A water treatment agent for circulating cooling water with high concentration ratio

Abstract

This application relates to the technical field of water treatment agents, and in particular to a water treatment agent for high-concentration-ratio circulating cooling water. This water treatment agent for high-concentration-ratio circulating cooling water comprises the following substances in parts by weight: 10-50 parts of an acrylic acid sulfonate multi-component copolymer; 10-50 parts of a polymer; 0.5-10 parts of zinc chloride; and 1-50 parts of water. This application optimizes the composition of the water treatment agent for high-concentration-ratio circulating cooling water, leveraging the excellent dispersibility, threshold effect, and synergistic effect of the acrylic acid sulfonate multi-component copolymer and the polymer to improve the scale inhibition performance of the scale inhibitor.

Description

Technical Field

[0001] The present application relates to the technical field of water treatment agents, and in particular to a water treatment agent for circulating cooling water with a high concentration ratio. Background Art

[0002] During operation, industrial circulating cooling water systems continuously concentrate the circulating water due to factors such as evaporation and air drying. This leads to increasing salt concentrations in the water, severe scaling and corrosion, reduced heat transfer efficiency, shortened equipment life, and significantly increased water usage. To conserve water usage, extend equipment life, and meet environmentally friendly drainage requirements, a series of industrial circulating water treatment agents have been developed.

[0003] Since the existing industrial circulating cooling water requires the use of high concentration ratio (concentration ratio ≥ 20) agents, but the existing high concentration ratio agents are not well studied, resulting in defects in the products developed therein. For example, the patent with the prior art publication number CN201910133328.3: A corrosion and scale inhibitor for high concentration ratio circulating water, this patent provides a corrosion and scale inhibitor for high concentration ratio circulating water. This invention patent also develops a kind of agent with good scale inhibition and slow release performance at high concentration ratio (concentration ratio ≥ 10), but the formula contains a high phosphorus content, which does not meet the requirements of environmental protection development. As time accumulates, the residual phosphorus will gradually cause eutrophication of the water body and the proliferation of algae. At the same time, in the corrosion test, the corrosion rate of carbon steel is barely up to standard, and there are certain hidden dangers in the corrosion performance of carbon steel containers in the actual production process.

[0004] In view of the above-mentioned prior art, the inventors found that the existing circulating water treatment agents at high concentration rates have poor stability, corrosion inhibition and scale inhibition, and the dosage is large. They contain non-environmentally friendly elements, which can easily cause water pollution and eutrophication. Summary of the Invention

[0005] In order to improve the defects of existing circulating water treatment agents at high concentration rates, such as poor stability, corrosion inhibition and scale inhibition, and large dosage, the present application provides a high concentration rate circulating cooling water treatment agent.

[0006] The present application provides a high concentration ratio circulating cooling water treatment agent, which adopts the following technical solution: a high concentration ratio circulating cooling water treatment agent, comprising the following substances in parts by weight:

[0007] 10-50 parts of acrylic acid sulfonate multipolymer;

[0008] 10-50 parts of polymer;

[0009] 0.5-10 parts of zinc chloride;

[0010] 1 to 50 parts of water.

[0011] By adopting the above-mentioned technical solution, the present application optimizes the composition of a water treatment agent for high-concentration circulating cooling water, utilizing the excellent dispersibility, threshold effect, and synergistic effect of the acrylic acid sulfonate multi-polymer and the polymer to improve the scale inhibition performance of the scale inhibitor. Because the long-chain anions present in the water treatment agent can cause scale-forming crystals to grow in a deformed direction, thereby inhibiting crystal growth, the deposition of crystals such as calcium carbonate and calcium phosphate can be effectively prevented in water with high hardness and high alkalinity. This reduces the amount of water treatment agent used and improves the stable corrosion and scale inhibition performance of the water treatment agent at high concentration rates.

[0012] Furthermore, the present invention uses zinc ions in zinc chloride as a cathode corrosion inhibitor to inhibit the cathode reaction during the corrosion process, thereby further improving the scale inhibition effect of the water treatment agent.

[0013] Preferably, the water treatment agent for high concentration ratio circulating cooling water comprises the following substances in parts by weight:

[0014] 45 parts of acrylic acid sulfonate multipolymer;

[0015] 22 parts of polymer;

[0016] 2.5 parts of zinc chloride;

[0017] 1.5 parts water.

[0018] By adopting the above technical solution, the present application further optimizes the components of the water treatment agent for high concentration ratio circulating cooling water, thereby further improving the stability, corrosion and scale inhibition and effectiveness of the water treatment agent prepared in the present application.

[0019] Preferably, the water treatment agent for high concentration ratio circulating cooling water further comprises 0.5 to 10 parts by weight of an organic matter, wherein the organic matter comprises benzotriazole.

[0020] By adopting the above technical solution, the present application modifies the water treatment agent by adding benzotriazole. Due to the synergistic effect of benzotriazole and zinc ions, the deposition of metal is inhibited, achieving the effect of corrosion inhibition, thereby further improving the corrosion inhibition performance of the water treatment agent on metal materials.

[0021] Preferably, the polymer comprises hydrolyzed polymaleic acid.

[0022] By adopting the above-mentioned technical solution, the present application inhibits the growth of grains through the dispersing effect of hydrolyzed polymaleic acid and combines it with the synergistic modification of acrylic acid sulfonate multipolymer. It can effectively prevent the deposition of crystals such as calcium carbonate and calcium phosphate in water with high hardness and high alkalinity, and achieve good scale inhibition effect.

[0023] Preferably, the water treatment agent for high concentration ratio circulating cooling water further comprises 5 to 15 parts by weight of an auxiliary film-forming agent, and the hydrophilic auxiliary film-forming agent comprises tannic acid and humic acid mixed in a mass ratio of 1:3.5 to 4.5.

[0024] By adopting the above technical solution, this application further optimizes the components of the water treatment agent. By adding an auxiliary film-forming agent, it can simultaneously inhibit scale and corrosion while also coating the surface with a protective layer, effectively improving the durability and long-term performance of the scale and corrosion inhibition. The effective combination of tannic acid and humic acid allows the humic acid to effectively fill the holes in the protective layer formed by the tannic acid coating, further improving the defect of poor corrosion inhibition caused by tannic acid alone.

[0025] Preferably, the humic acid is a highly concentrated modified humic acid, which is prepared by the following method:

[0026] Take humic acid and add sodium hydroxide solution dropwise, stir and mix, then add sulfonating agent, stir and mix, adjust pH to 10, keep warm for reaction and let stand to cool to room temperature;

[0027] The reactants are collected and centrifuged, the centrifuge liquid is collected and the pH value is adjusted to 2.0, the filtrate is centrifuged again, and the filtrate is dried and ground to prepare the high concentration ratio modified humic acid.

[0028] By adopting the above technical solution, the present application further modifies humic acid and makes the water solubility of humic acid even better through sulfonation treatment. On the one hand, it can effectively improve the integrity of the hydrophilic auxiliary film-forming agent coating in water; on the other hand, the further improvement of water solubility also further improves the dispersibility of the water treatment agent in water, so that it has stable corrosion and scale inhibition performance when used at a high concentration ratio.

[0029] Preferably, the acrylic acid sulfonate multipolymer includes acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer.

[0030] Preferably, the water treatment agent for high concentration ratio circulating cooling water further comprises 1 to 10 parts by weight of sulfuric acid.

[0031] By adopting the above technical solution, the present application adjusts the pH of the water treatment agent so that the agent is in reasonable reaction conditions and at the same time makes the agent meet the requirements of production and transportation.

[0032] In summary, this application has the following beneficial effects:

[0033] First, this application optimizes the composition of a water treatment agent for high-concentration circulating cooling water, leveraging the excellent dispersibility, threshold effect, and synergistic effects of acrylic acid sulfonate multi-polymers and polymers to improve the scale inhibition performance of the agent. Because the long-chain anions present in the water treatment agent can cause scale-forming crystals to grow in a deformed direction, thereby inhibiting crystal growth, the agent can effectively prevent the deposition of calcium carbonate, calcium phosphate, and other crystals in water with high hardness and high alkalinity. This reduces the amount of water treatment agent used and improves the agent's stable corrosion and scale inhibition performance at high concentrations.

[0034] Furthermore, the present invention uses zinc ions in zinc chloride as a cathode corrosion inhibitor to inhibit the cathode reaction during the corrosion process, thereby further improving the scale inhibition effect of the water treatment agent.

[0035] Second, this application further optimizes the components of the water treatment agent. By adding an auxiliary film-forming agent, it can simultaneously inhibit scale and corrosion while also providing a protective layer on the surface, effectively improving the durability and long-term performance of the scale and corrosion inhibition. The effective combination of tannic acid and humic acid allows the humic acid to effectively fill the pores in the protective layer formed by the tannic acid coating, further improving the poor corrosion inhibition effect caused by tannic acid alone.

[0036] Third, the present application further modifies humic acid by sulfonation treatment to make the water solubility of humic acid even better. On the one hand, it can effectively improve the integrity of the hydrophilic auxiliary film-forming agent coating in water; on the other hand, the further improvement of water solubility also further improves the dispersibility of the water treatment agent in water, thereby enabling it to have stable corrosion and scale inhibition performance when used at high concentration ratios. DETAILED DESCRIPTION

[0037] The present application is further described in detail below with reference to the embodiments.

[0038] Preparation Example 1: High Concentration Modified Humic Acid 1:

[0039] Take 200g of humic acid and add 10mL of 0.1mol / L sodium hydroxide solution dropwise. Stir and mix. Then add 6g of formaldehyde and 60g of 1.5% sodium bisulphite solution by mass. Stir and mix. Continue to add 0.1mol / L sodium hydroxide solution dropwise to adjust the pH to 10. Keep the reaction at 75℃ and let it cool to room temperature.

[0040] The reactants were collected and centrifuged, the centrifuged liquid was collected and the pH value was adjusted to 2.0 with 0.2 mol / L hydrochloric acid, the filtrate was centrifuged again, and the filtrate was dried and ground at 40° C. to prepare the high concentration ratio modified humic acid 1.

[0041] Preparation Example 2: High Concentration Modified Humic Acid 2:

[0042] Take 200g of humic acid and add 10mL of 0.1mol / L sodium hydroxide solution dropwise. Stir and mix. Then add 8g of formaldehyde and 80g of 1.5% sodium bisulphite solution by mass. Stir and mix. Continue to add 0.1mol / L sodium hydroxide solution dropwise to adjust the pH to 10. Keep the reaction at 80℃ and let it cool to room temperature.

[0043] The reactants were collected and centrifuged, the centrifuged liquid was collected and the pH value was adjusted to 2.0 with 0.2 mol / L hydrochloric acid, the filtrate was centrifuged again, and the filtrate was dried and ground at 45° C. to prepare the high concentration ratio modified humic acid 2.

[0044] Preparation Example 3: High Concentration Modified Humic Acid 3:

[0045] Take 200g of humic acid and add 10mL of 0.1mol / L sodium hydroxide solution dropwise. Stir and mix. Then add 10g of formaldehyde and 100g of 1.5% sodium bisulphite solution by mass. Stir and mix. Continue to add 0.1mol / L sodium hydroxide solution dropwise to adjust the pH to 10. Keep the mixture at 85℃ for reaction and let it cool to room temperature.

[0046] The reactants were collected and centrifuged, the centrifuged liquid was collected and the pH value was adjusted to 2.0 with 0.2 mol / L hydrochloric acid, the filtrate was centrifuged again, and the filtrate was dried and ground at 50° C. to prepare the high concentration ratio modified humic acid 3.

[0047] Preparation Example 4: Hydrophilic auxiliary film-forming agent 1:

[0048] 100 g of tannic acid and 350 g of highly concentrated modified humic acid 1 were stirred and mixed to prepare the hydrophilic auxiliary film-forming agent 1.

[0049] Preparation Example 5: Hydrophilic auxiliary film-forming agent 2:

[0050] 100 g of tannic acid and 400 g of highly concentrated modified humic acid 1 were stirred and mixed to prepare the hydrophilic auxiliary film-forming agent 2.

[0051] Preparation Example 6: Hydrophilic auxiliary film-forming agent 3:

[0052] 100 g of tannic acid and 450 g of the highly concentrated modified humic acid 1 were stirred and mixed to prepare the hydrophilic auxiliary film-forming agent 3.

[0053] Preparation Example 7: Hydrophilic auxiliary film-forming agent 4:

[0054] 100 g of tannic acid and 350 g of highly concentrated modified humic acid 2 were mixed and stirred to prepare the hydrophilic auxiliary film-forming agent 4.

[0055] Preparation Example 8: Hydrophilic auxiliary film-forming agent 5:

[0056] 100 g of tannic acid and 350 g of highly concentrated modified humic acid 3 were mixed and stirred to prepare the hydrophilic auxiliary film-forming agent 5.

[0057] Example

[0058] Example 1

[0059] A water treatment agent for circulating cooling water with a high concentration ratio comprises 10 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 50 kg of hydrolyzed polymaleic acid, 10 kg of zinc chloride and 30 kg of water.

[0060] Example 2

[0061] A water treatment agent for circulating cooling water with a high concentration ratio comprises 45 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 45 kg of hydrolyzed polymaleic acid, 9 kg of zinc chloride and 1 kg of water.

[0062] Example 3

[0063] A water treatment agent for circulating cooling water with a high concentration ratio comprises 50 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 10 kg of hydrolyzed polymaleic acid, 0.5 kg of zinc chloride and 39.5 kg of water.

[0064] Example 4

[0065] A water treatment agent for circulating cooling water with a high concentration ratio comprises 49 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 10 kg of hydrolyzed polymaleic acid, 0.5 kg of zinc chloride, 0.5 kg of benzotriazole and 40 kg of water.

[0066] Example 5

[0067] A water treatment agent for circulating cooling water with a high concentration ratio comprises 35 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 24 kg of hydrolyzed polymaleic acid, 2 kg of zinc chloride, 5.5 kg of sulfuric acid, 2 kg of benzotriazole and 1 kg of water.

[0068] Example 6

[0069] A water treatment agent for circulating cooling water with a high concentration ratio comprises 35 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 30 kg of hydrolyzed polymaleic acid, 2 kg of zinc chloride, 6 kg of sulfuric acid, 2 kg of benzotriazole and 10 kg of water.

[0070] Example 7

[0071] A water treatment agent for circulating cooling water with a high concentration ratio comprises 10 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 22 kg of hydrolyzed polymaleic acid, 1 kg of zinc chloride, 5 kg of sulfuric acid, 1 kg of benzotriazole and 16 kg of water.

[0072] Example 8

[0073] A water treatment agent for circulating cooling water with a high concentration ratio comprises 20 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 18 kg of hydrolyzed polymaleic acid, 1 kg of zinc chloride, 5 kg of sulfuric acid, 1.5 kg of benzotriazole and 17.5 kg of water.

[0074] Example 9

[0075] A water treatment agent for circulating cooling water with a high concentration ratio comprises 40 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 23 kg of hydrolyzed polymaleic acid, 1 kg of zinc chloride, 5 kg of sulfuric acid, 1.5 kg of benzotriazole and 7.5 kg of water.

[0076] Example 10

[0077] A high-concentration-ratio circulating cooling water treatment agent comprises 40 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 5 kg of a hydrophilic auxiliary film-forming agent 1, 23 kg of hydrolyzed polymaleic acid, 1 kg of zinc chloride, 5 kg of sulfuric acid, 1.5 kg of benzotriazole and 7.5 kg of water.

[0078] Example 11

[0079] A water treatment agent for circulating cooling water with a high concentration ratio comprises 40 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 10 kg of a hydrophilic auxiliary film-forming agent 1, 23 kg of hydrolyzed polymaleic acid, 1 kg of zinc chloride, 5 kg of sulfuric acid, 1.5 kg of benzotriazole and 7.5 kg of water.

[0080] Example 12

[0081] A water treatment agent for circulating cooling water with a high concentration ratio comprises 40 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 15 kg of a hydrophilic auxiliary film-forming agent 1, 23 kg of hydrolyzed polymaleic acid, 1 kg of zinc chloride, 5 kg of sulfuric acid, 1.5 kg of benzotriazole and 7.5 kg of water.

[0082] Example 13

[0083] A water treatment agent for circulating cooling water with a high concentration ratio comprises 40 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 5 kg of a hydrophilic auxiliary film-forming agent 2, 23 kg of hydrolyzed polymaleic acid, 1 kg of zinc chloride, 5 kg of sulfuric acid, 1.5 kg of benzotriazole and 7.5 kg of water.

[0084] Example 14

[0085] A water treatment agent for circulating cooling water with a high concentration ratio comprises 40 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 5 kg of a hydrophilic auxiliary film-forming agent 3, 23 kg of hydrolyzed polymaleic acid, 1 kg of zinc chloride, 5 kg of sulfuric acid, 1.5 kg of benzotriazole and 7.5 kg of water.

[0086] Example 15

[0087] A water treatment agent for circulating cooling water with a high concentration ratio comprises 40 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 5 kg of a hydrophilic auxiliary film-forming agent, 23 kg of hydrolyzed polymaleic acid, 1 kg of zinc chloride, 5 kg of sulfuric acid, 1.5 kg of benzotriazole and 7.5 kg of water.

[0088] Example 16

[0089] A high-concentration-ratio circulating cooling water treatment agent comprises 40 kg of acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer, 5 kg of a hydrophilic auxiliary film-forming agent 5, 23 kg of hydrolyzed polymaleic acid, 1 kg of zinc chloride, 5 kg of sulfuric acid, 1.5 kg of benzotriazole and 7.5 kg of water.

[0090] Performance testing

[0091] The high concentration ratio circulating cooling water treatment agent prepared in Examples 1 to 16 was tested, and the specific testing method is as follows:

[0092] (1) Scale inhibition performance test at high concentration rate

[0093] Different volumes of Yangtze River water containing a certain mass concentration of pharmaceuticals ρ(Ca 2+ )=96mg / L,ρ(HCO 3- )=100mg / L, concentrate 20, 22, 25 times respectively, use water treatment agent dosage of 45 / 37.5 and 30mg / L respectively, concentrate in (70+1)℃ water bath, control the volume of solution at about (100±2.5)℃ after concentration, continue to keep constant temperature at (80±1)℃ for 10h, take out, cool and filter, and measure Ca of filtrate 2+ content.

[0094] (2) Static calcium carbonate scale resistance test under high calcium hardness and high alkalinity conditions

[0095] When the water treatment agent dosage is 450 mg / L, ρ(Ca 2+ )=2000mg / L,ρ(HCO 3- )=2000mg / L, (all calculated as CaCO3) 500mL water sample (pH=8) was added into a volumetric flask, kept at (80±1)℃ for 10h, taken out, cooled and filtered, and the filtrate Ca 2+ content.

[0096] (3) Static corrosion test performance test under high calcium hardness and high alkalinity conditions

[0097] When the water treatment agent dosage is 450 mg / L, ρ(Ca 2+ )=2000mg / L,ρ(HCO 3- )=2000mg / L, (all calculated as CaCO3) pH=8, reaction temperature is (45±1)℃, rotating coupon corrosion monitoring method is adopted, reaction time is 72h, and coupon material is 20# carbon steel.

[0098] Table 1 Performance test table

[0099]

[0100] Combining the data of Examples 1 to 4, it can be found that the technical solution of the present application optimizes the composition of the water treatment agent for high concentration ratio circulating cooling water, thereby reducing the amount of water treatment agent used and improving the stable corrosion and scale inhibition performance of the water treatment agent at high concentration ratio.

[0101] Combined with the data of Examples 1 to 4 and Examples 5 to 9, it is further explained that the technical solution of this application is to add

[0102] The sulfonate multi-polymer is synergistically modified to inhibit the growth of grains. It can effectively prevent the deposition of crystals such as calcium carbonate and calcium phosphate in water with high hardness and high alkalinity, and has a good scale inhibition effect.

[0103] Finally, combining the data from Examples 10-16 with the data from Examples 5-9, we found that the technical solution of this application further optimizes the components of the water treatment agent. By adding an auxiliary film-forming agent, it can simultaneously inhibit scale and corrosion while also coating the surface with a protective layer, effectively improving the durability and long-term performance of the scale and corrosion inhibition. The effective combination of tannic acid and humic acid allows the humic acid to effectively fill the pores in the protective layer formed by the tannic acid coating, further improving the poor corrosion inhibition effect caused by tannic acid alone.

[0104] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A water treatment agent for circulating cooling water with a high concentration ratio, characterized in that: The composition includes the following materials in parts by weight: 10-50 parts of acrylic acid sulfonate multipolymer; 10-50 parts of polymer; 0.5-10 parts of zinc chloride; 1-50 parts water; 5 to 15 parts by weight of an auxiliary film-forming agent; The auxiliary film-forming agent includes tannic acid and humic acid mixed in a mass ratio of 1:3.5-4.5; The high concentration ratio circulating cooling water treatment agent further comprises 0.5 to 10 parts by weight of an organic substance, wherein the organic substance comprises benzotriazole; The polymer comprises hydrolyzed polymaleic acid; The water treatment agent for high concentration ratio circulating cooling water further comprises 1 to 10 parts by weight of sulfuric acid.

2. A water treatment agent for circulating cooling water with a high concentration ratio according to claim 1, characterized in that: The composition includes the following materials in parts by weight: 45 parts of acrylic acid sulfonate multipolymer; 22 parts of polymer; 2.5 parts of zinc chloride; 1.5 parts water.

3. A water treatment agent for circulating cooling water with a high concentration ratio according to claim 1, characterized in that: The humic acid is a highly concentrated modified humic acid, which is prepared by the following scheme: Take humic acid and add sodium hydroxide solution dropwise, stir and mix, then add sulfonating agent, stir and mix, adjust pH to 10, keep warm and react, and let stand to cool to room temperature; The reactants are collected and centrifuged, the centrifuge liquid is collected and the pH value is adjusted to 2.0, the filtrate is centrifuged again, and the filtrate is dried and ground to prepare the modified humic acid with a high concentration ratio.

4. A water treatment agent for circulating cooling water with a high concentration ratio according to claim 1, characterized in that: The acrylic acid sulfonate multipolymer includes acrylic acid-(2-acrylamide-2-methylpropanesulfonic acid)-hydroxypropyl acrylate multipolymer.

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