CN109110933B - Low-phosphorus scale and corrosion inhibitor and preparation method thereof - Google Patents
Low-phosphorus scale and corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN109110933B CN109110933B CN201810959661.5A CN201810959661A CN109110933B CN 109110933 B CN109110933 B CN 109110933B CN 201810959661 A CN201810959661 A CN 201810959661A CN 109110933 B CN109110933 B CN 109110933B
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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
- C02F5/14—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 phosphorus
- C02F5/145—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 phosphorus 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
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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Abstract
The invention discloses a low-phosphorus scale and corrosion inhibitor and a preparation method thereof, belonging to the technical field of water treatment agents and preparation thereof, and the technical scheme is characterized by comprising the following components in percentage by mass: 8-15% of hydrochloric acid, 1-6% of zinc salt, 30-40% of carboxylic acid-sulfonic acid-acrylate terpolymer, 8-10% of 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, 20-30% of hydrolyzed maleic anhydride and the balance of water; the hydrochloric acid is industrial hydrochloric acid with the mass percentage concentration of 31%. The low-phosphorus scale and corrosion inhibitor has low phosphorus and environmental protection, is suitable for high-pH high-temperature harsh water quality conditions, and has excellent scale inhibition and corrosion retarding effects. The invention correspondingly discloses a preparation method of the low-phosphorus scale and corrosion inhibitor, which has the advantages of simple process steps, low phosphorus environmental protection of the prepared low-phosphorus scale and corrosion inhibitor, suitability for harsh water quality conditions of high pH and high temperature, and excellent scale inhibition and corrosion retarding effects.
Description
Technical Field
The invention belongs to the technical field of water treatment agents and preparation thereof, and particularly relates to a low-phosphorus scale and corrosion inhibitor and a preparation method thereof.
Background
In industrial water, the amount of cooling water is in the first place, accounting for about 80%. The method for saving cooling water is to adopt circulating cooling water and increase the concentration times. However, in the circulating cooling water system, the hardness, alkalinity and pH value of circulating water are naturally increased due to the rising of water temperature, the evaporation of water and the concentration of various inorganic ions and organic substances, so that free and dissolved CO in the water2CaCO is formed in the water supply pipeline and the water using equipment due to large amount of loss3Precipitation of CaCO in the system3Scaling; and the electrolyte such as the soluble gas, corrosive salts and acids contained in the water contacts with the metal to precipitate Fe on the surface of the metal2+The equipment and pipeline metal are damaged. In order to reduce equipment corrosion, improve equipment utilization rate, save energy and water sources and ensure normal operation of production, the most common method at present is to add various water treatment agents into circulating cooling water. The largest dosage of the scale and corrosion inhibitor in the water treatment agent accounts for more than 80 percent of the dosage of the water treatment agent.
Since the scale and corrosion inhibitor is used in the circulating water in the 30 th century abroad, the water treatment agent is developed from a single chromium system to the existing silicon system, molybdenum system, phosphorus system, tungsten system, all-organic system and the like. The research in this aspect in China begins in the 70 s of the 20 th century, starts late but has high starting point and fast development, can produce hundreds of varieties at present, and can basically meet the requirements of domestic markets.
For example, in the prior art, chinese patent application publication No. CN104671454A discloses a scale and corrosion inhibitor for cooling water, which comprises the following components in parts by weight: 1-10 parts of sodium polyacrylate, 5-20 parts of sulfonate dispersant and 5-20 parts of phosphate.
However, a large amount of phosphate is used in the formula, the phosphorus content in the water body treated by the scale and corrosion inhibitor is greatly increased, the problems of water body eutrophication and the like are easily caused after the water body is discharged, and the development requirement of environmental protection is not met. Therefore, how to develop a low-phosphorus corrosion and scale inhibitor which does not contain phosphorus or contains low phosphorus and has excellent corrosion and scale inhibition effects is a problem to be solved in the industry.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a low-phosphorus scale and corrosion inhibitor which has the advantages of low phosphorus, environmental protection, suitability for harsh water quality conditions of high pH and high temperature, excellent scale inhibition and corrosion retarding effects.
In order to achieve the purpose, the invention provides the following technical scheme:
a low-phosphorus scale and corrosion inhibitor comprises the following components in percentage by mass,
8 to 15 percent of hydrochloric acid
1 to 6 percent of zinc salt
30-40% of carboxylic acid-sulfonic acid-acrylate terpolymer
8% -10% of 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane
20 to 30 percent of hydrolyzed maleic anhydride
The balance of water;
the hydrochloric acid is industrial hydrochloric acid with the mass percentage concentration of 31%.
By adopting the technical scheme, the method at least has the following advantages: 1. the formula does not contain phosphate, so that the phosphorus content is greatly reduced, and the environment is protected. 2. The local pH value of the solution near the cathode area in the microbattery at the corrosion position of the metal surface is increased, a large amount of zinc ions are generated after the zinc salt is hydrolyzed, the zinc ions react with hydroxyl to generate zinc hydroxide which is deposited in the cathode area, and the cathode reaction in the corrosion process is inhibited to play a corrosion role. 3. The carboxylic acid-sulfonic acid-acrylate terpolymer contains strong acid, weak acid and nonionic groups on a molecular chain, has an excellent dispersing effect, is suitable for being used under the conditions of high temperature, high pH value and high alkali, has an excellent inhibiting effect on iron oxide, calcium phosphate, zinc phosphate and calcium carbonate precipitates in water, has high tolerance on calcium and has good compatibility with other components. 4. The 2-phosphonic acid-1, 2, 4-butane tricarboxylate and zinc salt have a synergistic effect, are excellent in scale inhibition and corrosion inhibition effects, resistant to high temperature and chlorine decomposition, low in phosphorus content, small in environmental influence and suitable for harsh water quality conditions of high temperature, high hardness, high pH value and high concentration multiple. 5. The hydrolyzed maleic anhydride has obvious solubility limit effect at high temperature (350 ℃) and high pH value, has good dispersion effect on carbonate, and can resist scale for 100 hours; in addition, the hydrolyzed polymaleic anhydride has a synergistic corrosion inhibition effect with zinc salt. 6. On one hand, the industrial hydrochloric acid can neutralize alkaline substances in a water body with a high pH value, and the influence of a high pH environment on scale inhibition and corrosion inhibition effects of other components is reduced; on the other hand, the doping of the hydrochloric acid has the function of inhibiting the carbonate scale from being separated out from the water body, and the scale inhibition effect is excellent. 7. The low-phosphorus scale and corrosion inhibitor with the specific material ratio has low phosphorus content, is environment-friendly, has excellent scale and corrosion inhibition effects, and is suitable for being used in high-pH value and high-temperature water body environments.
Further, the zinc salt is any one of zinc chloride, zinc sulfate and zinc nitrate.
By adopting the technical scheme, the zinc chloride, the zinc sulfate and the zinc nitrate are all water-soluble zinc salts, the cost is low, a zinc hydroxide film can be rapidly generated to slow down the corrosion of the metal surface, the compatibility with other components is good, and the compound corrosion inhibition effect is better.
Further, the carboxylic acid-sulfonic acid-acrylate terpolymer is formed by copolymerizing a carboxylic acid monomer, a sulfonic acid monomer and an acrylate monomer, and the molecular weight is less than or equal to 500 Da; wherein the carboxylic acid monomer is selected from any one of crotonic acid, beta-phenylacrylic acid, maleic acid and fumaric acid; the sulfonic acid monomer is selected from any one of 2-acrylamide-2-methylpropanesulfonic acid and methacrylic sulfonic acid; the acrylate monomer is selected from any one of 2-methyl methacrylate, 2-ethyl methacrylate, methyl acrylate and ethyl acrylate.
By adopting the technical scheme, the carboxylic acid-sulfonic acid-acrylate terpolymer with overlarge molecular weight has overlong molecular chain and deviation of water solubility, and easily causes the viscosity of the scale and corrosion inhibitor to increase, so that the molecular weight is preferably less than or equal to 500 Da. The carboxylic acid-sulfonic acid-acrylate terpolymer selected by the specific monomers has good dispersibility and excellent scale inhibition effect.
Further comprises the following components in percentage by mass,
8 to 12 percent of hydrochloric acid
2 to 5 percent of zinc salt
30-35% of carboxylic acid-sulfonic acid-acrylate terpolymer
8% -10% of 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane
25 to 30 percent of hydrolyzed maleic anhydride
The balance of water;
the hydrochloric acid is industrial hydrochloric acid with the mass percentage concentration of 31%.
By adopting the technical scheme, the scale and corrosion inhibitor with the specific material ratio has low phosphorus, environmental protection and excellent scale and corrosion inhibition effects, and is particularly suitable for being used in the high-pH value and high-temperature water body environment.
Further comprises the following components in percentage by mass,
1 to 5 percent of organic acid
1 to 1.5 percent of chitosan
0.1 to 0.5 percent of 2-mercaptobenzothiazole
Imidazoline 0.1% -0.5%.
By adopting the technical scheme, the organic acid has a complexing effect on metal ions in the water body, so that the metal ions are mutually in a dispersed state, the aggregation and the separation of the difficult-to-dissolve carbonate are reduced, and meanwhile, the organic acid is difficult to complex with the metal ions to generate precipitates due to the existence of hydrochloric acid; the chitosan, the 2-mercaptobenzothiazole and the imidazoline all contain polar groups capable of providing electrons, can provide electrons in a metal corrosion micro battery, and play a role in inhibiting metal corrosion. In addition, the 2-mercapto benzothiazole and imidazoline also have certain bacteriostasis and algae killing effects.
Further, the organic acid is any one of lactic acid, malic acid, citric acid and benzoic acid.
By adopting the technical scheme, lactic acid, malic acid, citric acid and benzoic acid are common organic carboxylic acids, are low in price and easy to obtain, and are beneficial to controlling the manufacturing cost of the scale and corrosion inhibitor. Lactic acid, malic acid, citric acid and benzoic acid all belong to food or pharmaceutical additives, and the mixing amount is safe and harmless.
Further comprises the following components in percentage by mass,
1% -2% of ethanolamine derivative.
By adopting the technical scheme, the ethanolamine derivative also contains a polar group capable of providing electrons, and has excellent corrosion inhibition effect when being compounded with chitosan, 2-mercaptobenzothiazole and imidazoline.
Further, the molecular formula of the ethanolamine derivative is,
HOCH2CH2NXY，
wherein X is-H, -CH3、-CH2CH3and-CH2CH2CH2CH3Any one of (a); y is-CH3、-CH2CH3and-CH2CH2CH2CH3Any one of the above.
By adopting the technical scheme, the prepared scale and corrosion inhibitor has excellent scale and corrosion inhibition effects.
The invention also aims to provide a preparation method of the low-phosphorus scale and corrosion inhibitor, which has simple process steps, is low-phosphorus and environment-friendly, is suitable for harsh water quality conditions of high pH and high temperature, and has excellent scale inhibition and corrosion retarding effects.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of the low-phosphorus scale and corrosion inhibitor comprises the following steps,
weighing 31% by mass of hydrochloric acid, zinc salt, a carboxylic acid-sulfonic acid-acrylate terpolymer, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, hydrolyzed maleic anhydride and water according to the material ratio of claim 1;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid and zinc salt, and uniformly stirring;
measuring the temperature of the mixed solution in the reaction kettle, adding the carboxylic acid-sulfonic acid-acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane and hydrolyzed maleic anhydride after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring until no obvious solid particles exist in the mixed liquid, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
By adopting the technical scheme, the process steps are simple, and all the components for preparing the scale and corrosion inhibitor are added into the stirring kettle in sequence and stirred uniformly. The prepared low-phosphorus scale and corrosion inhibitor has good internal scale and corrosion inhibition effects, and is suitable for being used in high-temperature and high-pH water body environments.
Furthermore, the stirring speed in the second step and the third step is less than or equal to 1500 rpm.
By adopting the technical scheme, bubbles generated in the process of preparing the scale and corrosion inhibitor can be effectively reduced.
In conclusion, the invention has the following beneficial effects:
1. the formula does not contain phosphate, so that the phosphorus content is greatly reduced, and the environment is protected;
2. the partial pH value of the solution near the cathode region in the microbattery is raised after the metal surface is corroded, a large amount of zinc ions are generated after the zinc salt is hydrolyzed, and the zinc ions react with hydroxyl to generate zinc hydroxide which is deposited on the cathode region, so that the cathode reaction in the corrosion process is inhibited to play a corrosion role;
3. the carboxylic acid-sulfonic acid-acrylate terpolymer contains strong acid, weak acid and nonionic groups on a molecular chain, has an excellent dispersing effect, is suitable for being used under the conditions of high temperature, high pH value and high alkali, has an excellent inhibiting effect on iron oxide, calcium phosphate, zinc phosphate and calcium carbonate precipitates in water, has high tolerance on calcium and has good compatibility with other components;
4. the 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane and zinc salt have a synergistic effect, have excellent scale inhibition and corrosion inhibition effects, are high temperature resistant, chlorine decomposition resistant, low in phosphorus content, small in environmental influence and suitable for harsh water quality conditions of high temperature, high hardness, high pH value and high concentration doubling speed;
5. the hydrolyzed maleic anhydride has obvious solubility limit effect at high temperature (350 ℃) and high pH value, has good dispersion effect on carbonate, and can resist scale for 100 hours; in addition, the hydrolyzed polymaleic anhydride has a synergistic corrosion inhibition effect with zinc salt;
6. on one hand, the industrial hydrochloric acid can neutralize alkaline substances in a water body with a high pH value, and the influence of a high pH environment on scale inhibition and corrosion inhibition effects of other components is reduced; on the other hand, the doping of the hydrochloric acid has the function of inhibiting the carbonate scale from being separated out from the water body, and the scale inhibition effect is excellent;
7. the low-phosphorus scale and corrosion inhibitor with the specific material ratio has low phosphorus content, is environment-friendly, has excellent scale and corrosion inhibition effects, and is suitable for being used in high-pH and high-temperature water body environments;
8. the preparation method of the scale and corrosion inhibitor has the advantages of simple process steps, low phosphorus and environmental protection of the prepared low-phosphorus scale and corrosion inhibitor, suitability for harsh water quality conditions of high pH and high temperature, and excellent scale inhibition and corrosion retarding effects.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Examples 1 to 6
The low-phosphorus scale and corrosion inhibitor comprises the following components in percentage by mass,
TABLE 1 content of each component in examples 1-6
Wherein, the hydrochloric acid is industrial hydrochloric acid with the mass percentage concentration of 31%.
Zinc chloride can be replaced by zinc sulfate or zinc nitrate.
The carboxylic acid-sulfonic acid-acrylate terpolymer is formed by copolymerizing a carboxylic acid monomer, a sulfonic acid monomer and an acrylate monomer, and the molecular weight is less than or equal to 500 Da; wherein, the carboxylic acid monomer can be selected from any one of crotonic acid, beta-phenylacrylic acid, maleic acid and fumaric acid; the sulfonic acid monomer can be selected from any one of 2-acrylamide-2-methylpropanesulfonic acid and methacrylic sulfonic acid; the acrylate monomer may be selected from any one of 2-methyl methacrylate, 2-ethyl methacrylate, methyl acrylate and ethyl acrylate. The carboxylic acid-sulfonic acid-acrylate terpolymers selected in examples 1-6 are all beta-cinnamic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymers.
Examples 7 to 10
The low-phosphorus scale and corrosion inhibitor comprises the following components in percentage by mass,
TABLE 2 content of each component in examples 7-10
Wherein, the hydrochloric acid is industrial hydrochloric acid with the mass percentage concentration of 31%.
Zinc chloride can be replaced by zinc sulfate or zinc nitrate.
The carboxylic acid-sulfonic acid-acrylate terpolymer is formed by copolymerizing a carboxylic acid monomer, a sulfonic acid monomer and an acrylate monomer, and the molecular weight is less than or equal to 500 Da; wherein, the carboxylic acid monomer can be selected from any one of crotonic acid, beta-phenylacrylic acid, maleic acid and fumaric acid; the sulfonic acid monomer can be selected from any one of 2-acrylamide-2-methylpropanesulfonic acid and methacrylic sulfonic acid; the acrylate monomer may be selected from any one of 2-methyl methacrylate, 2-ethyl methacrylate, methyl acrylate and ethyl acrylate. The carboxylic acid-sulfonic acid-acrylate terpolymers selected in examples 1-6 are all beta-cinnamic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymers.
The organic acid can be any one of lactic acid, malic acid, citric acid and benzoic acid. Benzoic acid was used in each of examples 7 to 10.
Examples 11 to 14
The low-phosphorus scale and corrosion inhibitor comprises the following components in percentage by mass,
TABLE 3 table of contents of components in examples 11 to 14
Wherein, the hydrochloric acid is industrial hydrochloric acid with the mass percentage concentration of 31%.
Zinc chloride can be replaced by zinc sulfate or zinc nitrate.
The carboxylic acid-sulfonic acid-acrylate terpolymer is formed by copolymerizing a carboxylic acid monomer, a sulfonic acid monomer and an acrylate monomer, and the molecular weight is less than or equal to 500 Da; wherein, the carboxylic acid monomer can be selected from any one of crotonic acid, beta-phenylacrylic acid, maleic acid and fumaric acid; the sulfonic acid monomer can be selected from any one of 2-acrylamide-2-methylpropanesulfonic acid and methacrylic sulfonic acid; the acrylate monomer may be selected from any one of 2-methyl methacrylate, 2-ethyl methacrylate, methyl acrylate and ethyl acrylate. The carboxylic acid-sulfonic acid-acrylate terpolymers selected in examples 1-6 are all beta-cinnamic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymers.
The molecular formula of the ethanolamine derivative is HOCH2CH2NXY, wherein X is-H, -CH3、-CH2CH3and-CH2CH2CH2CH3Y is-CH3、-CH2CH3and-CH2CH2CH2CH3Any one of the above. The ethanolamine derivatives selected in examples 11 to 14 were all N, N' -dimethylethanolamine.
Example 15
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, a beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, hydrolyzed maleic anhydride and water according to the embodiment 1;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid and zinc chloride, and uniformly stirring at the rotating speed of 1500 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane and hydrolyzed maleic anhydride after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1500rpm until no obvious solid particles exist in the mixed solution, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 16
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, a beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, hydrolyzed maleic anhydride and water according to the embodiment 2;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid and zinc chloride, and stirring uniformly at the rotating speed of 1400 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding the beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane and hydrolyzed maleic anhydride after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1400rpm until no obvious solid particles exist in the mixed solution, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 17
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, a beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, hydrolyzed maleic anhydride and water according to the embodiment 3;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid and zinc chloride, and stirring uniformly at the rotating speed of 1300 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane and hydrolyzed maleic anhydride after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1300rpm until no obvious solid particles exist in the mixed solution, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 18
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, a beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, hydrolyzed maleic anhydride and water according to the embodiment 4;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid and zinc chloride, and stirring uniformly at the rotating speed of 1200 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane and hydrolyzed maleic anhydride after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1200rpm until no obvious solid particles exist in the mixed solution, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 19
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, a beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, hydrolyzed maleic anhydride and water according to the embodiment 5;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid and zinc chloride, and stirring uniformly at the rotating speed of 1100 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane and hydrolyzed maleic anhydride after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1100rpm until no obvious solid particles exist in the mixed solution, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 20
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, a beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, hydrolyzed maleic anhydride and water according to the embodiment 6;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid and zinc chloride, and stirring uniformly at the rotating speed of 1000 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane and hydrolyzed maleic anhydride after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1000rpm until no obvious solid particles exist in the mixed solution, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 21
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, a beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphono-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, benzoic acid, chitosan, 2-mercaptobenzothiazole, imidazoline and water according to the embodiment 7;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid, zinc chloride, benzoic acid and chitosan, and uniformly stirring at the rotating speed of 1000 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, 2-mercaptobenzothiazole and imidazoline after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1000rpm until no obvious solid particles exist in the mixed solution, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 22
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, a beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphono-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, benzoic acid, chitosan, 2-mercaptobenzothiazole, imidazoline and water according to the embodiment 8;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid, zinc chloride, benzoic acid and chitosan, and uniformly stirring at the rotating speed of 1000 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, 2-mercaptobenzothiazole and imidazoline after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1000rpm until no obvious solid particles exist in the mixed solution, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 23
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, a beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphono-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, benzoic acid, chitosan, 2-mercaptobenzothiazole, imidazoline and water according to the embodiment 9;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid, zinc chloride, benzoic acid and chitosan, and uniformly stirring at the rotating speed of 1000 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, 2-mercaptobenzothiazole and imidazoline after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1000rpm until no obvious solid particles exist in the mixed solution, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 24
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, a beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphono-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, benzoic acid, chitosan, 2-mercaptobenzothiazole, imidazoline and water according to the embodiment 10;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid, zinc chloride, benzoic acid and chitosan, and uniformly stirring at the rotating speed of 1000 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, 2-mercaptobenzothiazole and imidazoline after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1000rpm until no obvious solid particles exist in the mixed solution, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 25
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, benzoic acid, chitosan, 2-mercaptobenzothiazole, imidazoline, N' -dimethylethanolamine and water according to the embodiment 11;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid, zinc chloride, benzoic acid and chitosan, and uniformly stirring at the rotating speed of 1000 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, 2-mercaptobenzothiazole, imidazoline and N, N' -dimethylethanolamine after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1000rpm until no obvious solid particles exist in the mixed liquid, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 26
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, benzoic acid, chitosan, 2-mercaptobenzothiazole, imidazoline, N' -dimethylethanolamine and water according to the embodiment 12;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid, zinc chloride, benzoic acid and chitosan, and uniformly stirring at the rotating speed of 1000 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, 2-mercaptobenzothiazole, imidazoline and N, N' -dimethylethanolamine after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1000rpm until no obvious solid particles exist in the mixed liquid, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 27
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, benzoic acid, chitosan, 2-mercaptobenzothiazole, imidazoline, N' -dimethylethanolamine and water according to the embodiment 13;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid, zinc chloride, benzoic acid and chitosan, and uniformly stirring at the rotating speed of 1000 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, 2-mercaptobenzothiazole, imidazoline and N, N' -dimethylethanolamine after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1000rpm until no obvious solid particles exist in the mixed liquid, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Example 28
A preparation method of a low-phosphorus scale and corrosion inhibitor comprises the following steps,
step one, weighing 31% by mass of hydrochloric acid, zinc chloride, beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, benzoic acid, chitosan, 2-mercaptobenzothiazole, imidazoline, N' -dimethylethanolamine and water according to the embodiment 14;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid, zinc chloride, benzoic acid and chitosan, and uniformly stirring at the rotating speed of 1000 rpm;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, 2-mercaptobenzothiazole, imidazoline and N, N' -dimethylethanolamine after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring at the rotating speed of 1000rpm until no obvious solid particles exist in the mixed liquid, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
Performance testing
The low-phosphorus scale and corrosion inhibitors prepared by the preparation methods of the low-phosphorus scale and corrosion inhibitors of examples 15 to 28 were respectively used as test samples 1 to 14; a commercially available organophosphorus scale and corrosion inhibitor is taken as a comparison example 1, and an authorized publication number CN102583785B and a published example 1 named as 'circulating cooling water corrosion inhibitor and preparation and application thereof' are taken as a comparison example 2.
A Scale inhibition Performance test
The water adopted in the test is the make-up water of the circulating cooling water of a chemical enterprise, and the make-up water is naturally concentrated in a laboratory according to the multiple of 5.0.
The quality of the make-up water before concentration is shown in the following table:
TABLE 4 quality analysis of make-up water before concentration
TABLE 5 quality analysis of the make-up water after concentration
The test method refers to a calcium carbonate deposition method in a cooling water analysis and test method issued by petrochemical companies.
The test conditions are as follows: the test temperature is 80 +/-1 ℃; experiment time, 10 hours;
calculation of relative scale inhibition ratio (η):
the test results are shown in the following table:
table 6.
Table 7.
From the test results in tables 6 and 7, it is known that the relative scale inhibition rate of the low-phosphorus scale and corrosion inhibitor of the present invention or the low-phosphorus scale and corrosion inhibitor prepared by the preparation method of the present invention is more than 98.5%, which is much higher than that of comparative examples 1 and 2, and the low-phosphorus scale and corrosion inhibitor can effectively inhibit the precipitation of scales such as calcium carbonate and calcium phosphate in water, and has excellent scale inhibition effect. Meanwhile, after the organic acid, the chitosan, the 2-mercaptobenzothiazole, the imidazoline and the ethanolamine derivative are added into the formula, the scale inhibition performance of the low-phosphorus scale and corrosion inhibitor is slightly improved, but the range is not large.
B Corrosion inhibition Performance test
The test is carried out according to a 'rotating hanging piece weight loss method' in 'cooling water analysis and test method' issued by China petrochemical company;
test temperature: 45 +/-1 ℃;
adding concentration of the scale and corrosion inhibitor: 30mg/L;
the hanging sheet rotating speed is as follows: 75-80 r/min;
test piece: material, carbon steel; specific surface area 28cm2;
Experiment time: 72 hours (carbon steel);
calculation of corrosion rate:
wherein the content of the first and second substances,
c: calculation constant 8.76 × 104；
Δ W: weight loss of the test piece, g;
a: surface area of test piece, cm2;
T is experiment time and hours;
ρ: density of test piece in g/cm3。
The test results are shown in the following table:
table 8.
Table 9.
From the experimental data in tables 8 and 9, it can be seen that the corrosion inhibition effect of the low-phosphorus scale and corrosion inhibitor of the present invention or the low-phosphorus scale and corrosion inhibitor prepared by the method of the present invention is significantly better than that of comparative examples 1 and 2, and the corrosion rate of the metal test piece is only about 50% of that of comparative example 1 or comparative example 2. Meanwhile, after the organic acid, the chitosan, the 2-mercaptobenzothiazole and the imidazoline are added into the formula, the corrosion inhibition effect of the scale and corrosion inhibitor is improved, and the corrosion rate of the metal test piece is further reduced after the ethanolamine derivative is added.
The above-mentioned embodiments are merely illustrative and not restrictive, and those skilled in the art can modify the embodiments without inventive contribution as required after reading this specification, but only fall within the scope of the claims of the present invention.
Claims (6)
1. A low-phosphorus scale and corrosion inhibitor is characterized in that: comprises the following components in percentage by mass,
8 to 12 percent of hydrochloric acid
2 to 5 percent of zinc salt
30 to 35 percent of beta-phenylacrylic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer
8% -10% of phosphonic acid-1, 2, 4-tricarboxylic acid butane
25 to 30 percent of hydrolyzed maleic anhydride
1 to 5 percent of benzoic acid
1 to 1.5 percent of chitosan
0.1 to 0.5 percent of 2-mercaptobenzothiazole
Imidazoline 0.1% -0.5%
The balance of water;
the hydrochloric acid is industrial hydrochloric acid with the mass percentage concentration of 31%.
2. The low-phosphorus scale and corrosion inhibitor according to claim 1, which is characterized in that: the zinc salt is any one of zinc chloride, zinc sulfate and zinc nitrate.
3. The low-phosphorus scale and corrosion inhibitor according to claim 1, which is characterized in that: the composite material also comprises, by mass percent,
1% -2% of ethanolamine derivative.
4. The low-phosphorus scale and corrosion inhibitor according to claim 3, wherein: the molecular formula of the ethanolamine derivative is HOCH2CH2NXY, wherein X is-H, -CH3、-CH2CH3and-CH2CH2CH2CH3Any one of (a); y is-CH3、-CH2CH3and-CH2CH2CH2CH3Any one of the above.
5. A method for preparing the low-phosphorus scale and corrosion inhibitor according to claim 1, which is characterized in that: comprises the following steps of (a) carrying out,
weighing 31% by mass of hydrochloric acid, zinc salt, beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, benzoic acid, chitosan, 2-mercaptobenzothiazole, imidazoline and water according to the material ratio of claim 1;
step two, adding the weighed water into a stirring kettle, adding hydrochloric acid, zinc salt, benzoic acid and chitosan, and uniformly stirring;
measuring the temperature of the mixed solution in the reaction kettle, adding beta-phenylpropenoic acid/2-acrylamide-2-methylpropanesulfonic acid/methyl acrylate terpolymer, 2-phosphonic acid-1, 2, 4-tricarboxylic acid butane, hydrolyzed maleic anhydride, 2-mercaptobenzothiazole and imidazoline after the temperature is reduced to be less than or equal to 38 ℃, continuously stirring until no obvious solid particles exist in the mixed liquid, and discharging to obtain the low-phosphorus scale and corrosion inhibitor.
6. The preparation method of the low-phosphorus scale and corrosion inhibitor according to claim 5, characterized in that: and in the second step and the third step, the stirring speed is less than or equal to 1500 rpm.
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| CN112320975A (en) * | 2020-08-31 | 2021-02-05 | 嘉兴沃特泰科环保科技股份有限公司 | Phosphorus-containing scale inhibitor for industrial circulating water and preparation method and application thereof |
| CN112174343A (en) * | 2020-11-03 | 2021-01-05 | 西安热工研究院有限公司 | Green environment-friendly non-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN113684483B (en) * | 2021-08-26 | 2022-10-14 | 常州市武进盛源化工有限公司 | Zinc chloride compound corrosion inhibitor for circulating cooling water and preparation method thereof |
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