CN111809185B - Multi-metal surface protective agent and preparation method and application thereof - Google Patents
Multi-metal surface protective agent and preparation method and application thereof Download PDFInfo
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- CN111809185B CN111809185B CN202010482708.0A CN202010482708A CN111809185B CN 111809185 B CN111809185 B CN 111809185B CN 202010482708 A CN202010482708 A CN 202010482708A CN 111809185 B CN111809185 B CN 111809185B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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Abstract
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.
Description
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 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 salt corrosion inhibitors have a chemical reaction with the metals and then form a protective film on the metal surface to further prevent further corrosion, namely, the inorganic salt corrosion inhibitors can prevent the metals from contacting with water by corroding metal equipment to a certain degree, prevent 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 composite material;
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 pH regulator is prepared by mixing tolyltriazole and triethylamine at 58-63 deg.C for 55-62min, and cooling to room temperature.
Further, in the step of preparing the film forming agent, after adding the alcamines compound at the temperature of 80-100 ℃, continuously stirring for 0.5-1.5h, adding a mixed solution of benzotriazole and ethanol, then heating to the temperature of 110-130 ℃, and stirring for 1.5-2.5 h;
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 the deionized water or the soft water is replaced by the groundwater, 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 reason is 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, firstly, 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 (no continuous addition is carried out in the period) under 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 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 compounds to be triethanolamine and/or ethanolamine.
6. The invention provides a multi-metal surface protective agent, which is characterized in that 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 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 better understand the present invention, not to limit the best mode, and not to limit the content and protection scope of the present invention, and any product that is the same or similar to the present invention and is obtained by combining the present invention with other features of the prior art and the present invention falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a multi-metal surface protective agent, and the preparation method comprises the following steps:
preparing a film forming agent:
dissolving 5kg of benzotriazole in 5.5kg of ethanol to obtain a mixed solution for later use;
adding 25kg of deionized water into a reaction kettle, stirring and heating to 60 ℃, then adding 15kg of undecanedioic acid, 10kg of dodecanedioic acid, 12kg of gluconic acid and 15kg of benzoic acid, heating to 90 ℃ after the addition is finished, adding 15kg of triethanolamine and 3kg of ethanolamine, and continuously stirring for 0.5 h: and then adding the mixed solution, heating to 110 ℃, stirring for 1.5h, and naturally cooling to normal temperature to obtain the film-forming agent for later use.
Preparation of the occlusive agent:
uniformly mixing 30kg of deionized water and 10kg of ammonium citrate, adding 20kg of sebacic acid and 10kg of adipic acid at the temperature of 80 ℃, heating to 88 ℃, and stirring for 30 min; and continuously adding 15kg of triethanolamine, heating to 92 ℃, stirring for 130min, adding 5kg of ethanolamine, continuously stirring for 60min, cooling to 88 ℃, stirring for 360min, and naturally cooling to room temperature to obtain the closer.
Mixing the raw materials in the pH regulator:
a mixture of 25kg of methylbenzotriazole and 75kg of triethylamine is stirred at 60 ℃ for 55min and cooled to room temperature for later use.
Mixing raw materials in the catalyst:
uniformly mixing 45kg of citric acid and 30kg of deionized water, heating to 80 ℃, adding 25kg of lactic acid, continuously stirring for 53min, and cooling to room temperature for later use;
preparing a multi-metal surface protective agent:
and uniformly mixing 21kg of the closer and 50kg of the film forming agent, heating to 83 ℃, adding 12kg of the catalyst, continuing to heat to 110 ℃, stirring for 120min, cooling to 83 ℃, adding 20kg of the pH regulator, continuing to stir for 50min, cooling to room temperature, and standing for 72h to obtain the multi-metal surface protective agent.
Example 2
The embodiment provides a multi-metal surface protective agent, and a preparation method thereof comprises the following steps:
preparing a film forming agent:
dissolving 10kg of benzotriazole in 10kg of ethanol to obtain a mixed solution for later use;
adding 20kg of deionized water into a reaction kettle, stirring and heating to 60 ℃, then adding 20kg of undecanedioic acid, 15kg of dodecanedioic acid, 15kg of gluconic acid and 6kg of benzoic acid, heating to 80 ℃ after the addition is finished, adding 20kg of triethanolamine and 8kg of ethanolamine, and continuously stirring for 1.5 h: and then adding the mixed solution, heating to 120 ℃, stirring for 2.5 hours, and naturally cooling to normal temperature to obtain the film-forming agent for later use.
Preparation of the occlusive agent:
uniformly mixing 20kg of deionized water and 15kg of ammonium citrate, adding 25kg of sebacic acid and 15kg of adipic acid at 85 ℃, heating to 90 ℃, and stirring for 35 min; and continuously adding 20kg of triethanolamine, heating to 97 ℃, stirring for 110min, adding 3kg of ethanolamine, continuously stirring for 65min, cooling to 90 ℃, stirring for 350min, and naturally cooling to room temperature to obtain the closer.
Mixing the raw materials in the pH regulator:
a mixture of 30kg of methylbenzotriazole and 80kg of triethylamine is stirred at 63 ℃ for 62min and cooled to room temperature for later use.
Mixing raw materials in the catalyst:
uniformly mixing 35kg of citric acid and 35kg of deionized water, heating to 85 ℃, adding 30kg of lactic acid, continuously stirring for 64min, and cooling to room temperature for later use;
preparing a multi-metal surface protective agent:
and uniformly mixing 18kg of the closer and 55kg of the film forming agent, heating to 85 ℃, adding 9kg of the catalyst, continuing to heat to 110 ℃, stirring for 115min, cooling to 85 ℃, adding 17kg of the pH regulator, continuing to stir for 70min, cooling to room temperature, and standing for 68h to obtain the multi-metal surface protective agent.
Example 3
The embodiment provides a multi-metal surface protective agent, and the preparation method comprises the following steps:
preparing a film forming agent:
dissolving 8kg of benzotriazole in 7.2kg of ethanol to obtain a mixed solution for later use;
adding 16kg of deionized water into a reaction kettle, stirring and heating to 60 ℃, then adding 10kg of undecanedioic acid, 20kg of dodecanedioic acid, 8kg of gluconic acid and 10kg of benzoic acid, heating to 100 ℃ after the addition is finished, adding 10kg of triethanolamine and 5kg of ethanolamine, and continuously stirring for 1.0 h: and then adding the mixed solution, heating to 130 ℃, stirring for 2.0h, and naturally cooling to normal temperature to obtain the film-forming agent for later use.
Preparation of the occlusive agent:
uniformly mixing 25kg of deionized water and 5kg of ammonium citrate, adding 22kg of sebacic acid and 20kg of adipic acid at 75 ℃, heating to 85 ℃, and stirring for 25 min; and continuously adding 25kg of triethanolamine, heating to 90 ℃, stirring for 120min, adding 6kg of ethanolamine, continuously stirring for 55min, cooling to 85 ℃, stirring for 370min, and naturally cooling to room temperature to obtain the closer.
Mixing the raw materials in the pH regulator:
20kg of methylbenzotriazole and 70kg of triethylamine are mixed at 58 ℃ for 58min and cooled to room temperature for later use.
Mixing raw materials in the catalyst:
uniformly mixing 40kg of citric acid and 25kg of deionized water, heating to 75 ℃, adding 35kg of lactic acid, continuously stirring for 60min, and cooling to room temperature for later use;
preparing a multi-metal surface protective agent:
and uniformly mixing 15kg of the closer and 43kg of the film-forming agent, heating to 88 ℃, adding 15kg of the catalyst, continuing to heat to 120 ℃, stirring for 125min, cooling to 88 ℃, adding 23kg of the pH regulator, continuing to stir for 60min, cooling to room temperature, and standing for 75h to obtain the multi-metal surface protective agent.
Example 4
The embodiment provides a multi-metal surface protective agent, and the preparation method comprises the following steps:
preparing a film forming agent:
dissolving 5kg of benzotriazole in 5.5kg of ethanol to obtain a mixed solution for later use;
adding 25kg of deionized water into a reaction kettle, stirring and heating to 60 ℃, then adding 10kg of dodecanedioic acid, 12kg of gluconic acid and 15kg of benzoic acid, heating to 90 ℃ after the addition is finished, adding 15kg of triethanolamine and 3kg of ethanolamine, and continuously stirring for 0.5 h: and then adding the mixed solution, heating to 110 ℃, stirring for 1.5h, and naturally cooling to normal temperature to obtain the film-forming agent for later use.
Preparation of the occlusive agent:
uniformly mixing 30kg of deionized water and 10kg of ammonium citrate, adding 20kg of sebacic acid and 10kg of adipic acid at 80 ℃, heating to 88 ℃, and stirring for 30 min; and continuously adding 15kg of triethanolamine, heating to 92 ℃, stirring for 130min, adding 5kg of ethanolamine, continuously stirring for 60min, cooling to 88 ℃, stirring for 360min, and naturally cooling to room temperature to obtain the closer.
Mixing the raw materials in the pH regulator:
the mixture of 25kg of methylbenzotriazole and 75kg of triethylamine is stirred for 55min at 60 ℃ and cooled to room temperature for standby.
Mixing raw materials in the catalyst:
uniformly mixing 45kg of citric acid and 30kg of deionized water, heating to 80 ℃, adding 25kg of lactic acid, continuously stirring for 53min, and cooling to room temperature for later use;
preparing a multi-metal surface protective agent:
and uniformly mixing 21kg of the closer and 50kg of the film forming agent, heating to 83 ℃, adding 12kg of the catalyst, continuing to heat to 110 ℃, stirring for 120min, cooling to 83 ℃, adding 20kg of the pH regulator, continuing to stir for 50min, cooling to room temperature, and standing for 72h to obtain the multi-metal surface protective agent.
Example 5
The embodiment provides a multi-metal surface protective agent, and the preparation method comprises the following steps:
preparing a film forming agent:
dissolving 5kg of benzotriazole in 5.5kg of ethanol to obtain a mixed solution for later use;
adding 25kg of deionized water into a reaction kettle, stirring and heating to 60 ℃, then adding 15kg of undecanedioic acid, 10kg of dodecanedioic acid, 12kg of gluconic acid and 15kg of benzoic acid, heating to 90 ℃ after the addition is finished, adding 15kg of triethanolamine and 3kg of ethanolamine, and continuously stirring for 0.5 h: and then adding the mixed solution, heating to 110 ℃, stirring for 1.5h, and naturally cooling to normal temperature to obtain the film-forming agent for later use.
Preparation of the occlusive agent:
uniformly mixing 30kg of deionized water and 10kg of ammonium citrate, adding 20kg of sebacic acid at 80 ℃, heating to 88 ℃, and stirring for 30 min; and continuously adding 15kg of triethanolamine, heating to 92 ℃, stirring for 130min, adding 5kg of ethanolamine, continuously stirring for 60min, cooling to 88 ℃, stirring for 360min, and naturally cooling to room temperature to obtain the closer.
Mixing the raw materials in the pH regulator:
a mixture of 25kg of methylbenzotriazole and 75kg of triethylamine is stirred at 60 ℃ for 55min and cooled to room temperature for later use.
Mixing raw materials in the catalyst:
uniformly mixing 45kg of citric acid and 30kg of deionized water, heating to 80 ℃, adding 25kg of lactic acid, continuously stirring for 53min, and cooling to room temperature for later use;
preparing a multi-metal surface protective agent:
and uniformly mixing 21kg of the closer and 50kg of the film forming agent, heating to 83 ℃, adding 12kg of the catalyst, continuing to heat to 110 ℃, stirring for 120min, cooling to 83 ℃, adding 20kg of the pH regulator, continuing to stir for 50min, cooling to room temperature, and standing for 72h to obtain the multi-metal surface protective agent.
Example 6
The embodiment provides a multi-metal surface protective agent, and the preparation method comprises the following steps:
preparing a film forming agent:
dissolving 5kg of benzotriazole in 5.5kg of ethanol to obtain a mixed solution for later use;
adding 25kg of deionized water into a reaction kettle, stirring and heating to 60 ℃, then adding 15kg of undecanedioic acid, 10kg of dodecanedioic acid, 12kg of gluconic acid and 15kg of benzoic acid, heating to 90 ℃ after the addition is finished, adding 15kg of triethanolamine, and continuously stirring for 0.5 h: and then adding the mixed solution, heating to 110 ℃, stirring for 1.5h, and naturally cooling to normal temperature to obtain the film-forming agent for later use.
Preparation of the occlusive agent:
uniformly mixing 30kg of deionized water and 10kg of ammonium citrate, adding 20kg of sebacic acid and 10kg of adipic acid at 80 ℃, heating to 88 ℃, and stirring for 30 min; and continuously adding 15kg of triethanolamine, heating to 92 ℃, stirring for 130min, adding 5kg of ethanolamine, continuously stirring for 60min, cooling to 88 ℃, stirring for 360min, and naturally cooling to room temperature to obtain the closer.
Mixing the raw materials in the pH regulator:
a mixture of 25kg of methylbenzotriazole and 75kg of triethylamine is stirred at 60 ℃ for 55min and cooled to room temperature for later use.
Mixing raw materials in the catalyst:
uniformly mixing 45kg of citric acid and 30kg of deionized water, heating to 80 ℃, adding 25kg of lactic acid, continuously stirring for 53min, and cooling to room temperature for later use;
preparing a multi-metal surface protective agent:
and uniformly mixing 21kg of the closer and 50kg of the film forming agent, heating to 83 ℃, adding 12kg of the catalyst, continuing to heat to 110 ℃, stirring for 120min, cooling to 83 ℃, adding 20kg of the pH regulator, continuing to stir for 50min, cooling to room temperature, and standing for 72h to obtain the multi-metal surface protective agent.
Example 7
The embodiment provides a multi-metal surface protective agent, and the preparation method comprises the following steps:
preparing a film forming agent:
dissolving 5kg of benzotriazole in 5.5kg of ethanol to obtain a mixed solution for later use;
adding 25kg of deionized water into a reaction kettle, stirring and heating to 60 ℃, then adding 15kg of undecanedioic acid, 10kg of dodecanedioic acid, 12kg of gluconic acid and 15kg of benzoic acid, heating to 90 ℃ after the addition is finished, adding 15kg of triethanolamine and 3kg of ethanolamine, and continuously stirring for 0.5 h: and then adding the mixed solution, heating to 110 ℃, stirring for 1.5h, and naturally cooling to normal temperature to obtain the film-forming agent for later use.
Preparation of the occlusive agent:
uniformly mixing 30kg of deionized water and 10kg of ammonium citrate, adding 20kg of sebacic acid and 10kg of adipic acid at 80 ℃, heating to 88 ℃, and stirring for 30 min; and continuously adding 15kg of triethanolamine, heating to 92 ℃, stirring for 130min, adding 5kg of ethanolamine, continuously stirring for 60min, cooling to 88 ℃, stirring for 360min, and naturally cooling to room temperature to obtain the closer.
Mixing the raw materials in the pH regulator:
a mixture of 25kg of methylbenzotriazole and 75kg of triethylamine is stirred at 60 ℃ for 55min and cooled to room temperature for later use.
Mixing raw materials in the catalyst:
uniformly mixing 45kg of citric acid and 30kg of deionized water at room temperature, adding 25kg of lactic acid, and continuously stirring for 53min for later use;
preparing a multi-metal surface protective agent:
and uniformly mixing 21kg of the closer and 50kg of the film forming agent, heating to 83 ℃, adding 12kg of the catalyst, continuing to heat to 110 ℃, stirring for 120min, cooling to 83 ℃, adding 20kg of the pH regulator, continuing to stir for 50min, cooling to room temperature, and standing for 72h to obtain the multi-metal surface protective agent.
Example 8
The embodiment provides a multi-metal surface protective agent, and the preparation method comprises the following steps:
preparing a film forming agent:
dissolving 5kg of benzotriazole in 5.5kg of ethanol to obtain a mixed solution for later use;
adding 25kg of deionized water into a reaction kettle, stirring and heating to 60 ℃, then adding 15kg of undecanedioic acid, 10kg of dodecanedioic acid, 12kg of gluconic acid and 15kg of benzoic acid, heating to 90 ℃ after the addition is finished, adding 15kg of triethanolamine and 3kg of ethanolamine, and continuously stirring for 0.5 h: and then adding the mixed solution, heating to 110 ℃, stirring for 1.5h, and naturally cooling to normal temperature to obtain the film-forming agent for later use.
Preparation of the occlusive agent:
uniformly mixing 30kg of deionized water and 10kg of ammonium citrate, adding 20kg of sebacic acid and 10kg of adipic acid at 80 ℃, heating to 88 ℃, and stirring for 30 min; and continuously adding 15kg of triethanolamine, heating to 92 ℃, stirring for 130min, adding 5kg of ethanolamine, continuously stirring for 60min, cooling to 88 ℃, stirring for 360min, and naturally cooling to room temperature to obtain the closer.
Mixing the raw materials in the pH regulator:
a mixture of 25kg of tolyltriazole and 75kg of triethylamine is stirred at room temperature for 55 min.
Mixing raw materials in the catalyst:
uniformly mixing 45kg of citric acid and 30kg of deionized water, heating to 80 ℃, adding 25kg of lactic acid, continuously stirring for 53min, and cooling to room temperature for later use;
preparing a multi-metal surface protective agent:
and uniformly mixing 21kg of the closer and 50kg of the film forming agent, heating to 83 ℃, adding 12kg of the catalyst, continuing to heat to 110 ℃, stirring for 120min, cooling to 83 ℃, adding 20kg of pH regulator, continuing to stir for 50min, cooling to room temperature, and standing for 72h to obtain the multi-metal surface protective agent.
Comparative example 1
The comparative example provides a multimetal surface protectant prepared as follows:
preparing a film forming agent:
dissolving 5kg of benzotriazole in 5.5kg of ethanol to obtain a mixed solution for later use;
adding 25kg of deionized water into a reaction kettle, stirring and heating to 60 ℃, then adding 15kg of undecanedioic acid, 10kg of dodecanedioic acid, 12kg of gluconic acid and 15kg of benzoic acid, heating to 90 ℃ after the addition is finished, adding 15kg of triethanolamine and 3kg of ethanolamine, and continuously stirring for 0.5 h: and then adding the mixed solution, heating to 110 ℃, stirring for 1.5h, and naturally cooling to normal temperature to obtain the film-forming agent for later use.
Mixing the raw materials in the pH regulator:
a mixture of 25kg of methylbenzotriazole and 75kg of triethylamine is stirred at 60 ℃ for 55min and cooled to room temperature for later use.
Mixing raw materials in the catalyst:
uniformly mixing 45kg of citric acid and 30kg of deionized water, heating to 80 ℃, adding 25kg of lactic acid, continuously stirring for 53min, and cooling to room temperature for later use;
preparing a multi-metal surface protective agent:
heating 50kg of the film forming agent to 83 ℃, adding 12kg of the catalyst, heating to 110 ℃, stirring for 120min, cooling to 83 ℃, adding 20kg of the pH regulator, continuing stirring for 50min, cooling to room temperature, and standing for 72h to obtain the multi-metal surface protective agent.
Comparative example 2
The comparative example provides a multi-metal surface protective agent, and the preparation method comprises the following steps:
preparing a film forming agent:
dissolving 5kg of benzotriazole in 5.5kg of ethanol to obtain a mixed solution for later use;
adding 25kg of deionized water into a reaction kettle, stirring and heating to 60 ℃, then adding 15kg of undecanedioic acid, 10kg of dodecanedioic acid, 12kg of gluconic acid and 15kg of benzoic acid, heating to 90 ℃ after the addition is finished, adding 15kg of triethanolamine and 3kg of ethanolamine, and continuously stirring for 0.5 h: and then adding the mixed solution, heating to 110 ℃, stirring for 1.5h, and naturally cooling to normal temperature to obtain the film-forming agent for later use.
Preparation of the occlusive agent:
uniformly mixing 30kg of deionized water and 10kg of ammonium citrate, adding 20kg of sebacic acid and 10kg of adipic acid at 80 ℃, heating to 88 ℃, and stirring for 30 min; and continuously adding 15kg of triethanolamine, heating to 92 ℃, stirring for 130min, adding 5kg of ethanolamine, continuously stirring for 60min, cooling to 88 ℃, stirring for 360min, and naturally cooling to room temperature to obtain the closer.
Mixing raw materials in the catalyst:
uniformly mixing 45kg of citric acid and 30kg of deionized water, heating to 80 ℃, adding 25kg of lactic acid, continuously stirring for 53min, and cooling to room temperature for later use;
preparing a multi-metal surface protective agent:
and uniformly mixing 21kg of the closer and 50kg of the film forming agent, heating to 83 ℃, adding 12kg of the catalyst, continuing to heat to 110 ℃, stirring for 120min, cooling to 83 ℃, continuing to stir for 50min, cooling to room temperature, and standing for 72h to obtain the multi-metal surface protective agent.
Comparative example 3
The comparative example provides a multimetal surface protectant prepared as follows:
preparing a film forming agent:
dissolving 5kg of benzotriazole in 5.5kg of ethanol to obtain a mixed solution for later use;
adding 25kg of deionized water into a reaction kettle, stirring and heating to 60 ℃, then adding 15kg of undecanedioic acid, 10kg of dodecanedioic acid, 12kg of gluconic acid and 15kg of benzoic acid, heating to 90 ℃ after the addition is finished, adding 15kg of triethanolamine and 3kg of ethanolamine, and continuously stirring for 0.5 h: and then adding the mixed solution, heating to 110 ℃, stirring for 1.5h, and naturally cooling to normal temperature to obtain the film-forming agent for later use.
Preparation of the occlusive agent:
uniformly mixing 30kg of deionized water and 10kg of ammonium citrate, adding 20kg of sebacic acid and 10kg of adipic acid at 80 ℃, heating to 88 ℃, and stirring for 30 min; and continuously adding 15kg of triethanolamine, heating to 92 ℃, stirring for 130min, adding 5kg of ethanolamine, continuously stirring for 60min, cooling to 88 ℃, stirring for 360min, and naturally cooling to room temperature to obtain the closer.
Mixing the raw materials in the pH regulator:
a mixture of 25kg of methylbenzotriazole and 75kg of triethylamine is stirred at 60 ℃ for 55min and cooled to room temperature for later use.
Mixing raw materials in the catalyst:
uniformly mixing 45kg of citric acid and 30kg of deionized water, heating to 80 ℃, adding 25kg of lactic acid, continuously stirring for 53min, and cooling to room temperature for later use;
preparing a multi-metal surface protective agent:
and uniformly mixing 21kg of the closer and 50kg of the film forming agent, heating to 83 ℃, adding 20kg of the catalyst, continuing to heat to 110 ℃, stirring for 120min, cooling to 83 ℃, adding 20kg of the pH regulator, continuing to stir for 50min, cooling to room temperature, and standing for 72h to obtain the multi-metal surface protective agent.
Experimental example 1
The multi-metal surface protective agent prepared in each example and each comparative example is mixed with underground water according to the mass ratio of 1: 30, uniformly mixing to obtain a mixed solution; and then respectively taking 500g of the mixed solution and 500g of underground water, putting the mixed solution and the 500g of the underground water into 1000ml of beakers with the same specification, heating and evaporating at 100 ℃, cooling to room temperature after boiling for 30min, weighing the mass of the volatilized water if the mixed solution is transparent and uniform through visual observation, replenishing the underground water in equal amount, continuing heating and evaporating, and circulating the steps until floccules are generated through visual observation after cooling. The specific experimental results are shown in table 1.
TABLE 1 results of the experiment
| Total water content (including the initial 500g) when visible flocs appear after boiling and cooling | |
| Example 1 | 1276g |
| Example 2 | 1265g |
| Example 3 | 1268g |
| Example 4 | 1249g |
| Example 5 | 1250g |
| Example 6 | 1240g |
| Example 7 | 1227g |
| Example 8 | 1220g |
| Comparative example 1 | 401g |
| Comparative example 2 | 409g |
| Comparative example 3 | 398g |
| 500g of ground water | After boiling for 30min by first heating and cooling to room temperature, white precipitate can be seen by naked eyes. |
The data in the table show that the multi-metal surface protective agent provided by the invention has strong complexing ability against hard water in a water circulation system, can promote the chelation of calcium, magnesium and other ions in water and metal, prevents water from scaling and keeps stable water quality; and the requirement on water in the water circulation system is not high, and common underground water is only needed.
Experimental example 2
The multi-metal surface protective agent prepared in each example and each comparative example is mixed with corrosive water according to the mass ratio of 1: 30, uniformly mixing to obtain a mixed solution; the mixed solution is tested by respectively referring to a GB/T18175-2014 water treatment agent corrosion inhibition performance determination-rotary hanging sheet method, and the specific test conditions are as follows:
corrosive water: preparing water by adopting the standard in GB/T18175-2014;
test piece: the test piece specified in SH/T0085 and 1991 engine coolant corrosion determination method (glassware method) is adopted;
and (3) detecting the temperature: 90 ℃, time: 252 h. The specific experimental results are shown in table 2.
TABLE 2 results of the experiment
Note: the solder is the solder in SH/T0085-1991, and the aluminum is the cast aluminum in SH/T0085-1991.
As can be seen from the data in the table above, the multi-metal surface protective agent provided by the invention has excellent corrosion resistance and rust resistance on various metals; the multi-metal surface protective agent provided by the invention can form a firm, elastic and compact organic protective film on the surfaces of various metals, and further isolate the contact between water and the metal surfaces.
Experimental example 3
The multi-metal surface protective agent prepared in each example and each comparative example is mixed with corrosive water according to the mass ratio of 1: 30, uniformly mixing to obtain a mixed solution; testing the initial reserve alkalinity of each mixed solution and the reserve alkalinity of the mixed solution after the mixed solution is placed for 72 hours at room temperature by adopting a ZDJ-4B type automatic potentiometric titrator according to SH/T0091-91 (engine coolant and antirust reserve alkalinity determination method); wherein the corrosive water adopts standard configuration water in GB/T18175-2014. The specific test methods are shown in table 3 below.
TABLE 3 test results
As can be seen from the data in the table above, the multi-metal surface protective agent provided by the invention has excellent reserve alkalinity (pH value buffering capacity), so that the pH value of the system is kept between 9 and 10.5, and the excellent reserve alkalinity can prevent the system from generating chemical corrosion; but also can effectively inhibit the growth of microorganisms, is beneficial to forming a metal film, maintains the stability of the film and improves the long-term stability of the protective film (prolongs the service life of the protective film); in addition, the water quality can be kept stable and the comprehensive wastewater discharge standard GB 8978 and 1996 can be met. The mixed solution prepared by the multi-metal surface protective agent prepared by the comparative example has a low initial pH value, and precipitates are generated after the mixed solution is placed for 72 hours, so that the reserve alkalinity of the mixed solution is poor or is not generated, and the pH value and the reserve alkalinity after 72 hours do not need to be measured.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (13)
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 claim 1 or 2, 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 claim 1 or 2, wherein the alcohol amine compound is triethanolamine and/or ethanolamine.
6. 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: 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 closer 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: after 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 claim 7 or 8, characterized in that in the step of preparing the film-forming agent, after adding the alcohol amine compound at 80-100 ℃, the mixture is stirred for 0.5-1.5h, the mixture of benzotriazole and ethanol is added, and then the temperature is raised to 110-130 ℃ and the mixture is stirred for 1.5-2.5 h;
wherein the mass ratio of the benzotriazole to the ethanol is 1 (0.9-1.1).
11. The method according to claim 7 or 8, wherein the step of preparing the closer comprises adding the organic dibasic acid at 75-85 ℃, heating to 85-90 ℃, stirring for 25-35min, heating to 90-97 ℃, and adding the alkanolamine compound; 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.
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