JP2010121038A - Removing agent for acidic deposit and method of removing acidic deposit - Google Patents

Removing agent for acidic deposit and method of removing acidic deposit Download PDF

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JP2010121038A
JP2010121038A JP2008295923A JP2008295923A JP2010121038A JP 2010121038 A JP2010121038 A JP 2010121038A JP 2008295923 A JP2008295923 A JP 2008295923A JP 2008295923 A JP2008295923 A JP 2008295923A JP 2010121038 A JP2010121038 A JP 2010121038A
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alkali metal
acidic
carbonate
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cleaning liquid
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JP5277895B2 (en
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Shigeru Sakurai
茂 桜井
英樹 ▲高▼田
Hideki Takada
Tomoko Matsumoto
知子 松本
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AGC Inc
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Asahi Glass Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a removing agent for an acidic deposit that effectively removes an acidic deposit while inhibiting corrosion of an article to be washed, and to provide a method removing of an acidic deposit. <P>SOLUTION: The removing agent for an acidic deposit includes an alkali metal hydrogen carbonate salt and an alkali metal carbonate salt, where the ratio of the alkali metal hydrogen carbonate salt is 98-70 mass% and the ratio of the alkali metal carbonate salt is 2-30 mass% based on the total (100 mass%) of the alkali metal hydrogen carbonate salt and the alkali metal carbonate salt. The removing method of an acidic deposit includes spraying water and a washing liquid comprising the removing agent for an acidic deposit on an article to be washed having adsorbed thereon an acidic deposit containing a sulfur compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、装置、配管等に付着した硫黄化合物を含む酸性付着物を除去する酸性付着物除去剤および酸性付着物の除去方法に関する。   The present invention relates to an acidic deposit removing agent that removes acidic deposits containing sulfur compounds attached to devices, piping, and the like, and a method for removing acidic deposits.

重油、残渣油、石炭等の燃料を燃焼させると、該燃料に含まれる硫黄が燃焼し、二酸化硫黄（ＳＯ２）が生成する。該二酸化硫黄は、一部が酸化されて三酸化硫黄（ＳＯ３）となり、該三酸化硫黄が燃焼排ガス中の水分と反応して硫酸（Ｈ２ＳＯ４）を生成する。したがって、ボイラ等の燃焼炉から煙突までの間に設置された装置、配管等には、硫酸等の燃料由来の酸性成分と未燃灰とを含む混合物が付着しやすい。該混合物の付着は、特に、燃焼排ガスの温度が下がり、硫酸の露点以下になる温度領域にて顕著となる。また、脱硝を目的にアンモニアが注入される設備では、脱硝用に注入されたアンモニアのうちの余剰のアンモニアと、前記硫酸が反応することで生成する酸性硫安（硫酸水素アンモニウム：（ＮＨ４）ＨＳＯ４）が付着物中に含まれる。装置、配管等に付着した酸性付着物を洗浄することは、安定な運転の維持に欠くことができない。 When fuel such as heavy oil, residual oil, and coal is burned, sulfur contained in the fuel is burned, and sulfur dioxide (SO 2 ) is generated. The sulfur dioxide is partially oxidized to sulfur trioxide (SO 3 ), and the sulfur trioxide reacts with moisture in the combustion exhaust gas to produce sulfuric acid (H 2 SO 4 ). Therefore, a mixture containing an acidic component derived from a fuel such as sulfuric acid and unburned ash tends to adhere to an apparatus, piping, and the like installed between a combustion furnace such as a boiler and a chimney. Adhesion of the mixture becomes remarkable particularly in a temperature range where the temperature of the combustion exhaust gas is lowered and becomes lower than the dew point of sulfuric acid. In addition, in a facility in which ammonia is injected for the purpose of denitration, acidic ammonium sulfate (ammonium hydrogen sulfate: (NH 4 ) HSO produced by the reaction of surplus ammonia in the ammonia injected for denitration with the sulfuric acid. 4 ) is included in the deposit. Cleaning acidic deposits adhering to equipment, piping, etc. is essential to maintaining stable operation.

酸性付着物の除去方法としては、通常、工業用水を用いて酸性付着物を洗い流す方法が採用される。しかし、該方法では、酸性成分が水に溶解して酸性水溶液が生成し、装置、配管等の金属製部分において、腐食が発生しやすいため、設備寿命、安定した運転の継続の点で問題となる。   As a method for removing the acidic deposit, a method of washing away the acidic deposit with industrial water is usually employed. However, in this method, an acidic component dissolves in water to produce an acidic aqueous solution, and corrosion is likely to occur in metal parts such as equipment and piping, which is problematic in terms of equipment life and stable operation. Become.

そこで、腐食を発生させることなく酸性付着物を除去する方法として、炭酸水素ナトリウムまたは炭酸ナトリウムを含む洗浄液を用い、中和反応を利用して酸性付着物を効果的に除去する方法が提案されている（特許文献１）。しかし、該方法でも、下記の理由から、装置、配管等の金属製部分の腐食を充分に抑えることはできない（特許文献２）。   Therefore, as a method for removing acidic deposits without causing corrosion, a method of effectively removing acidic deposits using a neutralization reaction using a cleaning solution containing sodium hydrogen carbonate or sodium carbonate has been proposed. (Patent Document 1). However, even this method cannot sufficiently suppress the corrosion of metal parts such as devices and pipes for the following reasons (Patent Document 2).

すなわち、燃焼炉から煙突までの間に設置された装置、配管等の洗浄を実施する際、洗浄液中に含まれるアルカリ成分の量が、被洗浄物に付着している酸性成分の量より少ない時期または領域が存在する。特に、炭酸水素ナトリウムの水溶液を噴霧して洗浄する場合、洗浄初期において、洗浄液中に含まれるアルカリ成分の量が、被洗浄物に付着している酸性成分の量より少ない時期が存在する。また、ヒーティングエレメント（蓄熱要素部品）を有する蓄熱再生式回転型の熱交換器のように、複雑な形状の装置等では、狭隘部の洗浄液が置換しにくく、ある程度洗浄を継続した段階でも、洗浄液中に含まれるアルカリ成分の量が、被洗浄物に付着している酸性成分の量より少ない領域が存在する。   That is, when cleaning the equipment and piping installed between the combustion furnace and the chimney, the amount of alkali components contained in the cleaning liquid is less than the amount of acidic components adhering to the object to be cleaned Or there is an area. In particular, when cleaning is performed by spraying an aqueous solution of sodium hydrogen carbonate, there is a period in which the amount of the alkaline component contained in the cleaning liquid is less than the amount of the acidic component adhering to the object to be cleaned in the initial stage of cleaning. In addition, in a heat storage regenerative rotary heat exchanger having a heating element (heat storage element component), in a complicated shape device etc., it is difficult to replace the cleaning liquid of the narrow part, even at the stage where cleaning is continued to some extent, There is a region where the amount of the alkaline component contained in the cleaning liquid is smaller than the amount of the acidic component adhering to the object to be cleaned.

このように、洗浄液中に含まれるアルカリ成分の量が、被洗浄物に付着している酸性成分の量より少ない時期または領域では、洗浄液の水素イオン濃度（ｐＨ：ピーエイチ）が酸性領域となり、鉄系材料で構成される装置、配管等は、腐食環境にさらされることとなる。したがって、さらなる防錆対策を要する。
特開２００１−３４８６８９号公報 特開２００７−２１１０３７号公報 In this way, when the amount of alkaline component contained in the cleaning liquid is less than the amount of acidic component adhering to the object to be cleaned, the hydrogen ion concentration (pH: PH) of the cleaning liquid becomes acidic, Devices, pipes and the like made of system materials are exposed to a corrosive environment. Therefore, further rust prevention measures are required.
JP 2001-348689 A JP 2007-211037 A

本発明は、被洗浄物の腐食を抑制しつつ、酸性付着物を効果的に除去できる酸性付着物除去剤および酸性付着物の除去方法を提供する。   The present invention provides an acidic deposit removing agent and a method for removing an acidic deposit that can effectively remove acidic deposit while suppressing corrosion of an object to be cleaned.

本発明の酸性付着物除去剤は、アルカリ金属の炭酸水素塩と、アルカリ金属の炭酸塩とを含み、前記アルカリ金属の炭酸水素塩と前記アルカリ金属の炭酸塩との合計（１００質量％）のうち、アルカリ金属の炭酸水素塩の割合が、９８〜７０質量％であり、アルカリ金属の炭酸塩の割合が、２〜３０質量％であることを特徴とする。   The acidic deposit removing agent of the present invention includes an alkali metal hydrogen carbonate and an alkali metal carbonate, and is a total (100% by mass) of the alkali metal hydrogen carbonate and the alkali metal carbonate. Among them, the ratio of the alkali metal hydrogen carbonate is 98 to 70% by mass, and the ratio of the alkali metal carbonate is 2 to 30% by mass.

前記アルカリ金属の炭酸水素塩は、炭酸水素ナトリウムを主成分とすることが好ましい。
前記アルカリ金属の炭酸塩は、炭酸カリウムを主成分とすることが好ましい。 The alkali metal hydrogen carbonate preferably contains sodium hydrogen carbonate as a main component.
The alkali metal carbonate is preferably composed mainly of potassium carbonate.

本発明の酸性付着物の除去方法は、水と本発明の酸性付着物除去剤とを含む洗浄液を、硫黄化合物を含む酸性付着物が付着した被洗浄物に噴霧することを特徴とする。
前記被洗浄物は、燃焼炉から煙突までの間に配置された装置または配管であることが好ましい。
前記装置または配管は、熱交換器または電気集塵機であることが好ましい。 The method for removing acidic deposits of the present invention is characterized by spraying a cleaning liquid containing water and the acidic deposit removing agent of the present invention onto an object to be cleaned to which acidic deposits containing sulfur compounds are attached.
The object to be cleaned is preferably a device or a pipe arranged between the combustion furnace and the chimney.
The device or the pipe is preferably a heat exchanger or an electric dust collector.

本発明の酸性付着物除去剤および酸性付着物の除去方法によれば、被洗浄物の腐食を抑制しつつ、酸性付着物を効果的に除去できる。   According to the acidic deposit removing agent and the method for removing an acidic deposit of the present invention, the acidic deposit can be effectively removed while suppressing the corrosion of the object to be cleaned.

＜酸性付着物除去剤＞
本発明の酸性付着物除去剤は、アルカリ金属の炭酸水素塩と、アルカリ金属の炭酸塩とを含む。 <Acid deposit removal agent>
The acidic deposit removing agent of the present invention contains an alkali metal hydrogen carbonate and an alkali metal carbonate.

アルカリ金属の炭酸水素塩の割合は、アルカリ金属の炭酸水素塩とアルカリ金属の炭酸塩との合計（１００質量％）のうち、９８〜７０質量％であり、９８〜９０質量％が好ましい。
アルカリ金属の炭酸塩の割合は、アルカリ金属の炭酸水素塩とアルカリ金属の炭酸塩との合計（１００質量％）のうち、２〜３０質量％であり、２〜１０質量％が好ましい。 The ratio of the alkali metal hydrogen carbonate is 98 to 70% by mass and preferably 98 to 90% by mass in the total (100% by mass) of the alkali metal hydrogen carbonate and the alkali metal carbonate.
The ratio of the alkali metal carbonate is 2 to 30% by mass and preferably 2 to 10% by mass in the total (100% by mass) of the alkali metal hydrogen carbonate and the alkali metal carbonate.

アルカリ金属の炭酸塩の割合が２質量％以上であれば、添加による防錆効果が発揮されるが、アルカリ金属の炭酸塩の割合が３０質量％を超えると、添加による防錆効果の優位性が見られなくなる。このように、アルカリ金属の炭酸塩の割合が触媒量である場合に、高い防錆効果が発揮されることが確認されている。また、アルカリ金属の炭酸塩の割合が３０質量％を超えると、洗浄液のｐＨ値が高くなりすぎ、作業安全上かつ環境保全上好ましくない。   If the proportion of alkali metal carbonate is 2% by mass or more, the rust prevention effect by addition is exhibited, but if the proportion of alkali metal carbonate exceeds 30% by mass, the rust prevention effect by addition is superior. Can not be seen. Thus, it has been confirmed that when the proportion of the alkali metal carbonate is a catalytic amount, a high antirust effect is exhibited. On the other hand, if the proportion of the alkali metal carbonate exceeds 30% by mass, the pH value of the cleaning liquid becomes too high, which is not preferable for work safety and environmental protection.

本発明の酸性付着物除去剤は、アルカリ金属の炭酸水素塩とアルカリ金属の炭酸塩とがが、紙袋、フレキシブルコンテナーバック等の一包装単位にともに充填されたものであってもよく、アルカリ金属の炭酸水素塩とアルカリ金属の炭酸塩とが、別個に包装されてセットとして取り扱われるものであってもよい。取り扱いの便宜上、両者が一包装単位にともに充填されたものが好ましい。   The acidic deposit removing agent of the present invention may be one in which an alkali metal hydrogen carbonate and an alkali metal carbonate are filled together in one packaging unit such as a paper bag or a flexible container bag. The bicarbonate and the alkali metal carbonate may be separately packaged and handled as a set. For convenience of handling, it is preferable that both are packed in one packaging unit.

アルカリ金属の炭酸水素塩とアルカリ金属の炭酸塩とを一包装単位にともに充填する場合、両者は混合されていてもよく、混合されていなくてもよい。包装単位内での存在に偏りがあると、両者を水に溶解させる際に溶け残りを生じる場合があるため、できるだけ均一に混合させることが好ましい。   When the alkali metal hydrogen carbonate and the alkali metal carbonate are filled together in one packaging unit, both may be mixed or may not be mixed. If there is a bias in the presence of the packaging unit, undissolved parts may be produced when both are dissolved in water. Therefore, it is preferable to mix them as uniformly as possible.

アルカリ金属の炭酸水素塩とアルカリ金属の炭酸塩との混合は、工業的に用いられる混合器（Ｖ型混合器、リボンミキサー、遊星スクリュー型混合器等。）を用いて行えばよい。混合の際は、両者のうち一方を先に混合器へ投入してもよく、両者を同時に投入してもよい。   The mixing of the alkali metal hydrogen carbonate and the alkali metal carbonate may be performed using an industrially used mixer (V-type mixer, ribbon mixer, planetary screw type mixer, etc.). At the time of mixing, one of them may be charged into the mixer first, or both may be charged simultaneously.

（アルカリ金属の炭酸水素塩）
アルカリ金属の炭酸水素塩は、水に溶解させたときのｐＨが低く、弱アルカリ性であるため、水質汚濁防止法に定められているｐＨの規制値を超えず、かつ作業者が安全に取り扱うことができる。また、アルカリ金属の炭酸水素塩は、アルカリ金属の炭酸塩に比べ、物質単位質量あたりの発生可能な二酸化炭素の量が多いため、発泡による洗浄効果が高い。 (Alkali metal bicarbonate)
Alkali metal bicarbonate has a low pH when dissolved in water and is weakly alkaline, so it does not exceed the pH regulation value stipulated in the Water Pollution Control Law and should be handled safely by workers. Can do. In addition, since alkali metal hydrogencarbonate has a larger amount of carbon dioxide that can be generated per unit mass than alkali metal carbonate, the cleaning effect by foaming is high.

アルカリ金属の炭酸水素塩としては、炭酸水素ナトリウム、炭酸水素カリウム、これらの混合物等が挙げられる。
アルカリ金属の炭酸水素塩としては、物質単位質量あたりの発生可能な二酸化炭素の量が多く、発泡による高い洗浄効果が得られる点、および洗浄剤中の炭酸水素塩の濃度が飽和濃度となってもｐＨが８．５を超えることがなく、作業安全上かつ環境保全上好ましい点から、炭酸水素ナトリウムが好ましい。 Examples of the alkali metal hydrogen carbonate include sodium hydrogen carbonate, potassium hydrogen carbonate, and a mixture thereof.
Alkali metal hydrogen carbonate has a large amount of carbon dioxide that can be generated per unit mass of the substance, a high cleaning effect is obtained by foaming, and the concentration of hydrogen carbonate in the cleaning agent is saturated. However, sodium hydrogen carbonate is preferable because it does not exceed 8.5 and is preferable from the viewpoint of work safety and environmental protection.

よって、アルカリ金属の炭酸水素塩は、炭酸水素ナトリウムを主成分とすることが好ましい。主成分とは、アルカリ金属の炭酸水素塩（１００質量％）に占める割合が５０質量％以上であることをいう。
炭酸水素ナトリウムの割合は、アルカリ金属の炭酸水素塩（１００質量％）のうち、９０質量％以上が好ましく、９５質量％以上がより好ましく、１００質量％が特に好ましい。 Therefore, the alkali metal hydrogen carbonate preferably contains sodium hydrogen carbonate as a main component. The main component means that the proportion of alkali metal hydrogen carbonate (100% by mass) is 50% by mass or more.
The proportion of sodium hydrogen carbonate is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 100% by mass in the alkali metal hydrogen carbonate (100% by mass).

（アルカリ金属の炭酸塩）
アルカリ金属の炭酸塩としては、炭酸ナトリウム、炭酸カリウム、これらの混合物等が挙げられる。
アルカリ金属の炭酸塩としては、防錆効果の点から、炭酸カリウムが好ましい。 (Alkali metal carbonate)
Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, and a mixture thereof.
As the alkali metal carbonate, potassium carbonate is preferable from the viewpoint of the antirust effect.

よって、アルカリ金属の炭酸塩は、炭酸カリウムを主成分とすることが好ましい。主成分とは、アルカリ金属の炭酸塩（１００質量％）に占める割合が５０質量％以上であることをいう。
炭酸カリウムの割合は、アルカリ金属の炭酸塩（１００質量％）のうち、９０質量％以上が好ましく、９５質量％以上がより好ましく、１００質量％が特に好ましい。 Therefore, the alkali metal carbonate is preferably composed mainly of potassium carbonate. The main component means that the proportion of alkali metal carbonate (100% by mass) is 50% by mass or more.
The proportion of potassium carbonate is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 100% by mass in the alkali metal carbonate (100% by mass).

以上説明した本発明の酸性付着物除去剤にあっては、アルカリ金属の炭酸水素塩とアルカリ金属の炭酸塩とを含むため、酸性付着物を効果的に除去できる。すなわち、アルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩は、酸性付着物と反応して、二酸化炭素ガスを発生し、発泡するため、酸性付着物を発泡の機械的作用により剥離しながら溶解する。酸性付着物中の鉄錆、粉塵、煤等も同時に剥離して除去する。二酸化炭素の発泡により、洗浄効果が上がり、洗浄時間の短縮ができる。被洗浄物の形状が複雑で洗浄しにくいものであっても短時間に洗浄できる。
また、以上説明した本発明の酸性付着物除去剤にあっては、触媒量のアルカリ金属の炭酸塩を含むため、理由は明らかではないが、防錆効果が高く、被洗浄物の腐食を抑制できる。 Since the acidic deposit removing agent of the present invention described above contains an alkali metal hydrogen carbonate and an alkali metal carbonate, the acidic deposit can be effectively removed. That is, alkali metal hydrogen carbonate and alkali metal carbonate react with acidic deposits to generate carbon dioxide gas and foam, so that the acidic deposits are dissolved while being peeled off by the mechanical action of foaming. . Iron rust, dust, soot, etc. in acidic deposits are also peeled off and removed at the same time. The carbon dioxide foaming improves the cleaning effect and shortens the cleaning time. Even if the shape of the object to be cleaned is complicated and difficult to clean, it can be cleaned in a short time.
In addition, the acidic deposit removal agent of the present invention described above contains a catalytic amount of alkali metal carbonate, so the reason is not clear, but has a high rust prevention effect and suppresses corrosion of the object to be cleaned. it can.

＜酸性付着物の除去方法＞
本発明の酸性付着物の除去方法は、水と本発明の酸性付着物除去剤とを含む洗浄液を、硫黄化合物を含む酸性付着物が付着した被洗浄物に噴霧する方法である。 <Method for removing acidic deposit>
The method for removing acidic deposits of the present invention is a method of spraying a cleaning liquid containing water and the acidic deposit removing agent of the present invention onto an object to be cleaned to which acidic deposits containing sulfur compounds are attached.

（洗浄液）
洗浄液に含まれる酸性付着物除去剤は、溶解された状態であってもよく、一部が溶解せずに分散したスラリーの状態であってもよく、溶解された状態が好ましい。
水としては、工業用水、水道水、井戸水等が挙げられる。海水は、被洗浄物の腐食の要因となる塩化物イオンを含むため、適当ではない。 (Cleaning solution)
The acidic deposit removal agent contained in the cleaning liquid may be in a dissolved state, or may be in a slurry state in which a part of the acidic deposit removing agent is not dissolved, and is preferably in a dissolved state.
Examples of water include industrial water, tap water, and well water. Seawater is not suitable because it contains chloride ions that cause corrosion of the objects to be cleaned.

アルカリ金属の炭酸水素塩とアルカリ金属の炭酸塩との合計の含有率は、洗浄液（１００質量％）中、３〜３０質量％が好ましく、３〜２０質量％がより好ましく、アルカリ金属の炭酸水素塩が炭酸水素ナトリウムである場合は、３〜１６質量％がさらに好ましく、３〜１０質量％が特に好ましい。該含有率が３質量％以上であれば、水の使用量および排水量を少なくできる。該含有率が３０質量％以下であれば、未溶解のアルカリ金属の炭酸水素塩の割合を少なくでき、アルカリ金属の炭酸水素塩の固体が沈降して、たとえば薬液槽等の底や配管中に滞留し、アルカリ金属の炭酸水素塩が洗浄に有効に利用されなくなることを回避できる。また、有効に利用されずに滞留するアルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩が存在しなければ、これらを洗い流すために要する水量を少なくできる。   The total content of the alkali metal hydrogen carbonate and the alkali metal carbonate is preferably 3 to 30% by mass, more preferably 3 to 20% by mass in the cleaning liquid (100% by mass), and the alkali metal hydrogen carbonate. When the salt is sodium hydrogen carbonate, 3 to 16% by mass is more preferable, and 3 to 10% by mass is particularly preferable. If the content is 3% by mass or more, the amount of water used and the amount of drainage can be reduced. If the content is 30% by mass or less, the proportion of undissolved alkali metal hydrogen carbonate can be reduced, and the alkali metal hydrogen carbonate solid settles, for example, in the bottom or piping of a chemical tank or the like. It can be avoided that alkali metal hydrogen carbonate is effectively used for cleaning. Further, if there are no alkali metal hydrogen carbonate and alkali metal carbonate that remain without being effectively used, the amount of water required to wash them out can be reduced.

アルカリ金属塩化物（塩化ナトリウム等。）の含有率は、洗浄液（１００質量％）中、０．１質量％以下が好ましく、０．０５質量％以下がより好ましく、０．０１質量％以下が特に好ましい。アルカリ金属塩化物の含有量が０．１質量％以下であれば、塩素イオンが被洗浄物のステンレス鋼等を腐食させ、応力割れを起こす危険性を低減できる。   The content of alkali metal chloride (such as sodium chloride) is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and particularly preferably 0.01% by mass or less in the cleaning liquid (100% by mass). preferable. If the content of the alkali metal chloride is 0.1% by mass or less, the risk that the chloride ions corrode the stainless steel or the like of the object to be cleaned and causes stress cracking can be reduced.

洗浄液の調製方法としては、（ｉ）アルカリ金属の炭酸水素塩を含む水にアルカリ金属の炭酸塩を添加する方法、（ii）アルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩を同時に水に添加する方法が挙げられ、洗浄現場での調製作業の手間がかからず、洗浄作業時間が短く済む点から、（ii）の方法が好ましい。また、アルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩をあらかじめ充分に混合した後、水に添加する方法が、均一な溶解性または分散性を確保する点から好ましい。   The cleaning liquid was prepared by (i) adding alkali metal carbonate to water containing alkali metal hydrogen carbonate, (ii) adding alkali metal hydrogen carbonate and alkali metal carbonate to water at the same time. The method (ii) is preferred because the preparation work at the cleaning site does not take time and the cleaning work time is shortened. Further, a method in which an alkali metal hydrogen carbonate and an alkali metal carbonate are sufficiently mixed in advance and then added to water is preferable from the viewpoint of ensuring uniform solubility or dispersibility.

調製時の洗浄液の温度は、８０℃以下が好ましく、６０℃以下がより好ましい。調製時の温度が低いほど安全に作業できる。
調製時の洗浄液の温度は、５℃以上が好ましく、１５℃以上がより好ましい。調製時の温度が高いほど溶解しやすい。 The temperature of the cleaning liquid during preparation is preferably 80 ° C. or lower, and more preferably 60 ° C. or lower. The lower the temperature during preparation, the safer the work.
The temperature of the cleaning liquid during preparation is preferably 5 ° C. or higher, and more preferably 15 ° C. or higher. The higher the temperature during preparation, the easier it is to dissolve.

調製後の洗浄液は経時変化しにくく、有効成分であるアルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩には、常温での揮発性はないため、水溶液またはスラリーの状態で保管しても構わない。   The cleaning solution after the preparation is less likely to change with time, and the active ingredient alkali metal bicarbonate and alkali metal carbonate are not volatile at room temperature, so they may be stored in the form of an aqueous solution or slurry. .

使用時の洗浄液の温度は、８０℃以下が好ましく、６０℃以下がより好ましい。使用時の温度が低いほど安全に作業できる。
使用時の洗浄液の温度は、５℃以上が好ましく、１５℃以上がより好ましい。使用時の温度が高いほど洗浄効果が高い。 The temperature of the cleaning liquid during use is preferably 80 ° C. or lower, more preferably 60 ° C. or lower. The lower the temperature during use, the safer the work.
The temperature of the cleaning liquid during use is preferably 5 ° C or higher, and more preferably 15 ° C or higher. The higher the temperature during use, the higher the cleaning effect.

洗浄液を循環して洗浄に使用すると、組成が徐々に変化する。洗浄液の組成が洗浄に適切な範囲を保っているかどうかは、洗浄液のｐＨにより評価できる。洗浄液のｐＨは、６．５〜９．５が好ましく、６．９〜９．０がより好ましく、６．９〜８．５が特に好ましい。ｐＨが６．５未満では、除去した酸性付着物との反応により、アルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩が不足していることが推定される。該場合、高濃度のアルカリ金属の炭酸水素塩ならびにアルカリ金属の炭酸塩の水溶液、および／または粉末状のアルカリ金属の炭酸水素塩ならびにアルカリ金属の炭酸塩を添加することが好ましい。ｐＨが９．５を超えると、被洗浄物がアルカリにより侵食される場合がある。特に、被洗浄物がほうろうコーティングされている場合は、アルカリにより侵食される場合がある。該場合、洗浄液中に水を添加することが好ましい。
洗浄液を循環して使用する場合は、使用中の液に含まれる付着物由来の不溶解分の量が増大する場合、定期的に洗浄液全体を交換することが好ましい。 When the cleaning liquid is circulated and used for cleaning, the composition gradually changes. Whether or not the composition of the cleaning liquid is maintained in an appropriate range for cleaning can be evaluated by the pH of the cleaning liquid. The pH of the cleaning liquid is preferably 6.5 to 9.5, more preferably 6.9 to 9.0, and particularly preferably 6.9 to 8.5. When the pH is less than 6.5, it is presumed that the alkali metal bicarbonate and the alkali metal carbonate are insufficient due to the reaction with the removed acidic deposit. In this case, it is preferable to add a high concentration of an alkali metal hydrogen carbonate and an aqueous solution of an alkali metal carbonate and / or a powdery alkali metal hydrogen carbonate and an alkali metal carbonate. If the pH exceeds 9.5, the object to be cleaned may be eroded by alkali. In particular, when an object to be cleaned is enamel coated, it may be eroded by alkali. In this case, it is preferable to add water to the cleaning liquid.
When the cleaning liquid is circulated and used, it is preferable to periodically replace the entire cleaning liquid when the amount of insoluble matter derived from deposits contained in the liquid in use increases.

（酸性付着物）
酸性付着物は、アルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩で除去可能な酸性の付着物であればよく、硫黄化合物を含む酸性付着物が好ましい。
本発明は、燃焼排ガスに由来する酸性付着物、特にボイラの燃焼排ガスに由来する酸性付着物に好適に適用できる。燃焼排ガスとしては、ボイラ、焼却炉等の燃焼炉から発生する排ガスが挙げられる。 (Acid deposits)
The acidic deposit may be an acidic deposit that can be removed with an alkali metal hydrogen carbonate and an alkali metal carbonate, and an acidic deposit containing a sulfur compound is preferable.
The present invention can be suitably applied to acidic deposits derived from combustion exhaust gas, particularly acidic deposits derived from boiler combustion exhaust gas. Examples of the combustion exhaust gas include exhaust gas generated from a combustion furnace such as a boiler or an incinerator.

燃焼排ガスに由来する酸性付着物に含まれる硫黄化合物としては、硫酸または硫酸塩が挙げられる。すなわち、酸性付着物は、不溶解分である未燃カーボン、鉄錆、フライアッシュのほか、燃料に含まれる硫黄由来の硫酸（Ｈ２ＳＯ４）、酸性硫安（硫酸水素アンモニウム：（ＮＨ４）ＨＳＯ４）等を含み、水に溶解すると強酸性を示すものである。酸性硫安は、前記硫酸と、脱硝用に注入されるアンモニアの余剰分（リークアンモニア）との反応により生成する。 Sulfuric acid or sulfate is mentioned as a sulfur compound contained in the acidic deposit derived from combustion exhaust gas. That is, in addition to undissolved carbon, iron rust, and fly ash that are insoluble components, acidic deposits include sulfuric acid derived from sulfur (H 2 SO 4 ), ammonium sulfate (ammonium hydrogen sulfate: (NH 4 )) HSO 4 ) and the like, and exhibits strong acidity when dissolved in water. Acidic ammonium sulfate is produced by a reaction between the sulfuric acid and a surplus of ammonia (leaked ammonia) injected for denitration.

（被洗浄物）
被洗浄物としては、燃焼炉（ボイラ、焼却炉等。）から発生する燃焼排ガスが接触する装置、煙道配管等が挙げられる。本発明は、ボイラの燃焼炉から煙突までの間に配置された装置（その構成部品を含む。）または煙道配管が被洗浄物である場合に好適に適用できる。 (Object to be cleaned)
Examples of the objects to be cleaned include devices that come into contact with combustion exhaust gas generated from a combustion furnace (boiler, incinerator, etc.), flue pipes, and the like. The present invention can be suitably applied when an apparatus (including its constituent parts) or a flue pipe disposed between a boiler combustion furnace and a chimney is an object to be cleaned.

装置としては、熱交換器（ガスエアヒーター（ＧＡＨ）、ガスガスヒーター（ＧＧＨ）、排ガス熱回収器（ＳＯ３凝縮器等。）、節炭器等。）、電機集塵機（ＥＰ）、排煙脱硫装置、排煙脱硝装置等が挙げられる。 The equipment includes heat exchangers (gas air heater (GAH), gas gas heater (GGH), exhaust gas heat recovery device (SO 3 condenser, etc.), economizer, etc.), electric dust collector (EP), flue gas desulfurization. Apparatus, flue gas denitration device, and the like.

被洗浄物が、熱交換器、特に蓄熱再生式回転型のガスエアヒーターまたはガスガスヒーターである場合は、ヒーティングエレメント（蓄熱要素部品）の形状が複雑であること、低温部がエナメルコーティングされた鉄系材料（ほうろう用鋼板）または鉄系耐食鋼であること、高温部が鉄系耐食鋼または冷間圧延鋼板（ＳＰＣＣ）であることが多いこと、等から、本発明の効果が顕著である。通常のシェル＆チューブ型熱交換器の場合でも、同様に良好な結果が得られる。   If the object to be cleaned is a heat exchanger, especially a heat storage regenerative rotary gas air heater or gas gas heater, the shape of the heating element (heat storage element component) is complicated, and the low temperature part is enamel coated. The effect of the present invention is remarkable because it is an iron-based material (enamel steel plate) or iron-based corrosion-resistant steel, and the high-temperature portion is often iron-based corrosion-resistant steel or cold-rolled steel plate (SPCC). . In the case of a normal shell and tube heat exchanger, good results are obtained as well.

被洗浄物が、電機集塵機である場合は、設備から取り外して洗浄液中に浸漬して洗浄することができず、内部は洗浄液の噴霧による洗浄しかできないため、本発明を好適に適用できる。   When the object to be cleaned is an electric dust collector, it cannot be removed from the equipment and immersed in the cleaning liquid for cleaning, and the inside can only be cleaned by spraying the cleaning liquid, and therefore the present invention can be suitably applied.

（酸性付着物の除去）
以下、縦型（Ｖ型）の蓄熱再生式回転型熱交換器から酸性付着物を除去する場合を例にとり、本発明の酸性付着物の除去方法について説明する。なお、横型（Ｈ型）の蓄熱再生式回転型熱交換器や、シェル＆チューブ型熱交換器でも同様の方法で良好な効果を得ることができる。 (Removal of acid deposits)
Hereinafter, the method for removing acidic deposits of the present invention will be described by taking as an example the case of removing acidic deposits from a vertical (V-type) heat storage and regeneration type rotary heat exchanger. In addition, a horizontal (H type) heat storage regenerative rotary heat exchanger or a shell and tube heat exchanger can obtain a good effect by the same method.

図１は、本発明の酸性付着物の除去方法を実施する設備の概略構成図である。該設備は、蓄熱再生式回転型熱交換器のヒーティングエレメント１に対して、上方から洗浄液を噴霧する複数のノズル２，２・・・と、下方から洗浄液を噴霧する複数のノズル３，３・・・と、洗浄液が貯留される洗浄液槽５と、洗浄液槽５の洗浄液を前記ノズルに循環供給する循環ポンプ６と、酸性付着物除去剤を溶解して洗浄液槽５に供給する薬剤溶解槽７とから概略構成される。   FIG. 1 is a schematic configuration diagram of equipment for carrying out the method for removing acidic deposits of the present invention. The equipment includes a plurality of nozzles 2, 2... For spraying the cleaning liquid from above and a plurality of nozzles 3, 3 for spraying the cleaning liquid from below on the heating element 1 of the regenerative rotary heat exchanger. ..., a cleaning liquid tank 5 in which the cleaning liquid is stored, a circulation pump 6 that circulates and supplies the cleaning liquid in the cleaning liquid tank 5 to the nozzle, and a chemical dissolution tank that dissolves the acidic deposit removing agent and supplies it to the cleaning liquid tank 5 7.

循環ポンプ６は、一端が洗浄液槽５に挿入された主配管１１に設けられている。主配管１１の他端は、ノズル２，２・・・に洗浄液を供給する上側配管１２およびノズル３，３・・・に洗浄液を供給する下側配管１３の双方の上流側に接続している。また、洗浄後の洗浄液を回収して洗浄液槽５に戻す戻り配管１４が設けられている。さらに、工業用水を供給する水供給管１５が、上側配管１２および下側配管１３の双方の上流側に接続している。薬剤溶解槽７には撹拌装置１７が設けられている。また、薬剤溶解槽７から溶解液を洗浄液槽５に供給する溶解液供給管１８が設けられている。また、循環ポンプ６の吐出側の主配管１１から分岐し、廃水処理設備または廃水貯留設備へつながる配管１９が設けられている。   The circulation pump 6 is provided in the main pipe 11 having one end inserted into the cleaning liquid tank 5. The other end of the main pipe 11 is connected to the upstream side of both the upper pipe 12 that supplies the cleaning liquid to the nozzles 2, 2... And the lower pipe 13 that supplies the cleaning liquid to the nozzles 3, 3. . A return pipe 14 is provided for collecting the cleaning liquid after cleaning and returning it to the cleaning liquid tank 5. Further, a water supply pipe 15 for supplying industrial water is connected to the upstream side of both the upper pipe 12 and the lower pipe 13. The chemical dissolution tank 7 is provided with a stirring device 17. In addition, a solution supply pipe 18 for supplying the solution from the drug solution tank 7 to the cleaning solution tank 5 is provided. Further, a pipe 19 is provided which branches from the main pipe 11 on the discharge side of the circulation pump 6 and leads to a waste water treatment facility or a waste water storage facility.

図１の設備にてヒーティングエレメント１を洗浄するには、まず、薬剤溶解槽７で酸性付着物除去剤を溶解し、これを洗浄液槽５に供給する。そして、洗浄液槽５の洗浄液を循環ポンプ６により、ノズル２，２・・・およびノズル３，３・・・から噴霧する。噴霧の水圧は、０．１〜２０ＭＰａが好ましい。水圧が０．１ＭＰａ以上であれば、高い洗浄効果が得られる。水圧が２０ＭＰａ以下であれば、ヒーティングエレメント１を傷めにくくなる。なお、噴霧する洗浄液には、未溶解の酸性付着物除去剤成分が含まれていてもよい。   In order to clean the heating element 1 using the equipment shown in FIG. 1, first, the acidic deposit removing agent is dissolved in the chemical dissolution tank 7 and supplied to the cleaning liquid tank 5. Then, the cleaning liquid in the cleaning liquid tank 5 is sprayed from the nozzles 2, 2... And the nozzles 3, 3. The spray water pressure is preferably 0.1 to 20 MPa. If the water pressure is 0.1 MPa or more, a high cleaning effect can be obtained. If the water pressure is 20 MPa or less, the heating element 1 is hardly damaged. The cleaning liquid to be sprayed may contain an undissolved acidic deposit removal agent component.

洗浄後の洗浄液は、戻り配管１４により洗浄液槽５に戻され循環使用される。循環を繰り返すと、除去した酸性付着物の溶解等により洗浄液の組成が変化してｐＨが低下するため、適宜洗浄液の組成を調整する。具体的には、ｐＨが所定の基準値（たとえばエアヒーターメーカーによる洗浄終了時の管理基準である工業用水のｐＨ値マイナス１が挙げられる。）より低下した場合、薬剤溶解槽７から高濃度のアルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩の水溶液または高濃度の酸性付着物除去剤の水溶液を洗浄液槽５に供給する。また、定期的に洗浄液槽５の洗浄液全体を交換する。洗浄液を交換したり廃棄したりする場合は、廃水処理設備等へ接続される配管１９を用い、洗浄液槽５より洗浄液を排出する。   The cleaning liquid after cleaning is returned to the cleaning liquid tank 5 through the return pipe 14 and used in a circulating manner. When the circulation is repeated, the composition of the cleaning liquid is changed due to dissolution of the removed acidic deposits and the pH is lowered. Therefore, the composition of the cleaning liquid is appropriately adjusted. Specifically, when the pH falls below a predetermined reference value (for example, the pH value of industrial water minus 1 which is a management standard at the end of cleaning by an air heater manufacturer), a high concentration from the chemical dissolution tank 7 is obtained. An aqueous solution of an alkali metal hydrogen carbonate and an alkali metal carbonate or an aqueous solution of a high concentration acidic deposit removing agent is supplied to the cleaning liquid tank 5. Further, the entire cleaning liquid in the cleaning liquid tank 5 is periodically replaced. When the cleaning liquid is exchanged or discarded, the cleaning liquid is discharged from the cleaning liquid tank 5 using a pipe 19 connected to a wastewater treatment facility or the like.

洗浄液で洗浄した後は、循環ポンプ６による洗浄液の噴霧を中止し、代わりに工業用水をノズル２，２・・・およびノズル３，３・・・から噴霧し、水洗浄を行う。水洗浄は、洗浄後の水のｐＨが６．０〜８．０になるまで行う。洗浄後の水のｐＨが６．０未満では、酸性付着物が残留している可能性が高い。洗浄後の水のｐＨが８．０を超えると、アルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩が残留している場合がある。洗浄後の水のｐＨは６．５〜７．５が特に好ましい。
なお、水洗浄は必須ではなく、アルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩が残留した状態のまま洗浄を終了してもよい。 After cleaning with the cleaning liquid, spraying of the cleaning liquid by the circulation pump 6 is stopped, and industrial water is sprayed from the nozzles 2, 2... And the nozzles 3, 3. The water washing is performed until the pH of the water after washing becomes 6.0 to 8.0. If the pH of the water after washing is less than 6.0, there is a high possibility that acidic deposits remain. When the pH of the water after washing exceeds 8.0, alkali metal hydrogen carbonate and alkali metal carbonate may remain. The pH of the water after washing is particularly preferably 6.5 to 7.5.
The washing with water is not essential, and the washing may be completed with the alkali metal bicarbonate and the alkali metal carbonate remaining.

以上説明した本発明の酸性付着物の除去方法は、本発明の酸性付着物除去剤とを含む洗浄液を用いているため、被洗浄物の腐食を抑制しつつ、酸性付着物を効果的に除去できる。   The method for removing acidic deposits of the present invention described above uses a cleaning liquid containing the acidic deposit remover of the present invention, so that acidic deposits are effectively removed while suppressing corrosion of the object to be cleaned. it can.

以下、実施例を示す。例１は比較例であり、例２〜６は実施例である。
実施例における防錆効果は以下のように評価した。 Examples are shown below. Example 1 is a comparative example, and Examples 2 to 6 are examples.
The antirust effect in the examples was evaluated as follows.

（試験片）
縦：３０ｍｍ、横：１４．６５ｍｍ、厚さ：１．６５ｍｍの冷間圧延鋼板（ＳＰＣＣ）に、直径：３．５ｍｍの孔を２つ設け、アセトンで脱脂したもの（総表面積：１０．５２ｄｍ２）を試験片とした。 (Test pieces)
A cold rolled steel plate (SPCC) having a length of 30 mm, a width of 14.65 mm, and a thickness of 1.65 mm provided with two holes of 3.5 mm in diameter and degreased with acetone (total surface area: 10.52 dm 2 ) was used as a test piece.

（防錆効果の測定）
試験液（２２℃）の１Ｌを、溶出試験機（富山産業社製、ＮＴＲ−ＶＳ６Ｐ）のビーカーに充填した。あらかじめ質量を計測した試験片全体を通電性のない糸で吊るし、試験液中に試験片全体を浸し、２００ｒｐｍの回転数で回転する撹拌羽根により撹拌した。試験液の液温を２２℃に保ったまま、この状態を２時間継続した。その後、試験片を取り出して錆の部分を磨き落とした際の試験片の質量を計測し、試験液浸漬前後の質量差を求めた。なお、撹拌羽としては、日本薬局方一般試験法溶出試験法第２法（パドル法）で規定されているものを用いた。 (Measurement of rust prevention effect)
1 L of the test solution (22 ° C.) was filled into a beaker of a dissolution tester (manufactured by Toyama Sangyo Co., Ltd., NTR-VS6P). The whole test piece whose mass was measured in advance was hung with a non-electrically conductive thread, the whole test piece was immersed in the test solution, and stirred with a stirring blade rotating at a rotation speed of 200 rpm. This state was continued for 2 hours while keeping the temperature of the test solution at 22 ° C. Then, the mass of the test piece when the test piece was taken out and the rust portion was polished off was measured, and the mass difference before and after immersion in the test solution was determined. In addition, as a stirring blade, what was prescribed | regulated by the Japanese Pharmacopoeia general test method dissolution test method 2nd method (paddle method) was used.

（腐食量）
下式から、試験液による試験片の腐食量を求めた。
腐食量［ｍｇ／（ｄｍ２・ｄａｙ）］
＝試験液浸漬前後の試験片の質量差［ｍｇ］÷試験片の表面積［ｄｍ２］÷浸漬時間［ｄａｙ］
＝試験液浸漬前後の試験片の質量差［ｍｇ］÷１０．５２［ｄｍ２］÷２／２４［ｄａｙ］。 (Corrosion amount)
From the following formula, the amount of corrosion of the test piece by the test solution was determined.
Corrosion amount [mg / (dm 2 · day)]
= Mass difference of test piece before and after immersion in test solution [mg] ÷ Surface area of test piece [dm 2 ] ÷ Immersion time [day]
= Mass difference of test piece before and after immersion in test solution [mg] ÷ 10.52 [dm 2 ] ÷ 2/24 [day].

（防錆率）
下式から、試験片の防錆率を求めた。
防錆率［％］
＝｛例１〜６のいずれかの試験液浸漬前後の試験片の質量差［ｍｇ］
−例１の試験液浸漬前後の試験片の質量差［ｍｇ］｝
÷例１の試験液浸漬前後の試験片の質量差［ｍｇ］×１００。 (Rust prevention rate)
From the following formula, the rust prevention rate of the test piece was determined.
Rust prevention rate [%]
= {Mass difference between test pieces before and after immersion in any one of Examples 1 to 6 [mg]
-Mass difference of test piece before and after immersion in test solution of Example 1 [mg]}
÷ Mass difference [mg] × 100 between test pieces before and after immersion in the test solution of Example 1.

〔例１〕
純水９５０ｇに、炭酸水素ナトリウム（ＮａＨＣＯ３、旭硝子社製、商品名：サンファイブパワー）の５０ｇを溶解し洗浄液１を調製した。
洗浄液１の１０００ｇに、酸性硫安（硫酸水素アンモニウム：（ＮＨ４）ＨＳＯ４、関東化学社製）の７７．０ｇを溶解することによって、洗浄初期や、被洗浄物の狭隘部分において、洗浄液中の中和に供するアルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩が消耗して酸性（ｐＨ：約２．０３）となった状況に相当する試験液１を調製した。該試験液１は、防錆率の評価の基準となる。
試験液１を用いて、防錆効果の評価を行った。結果を表１に示す。 [Example 1]
A cleaning solution 1 was prepared by dissolving 50 g of sodium hydrogen carbonate (NaHCO 3 , manufactured by Asahi Glass Co., Ltd., trade name: Sun Five Power) in 950 g of pure water.
By dissolving 77.0 g of acidic ammonium sulfate (ammonium hydrogen sulfate: (NH 4 ) HSO 4 , manufactured by Kanto Chemical Co., Ltd.) in 1000 g of the cleaning liquid 1, in the cleaning liquid at the initial stage of cleaning or in the narrow part of the object to be cleaned, Test solution 1 corresponding to a situation where the alkali metal bicarbonate and alkali metal carbonate to be neutralized were consumed and became acidic (pH: about 2.03) was prepared. The test solution 1 is a standard for evaluating the rust prevention rate.
The test solution 1 was used to evaluate the antirust effect. The results are shown in Table 1.

〔例２〕
純水９５０ｇに、炭酸水素ナトリウム（ＮａＨＣＯ３、旭硝子社製、商品名：サンファイブパワー）の４９ｇおよび炭酸カリウム（Ｋ２ＣＯ３）の１ｇを溶解し、洗浄液２を調製した。
洗浄液２の１０００ｇに、酸性硫安（硫酸水素アンモニウム：（ＮＨ４）ＨＳＯ４、関東化学社製）の７９．４ｇを溶解することによって、洗浄初期や、被洗浄物の狭隘部分において、洗浄液中の中和に供するアルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩が消耗して酸性（ｐＨ：約２．０１）となった状況に相当する試験液２を調製した。
試験液２を用いて、防錆効果の評価を行った。結果を表１に示す。 [Example 2]
In 950 g of pure water, 49 g of sodium hydrogen carbonate (NaHCO 3 , manufactured by Asahi Glass Co., Ltd., trade name: Sun Five Power) and 1 g of potassium carbonate (K 2 CO 3 ) were dissolved to prepare a cleaning solution 2.
By dissolving 79.4 g of acidic ammonium sulfate (ammonium hydrogen sulfate: (NH 4 ) HSO 4 , manufactured by Kanto Chemical Co., Ltd.) in 1000 g of the cleaning liquid 2, in the initial stage of cleaning and in the narrow part of the object to be cleaned, A test solution 2 corresponding to a situation where the alkali metal bicarbonate and alkali metal carbonate to be neutralized were consumed and became acidic (pH: about 2.01) was prepared.
The test solution 2 was used to evaluate the antirust effect. The results are shown in Table 1.

〔例３〕
純水９５０ｇに、炭酸水素ナトリウム（ＮａＨＣＯ３、旭硝子社製、商品名：サンファイブパワー）の４８ｇおよび炭酸カリウム（Ｋ２ＣＯ３）の２ｇを溶解し、洗浄液３を調製した。
洗浄液３の１０００ｇに、酸性硫安（硫酸水素アンモニウム：（ＮＨ４）ＨＳＯ４、関東化学社製）の８１．０ｇを溶解することによって、洗浄初期や、被洗浄物の狭隘部分において、洗浄液中の中和に供するアルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩が消耗して酸性（ｐＨ：約１．９８）となった状況に相当する試験液３を調製した。
試験液３を用いて、防錆効果の評価を行った。結果を表１に示す。 [Example 3]
In 950 g of pure water, 48 g of sodium hydrogen carbonate (NaHCO 3 , manufactured by Asahi Glass Co., Ltd., trade name: Sun Five Power) and 2 g of potassium carbonate (K 2 CO 3 ) were dissolved to prepare a cleaning solution 3.
By dissolving 81.0 g of acidic ammonium sulfate (ammonium hydrogen sulfate: (NH 4 ) HSO 4 , manufactured by Kanto Chemical Co., Ltd.) in 1000 g of the cleaning liquid 3, in the initial stage of cleaning and in a narrow part of the object to be cleaned, A test solution 3 corresponding to a situation where the alkali metal bicarbonate and alkali metal carbonate to be neutralized were consumed and became acidic (pH: about 1.98) was prepared.
The test solution 3 was used to evaluate the antirust effect. The results are shown in Table 1.

〔例４〕
純水９５０ｇに、炭酸水素ナトリウム（ＮａＨＣＯ３、旭硝子社製、商品名：サンファイブパワー）の４５ｇおよび炭酸カリウム（Ｋ２ＣＯ３）の５ｇを溶解し、洗浄液４を調製した。
洗浄液４の１０００ｇに、酸性硫安（硫酸水素アンモニウム：（ＮＨ４）ＨＳＯ４、関東化学社製）の７８．９ｇを溶解することによって、洗浄初期や、被洗浄物の狭隘部分において、洗浄液中の中和に供するアルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩が消耗して酸性（ｐＨ：約２．０１）となった状況に相当する試験液４を調製した。
試験液４を用いて、防錆効果の評価を行った。結果を表１に示す。 [Example 4]
In 950 g of pure water, 45 g of sodium hydrogen carbonate (NaHCO 3 , manufactured by Asahi Glass Co., Ltd., trade name: Sun Five Power) and 5 g of potassium carbonate (K 2 CO 3 ) were dissolved to prepare a cleaning solution 4.
By dissolving 78.9 g of acidic ammonium sulfate (ammonium hydrogen sulfate: (NH 4 ) HSO 4 , manufactured by Kanto Chemical Co., Ltd.) in 1000 g of the cleaning liquid 4, in the initial stage of cleaning and in the narrow part of the object to be cleaned, A test solution 4 corresponding to a situation in which the alkali metal hydrogen carbonate and alkali metal carbonate to be neutralized were consumed and became acidic (pH: about 2.01) was prepared.
The test solution 4 was used to evaluate the antirust effect. The results are shown in Table 1.

〔例５〕
純水９５０ｇに、炭酸水素ナトリウム（ＮａＨＣＯ３、旭硝子社製、商品名：サンファイブパワー）の４０ｇおよび炭酸カリウム（Ｋ２ＣＯ３）の１０ｇを溶解し、洗浄液５を調製した。
洗浄液５の１０００ｇに、酸性硫安（硫酸水素アンモニウム：（ＮＨ４）ＨＳＯ４、関東化学社製）の８０．２ｇを溶解することによって、洗浄初期や、被洗浄物の狭隘部分において、洗浄液中の中和に供するアルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩が消耗して酸性（ｐＨ：約２．０２）となった状況に相当する試験液５を調製した。
試験液５を用いて、防錆効果の評価を行った。結果を表１に示す。 [Example 5]
In 950 g of pure water, 40 g of sodium hydrogen carbonate (NaHCO 3 , manufactured by Asahi Glass Co., Ltd., trade name: Sun Five Power) and 10 g of potassium carbonate (K 2 CO 3 ) were dissolved to prepare a cleaning solution 5.
By dissolving 80.2 g of acidic ammonium sulfate (ammonium hydrogen sulfate: (NH 4 ) HSO 4 , manufactured by Kanto Chemical Co., Inc.) in 1000 g of the cleaning liquid 5, in the initial stage of cleaning and in a narrow part of the object to be cleaned, A test solution 5 corresponding to a situation where the alkali metal bicarbonate and alkali metal carbonate to be neutralized were consumed and became acidic (pH: about 2.02) was prepared.
The test solution 5 was used to evaluate the antirust effect. The results are shown in Table 1.

〔例６〕
純水９５０ｇに、炭酸水素ナトリウム（ＮａＨＣＯ３、旭硝子社製、商品名：サンファイブパワー）の３５ｇおよび炭酸カリウム（Ｋ２ＣＯ３）の１５ｇを溶解し、洗浄液６を調製した。
洗浄液６の１０００ｇに、酸性硫安（硫酸水素アンモニウム：（ＮＨ４）ＨＳＯ４、関東化学社製）の８３．１ｇを溶解することによって、洗浄初期や、被洗浄物の狭隘部分において、洗浄液中の中和に供するアルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩が消耗して酸性（ｐＨ：約２．０２）となった状況に相当する試験液６を調製した。
試験液６を用いて、防錆効果の評価を行った。結果を表１に示す。 [Example 6]
In 950 g of pure water, 35 g of sodium hydrogen carbonate (NaHCO 3 , manufactured by Asahi Glass Co., Ltd., trade name: Sun Five Power) and 15 g of potassium carbonate (K 2 CO 3 ) were dissolved to prepare a cleaning solution 6.
By dissolving 83.1 g of acidic ammonium sulfate (ammonium hydrogen sulfate: (NH 4 ) HSO 4 , manufactured by Kanto Chemical Co., Ltd.) in 1000 g of the cleaning liquid 6, in the initial stage of cleaning and in the narrow part of the object to be cleaned, A test solution 6 corresponding to a situation in which the alkali metal bicarbonate and alkali metal carbonate to be neutralized were consumed and became acidic (pH: about 2.02) was prepared.
The test solution 6 was used to evaluate the antirust effect. The results are shown in Table 1.

Figure 2010121038
Figure 2010121038

以上の結果より、洗浄初期や、被洗浄物の狭隘部分において、洗浄液中の中和に供するアルカリ金属の炭酸水素塩およびアルカリ金属の炭酸塩が消耗して酸性となった状況に相当する低いｐＨであっても、アルカリ金属の炭酸塩が、防錆効果を発揮することが分かった。   From the above results, low pH corresponding to the situation where the alkali metal carbonate and alkali metal carbonate used for neutralization in the cleaning liquid are exhausted and become acidic at the initial stage of cleaning or in a narrow part of the object to be cleaned. Even so, it has been found that the alkali metal carbonate exhibits an antirust effect.

本発明の酸性付着物除去剤および酸性付着物の除去方法は、燃焼炉から煙突までの間に配置された装置、配管等に付着した硫黄化合物を含む酸性付着物の除去に有用である。   INDUSTRIAL APPLICABILITY The acidic deposit removal agent and the method for removing acidic deposits of the present invention are useful for removing acidic deposits containing sulfur compounds attached to devices, pipes and the like disposed between the combustion furnace and the chimney.

本発明の酸性付着物の除去方法を実施する設備の概略構成図である。It is a schematic block diagram of the equipment which implements the removal method of the acidic deposit of this invention.

符号の説明Explanation of symbols

１ ヒーティングエレメント
２ ノズル
３ ノズル
５ 洗浄液槽
６ 循環ポンプ
７ 薬剤溶解槽 DESCRIPTION OF SYMBOLS 1 Heating element 2 Nozzle 3 Nozzle 5 Cleaning liquid tank 6 Circulation pump 7 Chemical dissolution tank

Claims (6)

アルカリ金属の炭酸水素塩と、
アルカリ金属の炭酸塩とを含み、
前記アルカリ金属の炭酸水素塩と前記アルカリ金属の炭酸塩との合計（１００質量％）のうち、アルカリ金属の炭酸水素塩の割合が、９８〜７０質量％であり、アルカリ金属の炭酸塩の割合が、２〜３０質量％である、酸性付着物除去剤。 An alkali metal bicarbonate,
An alkali metal carbonate,
Of the total (100% by mass) of the alkali metal bicarbonate and the alkali metal carbonate, the proportion of the alkali metal bicarbonate is 98 to 70% by mass, and the proportion of the alkali metal carbonate However, it is 2-30 mass%. 前記アルカリ金属の炭酸水素塩が、炭酸水素ナトリウムを主成分とする、請求項１に記載の酸性付着物除去剤。   The acidic deposit removing agent according to claim 1, wherein the alkali metal hydrogen carbonate contains sodium hydrogen carbonate as a main component. 前記アルカリ金属の炭酸塩が、炭酸カリウムを主成分とする、請求項１または２に記載の酸性付着物除去剤。   The acidic deposit removal agent according to claim 1 or 2, wherein the alkali metal carbonate is mainly composed of potassium carbonate. 水と請求項１〜３のいずれかに記載の酸性付着物除去剤とを含む洗浄液を、硫黄化合物を含む酸性付着物が付着した被洗浄物に噴霧する、酸性付着物の除去方法。   The removal method of acidic deposits which sprays the washing | cleaning liquid containing water and the acidic deposit removal agent in any one of Claims 1-3 to the to-be-washed object to which the acidic deposit containing a sulfur compound adhered. 前記被洗浄物が、燃焼炉から煙突までの間に配置された装置または配管である、請求項４に記載の酸性付着物の除去方法。   The method for removing acidic deposits according to claim 4, wherein the object to be cleaned is a device or a pipe arranged between a combustion furnace and a chimney. 前記装置または配管が、熱交換器または電気集塵機である、請求項４または５に記載の酸性付着物の除去方法。   The method for removing acidic deposits according to claim 4 or 5, wherein the device or the pipe is a heat exchanger or an electric dust collector.
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CN103591677A (en) * 2013-11-25 2014-02-19 江苏爵格工业设备有限公司 Water warming system used for eye washing

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