム
３３重量部
製剤例２
タンニン酸 ２０重量部
モノエタノールアミン ｌＯ／ｌ
水 １０ ｕ例えば、
上記製剤例１の粉剤をｐＨ約６の塩化カルシウムブライ
ンに３０００ ｐｐｍ相当添加した際には該ブラインの
ｐＨは８．２に調整されると共にタンニン酸２０００
ｐｐｍ相当が添加されたこととなり、同じく製剤例２の
液剤を１００００ ｐｐｍ相当添加した際にはｐＨは９
．０ ＶＣ調整されると共にタンニン酸２０００ ｐｐ
ｍ相当が添加されたこととなりことに優れた防食効果が
得られることになる。Formulation example 1 Tannic acid 67] 1 (parts by weight Potassium hydroxide 33 parts by weight Formulation example 2 Tannic acid 20 parts by weight Monoethanolamine lO/l Water 10 u For example,
When the powder of Formulation Example 1 was added in an amount equivalent to 3000 ppm to calcium chloride brine having a pH of approximately 6, the pH of the brine was adjusted to 8.2, and tannic acid 2000 ppm was added.
This means that the equivalent of 10,000 ppm of the liquid preparation of Formulation Example 2 was added, and the pH was 9.
．． 0 VC adjusted and tannic acid 2000 pp
Since the amount equivalent to m is added, an excellent anticorrosion effect can be obtained.
なお、塩化カルシウムブライン系に銅系金属が含まれる
場合には公知の銅系防食剤、例えばトリアゾール＠を同
時に添加してもよく、上記製剤中にトリアゾール類をさ
らに含有させておいてもよい。扱者の場合にはトリアゾ
ールによってｐＨが上昇するため製剤時の本願有効成分
の溶解性からも好ましいといえる。In addition, when the calcium chloride brine system contains a copper-based metal, a known copper-based anticorrosive agent, such as triazole@, may be added at the same time, or the above-mentioned formulation may further contain triazoles. In the case of the operator, triazole increases the pH, so it can be said to be preferable from the viewpoint of the solubility of the active ingredient of the present application during formulation.
上記併用により、ブライン中の鉄基金属及び銅糸金属の
腐食抑制が可能となる。By using the above combination, corrosion of iron-based metals and copper thread metals in brine can be suppressed.
以下実施例に基づいてこの発明を更に詳しく説明するが
、これによってこの発明が限定されるものではない。The present invention will be described in more detail below based on Examples, but the present invention is not limited thereby.
実施例１゜
ヒーカー（１！容）に工業用塩化カルシウム２５Ｗ／Ｖ
％を含む水溶液１！を加える。〔現場条件に近づけるた
め工業用の塩化カルシウムを使用した。〕これに表−１
ＶＣ示す薬剤を所定量（２０００ＰＩ）ｍ ）添加し、
ｐＴ（ｔｌｆｉｉｌＥＬ、ないか、ｐＨ８整剤を用いて
ｐＨを７〜１０前後に調整した後、軟鋼の試験片（厚さ
１６ｘ３０６Ｘ５０ｍ〕を撓拌捧に懸吊し、液中におい
て１００ ｒｐｍで回転を与える。この状急でサーモス
タンドとヒータを用いて３０℃の液温に保ちつつ５日間
試験を行う。テスト終了後試験片を１５％［Ｌ酸に３０
秒間浸漬し、水洗乾燥してそのテスト後の重量を測定す
る。予め測定したテスト前の重量Ｃ’９）と前記テスト
後の重Ｊｉ倉用いて、次式により１日１ｒ１ｆ当りの腐
食減量、シ１」ちｍ、ｄ、ｄ、 （ｗ／ 、ｍ’ °ｄ
ａｙ ）を算出する。Example 1 Industrial calcium chloride 25W/V in a heater (1 volume)
Aqueous solution containing 1! Add. [Industrial calcium chloride was used to approximate field conditions. ]Table-1
A predetermined amount (2000 PI) m ) of a drug showing VC is added,
After adjusting the pH to around 7 to 10 using a pH 8 adjuster, a mild steel test piece (thickness 16 x 306 x 50 m) was suspended in a stirrer and rotated at 100 rpm in the liquid. In this condition, the test is carried out for 5 days while keeping the liquid temperature at 30℃ using a thermostand and heater.After the test, the test piece is diluted with 15% [30℃ of L acid].
Dip for a second, wash with water, dry, and measure the weight after the test. Using the pre-measured weight C'9) before the test and the heavy duty tank after the test, the corrosion loss per 1r1f per day is determined by the following formula: m, d, d, (w/ , m' ° d
ay ) is calculated.
条件および試験結果を比較例と共に表１に示す。The conditions and test results are shown in Table 1 along with comparative examples.
なお、使用したタンニン酸はガロタンニン相当品でアリ
、リグニンスルホン酸ハ、サンエキスパニレツクス（山
場国策パルプ社製）を用いた。The tannic acid used was an equivalent to gallotannin, and lignin sulfonic acid and Sunexpanirex (manufactured by Yamaba Kokusaku Pulp Co., Ltd.) were used.
表−１
表１ （続き）
、！１（続″−札
上記表より明らかなように、この発明の防食剤は明らか
に防食効果を有しており、ことにｐＨ７，０以上の条件
にて顕著な防食効果を発揮することがわかる。Table-1 Table 1 (continued) ,! 1 (Continued) As is clear from the table above, the anticorrosive agent of the present invention clearly has an anticorrosive effect, and particularly exhibits a remarkable anticorrosive effect under conditions of pH 7.0 or higher. .
実施例２゜
塩化カルシウム溶液の濃度を変え、ｐＨを８．ＯＫ＃節
し、タンニン酸２０００ ｐｐｍ添加に固定する以外、
実施例１と同様な試験を行なった。Example 2゜The concentration of calcium chloride solution was changed and the pH was adjusted to 8. OK# section, except for fixing the tannic acid addition to 2000 ppm.
A test similar to Example 1 was conducted.
結果を、比較例と共に！７＜２に示す。Results along with comparative examples! 7<2.
表−２
上記表より明らかなように、通常の一般水のことき塩化
カルシウム濃度が低い溶液中においてはタンニン酸の防
食効果はほとんど発揮されていないが塩化カルシウムブ
ラインのごとき高濃度（１０〜３０ ｗｔ％）溶液中に
おいては、優れた防食効果が得られていることがわかる
。Table 2 As is clear from the above table, the anticorrosion effect of tannic acid is hardly exhibited in solutions with low concentrations of calcium chloride, such as ordinary water, but with high concentrations (10 to 30 It can be seen that an excellent anticorrosive effect was obtained in the solution (wt%).
Claims (1)
ること′ｆｔ特徴とする塩化カルシウムプライン用防食
剤。 ２、タンニンｎｉｌ、 ピロガロールタンニン、カテ
コールタンニン、加水分解性タンニン又はタンニン酸で
ある特許請求の範囲第１項に記載の防食剤。 ３、リグニン類が、酸リグニン、酸化銅アンモニアリグ
ニン、過ヨウ素酸リグニン、アルカリリグニン、リグニ
ンスルホン酸、チオリグニン、クロルリグニン、ブラウ
ンス天然リグニン、プジョルクマンリグニン、ジオキサ
ンリグニン、ハイドロトロピックリグニン、アルコール
リグニン、フェノールリグニン又は酢酸リグニンである
特許請求の範囲第１項に記載の防食剤。[Claims] 1. An anticorrosive agent for calcium chloride prine, characterized by containing tannins or lignins as an active ingredient. 2. The anticorrosive agent according to claim 1, which is tannin nil, pyrogallol tannin, catechol tannin, hydrolyzable tannin, or tannic acid. 3. The lignins include acid lignin, cupric ammonium oxide lignin, periodic acid lignin, alkaline lignin, lignin sulfonic acid, thiolignin, chlorlignin, Brown's natural lignin, Pujolkmann lignin, dioxane lignin, hydrotropic lignin, alcohol lignin, The anticorrosive agent according to claim 1, which is phenol lignin or acetic acid lignin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7183382A JPS58189379A (en) | 1982-04-28 | 1982-04-28 | Anticorrosive for calcium chloride brine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7183382A JPS58189379A (en) | 1982-04-28 | 1982-04-28 | Anticorrosive for calcium chloride brine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58189379A true JPS58189379A (en) | 1983-11-05 |
| JPH0147549B2 JPH0147549B2 (en) | 1989-10-16 |
Family
ID=13471936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7183382A Granted JPS58189379A (en) | 1982-04-28 | 1982-04-28 | Anticorrosive for calcium chloride brine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58189379A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030227B (en) * | 2011-09-29 | 2014-12-17 | 中国石油化工股份有限公司 | Circulating water treatment method adopting deionized water as supplement water |
-
1982
- 1982-04-28 JP JP7183382A patent/JPS58189379A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0147549B2 (en) | 1989-10-16 |
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