Polymer organic amine salt composite boiler water treatment agent, and preparation method and application thereof

Abstract

The application provides a polymer organic amine salt composite boiler water treatment agent and a preparation method and application thereof, and belongs to the technical field of water treatment agent preparation. The water treatment agent takes an acid type acrylic acid / 2-acrylamide-2-methylpropane sulfonic acid / itaconic acid terpolymer as a scale inhibition and dispersion skeleton, forms a composite system through step-by-step amination of 2-amino-2-methyl-1-propanol and monoethanolamine, and realizes association and wet dispersion by combining with gluconic acid and a low-foaming EO / PO block polyether; the system does not depend on phosphate, phosphonate or sodium salt type polymers, and the neutralization amine is not only used for adjusting pH, but also used as a polymer counter ion and a deposition precursor dispersion component, which is helpful to improve the ionization and high-temperature hydration dispersion stability of the acid type polymer under sodium-free conditions; the obtained water treatment agent is used for boiler water treatment, has a dispersion control effect on calcium magnesium scale, iron oxide and silicon type deposition precursors, and is conducive to maintaining the stability of the pH and electric conductivity of the boiler water.

Description

Technical Field

[0001] This invention belongs to the field of water treatment agent preparation technology, and relates to a polymer organic amine salt composite boiler water treatment agent, its preparation method and application. Background Technology

[0002] During boiler operation, after being heated, evaporated, and concentrated, the feedwater contains calcium, magnesium, iron, silicon, and other components that easily form carbonate scale, silicate scale, iron oxide deposits, or complex deposits. These deposits adhere to the heated surfaces and pipe walls, affecting heat transfer efficiency and increasing localized corrosion, overheating, and operational risks. Therefore, it is usually necessary to add scale inhibitors, dispersants, pH adjusters, and other water treatment agents to the boiler water to maintain stable boiler water quality.

[0003] Existing boiler water treatment agents commonly employ phosphate, phosphonate, or phosphorus-containing compound systems. However, phosphorus-containing agents have high requirements for dosage and boiler water control, and may increase the burden of blowdown treatment. With the increasing demands for environmental emissions, steam quality, and conductivity control in boiler systems, phosphorus-free boiler water treatment agents are gradually gaining attention.

[0004] Currently, common phosphorus-free scale inhibitors and dispersants are mostly polymer systems such as polyacrylates, polymaleates, polyaspartates, and polyepoxysuccinates. Among them, sodium salt polymers are widely used due to their good water solubility and ionization, but they introduce sodium ions into the boiler water, which is not conducive to sodium-free treatment and conductivity control. If ordinary acidic polymers are directly used to replace sodium salt polymers, insufficient neutralization can easily lead to problems such as insufficient ionization of acidic sites, unstable chain segment hydration and dispersion, and decreased high-temperature dispersion stability, thus limiting their ability to control calcium and magnesium scale, iron oxides, and silicon deposit precursors.

[0005] Furthermore, while neutralizing amines can be used to adjust boiler water pH, their ability to inhibit and disperse scale precursors is limited. Simply combining neutralizing amines with conventional phosphate-free scale inhibitors cannot simultaneously address issues such as insufficient dispersion of acidic polymers, pH stability, and boiler water conductivity control under sodium-free conditions. Therefore, it is necessary to develop a polymer-organic amine salt composite boiler water treatment agent that can simultaneously achieve scale inhibition, pH adjustment, and water quality stability control without relying on phosphate, phosphonate, and sodium salt polymers. Summary of the Invention

[0006] To address the aforementioned problems, the present invention aims to provide a polymer organic amine salt composite boiler water treatment agent, its preparation method, and its application. This addresses the issues that existing boiler water treatment agents, when being improved towards phosphorus-free and sodium-free formulations, suffer from insufficient ionization of acidic sites, unstable chain segment hydration and dispersion, and decreased high-temperature dispersion stability when the neutralization degree of ordinary acidic polymers is insufficient. Furthermore, neutralizing amines alone are insufficient to effectively control calcium and magnesium scale, iron oxides, and silicon deposit precursors.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a polymeric organic amine salt composite boiler water treatment agent, comprising an acidic terpolymer, 2-amino-2-methyl-1-propanol, monoethanolamine, gluconic acid, low-foaming EO / PO block polyether, and deionized water; wherein the acidic terpolymer is a copolymer of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, and itaconic acid; wherein the 2-amino-2-methyl-1-propanol, monoethanolamine, and acidic terpolymer form a polymeric organic amine salt, and the polymeric organic amine salt, gluconic acid, and low-foaming EO / PO block polyether constitute a composite system.

[0009] In this application, the "polymer organic amine salt" refers to a polymer salt with organic ammonium ions as counterions, formed by partially neutralizing the acidic groups of an acidic terpolymer with 2-amino-2-methyl-1-propanol and monoethanolamine; the "composite system" refers to a compound system formed by the polymer organic amine salt, gluconic acid, and low-foaming EO / PO block polyether in an aqueous phase.

[0010] Secondly, the present invention provides a method for preparing a polymer organic amine salt composite boiler water treatment agent, the preparation method comprising:

[0011] S1: Add 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, and deionized water to a reaction vessel, stir and dissolve to obtain monomer solution A; add acrylic acid to deionized water to obtain monomer solution B; add mercaptoacetic acid to monomer solution A, purge with nitrogen and heat, add ferrous sulfate, then add monomer solution B, hydrogen peroxide aqueous solution, and isoascorbic acid aqueous solution dropwise to obtain a mixed reaction solution, and keep the reaction at the temperature; after the reaction is completed, remove residual volatile small molecules and peroxide decomposition gases, and cool to obtain an acidic terpolymer aqueous solution;

[0012] S2: Add the aqueous solution of the acidic terpolymer into a closed compounding vessel, and add 2-amino-2-methyl-1-propanol dropwise under stirring to carry out the first stage of ammoniation, and obtain the first stage ammoniation solution.

[0013] S3: Add a portion of monoethanolamine to the first-stage ammonium salting solution, followed by simultaneous addition of gluconic acid aqueous solution and the remaining monoethanolamine. After the addition is completed, continue stirring to obtain a preliminary ammonium salting association system. Then, seal the compounding vessel and heat and stir under nitrogen protection to obtain a polymer organic amine salt composite solution.

[0014] S4: Cool the polymer organic amine salt composite solution, add low-foaming EO / PO block polyether and deionized water, stir and homogenize to obtain a compound solution; mature, cool and filter the compound solution to obtain a polymer organic amine salt composite boiler water treatment agent.

[0015] Preferably, in S1, the molar ratio of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and itaconic acid is (55-68):(22-35):(8-12); the ratio of the total mass of the three monomers 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid and acrylic acid to the total mass of deionized water is 1:(1.8-3.8).

[0016] Preferably, in S1, the mass ratio of mercaptoacetic acid to the total mass of the three monomers is (0.3-1.2):100; nitrogen is introduced for purging for 20-40 minutes, followed by heating to 60-75°C; the amount of ferrous sulfate used is based on Fe... 2+ The mass of the raw materials in S1 is (0.5-5) mg / kg.

[0017] Preferably, in S1, the mass fraction of the hydrogen peroxide aqueous solution is 20-35 wt%; the ratio of hydrogen peroxide (based on the effective H2O2 mass) to the total mass of the three monomers is (0.4-1.5):100; the mass ratio of isoascorbic acid to the total mass of the three monomers is (0.05-0.50):100; and the mass ratio of isoascorbic acid to deionized water in the isoascorbic acid aqueous solution is 1:(8-25).

[0018] Preferably, in S1, the total dropping time of monomer solution B, hydrogen peroxide aqueous solution, and isoascorbic acid aqueous solution is 2-4 hours. During the dropping process, the reaction temperature is controlled at 60-78℃. After the dropping is completed, the reaction is kept at 65-80℃ for 1-3 hours. After the reaction is completed, residual volatile small molecules and peroxide decomposition gases are removed at 50-70℃ and a vacuum degree of 0.06-0.09MPa for 30-90 minutes.

[0019] Preferably, the solid content of the aqueous solution of the acidic terpolymer obtained in S1 is 20-36 wt%, and the weight-average molecular weight Mw of the acidic terpolymer is 8000-20000.

[0020] Preferably, in S2, the system temperature is controlled at 30-45℃; the amino equivalent of 2-amino-2-methyl-1-propanol accounts for 35-50% of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine; the dropping time of 2-amino-2-methyl-1-propanol is 20-60 min, and stirring is continued for 30-90 min after the dropping is completed.

[0021] Preferably, in S3, the amino equivalent of monoethanolamine is the remainder of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine; the ratio of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine to the total acid equivalent of carboxyl groups and sulfonic acid groups in the acidic terpolymer and carboxyl groups in gluconic acid is (0.60-0.90):1; when the amount of monoethanolamine added reaches 40-70% of its total amount, a 40-60 wt% aqueous solution of gluconic acid and the remaining monoethanolamine are added simultaneously.

[0022] Preferably, in S3, the mass ratio of gluconic acid to acidic terpolymer solid is (8-22):100; after the addition is completed, the mixture is stirred at 30-45℃ for 1-2 hours to obtain a preliminary ammonium salting association system; then the compounding vessel is sealed and heated to 65-80℃ under nitrogen protection, and stirred for 2-4 hours to obtain a polymer organic amine salt composite solution.

[0023] Preferably, in step S4, after cooling the polymer organic amine salt composite solution to 35-55°C, low-foaming EO / PO block polyether is added; the mass ratio of the low-foaming EO / PO block polyether to the acidic terpolymer solid is (0.5-2.5):100.

[0024] Preferably, the low-foaming EO / PO block polyether is a polyoxyethylene-polyoxypropylene block copolymer with a number average molecular weight of 1500-4000 and an EO content of 10-40 wt%.

[0025] Preferably, in step S4, deionized water is added to make the total mass of the acidic terpolymer solid, 2-amino-2-methyl-1-propanol, monoethanolamine, gluconic acid, and low-foaming EO / PO block polyether account for 28-33 wt% of the total mass of the compound solution; the mixture is stirred and homogenized at 35-55°C for 1-3 hours to obtain the compound solution; the compound solution is then aged at 35-60°C for 2-6 hours, cooled to 20-35°C, and filtered through a 5-20 μm filter.

[0026] This application does not involve the conventional compounding of neutralizing amines, polymer scale inhibitors, and surfactants. Instead, it addresses the contradiction in phosphorus-free and sodium-free systems where "the degree of ionization of acidic sites, the hydration and dispersion state of chain segments, and high-temperature dispersion stability are difficult to balance when the degree of neutralization is insufficient." Instead, it constructs a synergistic system of organic amine salting between acidic terpolymers and functionalized neutralizing amines.

[0027] The acidic terpolymer is formed by copolymerizing acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, and itaconic acid. The acrylic acid unit provides carboxyl interaction sites, enabling it to participate in the adsorption and dispersion of calcium and magnesium scale-forming ions and deposition precursors. The 2-acrylamido-2-methylpropanesulfonic acid unit provides sulfonic acid hydration sites, which helps maintain the extension and dispersion stability of polymer segments in the aqueous phase. The itaconic acid unit contains a dicarboxyl structure, which enhances its localized multi-point interaction capability. The combination of these three types of units gives the copolymer carboxyl, sulfonic acid, and dicarboxyl sites, providing a structural basis for subsequent ammoniation and deposition precursor dispersion under sodium-free conditions.

[0028] This application employs a redox initiation system composed of hydrogen peroxide, isoascorbic acid, and ferrous ions during the polymerization stage, instead of using sodium salt initiators, phosphorus-containing chain transfer agents, or ammonium salt initiators. This avoids the intentional introduction of sodium ions, inorganic ammonium ions, or phosphorus-containing structures during polymerization, ensuring that the resulting terpolymer remains predominantly acidic, providing acidic sites for subsequent organic amine salt formation. This configuration allows the subsequent addition of 2-amino-2-methyl-1-propanol and monoethanolamine to not only adjust the system pH but also participate as organic counterions in the construction of the polymer organic amine salt, expanding the role of the neutralizing amine from a simple pH adjuster to a multifunctional component encompassing pH adjustment, polymer counterion formation, and dispersion assistance.

[0029] This application employs a stepwise ammoniation method, with 2-amino-2-methyl-1-propanol added first, followed by monoethanolamine. 2-amino-2-methyl-1-propanol first undergoes a first-stage ammoniation reaction with the sulfonic acid and carboxyl groups in the acidic terpolymer. Because 2-amino-2-methyl-1-propanol contains a branched dimethyl substituted structure, amino groups, and primary hydroxyl groups, the resulting organoammonium ions have a larger spatial volume and a certain degree of hydration compared to the organoammonium ions corresponding to monoethanolamine. This helps to form a relatively stable hydration environment and steric hindrance around the polymer segments, reducing the tendency for excessive association of polymer segments under sodium-free conditions. Subsequently, monoethanolamine continues to participate in the ammoniation. Its smaller molecular size and stronger hydrophilicity of hydroxyl groups further replenish the neutralization sites of carboxyl and sulfonic acid groups on the polymer segments, enabling the copolymer to achieve high aqueous ionization and hydration dispersion capabilities without conversion to sodium salts.

[0030] This application does not add gluconic acid separately after ammonium salting; instead, it introduces the aqueous solution of gluconic acid and the remaining monoethanolamine simultaneously during the dropwise addition of monoethanolamine. This method allows the carboxyl group of gluconic acid to participate in the acid-base balance of the system in the presence of organic amines. Its polyhydroxy structure can form hydrogen bonds or ionic associations with the forming polymer organic amine salt segments, making gluconic acid more readily involved in the polymer organic amine salt complex system, rather than being added in a relatively free small molecule state after ammonium salting. Therefore, gluconic acid can work together with the polymer organic amine salt system to act on iron ions, iron oxides, and silicon-based deposition precursors, improving the system's auxiliary dispersion and stabilization effect.

[0031] Simultaneously, this application incorporates a closed-loop heating and holding stage after low-temperature ammonium salting. The low-temperature stage primarily completes acid-base neutralization and preliminary ion pair formation; the heating and holding stage further homogenizes the acid-base interactions, ion associations, and hydrogen bonding among polymer segments, organic ammonium ions, and gluconic acid, thereby improving the stability of the polymer organic amine salt composite system in a high-temperature aquatic environment. Through stepwise ammonium salting, simultaneous addition of gluconic acid, and heating and holding treatment, the neutralized amine, in addition to participating in pH adjustment, can also act as a polymer organic counterion and assist in maintaining segment hydration and the dispersion state of deposition precursors.

[0032] Finally, the low-foaming EO / PO block polyether is added after the polymer organic amine salt composite solution is formed. This primarily helps improve the wetting and dispersion of fine deposited particles and colloidal precursors, and is beneficial for the later homogenization of the compound solution. This subsequent addition reduces its impact on the initial acid-base neutralization and ammonium salt formation processes. Furthermore, the selection of a low-foaming EO / PO block polyether helps to balance the wetting and dispersion effects with the low-foaming requirements of the boiler water system.

[0033] This application provides a structured solution to the problem of acidic polymers failing to stably exert their scale inhibition and dispersion effects in phosphorus-free and sodium-free boiler water treatment systems by avoiding the intentional introduction of sodium salts, inorganic ammonium salts, and phosphorus-containing components during the polymerization stage. This is achieved by combining the stepwise ammoniation of 2-amino-2-methyl-1-propanol and monoethanolamine, the simultaneous addition of gluconic acid in the middle and late stages, and subsequent heating and heat preservation homogenization treatment. This transforms the neutralizing amine from a conventional pH adjuster into an organic counterion of the acidic polymer and a synergistic component for dispersing deposition precursors.

[0034] Thirdly, the present invention provides an application of a polymer organic amine salt composite boiler water treatment agent in boiler water treatment.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0036] This application prepares acidic terpolymers through a redox initiation system of hydrogen peroxide, isoascorbic acid, and ferrous ions, avoiding the intentional introduction of sodium ions, inorganic ammonium ions, or phosphorus-containing structures during the polymerization stage. This allows the acidic sites of the acidic terpolymers to be used for subsequent organic amine salting, which is different from phosphorus-free water treatment systems that directly use sodium salt polymers or ammonium salt polymers.

[0037] This application employs stepwise ammonitization of acidic terpolymers with 2-amino-2-methyl-1-propanol and monoethanolamine, enabling the neutralizing amine to not only regulate pH but also participate as an organic counterion in the hydration and ionization dispersion of polymer segments. This improves the problems of insufficient ionization of acidic sites and unstable hydration and dispersion of segments in ordinary acidic polymers under sodium-free conditions.

[0038] This application introduces gluconic acid aqueous solution and residual monoethanolamine simultaneously during the dropwise addition of monoethanolamine, so that gluconic acid can participate in acid-base balance, hydrogen bonding, and ion association during the formation of the polymer organic amine salt system, rather than being added as a relatively free small molecule component after the ammonium salting is completed. This is beneficial to enhance the auxiliary dispersion and stabilization effect of the system on iron oxide and silicon deposition precursors.

[0039] This application combines low-temperature ammonium salting with closed-loop heating and heat preservation to further homogenize the acid-base interactions, ion associations, and hydrogen bonding among the acidic terpolymer, organic amine, and gluconic acid. This helps to improve the stability of the polymer organic amine salt composite system and improve problems such as uneven distribution of amine components and unstable ionization state of polymer segments in simple physical compounding.

[0040] This application arranges the low-foaming EO / PO block polyether to be added after the formation of the polymer organic amine salt composite solution. This can further assist the wetting and dispersion of fine deposited particles after the simultaneous association of ammonium salting and gluconic acid in the early stage, and reduce the risk of foaming problems caused by ordinary surfactants. Attached Figure Description

[0041] Figure 1 This is a photograph of the polymer organic amine salt composite boiler water treatment agent prepared in Example 1 of the present invention. Detailed Implementation

[0042] The technical solutions of the present invention will be described in detail below with reference to specific embodiments and accompanying drawings. The embodiments described herein are specific implementations of the present invention, used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary, and should not be construed as limiting the implementation methods or the scope of protection of the present invention. In addition to the embodiments described herein, those skilled in the art can employ other obvious technical solutions based on the content disclosed in the claims and specification of this application. These technical solutions include any obvious substitutions and modifications made to the embodiments described herein.

[0043] The chemical reagents used in the embodiments and comparative examples of this invention are all commercially available products and have not undergone further purification or processing.

[0044] Example 1

[0045] This embodiment provides a polymer-organic amine salt composite boiler water treatment agent and its preparation method. The preparation method of the polymer-organic amine salt composite boiler water treatment agent specifically includes the following steps:

[0046] S1: Add 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, and deionized water to a reaction vessel, stir and dissolve to obtain monomer solution A; add acrylic acid to deionized water to obtain monomer solution B, wherein the molar ratio of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, and itaconic acid is 60:30:10, and the total mass ratio of the three monomers (2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, and acrylic acid) to the total mass ratio of deionized water is 1:2.5; add mercaptoacetic acid to monomer solution A, wherein the mass ratio of mercaptoacetic acid to the total mass of the three monomers is 0.8:100, purge with nitrogen for 30 min, raise the temperature to 65℃, and add ferrous sulfate, wherein the amount of ferrous sulfate is based on Fe 2+ The mass ratio of the total mass of all raw materials in S1 was 2 mg / kg. Subsequently, monomer solution B, a 25 wt% hydrogen peroxide aqueous solution, and an isoascorbic acid aqueous solution were added dropwise to obtain a mixed reaction solution. The ratio of hydrogen peroxide (based on effective H2O2) to the total mass of the three monomers was 1.0:100, the ratio of isoascorbic acid to the total mass of the three monomers was 0.2:100, and the mass ratio of isoascorbic acid to deionized water in the isoascorbic acid aqueous solution was 1:15. The total dropwise addition time was 3 hours, and the reaction temperature was controlled at 65℃ during the dropwise addition. After the dropwise addition was completed, the reaction was maintained at 70℃ for 2 hours. After the reaction was completed, residual volatile small molecules and peroxide decomposition gases were removed at 60℃ and a vacuum of 0.07 MPa for 60 minutes. After cooling, an acidic terpolymer aqueous solution was obtained.

[0047] S2: Add the aqueous solution of the acidic terpolymer into a closed compounding vessel, control the temperature at 35℃, and add 2-amino-2-methyl-1-propanol dropwise under stirring to carry out the first stage of amination, wherein the amino equivalent of 2-amino-2-methyl-1-propanol accounts for 40% of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine, the dropwise addition time is 40 min, and after the dropwise addition is completed, continue stirring for 60 min to obtain the first stage amination solution;

[0048] S3: Monoethanolamine is added dropwise to the first-stage ammonium salting solution. When the amount of monoethanolamine added reaches 50% of its total amount, a 50wt% aqueous solution of gluconic acid and the remaining monoethanolamine are added dropwise simultaneously. The amino equivalent of the monoethanolamine is the remainder of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine. The ratio of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine to the total acid equivalent of carboxyl and sulfonic acid groups in the acidic terpolymer and carboxyl groups in gluconic acid is 0.75:1. The solid mass ratio of gluconic acid to the acidic terpolymer is 15:100. After the addition is completed, the mixture is stirred at 38℃ for 1.5h to obtain a preliminary ammonium salting association system. Then, the compounding vessel is sealed and heated to 70℃ under nitrogen protection, and stirred for 3h to obtain a polymer organic amine salt composite solution.

[0049] S4: Cool the polymer organic amine salt composite solution to 45°C, add low-foaming EO / PO block polyether, wherein the mass ratio of low-foaming EO / PO block polyether to acidic terpolymer solid is 1.5:100; continue to add deionized water, so that the total mass of acidic terpolymer solid, 2-amino-2-methyl-1-propanol, monoethanolamine, gluconic acid, and low-foaming EO / PO block polyether accounts for 30wt% of the total mass of the compound solution; stir and homogenize at 40°C for 2 hours to obtain the compound solution; mature the compound solution at 45°C for 4 hours, cool it to 25°C, and filter it through a 10μm filter to obtain the following... Figure 1 The polymer organic amine salt composite boiler water treatment agent shown is shown.

[0050] Example 2

[0051] This embodiment provides a polymer-organic amine salt composite boiler water treatment agent and its preparation method. The preparation method of the polymer-organic amine salt composite boiler water treatment agent specifically includes the following steps:

[0052] S1: Add 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, and deionized water to a reaction vessel, stir and dissolve to obtain monomer solution A; add acrylic acid to deionized water to obtain monomer solution B, wherein the molar ratio of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, and itaconic acid is 55:22:8, and the total mass ratio of the three monomers (2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, and acrylic acid) to the total mass ratio of deionized water is 1:1.8; add mercaptoacetic acid to monomer solution A, wherein the mass ratio of mercaptoacetic acid to the total mass of the three monomers is 0.3:100, purge with nitrogen for 20 min, raise the temperature to 60℃, and add ferrous sulfate, wherein the amount of ferrous sulfate is based on Fe 2+ The mass ratio of the total mass of all raw materials in S1 was 0.5 mg / kg. Subsequently, monomer solution B, a 20 wt% hydrogen peroxide aqueous solution, and an isoascorbic acid aqueous solution were added dropwise to obtain a mixed reaction solution. The ratio of hydrogen peroxide (based on the effective H2O2 mass) to the total mass of the three monomers was 0.4:100, the ratio of isoascorbic acid to the total mass of the three monomers was 0.05:100, and the mass ratio of isoascorbic acid to deionized water in the isoascorbic acid aqueous solution was 1:8. The total dropwise addition time was 2 h, and the reaction temperature was controlled at 60 °C during the dropwise addition. After the dropwise addition was completed, the reaction was kept at 65 °C for 1 h. After the reaction was completed, residual volatile small molecules and peroxide decomposition gases were removed at 50 °C and a vacuum of 0.06 MPa for 30 min. After cooling, an acidic terpolymer aqueous solution was obtained.

[0053] S2: Add the aqueous solution of the acidic terpolymer into a closed compounding vessel, control the temperature at 30℃, and add 2-amino-2-methyl-1-propanol dropwise under stirring to carry out the first stage of ammoniation, wherein the amino equivalent of 2-amino-2-methyl-1-propanol accounts for 35% of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine, the dropwise addition time is 20 min, and after the dropwise addition is completed, continue stirring for 30 min to obtain the first stage of ammoniation solution;

[0054] S3: Monoethanolamine is added dropwise to the first-stage ammonium salting solution. When the amount of monoethanolamine added reaches 40% of its total amount, a 40wt% aqueous solution of gluconic acid and the remaining monoethanolamine are added dropwise simultaneously. The amino equivalent of monoethanolamine is the remainder of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine. The ratio of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine to the total acid equivalent of carboxyl and sulfonic acid groups in the acidic terpolymer and carboxyl groups in gluconic acid is 0.60:1. The solid mass ratio of gluconic acid to the acidic terpolymer is 8:100. After the addition is completed, the mixture is stirred at 30°C for 1 hour to obtain a preliminary ammonium salting association system. Subsequently, the compounding vessel is sealed and heated to 65°C under nitrogen protection, and stirred for 2 hours to obtain a polymer organic amine salt composite solution.

[0055] S4: Cool the polymer organic amine salt composite solution to 35°C, add low-foaming EO / PO block polyether, wherein the mass ratio of low-foaming EO / PO block polyether to acidic terpolymer solid is 0.5:100; continue to add deionized water so that the total mass of acidic terpolymer solid, 2-amino-2-methyl-1-propanol, monoethanolamine, gluconic acid and low-foaming EO / PO block polyether accounts for 28wt% of the total mass of the compound solution; stir and homogenize at 35°C for 1 hour to obtain the compound solution; mature the compound solution at 35°C for 2 hours, cool it to 20°C and filter it through a 5μm filter to obtain the polymer organic amine salt composite boiler water treatment agent.

[0056] Example 3

[0057] This embodiment provides a polymer-organic amine salt composite boiler water treatment agent and its preparation method. The preparation method of the polymer-organic amine salt composite boiler water treatment agent specifically includes the following steps:

[0058] S1: Add 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, and deionized water to a reaction vessel, stir and dissolve to obtain monomer solution A; add acrylic acid to deionized water to obtain monomer solution B, wherein the molar ratio of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, and itaconic acid is 68:35:12, and the total mass ratio of the three monomers (2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, and acrylic acid) to the total mass ratio of deionized water is 1:3.8; add mercaptoacetic acid to monomer solution A, wherein the mass ratio of mercaptoacetic acid to the total mass of the three monomers is 1.2:100, purge with nitrogen for 40 min, raise the temperature to 75℃, and add ferrous sulfate, wherein the amount of ferrous sulfate is based on Fe 2+ The mass ratio of the total mass of all raw materials in S1 was 5 mg / kg. Subsequently, monomer solution B, a 35 wt% hydrogen peroxide aqueous solution, and an isoascorbic acid aqueous solution were added dropwise to obtain a mixed reaction solution. The ratio of hydrogen peroxide (based on effective H2O2) to the total mass of the three monomers was 1.5:100, the ratio of isoascorbic acid to the total mass of the three monomers was 0.50:100, and the ratio of isoascorbic acid to deionized water in the isoascorbic acid aqueous solution was 1:25. The total addition time was 4 hours, and the reaction temperature was controlled at 78℃ during the addition. After the addition was completed, the reaction was maintained at 80℃ for 3 hours. After the reaction was completed, residual volatile small molecules and peroxide decomposition gases were removed at 70℃ and a vacuum of 0.09 MPa for 90 minutes. After cooling, an acidic terpolymer aqueous solution was obtained.

[0059] S2: Add the aqueous solution of the acidic terpolymer into a closed compounding vessel, control the temperature at 45℃, and add 2-amino-2-methyl-1-propanol dropwise under stirring to carry out the first stage of amination, wherein the amino equivalent of 2-amino-2-methyl-1-propanol accounts for 50% of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine, the dropwise addition time is 60 min, and after the dropwise addition is completed, continue stirring for 90 min to obtain the first stage amination solution;

[0060] S3: Monoethanolamine is added dropwise to the first-stage ammonium salting solution. When the amount of monoethanolamine added reaches 70% of its total amount, a 60wt% aqueous solution of gluconic acid and the remaining monoethanolamine are added dropwise simultaneously. The amino equivalent of the monoethanolamine is the remainder of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine. The ratio of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine to the total acid equivalent of carboxyl and sulfonic acid groups in the acidic terpolymer and carboxyl groups in gluconic acid is 0.90:1. The solid mass ratio of gluconic acid to the acidic terpolymer is 22:100. After the addition is completed, the mixture is stirred at 45℃ for 2 hours to obtain a preliminary ammonium salting association system. Then, the compounding vessel is sealed and heated to 80℃ under nitrogen protection, and stirred for 4 hours to obtain a polymer organic amine salt composite solution.

[0061] S4: Cool the polymer organic amine salt composite solution to 55°C, add low-foaming EO / PO block polyether, wherein the mass ratio of low-foaming EO / PO block polyether to acidic terpolymer solid is 2.5:100; continue to add deionized water so that the total mass of acidic terpolymer solid, 2-amino-2-methyl-1-propanol, monoethanolamine, gluconic acid and low-foaming EO / PO block polyether accounts for 33wt% of the total mass of the compound solution; stir and homogenize at 55°C for 3h to obtain the compound solution; mature the compound solution at 60°C for 6h, cool it to 35°C and filter it through a 20μm filter to obtain the polymer organic amine salt composite boiler water treatment agent.

[0062] Example 4

[0063] This embodiment provides a polymer-organic amine salt composite boiler water treatment agent and its preparation method. The preparation method of the polymer-organic amine salt composite boiler water treatment agent specifically includes the following steps:

[0064] S1: Add 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, and deionized water to a reaction vessel, stir and dissolve to obtain monomer solution A; add acrylic acid to deionized water to obtain monomer solution B, wherein the molar ratio of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, and itaconic acid is 65:28:11, and the total mass ratio of the three monomers (2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, and acrylic acid) to the total mass ratio of deionized water is 1:3.5; add mercaptoacetic acid to monomer solution A, wherein the mass ratio of mercaptoacetic acid to the total mass of the three monomers is 1.0:100, purge with nitrogen for 35 min, raise the temperature to 70℃, and add ferrous sulfate, wherein the amount of ferrous sulfate is based on Fe 2+ The mass ratio of the total mass of all raw materials in S1 was 4 mg / kg. Subsequently, monomer solution B, a 30 wt% hydrogen peroxide aqueous solution, and an isoascorbic acid aqueous solution were added dropwise to obtain a mixed reaction solution. The ratio of hydrogen peroxide (based on available H2O2) to the total mass of the three monomers was 1.2:100, the ratio of isoascorbic acid to the total mass of the three monomers was 0.4:100, and the ratio of isoascorbic acid to deionized water in the isoascorbic acid aqueous solution was 1:20. The total dropwise addition time was 3.5 h, and the reaction temperature was controlled at 75 °C during the dropwise addition. After the dropwise addition was completed, the reaction was maintained at 75 °C for 2.5 h. After the reaction was completed, residual volatile small molecules and peroxide decomposition gases were removed at 65 °C and a vacuum of 0.08 MPa for 80 min. After cooling, an acidic terpolymer aqueous solution was obtained.

[0065] S2: Add the aqueous solution of the acidic terpolymer into a closed compounding vessel, control the temperature at 40℃, and add 2-amino-2-methyl-1-propanol dropwise under stirring to carry out the first stage of amination, wherein the amino equivalent of 2-amino-2-methyl-1-propanol accounts for 45% of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine, the dropwise addition time is 50 min, and after the dropwise addition is completed, continue stirring for 80 min to obtain the first stage amination solution;

[0066] S3: Monoethanolamine was added dropwise to the first-stage ammonium salting solution. When the amount of monoethanolamine added reached 60% of its total amount, a 55wt% aqueous solution of gluconic acid and the remaining monoethanolamine were added dropwise simultaneously. The amino equivalent of the monoethanolamine was the remainder of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine. The ratio of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine to the total acid equivalent of carboxyl and sulfonic acid groups in the acidic terpolymer and carboxyl groups in gluconic acid was 0.85:1. The solid mass ratio of gluconic acid to the acidic terpolymer was 20:100. After the addition was completed, the mixture was stirred at 40°C for 1.8 h to obtain a preliminary ammonium salting association system. Subsequently, the compounding vessel was sealed and heated to 75°C under nitrogen protection and stirred for 3.5 h to obtain a polymer organic amine salt composite solution.

[0067] S4: Cool the polymer organic amine salt composite solution to 50°C, add low-foaming EO / PO block polyether, wherein the mass ratio of low-foaming EO / PO block polyether to acidic terpolymer solid is 2.0:100; continue to add deionized water so that the total mass of acidic terpolymer solid, 2-amino-2-methyl-1-propanol, monoethanolamine, gluconic acid and low-foaming EO / PO block polyether accounts for 31 wt% of the total mass of the compound solution; stir and homogenize at 50°C for 2.5 h to obtain the compound solution; mature the compound solution at 55°C for 5 h, cool it to 30°C and filter it through a 15 μm filter to obtain the polymer organic amine salt composite boiler water treatment agent.

[0068] Comparative Example 1

[0069] This comparative example provides a polymer organic amine salt composite boiler water treatment agent and its preparation method. The difference from Example 1 is that the stepwise amine salting method of adding 2-amino-2-methyl-1-propanol first and then monoethanolamine is not used. The acidic terpolymer aqueous solution obtained in S1 is added to a closed compounding reactor, and the system temperature is controlled at 35°C. The amount of 2-amino-2-methyl-1-propanol and monoethanolamine used in Example 1 are pre-mixed and added to the acidic terpolymer aqueous solution at one time under stirring. After the addition is completed, the mixture is stirred at 35°C for 100 min. Then the system temperature is adjusted to 38°C, and an equal amount of 50wt% gluconic acid aqueous solution is added dropwise. After the dropwise addition is completed, the mixture is stirred at 38°C for 1.5 h. Then the compounding reactor is sealed and heated to 70°C under nitrogen protection, and stirred for 3 h. Other operating steps and process parameters are exactly the same as in Example 1.

[0070] Comparative Example 2

[0071] This comparative example provides a polymer organic amine salt composite boiler water treatment agent and its preparation method. The difference from Example 1 is that 2-amino-2-methyl-1-propanol is not added, but is replaced entirely with monoethanolamine of equal amino equivalent. Other operating steps and process parameters are exactly the same as in Example 1.

[0072] Comparative Example 3

[0073] This comparative example provides a polymer organic amine salt composite boiler water treatment agent and its preparation method. The difference from Example 1 is that monoethanolamine is not added, but is replaced entirely with 2-amino-2-methyl-1-propanol of equal amino equivalent. Other operating steps and process parameters are exactly the same as in Example 1.

[0074] Comparative Example 4

[0075] This comparative example provides a polymer organic amine salt composite boiler water treatment agent and its preparation method. The difference from Example 1 is that in S3, gluconic acid aqueous solution is not added simultaneously when the amount of monoethanolamine added reaches 50% of its total amount. After the monoethanolamine is added, the mixture is stirred at 38°C for 1.5 hours. Then, the mixing vessel is sealed, heated to 70°C under nitrogen protection, and stirred for 3 hours. After the temperature is maintained, the system is cooled to 38°C, and gluconic acid aqueous solution is added. After the addition is completed, the mixture is stirred at 38°C for 1.5 hours. Then, the system temperature is adjusted to 45°C, and the operation is continued according to S4 of Example 1. Other operation steps and process parameters are exactly the same as in Example 1.

[0076] Comparative Example 5

[0077] This comparative example provides a polymer organic amine salt composite boiler water treatment agent and its preparation method. The difference from Example 1 is that after the addition of monoethanolamine and gluconic acid aqueous solution in S3, the mixture is stirred at 38°C for 1.5 hours as in Example 1. Subsequently, instead of heating to 70°C and stirring at that temperature for 3 hours, the mixture is stirred at 38°C for 3 hours. Other operating steps and process parameters are exactly the same as in Example 1.

[0078] The performance of the polymer organic amine salt composite boiler water treatment agents of Examples 1-4 and Comparative Examples 1-5 was tested, and the specific process is as follows:

[0079] High-temperature water quality stability test: Deionized water was used to prepare test samples. The reagents obtained in each example and comparative example were added to the test samples according to the effective component concentration, making the effective component concentration 100 mg / L. The water samples were placed in a high-pressure reactor, sealed, and heated to 250°C for aging for 6 hours. After cooling to 25°C, the samples were removed. The pH value of the water samples before and after aging, as well as the hydrogen conductivity after treatment with an H-type cation exchange column, were measured. The pH change and hydrogen conductivity change rate (%) were calculated.

[0080] Rate of change of hydrogen conductivity = ×100%.

[0081] High-temperature composite deposition control test: Preparation of simulated boiler concentrate containing calcium, magnesium, iron, and silicon, wherein Ca... 2+ The concentration is 80 mg / L, Mg 2+ The concentration is 30 mg / L, Fe 3+ The concentration of colloidal silica (SiO2) was 120 mg / L, and the reagents obtained in each example and comparative example were added according to the effective component to make the effective component concentration 100 mg / L. After stirring evenly, the pH of the water sample was adjusted to 10.0 ± 0.2 using an organic amine mixture composed of 2-amino-2-methyl-1-propanol and monoethanolamine with an amino equivalent ratio of 40:60. The water sample was placed in a high-pressure reactor and kept at 200℃ for 6 h. After cooling, it was filtered through a 0.45 μm filter membrane. The filter membrane residue was dried at 105℃ to constant weight, and the sediment mass was measured. A blank group without the test water treatment agent was also set up. Except for the absence of the test water treatment agent, the water sample composition, pH adjustment method, high-temperature treatment, filtration and drying conditions of the blank group were the same as those of the dosing group, and the composite sedimentation control rate (%) was calculated according to the following formula:

[0082] Composite deposition control rate = ×100%.

[0083] Iron-silicon dispersion stability test: An iron-silicon dispersion test solution was prepared, wherein the concentration of Fe2O3 nanoparticles was 50 mg / L and the concentration of colloidal silica (SiO2) was 150 mg / L. The test solution was prepared by adjusting the pH to 10.0 ± 0.2 using an organic amine mixture composed of 2-amino-2-methyl-1-propanol and monoethanolamine with an amino equivalent ratio of 40:60. The reagents obtained in the examples and comparative examples were added according to the effective component to make the effective component concentration 80 mg / L. The test solution was placed in a high-pressure reactor and kept at 200℃ for 4 h. After cooling, it was allowed to stand for 30 min and then filtered through a 0.45 μm filter membrane.

[0084] The mass concentrations of iron and silicon in the filtrate were determined by inductively coupled plasma atomic emission spectrometry and calculated using the following formula:

[0085] Iron retention rate = (mass concentration of iron in the filtrate after filtration / initial mass concentration of iron in the test solution) × 100%;

[0086] Silicon retention rate = (mass concentration of silicon in the filtrate after filtration / initial mass concentration of silicon in the test solution) × 100%.

[0087] The initial iron and silicon concentrations of the test solution were calculated based on the amount of Fe2O3 and SiO2 added and their elemental mass fractions, respectively.

[0088] The test results are shown in Table 1.

[0089] Table 1 Performance test results of polymer organic amine salt composite boiler water treatment agents in Examples 1-4 and Comparative Examples 1-5

[0090]

[0091] As shown in Table 1, the test results of Example 1 and Comparative Example 1 indicate that adding 2-amino-2-methyl-1-propanol and monoethanolamine to the acidic terpolymer aqueous solution at once, instead of the stepwise construction method of first participating in the first stage of ammoniation with 2-amino-2-methyl-1-propanol and then supplementing with monoethanolamine in subsequent ammoniation, resulted in the simultaneous contact of the two amines with the carboxyl and sulfonic acid groups in the acidic terpolymer. This was not conducive to the formation of a relatively uniform distribution of ammoniation sites and the hydration state of the chain segments. During high-temperature aging, the stability of the organic amine ammoniation structure in the system was relatively insufficient, and the pH and hydrogen conductivity fluctuated more after aging, thus increasing the pH change value and the rate of change of hydrogen conductivity. At the same time, the adsorption and dispersion ability of the acidic terpolymer for calcium and magnesium scale-forming ions and composite deposition precursors decreased, leading to a decrease in the composite deposition control rate. Due to the weakened stabilizing effect of the polymer organic amine salt system on iron oxide particles and silicon colloidal precursors, the iron retention rate and silicon retention rate also decreased accordingly.

[0092] As shown in Table 1, the test results of Example 1 and Comparative Example 2 indicate that without the addition of 2-amino-2-methyl-1-propanol and with monoethanolamine as the sole substitute, the steric hindrance of the branched alkyl groups provided by 2-amino-2-methyl-1-propanol in the first stage of ammoniation and the hydration environment in which it participates in the construction are lacking. This results in insufficient stabilization of the initial ammoniation structure of the acidic terpolymer on the chain segment conformation. Under high temperature conditions, polymer chains are more prone to local association or a decrease in dispersion, thus increasing the pH change and hydrogen conductivity change rate. Although monoethanolamine can still provide some neutralization, its auxiliary effect on the steric stabilization of polymer chains and the dispersion of silicon precursors is relatively insufficient, leading to a decrease in the composite deposition control rate. At the same time, due to the lack of relatively stable hydration and steric stabilization effects of the organic ammonium ions formed by 2-amino-2-methyl-1-propanol around the iron oxide particles and silicon oligomers, the iron retention rate and silicon retention rate are both lower than in Example 1.

[0093] As shown in Table 1, the test results of Example 1 and Comparative Example 3 indicate that without the addition of monoethanolamine and with 2-amino-2-methyl-1-propanol as the sole substitute, the subsequent addition of monoethanolamine for ammonium salting resulted in insufficient neutralization and hydration of carboxyl and sulfonic acid sites, leading to relatively inadequate uniformity of ammonium salting site distribution and insufficient chain segment hydration dispersion in the acidic terpolymer. After high-temperature aging, the balance of effective ammonium salting sites in the system was poor, resulting in increased pH change and hydrogen conductivity change rate. Simultaneously, the lack of monoethanolamine hindered the neutralization and homogenization of ammonium salting site distribution, thereby weakening the polymer dispersion and reducing the composite deposition control rate. Although 2-amino-2-methyl-1-propanol still had a certain auxiliary stabilizing effect on the iron-silicon precursor, the lack of monoethanolamine for hydration resulted in insufficient overall dispersion uniformity of the system, and the iron retention rate and silicon retention rate were still lower than in Example 1.

[0094] As shown in Table 1, the test results of Example 1 and Comparative Example 4 indicate that when gluconic acid was replaced with amine salting followed by heating and heat preservation, the process of gluconic acid participating simultaneously in the formation of the polymer-organic amine-gluconic acid association system during the later stages of monoethanolamine addition was missing. The degree of association between gluconic acid and the polymer-organic amine salt system was relatively low, making it difficult to fully participate in the formation of the polymer-organic amine salt association system. Therefore, during high-temperature aging, the water quality stability of the system decreased relatively, manifested as an increase in pH change and hydrogen conductivity change rate. Because gluconic acid failed to fully participate in the early stage of composite system formation, its synergistic dispersion effect on composite deposition precursors was weakened, resulting in a lower composite deposition control rate. Simultaneously, the auxiliary stabilizing effect of gluconic acid on iron ions, iron oxides, and silicon precursors could not fully cooperate with the polymer-organic amine salt system, leading to a decrease in iron retention and silicon retention. The differences in iron and silicon dispersion-related indicators further highlight the role of the timing of gluconic acid's simultaneous addition.

[0095] As can be seen from the test results of Example 1 and Comparative Example 5 in Table 1, Comparative Example 5 did not undergo a closed heating and heat preservation treatment after completing the low-temperature ammonium salting and simultaneous addition of gluconic acid. This lack of heating and heat preservation further homogenized and stabilized the composite system, resulting in relatively insufficient stability of the polymer organic amine salt composite system under high-temperature aging conditions. Under high-temperature aging conditions, the pH and hydrogen conductivity of the system fluctuated more, thus increasing the pH change value and the rate of change of hydrogen conductivity. At the same time, the composite system weakened its dispersion and stabilization effect on calcium and magnesium scale-forming ions, iron oxide particles and silicon colloidal precursors, resulting in a lower composite deposition control rate, iron retention rate and silicon retention rate than in Example 1.

[0096] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A polymer-organic amine salt composite boiler water treatment agent, characterized in that, The product comprises an acidic terpolymer, 2-amino-2-methyl-1-propanol, monoethanolamine, gluconic acid, low-foaming EO / PO block polyether, and deionized water; the acidic terpolymer is a copolymer of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, and itaconic acid; the 2-amino-2-methyl-1-propanol, monoethanolamine, and acidic terpolymer form a polymeric organic amine salt, and the polymeric organic amine salt, gluconic acid, and low-foaming EO / PO block polyether constitute a composite system.

2. The polymer organic amine salt composite boiler water treatment agent according to claim 1, characterized in that, The molar ratio of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and itaconic acid is (55-68):(22-35):(8-12).

3. The polymer organic amine salt composite boiler water treatment agent according to claim 1, characterized in that, The total mass of the acidic terpolymer solid, 2-amino-2-methyl-1-propanol, monoethanolamine, gluconic acid, and low-foaming EO / PO block polyether accounts for 28-33 wt% of the total mass of the polymer organic amine salt composite boiler water treatment agent; the mass ratio of gluconic acid to acidic terpolymer solid is (8-22):100; the mass ratio of low-foaming EO / PO block polyether to acidic terpolymer solid is (0.5-2.5):

100.

4. The polymer organic amine salt composite boiler water treatment agent according to claim 1, characterized in that, The ratio of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine to the total acid equivalent of carboxyl groups and sulfonic acid groups in the acidic terpolymer and carboxyl groups in gluconic acid is (0.60-0.90):1; the amino equivalent of 2-amino-2-methyl-1-propanol accounts for 35-50% of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine, and the amino equivalent of monoethanolamine is the remainder of the total amino equivalent of 2-amino-2-methyl-1-propanol and monoethanolamine.

5. A method for preparing a polymer organic amine salt composite boiler water treatment agent according to any one of claims 1-4, characterized in that, Includes the following steps: S1: Mix 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid and deionized water to obtain monomer solution A; add acrylic acid to deionized water to obtain monomer solution B; add mercaptoacetic acid to monomer solution A, purge with nitrogen and heat, add ferrous sulfate, then add monomer solution B, hydrogen peroxide aqueous solution and isoascorbic acid aqueous solution dropwise to react, remove residual volatile small molecules and peroxide decomposition gas after reaction, and obtain acidic terpolymer aqueous solution after cooling; S2: Add the aqueous solution of the acidic terpolymer into a closed compounding vessel, and add 2-amino-2-methyl-1-propanol dropwise under stirring to carry out the first stage of ammoniation, and obtain the first stage ammoniation solution. S3: Add a portion of monoethanolamine to the first-stage ammonium salting solution, followed by simultaneous addition of gluconic acid aqueous solution and the remaining monoethanolamine. After the addition is completed, continue stirring to obtain a preliminary ammonium salting association system. Then, seal the compounding vessel and heat and stir under nitrogen protection to obtain a polymer organic amine salt composite solution. S4: Cool the polymer organic amine salt composite solution, add low-foaming EO / PO block polyether and deionized water, stir and homogenize to obtain a compound solution; mature, cool and filter the compound solution to obtain a polymer organic amine salt composite boiler water treatment agent.

6. The preparation method according to claim 5, characterized in that, In S1, the ratio of the total mass of the three monomers, 2-acrylamido-2-methylpropanesulfonic acid, itaconic acid, and acrylic acid, to the total mass of deionized water is 1:(1.8-3.8); the ratio of the mass of mercaptoacetic acid to the total mass of the three monomers is (0.3-1.2):100; the amount of ferrous sulfate used, based on the mass of Fe²⁺, is (0.5-5) mg / kg relative to the total mass of all raw materials in S1.

7. The preparation method according to claim 5, characterized in that, In S1, the mass fraction of hydrogen peroxide aqueous solution is 20-35 wt%, the ratio of hydrogen peroxide (based on the effective H2O2 mass) to the total mass of the three monomers is (0.4-1.5):100; the ratio of isoascorbic acid to the total mass of the three monomers is (0.05-0.50):100; and the mass ratio of isoascorbic acid to deionized water in the isoascorbic acid aqueous solution is 1:(8-25).

8. The preparation method according to claim 5, characterized in that, In S1, nitrogen gas is introduced for 20-40 minutes for purging, and ferrous sulfate is added after the temperature is raised to 60-75℃. The total time for adding monomer solution B, hydrogen peroxide aqueous solution, and isoascorbic acid aqueous solution is 2-4 hours. During the addition, the reaction temperature is controlled at 60-78℃. After the addition is completed, the reaction is kept at 65-80℃ for 1-3 hours. After the reaction is completed, residual volatile small molecules and peroxide decomposition gases are removed at 50-70℃ and a vacuum of 0.06-0.09MPa for 30-90 minutes.

9. The preparation method according to claim 5, characterized in that, In S2, the system temperature is controlled at 30-45℃, the dropping time of 2-amino-2-methyl-1-propanol is 20-60 min, and stirring is continued for 30-90 min after the dropping is completed.

10. The preparation method according to claim 5, characterized in that, In S3, when the amount of monoethanolamine added reaches 40-70% of the total amount of monoethanolamine, a 40-60 wt% aqueous solution of gluconic acid and the remaining monoethanolamine are added simultaneously. After the addition is completed, the mixture is stirred at 30-45℃ for 1-2 hours, and then the temperature is raised to 65-80℃ and stirred for 2-4 hours.

11. The preparation method according to claim 5, characterized in that, In S4, after cooling the polymer organic amine salt composite solution to 35-55℃, add low-foaming EO / PO block polyether and deionized water, and stir and homogenize at 35-55℃ for 1-3 hours to obtain the compound solution; mature the compound solution at 35-60℃ for 2-6 hours, cool it to 20-35℃, and then filter it through a 5-20μm filter.

12. The application of the polymer organic amine salt composite boiler water treatment agent according to any one of claims 1-4 in boiler water treatment.

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