Circulating water system protective agent and preparation method thereof

Abstract

The invention relates to the technical field of circulating water systems, in particular to a circulating water system protective agent and a preparation method thereof.The circulating water system protective agent is prepared from, by weight, 20-40 parts of lipid matrixes, 10-20 parts of carboxyl-containing organic compounds, 8-15 parts of ester-containing organic compounds, 5-12 parts of hydrophilic functional auxiliaries, 5-8 parts of modified functional agents, 4-7 parts of nano silver powder, 1-3 parts of dispersing agents and 4-7 parts of auxiliary agents. The polyol ester in the formula can form a stable complex with calcium and magnesium ions in water, and crystal nucleus formation and growth of carbonate and sulfate scales are inhibited; the carboxyl-containing organic compounds (adipic acid and sebacic acid) have strong chelating ability, and can disperse scale forming ions in water and prevent deposition of scale bodies.

Description

Technical Field

[0001] This invention relates to the field of circulating water system technology, and specifically to a circulating water system protectant and its preparation method. Background Technology

[0002] Circulating water systems are widely used in industries such as power, chemical, metallurgy, and refrigeration. Their core function is to achieve heat exchange through the circulation of water. Currently, circulating water systems generally face the industry pain point of a "triple whammy" of corrosion, biological slime, and scaling: these three factors form a vicious cycle, with corrosion promoting slime growth, slime accelerating scaling, and scaling exacerbating corrosion, significantly increasing system energy consumption. Existing circulating water protective agents have limited functionality, poor scale inhibition and corrosion prevention effects, short-lasting antibacterial properties, and unstable performance in high-conductivity water and over a wide temperature range, limiting product efficiency. Therefore, this invention provides further improvements to these systems. Summary of the Invention

[0003] In view of the deficiencies of the prior art, the purpose of this invention is to provide a protective agent for circulating water systems and its preparation method, so as to solve the problems mentioned in the background art.

[0004] The present invention solves the technical problem by adopting the following technical solution: This invention provides a protective agent for circulating water systems, which is composed of the following raw materials in parts by weight: 20-40 parts of lipid matrix, 10-20 parts of carboxyl-containing organic compound, 8-15 parts of ester-containing organic compound, 5-12 parts of hydrophilic functional agent, 5-8 parts of modified functional agent, 4-7 parts of nano silver powder, 1-3 parts of dispersant, and 4-7 parts of auxiliary agent.

[0005] Preferably, the lipid matrix is ​​a polyol ester; the carboxyl-containing organic compound is an aliphatic carboxylic acid containing at least two -COOH groups; The ester-containing organic compound is an organic ester compound; the hydrophilic functional agent is a polyether compound containing -OH.

[0006] Preferably, the polyol ester is a pentaerythritol ester; The carboxyl-containing organic compound is at least one of adipic acid and sebacic acid; the ester-containing organic compound is at least one of ethyl acetate and dibutyl phthalate; the hydrophilic functional additive is a polyether polyol; and the dispersant is polyethylene glycol.

[0007] Preferably, the method for preparing the modified functional agent is as follows: S01: Add 2-4 parts graphene, 3-5 parts calcium sulfate whiskers and 1-2 parts hydroxyapatite to 5-8 parts ethanol aqueous solution, and then add 2-3 parts silane coupling agent and stir evenly to obtain graphene-whisker functional regulating solution. S02: The β-cyclodextrin modified liquid and bentonite agent were ball-milled at a weight ratio of (3-5):7, with a ball milling speed of 1200-1500 r / min for 2 hours. After ball milling, the mixture was filtered and dried to obtain the bentonite-β-cyclodextrin refolding agent. The preparation method of the bentonite agent is as follows: heat-treat bentonite at 310-330℃ for 10 min, then cool it to 55℃ at a rate of 1-3℃ / min and keep it at the temperature; stir the bentonite and 5% sodium silicate solution at a weight ratio of (2-4):5 to obtain the bentonite agent. S03: Graphene-whisker functional regulating liquid and bentonite-β-cyclodextrin refolding agent were ball-milled at a weight ratio of (5-7):8 for 1-2 hours at a speed of 1500 r / min. After ball milling, the mixture was filtered and dried to obtain the modified functional agent.

[0008] Preferably, the ethanol aqueous solution has a mass fraction of 85-90%; the silane coupling agent is silane coupling agent KH560.

[0009] Preferably, the preparation method of the β-cyclodextrin modified liquid is as follows: S02a: Prepare a nanocellulose solution by mixing nanocellulose, sodium alginate solution and lanthanum oxide in a weight ratio of (4-5):7:(1-3); S02b: Mesoporous silica is stirred thoroughly in a sufficient amount of 10% sulfuric acid solution, then washed with water, filtered, and dried. 4-7 parts of the dried mesoporous silica, 2-5 parts of β-cyclodextrin, and 5-8 parts of nanocellulose solution are mixed and stirred to obtain a β-cyclodextrin modified solution.

[0010] Preferably, the stirring speed of the blending process is 350-400 r / min, the stirring time is 1 h, and the stirring temperature is 50-55℃; the mass fraction of the sodium alginate solution is 5-8%.

[0011] Preferably, the preparation method of the auxiliary agent is as follows: S11: Stir nano-alumina thoroughly in a sufficient amount of 8% potassium permanganate solution, then wash with water, filter, and dry. Preheat the dried nano-alumina at 55-65℃ for 1 hour to obtain preheated nano-alumina. S12: Preheated nano-alumina and auxiliary liquid are ball-milled at a weight ratio of (11-13):5, with a ball milling speed of 1200-1500 r / min for 2 hours. After ball milling, the mixture is filtered and dried to obtain the auxiliary agent. The auxiliary solution comprises the following raw materials in parts by weight: 2-4 parts humic acid, 1-3 parts nano-zirconia, 5-8 parts carbon nanotubes, and 8-12 parts sodium dodecylbenzenesulfonate solution.

[0012] Preferably, the sodium dodecylbenzenesulfonate solution has a mass fraction of 5-8%.

[0013] This invention also provides a method for preparing a protective agent for a circulating water system, comprising the following steps: Step 1: Place the lipid matrix in a reaction vessel and heat it to 80~120℃ to melt it, while controlling the stirring speed at 100~200 rpm; Step 2: Add carboxyl-containing organic compounds and ester-containing organic compounds to the molten lipid matrix, heat to 130-160℃ at a rate of 5-10℃ / min, and maintain the temperature for 2-4 hours to form a lipid complex. Step 3: Cool the reaction system to 90~110℃, add hydrophilic functional additives, nano silver powder, modified functional agents, auxiliary agents and dispersants, stir and disperse for 30~60min, increase the stirring speed to 200~300rpm, and then let the mixed system cool naturally to room temperature to obtain the circulating water system protectant of the present invention.

[0014] Compared with the prior art, the present invention has the following beneficial effects: The polyol esters in the formulation of this invention can form stable complexes with calcium and magnesium ions in water, inhibiting the formation and growth of carbonate and sulfate scale crystals; the carboxyl-containing organic compounds (adipic acid, sebacic acid) have strong chelating ability, which can disperse scale-forming ions in water and prevent scale deposition; the ester matrix forms a dense hydrophobic protective film on the metal surface, isolating the metal substrate from contact with corrosive media such as oxygen and chloride ions; the ester-containing organic compounds (ethyl acetate, dibutyl phthalate) can enhance the adhesion of the protective film and delay film peeling; the nano silver powder has a strong bactericidal effect, which can destroy bacterial cell membranes and inhibit microbial metabolism; and the product is suitable for water with a high conductivity of 50,000 μS / cm and a wide temperature range of -25~200℃. The graphene in the modified functional agent has an ultra-large specific surface area, the calcium sulfate whiskers have a needle-like crystal structure, and the bentonite-β-cyclodextrin refolding agent (after high-temperature activation of bentonite and modification with sodium silicate) forms a porous layered structure. The three work synergistically to efficiently adsorb Ca from water. 2 ⁺、Mg 2 ⁺, HCO3⁻ and other scale-forming ions, as well as tiny scale particles (such as calcium carbonate microcrystals), prevent them from agglomerating, growing and depositing on the equipment surface; The sheet-like structure of graphene can form a physical barrier layer on the metal surface, isolating corrosive media (oxygen, chloride ions); hydroxyapatite can combine with iron ions on the metal surface to form a hydroxyapatite-iron composite passivation film, filling the tiny pits on the metal surface and repairing the initial corrosion sites; the layered structure of bentonite-β-cyclodextrin refolding agent can enhance the adhesion of the passivation film and delay the film peeling. When preparing graphene-whisker functional conditioning liquid, silane coupling agent KH560 can chemically bond graphene, calcium sulfate whiskers and metal substrate, thereby improving the adsorption strength of the modified functional agent on the metal surface and further strengthening the anti-corrosion barrier. The β-cyclodextrin in the bentonite-β-cyclodextrin refolding agent has a cavity structure, which can encapsulate the nano-silver powder in the protectant, enabling the slow release of nano-silver and extending the antibacterial efficacy. The sheet-like structure of graphene and the interlayer structure of bentonite provide synergistic load-bearing capacity, optimizing the antibacterial durability of the product. Nanocellulose and sodium alginate (from the β-cyclodextrin modified liquid) have good hydrophilicity and dispersibility, which can prevent the modified functional agent from agglomerating and ensure its uniform dispersion in the protectant system composed of lipid matrix and carboxyl / ester compounds. The high-temperature activated bentonite, the graphene-whisker complex modified by silane coupling agent, and the rigid structure of mesoporous silica make the modified functional agent structurally stable in the temperature range of -5℃ to 95℃, and it will not react with salt ions and become ineffective in water with high conductivity (>5000μS / cm), ensuring the performance continuity of the protectant under complex working conditions. The auxiliary agent is made of nano-alumina activated with potassium permanganate solution and optimized by preheating. It is also improved by ball milling of the auxiliary liquid. The auxiliary liquid is made of nano-zirconia and carbon nanotubes through blending and synergistic effects. It is also optimized by humic acid and sodium dodecylbenzenesulfonate solution. Through the co-blending and improvement of raw materials, the auxiliary agent is further synergistically modified with functional agents, thereby further improving the performance of the product. Detailed Implementation

[0015] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to specific examples. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0016] This embodiment of a circulating water system protectant is composed of the following raw materials in parts by weight: 20-40 parts of lipid matrix, 10-20 parts of carboxyl-containing organic compound, 8-15 parts of ester-containing organic compound, 5-12 parts of hydrophilic functional additive, 5-8 parts of modified functional agent, 4-7 parts of nano silver powder, 1-3 parts of dispersant, and 4-7 parts of auxiliary agent.

[0017] The lipid matrix in this embodiment is a polyol ester; the carboxyl-containing organic compound is an aliphatic carboxylic acid containing at least two -COOH groups; The ester-containing organic compound is an organic ester compound; the hydrophilic functional agent is a polyether compound containing -OH.

[0018] The polyol ester in this embodiment is a pentaerythritol ester; The carboxyl-containing organic compound is at least one of adipic acid and sebacic acid; the ester-containing organic compound is at least one of ethyl acetate and dibutyl phthalate; the hydrophilic functional additive is a polyether polyol; and the dispersant is polyethylene glycol.

[0019] The preparation method of the modified functional agent in this embodiment is as follows: S01: Add 2-4 parts graphene, 3-5 parts calcium sulfate whiskers and 1-2 parts hydroxyapatite to 5-8 parts ethanol aqueous solution, and then add 2-3 parts silane coupling agent and stir evenly to obtain graphene-whisker functional regulating solution. S02: The β-cyclodextrin modified liquid and bentonite agent were ball-milled at a weight ratio of (3-5):7, with a ball milling speed of 1200-1500 r / min for 2 hours. After ball milling, the mixture was filtered and dried to obtain the bentonite-β-cyclodextrin refolding agent. The preparation method of the bentonite agent is as follows: heat-treat bentonite at 310-330℃ for 10 min, then cool it to 55℃ at a rate of 1-3℃ / min and keep it at the temperature; stir the bentonite and 5% sodium silicate solution at a weight ratio of (2-4):5 to obtain the bentonite agent. S03: Graphene-whisker functional regulating liquid and bentonite-β-cyclodextrin refolding agent were ball-milled at a weight ratio of (5-7):8 for 1-2 hours at a speed of 1500 r / min. After ball milling, the mixture was filtered and dried to obtain the modified functional agent.

[0020] In this embodiment, the ethanol aqueous solution has a mass fraction of 85-90%; the silane coupling agent is silane coupling agent KH560.

[0021] The preparation method of the β-cyclodextrin modified liquid in this embodiment is as follows: S02a: Prepare a nanocellulose solution by mixing nanocellulose, sodium alginate solution and lanthanum oxide in a weight ratio of (4-5):7:(1-3); S02b: Mesoporous silica is stirred thoroughly in a sufficient amount of 10% sulfuric acid solution, then washed with water, filtered, and dried. 4-7 parts of the dried mesoporous silica, 2-5 parts of β-cyclodextrin, and 5-8 parts of nanocellulose solution are mixed and stirred to obtain a β-cyclodextrin modified solution.

[0022] In this embodiment, the stirring speed for the blending process is 350-400 r / min, the stirring time is 1 h, and the stirring temperature is 50-55℃; the mass fraction of the sodium alginate solution is 5-8%.

[0023] The preparation method of the auxiliary agent in this embodiment is as follows: S11: Stir nano-alumina thoroughly in a sufficient amount of 8% potassium permanganate solution, then wash with water, filter, and dry. Preheat the dried nano-alumina at 55-65℃ for 1 hour to obtain preheated nano-alumina. S12: Preheated nano-alumina and auxiliary liquid are ball-milled at a weight ratio of (11-13):5, with a ball milling speed of 1200-1500 r / min for 2 hours. After ball milling, the mixture is filtered and dried to obtain the auxiliary agent. The auxiliary solution comprises the following raw materials in parts by weight: 2-4 parts humic acid, 1-3 parts nano-zirconia, 5-8 parts carbon nanotubes, and 8-12 parts sodium dodecylbenzenesulfonate solution.

[0024] The sodium dodecylbenzenesulfonate solution in this embodiment has a mass fraction of 5-8%.

[0025] The preparation method of a circulating water system protective agent according to this embodiment includes the following steps: Step 1: Place the lipid matrix in a reaction vessel and heat it to 80~120℃ to melt it, while controlling the stirring speed at 100~200 rpm; Step 2: Add carboxyl-containing organic compounds and ester-containing organic compounds to the molten lipid matrix, heat to 130-160℃ at a rate of 5-10℃ / min, and maintain the temperature for 2-4 hours to form a lipid complex. Step 3: Cool the reaction system to 90~110℃, add hydrophilic functional additives, nano silver powder, modified functional agents, auxiliary agents and dispersants, stir and disperse for 30~60min, increase the stirring speed to 200~300rpm, and then let the mixed system cool naturally to room temperature to obtain the circulating water system protectant of the present invention.

[0026] Example 1. The circulating water system protectant of this embodiment is composed of the following raw materials in parts by weight: 20 parts of lipid matrix, 10 parts of carboxyl-containing organic compound, 8 parts of ester-containing organic compound, 5 parts of hydrophilic functional agent, 5 parts of modified functional agent, 4 parts of nano silver powder, 1 part of dispersant and 4 parts of auxiliary agent.

[0027] The polyol ester in this embodiment is a pentaerythritol ester; The carboxyl-containing organic compound is adipic acid; the ester-containing organic compound is ethyl acetate; the hydrophilic functional agent is a polyether polyol; and the dispersant is polyethylene glycol.

[0028] The preparation method of the modified functional agent in this embodiment is as follows: S01: Add 2 parts graphene, 3 parts calcium sulfate whiskers and 1 part hydroxyapatite to 5 parts ethanol aqueous solution, then add 2 parts silane coupling agent and stir evenly to obtain graphene-whisker functional regulating solution. S02: The β-cyclodextrin modified liquid and bentonite agent were ball-milled at a weight ratio of 3:7. The ball milling speed was 1200 r / min and the ball milling time was 2 h. After the ball milling was completed, the mixture was filtered and dried to obtain the bentonite-β-cyclodextrin refolding agent. The preparation method of the bentonite agent is as follows: Bentonite is heat-treated at 310℃ for 10 min, then cooled to 55℃ at a rate of 1℃ / min and kept at the temperature; the bentonite kept at the temperature and a sodium silicate solution with a mass fraction of 5% are stirred evenly at a weight ratio of 2:5 to obtain the bentonite agent. S03: Graphene-whisker functional regulating solution and bentonite-β-cyclodextrin refolding agent were ball-milled at a weight ratio of 5:8 for 1 hour at a speed of 1500 r / min. After ball milling, the mixture was filtered and dried to obtain the modified functional agent.

[0029] In this embodiment, the ethanol aqueous solution has a mass fraction of 85%; the silane coupling agent is silane coupling agent KH560.

[0030] The preparation method of the β-cyclodextrin modified liquid in this embodiment is as follows: S02a: Nanocellulose solution is prepared by mixing nanocellulose, sodium alginate solution and lanthanum oxide in a weight ratio of 4:7:1; S02b: Mesoporous silica was stirred thoroughly in a sufficient amount of 10% sulfuric acid solution, then washed with water, filtered, and dried. Four parts of dried mesoporous silica, two parts of β-cyclodextrin, and five parts of nanocellulose solution were mixed and stirred to obtain β-cyclodextrin modified solution.

[0031] In this embodiment, the stirring speed for the blending process was 350 r / min, the stirring time was 1 h, and the stirring temperature was 50 °C; the mass fraction of the sodium alginate solution was 5%.

[0032] The preparation method of the auxiliary agent in this embodiment is as follows: S11: The nano-alumina is stirred thoroughly in a sufficient amount of 8% potassium permanganate solution, then washed with water, filtered and dried. The dried nano-alumina is preheated at 55°C for 1 hour to obtain preheated nano-alumina. S12: Preheated nano-alumina and auxiliary liquid are ball-milled at a weight ratio of 11:5 at a speed of 1200 r / min for 2 hours. After ball milling, the mixture is filtered and dried to obtain the auxiliary agent. The auxiliary solution comprises the following raw materials in parts by weight: 2 parts humic acid, 1 part nano-zirconia, 5 parts carbon nanotubes, and 8 parts sodium dodecylbenzenesulfonate solution.

[0033] The sodium dodecylbenzenesulfonate solution in this embodiment has a mass fraction of 5%.

[0034] The preparation method of a circulating water system protective agent according to this embodiment includes the following steps: Step 1: Place the lipid matrix in a reaction vessel, heat it to 80°C to melt it, and control the stirring speed at 100 rpm; Step 2: Add carboxyl-containing organic compounds and ester-containing organic compounds to the molten lipid matrix, heat to 130°C at a rate of 5°C / min, and maintain the temperature for 2 hours to form a lipid complex. Step 3: Cool the reaction system to 90°C, add hydrophilic functional additives, nano silver powder, modified functional agents, auxiliary agents and dispersants, stir and disperse for 30 minutes, increase the stirring speed to 200 rpm, and then let the mixed system cool naturally to room temperature to obtain the circulating water system protectant of the present invention.

[0035] Example 2. The circulating water system protectant of this embodiment is composed of the following raw materials in parts by weight: 40 parts of lipid matrix, 20 parts of carboxyl-containing organic compound, 15 parts of ester-containing organic compound, 12 parts of hydrophilic functional agent, 8 parts of modified functional agent, 7 parts of nano silver powder, 3 parts of dispersant and 7 parts of auxiliary agent.

[0036] The polyol ester in this embodiment is a pentaerythritol ester; The carboxyl-containing organic compound is sebacic acid; the ester-containing organic compound is ethyl acetate; the hydrophilic functional agent is a polyether polyol; and the dispersant is polyethylene glycol.

[0037] The preparation method of the modified functional agent in this embodiment is as follows: S01: Add 4 parts graphene, 5 parts calcium sulfate whiskers and 2 parts hydroxyapatite to 8 parts ethanol aqueous solution, and then add 3 parts silane coupling agent and stir evenly to obtain graphene-whisker functional regulating solution. S02: The β-cyclodextrin modified liquid and bentonite agent were ball-milled at a weight ratio of 5:7. The ball milling speed was 1500 r / min and the ball milling time was 2 h. After the ball milling was completed, the mixture was filtered and dried to obtain the bentonite-β-cyclodextrin refolding agent. The preparation method of the bentonite agent is as follows: Bentonite is heat-treated at 330℃ for 10 min, then cooled to 55℃ at a rate of 3℃ / min and kept at the temperature; the bentonite kept at the temperature and a 5% sodium silicate solution are stirred evenly at a weight ratio of 4:5 to obtain the bentonite agent. S03: Graphene-whisker functional regulating solution and bentonite-β-cyclodextrin refolding agent were ball-milled at a weight ratio of 7:8 for 2 hours at a speed of 1500 r / min. After ball milling, the mixture was filtered and dried to obtain the modified functional agent.

[0038] In this embodiment, the ethanol aqueous solution has a mass fraction of 90%; the silane coupling agent is silane coupling agent KH560.

[0039] The preparation method of the β-cyclodextrin modified liquid in this embodiment is as follows: S02a: Nanocellulose solution is prepared by mixing nanocellulose, sodium alginate solution and lanthanum oxide in a weight ratio of 5:7:3; S02b: Mesoporous silica was stirred thoroughly in a sufficient amount of 10% sulfuric acid solution, then washed with water, filtered, and dried. Seven parts of the dried mesoporous silica, five parts of β-cyclodextrin, and eight parts of nanocellulose solution were mixed and stirred to obtain a β-cyclodextrin modified solution.

[0040] In this embodiment, the stirring speed for the blending process was 400 r / min, the stirring time was 1 h, and the stirring temperature was 55 °C; the mass fraction of the sodium alginate solution was 8%.

[0041] The preparation method of the auxiliary agent in this embodiment is as follows: S11: The nano-alumina is stirred thoroughly in a sufficient amount of 8% potassium permanganate solution, then washed with water, filtered and dried. The dried nano-alumina is preheated at 65°C for 1 hour to obtain preheated nano-alumina. S12: Preheated nano-alumina and auxiliary liquid are ball-milled at a weight ratio of 13:5 at a speed of 1500 r / min for 2 hours. After ball milling, the mixture is filtered and dried to obtain the auxiliary agent. The auxiliary solution comprises the following raw materials in parts by weight: 4 parts humic acid, 3 parts nano-zirconia, 8 parts carbon nanotubes, and 12 parts sodium dodecylbenzenesulfonate solution.

[0042] The sodium dodecylbenzenesulfonate solution in this embodiment has a mass fraction of 8%.

[0043] The preparation method of a circulating water system protective agent according to this embodiment includes the following steps: Step 1: Place the lipid matrix in a reaction vessel and heat it to 120°C to melt it, while controlling the stirring speed at 200 rpm; Step 2: Add carboxyl-containing organic compounds and ester-containing organic compounds to the molten lipid matrix, heat to 160°C at a rate of 10°C / min, and maintain the temperature for 4 hours to form a lipid complex. Step 3: Cool the reaction system to 110°C, add hydrophilic functional additives, nano silver powder, modified functional agents, auxiliary agents and dispersants, stir and disperse for 60 minutes, increase the stirring speed to 300 rpm, and then let the mixed system cool naturally to room temperature to obtain the circulating water system protectant of the present invention.

[0044] Example 3. The circulating water system protectant of this embodiment is composed of the following raw materials in parts by weight: 30 parts of lipid matrix, 15 parts of carboxyl-containing organic compound, 11 parts of ester-containing organic compound, 8 parts of hydrophilic functional agent, 6.5 parts of modified functional agent, 5.5 parts of nano silver powder, 2 parts of dispersant and 5.5 parts of auxiliary agent.

[0045] The polyol ester in this embodiment is a pentaerythritol ester; The carboxyl-containing organic compound is adipic acid; the ester-containing organic compound is dibutyl phthalate; the hydrophilic functional additive is a polyether polyol; and the dispersant is polyethylene glycol.

[0046] The preparation method of the modified functional agent in this embodiment is as follows: S01: Add 3 parts graphene, 4 parts calcium sulfate whiskers and 1.5 parts hydroxyapatite to 6.5 parts ethanol aqueous solution, and then add 2.5 parts silane coupling agent and stir evenly to obtain graphene-whisker functional regulating solution. S02: The β-cyclodextrin modified liquid and bentonite agent were ball-milled at a weight ratio of 4:7. The ball milling speed was 1300 r / min and the ball milling time was 2 h. After the ball milling was completed, the mixture was filtered and dried to obtain the bentonite-β-cyclodextrin refolding agent. The preparation method of the bentonite agent is as follows: Bentonite is heat-treated at 320℃ for 10 min, then cooled to 55℃ at a rate of 2℃ / min and kept at the temperature; the bentonite kept at the temperature and a 5% sodium silicate solution are stirred evenly at a weight ratio of 3:5 to obtain the bentonite agent. S03: Graphene-whisker functional regulating solution and bentonite-β-cyclodextrin refolding agent were ball-milled at a weight ratio of 6:8 for 1.5 hours at a speed of 1500 r / min. After ball milling, the mixture was filtered and dried to obtain the modified functional agent.

[0047] In this embodiment, the ethanol aqueous solution has a mass fraction of 88%; the silane coupling agent is silane coupling agent KH560.

[0048] The preparation method of the β-cyclodextrin modified liquid in this embodiment is as follows: S02a: Nanocellulose solution is prepared by mixing nanocellulose, sodium alginate solution and lanthanum oxide in a weight ratio of 4.5:7:2; S02b: Mesoporous silica was stirred thoroughly in a sufficient amount of 10% sulfuric acid solution, then washed with water, filtered, and dried. 5.5 parts of dried mesoporous silica, 3.5 parts of β-cyclodextrin, and 6.5 parts of nanocellulose solution were mixed and stirred to obtain β-cyclodextrin modified solution.

[0049] In this embodiment, the stirring speed for the blending process was 370 r / min, the stirring time was 1 h, and the stirring temperature was 52 °C; the mass fraction of the sodium alginate solution was 6.5%.

[0050] The preparation method of the auxiliary agent in this embodiment is as follows: S11: The nano-alumina is stirred thoroughly in a sufficient amount of 8% potassium permanganate solution, then washed with water, filtered and dried. The dried nano-alumina is preheated at 60°C for 1 hour to obtain preheated nano-alumina. S12: Preheated nano-alumina and auxiliary liquid are ball-milled at a weight ratio of 12:5 at a speed of 1350 r / min for 2 hours. After ball milling, the mixture is filtered and dried to obtain the auxiliary agent. The auxiliary solution comprises the following raw materials in parts by weight: 3 parts humic acid, 2 parts nano-zirconia, 6.5 parts carbon nanotubes, and 10 parts sodium dodecylbenzenesulfonate solution.

[0051] The sodium dodecylbenzenesulfonate solution in this embodiment has a mass fraction of 65%.

[0052] The preparation method of a circulating water system protective agent according to this embodiment includes the following steps: Step 1: Place the lipid matrix in a reaction vessel, heat it to 100℃ to melt it, and control the stirring speed at 150 rpm; Step 2: Add carboxyl-containing organic compounds and ester-containing organic compounds to the molten lipid matrix, heat to 145℃ at a rate of 7.5℃ / min, and maintain the temperature for 3 hours to form a lipid complex; Step 3: Cool the reaction system to 100°C, add hydrophilic functional additives, nano silver powder, modified functional agents, auxiliary agents and dispersants, stir and disperse for 45 minutes, increase the stirring speed to 250 rpm, and then let the mixed system cool naturally to room temperature to obtain the circulating water system protectant of the present invention.

[0053] Comparative Example 1. Unlike Example 3, no modifying functional agent was added.

[0054] Comparative Example 2. Unlike Example 3, the graphene-whisker functional regulating liquid was not added in the preparation method of the modified functional agent.

[0055] Comparative Example 3. Unlike Example 3, calcium sulfate whiskers and hydroxyapatite were not added to the graphene-whisker functional conditioning solution.

[0056] Comparative Example 4. Unlike Example 3, the preparation method of the modified functional agent did not include bentonite-β-cyclodextrin refolding agent.

[0057] Comparative Example 5. Unlike Example 3, no bentonite agent was added in the preparation of the bentonite-β-cyclodextrin refolding agent.

[0058] Comparative Example 6. Unlike Example 3, no β-cyclodextrin modifying solution was added in the preparation of the bentonite-β-cyclodextrin refolding agent.

[0059] Comparative Example 7. Unlike Example 3, no dried mesoporous silica or β-cyclodextrin was added in the preparation of the β-cyclodextrin modified solution.

[0060] Comparative Example 8. Unlike Example 3, no nanocellulose solution was added in the preparation of the β-cyclodextrin modified solution.

[0061] Comparative Example 9. Unlike Example 3, no additives were added.

[0062] Comparative Example 10. Unlike Example 3, no auxiliary liquid was added during the preparation of the auxiliary agent.

[0063] Comparative Example 11. Unlike Example 3, humic acid and nano-zirconia were not added in the preparation of the auxiliary liquid.

[0064] Comparative Example 12. Unlike Example 3, carbon nanotubes were not added in the preparation of the auxiliary liquid.

[0065] Examples 1-3 and Comparative Examples 1-12 were tested for product performance, including scale inhibition rate, corrosion rate, and 72-hour antibacterial rate. Simultaneously, the performance stability under high conductivity (simulating high-salt circulating water conditions (conductivity 50000 μS / cm)) and wide temperature range conditions (one cycle of freezing at -25℃ for 24 hours → placing at room temperature for 6 hours → heating at 200℃ for 24 hours, repeated 3 times) was tested. The performance test results are shown in Table 1 below. Table 1 is the comprehensive performance test result table of the product. Table 1: As can be seen from Comparative Examples 1-12 and Examples 1-3; Example 3: The product exhibits excellent scale inhibition, corrosion prevention, and long-lasting antibacterial properties, while demonstrating significant performance stability in high conductivity water and over a wide temperature range. The product's performance deteriorates significantly if neither of the functional modifiers nor the additives are added. However, by blending and combining the two, the product's performance is significantly improved. The preparation methods of the modified functional agents did not include graphene-whisker functional regulating liquid, nor did they include calcium sulfate whiskers and hydroxyapatite. Furthermore, the preparation methods of the modified functional agents did not include bentonite-β-cyclodextrin refolding agent, bentonite agent, β-cyclodextrin modifying liquid, dried mesoporous silica, β-cyclodextrin, or nanocellulose liquid. All of these methods resulted in varying degrees of performance degradation. The modified functional agents obtained using the specific method of this invention exhibited the most significant performance improvement. The graphene-whisker functional regulating liquid and bentonite-β-cyclodextrin refolding agent obtained by the specific method of this invention are synergistically enhanced and improve each other, resulting in a modified functional agent that has the best performance effect on the product. At the same time, the preparation of the bentonite-β-cyclodextrin refolding agent is unique, and the performance effect of the product is most obvious when using the technical solution of this invention. In the preparation of the auxiliary agent, no auxiliary liquid was added. In the preparation of the auxiliary liquid, no humic acid, nano-zirconia, or carbon nanotubes were added. As a result, the performance of the product deteriorated to varying degrees. The auxiliary agent obtained by the method of this invention has the most significant performance effect. In the preparation of the auxiliary liquid, all raw materials are indispensable. Only by using the specific raw material ratio of this invention can the effect be as significant as that of this invention. Using other raw material ratios will not be as significant as that of this invention.

[0066] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0067] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A protective agent for a circulating water system, characterized in that, It is composed of the following raw materials in parts by weight: 20-40 parts of lipid matrix, 10-20 parts of carboxyl-containing organic compound, 8-15 parts of ester-containing organic compound, 5-12 parts of hydrophilic functional agent, 5-8 parts of modified functional agent, 4-7 parts of nano silver powder, 1-3 parts of dispersant and 4-7 parts of auxiliary agent.

2. The circulating water system protectant according to claim 1, characterized in that, The lipid matrix is ​​a polyol ester; the carboxyl-containing organic compound is an aliphatic carboxylic acid containing at least two -COOH groups; The ester-containing organic compound is an organic ester compound; the hydrophilic functional agent is a polyether compound containing -OH.

3. The circulating water system protectant according to claim 2, characterized in that, The polyol ester is pentaerythritol ester; The carboxyl-containing organic compound is at least one of adipic acid and sebacic acid; the ester-containing organic compound is at least one of ethyl acetate and dibutyl phthalate; the hydrophilic functional additive is a polyether polyol; and the dispersant is polyethylene glycol.

4. The circulating water system protectant according to claim 1, characterized in that, The preparation method of the modified functional agent is as follows: S01: Add 2-4 parts graphene, 3-5 parts calcium sulfate whiskers and 1-2 parts hydroxyapatite to 5-8 parts ethanol aqueous solution, and then add 2-3 parts silane coupling agent and stir evenly to obtain graphene-whisker functional regulating solution. S02: The β-cyclodextrin modified liquid and bentonite agent were ball-milled at a weight ratio of (3-5):7, with a ball milling speed of 1200-1500 r / min for 2 hours. After ball milling, the mixture was filtered and dried to obtain the bentonite-β-cyclodextrin refolding agent. The preparation method of the bentonite agent is as follows: heat-treat bentonite at 310-330℃ for 10 min, then cool it to 55℃ at a rate of 1-3℃ / min and keep it at that temperature; The heat-insulating bentonite and a 5% sodium silicate solution are mixed evenly at a weight ratio of (2-4):5 to obtain the bentonite agent; S03: Graphene-whisker functional regulating liquid and bentonite-β-cyclodextrin refolding agent were ball-milled at a weight ratio of (5-7):8 for 1-2 hours at a speed of 1500 r / min. After ball milling, the mixture was filtered and dried to obtain the modified functional agent.

5. A circulating water system protectant according to claim 4, characterized in that, The ethanol aqueous solution has a mass fraction of 85-90%; the silane coupling agent is silane coupling agent KH560.

6. The circulating water system protectant according to claim 4, characterized in that, The preparation method of the β-cyclodextrin modified liquid is as follows: S02a: Prepare a nanocellulose solution by mixing nanocellulose, sodium alginate solution and lanthanum oxide in a weight ratio of (4-5):7:(1-3); S02b: Mesoporous silica is stirred thoroughly in a sufficient amount of 10% sulfuric acid solution, then washed with water, filtered, and dried. 4-7 parts of the dried mesoporous silica, 2-5 parts of β-cyclodextrin, and 5-8 parts of nanocellulose solution are mixed and stirred to obtain a β-cyclodextrin modified solution.

7. A circulating water system protectant according to claim 6, characterized in that, The mixing speed for the blending process is 350-400 r / min, the mixing time is 1 h, and the mixing temperature is 50-55℃; the mass fraction of the sodium alginate solution is 5-8%.

8. The circulating water system protectant according to claim 1, characterized in that, The preparation method of the auxiliary agent is as follows: S11: Stir nano-alumina thoroughly in a sufficient amount of 8% potassium permanganate solution, then wash with water, filter, and dry. Preheat the dried nano-alumina at 55-65℃ for 1 hour to obtain preheated nano-alumina. S12: Preheated nano-alumina and auxiliary liquid are ball-milled at a weight ratio of (11-13):5, with a ball milling speed of 1200-1500 r / min for 2 hours. After ball milling, the mixture is filtered and dried to obtain the auxiliary agent. The auxiliary solution comprises the following raw materials in parts by weight: 2-4 parts humic acid, 1-3 parts nano-zirconia, 5-8 parts carbon nanotubes, and 8-12 parts sodium dodecylbenzenesulfonate solution.

9. A circulating water system protectant according to claim 8, characterized in that, The sodium dodecylbenzenesulfonate solution has a mass fraction of 5-8%.

10. A method for preparing a circulating water system protectant as described in any one of claims 1 to 9, characterized in that, Includes the following steps: Step 1: Place the lipid matrix in a reaction vessel and heat it to 80~120℃ to melt it, while controlling the stirring speed at 100~200 rpm; Step 2: Add carboxyl-containing organic compounds and ester-containing organic compounds to the molten lipid matrix, heat to 130-160℃ at a rate of 5-10℃ / min, and maintain the temperature for 2-4 hours to form a lipid complex. Step 3: Cool the reaction system to 90~110℃, add hydrophilic functional additives, nano silver powder, modified functional agents, auxiliary agents and dispersants, stir and disperse for 30~60min, increase the stirring speed to 200~300rpm, and then let the mixed system cool naturally to room temperature to obtain the circulating water system protectant of the present invention.

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