CN102719834B - Chemical cleaning agent for superheater heat exchange pipe of station boiler - Google Patents
Chemical cleaning agent for superheater heat exchange pipe of station boiler Download PDFInfo
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- CN102719834B CN102719834B CN 201210180797 CN201210180797A CN102719834B CN 102719834 B CN102719834 B CN 102719834B CN 201210180797 CN201210180797 CN 201210180797 CN 201210180797 A CN201210180797 A CN 201210180797A CN 102719834 B CN102719834 B CN 102719834B
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Abstract
The invention relates to a chemical cleaning agent of a superheater heat exchange pipe of a station boiler, which comprises the components by mass percent: 1.0-50.0% of MAC, 0.1-0.5wt% of corrosion inhibitor, 0.05-1.5wt% of reducing agent, 0.05-0.2wt% of surfactant and de-mineralized water, wherein the MAC is a key component, and the other components are auxiliary components. The process condition is to control pH at 1.0-7.0. The cleaning formula has an excellent dissolving and dispersing effect on scale of various superheater heat exchange pipes, and simultaneously can control the material corrosion within a safety range and standard set value. The chemical cleaning agent is suitable for chemical cleaning of superheater heat exchange pipes of various station boilers, boilers and other equipment.
Description
Technical field
The invention belongs to the chemical of chemical field, be specifically related to a kind of Utility Boiler Superheater heat transfer tube chemical.
Background technology
The coming off of overcritical and super (super-) critical unit boiler superheater heat transfer tube steam side oxide skin, blockage problem become increasingly conspicuous, and have a strong impact on the safe and stable operation in fuel-burning power plant.Adopt chemical cleaning technique can remove the oxide skin of superheater heat transfer tube steam side, can increase substantially the thermo-efficiency of boiler simultaneously.But because the situations such as the structure of superheater, material, operation condition are very large with the difference of boiler body, therefore adopt the prescription of existing boiler body cleaning and matting that technique is carried out the superheater heat transfer tube to have following technical barrier:
1) most power station pot adopts the π types to arrange, superheater contains a large amount of vertically arranged U (W) type pipe, cleans that residue is stifled easily to be stopped up in U (W) type pipe bottom deposition, causes to clean to interrupt or clean unsuccessfully;
2) the superheater heat transfer tube relates to the various metals material, contain various ferritic steels (such as T22, T23, T91 etc.) and austenitic steel stainless steel (such as TP347H, Super304H, HR3C etc.), and the welding joint with many dissimilar steel, easily produce intergranular corrosion and the stress corrosion of austenitic stainless steel when therefore carrying out matting, and the corrosion of Dissimilar Steel Welded Joint, corrosion location occurs and crack destruction or material mechanical performance reduction situation, thereby cause brokenly ring or produce potential safety hazard to unit;
3) run under the steam condition of high temperature, high pressure owing to boiler superheater, the characteristics such as the oxide compound amount of having that superheater heat transfer tube inwall forms is many, compact structure, multilayered structure, therefore oxide compound is difficult to dissolving, adopts conventional cleaning technique not reach good cleaning performance.
Summary of the invention
The object of the present invention is to provide a kind of Utility Boiler Superheater heat transfer tube chemical that is applicable to contain the overcritical of austenitic stainless steel and super (super-) critical boiler superheater, especially contain the superheater that is arranged vertically U (or W) type heat transfer tube, also be applicable to the furnace body of subcritical, overcritical and super (super-) critical boiler and the cleaning of stokehold.
For achieving the above object, the technical solution used in the present invention is: contain by mass percentage 1.0 ~ 50.0% MAC, 0.1% ~ 0.5% inhibiter, 0.05% ~ 1.5% reductive agent, 0.05% ~ 0.2%wt tensio-active agent, surplus is de-mineralized water.
Described MAC is mixed by methylsulphonic acid, nitrilotriacetic acid, diethylene triamine pentacetic acid (DTPA), ethylenediamine tetraacetic acid (EDTA) and ammoniacal liquor and forms, methylsulphonic acid accounts for 5% ~ 25% by mass percentage, nitrilotriacetic acid accounts for 20% ~ 50%, diethylene triamine pentacetic acid (DTPA) accounts for 20% ~ 40%, ethylenediamine tetraacetic acid (EDTA) accounts for 10% ~ 30%, and surplus is pH adjusting agent ammoniacal liquor.
Described inhibiter is mixed by hexamethylene amine, urotropine, diamine, mercapto benzothiazole, benzotriazole and de-mineralized water and forms, hexamethylene amine accounts for 5% ~ 25% by mass percentage, urotropine accounts for 10% ~ 30%, diamine 20% ~ 40%, mercapto benzothiazole 10% ~ 30%, benzotriazole 5% ~ 25%, and surplus is de-mineralized water.
Described reductive agent is the mixture of one or more arbitrary proportions in sodium iso-vc, hydrazine, the acetoxime.
Described tensio-active agent is the mixture of one or more arbitrary proportions in Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene or the alkylphenol polyethylene oxide ether.
It is acid that Utility Boiler Superheater heat transfer tube chemical of the present invention is, pH=1.0 ~ 7.0; Use temperature is 50 ℃ ~ 100 ℃, to moving the oxide skin that rear austenite and ferrite superheater heat transfer tube adhere to excellent cleaning characteristics is arranged; Very little to moving oxide skin separability in cleaning process that rear austenite and ferrite superheater heat transfer tube adhere to; Very high to moving the oxide skin dissolution rate that rear austenite and ferrite superheater heat transfer tube peel off; Can keep the rich chromium zone of oxidation of bottom in the overheated Tube Sheet of Heat Exchanger of austenitic steel; Under cleaning condition, austenitic stainless steel is not had intergranular corrosion, to loading the austenitic stainless steel stress-free corrosion of ultimate stress, artificially add behind the 50mg/L chlorion under cleaning condition austenitic stainless steel without intergranular corrosion; Behind the artificial 100mg/L of the interpolation chlorion under cleaning condition to loading the austenitic stainless steel stress-free corrosion of ultimate stress; The artificial not impact of mechanical property of adding behind the 100mg/L chlorion under cleaning condition austenitic stainless steel; Under cleaning condition, ferritic erosion rate is satisfied the requirement of relevant power industry standard; Under cleaning condition, the erosion rate of dissimilar steel weld is satisfied the requirement of relevant power industry standard.
Embodiment
Embodiment 1:
Contain by mass percentage 1.0% MAC, 0.3% inhibiter, 0.5% reductive agent sodium iso-vc, 0.1% tensio-active agent Sodium dodecylbenzene sulfonate, surplus is de-mineralized water.
Wherein, MAC is comprised of the material of following mass percent: methylsulphonic acid accounts for 5%, and nitrilotriacetic acid accounts for 20%, and diethylene triamine pentacetic acid (DTPA) accounts for 20%, and ethylenediamine tetraacetic acid (EDTA) accounts for 10%, and surplus is pH adjusting agent ammoniacal liquor;
Inhibiter is comprised of the material of following mass percent: hexamethylene amine accounts for 25%, urotropine accounts for 10%, diamine 20%, mercapto benzothiazole 20%, benzotriazole 20%, and surplus is de-mineralized water;
Get the clean-out system of 100mL the present embodiment, be warming up to 95 ℃, under the air tight condition, austenitic stainless steel superheater oxide skin after the operation that cleaning 1.5g peels off was cleaned 24 hours, and dissolution rate is 92.3%.
Embodiment 2:
Contain by mass percentage 10% MAC, 0.3% inhibiter, 1.5% reductive agent hydrazine, 0.1% tensio-active agent alkylphenol polyoxyethylene, surplus is de-mineralized water.
Wherein, MAC is comprised of the material of following mass percent: methylsulphonic acid accounts for 10%, and nitrilotriacetic acid accounts for 30%, and diethylene triamine pentacetic acid (DTPA) accounts for 30%, and ethylenediamine tetraacetic acid (EDTA) accounts for 15%, and surplus is pH adjusting agent ammoniacal liquor;
Inhibiter is comprised of the material of following mass percent: hexamethylene amine accounts for 5%, urotropine accounts for 30%, diamine 25%, mercapto benzothiazole 10%, benzotriazole 5%, and surplus is de-mineralized water;
Get the clean-out system of 180mL the present embodiment, be warming up to 85 ℃, under the air tight condition, clean postrun T23 steel and austenitic stainless steel TP347 superheater tube sample, after 50 hours, the descaling rate of T23 pipe is 100.0%, the descaling rate of TP347 pipe is that the rich chromium layer of 90.3%, TP347 bottom keeps fully.TP347 and Super304H corrosion indicator do not have corrosion weight loss, and do not observe the situation of intergranular corrosion under 1000 times of metaloscopes, and the erosion rate of G20 steel test piece is 0.26g/ (m
2H), the residue rate of T23 pipe is 0.2%.
Embodiment 3:
Contain by mass percentage 20% MAC, 0.3% inhibiter, 1.5% reductive agent isopropyl ketoxime, 0.1%wt tensio-active agent alkylphenol polyethylene oxide ether, surplus is de-mineralized water.
Wherein, MAC is comprised of the material of following mass percent: methylsulphonic acid accounts for 15%, and nitrilotriacetic acid accounts for 40%, and diethylene triamine pentacetic acid (DTPA) accounts for 25%, and ethylenediamine tetraacetic acid (EDTA) accounts for 12%, and surplus is pH adjusting agent ammoniacal liquor;
Inhibiter is comprised of the material of following mass percent: hexamethylene amine accounts for 10%, urotropine accounts for 15%, diamine 40%, mercapto benzothiazole 15%, benzotriazole 10%, and surplus is de-mineralized water;
Get the clean-out system of 180mL the present embodiment, and add 50mg/LCl
-With 2.4g oxide skin, be warming up to 65 ℃, under the air tight condition, after cleaning finished, TP347 and Super304H Corrosion of Stainless Steel indication test piece did not have corrosion weight loss, do not observe the situation of intergranular corrosion under 1000 times of metaloscopes.
Embodiment 4:
Contain by mass percentage 30% MAC, 0.3% inhibiter, 0.7% reductive agent sodium iso-vc, 0.8% reductive agent hydrazine, 0.1% tensio-active agent Sodium dodecylbenzene sulfonate, surplus is de-mineralized water.
Wherein, MAC is comprised of the material of following mass percent: methylsulphonic acid accounts for 8%, and nitrilotriacetic acid accounts for 50%, and diethylene triamine pentacetic acid (DTPA) accounts for 22%, and ethylenediamine tetraacetic acid (EDTA) accounts for 13%, and surplus is pH adjusting agent ammoniacal liquor;
Inhibiter is comprised of the material of following mass percent: hexamethylene amine accounts for 15%, urotropine accounts for 10%, diamine 20%, mercapto benzothiazole 25%, benzotriazole 25%, and surplus is de-mineralized water;
Get the clean-out system of 180mL the present embodiment, and add 50mg/LCl
-With 2.4g oxide skin, be warming up to 60 ℃, under the air tight condition, after cleaning finished, the corrosion of superheater indicating piece TP347-T91 of dissimilar steel welding and the erosion rate of TP347-T22 were respectively 4.07g/ (m
2H) and 5.60g/ (m
2H).
Embodiment 5:
Contain by mass percentage 40% MAC, 0.3% inhibiter, 0.3% sodium iso-vc, 0.5% hydrazine, 0.7% acetoxime, 0.1% tensio-active agent alkylphenol polyoxyethylene, surplus is de-mineralized water.
Wherein, MAC is comprised of the material of following mass percent: methylsulphonic acid accounts for 20%, and nitrilotriacetic acid accounts for 25%, and diethylene triamine pentacetic acid (DTPA) accounts for 28%, and ethylenediamine tetraacetic acid (EDTA) accounts for 18%, and surplus is pH adjusting agent ammoniacal liquor;
Inhibiter is comprised of the material of following mass percent: hexamethylene amine accounts for 20%, urotropine accounts for 20%, diamine 25%, mercapto benzothiazole 10%, benzotriazole 25%, and surplus is de-mineralized water;
Get the clean-out system of 180mL the present embodiment, and add 100mg/LCl
-With 2.4g oxide skin, be warming up to 50 ℃, under the air tight condition, after cleaning finishes, load TP347 and the Super304H C type ring sample of ultimate stress, observable stress corrosion cracking does not appear.
Embodiment 6:
Contain by mass percentage 50% MAC, 0.3% inhibiter, 1.5% reductive agent sodium iso-vc, 0.1%wt tensio-active agent alkylphenol polyethylene oxide ether, surplus is de-mineralized water.
Wherein, MAC is comprised of the material of following mass percent: methylsulphonic acid accounts for 12%, and nitrilotriacetic acid accounts for 30%, and diethylene triamine pentacetic acid (DTPA) accounts for 30%, and ethylenediamine tetraacetic acid (EDTA) accounts for 23%, and surplus is pH adjusting agent ammoniacal liquor;
Inhibiter is comprised of the material of following mass percent: hexamethylene amine accounts for 12%, urotropine accounts for 10%, diamine 20%, mercapto benzothiazole 30%, benzotriazole 8%, and surplus is de-mineralized water;
Get the clean-out system of 180mL the present embodiment, and add 100mg/LCl
-With 2.4g oxide skin, be warming up to 55 ℃, under the air tight condition, after clean finishing, TP347 and Super304H corrosion indicator carry out stretch test result and show, its mechanical property with clean before compare, obvious reduction situation does not occur.
Embodiment 7:
Contain by mass percentage 25% MAC, 0.1% inhibiter, 0.05% reductive agent acetoxime, 0.05%wt tensio-active agent Sodium dodecylbenzene sulfonate, surplus is de-mineralized water.
Wherein, MAC is comprised of the material of following mass percent: methylsulphonic acid accounts for 18%, and nitrilotriacetic acid accounts for 35%, and diethylene triamine pentacetic acid (DTPA) accounts for 23%, and ethylenediamine tetraacetic acid (EDTA) accounts for 16%, and surplus is pH adjusting agent ammoniacal liquor;
Inhibiter is comprised of the material of following mass percent: hexamethylene amine accounts for 18%, urotropine accounts for 25%, diamine 30%, mercapto benzothiazole 12%, benzotriazole 10%, and surplus is de-mineralized water.
Embodiment 8:
Contain by mass percentage 36% MAC, 0.2% inhibiter, 1.2% reductive agent hydrazine, 0.03% Sodium dodecylbenzene sulfonate, 0.05% alkylphenol polyoxyethylene, surplus is de-mineralized water.
Wherein, MAC is comprised of the material of following mass percent: methylsulphonic acid accounts for 25%, and nitrilotriacetic acid accounts for 20%, and diethylene triamine pentacetic acid (DTPA) accounts for 40%, and ethylenediamine tetraacetic acid (EDTA) accounts for 10%, and surplus is pH adjusting agent ammoniacal liquor;
Inhibiter is comprised of the material of following mass percent: hexamethylene amine accounts for 8%, urotropine accounts for 12%, diamine 28%, mercapto benzothiazole 12%, benzotriazole 23%, and surplus is de-mineralized water;
Embodiment 9:
Contain by mass percentage 18% MAC, 0.5% inhibiter, 1.0% reductive agent acetoxime, 0.05% Sodium dodecylbenzene sulfonate, 0.08% alkylphenol polyoxyethylene, 0.07% alkylphenol polyethylene oxide ether, surplus is de-mineralized water.
Wherein, MAC is comprised of the material of following mass percent: methylsulphonic acid accounts for 10%, and nitrilotriacetic acid accounts for 25%, and diethylene triamine pentacetic acid (DTPA) accounts for 25%, and ethylenediamine tetraacetic acid (EDTA) accounts for 30%, and surplus is pH adjusting agent ammoniacal liquor;
Inhibiter is comprised of the material of following mass percent: hexamethylene amine accounts for 15%, urotropine accounts for 15%, diamine 35%, mercapto benzothiazole 15%, benzotriazole 5%, and surplus is de-mineralized water.
Claims (4)
1. Utility Boiler Superheater heat transfer tube chemical, it is characterized in that: contain by mass percentage 1.0～50.0% MAC, 0.1%～0.5% inhibiter, 0.05%～1.5% reductive agent, 0.05%～0.2%wt tensio-active agent, surplus is de-mineralized water;
Described MAC is mixed by methylsulphonic acid, nitrilotriacetic acid, diethylene triamine pentacetic acid (DTPA), ethylenediamine tetraacetic acid (EDTA) and ammoniacal liquor and forms, methylsulphonic acid accounts for 5%～25% by mass percentage, nitrilotriacetic acid accounts for 20%～50%, diethylene triamine pentacetic acid (DTPA) accounts for 20%～40%, ethylenediamine tetraacetic acid (EDTA) accounts for 10%～30%, and surplus is pH adjusting agent ammoniacal liquor.
2. Utility Boiler Superheater heat transfer tube chemical according to claim 1, it is characterized in that: described inhibiter is mixed by hexamethylene amine, urotropine, diamine, mercapto benzothiazole, benzotriazole and de-mineralized water and forms, hexamethylene amine accounts for 5%～25% by mass percentage, urotropine accounts for 10%～30%, diamine 20%～40%, mercapto benzothiazole 10%～30%, benzotriazole 5%～25%, and surplus is de-mineralized water.
3. Utility Boiler Superheater heat transfer tube chemical according to claim 1, it is characterized in that: described reductive agent is the mixture of one or more arbitrary proportions in sodium iso-vc, hydrazine, the acetoxime.
4. Utility Boiler Superheater heat transfer tube chemical according to claim 1, it is characterized in that: described tensio-active agent is the mixture of one or more arbitrary proportions in Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene or the alkylphenol polyethylene oxide ether.
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| CN 201210180797 CN102719834B (en) | 2012-06-04 | 2012-06-04 | Chemical cleaning agent for superheater heat exchange pipe of station boiler |
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| CN 201210180797 CN102719834B (en) | 2012-06-04 | 2012-06-04 | Chemical cleaning agent for superheater heat exchange pipe of station boiler |
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Effective date of registration: 20160815 Address after: 710075 Shaanxi city of Xi'an province high tech Zone Road Torch Hotel B Patentee after: XI'AN XIRE POWER STATION CHEMICAL SCIENCE & TECHNOLOGY CO., LTD. Address before: 710032 Xingqing Road, Shaanxi, China, No. 136, No. Patentee before: Xi'an Thermal Power Research Institute Co., Ltd. |
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