CN114804460A - Electrochemical sterilization method for circulating cooling system - Google Patents
Electrochemical sterilization method for circulating cooling system Download PDFInfo
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- CN114804460A CN114804460A CN202210549181.8A CN202210549181A CN114804460A CN 114804460 A CN114804460 A CN 114804460A CN 202210549181 A CN202210549181 A CN 202210549181A CN 114804460 A CN114804460 A CN 114804460A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention belongs to the technical field of water treatment. The invention provides a method for electrochemically sterilizing a circulating cooling system, wherein a scale and corrosion inhibitor is added into circulating cooling water, so that circulating water runs under a high-salt condition, and the salinity is more than or equal to 7 per thousand; can improve the efficiency and the sterilization effect of the next step of electrolysis and replace the addition of chemical bactericide. The invention carries out electrolysis on the obtained high-salt cooling water, and chloride ions in the water can be oxidized into strong oxidizing radicals in the electrolysis process, thereby having the sterilization effect. The method greatly improves the treatment effect on the circulating cooling water system, reduces the use of chemical sterilization agents, can reduce ammonia nitrogen and COD (chemical oxygen demand) of circulating water, improves the water quality of the system and reduces the corrosion of equipment by combining the modes of adding the scale and corrosion inhibitor and electrolysis.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to an electrochemical sterilization method for a circulating cooling system.
Background
The circulating cooling water system is a water supply system, which uses water as a cooling medium and recycles the water. In the operation process, cold water flows through heat exchange equipment needing cooling, the water temperature of the cooling tower is cooled back after heat is taken away, and then the water is continuously used and is in circulation. The circulating cooling system avoids the one-time use of temperature-rising cold water, greatly reduces the consumption of fresh water and saves precious water resources. However, in the circulating cooling process, due to continuous evaporation and concentration, the concentration of various ions in water is multiplied, the circulating water is in a eutrophic state, bacteria and algae are easy to breed, and the sterilization and algae removal treatment is usually carried out by adding a chemical bactericide. Water treatment technology will also strive towards cleaner production, minimizing or avoiding the use of pharmaceutical agents, which will be a necessary trend in industry development. The invention provides an electrochemical sterilization technology, which replaces the use of chemical agents, utilizes the inherent chloride ions in the circulating water to convert the chloride ions into strong oxidizing radicals with sterilization effect through an electrochemical process, and realizes sterilization and algae removal.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an electrochemical sterilization method for a circulating cooling system.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an electrochemical sterilization method for a circulating cooling system, which comprises the following steps:
(1) adding a scale and corrosion inhibitor into the circulating cooling water to obtain high-salt cooling water;
(2) electrolyzing the high-salt cooling water to finish the treatment.
Preferably, the scale and corrosion inhibitor in the step (1) comprises the following components in parts by mass:
10-20 parts of acrylic acid-acrylamide copolymer, 1-9 parts of maleic anhydride-acrylamide copolymer, 2-6 parts of sodium acrylate-vinyl sulfonic acid copolymer, 0.5-2 parts of hexadecyl dimethyl benzyl ammonium chloride, 2-7 parts of acrylic acid-isopropenyl phosphoric acid copolymer and 55-85 parts of water.
Preferably, the adding amount of the scale and corrosion inhibitor in the step (1) is 20-50 mg/L.
Preferably, the salinity of the high-salinity cooling water in the step (1) is more than or equal to 7 per thousand.
Preferably, the electrolytic anode material surface coating in the step (2) is a titanium-based coating, and the titanium-based coating is a Ru-Ir-Ti-Sn coating or a graphene-Ru-Ir-Ti-Sn coating.
Preferably, the cathode material for electrolysis in step (2) is stainless steel, carbon steel or titanium plate.
Preferably, the current for electrolysis in the step (2) is 10-20A.
Preferably, the electrode distance of the electrolysis in the step (2) is 15-25 mm.
Preferably, the time for electrolysis in the step (2) is 15-25 min.
The invention provides an electrochemical sterilization method for a circulating cooling system, and a scale and corrosion inhibitor is added into circulating cooling water, so that circulating water runs under a high-salt condition, the next step of electrolysis efficiency and sterilization effect can be improved, and the addition of a chemical bactericide is avoided. The obtained high-salt cooling water is electrolyzed, chloride ions in the water can be oxidized into hypochlorite in the electrolysis process, and the hypochlorite is a strong oxidizing group and can kill bacteria in the water, so that the sterilization effect is achieved; meanwhile, the COD and ammonia nitrogen content in the circulating water are greatly reduced, the nutritive degree of water quality can be effectively reduced, and the condition for the growth and the propagation of bacteria caused by the fact that the circulating water is changed into eutrophic water is avoided. The method greatly improves the treatment effect of the circulating cooling water system by combining the modes of adding the scale and corrosion inhibitor and electrolysis, can reduce ammonia nitrogen and COD in water, reduce the concentration of corrosive chloride ions, reduce equipment corrosion, replace the addition of a bactericide, improve the quality of circulating cooling water and ensure the good and stable operation of the system.
Detailed Description
The invention provides an electrochemical sterilization method for a circulating cooling system, which comprises the following steps:
(1) adding a scale and corrosion inhibitor into the circulating cooling water to obtain high-salt cooling water;
(2) electrolyzing the high-salt cooling water to finish the treatment.
In the present invention, the scale and corrosion inhibitor in step (1) preferably comprises the following components in parts by mass:
10-20 parts of acrylic acid-acrylamide copolymer, 1-9 parts of maleic anhydride-acrylamide copolymer, 2-6 parts of sodium acrylate-vinyl sulfonic acid copolymer, 0.5-2 parts of hexadecyl dimethyl benzyl ammonium chloride, 2-7 parts of acrylic acid-isopropenyl phosphoric acid copolymer and 55-85 parts of water.
In the present invention, the acrylic acid-acrylamide copolymer is preferably 12 to 18 parts, more preferably 13 to 17 parts, and even more preferably 14 to 16 parts.
In the present invention, the maleic anhydride-acrylamide copolymer is preferably 2 to 8 parts, more preferably 3 to 7 parts, and even more preferably 4 to 6 parts.
In the present invention, the sodium acrylate-vinylsulfonic acid copolymer is preferably 3 to 5 parts, and more preferably 3.5 to 4.5 parts.
In the present invention, the cetyldimethylbenzylammonium chloride is preferably 0.6 to 1.8 parts, more preferably 0.8 to 1.6 parts, and even more preferably 1.0 to 1.4 parts.
In the present invention, the acrylic acid-isopropenylphosphoric acid copolymer is preferably 3 to 6 parts, more preferably 4 to 5 parts, and even more preferably 4.4 to 4.6 parts.
In the present invention, the water is preferably 60 to 80 parts, more preferably 65 to 75 parts, and still more preferably 70 parts.
In the invention, the invention also provides a preparation method of the scale and corrosion inhibitor, which comprises the following steps:
uniformly mixing acrylic acid-acrylamide copolymer, maleic anhydride-acrylamide copolymer and first part of water, and then adding sodium acrylate-vinyl sulfonic acid copolymer for mixing; adding the acrylic acid-isopropenyl phosphoric acid copolymer into the mixture, stirring until the mixture is uniformly mixed, adding the rest water, and stirring and uniformly mixing; adding hexadecyl dimethyl benzyl ammonium chloride and mixing uniformly to prepare the scale and corrosion inhibitor.
In the invention, the adding amount of the scale and corrosion inhibitor in the step (1) is preferably 20-50 mg/L, more preferably 25-45 mg/L, and even more preferably 30-40 mg/L.
In the present invention, the salinity of the high-salinity cooling water in step (1) is preferably equal to or greater than 7%, more preferably equal to or greater than 8%, and still more preferably equal to or greater than 9%.
In the invention, the electrolytic anode material surface coating in the step (2) is preferably a titanium-based coating, and the titanium-based coating is preferably a Ru-Ir-Ti-Sn coating or a graphene-Ru-Ir-Ti-Sn coating.
In the invention, the titanium-based coating has low chlorine evolution potential, can reduce the side reaction of the anode, improve the yield of active chlorine, improve the sterilization effect and reduce the energy consumption of electrolysis.
In the present invention, the cathode material for the electrolysis in step (2) is preferably a stainless steel, carbon steel or titanium plate.
In the present invention, the current for electrolysis in step (2) is preferably 10 to 20A, more preferably 12 to 18A, and still more preferably 14 to 16A.
In the present invention, the electrode pitch of the electrolysis in the step (2) is preferably 15 to 25mm, more preferably 17 to 23mm, and still more preferably 19 to 21 mm.
In the present invention, the time for the electrolysis in step (2) is preferably 15 to 25min, more preferably 16 to 24min, and still more preferably 18 to 22 min.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding a scale and corrosion inhibitor into the circulating cooling water in an amount of 30mg/L, wherein the scale and corrosion inhibitor comprises the following components in parts by mass: 15 parts of acrylic acid-acrylamide copolymer, 5 parts of maleic anhydride-acrylamide copolymer, 4 parts of sodium acrylate-vinyl sulfonic acid copolymer, 1 part of hexadecyl dimethyl benzyl ammonium chloride, 5 parts of acrylic acid-isopropenyl phosphoric acid copolymer and 70 parts of water; after adding the scale and corrosion inhibitor, the water quality is as shown in Table 1.
TABLE 1 Water quality Condition
| Water quality project | Data of |
| Salinity (‰) | 8.55 |
| Conductance (ms/cm) | 15.79 |
| Dissolved oxygen (mg/L) | 6.93 |
| Ca 2+ (mg/L) | 1814.1 |
| Total hardness (mg/L) | 4437.1 |
| Cl - (mg/L) | 2920.2 |
| Alkalinity (mg/L) | 100.8 |
| COD(mg/L) | 632.1 |
| Ammonia nitrogen (mg/L) | 29.16 |
Electrolyzing the high-salt cooling water, wherein the titanium-based coating on the anode material is a Ru-Ir-Ti-Sn coating, the cathode is stainless steel, the current is controlled to be 12A, the electrode spacing is 23mm, and electrolyzing for 23min to finish the treatment.
The water quality after electrolysis is as follows, the COD content is 346.1mg/L, and the removal rate is 45.2%; the ammonia nitrogen content is 7.44mg/L, and the removal rate is 74.5 percent; the content of chloride ions was 1722.92mg/L, and the removal rate was 41%.
Example 2
Adding a scale and corrosion inhibitor into the circulating cooling water in an amount of 40mg/L, wherein the scale and corrosion inhibitor comprises the following components in parts by mass: 18 parts of acrylic acid-acrylamide copolymer, 2 parts of maleic anhydride-acrylamide copolymer, 3 parts of sodium acrylate-ethylene sulfonic acid copolymer, 1.8 parts of hexadecyl dimethyl benzyl ammonium chloride, 2.5 parts of acrylic acid-isopropenyl phosphoric acid copolymer and 60 parts of water; after adding the scale and corrosion inhibitor, the water quality is as shown in Table 2.
TABLE 2 Water quality conditions
| Water quality project | Data of |
| Salinity (‰) | 7.86 |
| Conductance (ms/cm) | 14.32 |
| Dissolved oxygen (mg/L) | 6.98 |
| Ca 2+ (mg/L) | 1921.3 |
| Total hardness (mg/L) | 4327.6 |
| Cl - (mg/L) | 2834.5 |
| Alkalinity (mg/L) | 98.7 |
| COD(mg/L) | 627.8 |
| Ammonia nitrogen (mg/L) | 30.4 |
Electrolyzing the high-salt cooling water, wherein the titanium-based coating on the anode material is a graphene-Ru-Ir-Ti-Sn coating, the cathode is carbon steel, the current is controlled to be 15A, the electrode spacing is 18mm, and the treatment is completed after 20min of electrolysis.
The water quality after electrolysis is as follows, the COD content is 328.7mg/L, and the removal rate is 47.6 percent; the ammonia nitrogen content is 7.86mg/L, and the removal rate is 74.1 percent; the content of chloride ions was 1657.3mg/L, and the removal rate was 41.53%.
Example 3
Adding a scale and corrosion inhibitor into the circulating cooling water in an amount of 25mg/L, wherein the scale and corrosion inhibitor comprises the following components in parts by mass: 17 parts of acrylic acid-acrylamide copolymer, 7 parts of maleic anhydride-acrylamide copolymer, 5.3 parts of sodium acrylate-vinyl sulfonic acid copolymer, 1.6 parts of hexadecyl dimethyl benzyl ammonium chloride, 6 parts of acrylic acid-isopropenyl phosphoric acid copolymer and 80 parts of water; after adding the scale and corrosion inhibitor, the water quality is as shown in Table 3.
TABLE 3 Water quality conditions
Electrolyzing the high-salt cooling water, wherein the titanium-based coating on the anode material is a graphene-Ru-Ir-Ti-Sn coating, the cathode is stainless steel, the current is controlled to be 17A, the electrode spacing is 20mm, and the treatment is completed after 16min of electrolysis.
The water quality after electrolysis is as follows, the COD content is 318.7mg/L, and the removal rate is 50.7%; the ammonia nitrogen content is 7.15mg/L, and the removal rate is 74.7 percent; the content of chloride ions is 1637.4mg/L, and the removal rate is 40.23%.
Example 4
Adding a scale and corrosion inhibitor into the circulating cooling water in an amount of 22mg/L, wherein the scale and corrosion inhibitor comprises the following components in parts by mass: 12 parts of acrylic acid-acrylamide copolymer, 8.5 parts of maleic anhydride-acrylamide copolymer, 2 parts of sodium acrylate-vinyl sulfonic acid copolymer, 0.5 part of hexadecyl dimethyl benzyl ammonium chloride, 7 parts of acrylic acid-isopropenyl phosphoric acid copolymer and 84 parts of water; after adding the scale and corrosion inhibitor, the water quality is as shown in Table 4.
TABLE 4 Water quality conditions
Electrolyzing the high-salt cooling water, wherein the titanium-based coating on the anode material is a graphene-Ru-Ir-Ti-Sn coating, the cathode is a titanium plate, the current is controlled to be 19A, the electrode spacing is 15mm, and the treatment is completed after 23min of electrolysis.
The water quality after electrolysis is as follows, the COD content is 338.2mg/L, and the removal rate is 48.53 percent; the ammonia nitrogen content is 5.27mg/L, and the removal rate is 82.2%; the content of chloride ions is 1449.7mg/L, and the removal rate is 48.3%.
According to the embodiment, the invention provides the electrochemical sterilization method for the circulating cooling system, and the scale and corrosion inhibitor is added and the electrolysis mode is combined, so that chloride ions in water can be oxidized into hypochlorite in the electrolysis process to achieve the sterilization effect; the COD and ammonia nitrogen content in the circulating water are greatly reduced, the nutrition degree of the water quality can be effectively reduced, and the circulating water is prevented from being changed into eutrophic water body, so that conditions are brought to the growth and the propagation of bacteria; the method provided by the invention greatly improves the treatment effect on the circulating cooling water system. According to the conditions of the embodiment, the treatment method provided by the invention has the advantages that the removal rate of COD is up to 50.7%, the removal rate of ammonia nitrogen is up to 82.2%, the removal rate of chloride ions is up to 48.3%, the concentration of corrosive chloride ions is reduced, the corrosion of equipment is reduced, the addition of a bactericide is replaced, the quality of circulating cooling water is improved, and the good and stable operation of a system is guaranteed.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A method for electrochemically sterilizing a recirculating cooling system, comprising the steps of:
(1) adding a scale and corrosion inhibitor into the circulating cooling water to obtain high-salt cooling water;
(2) electrolyzing the high-salt cooling water to finish the treatment.
2. The method of claim 1, wherein the scale and corrosion inhibitor in the step (1) comprises the following components in parts by mass:
10-20 parts of acrylic acid-acrylamide copolymer, 1-9 parts of maleic anhydride-acrylamide copolymer, 2-6 parts of sodium acrylate-vinyl sulfonic acid copolymer, 0.5-2 parts of hexadecyl dimethyl benzyl ammonium chloride, 2-7 parts of acrylic acid-isopropenyl phosphoric acid copolymer and 55-85 parts of water.
3. The method of claim 1 or 2, wherein the scale and corrosion inhibitor is added in the amount of 20-50 mg/L in step (1).
4. The method of claim 3, wherein the salinity of the high-salinity cooling water in the step (1) is greater than or equal to 7 per thousand.
5. The method of claim 1 or 4, wherein the electrolytic anode material surface coating in step (2) is a titanium-based coating, and the titanium-based coating is a Ru-Ir-Ti-Sn coating or a graphene-Ru-Ir-Ti-Sn coating.
6. The method of claim 5, wherein the cathode material for electrolysis in step (2) is stainless steel, carbon steel or titanium plate.
7. The method of claim 6, wherein the electrolysis current in step (2) is 10-20A.
8. The method of claim 1, 2, 4, 6 or 7, wherein the electrode spacing for the electrolysis in step (2) is 15 to 25 mm.
9. The method of claim 8, wherein the time for the electrolysis in step (2) is 15 to 25 min.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08164390A (en) * | 1991-04-30 | 1996-06-25 | Konica Corp | Electrochemical treatment of water to be treated |
| JP2005200721A (en) * | 2004-01-16 | 2005-07-28 | Hakuto Co Ltd | Treatment method for open circulating cooling water system |
| JP2006098003A (en) * | 2004-09-30 | 2006-04-13 | Kurita Water Ind Ltd | Electrolytic treating method and electrolytic treating device for circulating type cooling water system |
| CN105819594A (en) * | 2015-01-09 | 2016-08-03 | 中国石油化工股份有限公司 | Recirculated cooling water processing method |
| WO2019050079A1 (en) * | 2017-09-06 | 2019-03-14 | (주) 테크로스 | Water treatment apparatus for simultaneously generating hydrogen peroxide and hypochlorite ion |
| CN110183012A (en) * | 2019-06-25 | 2019-08-30 | 河北省科学院能源研究所 | A kind of method for treating circulating cooling water |
| CN114032582A (en) * | 2021-11-02 | 2022-02-11 | 广州新奥环境技术有限公司 | Sodium hypochlorite generator scale inhibitor and scale inhibition method |
-
2022
- 2022-05-20 CN CN202210549181.8A patent/CN114804460A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08164390A (en) * | 1991-04-30 | 1996-06-25 | Konica Corp | Electrochemical treatment of water to be treated |
| JP2005200721A (en) * | 2004-01-16 | 2005-07-28 | Hakuto Co Ltd | Treatment method for open circulating cooling water system |
| JP2006098003A (en) * | 2004-09-30 | 2006-04-13 | Kurita Water Ind Ltd | Electrolytic treating method and electrolytic treating device for circulating type cooling water system |
| CN105819594A (en) * | 2015-01-09 | 2016-08-03 | 中国石油化工股份有限公司 | Recirculated cooling water processing method |
| WO2019050079A1 (en) * | 2017-09-06 | 2019-03-14 | (주) 테크로스 | Water treatment apparatus for simultaneously generating hydrogen peroxide and hypochlorite ion |
| CN110183012A (en) * | 2019-06-25 | 2019-08-30 | 河北省科学院能源研究所 | A kind of method for treating circulating cooling water |
| CN114032582A (en) * | 2021-11-02 | 2022-02-11 | 广州新奥环境技术有限公司 | Sodium hypochlorite generator scale inhibitor and scale inhibition method |
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| 刘智安: "《工业循环冷却水处理》", 30 September 2017, 中国轻工业出版社, pages: 164 * |
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