CN107304080B - Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof - Google Patents
Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof Download PDFInfo
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- CN107304080B CN107304080B CN201610248305.3A CN201610248305A CN107304080B CN 107304080 B CN107304080 B CN 107304080B CN 201610248305 A CN201610248305 A CN 201610248305A CN 107304080 B CN107304080 B CN 107304080B
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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
- 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
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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
- C02F2303/04—Disinfection
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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 relates to the field of water treatment, and discloses a corrosion-inhibition, scale-inhibition and sterilization composition and application thereof, wherein the composition contains water-soluble tin salt, a carboxyl-group-containing homopolymer, a nitrogen-containing heterocyclic compound and a copolymer, the copolymer contains a structural unit provided by 2-acrylamide-2-methylpropanesulfonic acid, and the weight percentage of the structural unit provided by 2-acrylamide-2-methylpropanesulfonic acid is more than 20% on the basis of the total amount of the copolymer, wherein the weight ratio of the water-soluble tin salt to the carboxyl-group-containing homopolymer to the nitrogen-containing heterocyclic compound to the copolymer is 1:1-20:1-12:1-20, and the weight of the water-soluble tin salt is calculated by tin ions. The corrosion-inhibition, scale-inhibition and sterilization composition has better corrosion inhibition, scale inhibition and sterilization performances, and the dosage is lower when the composition is used. Moreover, the composition of the invention does not contain phosphorus and is green and environment-friendly.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a corrosion-inhibition, scale-inhibition and sterilization composition and application thereof in circulating cooling water treatment.
Background
The problems of corrosion, scaling and bacterial growth can be caused when the circulating cooling water is operated for a long time, and a corrosion inhibitor, a scale inhibitor and a bactericide are required to be added respectively. The research of nontoxic and high-efficiency multifunctional water treatment agents is the direction of medicament research and development. Most petrochemical enterprises apply the compound corrosion and scale inhibitor. The widely used formula includes phosphorus system (composed of polyphosphate, polycarboxylic acid and copolymer, zinc salt, etc.), and all organic system (composed of organic phosphonic acid, polycarboxylic acid and copolymer, azole compound with or without zinc salt). In the process of adding the water treatment agent, the compatibility problem of the scale and corrosion inhibitor and the bactericide is often existed. Chlorine bactericide commonly used for circulating water has oxidation effect on a plurality of scale and corrosion inhibitors, thereby reducing the corrosion and scale inhibition effect.
At present, most of common corrosion and scale inhibitors for domestic and overseas circulating cooling water treatment are composite formulas of phosphorus water treatment agents. However, with the increase of global environmental protection and safety awareness, many countries and regions continue to take phosphorus prohibition and phosphorus limitation measures. Therefore, the low-phosphorus and phosphorus-free corrosion and scale inhibitor has become the development direction of domestic and foreign water treatment agents.
CN102578088A discloses a compound medicament with bactericidal, corrosion-inhibiting and scale-inhibiting effects, which comprises polyamides, quaternary ammonium salts, organic phosphonic acid polymers, inorganic salts and water. However, the agent contains a large amount of organic phosphine and is added in a large amount.
CN102730851A discloses a water treatment agent with corrosion and scale inhibition and biocidal efficacy and a preparation method thereof. The water treatment agent is a polyepoxysuccinic acid/Broboer copolymer which contains no phosphorus, is biodegradable and has a certain biocidal effect due to the existence of oxidizing bromine atoms. But the corrosion inhibition effect of the agent is general, and the sterilization effect is poor.
Therefore, the research and development of the low-phosphorus (or phosphorus-free) water treatment agent which has better corrosion inhibition, scale inhibition and sterilization performances and is low in dosage during use is of great significance.
Disclosure of Invention
The invention aims to overcome the defect that the existing low-phosphorus (or phosphorus-free) water treatment agent is difficult to have better corrosion inhibition, scale inhibition and sterilization performances at the same time, and provides a low-phosphorus (or phosphorus-free) water treatment agent which has better corrosion inhibition, scale inhibition and sterilization performances and is low in dosage during use.
The inventor of the invention discovers in research that the water-soluble tin salt and the nitrogen-containing heterocyclic compound have obvious synergistic corrosion inhibition effect, the copolymer can play a role in stabilizing tin ions, in addition, tin hydroxide generated by hydrolysis of the water-soluble tin salt has a sterilization effect, and the tin hydroxide is compounded with the carboxyl-group-containing homopolymer to obtain the medicament with the corrosion inhibition, scale inhibition and sterilization performances. Therefore, the composition for corrosion, scale and sterilization is used for treating circulating cooling water without adding a bactericide additionally or only adding a small amount of bactericide, and can achieve good corrosion, scale and sterilization effects. Therefore, in order to achieve the above object, the present invention provides a corrosion-inhibition, scale-inhibition and sterilization composition, which comprises a water-soluble tin salt, a carboxylic group-containing homopolymer, a nitrogen-containing heterocyclic compound and a copolymer, wherein the copolymer comprises a structural unit provided by 2-acrylamido-2-methylpropanesulfonic acid, and the weight percentage of the structural unit provided by 2-acrylamido-2-methylpropanesulfonic acid is 20% or more based on the total amount of the copolymer, wherein the weight ratio of the water-soluble tin salt, the carboxylic group-containing homopolymer, the nitrogen-containing heterocyclic compound and the copolymer is 1:1-20:1-12:1-20, and the weight of the water-soluble tin salt is calculated by tin ions.
In addition, the invention also provides the application of the composition in treating circulating cooling water.
The corrosion-inhibition, scale-inhibition and sterilization composition has better corrosion inhibition, scale inhibition and sterilization performances, and the dosage is lower when the composition is used. Moreover, the composition of the invention does not contain phosphorus and is green and environment-friendly.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the present invention, unless otherwise specified, the weight of each material is in terms of an effective amount (or dry basis), e.g., the amount of polymer (including homopolymers and copolymers) is on a dry basis.
The composition for corrosion inhibition, scale inhibition and sterilization (preferably containing no phosphorus) comprises a water-soluble tin salt, a carboxyl group-containing homopolymer, a nitrogen-containing heterocyclic compound and a copolymer, wherein the copolymer contains a structural unit provided by 2-acrylamide-2-methylpropanesulfonic acid, and the weight percentage of the structural unit provided by 2-acrylamide-2-methylpropanesulfonic acid is more than 20% based on the total weight of the copolymer, wherein the weight ratio of the water-soluble tin salt to the carboxyl group-containing homopolymer to the nitrogen-containing heterocyclic compound to the copolymer is 1 (1-20) to (1-12) to (1-20), and the weight of the water-soluble tin salt is calculated by tin ions.
Preferably, the weight ratio of the water-soluble tin salt to the carboxylic acid group-containing homopolymer is 1 (4-16) (e.g., 1:4, 1:5, 1:5.5, 1:8, 1:10, 1:11, 1:12, 1:14, 1:15, 1:16, or any value therebetween); and/or the weight ratio of the water-soluble tin salt to the nitrogen-containing heterocyclic compound is 1 (3-10) (such as 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10 or any value between the aforementioned values); and/or the weight ratio of the water-soluble tin salt to the copolymer is 1 (4-16) (e.g., 1:4, 1:5, 1:8, 1:8.5, 1:10, 1:11, 1:12, 1:14, 1:15, 1:16, or any value therebetween).
Wherein, the contents of the above components may be the same or different. Preferably, the composition consists of the above ingredients.
According to the invention, the water-soluble tin salt may be a water-soluble tin salt (solubility ≥ 1g/100g water at 20 ℃) as is common in the art. Preferably, the water-soluble tin salt is selected from at least one of tin chloride, stannous chloride, tin sulfate and tin nitrate.
According to the present invention, the carboxylic acid group-containing homopolymer can be various phosphorus-free homopolymers (such as unsaturated carboxylic acid (carbon number is 3-10 (such as C) and the like) commonly used in the art3、C4、C5、C6、C7、C8、C9Or C10) Non-phosphorus-containing homopolymers) of (a) preferably having a weight average molecular weight in the range of 400-5000. More preferably, the carboxylic acid group-containing homopolymer is at least one of polyaspartic acid, polyepoxysuccinic acid, and polyacrylic acid. The water-soluble tin salt and the homopolymer containing carboxylic groups have good synergistic effect, and can obtain excellent corrosion and scale inhibition effects when the circulating cooling water is treated.
According to the present invention, the nitrogen-containing heterocyclic compound is a heterocyclic compound in which the hetero atom is nitrogen (the number of hetero atoms (nitrogen atoms) is 1, 2 or 3). In the present invention, the heterocyclic compound may be various nitrogen-containing heterocyclic compounds common in the art, preferably at least one selected from a group consisting of a (substituted or unsubstituted) five-membered heterocyclic compound, a (substituted or unsubstituted) six-membered heterocyclic compound, and a (substituted or unsubstituted) benzene-fused heterocyclic compound (e.g., a heterocyclic compound in which a benzene ring is fused with a five-membered heterocyclic ring and/or a heterocyclic compound in which a benzene ring is fused with a six-membered heterocyclic ring), for example, pyrrole (substituted or unsubstituted), benzopyrrole (substituted or unsubstituted), imidazole (substituted or unsubstituted), benzimidazole (substituted or unsubstituted), pyrazole (substituted or unsubstituted), pyridine (substituted or unsubstituted), pyrazine (substituted or unsubstituted), pyrimidine (substituted or unsubstituted), benzopyrrole (substituted or unsubstituted), At least one of (substituted or unsubstituted) benzopyrimidine, (substituted or unsubstituted) quinoline, (substituted or unsubstituted) isoquinoline, and (substituted or unsubstituted) benzotriazole.
Wherein, the substituted group can be phenyl, hydroxyl, amino, methoxyl, nitryl and C1-C3At least one of alkyl groups (such as methyl group) of (a).
Further preferably, the nitrogen-containing heterocyclic compound is selected from at least one of benzopyrrole, 2-methylimidazole, 3, 5-diphenylpyrazole, 2-phenylpyridine, 2-hydroxypyrazine, 2-amino-5-methoxypyrimidine, 4-methylquinoline, 5-nitroisoquinoline, benzotriazole and methylbenzotriazole.
According to the present invention, the weight percentage of the structural unit provided by 2-acrylamido-2-methylpropanesulfonic acid is 20% or more (preferably 20 to 30%) based on the total amount of the copolymer. The copolymer contains less than 80 wt% (preferably 70-80 wt%) of other structural units.
Preferably, the copolymer has an intrinsic viscosity at 30 ℃ of 0.06 to 0.1dl/g (preferably 0.07 to 0.08 dl/g).
According to the present invention, as long as the copolymer contains a structural unit provided by 2-acrylamido-2-methylpropanesulfonic acid, other structural units contained therein are not particularly limited and may be provided by various monomers commonly used in the art for preparing water treatment agents. Preferably, the other structural unit (not 2-acrylamido-2-methylpropanesulfonic acid) contained in the copolymer is provided by at least one or at least two of an unsaturated organic acid, a salt of an unsaturated organic acid, an unsaturated organic acid anhydride, an unsaturated amide, and an unsaturated organic acid ester.
The unsaturated organic acid is preferably acrylic acid, maleic acid and C2-C10At least one of unsaturated sulfonic acids. Said C is2-C10The unsaturated sulfonic acid (C) may be various conventional unsaturated sulfonic acids, and may contain a phenyl group, an amide group, etc. in addition to an alkyl group, an alkenyl group and a sulfonic acid group2-C10The unsaturated sulfonic acid of (b) may be at least one of styrene sulfonic acid, allyl sulfonic acid, vinyl sulfonic acid, and 2-methyl-2' -acrylamidopropane sulfonic acid.
The salt of the unsaturated organic acid may be a salt (e.g., sodium salt and/or potassium salt) of the above-mentioned unsaturated organic acid.
The unsaturated organic acid anhydride is an acid anhydride (e.g., maleic anhydride) of the above unsaturated organic acid.
The unsaturated amide may be an amide formed from the above-mentioned unsaturated organic acid, such as acrylamide and/or methacrylamide.
The unsaturated organic acid ester is an ester of the above unsaturated organic acid (such as acrylic acid ester (such as acrylic acid C)1-C8(C1、C2、C3、C4、C5、C6、C7Or C8) Esters) such as methyl acrylate or hydroxypropyl acrylate).
More preferably, the other structural units contained in the copolymer are provided by at least one or at least two of acrylic acid, maleic anhydride, acrylamide, methacrylamide, styrene sulfonic acid, sodium styrene sulfonate, methyl acrylate, ethyl acrylate, hydroxypropyl acrylate.
Further preferably, the copolymer contains additional structural units provided by acrylic acid, acrylamide, acrylic acid and methyl acrylate, acrylic acid and ethyl acrylate, acrylic acid and hydroxypropyl acrylate, acrylic acid and maleic anhydride, acrylic acid and styrene sulfonic acid, acrylic acid and styrene sodium sulfonate, or acrylamide and methacrylamide.
In practical application, the corrosion-inhibition, scale-inhibition and sterilization composition can be prepared before use, for example, the components are mixed according to the formula and then added into circulating cooling water; the components can also be added directly to the recirculating cooling water in accordance with the foregoing formulation without a mixing step. In order to prevent the water-soluble tin salt from being hydrolyzed to influence the corrosion, scale and sterilization effects of the composition, the carboxylic group-containing homopolymer, the nitrogen-containing heterocyclic compound and the copolymer are preferably added into circulating cooling water, and the water-soluble tin salt is then added, and similarly, the adding sequence of the carboxylic group-containing homopolymer, the nitrogen-containing heterocyclic compound and the copolymer is not limited. In actual use, the copolymer may be added in an effective amount (weight on a dry basis) of 2 to 10 mg/L.
The invention also provides the application of the composition in treating circulating cooling water. The amount of the composition is preferably 6.5 to 28mg/L of circulating water, more preferably 11.5 to 22mg/L of circulating water.
The present invention will be described in detail below by way of examples.
In the following examples, polyaspartic acid (weight average molecular weight of 2000), polyepoxysuccinic acid (weight average molecular weight of 1000), polyacrylic acid (weight average molecular weight of 3000), and copolymers were obtained from Shandong Tai and Water treatment science and technology, Inc.
In the following examples, the water quality of test raw water is shown in table 1. Wherein Ca2+Total alkalinity and total hardness are all as CaCO3The water quality measuring method refers to the cooling water analysis and test method written by the department of production and development of the general petrochemical company of China (1993, published by the information center of the general petrochemical plant in Anqing).
TABLE 1
Test example 1
The stability of the copolymer was evaluated in the following manner.
Preparing Ca from distilled water2+The copolymer (1-8) was added to test water having a concentration of 250mg/L, a basicity of 250mg/L and a tin ion of 5mg/L in accordance with Table 2, and allowed to stand in a constant-temperature water bath at 80. + -. 1 ℃ for 10 hours, and the concentration of the remaining tin ions in the water was analyzed by sampling (by a potassium dichromate method), while making a blank sample, and the tin stability was calculated. The higher the tin stability, the better the stability of the tin salt in water, and the better the performance of the copolymer in stabilizing the tin salt.
The tin stability rate calculation formula is as follows: stable tin rate (C-C)0)/(C1-C0)×100％
C: the concentration (mg/L) of tin ions was measured
C0: concentration of tin ion (mg/L) of blank sample
C1: concentration of tin ion in raw Water (mg/L)
TABLE 2
As can be seen from the test results in Table 2, the copolymer containing a specific amount of the structural unit provided by 2-acrylamido-2-methylpropanesulfonic acid has a very good stabilizing effect on tin salt, which is far superior to other copolymers.
Examples 1 to 4
The test water was dosed with the agents as shown in table 3 and tested for scale inhibition, corrosion inhibition and sterilization performance, the specific test methods being as follows. mg/L in table 3 indicates the effective (dry basis) content, and the tin salt is in terms of tin ions.
Evaluation of Scale inhibition Property
Adding the medicinal preparation into test water, evaporating and concentrating in 80 + -1 deg.C constant temperature water bath to 5 times of concentration ratio, sampling and analyzing residual Ca in water2+While making blank sample, and calculating the scale inhibitionAnd (4) rate. The calculation formula of the scale inhibition rate is as follows: scale inhibition rate ═ C-C0)/(nC1-C0) X 100%, wherein,
c: residual Ca in water2+Concentration (mg/L)
C0: ca of blank2+Concentration (mg/L)
C1: ca in raw water2+Concentration (mg/L)
n: multiple of concentration
Evaluation of Corrosion inhibition Properties
Fixing 20# high-quality carbon steel test piece on a coupon instrument, putting the test piece into test water (obtained by concentrating test raw water by 5 times and adjusting the pH value) added with a medicament according to each example or comparative example, keeping the constant temperature at 40 +/-1 ℃, keeping the rotating speed at 75rpm for 72 hours, recording the weight of the test piece before and after the test, calculating the average corrosion speed (F), adjusting the pH value in the test process, and calculating the average corrosion speed (F) according to the formula that F is (C multiplied by △ W)/(A multiplied by T multiplied by rho), wherein,
c: the constants were calculated, and when mm/a (mm/year) is used, C is 8.76 × 107
△ W corrosion weight loss (g) of test piece
A: area of test piece (cm)2)
T: corrosion test time (h)
ρ: density of test piece Material (kg/m)3)
Determination of fungicidal Properties
The method for measuring the sterilization performance of the medicament refers to the regulation of static sterilization test of heterotrophic bacteria in the cooling water analysis and test method compiled by the department of production and development of the general chemical company of China.
TABLE 3
From the results in table 3, it can be seen that the corrosion, scale and sterilization composition of the present invention has good corrosion, scale and sterilization performance.
Comparative example 1
The reagents were dosed as in example 1, except that copolymer 1 was replaced by copolymer 6, and the scale inhibition was measured to be 61.8%, F was 0.085mm/a, and the sterilization rates at different times (1h, 4h, 8h, 12h and 24h) were 80.7%, 74.5%, 57.1%, 48.3% and 35.5%, respectively.
Comparative example 2
The formulation was dosed as in example 1, except that copolymer 1 was replaced by copolymer 7, and the scale inhibition was found to be 59.2%, F was 0.091mm/a, and the sterilization rates at different times (1h, 4h, 8h, 12h and 24h) were 81.0%, 73.2%, 55.6%, 41.7% and 28.6%, respectively.
Example 5
To simulate the field, dynamic simulation tests were performed. The dynamic simulation test method is carried out according to the chemical industry standard HG/T2160-91 of the people's republic of China, and the control parameters are as follows.
Water quality: test raw water 1, see table 1.
Concentration multiple: tower A4.0 plus or minus 0.2 tower B4.0 plus or minus 0.2
pH: tower A control 8.0 plus or minus 0.2 tower B control 8.0 plus or minus 0.2
Flow rate: 1.0m/s
Medicament:
tower A: weighing 5g of polyaspartic acid with the solid content of 40 percent by weight, 15g of polyepoxysuccinic acid with the solid content of 40 percent by weight, 3g of benzotriazole and 26.7g of copolymer 1 with the solid content of 30 percent by weight, dissolving in 48.8g of water, finally adding 1.5g of stannic chloride pentahydrate, fully dissolving, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into water according to the medicament concentration of 100mg/L, the effective concentrations of polyaspartic acid, polyepoxysuccinic acid, benzotriazole, copolymer 1 and tin ions in the water are respectively 2mg/L, 6mg/L, 3mg/L, 8mg/L and 0.5 mg/L.
Tower B: 10g of polyepoxysuccinic acid with a solid content of 40 percent by weight, 26.7g of polyacrylic acid with a solid content of 30 percent by weight (the limiting viscosity number at 30 ℃ is 0.072dl/g) and 33.3g of copolymer 8 with a solid content of 30 percent by weight are weighed, dissolved in 24.1g of water, and finally 5.9g of tin tetrachloride pentahydrate is added to be fully dissolved and shaken evenly, thus obtaining 100g of the medicament required to be prepared.
When the prepared medicament is added into water according to the medicament concentration of 100mg/L, the effective concentrations of polyepoxysuccinic acid, polyacrylic acid, copolymer 8 and tin ions in the water are respectively 4mg/L, 6mg/L, 10mg/L and 2 mg/L.
Inlet temperature: temperature difference of 32. + -. 1 ℃:10 deg.C
The heterotrophic bacteria monitoring results during the dynamic simulation test are shown in table 4, and the test tube results are shown in table 5.
TABLE 4
TABLE 5
The corrosion speed of the carbon steel pipe wall of the open system is less than or equal to 0.125mm/a as specified in the national standard GB50050-95 design Specification for Industrial circulating Cooling Water treatment 3.1.6; in the cooling water analysis and test method compiled by the production department and the development department of the general company of petrochemical industry, the laboratory small simulation test method stipulates that the corrosion speed of carbon steel is in a good grade between 0 and 0.028mm/a, in a good grade between 0.028 and 0.056mm/a and in an allowable grade between 0.056 and 0.070 mm/a; the adhesion speed is of the order of "good" at 0-6mcm, of "good" at 6-15mcm and of "permissible" at 15-20 mcm.
Therefore, the corrosion rate of the test tube is 0.020mm/a, the corrosion rate reaches the medium petrochemical good-grade standard, the adhesion rate is 5.2 mm, the corrosion rate reaches the good-grade standard, and the corrosion rate is superior to that of a comparative example. The test result shows that the corrosion-inhibition, scale-inhibition and sterilization composition has good comprehensive performance, good calcium carbonate scale inhibition performance and corrosion inhibition performance, and good sterilization performance, and is suitable for the treatment of circulating cooling water.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (15)
1. The composition is characterized by comprising a water-soluble tin salt, a carboxyl group-containing homopolymer, a nitrogen-containing heterocyclic compound and a copolymer, wherein the copolymer contains a structural unit provided by 2-acrylamide-2-methylpropanesulfonic acid, and the weight percentage of the structural unit provided by 2-acrylamide-2-methylpropanesulfonic acid is more than 20% based on the total amount of the copolymer, wherein the weight ratio of the water-soluble tin salt to the carboxyl group-containing homopolymer to the nitrogen-containing heterocyclic compound to the copolymer is 1:1-20:1-12:1-20, and the weight of the water-soluble tin salt is calculated by tin ions.
2. The composition of claim 1, wherein the water-soluble tin salt, carboxylic acid group-containing homopolymer, nitrogen-containing heterocyclic compound, and copolymer are present in a weight ratio of 1:4 to 16:3 to 10:4 to 16.
3. The composition of claim 1 or 2, wherein the water soluble tin salt is selected from at least one of tin chloride, stannous chloride, tin sulfate, and tin nitrate.
4. The composition of claim 1 or 2, wherein the carboxylic acid group-containing homopolymer is C3-C10Homopolymers of unsaturated carboxylic acids.
5. The composition of claim 4, wherein the carboxylic acid group-containing homopolymer is at least one of polyaspartic acid, polyepoxysuccinic acid, and polyacrylic acid.
6. The composition as claimed in claim 5, wherein the carboxylic acid group-containing homopolymer has a weight average molecular weight of 400-5000.
7. The composition according to claim 1 or 2, wherein the nitrogen-containing heterocyclic compound is at least one selected from the group consisting of a substituted or unsubstituted five-membered heterocyclic compound, a substituted or unsubstituted six-membered heterocyclic compound, and a substituted or unsubstituted benzene-fused heterocyclic compound.
8. The composition of claim 7, wherein the nitrogen-containing heterocyclic compound is selected from at least one of benzopyrrole, 2-methylimidazole, 3, 5-diphenylpyrazole, 2-phenylpyridine, 2-hydroxypyrazine, 2-amino-5-methoxypyrimidine, 4-methylquinoline, 5-nitroisoquinoline, benzotriazole and methylbenzotriazole.
9. The composition according to claim 1 or 2, wherein the copolymer has an ultimate viscosity at 30 ℃ of 0.06-0.1 dl/g.
10. The composition according to claim 1 or 2, wherein the copolymer contains other structural units provided by at least one of an unsaturated organic acid, a salt of an unsaturated organic acid, an unsaturated organic acid anhydride, an unsaturated amide and an unsaturated organic acid ester.
11. The composition of claim 10, wherein the copolymer contains additional structural units provided by at least one of acrylic acid, maleic anhydride, acrylamide, methacrylamide, styrene sulfonic acid, sodium styrene sulfonate, methyl acrylate, ethyl acrylate, hydroxypropyl acrylate.
12. The composition of claim 11, wherein the copolymer contains additional structural units provided by acrylic acid, acrylamide, acrylic acid and methyl acrylate, acrylic acid and ethyl acrylate, acrylic acid and hydroxypropyl acrylate, acrylic acid and maleic anhydride, acrylic acid and styrene sulfonic acid, sodium acrylic acid and styrene sulfonate, or acrylamide and methacrylamide.
13. Use of a composition according to any one of claims 1 to 12 for the treatment of recirculating cooling water.
14. Use according to claim 13, wherein the composition is used in an amount of 6.5-28mg/L of circulating water.
15. The use according to claim 14, wherein the composition is used in an amount of 11.5-22mg/L circulating water.
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