CN108342738B - Water-based cleaning agent for nuclear power equipment and preparation method thereof - Google Patents
Water-based cleaning agent for nuclear power equipment and preparation method thereof Download PDFInfo
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- CN108342738B CN108342738B CN201810046779.9A CN201810046779A CN108342738B CN 108342738 B CN108342738 B CN 108342738B CN 201810046779 A CN201810046779 A CN 201810046779A CN 108342738 B CN108342738 B CN 108342738B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
- C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
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Abstract
The invention provides a water-based cleaning agent for nuclear power equipment, which comprises raw materials of an inorganic salt cleaning auxiliary agent, a metal corrosion inhibitor, a nonionic surfactant, an anionic surfactant, a solubilizer, a defoaming agent and the balance of water. The water-based cleaning agent for the nuclear power equipment provided by the invention is low in foam, can be used in various cleaning modes such as spray cleaning, ultrasonic cleaning and bubbling cleaning, is wide in application range, is flexible and various in use method, has a good cleaning effect on grinding oil, cutting fluid, metal dust and the like in the production and processing process of the nuclear power equipment, does not influence subsequent surface treatment, has a certain rust prevention function, is far lower than a limiting concentration standard in concentration, is easy to biodegrade and treat and discharge, and is simple in preparation process, lower in preparation difficulty and lower in manpower requirement compared with the existing cleaning agent for the nuclear power equipment.
Description
Technical Field
The invention belongs to the technical field of industrial cleaning, and particularly relates to a water-based cleaning agent for nuclear power equipment and a preparation method thereof.
Background
The decontamination of nuclear power equipment is to remove radioactive substances on the surfaces of related equipment, devices and the like by applying mechanical, chemical or electrochemical methods according to the equipment and pollution conditions, wherein the radioactive substances are mainly iron oxides and corrosion products of cobalt, chromium and nickel, and the decontamination of the nuclear power equipment is an important measure for maintaining the safe operation of a nuclear power station and is an indispensable prior step for major overhaul of the nuclear power station. The decontamination method can be divided into a mechanical method and a chemical method according to the property, as the name suggests, the mechanical method comprises washing, scrubbing, polishing, sand blasting and the like, a special tool is required, and the decontamination method is only suitable for local decontamination of parts and pipe sections with relatively flat surfaces, and has low efficiency and large limitation. The chemical decontamination, namely the removal of surface pollutants by applying appropriate chemicals and processes, has high efficiency and wide applicability, and can be used for the decontamination of the whole system of the nuclear power station. In addition, in the production process of nuclear power equipment, the surface treatment process of metal is also involved, and the surface of a workpiece needs to be cleaned before surface treatment, so that the structural strength and the surface cleanliness of the workpiece cannot meet the requirements of terminal use.
Chemical decontamination is the overall decontamination performed with the goal of reducing the total spatial radiation dose of a nuclear power plant, and the basic process of chemical decontamination can be divided into three steps: (1) adding the cleaning agent into cooling water; (2) recycling and dissolving the radioactive oxide; (3) the decontamination effluent is removed from the circuit. The three processes can be partially or completely performed simultaneously according to different specific processes. In the evaluation of the quality of the decontamination process of the nuclear power plant, three aspects of decontamination factor, corrosion speed and wastewater quantity can be considered. The ideal cleaning agent should have the following conditions: (1) high decontamination capability and reasonable decontamination speed; (2) the corrosion to structural materials is small; (3) the waste liquid amount is small and easy to treat; (4) stability to heat and radioactive radiation; (5) the use is simple, the metal dissolved substance does not generate secondary precipitation, and the washing is easy; (6) the price is low. The decontamination rate not only affects the overall decontamination efficiency, but also requires that the entire decontamination process be completed as quickly as possible due to the relatively high down time costs of the reactor. Moreover, the safe disposal and disposal of radioactive waste is a difficult and costly process. When selecting the cleaning agent, attention should be paid to selecting a reactant with low metering, high decontamination efficiency, small waste liquid amount and low residual quantity. Due to the strict corrosion control requirements on the reactor system, detergents which are not only less aggressive to the base metal during the decontamination process, but also less aggressive to residual chemicals and their decomposition products under operating conditions, should also be considered for decontamination. At present, the commonly used cleaning agents are mainly organic acids, such as citric acid, monoacid, aminocarboxylic acid and salts thereof. Hydrochloric acid is generally applied to cleaning power boilers, is effective in removing carbonate scales, but the dissolution speed of a single hydrochloric acid solution on metal oxides cannot meet the requirement of decontamination of a reactor, and even if a corrosion inhibitor is added, the single hydrochloric acid solution still has high corrosivity on equipment, and a large amount of austenitic stainless steel equipment and pipelines are adopted in a nuclear reactor loop, so that the hydrochloric acid is not suitable for decontamination of a nuclear power station.
CN102747380A discloses an environment-friendly cleaning agent, which is prepared from a high-purity hydrocarbon solvent D60, a high-purity hydrocarbon solvent D80, ethylene glycol monobutyl ether, isooctanol, n-octanol, dimethyl maleate, dimethyl succinate and dimethyl adipate. CN103726042A discloses an antirust treatment agent for cleaning and converting the inner wall of an acrylic acid reactor of 559 tons for a nuclear power station, which comprises phosphoric acid, zinc oxide, citric acid, tartaric acid, nickel nitrate, potassium dichromate, ammonium molybdate, triethanolamine, ethylene glycol monobutyl ether, a special low-foam surfactant for spray degreasing and oil removal and water allowance, compared with the prior art, the invention only needs a high-pressure acid-resistant pump to spray the treatment agent for 1-4 hours,to 559 tons of acrylic acid reactor inner cavity and 32000
The waste liquid is discharged after neutralization, condensation and precipitation on the inner wall of the pipe with the length of 11 meters, and then the inner cavity and the inner wall of the 32000 pipe are dried by high pressure by adopting a multipurpose wind fire extinguisher 6MF-32, so that the antirust function can be realized while cleaning, the antirust treatment is not needed to be independently carried out in the next procedure, the antirust time is long and can reach more than 30 days.
In view of the above, in view of the high requirements for nuclear power equipment cleaning, there is still a need to develop a cleaning agent with good cleaning ability, which has good cleaning effect on contaminants such as polishing paste, cutting fluid and metal powder, has no residue after cleaning, is non-corrosive to metal materials, has a certain rust-proof function, has low foam, is suitable for cleaning modes such as spray cleaning, ultrasonic cleaning and bubbling cleaning, and is easy to biodegrade and treat and discharge.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a water-based cleaning agent for nuclear power equipment.
The invention also aims to provide a preparation method of the water-based cleaning agent.
In order to achieve the purpose, the invention adopts the following technical scheme:
a water-based cleaning agent for nuclear power equipment comprises the following raw materials in percentage by mass:
1-15% of inorganic salt cleaning auxiliary agent,
3 to 15 percent of metal corrosion inhibitor,
10 to 35 percent of nonionic surfactant,
10 to 35% of an anionic surfactant,
1 to 15 percent of solubilizer,
0.1 to 5 percent of defoaming agent,
the balance being water.
Preferably, the inorganic salt cleaning assistant is at least one of anhydrous sodium metasilicate, sodium pyrophosphate, potassium tripolyphosphate and sodium carbonate.
Further preferably, the purity of the inorganic salt cleaning aid is analytically pure.
Preferably, the metal corrosion inhibitor is at least one of benzotriazole, boric acid, triethanolamine and tribasic acid amide.
Preferably, the nonionic surfactant is fatty alcohol-polyoxyethylene ether.
Preferably, the anionic surfactant is at least one of a carboxylate type surfactant and a phosphate type surfactant.
Further preferably, the carboxylate surfactant is AEC-9 Na.
Further preferably, the phosphate-based surfactant is MAEP.
Preferably, the solubilizer is at least one of phosphoric acid polyether ester potassium salt Triton H66 and castor oil polyoxyethylene 35 ether.
Preferably, the defoaming agent is at least one of polydimethylsiloxane, polyoxypropylene ethylene oxide glycerol ether.
Preferably, the water is high-purity water, the resistivity of the high-purity water at 25 ℃ is more than or equal to 18M omega cm, the total organic carbon is less than or equal to 50 mu g/L, the sodium ion is less than or equal to 1 mu g/L, the chloride ion is less than or equal to 1 mu g/L, and the silicon content is less than or equal to 10 mu g/L.
A preparation method of a water-based cleaning agent for nuclear power equipment comprises the following steps:
weighing the components according to the proportion, firstly adding high-purity water into a reaction kettle at normal temperature and normal pressure, and then sequentially stirring and adding the inorganic salt cleaning auxiliary agent, the metal corrosion inhibitor, the nonionic surfactant, the anionic surfactant, the solubilizer and the defoaming agent.
Preferably, when adding components, one component to be added is required to be completely dissolved before the next component can be added.
Preferably, before the reaction kettle is used, the reaction kettle is cleaned by high-purity water until the discharged cleaning water is qualified.
Further preferably, the washing water is qualified as having a pH of 7 and a refractive index of 0.
The invention has the advantages of
1. The water-based cleaning agent for the nuclear power equipment provided by the invention has low foam, can be used in various cleaning modes such as spray cleaning, ultrasonic cleaning and bubbling cleaning, and has wide application range and flexible and various use methods;
2. the water-based cleaning agent for nuclear power equipment provided by the invention has a good cleaning effect on grinding oil, cutting fluid, metal dust and the like in the production and processing processes of nuclear power equipment, does not influence the subsequent surface treatment, and has a certain antirust function;
3. the water-based cleaning agent for nuclear power equipment provided by the invention has the advantages that the concentration of harmful substances is far lower than the limiting concentration standard, and the cleaning agent is easy to biodegrade and treat and discharge;
4. compared with the existing cleaning agent for nuclear power equipment, the water-based cleaning agent provided by the invention is simple in preparation process, reduces the preparation difficulty and reduces the manpower requirement.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
In the following examples, the respective raw materials in the formulation are commercially available conventional ones unless otherwise specified.
Example 1
The present embodiment provides three formulations of water-based cleaning agents for nuclear power plants, namely formulation a, formulation B and formulation C, wherein the inorganic salt adjuvant used in the present embodiment is directly purchased from seikagan chemical company, the corrosion inhibitor is purchased from shanghai millin chemical company, and the surfactant is purchased from nanjing gutian company and guangzhou dragon comet company.
The specific formula is as follows:
formula 1:
inorganic salt cleaning aid: anhydrous sodium metasilicate 1% (analytical grade), sodium carbonate 2% (analytical grade), potassium tripolyphosphate 2% (analytical grade)
Metal corrosion inhibitor: 0.5 percent of benzotriazole and 5 percent of tribasic acid amide;
nonionic surfactant: LF-22110%, LF-4035%;
anionic surfactant: AEC-9Na 15%;
solubilizer: 5% of oleyl alcohol polyoxyethylene ether;
defoaming agent: 0.1% of polydimethylsiloxane;
54.4 percent of high-purity water.
And (2) formula:
inorganic salt cleaning aid: sodium pyrophosphate 1% (analytically pure), sodium carbonate 2% (analytically pure);
metal corrosion inhibitor: 0.5 percent of benzotriazole and 5 percent of tribasic acid amide;
nonionic surfactant: LF-22115%, LF-4033%;
anionic surfactant: 15% of MAEP;
solubilizer: 8% of polysorbate;
defoaming agent: 1% of polyoxypropylene ethylene oxide glycerol ether;
49.5 percent of high-purity water.
And (3) formula:
inorganic salt cleaning aid: 1 percent of anhydrous sodium metasilicate (analytically pure) and 2 percent of potassium tripolyphosphate (analytically pure);
metal corrosion inhibitor: 0.5 percent of benzotriazole, 5 percent of boric acid and 5.5 percent of triethanolamine;
nonionic surfactant: LF-22110%, LF-40310%;
anionic surfactant: AEC-9Na 5%, MAEP 5%;
solubilizer: 2% of oleyl alcohol polyoxyethylene ether and 3% of polysorbate;
defoaming agent: 0.1% of polydimethylsiloxane;
50.9 percent of high-purity water.
Comparative formulation 1:
inorganic salt cleaning aid: anhydrous sodium metasilicate 1% (chemical purity), sodium carbonate 2% (chemical purity), potassium tripolyphosphate 2% (chemical purity);
metal corrosion inhibitor: 0.5 percent of benzotriazole and 5 percent of tribasic acid amide;
nonionic surfactant: LF-22110%, LF-4035%;
anionic surfactant: AEC-9Na 15%;
solubilizer: 5% of oleyl alcohol polyoxyethylene ether;
defoaming agent: 0.1% of polydimethylsiloxane;
54.4 percent of high-purity water.
Comparative formulation 2 is a commercially available water-based metal rust inhibitor.
Comparative formulation 3 is another commercially available water-based metal cleaner.
Example 2
The embodiment provides a preparation method of a water-based cleaning agent for nuclear power equipment, which specifically comprises the following steps:
(1) firstly, washing a reaction kettle by using high-purity water until the pH value of discharged washing water is 7 and the refractive index is 0;
(2) weighing the raw materials according to a ratio, adding high-purity water into a reaction kettle at normal temperature and normal pressure, sequentially stirring and adding an inorganic salt cleaning auxiliary agent, a metal corrosion inhibitor, a nonionic surfactant, an anionic surfactant, a solubilizer and a defoaming agent, and adding one of the components until the next component is added after one of the added components is completely dissolved.
Example 3
By using the preparation method provided in example 2 and the formulation of example 1, corresponding cleaning agents were prepared, the properties of which are shown in table 1.
TABLE 1 comparison of the Properties of the cleaning Agents of different formulations
The hazardous substance concentration limits of the cleaning agent are shown in table 2.
TABLE 2 cleaning agent harmful substance concentration limit
As can be seen from comparison of tables 1 and 2, the cleaning rate of the cleaning agent with the formula provided by the invention is far higher than that of a certain commercially available water-based metal antirust agent with the formula 2. Although the cleaning rate of another commercial water-based metal cleaner of comparative formula 3 also reached 91, it was corrosive to steel No. 45, cast iron Z30, brass H62, and LY12 duralumin, and the contents of fluorine, chlorine, and phosphorus in the harmful substances exceeded the limits.
Claims (3)
1. The water-based cleaning agent for the nuclear power equipment is characterized by comprising the following components in percentage by mass:
inorganic salt cleaning aid: 1% of analytically pure sodium pyrophosphate and 2% of analytically pure sodium carbonate;
metal corrosion inhibitor: 0.5 percent of benzotriazole and 5 percent of tribasic acid amide;
nonionic surfactant: LF-22115%, LF-4033%;
anionic surfactant: 15% of MAEP;
solubilizer: 8% of polysorbate;
defoaming agent: 1% of polyoxypropylene ethylene oxide glycerol ether;
49.5 percent of high-purity water, wherein the resistivity of the high-purity water at 25 ℃ is more than or equal to 18M omega cm, the total organic carbon is less than or equal to 50 mu g/L, the sodium ion is less than or equal to 1 mu g/L, the chloride ion is less than or equal to 1 mu g/L, and the silicon content is less than or equal to 10 mu g/L.
2. The preparation method of the water-based cleaning agent for the nuclear power equipment as claimed in claim 1, wherein the preparation method comprises the following steps: weighing the components according to the proportion, adding water into a reaction kettle at normal temperature and normal pressure, and then sequentially stirring and adding the inorganic salt cleaning auxiliary agent, the metal corrosion inhibitor, the nonionic surfactant, the anionic surfactant, the solubilizer and the defoaming agent.
3. The preparation method of the water-based cleaning agent for the nuclear power equipment as recited in claim 2, wherein when the components are added, the next component is added after one added component is completely dissolved.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109023398A (en) * | 2018-08-24 | 2018-12-18 | 深圳市天正隆科技有限公司 | A kind of cleaning agent and preparation method thereof and application method for ultrasonic wave spray |
| CN109023404A (en) * | 2018-08-27 | 2018-12-18 | 合肥绿洁环保科技有限公司 | A kind of antirust low foam metal cleaner |
| CN109136963A (en) * | 2018-09-07 | 2019-01-04 | 合肥绿洁环保科技有限公司 | A kind of fungi-proofing anti-corrosion cleaning agent of metal cleaning |
| CN109487283A (en) * | 2018-12-19 | 2019-03-19 | 长沙艾森设备维护技术有限公司 | Neutral anti-rust water-based cleaning agent and preparation method |
| CN115851382A (en) * | 2021-09-23 | 2023-03-28 | 河北轩屹电力科技有限公司 | Hydrophobic insulating cleaning agent and preparation method thereof |
| CN114747575B (en) * | 2022-05-17 | 2024-03-26 | 山东新华莎罗雅生物技术有限公司 | Peracetic acid disinfectant and preparation method thereof |
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| CN102605381A (en) * | 2012-03-31 | 2012-07-25 | 大连理工大学 | Washing passivation solution of surface iron pollution of austenitic stainless steel and preparation method thereof |
| CN103726042A (en) * | 2013-12-11 | 2014-04-16 | 三达奥克化学股份有限公司 | Treating agent for cleaning and performing coating conversion and rust prevention on inner wall of nuclear power plant used 559 ton acrylic acid reactor |
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| CN101538512B (en) * | 2009-03-11 | 2011-06-08 | 上海九盛实业有限公司 | Water-based cleaner |
| CN103774164A (en) * | 2014-02-20 | 2014-05-07 | 苏州龙腾万里化工科技有限公司 | Water-based metal-degreasing cleaning agent |
| CN105063644A (en) * | 2015-08-06 | 2015-11-18 | 苏州好洁清洁器具有限公司 | Preparation method of water-based cleaning agent for aluminum alloy pipe |
| CN106833993A (en) * | 2016-12-27 | 2017-06-13 | 东莞市先飞电子材料有限公司 | A kind of aqueous cleaning agent and preparation method thereof |
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|---|---|---|---|---|
| EP2378524A1 (en) * | 2010-04-15 | 2011-10-19 | Cristanini Spa | Decontamination/detoxification composition |
| CN102605381A (en) * | 2012-03-31 | 2012-07-25 | 大连理工大学 | Washing passivation solution of surface iron pollution of austenitic stainless steel and preparation method thereof |
| CN103726042A (en) * | 2013-12-11 | 2014-04-16 | 三达奥克化学股份有限公司 | Treating agent for cleaning and performing coating conversion and rust prevention on inner wall of nuclear power plant used 559 ton acrylic acid reactor |
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