阅读说明：本技术 适用于高炉密闭循环水的复合杀菌剂及制备、使用方法 (Composite bactericide suitable for blast furnace closed circulating water and preparation and use methods thereof ) 是由 王坤鹏 孙辉 胡文军 陶贵立 张宇 李红 陈奇 于 2021-09-06 设计创作，主要内容包括：适用于高炉密闭循环水的复合杀菌剂及制备、使用方法,所述复合杀菌剂包括复合剂A、混合剂B；所述复合剂A的组成成分及重量份数为：高铁酸钾10-35份、碳酸钠25-45份、去离子水30-60份；所述混合剂B的组成成分及重量份数为：棉隆5-18份、福美钠10-30份、二乙基羟胺8-28份、去离子水20-45份。该复合杀菌剂投加量少、杀菌效率高、适用于PH在10以上的高炉闭路循环冷却水系统,该药剂本身低毒、易降解、杀菌效率高、抑菌时间长,在168h后杀菌效率仍有99.4％,适用于高炉闭路循环冷却水系统使用。(The composite bactericide suitable for the closed circulating water of the blast furnace and the preparation and use methods thereof, wherein the composite bactericide comprises a complexing agent A and a mixing agent B; the complexing agent A comprises the following components in parts by weight: 10-35 parts of potassium ferrate, 25-45 parts of sodium carbonate and 30-60 parts of deionized water; the mixture B comprises the following components in parts by weight: 5-18 parts of dazomet, 10-30 parts of sodium ferbamate, 8-28 parts of diethylhydroxylamine and 20-45 parts of deionized water. The composite bactericide has the advantages of small dosage, high sterilization efficiency, suitability for a blast furnace closed-loop circulating cooling water system with the PH of more than 10, low toxicity, easy degradation, high sterilization efficiency and long bacteriostasis time, the sterilization efficiency is still 99.4 percent after 168 hours, and the composite bactericide is suitable for the blast furnace closed-loop circulating cooling water system.)

1. The composite bactericide suitable for the closed circulating water of the blast furnace is characterized by comprising a complexing agent A and a mixing agent B;

the complexing agent A comprises the following components in parts by weight: 10-35 parts of potassium ferrate, 25-45 parts of sodium carbonate and 30-60 parts of deionized water;

the mixture B comprises the following components in parts by weight: 5-18 parts of dazomet, 10-30 parts of sodium ferbamate, 8-28 parts of diethylhydroxylamine and 20-45 parts of deionized water.

2. The preparation method of the composite bactericide suitable for the blast furnace closed circulating water as claimed in claim 1, characterized by comprising the following steps:

1) preparing a complexing agent A: mixing and stirring sodium carbonate and deionized water at normal temperature for 10-20 min, adding potassium ferrate, regulating the rotation speed to 5-20r/min, continuously stirring for 30-40 min, and uniformly mixing to obtain a complexing agent A;

2) preparing a mixture B: heating deionized water to 70-90 ℃, sequentially adding diethylhydroxylamine, dazomet and sodium ferbamate into the deionized water, wherein the interval between the addition of each component is 20-30 minutes, keeping the heating temperature at 70-90 ℃ in the adding process, continuously stirring, mixing and stirring all the components for 20-30 minutes after adding, and obtaining the complexing agent B.

3. The use method of the composite bactericide suitable for blast furnace closed circulating water according to claim 1, wherein the composite bactericide A is added at a water inlet pipe of a blast furnace closed circulating water system at a ratio of 10-30mg/L, and after the operation is carried out for 2-4 hours, the composite bactericide B is added at a water return pipe of the blast furnace closed circulating water system at a ratio of 20-50mg/L, and the operation is continuously carried out for 24 hours, 72 hours, 120 hours and 168 hours.

Technical Field

The invention relates to the technical field of water treatment, in particular to a composite bactericide suitable for closed circulating water of a blast furnace and preparation and use methods thereof.

Background

The corrosion inhibitor used in the domestic blast furnace closed-circuit circulating cooling water system mainly comprises nitrite and a compound thereof, the nitrite has low price and has a certain corrosion inhibition effect, and is widely used, but in long-term use, because a large amount of nitrate is easy to breed nitrobacteria, the excessive breeding of the nitrobacteria can cause the pH value of circulating water to be reduced, the corrosion rate to be increased, the equipment corrosion is caused by electrochemistry, and in order to inhibit the nitrobacteria, alkali is generally added into the water in the industry to increase the pH value to more than 10, so that the nitrobacteria can be effectively inhibited. Although the method inhibits nitrifying bacteria, part of microorganisms can exist under high alkalinity, and harm a closed-loop circulating cooling water system of the blast furnace, and a small amount of bactericide needs to be added for treatment.

At present, the bactericides of the blast furnace closed-loop circulating cooling water system mostly adopt non-oxidizing bactericides, common non-oxidizing bactericides such as quaternary ammonium salts and glutaraldehyde are applicable to PH generally less than 9, the sterilization effect is ideal, the general non-oxidizing bactericides used in the blast furnace closed circulating water system with PH above 10 can be hydrolyzed at an accelerated speed, the sterilization efficiency is greatly reduced, the treatment effect is not ideal enough, the sterilization efficiency is improved only by adopting a mode of increasing the adding amount, but the mode not only causes the waste of medicaments, but also is not economical and practical.

Disclosure of Invention

The invention aims to provide a composite bactericide suitable for closed circulating water of a blast furnace and preparation and use methods thereof, the composite bactericide has the advantages of small dosage, high sterilization efficiency, suitability for a closed circulating cooling water system of the blast furnace with the PH of more than 10, low toxicity, easy degradation, high sterilization efficiency, long bacteriostasis time, 99.4 percent of sterilization efficiency after 168 hours, and suitability for the closed circulating cooling water system of the blast furnace.

In order to achieve the purpose, the invention adopts the following technical scheme:

the composite bactericide is suitable for closed circulating water of a blast furnace, and comprises a complexing agent A and a mixing agent B;

the complexing agent A comprises the following components in parts by weight: 10-35 parts of potassium ferrate, 25-45 parts of sodium carbonate and 30-60 parts of deionized water;

the mixture B comprises the following components in parts by weight: 5-18 parts of dazomet, 10-30 parts of sodium ferbamate, 8-28 parts of diethylhydroxylamine and 20-45 parts of deionized water.

The preparation method of the composite bactericide suitable for the closed circulating water of the blast furnace comprises the following steps:

1) preparing a complexing agent A: mixing and stirring sodium carbonate and deionized water at normal temperature for 10-20 min, slowly adding potassium ferrate, regulating the rotation speed to 5-20r/min, continuously stirring for 30-40 min, and uniformly mixing to obtain a complexing agent A;

2) preparing a mixture B: heating deionized water to 70-90 ℃, sequentially adding diethylhydroxylamine, dazomet and sodium ferbamate into the deionized water, wherein the diethylhydroxylamine is alkaline after being dissolved, the subsequent added dazomet can be promoted to be dissolved, then adding the sodium ferbamate into the deionized water to completely fuse the medicaments, the interval between each addition of one component is 20-30 minutes, the heating temperature is kept at 70-90 ℃ in the adding process, continuously stirring is carried out, and after all the components are added, mixing and stirring are carried out for 20-30 minutes, so that the complexing agent B is obtained.

A method for using a composite bactericide suitable for blast furnace closed circulating water comprises the steps of adding a complexing agent A10-30mg/L at a water inlet pipe of a blast furnace closed circulating water system, adding a mixing agent B20-50mg/L at a water return pipe of the blast furnace closed circulating water system after running for 2-4 hours, continuously running for 24 hours, 72 hours, 120 hours and 168 hours, taking water to measure the total number of bacterial colonies in the water, and evaluating the sterilizing effect of the composite bactericide.

The complexing agent A is quite stable after being compounded by potassium ferrate, sodium carbonate and water, has no toxic or side effect, and is dissolved in water to generate Fe (OH) under the alkaline condition that the PH is more than or equal to 10₃The composite agent A can adsorb various anions and cations, simultaneously has strong oxidation performance to remove microorganisms in water, has obvious sterilization effect, has the effect of regulating pH value, and ensures that the effect of the composite agent A is more stable, and the contents of the composite agent A are 10-35 parts of potassium ferrate, 25-45 parts of sodium carbonate and 30-60 parts of deionized water.

The potassium ferrate has excellent sterilization, decoloration, deodorization and purification effects, is stable and not easy to decompose in a strong alkaline solution, is nontoxic, and is suitable for sterilization under high pH.

The mixing agent B is compounded by 5-18 parts of dazomet, 10-30 parts of sodium ferulate, 8-28 parts of diethylhydroxylamine and 20-45 parts of deionized water, wherein the dazomet and the sodium ferulate have the characteristics of stability under high pH, obvious effect of inhibiting slime microorganisms in water and coordination and synergism, the diethylhydroxylamine can remove oxygen in water to inhibit growth of nitrobacteria and form a passivation film on the surface of metal, and the diethylhydroxylamine has double effects of oxygen removal and protection.

The solubility of the dazomet is greatly influenced by the temperature, is 0.12 percent in water at 30 ℃, is kept at 70-90 ℃ when the mixture B is prepared, can ensure that the dazomet is completely dissolved, and can achieve the best using effect when being mixed with other components for use.

The sodium ferbamate is very soluble in water, can improve the sterilization effect by being compounded with the dazomet, has the coordination and synergism effect between the sodium ferbamate and the dazomet and has stable performance.

The composite bactericide comprises a complexing agent A and a mixing agent B, wherein the use method adopts a dosing mode of firstly adding the complexing agent A and then adding the mixing agent B, the main reason is that the temperatures of all parts of a blast furnace are inconsistent, so that the PH values of all parts of the blast furnace are high, low and unevenly distributed, the PH values of all parts of the blast furnace can be stabilized to be more than 10 by firstly adding the complexing agent A, microorganisms are removed once, and then the mixing agent B is added, so that a better use effect can be achieved.

Compared with the prior art, the invention has the beneficial effects that:

1) the bactericide is suitable for being used in a blast furnace closed circulating water system with the pH value of more than or equal to 10, and has higher sterilizing efficiency and longer bacteriostasis time than the traditional bactericide.

2) The bactericide disclosed by the invention is low in toxicity, easy to degrade and high in sterilization efficiency, and experiments prove that the bactericide still has a good sterilization effect after 168 hours, and the sterilization efficiency is 99.4%.

3) The bactericide of the invention, namely the dazomet and the thiram, has the characteristic of stability under high PH, has the coordination and synergism effect, and the bacteriostasis effect is better than that of the dazomet and the thiram which are used independently.

4) The bactericide disclosed by the invention is convenient to prepare, the application method can exert the maximum sterilization efficiency, the usage amount is small, the cost is low, and the long-term storage stability is good.

Detailed Description

The present invention will be described in detail with reference to examples, but it should be noted that the practice of the present invention is not limited to the following embodiments.

Example 1:

a composite bactericide suitable for blast furnace closed circulating water comprises a complexing agent A and a mixing agent B, wherein the complexing agent A comprises the following components in parts by weight: 15 parts of potassium ferrate, 40 parts of sodium carbonate and 45 parts of deionized water. The mixture B comprises the following components in parts by weight: 15 parts of dazomet, 12 parts of sodium ferbamate, 26 parts of diethylhydroxylamine and 25 parts of deionized water.

The preparation method of the composite bactericide of the embodiment specifically comprises the following operations:

1) compounding agent A: mixing and stirring sodium carbonate and deionized water for 10 minutes at normal temperature, slowly adding potassium ferrate, reducing the rotating speed to 20r/min, continuously stirring for 30 minutes, and uniformly mixing to obtain a complexing agent A;

2) mixture B: heating deionized water to 80 ℃, sequentially adding diethylhydroxylamine, dazomet and sodium ferbamate into the deionized water, keeping the heating temperature at 80 ℃ in the adding process, continuously stirring the mixture for 25 minutes after all the components are added in consideration of thorough medicament fusion, and obtaining the complexing agent B.

A use method of a composite bactericide suitable for blast furnace closed circulating water comprises the following specific operations:

20mg/L of complexing agent A is added at a water inlet pipe of a closed circulating water system of the blast furnace, 35mg/L of mixing agent B is added at a water return pipe of the closed circulating water system of the blast furnace after the closed circulating water system of the blast furnace operates for 3 hours, and the closed circulating water system of the blast furnace continuously operates for 24 hours, 72 hours, 120 hours and 168 hours.

Taking water to measure the total number of bacterial colonies in water for evaluating the sterilization effect of the composite bactericide, wherein the experimental water quality conditions are that the pH is 10.22, the conductivity is 1385 mu s/cm, the total hardness is 154mg/L (calculated by calcium carbonate), and the calcium hardness is 92mg/L (calculated as calcium carbonate), Cl^-143mg/L, total number of colonies 3.4X 10⁴CFU·ml^-1The bactericidal effect is shown in table 1 below.

Table 1: EXAMPLE 1 Bactericidal Effect

As can be seen from Table 1, the composite bactericide has excellent effect and long bactericidal action maintaining time, the bactericidal efficiency can still reach 99.7 percent after 168 hours of use, the effect of inhibiting microorganisms is remarkable, and the composite bactericide can be applied to a blast furnace closed circulating water system with the pH value of more than or equal to 10.

Example 2:

a composite bactericide suitable for blast furnace closed circulating water comprises a complexing agent A and a mixing agent B, wherein the complexing agent A comprises the following components in parts by weight: 25 parts of potassium ferrate, 30 parts of sodium carbonate and 30 parts of deionized water. The mixture B comprises the following components in parts by weight: 7 parts of dazomet, 28 parts of sodium ferbamate, 18 parts of diethylhydroxylamine and 30 parts of deionized water.

The preparation method of the composite bactericide of the embodiment specifically comprises the following operations:

1) compounding agent A: mixing and stirring sodium carbonate and deionized water for 20 minutes at normal temperature, slowly adding potassium ferrate, reducing the rotating speed to 5r/min, continuously stirring for 40 minutes, and uniformly mixing to obtain a complexing agent A;

2) mixture B: heating deionized water to 70 ℃, sequentially adding diethylhydroxylamine, dazomet and sodium ferbamate into the deionized water, keeping the heating temperature at 70 ℃ in the adding process and continuously stirring in consideration of thorough medicament fusion, and mixing and stirring all the components for 20 minutes after adding to obtain the complexing agent B.

A use method of a composite bactericide suitable for blast furnace closed circulating water comprises the following specific operations:

30mg/L of complexing agent A is added at a water inlet pipe of a closed circulating water system of the blast furnace, 20mg/L of mixing agent B is added at a water return pipe of the closed circulating water system of the blast furnace after 2 hours of operation, and the operation is continuously carried out for 24 hours, 72 hours, 120 hours and 168 hours.

Taking water to measure the total number of colonies in the water for evaluating the sterilization effect of the composite bactericide, wherein the experimental water quality conditions are that the pH is 10.78, the electric conductivity is 1621 mu s/cm, the total hardness is 124mg/L (calculated by calcium carbonate), the calcium hardness is 75mg/L (calculated by calcium carbonate), and Cl^-120mg/L, total number of colonies 2.8X 10⁴CFU·ml^-1The bactericidal effect is shown in table 2 below.

Table 2: examples sterilizing effects

As can be seen from Table 2, the composite bactericide has excellent effect and long bactericidal action maintaining time, the bactericidal efficiency can still reach 99.6 percent after 168 hours of use, the effect of inhibiting microorganisms is remarkable, and the composite bactericide can be applied to a blast furnace closed circulating water system with the pH value of more than or equal to 10.

Example 3:

a composite bactericide suitable for blast furnace closed circulating water comprises a complexing agent A and a mixing agent B, wherein the complexing agent A comprises the following components in parts by weight: 30 parts of potassium ferrate, 30 parts of sodium carbonate and 60 parts of deionized water. The mixture B comprises the following components in parts by weight: 10 parts of dazomet, 20 parts of sodium ferbamate, 8 parts of diethylhydroxylamine and 45 parts of deionized water.

The preparation method of the composite bactericide of the embodiment specifically comprises the following operations:

1) compounding agent A: mixing and stirring sodium carbonate and deionized water for 15 minutes at normal temperature, slowly adding potassium ferrate, reducing the rotating speed to 10r/min, continuously stirring for 35 minutes, and uniformly mixing to obtain a complexing agent A;

2) mixture B: heating deionized water to 90 ℃, sequentially adding diethylhydroxylamine, dazomet and sodium ferbamate into the deionized water, keeping the heating temperature at 90 ℃ during the addition process, continuously stirring the mixture in consideration of thorough medicament fusion, and mixing and stirring all the components for 30 minutes after the components are added to obtain the complexing agent B.

A use method of a composite bactericide suitable for blast furnace closed circulating water comprises the following specific operations:

adding a complexing agent A10mg/L at a water inlet pipe of a closed circulating water system of the blast furnace, adding a mixing agent B50 mg/L at a water return pipe of the closed circulating water system of the blast furnace after running for 4 hours, and continuously running for 24 hours, 72 hours, 120 hours and 168 hours.

Taking water to measure the total number of colonies in the water for evaluating the sterilization effect of the composite bactericide, wherein the experimental water quality conditions are that the PH is 10.55, the electric conductivity is 1328 mu s/cm, the total hardness is 155mg/L (calculated by calcium carbonate), the calcium hardness is 86mg/L (calculated by calcium carbonate), and the Cl^-117mg/L, total number of colonies 3.2X 10⁴CFU·ml^-1The bactericidal effect is shown in table 3 below.

Table 3: EXAMPLE 3 Bactericidal Effect

As can be seen from Table 3, the composite bactericide has excellent effect and long bactericidal action maintaining time, the bactericidal efficiency can still reach 99.5 percent after 168 hours of use, the effect of inhibiting microorganisms is remarkable, and the composite bactericide can be applied to a blast furnace closed circulating water system with the pH value of more than or equal to 10.

Example 4:

the composite bactericide of the invention has the following bactericidal effects compared with isothiazolinone, dithiocyano-methane and glutaraldehyde:

the sterilization experiment is carried out when the PH value of the blast furnace closed-loop circulating cooling water system is more than or equal to 10, the water quality condition of the experiment is that the PH value is 10.43, the conductivity is 1762 mu s/cm, the total hardness is 146mg/L (calculated by calcium carbonate), the calcium hardness is 90mg/L (calculated by calcium carbonate), and Cl^-134mg/L, total number of colonies 2.6X 10⁴CFU·ml^-1Comparison of example 1, example 2 and example 3 with isothiazolinone, dithiocyano-methane and glutaraldehyde at a concentration of 70mg/L for sterilization after 168hThe results are shown in Table 4.

Table 4: example 4 comparative results

From table 4, it can be seen that the implementation effects of the formulations of the examples 1, 2 and 3 are better than those of the existing bactericides isothiazolinone, dithiocyano-methane and glutaraldehyde, wherein the sterilization effect of the example 1 can reach 99.7%, and the sterilization and bacteriostasis effects are significant.

Example 5:

sterilization coordination synergism experiment:

the sterilization experiment is carried out when the PH value of the blast furnace closed-loop circulating cooling water system is more than or equal to 10, and the water quality conditions of the experiment are that the PH value is 10.05, the conductivity is 1352 mu s/cm, the total hardness is 135mg/L (calculated as calcium carbonate), the calcium hardness is 75mg/L (calculated as calcium carbonate), and Cl^-110mg/L, total number of colonies 3.8X 10⁴CFU·ml^-1The bactericidal performance of the dazomet, the thiram and the mixture B after 168 hours is compared when the concentration of the dazomet, the thiram and the mixture B is 30mg/L, and the experimental results are shown in Table 5.

From table 5, it can be seen that the bactericidal effect of the mixture B is better than the best bactericidal effect of the single use of the dazomet and the sodium ferbamate, which indicates that the dazomet and the sodium ferbamate are compounded and used together, and have a coordination and synergism effect.