阅读说明：本技术 一种多金属表面保护剂及其制备方法和应用 (Multi-metal surface protective agent and preparation method and application thereof ) 是由 赵桂林 金栋 王同泽 赵玉刚 宋兆桐 于 2020-05-29 设计创作，主要内容包括：本发明提供了一种多金属表面保护剂及其制备方法和应用,所述多金属表面保护剂包括如下重量份的原料：闭合剂15-21份,成膜剂43-55份,催化剂9-15份和pH调节剂17-23份；其中,所述成膜剂的原料包括有机酸,醇胺类化合物,苯并三氮唑和去离子水；所述闭合剂的原料包括有机二元酸,醇胺类化合物,柠檬酸铵和去离子水；所述催化剂包括柠檬酸和乳酸；所述pH调节剂包括甲基苯并三氮唑和三乙胺。本发明提供的多金属表面保护剂可应用于循环水系统,且对水循环系统中的水质没有要求,适用于去离子水、软水、地下水和地表水等水质,同时具有很强的抗硬水、良好的储备碱度以及抗酸碱、耐高温性的性能。(The invention provides a multi-metal surface protective agent, a preparation method and an application thereof, wherein the multi-metal surface protective agent comprises the following raw materials in parts by weight: 15-21 parts of a closer, 43-55 parts of a film forming agent, 9-15 parts of a catalyst and 17-23 parts of a pH regulator; wherein the raw materials of the film forming agent comprise organic acid, alcamines compounds, benzotriazole and deionized water; the raw materials of the closer comprise organic dibasic acid, an alcohol amine compound, ammonium citrate and deionized water; the catalyst comprises citric acid and lactic acid; the pH regulator comprises methylbenzotriazole and triethylamine. The multi-metal surface protective agent provided by the invention can be applied to a circulating water system, has no requirement on the water quality in the water circulating system, is suitable for the water qualities of deionized water, soft water, underground water, surface water and the like, and has strong hard water resistance, good reserve alkalinity, acid-base resistance and high temperature resistance.)

1. The multi-metal surface protective agent is characterized by comprising the following raw materials in parts by weight: 15-21 parts of a closer, 43-55 parts of a film forming agent, 9-15 parts of a catalyst and 17-23 parts of a pH regulator;

wherein the raw materials of the film forming agent comprise organic acid, alcamines compounds, benzotriazole and deionized water;

the raw materials of the closer comprise organic dibasic acid, an alcohol amine compound, ammonium citrate and deionized water;

the catalyst comprises citric acid and lactic acid;

the pH regulator comprises methylbenzotriazole and triethylamine.

2. The multi-metal surface protective agent according to claim 1, wherein the raw materials of the catalyst comprise 35-45 parts of citric acid and 25-35 parts of lactic acid;

the raw materials of the pH regulator comprise 20-30 parts of methylbenzotriazole and 70-80 parts of triethylamine.

3. The multi-metal surface protective agent according to claim 1 or 2, wherein the film forming agent comprises the following raw materials in parts by weight: 34-70 parts of organic acid, 13-28 parts of alcamines compounds, 5-10 parts of benzotriazole and 16-25 parts of deionized water;

the organic acid comprises 20-40 parts of long-chain dibasic acid and 14-30 parts of organic monobasic acid;

the long-chain dibasic acid is dodecanedioic acid and/or undecanedioic acid;

the organic monoacid is gluconic acid and benzoic acid.

4. The multi-metal surface protective agent according to any one of claims 1 to 3, wherein the closing agent comprises the following raw materials in parts by weight: 30-45 parts of organic dibasic acid, 18-31 parts of alcohol amine compound, 5-15 parts of ammonium citrate and 20-30 parts of deionized water;

the organic diacid is sebacic acid and/or adipic acid.

5. The multi-metal surface protecting agent according to any one of claims 1 to 4, wherein the alcohol amine compound is triethanolamine and/or ethanolamine.

6. The multi-metal surface protective agent according to any one of claims 1 to 5, wherein the film forming agent comprises the following raw materials in parts by weight: 10-20 parts of dodecanedioic acid; 10-20 parts of undecanedioic acid; 8-15 parts of gluconic acid; 6-15 parts of benzoic acid; 5-10 parts of benzotriazole; 10-20 parts of triethanolamine; 3-8 parts of ethanolamine and 16-25 parts of deionized water;

the occlusive agent comprises the following raw materials in parts by weight: 20-25 parts of sebacic acid, 10-20 parts of adipic acid, 15-25 parts of triethanolamine, 3-6 parts of ethanolamine, 5-15 parts of ammonium citrate and 20-30 parts of deionized water.

7. The preparation method of the multi-metal surface protective agent is characterized by comprising the following steps:

preparing a film forming agent: uniformly mixing deionized water and organic acid, sequentially adding an alcamine compound and benzotriazole, and stirring to obtain the composition;

preparation of the occlusive agent: uniformly mixing deionized water and ammonium citrate, sequentially adding organic dibasic acid and an alcohol amine compound, and stirring to obtain the ammonium citrate-sodium hydrogen phosphate;

preparing a multi-metal surface protective agent: after the closer and the film-forming agent are uniformly mixed, the catalyst and the pH regulator are sequentially added, stirred and stood to obtain the composition;

wherein the catalyst comprises citric acid and lactic acid;

the pH regulator comprises methylbenzotriazole and triethylamine.

8. The method as claimed in claim 7, wherein the catalyst is added at 83-88 ℃, the temperature is raised to 110-130 ℃ and the mixture is stirred for 115-125min, the temperature is lowered to 83-88 ℃, the pH regulator is added, the mixture is stirred for 50-70min, the temperature is lowered to room temperature, and the mixture is left to stand for 68-75 h.

9. The production method according to claim 7 or 8, characterized by further comprising a step of separately mixing raw materials of the catalyst and the pH adjuster;

wherein the mixing step of the catalyst comprises the steps of uniformly mixing citric acid and deionized water, heating to 75-85 ℃, adding lactic acid, continuously stirring for 53-64min, and cooling to room temperature;

the mixing step of the pH regulator is to stir the mixture of the methylbenzotriazole and the triethylamine at the temperature of 58-63 ℃ for 55-62min and then cool the mixture to room temperature.

10. The preparation method according to any one of claims 7 to 9, characterized in that in the step of preparing the film-forming agent, after adding the alcohol amine compound at 80 to 100 ℃, the stirring is continued for 0.5 to 1.5 hours, the mixed solution of benzotriazole and ethanol is added, and then the temperature is raised to 110-;

wherein the mass ratio of the benzotriazole to the ethanol is 1 (0.9-1.1).

11. The method according to any one of claims 7 to 10, wherein the closing agent is prepared by adding the organic dibasic acid at 75 to 85 ℃ and then heating to 85 to 90 ℃, stirring for 25 to 35min, and adding the alcohol amine compound at 90 to 97 ℃; then stirring for 55-65min, cooling to 85-90 ℃, stirring for 350-370min, and then naturally cooling to room temperature;

wherein, when more than one alcohol amine compound is added, the alcohol amine compounds are added separately, and the adding time interval is 110-130 min.

12. Use of a multimetal surface protection agent according to any one of claims 1 to 6 or produced by a process according to any one of claims 7 to 11 in a water circulation system.

13. Use according to claim 12, wherein the water in the water circulation system is any one of de-ionized water, soft water, ground water and surface water.

Technical Field

The invention relates to the technical field of water circulation systems, in particular to a multi-metal surface protective agent and a preparation method and application thereof.

Background

With the rapid development of economy and the rapid increase of population, the shortage of water resources becomes an important factor for restricting the economic construction and development of China. In China, a large amount of water resources are applied and consumed in industrial circulating water and urban heating circulating water, but as the water contains colloids, suspended matters, soluble salts of calcium, magnesium, potassium and the like, and oxidizing substances such as dissolved gas and the like, scaling (calcium carbonate, calcium sulfate, barium sulfate and the like) is inevitably generated in the application process of the circulating water, and the problems of bacteria breeding, corrosion under the scaling and the like are more prominent, so that the circulating water needs to be frequently replaced, the water resources are wasted, and equipment in a circulating system is corroded.

In order to reduce the frequency of replacing circulating water, save water, reduce corrosion to equipment of a water circulating system and ensure safe and economic operation of the circulating water system, a mode of continuously adding a corrosion inhibitor is mostly adopted. Most of the conventional corrosion inhibitors are inorganic salts, such as: chromate, nitrite, sulfite, phosphate, etc., wherein chromate and nitrite seriously pollute the environment and are internationally recognized carcinogens; the inorganic salt containing phosphorus is unstable in water and is easy to hydrolyze to generate orthophosphate, and the orthophosphate and calcium ions in water generate calcium phosphate scale to accelerate the corrosion of circulating equipment; in addition, the traditional inorganic salt corrosion inhibitors only have a slow release effect on one or two metals, specifically, the inorganic salts and the metals undergo chemical reaction, and then a layer of protective film is formed on the surface of the metals, so that the further corrosion is prevented, namely, the inorganic salt corrosion inhibitors can prevent the metals from contacting with water by causing certain corrosion to metal equipment, so as to prevent the further corrosion, and have the defects of poor corrosion inhibition effect and uneven corrosion inhibition.

In order to solve the above problems of the conventional inorganic salt corrosion inhibitors, researchers have developed composite corrosion inhibitors for water circulation systems, such as: chinese patent document CN103214107A discloses a silicate and polyamidoamine composite environment-friendly corrosion inhibitor for a deionized water circulating cooling system; chinese patent document CN107162225A discloses a corrosion inhibitor for a closed soft water circulating cooling water system, a method and application thereof; although the composite corrosion inhibitor solves the problems that the inorganic corrosion inhibitor contains phosphorus, is not environment-friendly, has poor and uneven corrosion inhibition effect and limited application range and can only have a slow release effect on one or two metals, the composite corrosion inhibitor is only suitable for a circulation system of deionized water or soft water, has no slow release effect on common underground water, salt water or seawater and the like, and can accelerate corrosion of circulation equipment.

Disclosure of Invention

Therefore, the technical problem to be solved by the invention is to overcome the defect that the corrosion inhibitor in the prior art has high requirement on circulating water, thereby providing the multi-metal surface protective agent and the preparation method and application thereof.

Therefore, the invention provides the following technical scheme:

the multi-metal surface protective agent comprises the following raw materials in parts by weight: 15-21 parts of a closer, 43-55 parts of a film forming agent, 9-15 parts of a catalyst and 17-23 parts of a pH regulator;

wherein the raw materials of the film forming agent comprise organic acid, alcamines compounds, benzotriazole and deionized water;

the raw materials of the closer comprise organic dibasic acid, an alcohol amine compound, ammonium citrate and deionized water;

the catalyst comprises citric acid and lactic acid;

the pH regulator comprises methylbenzotriazole and triethylamine.

Further, the raw materials of the catalyst comprise 35-45 parts of citric acid and 25-35 parts of lactic acid;

the raw materials of the pH regulator comprise 20-30 parts of methylbenzotriazole and 70-80 parts of triethylamine.

Further, the film forming agent comprises the following raw materials in parts by weight: 34-70 parts of organic acid, 13-28 parts of alcamines compounds, 5-10 parts of benzotriazole and 16-25 parts of deionized water;

the organic acid comprises 20-40 parts of long-chain dibasic acid and 14-30 parts of organic monobasic acid;

the long-chain dibasic acid is dodecanedioic acid and/or undecanedioic acid;

the organic monoacid is gluconic acid and benzoic acid.

Further, the closure agent comprises the following raw materials in parts by weight: 30-45 parts of organic dibasic acid, 18-31 parts of alcohol amine compound, 5-15 parts of ammonium citrate and 20-30 parts of deionized water;

the organic diacid is sebacic acid and/or adipic acid.

Further, the alcohol amine compound is triethanolamine and/or ethanolamine.

Further, the film forming agent comprises the following raw materials in parts by weight: 10-20 parts of dodecanedioic acid; 10-20 parts of undecanedioic acid; 8-15 parts of gluconic acid; 6-15 parts of benzoic acid; 5-10 parts of benzotriazole; 10-20 parts of triethanolamine; 3-8 parts of ethanolamine and 16-25 parts of deionized water;

the occlusive agent comprises the following raw materials in parts by weight: 20-25 parts of sebacic acid, 10-20 parts of adipic acid, 15-25 parts of triethanolamine, 3-6 parts of ethanolamine, 5-15 parts of ammonium citrate and 20-30 parts of deionized water.

The invention also provides a preparation method of the multi-metal surface protective agent, which comprises the following steps:

preparing a film forming agent: uniformly mixing deionized water and organic acid, sequentially adding an alcamine compound and benzotriazole, and stirring to obtain the composition;

preparation of the occlusive agent: uniformly mixing deionized water and ammonium citrate, sequentially adding organic dibasic acid and an alcohol amine compound, and stirring to obtain the ammonium citrate-sodium hydrogen phosphate;

preparing a multi-metal surface protective agent: after the closer and the film-forming agent are uniformly mixed, the catalyst and the pH regulator are sequentially added, stirred and stood to obtain the composition;

wherein the catalyst comprises citric acid and lactic acid;

the pH regulator comprises methylbenzotriazole and triethylamine.

Further, after adding the catalyst at 83-88 ℃, heating to 110-130 ℃ and stirring for 115-125min, cooling to 83-88 ℃, adding the pH regulator, continuing stirring for 50-70min, cooling to room temperature, and standing for 68-75 h.

Further, the preparation method of the multi-metal surface protective agent also comprises the step of mixing the raw materials of the catalyst and the pH regulator respectively;

wherein the mixing step of the catalyst comprises the steps of uniformly mixing citric acid and deionized water, heating to 75-85 ℃, adding lactic acid, continuously stirring for 53-64min, and cooling to room temperature;

the mixing step of the pH regulator is to stir the mixture of the methylbenzotriazole and the triethylamine at the temperature of 58-63 ℃ for 55-62min and then cool the mixture to room temperature.

Further, in the step of preparing the film forming agent, after adding the alcohol amine compound at the temperature of 80-100 ℃, continuing to stir for 0.5-1.5h, adding a mixed solution of benzotriazole and ethanol, then heating to the temperature of 110-;

wherein the mass ratio of the benzotriazole to the ethanol is 1 (0.9-1.1).

Further, in the preparation step of the closer, organic dibasic acid is added at 75-85 ℃, then the temperature is raised to 85-90 ℃, the mixture is stirred for 25-35min, and the alcohol amine compound is added when the temperature is raised to 90-97 ℃; then stirring for 55-65min, cooling to 85-90 ℃, stirring for 350-370min, and then naturally cooling to room temperature;

wherein, when more than one alcohol amine compound is added, the alcohol amine compounds are added separately, and the adding time interval is 110-130 min.

The invention also provides the application of the multi-metal surface protective agent or the multi-metal surface protective agent prepared by the preparation method of the multi-metal surface protective agent in a water circulation system.

Further, the water in the water circulation system is any one of deionized water, soft water, underground water and surface water.

The technical scheme of the invention has the following advantages:

1. the existing composite corrosion inhibitor has high requirement on water in a water circulation system, and the water in the water circulation system, such as industrial circulation water and urban heat supply circulation water, needs to be deionized water or soft water, but the consumption of the water in the water circulation system is large, and if the deionized water or the soft water is adopted, the cost is increased; if deionized water or soft water is replaced by underground water, the existing composite corrosion inhibitor not only cannot play a role in inhibiting corrosion, but also can accelerate the corrosion of equipment in a water circulation system, and the inventor considers that the main reasons are as follows through research: because of the influence of the water containing colloid, suspended substance, soluble salts of calcium, magnesium, potassium and other ions, dissolved gas and other oxidizing substances, the composite corrosion inhibitor loses alkali storage capacity (namely pH buffer capacity) in a water circulation system, and when the pH value of the circulating water is lower than 9, a protective film formed on the metal surface by the corrosion inhibitor is not elastic and is easy to damage; secondly, the growth of microorganisms in the water circulation system can be promoted, and the corrosion of the microorganisms to metal is accelerated; again, corrosion of ferrous and nonferrous heavy metals is promoted when the pH of the water is below 7.5.

The invention provides a brand-new corrosion inhibitor, namely a multi-metal surface protective agent, which comprises the following raw materials in parts by weight: 15-21 parts of a closer, 43-55 parts of a film forming agent, 9-15 parts of a catalyst and 17-23 parts of a pH regulator; wherein the raw materials of the film forming agent comprise organic acid, alcamines compounds, benzotriazole and deionized water; the raw materials of the closer comprise organic dibasic acid, an alcohol amine compound, ammonium citrate and deionized water; the catalyst comprises citric acid and lactic acid; the pH regulator comprises methylbenzotriazole and triethylamine.

The organic acid and the alcohol amine compound in the closing agent react under the action of ammonium citrate to generate a mixture of ester and amide, and the ester and the amide are interwoven into a protective film, and the protective film has a strong hard water resistance function, can quickly decompose calcium, magnesium and other ions in water and chelate with various metals, prevents scaling and keeps stable water quality. All raw materials in the film forming agent are subjected to staggered reaction and are connected together through amido bonds and ester bonds to form protective films with different carbon chains, and the protective films are adsorbed on the surface of water circulation system equipment; wherein, the benzotriazole and the alcamines compounds can play a synergistic effect: the pH value of the system is adjusted, the corrosion of equipment points is prevented, the adsorption capacity between the protective film and the water circulation equipment is increased, and the corrosion resistance effect is improved. The catalyst containing citric acid and lactic acid can promote the further reaction of the film forming agent, the closing agent, unreacted components in the film forming agent and the closing agent, the pH regulator and the catalyst, so that the reaction is complete and interwoven to form a compact protective film, holes in the protective film are prevented, the contact between water and the metal surface is isolated, and the damage of water flow to the metal surface is avoided. By adopting the pH regulator containing methylbenzotriazole and triethylamine, the whole circulating water system has good reserve alkalinity, the pH value is kept between 9 and 10.5, chemical corrosion is prevented, the growth of microorganisms is effectively inhibited, the corrosion of the microorganisms to metal equipment is prevented, and the metal film forming and the stability of the film are favorably maintained.

The multi-metal surface protective agent provided by the invention is prepared by adopting organic raw materials without adding inorganic matters and limiting the parts of the raw materials to play a synergistic effect: (1) the water treatment agent can be applied to a circulating water system, has no requirement on the water quality in the water circulating system, is suitable for the water quality of deionized water, soft water, underground water, surface water and the like, and meets the GB 8978-1996 integrated wastewater discharge standard; (2) has strong hard water resistance, effectively prevents scaling and keeps stable water quality; (3) the pH value of the system is kept between 9 and 10.5 due to good reserve alkalinity, the long-term stability of the protective film can be improved (the service life of the protective film is prolonged), and the effective period of the multi-metal surface protective agent can be kept for 5 to 7 years (without continuous addition) in a fully-sealed system environment; secondly, chemical corrosion is prevented, the growth of microorganisms is effectively inhibited, no microbial corrosion is caused, and the film forming of metal and the stability of the film are favorably maintained; (4) the organic protective film has strong adsorption force on the metal surface, can bear the impact of water flow in a water circulation system, avoids the damage of the water flow to the metal surface, effectively prevents the corrosion of a system to a water circulation pipeline and equipment and the occurrence of point corrosion, has a certain repair function on the wound of the metal surface, has good seepage prevention, increases the sealing performance of a water system, and prevents the fine leakage of the equipment and the pipeline of the water circulation system; (5) has the performances of acid and alkali resistance and high temperature resistance.

2. The multi-metal surface protective agent provided by the invention can further improve the elasticity of a protective film formed on the metal surface by the multi-metal surface protective agent and the pH buffering capacity of a water circulation system by limiting the parts of the raw materials in the catalyst and the pH regulator.

3. According to the multi-metal surface protective agent provided by the invention, the film forming property of the film forming agent can be further improved by limiting the organic acid in the film forming agent to be dodecanedioic acid and/or undecanedioic acid: the toughness, the rigidity and the adsorption force with metal of the protective film are improved, the characteristics of water impact resistance and high temperature resistance are improved, and the service life of the film forming agent is prolonged; by limiting the raw materials and the parts of the film forming agent, the corrosion inhibition performance of the multi-metal surface protective agent on multi-metal can be improved.

4. The multi-metal surface protective agent provided by the invention is characterized in that organic dibasic acid in the closing agent is defined to be sebacic acid and/or adipic acid; the toughness of the film and the complexing degree of the film and metal ions in water can be further improved, and the high temperature resistance and oxidation resistance of the film are improved; by limiting the raw materials and the parts thereof in the closing agent, the complexing capacity of the multi-metal surface protective agent against hard water can be further improved, and the stable water quality can be maintained.

5. The multi-metal surface protective agent provided by the invention can further improve the high temperature resistance and acid and alkali resistance of the multi-metal surface protective agent by limiting the alcohol amine compound to be triethanolamine and/or ethanolamine.

6. The invention provides a multi-metal surface protective agent, which is prepared by limiting a film forming agent to comprise the following raw materials in parts by weight: 10-20 parts of dodecanedioic acid; 10-20 parts of undecanedioic acid; 8-15 parts of gluconic acid; 6-15 parts of benzoic acid; 5-10 parts of benzotriazole; 10-20 parts of triethanolamine; 3-8 parts of ethanolamine and 16-25 parts of deionized water; the occlusive agent comprises the following raw materials in parts by weight: 20-25 parts of sebacic acid, 10-20 parts of adipic acid, 15-25 parts of triethanolamine, 3-6 parts of ethanolamine, 5-15 parts of ammonium citrate and 20-30 parts of deionized water. The comprehensive performances of the prepared multi-metal surface protective agent such as acid and alkali resistance, high temperature resistance, hard water resistance, protection (corrosion resistance) on various metals, alkali storage performance and the like can be improved, and the selection of water quality in a water circulation system is expanded.

7. The preparation method of the multi-metal surface protective agent provided by the invention can promote the raw materials to react completely by limiting the preparation methods of the film forming agent and the closing agent, limiting the types of the catalyst and the pH regulator and the charging sequence of the raw materials during the preparation of the multi-metal surface protective agent, and the prepared multi-metal surface protective agent has the following effects: (1) has strong hard water resistance, effectively prevents scaling and keeps stable water quality; (2) the organic protective film which is firm, elastic and compact can be formed on the surfaces of various metals, so that the contact between water and the metal surfaces is isolated, the damage of water flow to the metal surfaces is avoided, the corrosion of a system to a water circulation pipeline and equipment and the occurrence of point corrosion are effectively prevented, meanwhile, a certain repairing function is provided for the wound of the metal surfaces, and the organic protective film has good seepage prevention, the sealing property of a water system is improved, and the fine leakage of the equipment and the pipeline of a water circulation system is prevented; (3) the pH value of the system is kept between 9 and 10.5 due to good reserve alkalinity, the long-term stability of the formed protective film can be improved (the service life of the protective film is prolonged), and the effective period of the multi-metal surface protective agent can be kept for 5 to 7 years (the period is not added continuously) in the environment of a fully-sealed system; secondly, chemical corrosion is prevented, the growth of microorganisms is effectively inhibited, no microbial corrosion is caused, and the film is favorably attached to the surface of metal to form a film and maintain the stability of the film; (4) the product has acid and alkali resistance and high temperature resistance; (5) can be applied to a circulating water system, has no requirement on the water quality in the water circulating system, is suitable for the water quality of deionized water, soft water, underground water, surface water and the like, and meets the GB 8978-1996 integrated wastewater discharge standard.

8. According to the preparation method of the multi-metal surface protective agent provided by the invention, the reaction speed of each raw material can be improved by limiting the adding temperature and the reaction time of each raw material, and the hard water resistance function of the prepared multi-metal surface protective agent and the elasticity and compactness of a protective film formed on the metal surface are further improved. By limiting the standing time, the reaction completeness can be improved, the density of the formed protective film is improved, and the comprehensive performance of the multi-metal surface protective agent is improved.

9. According to the preparation method of the multi-metal surface protective agent, the raw materials in the catalyst and the pH regulator are respectively heated and mixed in advance, so that the pH buffering capacity of the multi-metal surface protective agent can be further improved.

10. The preparation method of the multi-metal surface protective agent provided by the invention can further improve the film forming property and the multi-metal protection property of the prepared multi-metal surface protective agent by limiting all parameters in the preparation method of the film forming agent.

11. According to the preparation method of the multi-metal surface protective agent provided by the invention, the hard water resistance of the prepared multi-metal surface protective agent can be further improved by limiting each parameter in the preparation method of the closing agent.

Detailed Description

The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.