CN114790042A - Non-phosphorus environment-friendly corrosion and scale inhibitor and preparation method and application thereof - Google Patents
Non-phosphorus environment-friendly corrosion and scale inhibitor and preparation method and application thereof Download PDFInfo
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- CN114790042A CN114790042A CN202110577359.5A CN202110577359A CN114790042A CN 114790042 A CN114790042 A CN 114790042A CN 202110577359 A CN202110577359 A CN 202110577359A CN 114790042 A CN114790042 A CN 114790042A
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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
- C02F5/125—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 combined with inorganic substances
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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
- C02F5/105—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 combined with inorganic substances
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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
- C02F2103/023—Water in cooling circuits
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
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Abstract
The invention provides a phosphorus-free environment-friendly corrosion and scale inhibitor, a preparation method and an application thereof, wherein the phosphorus-free environment-friendly corrosion and scale inhibitor comprises the following raw materials in parts by weight: 4-12 parts of inorganic salt, 2-15 parts of polyepoxysuccinic acid, 0.5-1 part of benzotriazole, 5-15 parts of polyaspartic acid, 5-10 parts of pH regulator, 2-4 parts of surfactant, 10-30 parts of tracer copolymer and water which are complemented to 100 parts. The slow-release scale inhibitor has excellent effect by the proportion of specific components and the preparation method, can form a protective film on the surface of metal to effectively resist the occurrence of pitting corrosion, has higher stability in a system by adding a specific tracer polymer, is not influenced by other factors, can accurately monitor the use condition of a medicament, and has excellent effect when being applied to the treatment of industrial circulating cooling water.
Description
Technical Field
The invention relates to the field of corrosion and scale inhibitors, in particular to a phosphorus-free environment-friendly corrosion and scale inhibitor and a preparation method and application thereof.
Background
The phosphorus-containing medicament is applied to the treatment of industrial circulating water on a large scale, but causes excessive phosphorus-containing compounds in industrial discharged water, thereby intensifying the eutrophication of the water, causing the large growth of algae in a water system and causing the occurrence of a red tide phenomenon. In order to meet the national requirements of green and environmental protection, the requirements on industrial circulating cooling water treatment are higher and higher, a circulating cooling water system starts to adopt a phosphorus reduction measure, a phosphorus-free environment-friendly water treatment medicament is researched more and more, and people are dedicated to developing a phosphorus-free corrosion and scale inhibitor which is environment-friendly, safe and excellent in performance. In order to ensure the effect of the corrosion and scale inhibitor in water treatment, the concentration of the corrosion and scale inhibitor in water needs to be monitored, however, in most of the phosphorus-free corrosion and scale inhibitors in the prior art, some fluorescent agents are additionally added, the use concentration of the fluorescent agents is reflected through the determination of the fluorescence value, however, the consumption of the fluorescent agents and the consumption of the corrosion and scale inhibitors are not proportional, the monitoring data can generate large deviation after long-term use, the action effect of the phosphorus-free corrosion and scale inhibitor is directly influenced, in addition, part of pitting corrosion is inevitably generated on metals by a plurality of phosphorus-free corrosion and scale inhibitors in the use process, and further corrosion on the metals is easily caused.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a phosphorus-free environment-friendly corrosion and scale inhibitor and a preparation method and application thereof, the slow-release scale inhibitor has excellent effect through the proportion of specific components, a protective film can be formed on the surface of metal to effectively resist the occurrence of pitting corrosion, and in addition, the specific tracing polymer is added, so that the stability in a system is higher, the influence of other factors is avoided, and the use condition of a medicament can be accurately monitored.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a phosphorus-free environment-friendly corrosion and scale inhibitor, which comprises the following raw materials in parts by weight: 4-12 parts of inorganic salt, 2-15 parts of polyepoxysuccinic acid, 0.5-1 part of benzotriazole, 5-15 parts of polyaspartic acid, 5-10 parts of pH regulator, 2-4 parts of surfactant, 10-30 parts of tracer copolymer and water which are complemented to 100 parts.
As a preferred technical solution, the inorganic salt includes zinc salt, citrate, and molybdate, and the weight ratio of the zinc salt to the citrate is 1: (1-2): (1-2).
As a preferred technical solution, the zinc salt includes one or more of zinc chloride, zinc sulfate heptahydrate and zinc sulfate monohydrate, the citrate includes potassium citrate or sodium citrate, and the molybdate includes one or more of ammonium molybdate, sodium molybdate, lithium molybdate and zinc molybdate.
As a preferable technical scheme, the weight ratio of the benzotriazole to the surfactant is 1: (2-6).
As a preferred embodiment, the surfactant comprises triethanolamine.
As a preferred technical scheme, the excitation wavelength of the tracer copolymer is 365nm, and the emission wavelength is 450 nm.
As a preferable technical scheme, the weight ratio of the tracer copolymer to the polyepoxysuccinic acid is (1.5-2.5): 1.
as a preferred technical scheme, the pH regulator comprises hydrochloric acid or sulfuric acid.
The second aspect of the invention provides a preparation method of a phosphorus-free environment-friendly corrosion and scale inhibitor, which comprises the following steps:
(1) mixing benzotriazole and surfactant uniformly to obtain a substance A for later use;
(2) adding inorganic salt into water one by one until the inorganic salt is completely dissolved to obtain a substance B;
(3) adding polyepoxysuccinic acid, polyaspartic acid, a pH regulator and a fluorescent polymer into the substance B, and uniformly mixing to obtain a substance C;
(4) adding the substance A into the substance C, and mixing uniformly to obtain the final product.
The third aspect of the invention provides an application of the phosphorus-free environment-friendly corrosion and scale inhibitor in treatment of industrial circulating cooling water.
Has the beneficial effects that:
(1) according to the invention, the inorganic salt is compounded by adopting zinc salt, citrate and molybdate in a specific proportion, a more compact protective film can be formed, the pitting corrosion of metal is reduced, the completeness of the metal protective film can be further promoted by adding benzotriazole and triethanolamine in a specific proportion, and meanwhile, the synergistic effect is generated with the inorganic salt, so that the corrosion inhibition performance is improved;
(2) the specific tracing type copolymer has high stability in a system, is not influenced by other factors, can accurately detect the use concentration of the corrosion and scale inhibitor, and can generate a synergistic effect by being compounded with the polyepoxysuccinic acid in a specific ratio, so that the corrosion and scale inhibitor has extremely strong chelating capacity on metal ions, and has more excellent scale inhibition effect;
(3) the specific preparation method can promote the dispersibility of the corrosion and scale inhibitor and reduce the agglomeration phenomenon, thereby ensuring the maximization of the slow-release scale inhibition effect;
(4) the non-phosphorus environment-friendly slow-release scale inhibitor is environment-friendly and safe, does not cause water eutrophication, and greatly reduces the post-treatment cost.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided herein, the definition of that term provided herein controls.
As used herein, a feature that is not limited to a single plural form is also intended to include plural forms of the feature unless the context clearly indicates otherwise. It will also be understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "containing," and/or "containing," when used in this specification denotes a stated composition, step, method, article, or apparatus, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or apparatuses. Furthermore, the use of "preferred," "preferably," "more preferred," and the like, when describing embodiments of the present invention, is intended to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to achieve the above object, the first aspect of the present invention provides a phosphorus-free environment-friendly corrosion and scale inhibitor, which comprises the following raw materials by weight: 4-12 parts of inorganic salt, 2-15 parts of polyepoxysuccinic acid, 0.5-1 part of benzotriazole, 5-15 parts of polyaspartic acid, 5-10 parts of pH regulator, 2-4 parts of surfactant, 10-30 parts of tracer copolymer and water which are complemented to 100 parts.
The applicant finds that when zinc salt, citrate and molybdate are compounded according to a specific proportion, a relatively compact protective film can be formed, and pitting corrosion of metal can be reduced, the applicant considers that the probable reason is that citrate ions can generate chelate with divalent and trivalent metal ions in water to promote the stability of zinc ions, meanwhile, the deposition of Ca2+ and Fe3+ on the metal surface is reduced, the metal surface is cleaned, the formation of a protective film on the metal surface is facilitated, and meanwhile, because the system is weakly alkaline, the selectivity of the metal protective film on ions can be adjusted by a mode of combining adsorption and deposition after the molybdate is added, the corrosion and scale inhibition effect is more excellent when the specific benzotriazole and triethanolamine are added, probably because the triethanolamine promotes the dissolution of the benzotriazole in a system, so that the benzotriazole can form an adsorption film on the surface of the metal to further promote the integrity of a metal protection film, and on the other hand, because lone-pair electrons and nitrogen atoms exist in the molecular structure of the triethanolamine, the adsorption is easy to generate at an interface, the two and inorganic salt generate good synergistic effect, and the corrosion inhibition performance is further improved.
In some preferred embodiments, the inorganic salt comprises zinc salt, citrate, molybdate, and the weight ratio of the three is 1: (1-2): (1-2).
Preferably, the inorganic salt comprises zinc salt, citrate and molybdate, and the weight ratio of the zinc salt to the citrate to the molybdate is 1: 1.5: 1.5.
in some preferred embodiments, the zinc salt comprises one or more of zinc chloride, zinc sulfate heptahydrate, zinc sulfate monohydrate, the citrate comprises potassium citrate or sodium citrate, and the molybdate comprises one or more of ammonium molybdate, sodium molybdate, lithium molybdate, and zinc molybdate.
Preferably, the zinc salt is zinc chloride, the citrate is sodium citrate, and the molybdate comprises sodium molybdate or lithium molybdate.
More preferably, the molybdate is lithium molybdate.
In some preferred embodiments, the weight ratio of polyaspartic acid to inorganic salt is (0.8-1.4): 1.
preferably, the weight ratio of the polyaspartic acid to the inorganic salt is 1.1: 1.
in some preferred embodiments, the weight ratio of the benzotriazole to the surfactant is 1: (2-6).
Preferably, the weight ratio of the benzotriazole to the surfactant is 1: (3-5).
More preferably, the weight ratio of the benzotriazole to the surfactant is 1: 4.
in some preferred embodiments, the surfactant comprises triethanolamine.
In some preferred embodiments, the tracer copolymer has an excitation wavelength of 365nm and an emission wavelength of 450 nm.
In some preferred embodiments, the weight ratio of tracer copolymer to polyepoxysuccinic acid is (1.5 to 2.5): 1.
preferably, the weight ratio of the tracer copolymer to the polyepoxysuccinic acid is 2: 1.
as for phosphorus-free scale and corrosion inhibitors, in the prior art, a fluorescent agent is mostly added into a corrosion and scale inhibitor, the concentration of the slow-release scale inhibitor is obtained by measuring a fluorescence value, but the consumption of the corrosion and scale inhibitor and the fluorescent agent is not proportional, the monitoring is inaccurate after long-term use, and the applicant finds in research that the original acrylic acid sulfonic acid terpolymer is replaced by a tracing copolymer synthesized by the company, the excitation wavelength of the tracing copolymer is 365nm, the emission wavelength is 450nm, the concentration of a medicament can be accurately detected by the tracing copolymer, the tracing copolymer has excellent scale inhibition performance and high stability in a system, is not influenced by other factors, the linear relation between the concentration of the tracing copolymer and the fluorescence intensity is good, the correlation coefficient can reach 0.998, and as the tracing copolymer contains a carboxylic group and a sulfonic group with strong polarity, the calcium tolerance can be increased, the dispersion performance is excellent, the particles can be effectively dispersed, and the calcium carbonate can be compounded with polyepoxysuccinic acid in a specific ratio to generate a synergistic effect, has extremely strong chelating capacity on metal ions, and has excellent scale inhibition effect on calcium carbonate, barium sulfate, calcium phosphate and the like.
The preparation method of the tracer copolymer specifically comprises the following steps:
s1: synthesis of fluorescent monomers
(1) Adding 355g of glacial acetic acid and 63g of 4-chloro-1, 8-naphthalic anhydride into a 500mL three-mouth glass bottle, starting stirring, slowly adding 30g of 3-dimethylaminopropylamine, heating to 110 ℃, keeping the temperature for 5 hours, then cooling to 40 ℃, stopping stirring, discharging into a 5L glass bottle, adding 2L of pure water, starting stirring, adding 460g of 48% sodium hydroxide with the mass concentration to adjust the pH value to 11, cooling to room temperature, stopping stirring, removing liquid to obtain a brown yellow solid, drying for 5 hours at 85 ℃, and crushing to obtain an intermediate 1;
(2) adding 95g of methanol, 26g of sodium methoxide and 20g of the intermediate 1 into a 500mL three-neck glass bottle, starting stirring, introducing nitrogen for 20 minutes, heating, controlling the temperature of the materials at 60 ℃, keeping the temperature for 6 hours, stopping introducing the nitrogen, then cooling to 45 ℃, adding 15g of concentrated hydrochloric acid with the mass concentration of 30% to adjust the pH value to 7.2, stopping stirring, filtering, and carrying out reduced pressure distillation on a liquid phase at the gas phase temperature of 48 ℃ to obtain a brown solid, namely the intermediate 2;
(3) adding 237g of acetone, 60g of chloropropene and 220 g of intermediate into the 500mL three-mouth glass bottle, starting stirring, heating to 42 ℃, keeping the temperature for 6 hours, cooling to room temperature, and drying to obtain a brown solid, washing the solid twice with acetone, wherein the amount of acetone used in each time is 100g, and drying the brown solid at 85 ℃ for 5 hours to obtain the fluorescent monomer.
S2: synthesis of tagged copolymers
Adding 0.5g of fluorescent monomer and 50ml of deionized water into a four-neck flask, stirring and heating to 85 ℃, then dripping a mixture of 3g of tert-butyl hydroperoxide and 1.5g of hydrogen peroxide, dripping 101.5g of acrylic monomer (AA) and 43.5g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) while stirring, keeping the temperature to continue stirring and reacting for 2h after finishing dripping for 2h, and cooling to room temperature to obtain the tracer copolymer.
In some preferred embodiments, the pH adjusting agent comprises hydrochloric acid or sulfuric acid.
In the prior art, the applicant finds that the specific preparation method adopted in the system can promote the dispersibility of the corrosion and scale inhibitor and reduce the agglomeration phenomenon, presumably because the solubility of the benzotriazole in water is not good, the application firstly mixes the benzotriazole and the surfactant uniformly to obtain a substance A, and the substance A is placed independently for standby, the solubility of the benzotriazole can be increased by triethanolamine serving as the surfactant in the process, then inorganic salts are sequentially added into the water to obtain a substance B, and one inorganic salt is required to be added after the other inorganic salt is completely dissolved, so that the full dissolution of the inorganic salts is ensured, and the generation of precipitates or complexes caused by the solubility difference and interaction is also avoided, and adding polyepoxysuccinic acid, polyaspartic acid, a pH regulator and a tracer copolymer into the substance B, uniformly mixing to obtain a substance C, and finally adding the substance A into the substance C for uniform mixing, so that the dissolution of the substance A in a system can be further promoted under the action of other components, the uniform state of the slow-release scale inhibitor is ensured, and the phenomenon of easy agglomeration in water is also reduced.
The second aspect of the invention provides a preparation method of a phosphorus-free environment-friendly corrosion and scale inhibitor, which comprises the following steps:
(1) mixing benzotriazole and surfactant uniformly to obtain a substance A for later use;
(2) adding inorganic salt into water one by one until the inorganic salt is completely dissolved to obtain a substance B;
(3) adding polyepoxysuccinic acid, polyaspartic acid, a pH regulator and a fluorescent polymer into the substance B, and uniformly mixing to obtain a substance C;
(4) adding the substance A into the substance C, and mixing uniformly to obtain the final product.
The third aspect of the invention provides an application of a phosphorus-free environment-friendly corrosion and scale inhibitor in treatment of industrial circulating cooling water.
Examples
In order to better understand the technical solutions, the technical solutions will be described in detail with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
The first aspect of the embodiment provides a phosphorus-free environment-friendly corrosion and scale inhibitor, which comprises the following raw materials in parts by weight: 8 parts of inorganic salt, 10 parts of polyepoxysuccinic acid, 0.7 part of benzotriazole, 8.8 parts of polyaspartic acid, 7.5 parts of hydrochloric acid, 2.8 parts of triethanolamine, 20 parts of trace copolymer and deionized water to make up to 100 parts.
The inorganic salt comprises zinc chloride, sodium citrate and lithium molybdate, and the weight ratio of the zinc chloride to the sodium citrate to the lithium molybdate is 1: 1.5: 1.5.
the polyepoxysuccinic acid is obtained from Nantong Runfeng petrochemical company, and the polyaspartic acid is obtained from Hebei collaborative environmental protection science and technology company, Inc.
The mass concentration of the hydrochloric acid is 30%.
The preparation method of the tracer copolymer specifically comprises the following steps:
s1: synthesis of fluorescent monomers
(1) Adding 355g of glacial acetic acid and 63g of 4-chloro-1, 8-naphthalic anhydride into a 500mL three-mouth glass bottle, starting stirring, slowly adding 30g of 3-dimethylaminopropylamine, heating to 110 ℃, keeping the temperature for 5 hours, then cooling to 40 ℃, stopping stirring, discharging into a 5L glass bottle, adding 2L of pure water, starting stirring, adding 460g of 48% sodium hydroxide with the mass concentration to adjust the pH value to 11, cooling to room temperature, stopping stirring, removing liquid to obtain a brown yellow solid, drying for 5 hours at 85 ℃, and crushing to obtain an intermediate 1;
(2) adding 95g of methanol, 26g of sodium methoxide and 20g of the intermediate 1 into a 500mL three-neck glass bottle, starting stirring, introducing nitrogen for 20 minutes, heating, controlling the temperature of the materials at 60 ℃, keeping the temperature for 6 hours, stopping introducing the nitrogen, then cooling to 45 ℃, adding 15g of concentrated hydrochloric acid with the mass concentration of 30% to adjust the pH value to 7.2, stopping stirring, filtering, and carrying out reduced pressure distillation on a liquid phase at the gas phase temperature of 48 ℃ to obtain a brown solid, namely the intermediate 2;
(3) adding 237g of acetone, 60g of chloropropene and 220 g of intermediate into the 500mL three-port glass bottle, starting stirring, heating to 42 ℃, keeping the temperature for 6 hours, cooling to room temperature, drying to obtain a brown solid, washing the solid twice with acetone, wherein the amount of acetone used in each time is 100g, and drying the brown solid at 85 ℃ for 5 hours to obtain the fluorescent monomer.
S2: synthesis of tagged copolymers
Adding 0.5g of fluorescent monomer and 50ml of deionized water into a four-neck flask, stirring and heating to 85 ℃, then dripping a mixture of 3g of tert-butyl hydroperoxide and 1.5g of hydrogen peroxide, dripping 101.5g of acrylic monomer (AA) and 43.5g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) while stirring, keeping the temperature for continuously stirring and reacting for 2h after dripping for 2h, and cooling to room temperature to obtain the tracking copolymer.
A second aspect of this embodiment provides a method for preparing a phosphorus-free environment-friendly corrosion and scale inhibitor, which includes the following steps:
(1) mixing benzotriazole and triethanolamine uniformly to obtain a substance A for later use;
(2) adding zinc chloride into water, adding sodium citrate after completely dissolving, adding lithium molybdate after completely dissolving, and obtaining a substance B after completely dissolving;
(3) adding polyepoxysuccinic acid, polyaspartic acid, hydrochloric acid and a tracing copolymer into the substance B, and uniformly mixing to obtain a substance C;
(4) adding the substance A into the substance C, and mixing uniformly to obtain the final product.
Example 2
The first aspect of the embodiment provides a phosphorus-free environment-friendly corrosion and scale inhibitor, which comprises the following raw materials in parts by weight: 5 parts of inorganic salt, 6 parts of polyepoxysuccinic acid, 0.6 part of benzotriazole, 5.5 parts of polyaspartic acid, 6 parts of hydrochloric acid, 3 parts of triethanolamine, 12 parts of tracing copolymer and deionized water to make up to 100 parts.
The inorganic salt comprises zinc chloride, sodium citrate and lithium molybdate, and the weight ratio of the zinc chloride to the sodium citrate to the lithium molybdate is 1: 1.5: 1.5.
the polyepoxysuccinic acid is purchased from Nantong Runfeng petrochemical company, and the polyaspartic acid is purchased from Hebei collaborative environmental protection science and technology company, Inc.
The mass concentration of the hydrochloric acid is 30%.
The preparation method of the tracer copolymer specifically comprises the following steps:
s1: synthesis of fluorescent monomers
(1) Adding 355g of glacial acetic acid and 63g of 4-chloro-1, 8-naphthalic anhydride into a 500mL three-mouth glass bottle, starting stirring, slowly adding 30g of 3-dimethylaminopropylamine, heating to 110 ℃, keeping the temperature for 5 hours, then cooling to 40 ℃, stopping stirring, discharging into a 5L glass bottle, adding 2L of pure water, starting stirring, adding 460g of 48% sodium hydroxide with the mass concentration to adjust the pH value to 11, cooling to room temperature, stopping stirring, removing liquid to obtain a brown yellow solid, drying for 5 hours at 85 ℃, and crushing to obtain an intermediate 1;
(2) adding 95g of methanol, 26g of sodium methoxide and 20g of the intermediate 1 into a 500mL three-mouth glass bottle, starting stirring, introducing nitrogen for 20 minutes, heating, controlling the temperature of the materials to be 60 ℃, keeping the temperature for 6 hours, stopping introducing the nitrogen, then cooling to 45 ℃, adding 15g of concentrated hydrochloric acid with the mass concentration of 30% to adjust the pH value to be 7.2, stopping stirring, filtering, and distilling a liquid phase under reduced pressure at the gas phase temperature of 48 ℃ to obtain a brown solid, namely an intermediate 2;
(3) adding 237g of acetone, 60g of chloropropene and 220 g of intermediate into the 500mL three-port glass bottle, starting stirring, heating to 42 ℃, keeping the temperature for 6 hours, cooling to room temperature, drying to obtain a brown solid, washing the solid twice with acetone, wherein the amount of acetone used in each time is 100g, and drying the brown solid at 85 ℃ for 5 hours to obtain the fluorescent monomer.
S2: synthesis of tagged copolymers
Adding 0.5g of fluorescent monomer and 50ml of deionized water into a four-neck flask, stirring and heating to 85 ℃, then dripping a mixture of 3g of tert-butyl hydroperoxide and 1.5g of hydrogen peroxide, dripping 101.5g of acrylic monomer (AA) and 43.5g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) while stirring, keeping the temperature for continuously stirring and reacting for 2h after dripping for 2h, and cooling to room temperature to obtain the tracking copolymer.
A second aspect of this embodiment provides a method for preparing a phosphorus-free environment-friendly corrosion and scale inhibitor, which includes the following steps:
(1) mixing benzotriazole and triethanolamine uniformly to obtain a substance A for later use;
(2) adding zinc chloride into water, adding sodium citrate after completely dissolving, adding lithium molybdate after completely dissolving, and obtaining a substance B after completely dissolving;
(3) adding polyepoxysuccinic acid, polyaspartic acid, hydrochloric acid and a tracing copolymer into the substance B, and uniformly mixing to obtain a substance C;
(4) adding the substance A into the substance C, and mixing uniformly to obtain the product.
Example 3
The first aspect of the embodiment provides a phosphorus-free environment-friendly corrosion and scale inhibitor, which comprises the following raw materials in parts by weight: 12 parts of inorganic salt, 14 parts of polyepoxysuccinic acid, 0.9 part of benzotriazole, 13.2 parts of polyaspartic acid, 9 parts of hydrochloric acid, 3.6 parts of triethanolamine, 28 parts of tracing copolymer and deionized water to make up to 100 parts.
The inorganic salt comprises zinc chloride, sodium citrate and lithium molybdate, and the weight ratio of the zinc chloride to the sodium citrate to the lithium molybdate is 1: 1.5: 1.5.
the polyepoxysuccinic acid is purchased from Nantong Runfeng petrochemical company, and the polyaspartic acid is purchased from Hebei collaborative environmental protection science and technology company, Inc.
The mass concentration of the hydrochloric acid is 30%.
The preparation method of the tracer copolymer specifically comprises the following steps:
s1: synthesis of fluorescent monomers
(1) Adding 355g of glacial acetic acid and 63g of 4-chloro-1, 8-naphthalic anhydride into a 500mL three-mouth glass bottle, starting stirring, slowly adding 30g of 3-dimethylaminopropylamine, heating to 110 ℃, keeping the temperature for 5 hours, cooling to 40 ℃, stopping stirring, discharging into a 5L glass bottle, adding 2L of pure water, starting stirring, adding 460g of sodium hydroxide with the mass concentration of 48% to adjust the pH value to 11, cooling to room temperature, stopping stirring, removing liquid to obtain a brown yellow solid, drying for 5 hours at 85 ℃, and crushing to obtain an intermediate 1;
(2) adding 95g of methanol, 26g of sodium methoxide and 20g of the intermediate 1 into a 500mL three-mouth glass bottle, starting stirring, introducing nitrogen for 20 minutes, heating, controlling the temperature of the materials to be 60 ℃, keeping the temperature for 6 hours, stopping introducing the nitrogen, then cooling to 45 ℃, adding 15g of concentrated hydrochloric acid with the mass concentration of 30% to adjust the pH value to be 7.2, stopping stirring, filtering, and distilling a liquid phase under reduced pressure at the gas phase temperature of 48 ℃ to obtain a brown solid, namely an intermediate 2;
(3) adding 237g of acetone, 60g of chloropropene and 220 g of intermediate into the 500mL three-mouth glass bottle, starting stirring, heating to 42 ℃, keeping the temperature for 6 hours, cooling to room temperature, and drying to obtain a brown solid, washing the solid twice with acetone, wherein the amount of acetone used in each time is 100g, and drying the brown solid at 85 ℃ for 5 hours to obtain the fluorescent monomer.
S2: synthesis of tagged copolymers
Adding 0.5g of fluorescent monomer and 50ml of deionized water into a four-neck flask, stirring and heating to 85 ℃, then dripping a mixture of 3g of tert-butyl hydroperoxide and 1.5g of hydrogen peroxide, dripping 101.5g of acrylic monomer (AA) and 43.5g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) while stirring, keeping the temperature for continuously stirring and reacting for 2h after dripping for 2h, and cooling to room temperature to obtain the tracking copolymer.
A second aspect of the present embodiment provides a preparation method of a phosphorus-free environment-friendly corrosion and scale inhibitor, comprising the following steps:
(1) mixing benzotriazole and triethanolamine uniformly to obtain a substance A for later use;
(2) adding zinc chloride into water, adding sodium citrate after completely dissolving, adding lithium molybdate after completely dissolving, and obtaining a substance B after completely dissolving;
(3) adding polyepoxysuccinic acid, polyaspartic acid, hydrochloric acid and a tracing copolymer into the substance B, and uniformly mixing to obtain a substance C;
(4) adding the substance A into the substance C, and mixing uniformly to obtain the final product.
Example 4
The embodiment provides a phosphorus-free environment-friendly corrosion and scale inhibitor and a preparation method thereof, and the specific implementation manner is the same as that of embodiment 1, except that the inorganic salt comprises zinc chloride, sodium citrate and lithium molybdate, and the weight ratio of the zinc chloride to the sodium citrate to the lithium molybdate is 1: 0.9: 0.9.
example 5
The embodiment provides a phosphorus-free environment-friendly corrosion and scale inhibitor and a preparation method thereof, and the specific implementation manner is the same as that of embodiment 1, except that 1.4 parts of triethanolamine is used.
Example 6
The embodiment provides a phosphorus-free environment-friendly corrosion and scale inhibitor and a preparation method thereof, and the specific implementation manner is the same as that in embodiment 1, the difference is that the weight ratio of the tracing copolymer to the polyepoxysuccinic acid is 1.2: 1.
example 7
The embodiment provides a phosphorus-free environment-friendly corrosion and scale inhibitor and a preparation method thereof, and the specific implementation manner is the same as that of embodiment 1, except that benzotriazole and triethanolamine are directly added into water, and then inorganic salts are sequentially added.
Example 8
The embodiment provides a phosphorus-free environment-friendly corrosion and scale inhibitor and a preparation method thereof, and the specific implementation mode is the same as that of embodiment 1, except that zinc chloride, sodium citrate and lithium molybdate are simultaneously added into water in the step (2) of the preparation method.
Performance testing
1. Corrosion rate testing
(1) Hanging method
The phosphorus-free corrosion and scale inhibitor prepared in the examples 1-6 is measured according to the GB/T18175-2014 standard, the material of the hanging piece is respectively measured by carbon steel and stainless steel, the adding concentration of the agent is 90ppm, and the test result is shown in the table 1.
And (3) determination standard: the corrosion rate of the carbon steel is less than 0.075 mm/a; the corrosion rate of the stainless steel is less than 0.005 mm/a.
(2) Dynamic corrosion Property measurement experiment
The phosphorus-free corrosion and scale inhibitor prepared in the examples 1-6 is measured according to the HG-T2160-2008 standard, the material of the test tube is carbon steel, the adding concentration of the reagent is 90ppm, and the test results are shown in Table 2.
And (3) determination standard: the corrosion rate of carbon steel is less than 0.075 mm/a.
2. Scale inhibition rate test
The phosphorus-free corrosion and scale inhibitor prepared in the examples 1-3, 7 and 8 is tested according to the GB/T-16632-.
TABLE 1
TABLE 2
| Example numbering | Corrosion Rate (mm/a) |
| Example 1 | 0.019 |
| Example 2 | 0.026 |
| Example 3 | 0.021 |
| Example 4 | 0.072 |
| Example 5 | 0.095 |
| Example 6 | 0.079 |
TABLE 3
Finally, it should be understood that the above-described embodiments are merely preferred embodiments of the present invention, and not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The non-phosphorus environment-friendly corrosion and scale inhibitor is characterized by comprising the following raw materials in parts by weight: 4-12 parts of inorganic salt, 2-15 parts of polyepoxysuccinic acid, 0.5-1 part of benzotriazole, 5-15 parts of polyaspartic acid, 5-10 parts of pH regulator, 2-4 parts of surfactant, 10-30 parts of tracer copolymer and water which are complemented to 100 parts.
2. The phosphorus-free environment-friendly corrosion and scale inhibitor of claim 1, wherein the inorganic salt comprises zinc salt, citrate and molybdate, and the weight ratio of the zinc salt to the citrate to the molybdate is 1: (1-2): (1-2).
3. The environment-friendly corrosion and scale inhibitor without phosphorus according to claim 2, wherein the zinc salt comprises one or more of zinc chloride, zinc sulfate heptahydrate and zinc sulfate monohydrate, the citrate comprises potassium citrate or sodium citrate, and the molybdate comprises one or more of ammonium molybdate, sodium molybdate, lithium molybdate and zinc molybdate.
4. The phosphorus-free environment-friendly corrosion and scale inhibitor according to claim 1 or 2, wherein the weight ratio of the benzotriazole to the surfactant is 1: (2-6).
5. The environment-friendly corrosion and scale inhibitor as claimed in claim 1 or 2, wherein the surfactant comprises triethanolamine.
6. The phosphorus-free environment-friendly corrosion and scale inhibitor according to claim 1 or 2, wherein the excitation wavelength of the tracer copolymer is 365nm, and the emission wavelength is 450 nm.
7. The phosphorus-free environment-friendly corrosion and scale inhibitor as claimed in claim 1 or 2, wherein the weight ratio of the tracer copolymer to the polyepoxysuccinic acid is (1.5-2.5): 1.
8. the phosphorus-free environment-friendly corrosion and scale inhibitor of claim 1, wherein the pH regulator comprises hydrochloric acid or sulfuric acid.
9. The preparation method of the phosphorus-free environment-friendly corrosion and scale inhibitor according to any one of claims 1 to 8, characterized by comprising the following steps:
(1) mixing benzotriazole and surfactant uniformly to obtain a substance A for later use;
(2) adding inorganic salt into water one by one until completely dissolving to obtain a substance B;
(3) adding polyepoxysuccinic acid, polyaspartic acid, a pH regulator and a fluorescent polymer into the substance B, and uniformly mixing to obtain a substance C;
(4) adding the substance A into the substance C, and mixing uniformly to obtain the final product.
10. The application of the phosphorus-free environment-friendly corrosion and scale inhibitor prepared according to the preparation method of claim 9 in treating industrial circulating cooling water.
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