JP5200326B2 - Scale cleaner and scale removal method - Google Patents
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- JP5200326B2 JP5200326B2 JP2006096058A JP2006096058A JP5200326B2 JP 5200326 B2 JP5200326 B2 JP 5200326B2 JP 2006096058 A JP2006096058 A JP 2006096058A JP 2006096058 A JP2006096058 A JP 2006096058A JP 5200326 B2 JP5200326 B2 JP 5200326B2
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- 238000000034 method Methods 0.000 title description 18
- 239000000463 material Substances 0.000 claims description 74
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 33
- 229910052742 iron Inorganic materials 0.000 claims description 33
- 239000012459 cleaning agent Substances 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 239000007769 metal material Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 5
- 235000010350 erythorbic acid Nutrition 0.000 claims description 5
- 239000004318 erythorbic acid Substances 0.000 claims description 5
- 229940026239 isoascorbic acid Drugs 0.000 claims description 5
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 28
- 238000004140 cleaning Methods 0.000 description 17
- 235000014655 lactic acid Nutrition 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 13
- 239000004310 lactic acid Substances 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004579 marble Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 pH is 4 or less Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Description
本発明は、スケール洗浄剤及びスケール除去方法に関し、詳細には同一水系内で水と接触するアルミニウム材と鉄材及び／又は銅材とを構成要素として含む装置・設備、例えばアルミフィン型放熱器、ラジエーター、軸受冷却水など、熱交換器で冷却水が循環している系において、前記金属材（アルミニウム材、鉄材、銅材）の表面に付着したスケールを、同時に除去することができるスケール洗浄剤及びそれを用いた金属材表面のスケール除去方法に関する。 The present invention relates to a scale cleaning agent and a descaling method, and more specifically, an apparatus / equipment including an aluminum material, an iron material, and / or a copper material, which are in contact with water in the same water system, as components, for example, an aluminum fin type radiator A scale cleaning agent that can simultaneously remove scale adhering to the surface of the metal material (aluminum material, iron material, copper material) in a system where cooling water circulates in a heat exchanger such as a radiator and bearing cooling water. The present invention also relates to a method for removing scale from the surface of a metal material using the same.
各種化学プラント、排水処理装置、ボイラプラントなど、熱交換器、加熱機器付近の配管、反応容器などの形で常時水（冷却水、ボイラ用水、各種処理水など）に接触する金属材を含む装置・設備においては、金属材表面に硬質のスケールが析出、付着して運転に支障をきたす場合があり、適宜洗浄除去する必要がある。
このようなスケールは、多くの場合、水中に含まれるカルシウム、マグネシウム、鉄、アルミニウム、珪素などが水に難溶な塩、水酸化物、酸化物などとなって蓄積したものである。
Various chemical plants, waste water treatment equipment, boiler plants, etc., equipment that contains metal materials that always come into contact with water (cooling water, boiler water, various treated water, etc.) in the form of heat exchangers, piping near heating equipment, reaction vessels, etc.・ In equipment, hard scale may deposit and adhere to the surface of metal materials, which may hinder operation and must be removed by washing as appropriate.
In many cases, such scales are obtained by accumulating calcium, magnesium, iron, aluminum, silicon, or the like contained in water as salts, hydroxides, oxides, or the like that are hardly soluble in water.
従来、排水処理装置、ボイラプラント、冷却水プラントなどにおける金属材、その他の金属製品などに付着したスケールを除去する方法として、塩酸、硫酸、クエン酸などの無機あるいは有機酸を主成分とする洗浄剤を用いた酸洗浄が行われているが、酸の種類によっては金属材の腐食やスケール溶解力の不足、使用済みスケール洗浄剤の処理などに問題がある。
これらの洗浄剤あるいは洗浄方法の改良技術も種々提案されており、例えば、特許文献１には、通常の酸洗浄に用いられている酸に、適当量のエリソルビン酸、Ｌ−アスコルビン酸、それらの塩及び誘導体の１種以上を配合してスケール溶解力を向上させた、金属酸化物を含むスケールの溶解除去組成物が開示されており、特許文献２には、酸としては比較的問題は少ないが、カルシウムイオンと反応して難溶性の塩を生成してしまう硫酸を用いてカルシウム系スケールの除去を可能にしたスケールの除去方法が開示されている。また、アルミニウム材のスケール除去のためには、硝酸が一般的に用いられているが、取り扱いの安全性や排水時の窒素規制などから、使用を抑える方向にある。
Conventionally, as a method of removing scale adhering to metal materials and other metal products in wastewater treatment equipment, boiler plants, cooling water plants, etc., cleaning mainly using inorganic or organic acids such as hydrochloric acid, sulfuric acid, citric acid, etc. Although acid cleaning using an agent is performed, depending on the type of acid, there are problems such as corrosion of metal materials, insufficient scale dissolving power, and treatment of used scale cleaning agents.
Various techniques for improving these cleaning agents or cleaning methods have also been proposed. For example, Patent Document 1 discloses an appropriate amount of erythorbic acid, L-ascorbic acid, and their acids used in normal acid cleaning. Disclosed is a scale-dissolving composition containing a metal oxide in which one or more salts and derivatives are added to improve scale dissolving power. Patent Document 2 has relatively few problems as an acid. However, there is disclosed a method for removing scales that enables removal of calcium-based scales using sulfuric acid that reacts with calcium ions to form sparingly soluble salts. In addition, nitric acid is generally used to remove the scale of the aluminum material, but it is in the direction of suppressing its use due to the safety of handling and nitrogen regulation during drainage.
しかしながら、従来のスケール除去技術は、単一の金属材に付着したスケールを対象とするものが主体であり、アルミニウム材（アルミニウム系材を含む）と鉄材（鉄系材を含む）及び／又は銅材（銅系材を含む）を複合的に用いている装置・設備において、アルミニウム、鉄、銅の金属表面に付着した硬質スケールを除去する場合には、アルミニウム材を含む部分と、鉄材、銅材を含む部分とを切り離し、それぞれの材質に応じた洗浄を行っている。
アルミニウム材と鉄材、銅材の混合系を一括して硝酸洗浄した場合、鉄材、銅材の腐食が著しく、また、アルカリ剤や無機酸（防食剤入り）を用いた場合はアルミニウム材への腐食が著しくなる。
有機酸を用いる場合には、材質に対する影響は少ないものの、カルシウム系スケールの場合には一旦溶解したスケールが再析出するなど、アルミニウム材を含む複合材使用系においては有効な除去効果は知られていなかった。特に船舶においては、船内機器等にアルミニウム材を用いることが多いうえに、洋上での付着物除去作業は作業環境が狭域であり、安全性が高く、また、ハンドリングに優れた洗浄剤が望まれていた。
However, conventional scale removal techniques are mainly for scales attached to a single metal material, and include aluminum materials (including aluminum-based materials), iron materials (including iron-based materials), and / or copper. In equipment and facilities that use materials (including copper-based materials) in combination, when removing hard scale adhering to the metal surface of aluminum, iron, or copper, parts containing aluminum material, iron materials, and copper The part containing the material is separated and cleaning is performed according to each material.
When the mixed system of aluminum, iron and copper is washed with nitric acid at once, the corrosion of the iron and copper materials is remarkable, and when an alkaline agent or inorganic acid (with anticorrosive agent) is used, the aluminum material is corroded. Becomes remarkable.
In the case of using an organic acid, there is little influence on the material, but in the case of a calcium-based scale, an effective removal effect is known in a system using a composite material including an aluminum material. There wasn't. In particular, in ships, aluminum materials are often used for inboard equipment, etc., and the removal of deposits on the ocean is expected to have a narrow working environment, high safety, and excellent handling. It was rare.
前記のとおり、同一水系内で水と接触するアルミニウム材と鉄材及び／又は銅材とを構成要素として含む装置・設備において、前記金属材の表面に付着したスケールを除去する場合には次のような問題点があった。
（ａ）アルミニウム材系と鉄材・銅材系とに切り離して洗浄する必要があり、作業が煩雑である。
（ｂ）アルミニウム材系と鉄材・銅材系とを一括して洗浄しようとする場合には、アルミニウム材か他の金属材のいずれかの腐食が顕著となる。
（ｃ）有機酸洗浄の場合、カルシウム系スケールには再析出の問題があり対応できない。（ｄ）鉄錆、炭酸カルシウム系スケールなど、付着物の種類に応じた除去方法を検討する必要がある。
本発明は、アルミニウム材と鉄材、銅材の混合系におけるスケール除去において、各材質の部分を切り離してそれぞれ別個に洗浄処理を行う必要がなく、また、何れの材質についても腐食が少なく、さらに、カルシウム系スケール及び鉄系スケールの何れにも対応できるスケール洗浄剤及びスケール除去方法を提供することを目的とするものである。
As described above, in the apparatus / equipment including the aluminum material and the iron material and / or the copper material which are in contact with water in the same water system as the constituent elements, the scale adhered to the surface of the metal material is removed as follows. There was a serious problem.
(A) It is necessary to separate and clean the aluminum material system and the iron material / copper material system, and the work is complicated.
(B) When the aluminum material and the iron / copper material are to be cleaned at once, the corrosion of either the aluminum material or the other metal material becomes significant.
(C) In the case of organic acid cleaning, the calcium-based scale cannot cope with reprecipitation problems. (D) It is necessary to examine a removal method according to the type of deposit such as iron rust and calcium carbonate scale.
In the present invention, in the scale removal in the mixed system of aluminum material, iron material, and copper material, it is not necessary to separate each material part and separately perform cleaning treatment, and there is little corrosion for any material, It is an object of the present invention to provide a scale cleaning agent and a scale removal method that can handle both calcium-based scales and iron-based scales.
本発明者等は、アルミニウム材と鉄材、銅材の混合系におけるスケール除去技術について種々検討した結果、酸成分として乳酸を使用することにより、アルミニウム材と鉄材、銅材の混合系のままでスケールの洗浄、除去が可能になることを見出した。
本発明はこれらの知見に基づいて完成されたものであり、下記の構成を採用することによって前記の課題を解決したものである。
The present inventors have, aluminum material and iron material, a result of various studies for scale removal technique in the mixed system of the copper material, the use of milk acid as the acid component, an aluminum material and iron material remains mixed system of copper material It was found that the scale can be washed and removed.
The present invention has been completed based on these findings, and has solved the above problems by adopting the following configuration.
（１）同一水系内で水と接触するアルミニウム材と鉄材及び／又は銅材とを構成要素として含む装置・設備において、前記各金属材の表面に付着したスケールを除去するための洗浄剤であって、乳酸と、還元剤及び／又はスケール再付着防止剤とを含み、ｐＨが４以下で、前記還元剤が、アスコルビン酸、エリソルビン酸、及びそれらの塩から選ばれる１種以上、前記スケール再付着防止剤が、グルコン酸及び／又はその塩であることを特徴とするスケール洗浄剤。
（２）同一水系内で水と接触するアルミニウム材と鉄材及び／又は銅材とを構成要素として含む装置・設備における前記各金属材のスケールが付着した表面に、前記（１）のスケール洗浄剤を接触させてスケールを溶解させた後、水洗することを特徴とするスケール除去方法。
(1) A cleaning agent for removing scale adhered to the surface of each metal material in an apparatus / equipment including an aluminum material, an iron material, and / or a copper material that are in contact with water in the same water system as constituent elements. Te, comprising: a milk acid, a reducing agent and / or scale antiredeposition agents, pH is 4 or less, the reducing agent is ascorbic acid, erythorbic acid, and one or more selected from salts thereof, the scale A scale cleaning agent , wherein the anti-redeposition agent is gluconic acid and / or a salt thereof .
(2) The scale cleaning agent according to (1 ) above, on the surface on which the scale of each metal material in an apparatus / equipment including an aluminum material, an iron material, and / or a copper material that are in contact with water in the same water system is attached. A scale removing method, wherein the scale is dissolved by contacting with water and then washed with water.
本発明のスケール洗浄剤を用いることにより、アルミニウム材と鉄材、銅材の混合系であっても、それぞれの金属材ごとに分割することなく、同一系内でスケール除去を行うことができる。また、付着スケールの種類に応じた付着物除去法を選定する必要がなく、一つの洗浄剤での処理が可能である。
また、本発明のスケール洗浄剤によれば、作業性の観点からハンドリング面が改善されただけでなく、各金属材に対する腐食性が大きく低減される効果がある。
さらに、スケール溶解過程において再析出したスケールも水洗程度で溶解できるので、全体として優れた洗浄効果が得られる。
By using the scale cleaning agent of the present invention, even if it is a mixed system of an aluminum material, an iron material, and a copper material, scale removal can be performed within the same system without dividing each metal material. Moreover, it is not necessary to select a deposit removal method according to the type of deposit scale, and processing with one cleaning agent is possible.
Moreover, according to the scale cleaning agent of the present invention, not only the handling surface is improved from the viewpoint of workability, but also the effect of greatly reducing the corrosiveness to each metal material.
Furthermore, since the scale re-deposited in the scale dissolution process can be dissolved by washing with water, an excellent cleaning effect as a whole can be obtained.
本発明のスケール洗浄剤は、乳酸を主成分として含むものであり、通常は乳酸を高濃度で含む水溶液として調製しておき、洗浄時に乳酸として０．１〜５０ｗｔ％の濃度となるように希釈して使用すればよい。また、本発明のスケール洗浄剤は、好ましくは乳酸に加えて還元剤及び／又はスケール再付着防止剤を含むものである。なお、乳酸塩を使用する場合には、スケール洗浄剤のｐＨが４以下となるように乳酸を併用する。 Scale cleaning agent of the present invention contains milk acid as a main component, usually leave prepared as an aqueous solution containing lactic at high concentrations to a concentration of 0.1-50% as lactic acid during cleaning It can be used after diluting. Further, scale cleaning agent of the present invention are preferably those containing a reducing agent and / or scale anti-redeposition agents in addition to lactate. In addition, when using a lactate, lactic acid is used together so that the scale detergent may have a pH of 4 or less.
本発明のスケール洗浄剤に使用する還元剤としては、エリソルビン酸、アスコルビン酸、及びこれらの酸の塩を挙げることができ、中でもエリソルビン酸又はその塩が好ましい。これらの還元剤を添加することにより、スケール溶解力が著しく増大する。還元剤の添加量は、乳酸と還元剤との割合が重量比で１０：９０〜９９：１とするのが好ましく、さらに好ましくは２０：８０〜６０：４０の範囲である。還元剤の添加割合をこの範囲とすることにより、顕著なスケール溶解力増大効果を得ることができる。 Examples of the reducing agent used in the scale cleaning agent of the present invention include erythorbic acid, ascorbic acid, and salts of these acids. Among them, erythorbic acid or a salt thereof is preferable. By adding these reducing agents, the scale dissolving power is remarkably increased. The amount of the reducing agent added is preferably such that the ratio of lactic acid to the reducing agent is 10:90 to 99: 1 by weight, more preferably 20:80 to 60:40. By making the addition ratio of the reducing agent within this range, a remarkable effect of increasing the scale dissolving power can be obtained.
本発明のスケール洗浄剤に使用するスケール再付着防止剤としては、グルコン酸、グルコン酸塩、各種キレート剤（ＥＤＴＡ、ＮＴＡ、ＭＧＴＡ及びそれらの塩）、カルボキシル基を有する低分子ポリマー（例えばアクリル酸ポリマー）、重合りん酸塩、珪酸塩、ホスホン酸塩などを挙げることができるが、中でもグルコン酸又はその塩が好ましい。これらのスケール再付着防止剤を添加することにより、一旦溶解したスケールの再付着を低減させることができ、また、再付着したスケールも水洗により簡単に除去できる効果がある。スケール再付着防止剤の添加量は、乳酸とスケール再付着防止剤との割合が重量比で９９：１〜１：１とするのが好ましく、さらに好ましくは９０：１０〜８０：２０の範囲である。スケール再付着防止剤の添加割合をこの範囲とすることにより、効果的にスケールの再付着を低減させることができる。 Examples of the scale re-adhesion inhibitor used in the scale cleaning agent of the present invention include gluconic acid, gluconate, various chelating agents (EDTA, NTA, MGTA and salts thereof), and a low molecular polymer having a carboxyl group (for example, acrylic acid). Polymer), polymerized phosphate, silicate, phosphonate and the like. Among them, gluconic acid or a salt thereof is preferable. By adding these scale re-adhesion preventive agents, it is possible to reduce the re-adhesion of the scale once dissolved, and there is an effect that the re-adhered scale can be easily removed by washing with water. The amount of the scale anti-redeposition agent added is preferably such that the ratio of lactic acid and scale anti-redeposition agent is 99: 1 to 1: 1 by weight, more preferably 90:10 to 80:20. is there. By making the addition ratio of the scale anti-redeposition agent within this range, it is possible to effectively reduce scale re-adhesion.
本発明のスケール洗浄剤を使用した、同一水系内で水と接触するアルミニウム材と鉄材及び／又は銅材とを構成要素として含む装置・設備における、アルミニウム、鉄、銅の金属材表面に付着した硬質スケールの除去は、アルミニウム材の部分と鉄材、銅材との部分を切り離すことなく、前記各金属材のスケールが付着した表面に、スケール洗浄剤を接触させてスケールを溶解させた後、水洗することによって行うことができる。
スケール付着面に洗浄剤を接触させる方法は特に制限されるものではないが、例えば、前記同一水系内の水に、スケール洗浄剤を乳酸（乳酸塩を併用する場合には乳酸の量に換算）と必要により添加される還元剤及び／又はスケール再付着防止剤の合計量の濃度が１〜５０ｗｔ％となるように添加し、５分以上循環させるか静置する方法、あるいは、スケール付着面にスケール洗浄剤を塗布し、５分以上放置するなどの方法を採ることができる。
Using the scale cleaning agent of the present invention, it adhered to the surface of a metal material of aluminum, iron, or copper in an apparatus / equipment including an aluminum material and an iron material and / or a copper material that are in contact with water in the same water system. The removal of the hard scale is performed by dissolving the scale by bringing the scale material into contact with the surface to which the scale of each metal material has adhered without separating the aluminum material portion and the iron material and copper material portion, and then washing with water. Can be done.
The method of bringing the cleaning agent into contact with the scale adhesion surface is not particularly limited. For example, the scale cleaning agent is lactic acid (converted to the amount of lactic acid when lactate is used in combination) in the water in the same aqueous system. And a method of adding the reducing agent and / or scale re-adhesion inhibitor added as necessary so that the concentration of the total amount is 1 to 50 wt% and circulating or standing for 5 minutes or more, or on the scale adhesion surface A method such as applying a scale cleaning agent and allowing it to stand for 5 minutes or more can be employed.
同一水系内にスケール洗浄剤を添加する方法の場合には、５分以上静置あるいは循環後、排水し、必要によりアルカリ（ＮａＯＨ、ＫＯＨなど）で中和したのち水洗し、スケール付着面にスケール洗浄剤を塗布する方法の場合には、５分以上放置した後、塗布した液体の約５倍以上の水で洗浄することによって、スケールの除去を行うことができる。
これにより、各金属材を腐食させることなく、スケールを溶解させて除去することができ、再付着したスケールも水洗により簡単に除去することができる。
In the case of adding a scale cleaning agent in the same aqueous system, leave it for 5 minutes or longer, circulate it, drain it, neutralize it with alkali (NaOH, KOH, etc.) if necessary, and wash it with water. In the case of a method of applying a cleaning agent, the scale can be removed by leaving it to stand for 5 minutes or more and then washing it with about 5 times or more of the applied liquid.
Accordingly, the scale can be dissolved and removed without corroding each metal material, and the reattached scale can be easily removed by washing with water.
本発明のスケール洗浄剤は、アルミニウム材、鉄材、銅材の表面に付着したカルシウム系及び鉄系のスケールをはじめ、その他の金属酸化物を含むスケールの除去に有効である。 The scale cleaning agent of the present invention is effective in removing scales containing other metal oxides such as calcium-based and iron-based scales adhered to the surfaces of aluminum, iron, and copper materials.
以下、実施例及び比較例により本発明をさらに具体的に説明する。
［実施例１、比較例１〜２］
（各種材質に対する腐食速度の測定）
各成分の薬剤を水に溶解させて表１に示す組成の洗浄液を調製した。それぞれの洗浄液に、表２に示す各材質のテストピース（寸法：５０ｍｍ×３０ｍｍ×１ｍｍ）をそれぞれ個別に浸漬し、３８〜４２℃で４時間攪拌した。各テストピースを引き上げ、流水中でブラシ洗浄した後、乾燥し、重量測定して減重量を算出し、テストピースの表面積から腐食速度〔ｍｇ／（ｃｍ2／ｈ）〕を求めた。結果を表２に示す。
表２から、クエン酸や乳酸などの有機酸を主成分とする洗浄剤は、塩酸を主成分とする洗浄剤に比較して、全ての材料に対して腐食性が低いことがわかる。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
[Example 1, Comparative Examples 1-2]
(Measurement of corrosion rate for various materials)
The chemical | medical agent of each component was dissolved in water and the washing | cleaning liquid of the composition shown in Table 1 was prepared. Test pieces (dimensions: 50 mm × 30 mm × 1 mm) of each material shown in Table 2 were individually immersed in each cleaning solution, and stirred at 38 to 42 ° C. for 4 hours. Each test piece was pulled up, washed with running water with a brush, dried, and weighed to calculate the weight loss, and the corrosion rate [mg / (cm 2 / h)] was determined from the surface area of the test piece. The results are shown in Table 2.
From Table 2, it can be seen that the cleaning agent mainly composed of an organic acid such as citric acid or lactic acid is less corrosive to all materials than the cleaning agent mainly composed of hydrochloric acid.
［実施例２、比較例３〜４］
（有機酸カルシウムの溶解性及び析出物の溶解性試験）
５０℃の水に、表３の組成物となるように各成分の薬剤を添加した。この溶液に前記と同じ寸法のＣ１２２０Ｐ（銅）のテストピースを浸漬し、さらに大理石５０ｇを金網に入れて液中に吊るし、５０℃で２４時間攪拌した。その後、水温を２０℃に下げ、テストピースを引き上げスケールの析出具合を目視で評価した。さらに、その析出物を水洗し、溶解状況を目視で評価した。結果を表４に示す。
表４から、乳酸を主成分とする洗浄剤は、同じ有機酸であるクエン酸やグリコール酸を主成分とする洗浄剤に比較して、良好なスケール溶解力を有することがわかる。
[Example 2, Comparative Examples 3 to 4]
(Solubility test for organic acid calcium and precipitates)
The chemical | medical agent of each component was added to water of 50 degreeC so that it might become a composition of Table 3. A test piece of C1220P (copper) having the same dimensions as described above was immersed in this solution, and 50 g of marble was placed in a wire mesh and suspended in the solution, and stirred at 50 ° C. for 24 hours. Thereafter, the water temperature was lowered to 20 ° C., the test piece was pulled up, and the degree of precipitation of the scale was visually evaluated. Further, the precipitate was washed with water, and the dissolution state was visually evaluated. The results are shown in Table 4.
From Table 4, it can be seen that the detergent mainly composed of lactic acid has a better scale dissolving power than the detergent mainly composed of citric acid and glycolic acid which are the same organic acids.
［実施例３〜５、比較例５］
（鉄／アルミニウム共存下における腐食性試験−１）
各成分の薬剤を水に溶解させて表５に示す組成の洗浄液を調製した。それぞれの洗浄液に、表６に示す各材質のテストピース（寸法は前記と同じ）を同時に浸漬し、３８〜４２℃で４時間攪拌した。各テストピースを引き上げ、流水中でブラシ洗浄した後、乾燥し、重量測定して減重量を算出し、テストピースの表面積から腐食速度〔ｍｇ／（ｃｍ２／ｈ）〕を求めた。結果を表６に示す。
表６から、乳酸を主成分とする本発明の洗浄剤は、鉄／アルミニウム共存下において、全ての材料に対して腐食性が低いことがわかる。
[Examples 3 to 5, Comparative Example 5]
(Corrosion test in the presence of iron / aluminum-1)
The chemical | medical agent of each component was dissolved in water and the washing | cleaning liquid of the composition shown in Table 5 was prepared. In each cleaning solution, test pieces of the respective materials shown in Table 6 (the dimensions are the same as above) were simultaneously immersed and stirred at 38 to 42 ° C. for 4 hours. Each test piece was pulled up, washed with a brush in running water, dried, and weighed to calculate the weight loss, and the corrosion rate [mg / (cm 2 / h)] was determined from the surface area of the test piece. The results are shown in Table 6.
From Table 6, it can be seen that the cleaning agent of the present invention containing lactic acid as a main component has low corrosiveness to all materials in the presence of iron / aluminum.
［実施例６〜８、比較例６］
（鉄／アルミニウム共存下における腐食性試験−２）
各成分の薬剤を水に溶解させ、実施例３〜５、比較例５と同様に表５に示す組成の洗浄液を調製し、さらに、腐食生成物が溶解したことを想定してＦｅ２Ｃｌ３をＦｅ３+が２０００ｍｇ／リットル、Ｃｌ−が３８００ｍｇ／リットルとなるように添加した。それぞれの洗浄液に、表６に示す各材質のテストピース（寸法は前記と同じ）を同時に浸漬し、３８〜４２℃で４時間攪拌した。各テストピースを引き上げ、流水中でブラシ洗浄した後、乾燥し、重量測定して減重量を算出し、テストピースの表面積から腐食速度〔ｍｇ／（ｃｍ２／ｈ）〕を求めた。結果を表７に示す。
表７から、乳酸を主成分とする本発明の洗浄剤は、鉄／アルミニウム共存下において、Ｆｅ２Ｃｌ３のような腐食生成物が溶解している状態においても、全ての材料に対して腐食性が低いことがわかる。
[Examples 6 to 8, Comparative Example 6]
(Corrosion test in the presence of iron / aluminum-2)
The drug of the respective components are dissolved in water, Examples 3-5, Comparative Example 5 in the same manner as in preparing the cleaning solution of the composition shown in Table 5, further assume that the corrosion products dissolved Fe 2 Cl 3 Was added so that Fe 3+ was 2000 mg / liter and Cl − was 3800 mg / liter. In each cleaning solution, test pieces of the respective materials shown in Table 6 (the dimensions are the same as above) were simultaneously immersed and stirred at 38 to 42 ° C. for 4 hours. Each test piece was pulled up, washed with a brush in running water, dried, and weighed to calculate the weight loss, and the corrosion rate [mg / (cm 2 / h)] was determined from the surface area of the test piece. The results are shown in Table 7.
From Table 7, the cleaning agent of the present invention containing lactic acid as a main component corrodes all materials in the presence of iron / aluminum, even in the state where corrosion products such as Fe 2 Cl 3 are dissolved. It turns out that the nature is low.
［実施例９〜１１、比較例７〜８］
（鉄／アルミニウム共存下における炭酸カルシウム溶解試験）
各成分の薬剤を水に溶解させて表８に示す組成の洗浄液を調製した。それぞれの洗浄液に、５ｇの大理石を樹脂製の網に入れて吊り下げ、表９に示す各材質のテストピース（寸法は前記と同じ）を同時に浸漬し、３８〜４２℃で４時間攪拌した。各テストピースを引き上げ、流水中でブラシ洗浄した後、乾燥し、重量測定して減重量を算出し、テストピースの表面積から腐食速度〔ｍｇ／（ｃｍ２／ｈ）〕を求めた。また、大理石については、その重量減から溶解した大理石の割合を求めた。それらの結果を表９に示す。
表９から、乳酸を主成分とする本発明の洗浄剤は、鉄／アルミニウム共存下において、全ての材料に対して腐食性が低く、しかもスケールの１成分である炭酸カルシウムの溶解力が高いことがわかる。
[Examples 9 to 11, Comparative Examples 7 to 8]
(Calcium carbonate dissolution test in the presence of iron / aluminum)
The chemical | medical agent of each component was dissolved in water and the washing | cleaning liquid of the composition shown in Table 8 was prepared. In each cleaning solution, 5 g of marble was placed in a resin net and suspended, and test pieces of the respective materials shown in Table 9 (the dimensions were the same as described above) were simultaneously immersed and stirred at 38 to 42 ° C. for 4 hours. Each test piece was pulled up, washed with a brush in running water, dried, and weighed to calculate the weight loss, and the corrosion rate [mg / (cm 2 / h)] was determined from the surface area of the test piece. Moreover, about the marble, the ratio of the marble which melt | dissolved from the weight reduction was calculated | required. The results are shown in Table 9.
From Table 9, the cleaning agent of the present invention containing lactic acid as a main component has low corrosiveness to all materials in the presence of iron / aluminum, and has high solubility of calcium carbonate, which is one component of the scale. I understand.
Claims (2)
前記還元剤が、アスコルビン酸、エリソルビン酸、及びそれらの塩から選ばれる１種以上、
前記スケール再付着防止剤が、グルコン酸及び／又はその塩である
ことを特徴とするスケール洗浄剤。 A cleaning agent for removing scale adhered to the surface of each metal material in an apparatus / equipment including an aluminum material and an iron material and / or a copper material which are in contact with water in the same water system, And a reducing agent and / or a scale re-adhesion preventing agent , the pH is 4 or less ,
The reducing agent is one or more selected from ascorbic acid, erythorbic acid, and salts thereof;
The scale cleaning agent, wherein the scale anti-redeposition agent is gluconic acid and / or a salt thereof .
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| KR20140095266A (en) | 2013-01-24 | 2014-08-01 | 한국원자력연구원 | Chelate free chemical decontamination reagent for removal of the dense radioactive oxide layer on the metal surface and chemical decontamination method using the same |
| KR101601201B1 (en) * | 2015-04-15 | 2016-03-09 | 한국원자력연구원 | Chelate free chemical decontamination reagent for removal of the dense radioactive oxide layer on the metal surface and chemical decontamination method using the same |
| JP2021041323A (en) * | 2019-09-10 | 2021-03-18 | Ｄｏｗａテクノロジー株式会社 | Cleaning liquid, method for producing cleaning liquid, and method for cleaning facility |
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| JPS5322546B2 (en) * | 1973-04-13 | 1978-07-10 | ||
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| JPS59164398A (en) * | 1983-03-08 | 1984-09-17 | 栗田工業株式会社 | Water tank detergent |
| JPS61221381A (en) * | 1985-03-26 | 1986-10-01 | Kawaken Fine Chem Co Ltd | Water soluble corrosion inhibitor |
| JP2650196B2 (en) * | 1989-07-14 | 1997-09-03 | 株式会社 片山化学工業研究所 | Water treatment agent and water treatment method for soft water boiler |
| JPH07122152B2 (en) * | 1990-06-19 | 1995-12-25 | 日本パーカライジング株式会社 | Acid cleaning solution for aluminum |
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| JP2000017291A (en) * | 1998-07-03 | 2000-01-18 | Masao Umemoto | Pot scale solubilizer |
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