WO2020217666A1 - Chemical cleaning method and chemical cleaning apparatus - Google Patents

Abstract

The purpose of the present invention is to provide a chemical cleaning method which makes it possible to remove residues generated in chemical cleaning using a sulfur-containing neutral cleaning agent. The chemical cleaning method according to the present disclosure is to clean equipment, as a cleaning target, using a metal matrix as a structural member. The method comprises a neutral cleaning step (S2) of cleaning an inside of the cleaning target by a main agent that dissolves scales containing a metal oxide, and a neutral cleaning agent containing a sulfur element, an oxidizing treatment step (S4) of, after the neutral cleaning step (S2), supplying an oxidizing agent to the inside of the cleaning target, and a dissolving treatment step (S6) of, after the oxidizing treatment step (S4), supplying an oxide solution to the inside of the cleaning target, the oxide solution being regulated using a pH regulator showing basicity to have a pH of 2.5-7.0. The oxide solution contains a chelating agent, an organic acid having a chelating effect, and a solubilizer selected from organic acid salts having a chelating effect.

Description

Chemical cleaning method and chemical cleaning equipment

This disclosure relates to a chemical cleaning method and a chemical cleaning device.

In an evaporation pipe (hereinafter referred to as a boiler) of a thermal power plant or the like, a scale mainly composed of iron oxide (Fe ₂ O ₃ , Fe ₃ O _4, etc.) adheres to the inner surface thereof by operation. As the scale grows due to long-term operation, the boiler can suffer damage such as increased differential pressure, reduced plant efficiency, damage accidents due to overheating and corrosion, and blasting due to overheating of the metal temperature due to heat transfer inhibition. There is sex.

In order to prevent the occurrence of such troubles, the transition of the amount of scale adhesion such as iron oxide is investigated by maintenance and inspection, and chemical cleaning is carried out to remove the scale such as iron oxide on a regular basis.

In the conventional general boiler chemical cleaning, a method of cleaning by raising the temperature from 80 ° C. to 90 ° C. using an acid solution such as hydrochloric acid or organic acid (hereinafter referred to as an acidic cleaning solution) is adopted (acidic / high temperature cleaning). ).

Acidic and high temperature cleaning has the following problems.
(1) There is a potential risk that hydrogen gas will be generated due to corrosion of the material to be cleaned (metal base material), and the vicinity of the workplace during cleaning work will be a strictly prohibited area for fire. Therefore, parallel work with other works that may cause fire cannot be performed.
(2) For high temperature (80 ° C. to 90 ° C.) treatment, a temperature raising means for raising the temperature of the acidic cleaning liquid is required.
(3) As water supply management, a scale mainly composed of hematite (Fe ₂ O ₃ ) is generated by water treatment such as oxygen treatment. Hematite has the property of being difficult to dissolve in acidic cleaning solutions. Therefore, the scale mainly composed of hematite is collected as sludge from the system to be cleaned by circulating an acidic cleaning solution. However, at this time, there is a portion where the flow of the acidic cleaning liquid stays, and sludge remains in the system at this portion. Therefore, it is necessary to carry out an additional step of physical cleaning by jet water flow or the like.
(4) If the boiler is started with sludge remaining in the system, there is a possibility of inducing trouble (blasting, etc.) due to local heating or the like at the sludge residual site.

Due to the above background, in recent years, safe and secure chemical cleaning technology that does not generate hydrogen at room temperature has been developed (Patent Document 1). Patent Document 1 discloses a dissolution-removal composition containing a dissolution-removal agent that dissolves and removes rust and scale, and a sulfur-based reducing agent. The dissolution-removal composition of Patent Document 1 is a neutral cleaning solution, and can dissolve and remove scales mainly composed of hematite at room temperature. In the cleaning using the neutral cleaning solution, the scale solubility is enhanced by the sulfur-based reducing agent, and the metal ions dissolved in the cleaning solution are removed by acting with the dissolving and removing agent.

JP-A-2015-105411

While the inventors of the present application are studying chemical cleaning using a neutral cleaning solution, the material to be cleaned (hereinafter referred to as a metal base material or simply a base material) is used by using the dissolution removal composition described in Patent Document 1. The presence of residues was confirmed on the surface of the metal base material in the system after the chemical cleaning described).

As a result of the analysis, it was found that the residue was a metal sulfide (mainly FeS ₂ and MoS ₂ ). It is considered that this metal sulfide reacts with sulfur contained in the dissolution removal composition and precipitates during the corrosion process of the metal base material. From this, it is expected that the generation state of the residue will change depending on the amount of the dissolution-removal composition used (concentration and absolute amount of the dissolution-removal composition, washing time, etc.). For example, in cleaning the evaporation tube of a boiler with a large amount of scale adhesion, a sulfur-based reducing agent is used to improve scale solubility. In such a cleaning target, a residue may be generated on the surface of the metal base material after cleaning.

If the boiler is started with the residue remaining on the surface of the metal base material after cleaning, sulfide ions may be generated from the residue, causing a problem of corrosion of the metal base material. The presence of the residue may interfere with the visual determination of the end of cleaning (removal) of the scale.

Therefore, it is desirable to remove the residue before starting the boiler.

The present disclosure has been made in view of such circumstances, and provides a chemical cleaning method and a chemical cleaning apparatus capable of removing residues that may be generated in chemical cleaning using a neutral cleaning liquid containing sulfur. The purpose is to do.

In order to solve the above problems, the chemical cleaning method and the chemical cleaning apparatus of the present disclosure employ the following means.

The present disclosure is a chemical cleaning method for cleaning equipment in which a metal base material is used as a constituent member, and the cleaning target is a neutral cleaning liquid containing a main agent that dissolves a scale containing a metal oxide and a sulfur element. After the neutral cleaning step of cleaning the inside, the oxidation treatment step of supplying an oxidizing agent into the cleaning target after the neutral cleaning step, and the pH showing basicity in the cleaning target after the oxidation treatment step. A dissolution treatment step of supplying an oxide solution having a pH adjusted to 2.5 or more and 7 or less using an adjusting agent is included, and the oxide solution has a chelating agent, an organic acid having a chelating action, and a chelating action. Provided is a chemical cleaning method containing a solubilizer selected from organic acid salts.

The above neutral cleaning solution can dissolve and remove scales containing metal oxides. The oxidizing agent supplied in the oxidation treatment step oxidizes the metal sulfide generated on the surface of the metal base material to be cleaned to obtain a metal treatment product. The pH is adjusted to 2.5 or more, 7 or less, preferably 3.0 or more and 5.0 or less, and more preferably 3.5 or more and 4.3 or less by a pH adjusting agent that contains a dissolving agent having a chelating action and exhibits basicity. By supplying the prepared oxide solution to the cleaning target, the metal-treated product on the surface of the metal base material can be dissolved and removed. The metal base material is, for example, alloy steel or the like, and may be low alloy steel. The pH adjuster showing basicity is, for example, aqueous ammonia.

In one aspect of the present disclosure, it is preferable to select aqueous ammonia as the pH adjuster exhibiting basicity.

Ammonia water is easily available and can improve the removal rate of residues as compared with other basic pH adjusters (for example, potassium hydroxide).

In one aspect of the present disclosure, it is preferable to select citric acid or tartaric acid as the dissolving agent.

Citric acid and tartaric acid are easily available, and the risk of damaging the metal base material can be reduced by adjusting the pH using a pH adjuster showing basicity.

In one aspect of the present disclosure, it is preferable to select hydrogen peroxide as the oxidizing agent.

Hydrogen peroxide is easily available and does not damage the metal base material. Hydrogen peroxide does not contain dissimilar element species such as metal elements, and is finally decomposed into harmless water and oxygen, so that it has high environmental affinity and convenience of wastewater treatment.

In one aspect of the present disclosure, the first water washing step further comprises a first water washing step of supplying, circulating, and blowing water into the cleaning target between the neutral washing step and the oxidation treatment step. In the first circulating water, the component concentration derived from the neutral cleaning solution was measured, and when the measured component concentration derived from the neutral cleaning solution became equal to or less than the reference value, the end of the first water washing step was determined. It is desirable to carry out the water blow according to the determination. When the concentration of the component derived from the neutral cleaning liquid of the first circulating water exceeds the reference value, it is desirable to additionally carry out the same water washing step as the first water washing step.

By supplying, circulating, and blowing water in the first water washing process, the neutral cleaning liquid can be washed out from the cleaning target. By measuring the concentration of the component derived from the neutral cleaning solution of the first circulating water and determining the end of the first water washing step based on the measured value, the amount of the component derived from the neutral cleaning solution remaining in the cleaning target can be controlled. The less the component derived from the neutral cleaning solution remaining, the higher the removal rate of the residue.

In one aspect of the present disclosure, the residual allowable concentration of the component concentration derived from the neutral cleaning liquid is 0.2% by mass, preferably 0.1% by mass, and more preferably 0.05% by mass.

When the component concentration derived from the neutral cleaning liquid is 0.2% by mass or less, the removal rate of the residue can be 80% or more. When the concentration of the component derived from the neutral cleaning liquid is 0.1% by mass or less, the removal rate of the residue can be 90% or more. When the concentration of the component derived from the neutral cleaning liquid is 0.05% by mass or less, the removal rate of the residue can be 100%.

In one aspect of the present disclosure, a second water washing step of supplying, circulating, and blowing water into the washing target is further included between the oxidation treatment step and the dissolution treatment step, in the second water washing step. , The oxidant concentration of the second circulating water is measured, and when the measured oxidant concentration becomes equal to or less than the reference value, the end of the second water washing step is determined, and the water is blown according to the determination. Is desirable. When the oxidant concentration of the second circulating water exceeds the reference value, it is desirable to additionally carry out the same water washing step as the second water washing step.

By supplying, circulating, and blowing water in the second washing step, the oxidizing agent can be washed out from the cleaning target. By measuring the oxidant concentration of the second circulating water and determining the end of the second washing step based on the measured value, the amount of the oxidant remaining in the cleaning target can be controlled. The less oxidant remains, the higher the rate of residue removal.

In one aspect of the present disclosure, the reference value of the oxidizing agent concentration is 0.4% by mass, preferably 0.2% by mass, and more preferably 0.1% by mass.

When the oxidant concentration is 0.4% by mass or less, the residue removal rate can be 80% or more. When the oxidant concentration is 0.2% by mass or less, the residue removal rate can be 90% or more. When the oxidant concentration is 0.1% by mass or less, the removal rate of the residue can be 100%.

The present disclosure is a chemical cleaning device for cleaning a cleaning target portion of equipment in which a metal base material is used as a constituent member, and supplies a neutral cleaning liquid containing a sulfur element to the cleaning target portion. 2.5 or more and 7.0 or less containing an oxidizing agent supply part that supplies an oxidizing agent to the cleaning target part, a pH adjusting agent that exhibits basicity, and a dissolving agent having a chelating action in the cleaning target part. The oxide solution supply unit that supplies the oxide solution, the water supply unit that supplies water to the cleaning target site, the circulation flow path that circulates the fluid supplied to the cleaning target site, and the cleaning. A concentration measuring unit connected to the blow flow path for discharging the fluid supplied to the target site and the circulation flow path for measuring the concentration of components derived from the neutral cleaning liquid and / or the concentration of the oxidizing agent in the fluid. And / or a control unit connected to the cleaning target portion and / or controlling the discharge of the fluid supplied to the cleaning target portion, and the control unit is measured by the concentration measuring unit. According to the determination unit, which determines that the fluid supplied to the cleaning target site is discharged when the component concentration and / or the oxidizing agent concentration derived from the obtained neutral cleaning solution becomes equal to or less than the reference value, and according to the determination. Provided is a chemical cleaning apparatus including a transmission unit that transmits a discharge signal so as to discharge the fluid supplied to the cleaning target portion.

According to the present disclosure, a residue that may be generated in a chemical cleaning using a neutral cleaning solution containing sulfur is oxidized with an oxidizing agent and then treated with a dissolving agent having a chelating action to remove the residue. A possible chemical cleaning method can be presented.

It is a process drawing of the chemical cleaning method which concerns on 1st Embodiment. It is a figure which shows an example of the temperature transition in each process of FIG. It is a figure which shows the relationship between the pH of an oxide solution and the removal rate of a residue. It is a figure which shows the relationship between the component concentration derived from a neutral cleaning liquid, and the removal rate of a residue. It is a figure which shows the relationship between the oxidant concentration and the removal rate of a residue. It is a schematic diagram which shows the arrangement example of a chemical cleaning apparatus. It is a schematic diagram which shows an example of a chemical cleaning apparatus. It is a block diagram of a control part.

The chemical cleaning method and the chemical cleaning device according to the present disclosure target equipment for which the material to be cleaned is used as a component, for example, a boiler of a power plant. The metal base material of the material to be cleaned is, for example, alloy steel or the like, and may be low alloy steel.

[First Embodiment]
FIG. 1 shows a process diagram of the chemical cleaning method according to the present embodiment. FIG. 2 shows an example of the temperature transition in each process. In FIG. 2, the horizontal axis represents time and the vertical axis represents the temperature (° C.) in the system to be cleaned. The chemical cleaning method according to the present embodiment includes steps 1 << S1 >> to step 9 << S9 >> in order.

<< S1 >> Temporary system (cleaning and storage device) connection First, a temporary system for supplying fluid into the cleaning target is connected. After that, a fluid such as a cleaning liquid is injected into the cleaning target from the temporary system.

<< S2 >> Neutral cleaning Water is filled in the cleaning target, and the water is circulated in the cleaning target at room temperature (15 ° C to 55 ° C, preferably 30 ° C to 50 ° C, more preferably 35 ° C to 45 ° C). .. While circulating the water, a neutral cleaning solution is injected from the temporary system to fill the cleaning target with the neutral cleaning solution, and the circulation is continued. The neutral cleaning is not limited to circulating the neutral cleaning liquid, and may be static cleaning (swing blow). When the neutral cleaning is completed, the neutral cleaning liquid in the cleaning target is blown.

The pH of the neutral cleaning solution is 5.0 to 8.0. The neutral cleaning solution contains (A) a main agent and (B) a sulfur-based compound. The neutral cleaning solution may further contain at least one of (C) a reducing organic acid, (D) an amphoteric surfactant and a nonionic surfactant.

(A) Main agent The main agent has a dissolving ability for scales containing metal oxides such as rust. The base agent may include at least one selected from chelating agents and organic acids.

The chelating agent should be selected as a component in which the iron complex and iron salt produced by the dissolution reaction of the scale show reducing properties. Chelating agents are aminocarboxylic acids and their salts or phosphonic acids and their salts.

For example, aminocarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, and triethylenetetraminehexacetic acid.

For example, phosphonic acids include phosphonic acid, aminotris (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid (HEDP), ethylenediaminetetrax (methylenephosphonic acid), hexamethylenediaminetetrax (methylenephosphonic acid), Diethylenetetraminepentakis (methylenephosphonic acid), 2-phosphonobutane-1,2,4-tricarboxylic acid and the like. As these chelating agents, one type may be used alone, or two or more types may be used in combination.

Organic acids include, for example, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, decane-1,10-dicarboxylic acid, and salts of dicarboxylic acids. Diglycolic acid, thiodiglycolic acid, oxalacetic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, carboxymethyltaltronic acid, and salts thereof, malic acid, tartaric acid, citric acid, itaconic acid, methylsuccinic acid, 3-methylglutal Acid, 2,2-dimethylmalonic acid, maleic acid, fumaric acid, 1,2,3-propanetricarboxylic acid, aconitic acid, 3-butene-1,2,3-tricarboxylic acid, butane-1,2,3 4-Tetracarboxylic acid, ethanetetracarboxylic acid, ethenetetracarboxylic acid, n-alkenylaconytic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, phthalic acid, trimesic acid, hemimeric acid, pyromellitic acid, Benzenehexacarboxylic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-2,2,5,5-tetracarboxylic acid, salts thereof and the like. As these organic acids, one type may be used alone, or two or more types may be used in combination.

The blending amount of the main agent is 0.1% by mass or more and 40% by mass or less, preferably 0.5, based on the total mass of the neutral cleaning liquid from the viewpoint of removing scale containing metal oxides and suppressing corrosion of the metal base material. It is by mass% or more and 20% by mass or less, more preferably 1% by mass or more and 10% by mass or less. If it is less than 0.1% by mass, the scale solubility becomes insufficient. If it exceeds 40% by mass, the corrosion resistance becomes insufficient.

The main agent may contain hydroxides of various alkali metals such as potassium hydroxide. The main agent may contain inorganic acids such as hydrochloric acid, sulfuric acid and salts thereof, and inorganic acid salts.

(B) Sulfur-based compound The sulfur-based compound is at least (B-1) a reducing agent containing a sulfur element (sulfur-based reducing agent) and (B-2) a corrosion inhibitor containing a sulfur element (sulfur-based corrosion inhibitor). Includes one.

(B-1) Sulfur-based reducing agent The sulfur-based reducing agent has a scale component reducing property. Sulfur-based reducing agents include thiourea compounds, thiourea dioxide compounds, thioglycolates, dithionates, sulfites, hydrogen sulfites, pyrosulfates, thiosulfates, thionates and polythionic acids. Can be mentioned. One of these reducing agents may be used alone, or two or more thereof may be used in combination. Sulfur-based reducing agents promote the dissolution of scale components by their reducing action. In addition, the sulfur element contained in the reducing agent is adsorbed on the metal to strengthen the protective film.

Thiourea compounds are thiourea, guanylthiourea and the like. The thiourea dioxide compound is thiourea dioxide or the like. The thioglycolate is sodium thioglycolate, potassium thioglycolate, ammonium thioglycolate and the like. The dithionate salt is sodium dithionite or the like. Sulfites include sodium sulfite, potassium sulfite, calcium sulfite, zinc sulfite, ammonium sulfite and the like. The hydrogen sulfite salt is sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite and the like. The pyrosulfite is sodium pyrosulfite, potassium pyrosulfite, ammonium pyrosulfite and the like. The thiosulfate is sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate and the like. The thionate is sodium thionate, potassium thioate, ammonium thioate and the like. The polythionic acid salt is sodium trithionate, sodium tetrathionate and the like.

The blending amount of the sulfur-based reducing agent is 0.0025 parts by mass or more and 1000 parts by mass or less, preferably 0.05 parts by mass or more and 20 parts by mass or less, and more preferably 0.2 parts by mass or more with respect to 100 parts by mass of the main agent. It is 8 parts by mass or less.

The blending amount of the sulfur-based reducing agent is 0.01% by mass or more and 1% by mass or less, preferably 0.01% by mass or more and 0.1% by mass or less, more preferably 0.% by mass, based on the total mass of the neutral cleaning liquid. It is 02% by mass or more and 0.08% by mass or less. If it is less than 0.01% by mass, the scale solubility becomes insufficient. If it exceeds 1% by mass, the anticorrosion property becomes insufficient.

(B-2) Sulfur-based corrosion inhibitor As the sulfur-based corrosion inhibitor, an alkali metal salt (NaS-, KS-, LiS-) of a mercaptan group (HS-), a thiocyanate group (-SCN) or a mercaptan group is used. Examples thereof include sulfur organic compounds having. As a sulfur-based corrosion inhibitor, it is advisable to select a sulfur organic compound having strong adsorption to iron as a measure against galvanic corrosion. Examples of such sulfur organic compounds include 2,5-dithioacetic acid-1,3,4-thiathiolazole, 2-thioacetic acid-5-mercapto-1,3,4-thiadiazole, and 2,5-dimercapto-1,3. , 4-Thiadiol, mercaptobenzothiazole, mercaptobenzoimidazole, 2,4,6-trimercapto-S-triazine, 2-dibutylamino-4,6-dimercapto-S-triazine, 2-anilino-4,6-dimercapto -S-triazine, 3-mercapto-1-propanesulfonic acid, 1-thioglycerol, 2-aminothiophenol, 4-aminothiophenol, thiobenzoic acid, glycerol-monothioglycolate, β-mercaptopropionic acid, β -Mercaptoacetic acid, β-mercaptomaleic acid, β-mercaptoethanol, P-hydroxythiophenol, thiosalicylic acid, thioterephthalic acid, 2-mercaptoethanol, mercaptophenol, thioacetic acid, α-mercaptoethanol, sodium thiosianate, thiocyan Examples thereof include potassium acid acid, lithium thiocyanate, ammonium thiocyanate, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate and the like. The sulfur organic compound has a high adsorption power to a metal surface.

The blending amount of the sulfur-based corrosion inhibitor is 0.0025 parts by mass or more and 1000 parts by mass or less, preferably 0.05 parts by mass or more and 20 parts by mass or less, and more preferably 0.25 parts by mass with respect to 100 parts by mass of the main agent. It is 5 parts by mass or less.

The blending amount of the sulfur-based corrosion inhibitor is 0.001% by mass or more and 1% by mass or less, preferably 0.005% by mass or more and 0.1% by mass or less, more preferably 0, based on the total mass of the neutral cleaning liquid. It is 0.01% by mass or more and 0.05% by mass or less. If it is less than 0.001% by mass, the anticorrosion property becomes insufficient.

(C) Reducing Organic Acid For the reducing organic acid, it is advisable to select a component having excellent oxygen removal property and sustainability. Examples of such organic acids include ascorbic acid and elsorbic acid.

From the viewpoint of removing scale containing metal oxides and suppressing corrosion of the metal base material, the amount of the reducing organic acid to be blended is 0.025 parts by mass or more and 8000 parts by mass or less, preferably 0. It is 5 parts by mass or more and 1000 parts by mass or less, more preferably 5 parts by mass or more and 300 parts by mass or less.

The blending amount of the reducing organic acid is 0.01% by mass or more and 8% by mass or less, preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass, based on the total mass of the neutral cleaning liquid. % Or more and 3% by mass or less. If it is less than 0.01% by mass, the scale solubility becomes insufficient. If it exceeds 8% by mass, the anticorrosion property becomes insufficient.

(D) Amphoteric Surfactant and Nonionic Surfactant (D-1) Amphoteric Surfactant Examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine and 2-alkyl. Examples include -N-carboxyethyl-N-hydroxyethyl imidazolinium betaine and alkali metal salts of β-alkylaminocarboxylic acid (eg, sodium β-alkylaminopropionate). As the amphoteric surfactant, one type may be used alone, or two or more types may be used in combination. Since the amphoteric surfactant has a carboxylic acid group and a nitrogen atom, these substituents adsorb the amphoteric surfactant on the surface of the metal base material, while making it difficult to adsorb on the surface of rust and scale. As a result, the rust and scale dissolution removal performance can be further improved, and the corrosion resistance of the metal base material can be further improved.

The amount of the amphoteric surfactant to be blended is 0.01 parts by mass or more and 1000 parts by mass or less, preferably 0.05 parts by mass or more and 750 parts by mass or less, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the main agent. It is 500 parts by mass or less.

The blending amount of the amphoteric surfactant is 0.001% by mass or more and 10% by mass or less, preferably 0.005% by mass or more and 5% by mass or less, more preferably 0.01% by mass, based on the total mass of the neutral cleaning liquid. % Or more and 2% by mass or less.

(D-2) Nonionic Surfactant Examples of the nonionic surfactant include polyoxyalkylene glycol fatty acid esters, polyalkylene glycol fatty acid esters and polyoxyalkylene alkyl ethers. As the nonionic surfactant, one type may be used alone, or two or more types may be used in combination. For example, from the viewpoint of removing scale containing metal oxides and suppressing corrosion of the metal base material, the nonionic surfactants are polyethylene glycol monooleic acid ester, polyethylene glycol monolauric acid ester and polyethylene glycol monostearic acid ester. Is desirable.

The blending amount of the nonionic surfactant is 0.01 part by mass or more and 500 parts by mass or less, preferably 0.05 part by mass or more and 400 parts by mass or less, and more preferably 0.1 part by mass with respect to 100 parts by mass of the main agent. More than 300 parts by mass or less.

The blending amount of the nonionic surfactant is 0.001% by mass or more and 10% by mass or less, preferably 0.005% by mass or more and 5% by mass or less, more preferably 0.01, based on the total mass of the neutral cleaning liquid. It is mass% or more and 2 mass% or less.

In the neutral cleaning liquid, the concentrations of the chelating agent, the reducing agent and the corrosion inhibitor are appropriately adjusted so that the desired cleaning capacity and cleaning time can be obtained.

<< S3 >> Washing with water (first washing with water)
When the neutral cleaning is completed, blow the neutral cleaning solution. After that, water is filled in the cleaning target, the neutral cleaning liquid remaining in the cleaning target is replaced with the water, and the water is circulated, and when the first water washing is completed, the water is blown.

<< S4 >> Oxidation treatment Water is filled in the cleaning target, and the water is heated to about 50 ° C. and circulated. While circulating the water, the oxidant solution is injected from the temporary system, the inside of the cleaning target is filled with the oxidant solution, and the circulation is continued. In order to set the oxidation treatment time to, for example, about 1 hour or less, it is preferable to raise the temperature to about 50 ° C. When the oxidation treatment is completed, the oxidizing agent solution is blown from the cleaning target.

The oxidizing agent solution is an aqueous solution containing an oxidizing agent such as peroxide, permanganate, hypochlorous acid, chloric acid, chloric acid or perchloric acid. The oxidizing agent solution is preferably a hydrogen peroxide solution. The use of hydrogen peroxide solution is environmentally friendly because it does not damage the base material, is convenient for wastewater treatment, is easily available, does not contain dissimilar element species such as metal elements, and is finally decomposed into harmless water and oxygen. It has the advantage of high sex. The concentration of hydrogen peroxide in the oxidizing agent solution is preferably 0.3% by mass or more and 2% by mass or less, preferably 0.5% by mass or more and 2% by mass or less.

<< S5 >> Flushing (second flushing)
After blowing the oxidant solution, water is filled in the cleaning target, the oxidant solution remaining in the cleaning target is replaced with the water, and the water is circulated and the water is blown. The second washing with water may be carried out at a temperature (40 ° C. to 50 ° C.) similar to that of the oxidation treatment. By setting the temperature to the same level, the temperature of the base metal is maintained and smooth processing is performed in the next process.

<< S6 >> Dissolution treatment Water is filled in the cleaning target, and the water is circulated in the cleaning target at 40 ° C to 50 ° C. While circulating the water, the oxide solution is injected from the temporary system to fill the cleaning target with the oxide solution, and the oxidation-treated product is dissolved.

The oxide solution is an aqueous solution containing a dissolving agent capable of dissolving a metal oxide. The solubilizer is selected from a chelating agent, an organic acid having a chelating action, and an organic acid salt having a chelating action. More specifically, examples of the solubilizer include citric acid, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), ethylenediaminetetraacetic acid (EDTA), tartaric acid and the like. As the dissolving agent, it is preferable to use citric acid or tartaric acid, which are easily available and do not damage the base material. The concentration of citric acid in the oxide solution is preferably 0.5% by mass or more and 3.0% by mass or less, preferably 1.5% by mass or more and 2.5% by mass or less.

The pH of the oxide solution is pH 2.5 or more and pH 7.0 or less, preferably pH 3.0 or more and pH 5.0 or less, and more preferably pH 3.5 or more and 4.3 or less. The pH of the oxide solution is adjusted with a pH adjuster showing basicity (hereinafter referred to as aqueous ammonia).

<< S7 >> Anti-corrosion pretreatment After the dissolution treatment of the oxidized product is completed, the oxide solution is circulated and ammonia water is further supplied to the cleaning target to perform the neutralization treatment. The supplied ammonia water is circulated and the temperature is raised to 90 ° C. ± 5 ° C.

The pH of the ammonia water circulated in the neutralization treatment is 9.0 or more and 11.0 or less, preferably 9.5 or more and 10.5 or less. Ammonia water may be replaced with a solution containing an ammonia-based compound. Ammonia-based compounds are, for example, volatile amines selected from 2-amino-2-methyl-1-propanol, monoethanolamine, monoisopropanolamine, cyclohexylamine, diethylethanolamine, morpholine, 3-methoxypropylamine, and ammonia. It is a compound.

<< S8 >> Rust prevention treatment While circulating the ammonia water, hydrazine is injected into the object to be cleaned to form a rust prevention film. After the rust prevention treatment is completed, blow hydrazine water.

<< S9 >> Dismantling the temporary system After the above S8, the temporary system is dismantled.

The cleaning of S2 to S6 may be performed only once or may be performed a plurality of times.

If the equipment to be cleaned has a permanent cleaning system, the above S1 and S9 are omitted.

[Second Embodiment]
The present embodiment is different from the first embodiment in that in << S3 >> water washing (first water washing step), the completion of water washing is determined based on the concentration of the component derived from the neutral washing liquid in the blown water. In the present embodiment, the steps common to the first embodiment will not be described.

In the present embodiment, the concentration of the component derived from the neutral washing solution of the washing water (first circulating water) circulating in the washing target was measured by washing with water of << S3 >>, and the concentration of the component became equal to or less than the reference value. Is determined to be the end of washing with water. The reference value is 0.2% by mass, preferably 0.1% by mass, and more preferably 0.05% by mass from the viewpoint of the allowable residual chemical concentration in the oxidation treatment agent in the next step.

The components derived from the neutral cleaning solution include aminocarboxylic acids such as nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminetetraacetic acid, and triethylenetetraminehexacetic acid, and phosphonic acids such as phosphonic acid and aminotris (methylene). Phosphonate), 1-hydroxyethane-1,1-diphosphonic acid (HEDP), ethylenediaminetetrax (methylenephosphonic acid), hexamethylenediaminetetrax (methylenephosphonic acid), diethylenetetraminepentakis (methylenephosphonic acid), and 2- Phosphonobtan-1,2,4-tricarboxylic acid and the like. The concentration of components derived from the neutral cleaning solution can be determined by measuring the concentration (P) by the molybdenum blue absorptiometry after thermal decomposition by the potassium peroxobis sulfate method, or by inductively coupled plasma emission spectrometry (ICP-AES). ) It can be measured by a method of measuring the concentration, a method of detecting components by ion chromatography and capillary electrophoresis, or the like. The measurement of the component concentration may be carried out continuously or intermittently.

[Third Embodiment]
This embodiment is different from the first embodiment in that in << S5 >> water washing (second water washing step), the completion of water washing is determined based on the concentration of the oxidizing agent in the blown water. In the present embodiment, the steps common to the first embodiment will not be described.

In the present embodiment, the oxidant concentration of the water-washed water (second circulating water) circulating in the washing target is measured by the water-washing of << S5 >>, and the washing is completed when the oxidant concentration becomes equal to or less than the reference value. Is determined. The reference value is 0.4% by mass, preferably 0.1% by mass, from the viewpoint of the allowable residual chemical concentration for the dissolution treatment in the next step.

When the oxidizing agent is hydrogen peroxide, the hydrogen peroxide concentration can be measured by the 4-aminoantipyrine colorimetric method (Kyoritsu Rikagaku Kenkyusho, hydrogen peroxide pack test) or the like. The measurement of the oxidant concentration may be carried out continuously or intermittently.

This embodiment may be implemented in combination with the second embodiment.

The effects of the first to third embodiments will be described below.
In the chemical cleaning methods according to the first to third embodiments, a neutral cleaning solution containing a main agent and a sulfur-based compound (sulfur-based reducing agent and / or sulfur-based corrosion inhibitor) is used, so that hydrogen is less likely to be generated (conditions (). Scales such as rust can be dissolved and removed at pH 5.0 to 8.0).

Even if a residue (metal sulfide) is generated on the surface of the base metal after cleaning with a neutral cleaning solution containing sulfur elements, an oxide solution (pH 2) having a scale action is applied after the oxidizing agent is supplied in the oxidation treatment step. The residue can be removed by treating with 0.5 to 7.0).

(Oxidant)
Table 1 shows the results of cleaning the boiler tube of the actual machine according to << S1 >> to << S9 >> of the first embodiment, and after the cleaning is completed, SEM observation of the surface of the base material to confirm the amount of decrease in the residue component (Mo). Is shown. The neutral cleaning solution was 3% by mass of ethylenediaminetetraacetic acid (EDTA), 0.03% by mass of a sulfur-based reducing agent, a 0.5% by mass aqueous solution of an amphoteric surfactant, and a 0.5% by mass aqueous solution of a nonionic surfactant (pH 6. 0) was used. As the oxidizing agent solution, hydrogen peroxide solution (2.0% by mass) or potassium permanganate water (0.05% by mass) was used. As the oxide solution, 2.0% by mass of citric acid adjusted to pH 4.0 out of pH 3.0 to 5.0, which is a preferable range with aqueous ammonia, was used.

Regardless of whether hydrogen peroxide or potassium permanganate was used as the oxidizing agent, 80% or more of the residue could be removed. This confirmed that the residue could be removed with an oxidizing agent.

The residue is a metal sulfide (FeS ₂ , MoS _2, etc.). Oxidizing agents oxidize metal sulfides to metal oxides and ionize sulfur. It is considered that the ionized sulfur (sulfur compound) is removed together with the blow water after the rust prevention treatment. The metal oxide can be dissolved and removed by the oxide solution.

The reaction formulas assumed when hydrogen peroxide is used as the oxidizing agent are shown in the formulas (1) and (2).
_{3FeS 2 + 28H 2 O 2 →} Fe 3 O 4 + 6SO 4 2- + 28H 2 O ··· (1)
2MoS ₂ + 22H ₂ O ₂ → 2MoO ₃ + 4SO ₄ ^2- + 22H ₂ O ... (2)

(Dissolving agent)
Table 2 shows the results of cleaning the boiler tube of the actual machine according to << S1 >> to << S9 >> of the first embodiment by changing the dissolving agent. The surface of the base metal after cleaning was observed by SEM to confirm the amount of residue component (Mo) reduction. The neutral cleaning solution was 3% by mass of ethylenediaminetetraacetic acid (EDTA), 0.03% by mass of a sulfur-based reducing agent, a 0.5% by mass aqueous solution of an amphoteric surfactant, and a 0.5% by mass aqueous solution of a nonionic surfactant (pH 6. 0) was used. Hydrogen peroxide solution (2.0% by mass) was used as the oxidizing agent solution. As the solubilizer, citric acid, ethylenediaminetetraacetic acid (EDTA), 1-hydroxyetidronic acid-1,1-diphosphonic acid (HEDP), acetic acid and tartaric acid were used. The dissolving agent concentration of the oxide solution was 2.0% by mass. All oxide lysates were adjusted to pH 4.0 with aqueous ammonia.

According to Table 2, it was confirmed that 80% or more of the residue could be removed by using a dissolving agent other than acetic acid.

(PH of oxide solution)
Table 3 and FIG. 3 show the results of cleaning the boiler tube of the actual machine according to << S1 >> to << S9 >> of the first embodiment by adjusting the pH of the oxide solution. The surface of the base metal after cleaning was observed by SEM to confirm the amount of residue component (Mo) reduction. In FIG. 3, the horizontal axis represents the pH of the oxide solution, and the vertical axis represents the residue removal rate (%).

The neutral cleaning solution is ethylenediaminetetraacetic acid (EDTA) 3% by mass, sulfur-based reducing agent 0.03% by mass, amphoteric surfactant 0.5% by mass aqueous solution, nonionic surfactant 0.5% by mass aqueous solution (pH 6. 0) was used. A 2.0% by mass hydrogen peroxide solution was used as the oxidizing agent solution. 2.0% by mass citric acid was used as the solubilizer. The pH of the oxide solution was adjusted from 2.5 to 8.0 with aqueous ammonia.

According to Table 3 and FIG. 3, 80% or more of the residue is at pH 2.5 or more and 7.0 or less, 90% or more at pH 3.0 or more and 5.0 or less, and 100% at pH 3.5 or more and 4.3 or less. I was able to remove it.

There is a concern that hydrogen will be generated when the pH falls below 3. Therefore, in order to carry out the treatment under conditions where hydrogen is unlikely to be generated, the pH of the oxide solution is preferably 3 or more. When the pH exceeds 7.0, the residue removal rate falls below 80%. Therefore, the pH of the oxide solution is preferably 2.5 or more and 7.0 or less, preferably 3.0 or more and 5.0 or less, and more preferably 3.5 or more and 4.3 or less.

(PH regulator)
Table 4 shows the results of cleaning the boiler tube of the actual machine according to << S1 >> to << S9 >> of the first embodiment by changing the pH adjusting solution for adjusting the pH of the oxide solution. The surface of the base metal after cleaning was observed by SEM to confirm the amount of residue component (Mo) reduction. The neutral cleaning solution was 3% by mass of ethylenediaminetetraacetic acid (EDTA), 0.03% by mass of a sulfur-based reducing agent, a 0.5% by mass aqueous solution of an amphoteric surfactant, and a 0.5% by mass aqueous solution of a nonionic surfactant (pH 6. 0) was used. A 2.0% by mass hydrogen peroxide solution was used as the oxidizing agent solution. Citric acid was used as the solubilizer. Ammonia water, triethanolamine, potassium hydroxide and 2-amino-2-methyl-1-propanol were used as the pH adjusting solution. The dissolving agent concentration of the oxide solution was 2.0% by mass, and the pH was 4.0.

According to Table 4, it was confirmed that aqueous ammonia is suitable as the pH adjusting solution for the oxide solution.

(Effect of residual components derived from neutral cleaning solution)
Tables 5 and 4 show the results of cleaning the boiler tube of the actual machine according to << S1 >> to << S9 >> of the second embodiment. As for the removal rate of the residue, the surface of the base material after washing was observed by SEM, and the amount of decrease in the residue component (Mo) was confirmed. In FIG. 4, the horizontal axis is the component concentration (mass%) derived from the neutral cleaning liquid in the first circulating water, and the vertical axis is the residue removal rate (%).

The neutral cleaning solution is ethylenediaminetetraacetic acid (EDTA) 3% by mass, sulfur-based reducing agent 0.03% by mass, amphoteric surfactant 0.5% by mass aqueous solution, nonionic surfactant 0.5% by mass aqueous solution (pH 6. 0) was used. A 2.0% by mass hydrogen peroxide solution was used as the oxidizing agent solution. As the oxide solution, 2.0% by mass citric acid adjusted to pH 4.0 with aqueous ammonia was used.

According to Table 5 and FIG. 4, the component concentration derived from the neutral cleaning solution in the first circulating water is 80% or more when 0.2% by mass or less, 90% or more when 0.10% by mass or less, and 0.05% by mass or less. Was able to remove 100% of the residue.

If the first circulating water contains a large amount of components derived from the neutral cleaning solution, that is, if a large amount of components derived from the neutral cleaning solution remain in the cleaning target, there is a concern that the action of the oxidizing agent supplied later may be hindered or the base material may be corroded. Will be done. Therefore, it is desirable that the concentration of components derived from the neutral cleaning solution of the first circulating water is low. According to Table 5 and FIG. 4, until the component concentration derived from the neutral cleaning liquid in the first circulating water is 0.2% by mass or less, preferably 0.1% by mass or less, and more preferably 0.05% by mass or less. By washing with water, the residue can be removed more reliably.

(Effect of residual oxidant)
Table 6 and FIG. 5 show the results of cleaning the boiler tube of the actual machine according to << S1 >> to << S9 >> of the third embodiment. As for the removal rate of the residue, the surface of the base metal after cleaning was observed by SEM, and the amount of decrease in the residue component (Mo) was confirmed. In FIG. 5, the horizontal axis represents the oxidant concentration (mass%) in the second circulating water, and the vertical axis represents the residue removal rate (%).

The neutral cleaning solution is ethylenediaminetetraacetic acid (EDTA) 3% by mass, sulfur-based reducing agent 0.03% by mass, amphoteric surfactant 0.5% by mass aqueous solution, nonionic surfactant 0.5% by mass aqueous solution (pH 6. 0) was used. A 2.0% by mass hydrogen peroxide solution was used as the oxidizing agent solution. As the oxide solution, 2.0% by mass citric acid adjusted to pH 4.0 with aqueous ammonia was used.

According to Table 6 and FIG. 5, the oxidant concentration in the second circulating water is 80% or more when 0.4% by mass or less, 90% or more when 0.2% by mass or less, and 100% when 0.1% by mass or less. The residue could be removed.

If the second circulating water contains a large amount of oxidant, that is, if a large amount of oxidant remains in the cleaning target, there is a concern that the action of the oxide solution supplied later may be hindered or the base material may be corroded. Therefore, it is desirable that the concentration of the oxidizing agent in the second circulating water is low. According to Table 6 and FIG. 5, by washing with water until the concentration of the oxidizing agent in the second circulating water is 0.4% by mass or less, preferably 0.2% by mass or less, and more preferably 0.1% by mass or less. , The residue can be removed more reliably.

(Processing conditions)
Table 7 shows the results of cleaning the boiler tube of the actual machine according to << S1 >> to << S9 >> of the first embodiment. For the judgment, the surface of the base material after cleaning was observed by SEM, the amount of decrease in the residue component (Mo) was confirmed, and a residue removal rate of 80% or more was regarded as a good judgment.

The neutral cleaning solution is ethylenediaminetetraacetic acid (EDTA) 3% by mass, sulfur-based reducing agent 0.03% by mass, amphoteric surfactant 0.5% by mass aqueous solution, nonionic surfactant 0.5% by mass aqueous solution (pH 6. 0) was used. Neutral washing was performed at 40 ° C. A 2.0% by mass or 1.0% by mass hydrogen peroxide solution was used as the oxidizing agent solution. As the oxide solution, 0.5% by mass, 1% by mass or 2.0% by mass of citric acid was used. Ammonia water was used as the pH adjusting solution, and the oxide solution was adjusted to pH 4.0.

No. in Table 7 According to No. 10, after performing a neutral wash at 40 ° C., oxidation treatment and oxidation treatment at 50 ° C. using 2.0 mass% hydrogen peroxide (H ₂ O ₂ ) water and 2.0 mass% citric acid solution, respectively. By carrying out the dissolution treatment, the residue could be removed within 1 hour in each step.

No. in Table 7 According to ₂ , 3, 5, and 9, the treatment of each step is performed even when the hydrogen peroxide (H ₂ O ₂ ) concentration and the citric acid concentration are lowered, or the treatment temperature is lowered below 50 ° C. It was confirmed that the residue can be removed by extending the time.

If the hydrogen peroxide concentration is too high, there is a concern that the chemical solution cost will increase. If the citric acid concentration is high, the treatment can be performed in a short time, but there is a concern that the chemical solution cost will increase. Therefore, it is preferable that the hydrogen peroxide concentration and the citric acid solution concentration are not too high.

The chemical cleaning method according to the first to third embodiments is a once-through boiler equipped with an economizer 1, a fireplace wall tube 2 (evaporation tube), and an air-water separator 3, and in particular, a scale as shown in FIG. It is suitable for cleaning the part where the scale easily adheres (for example, the furnace wall tube where the scale easily adheres due to the temperature and pressure conditions). In FIG. 6, a temporary system (chemical cleaning device) 4 is connected so that the cleaning liquid is supplied to the furnace wall tube.
For example, the chemical cleaning device 4 is connected to the inlet of the economizer 1 and the drain discharge portion of the steam separator.

Next, the configuration of a temporary system (chemical cleaning device) capable of carrying out the chemical cleaning method according to the above embodiment will be described.
The chemical cleaning apparatus according to the present embodiment includes a neutral cleaning liquid supply unit, an oxidant supply unit, an oxide solution supply unit, a water supply unit, a blow flow path, a concentration measurement unit, and a control unit.

FIG. 7 illustrates a schematic diagram of the chemical cleaning apparatus 10. The chemical cleaning device 10 is connected to the cleaning target portion 11.

The neutral cleaning liquid supply unit is a device provided with a neutral cleaning liquid tank 12 and supplying a neutral cleaning liquid containing a sulfur element to the cleaning target portion 11. The oxidant supply unit is a device provided with an oxidant tank 13 and supplying the oxidant to the cleaning target portion 11. The oxide solution supply unit is provided with an oxide solution tank 14, and an oxide solution having a pH of 2.5 or more and 7 or less containing a pH adjuster showing basicity and a dissolving agent having a chelating action is provided at the cleaning target site 11. It is a device to supply.

In FIG. 7, the neutral cleaning liquid tank 12, the oxidant tank 13, and the oxide solution tank 14 are connected in parallel to the cleaning target portion 11 via the connecting pipe 16 and the circulation flow path 17.

In the middle of the connection pipe 16, a pump 18 for feeding the solution stored in the tank into the circulation channel 17, and the valve V ₄ is provided from the valve V _1. The valve V ₁ is arranged between the neutral cleaning liquid tank 12 and the pump 18. The valve V ₂ is arranged between the oxidant tank 13 and the pump 18. The valve V ₃ is arranged between the oxide solution tank 14 and the pump 18. The valve V ₄ is arranged between the pump 18 and the circulation flow path 17.

In the circulation flow path 17, one end of the circulation flow path 17 is connected to the fluid inlet of the cleaning target part 11 and the other end of the circulation flow path 17 is the cleaning target part 11 so that the fluid can be circulated in the cleaning target part 11. It is connected to the fluid outlet. A pump 19 for circulating a fluid and valves V ₅ and ₆ arranged so as to sandwich the pump 19 are provided in the middle of the circulation flow path 17.

The water supply unit is a device including a water tank 15 for storing water and supplying water to a part to be cleaned. The water tank 15 is connected in the middle of the circulation flow path 17 via the connection pipe 20. A valve V ₇ is provided in the middle of the connecting pipe 20. In FIG. 7, the connection pipe 20 is connected to the circulation flow path 17 on the upstream side of the connection portion of the connection pipe 16, but the connection position of the water tank 15 is not limited to this.

The blow flow path 21 can discharge the fluid supplied to the cleaning target portion 11 to the drain tank 22. In FIG. 7, the blow flow path 21 is a first flow path 21a connected to a connecting pipe (not shown) connected to the fluid inlet of the cleaning target portion, and a second flow path 21a connected to both ends of the circulation flow path 17. The flow path 21b and the third flow path 21c merge in the middle. In the middle of the first flow path 21a is disposed the valve V ₈ is. A valve V ₉ is arranged in the middle of the second flow path. A valve V ₁₀ is arranged in the middle of the third flow path.

The concentration measuring unit 23 is connected to the circulation flow path 17 so that the concentration of the component derived from the neutral cleaning liquid and / or the concentration of the oxidizing agent in the fluid in the cleaning target portion 11 and the circulation flow path 17 can be measured. The concentration of the component derived from the neutral cleaning solution and / or the concentration of the oxidizing agent can be determined by, for example, measuring the phosphorus (P) concentration by the molybdenum blue absorptiometry after thermal decomposition by the potassium peroxo2 sulfate method or inductively coupled plasma emission. It can be measured by measuring the phosphorus (P) concentration by spectroscopic analysis (ICP-AES), detecting the component by ion chromatography or capillary electrophoresis, and the like. If the oxidizing agent is hydrogen peroxide, the concentration can be measured using the 4-aminoantipyrine colorimetric method (for example, Kyoritsu Institute of Physical and Chemical Research, hydrogen peroxide pack test, etc.). In FIG. 7, the concentration measuring unit 23 is connected to the circulation flow path 17 on the upstream side of the circulation pump 19 of the circulation flow path 17, but the connection position of the concentration measuring unit 23 is not limited to this. ..

The control unit 24 is connected to the circulation flow path 17 via the concentration measuring unit 23, and at least controls the opening and closing of the valve V ₁₀ from the valve V ₈ to water or the inside of the circulation flow path 17 including the cleaning target portion 11. A sex cleaning solution or an oxidizing agent can be discharged. The functions of the control unit 24 is not limited to this, for example, the valve V ₁ may be controlled to open and close the valve V _7. That is, the control unit 24 supplies water by the water supply unit and the neutral cleaning liquid by the neutral cleaning liquid supply unit, in addition to discharging the water or the neutral cleaning liquid or the oxidizing agent in the circulation flow path 17 including the cleaning target portion 11. The supply of the oxidant, the supply of the oxidant by the oxidant supply unit, and the supply of the oxide solution by the oxide solution supply unit may be controlled.

The control unit 24 is composed of, for example, a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), a computer-readable storage medium, and the like. As an example, a series of processes for realizing various functions are stored in a storage medium or the like in the form of a program, and the CPU reads this program into a RAM or the like to execute information processing / arithmetic processing. As a result, various functions are realized. The program is installed in a ROM or other storage medium in advance, is provided in a state of being stored in a computer-readable storage medium, or is distributed via a wired or wireless communication means. Etc. may be applied. Computer-readable storage media include magnetic disks, magneto-optical disks, CD-ROMs, DVD-ROMs, semiconductor memories, and the like.

FIG. 8 illustrates a configuration diagram of the control unit 24. The control unit 24 includes a determination unit 25 and a transmission unit 26. The determination unit 25 receives the measurement result of the concentration measurement unit 23. The determination unit 25 compares the received measurement result of the concentration measurement unit 23 with the reference value stored in advance, and when the measurement result is equal to or less than the reference value, the circulation flow path 17 including the cleaning target portion 11 Judge that water or neutral cleaning solution or oxidizing agent is discharged. Transmission unit 26 receives the determination result of the determination unit 25 sends the discharge portion so as to open the _{V 10} from the valve _{V 8} open signal (discharging signal) to (unillustrated drive unit _{V 10} from the valve _{V 8).} Upon receiving the open signal, the drive unit opens valves V ₈ to V ₁₀ .

The concentration measuring unit 23 measures the concentration of the component derived from the neutral cleaning liquid, and when the measured value is equal to or less than the reference value, the transmitting unit 26 further opens the valve V ₂ and the valve V ₄ so that the oxidant supply unit ( valve V _2, and sends the open signal to the driving unit (not shown) of the valve V _4). The drive unit which receives the open signal to open the valve V ₂ and valve V _4.

The concentration of the oxidizing agent was measured by the concentration measuring unit 23, when the measured value is equal to or less than the reference value, the transmission unit 26 is further valve V _3, oxide solution supplying unit so as to open the valve V ₄ (valve V _3, Send open signal to the driving unit) not shown of the valve V _4. The drive unit which receives the open signal to open the valve V ₃ and valve V _4.

The present disclosure is not limited to the above-described embodiment, and various modifications can be made without departing from the gist of the invention.

1 Economizer 2 Fireplace wall pipe 3 Brackish water separator 4,10 Temporary system (chemical cleaning equipment)
11 Part to be cleaned 12 Neutral cleaning liquid tank 13 Oxidizing agent tank 14 Oxide solution tank 15 Water tank 16, 20 Connection piping 17 Circulation flow path 18, 19 Pump 21 Blow flow path 21a First flow path 21b Second flow path 21c 3rd flow path 22 Drainage tank 23 Concentration measurement unit 24 Control unit 25 Judgment unit 26 Transmission unit

Claims (11)

1. A chemical cleaning method that targets equipment that uses a metal base material as a component.
   A neutral cleaning step of cleaning the inside of the cleaning target with a neutral cleaning solution containing a main agent that dissolves scales containing metal oxides and sulfur elements.
   After the neutral cleaning step, an oxidation treatment step of supplying an oxidizing agent into the cleaning target, and
   After the oxidation treatment step, a dissolution treatment step of supplying an oxide solution whose pH has been adjusted to 2.5 or more and 7 or less by using a pH adjusting agent showing basicity in the cleaning target is included.
   The chemical cleaning method containing a solubilizer selected from a chelating agent, an organic acid having a chelating action, and an organic acid salt having a chelating action.
2. The chemical cleaning method according to claim 1, wherein ammonia water is selected as the pH adjuster exhibiting basicity.
3. The chemical cleaning method according to claim 1 or 2, wherein citric acid or tartaric acid is selected as the dissolving agent.
4. The chemical cleaning method according to any one of claims 1 to 3, wherein hydrogen peroxide is selected as the oxidizing agent.
5. The chemical cleaning method according to any one of claims 1 to 4, wherein the pH of the oxide solution is adjusted to 3.0 or more and 5.0 or less.
6. The chemical cleaning method according to any one of claims 1 to 4, wherein the pH of the oxide solution is adjusted to 3.5 or more and 4.3 or less.
7. In the first water washing step, a first water washing step of supplying, circulating, and blowing water into the cleaning target is further included between the neutral washing step and the oxidation treatment step.
   The concentration of the component derived from the neutral cleaning solution of the first circulating water was measured, and
   The end of the first water washing step is determined when the measured component concentration derived from the neutral cleaning liquid becomes equal to or less than the reference value.
   The chemical cleaning method according to any one of claims 1 to 6, wherein the water is blown according to the determination.
8. The chemical cleaning method according to claim 7, wherein the reference value of the component concentration derived from the neutral cleaning liquid is 0.2% by mass.
9. In the second water washing step, a second water washing step of supplying, circulating, and blowing water into the washing target is further included between the oxidation treatment step and the dissolution treatment step.
   Measure the oxidant concentration in the second circulating water and
   When the measured oxidant concentration becomes equal to or less than the reference value, the end of the second washing step is determined.
   The chemical cleaning method according to any one of claims 1 to 8, wherein the water is blown according to the determination.
10. The chemical cleaning method according to claim 9, wherein the reference value of the oxidizing agent concentration is 0.4% by mass.
11. A chemical cleaning device for cleaning the parts to be cleaned of equipment in which a metal base material is used as a component.
    A neutral cleaning liquid supply unit that supplies a neutral cleaning liquid containing a sulfur element to the cleaning target site,
    An oxidant supply unit that supplies an oxidant to the cleaning target site,
    An oxide solution supply unit that supplies an oxide solution having a pH of 2.5 or more and 7.0 or less, which contains a pH adjuster showing basicity and a dissolving agent having a chelating action, to the site to be cleaned.
    A water supply unit that supplies water to the cleaning target site,
    A circulation flow path that circulates the fluid supplied to the cleaning target site,
    A blow flow path for discharging the fluid supplied to the cleaning target site, and
    A concentration measuring unit connected to the circulation flow path and measuring the concentration of a component derived from the neutral cleaning solution and / or the concentration of the oxidizing agent in the fluid.
    A control unit connected to the cleaning target portion and / or the circulation flow path and controlling the discharge of the fluid supplied to the cleaning target portion.
    The control unit is provided with
    When the concentration of the component derived from the neutral cleaning liquid and / or the concentration of the oxidizing agent obtained by the measurement of the concentration measuring unit becomes equal to or less than the reference value, it is determined that the fluid supplied to the cleaning target site is discharged. Judgment unit and
    A chemical cleaning device including a transmission unit that transmits a discharge signal so as to discharge the fluid supplied to the cleaning target portion according to the determination.
    

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