CN110803785B - Composite corrosion and scale inhibitor containing urotropine, application thereof and method for inhibiting corrosion of circulating cooling water containing sulfur - Google Patents
Composite corrosion and scale inhibitor containing urotropine, application thereof and method for inhibiting corrosion of circulating cooling water containing sulfur Download PDFInfo
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- CN110803785B CN110803785B CN201810885329.9A CN201810885329A CN110803785B CN 110803785 B CN110803785 B CN 110803785B CN 201810885329 A CN201810885329 A CN 201810885329A CN 110803785 B CN110803785 B CN 110803785B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
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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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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Abstract
The invention relates to the field of corrosion of circulating cooling water containing sulfur, and discloses a composite corrosion and scale inhibitor containing urotropine, application thereof and a method for inhibiting corrosion of circulating cooling water containing sulfur. The composite corrosion and scale inhibitor contains zinc salt, hydroxyethylidene diphosphonic acid, 2-hydroxyphosphonoacetic acid, sulfonate copolymer and urotropine, wherein the weight ratio of the zinc salt, the hydroxyethylidene diphosphonic acid, the 2-hydroxyphosphonoacetic acid, the sulfonate copolymer and the urotropine is 1:2-5:2-5:4-10:125-250, and the weight of the zinc salt is calculated by zinc ions. The method provided by the invention uses the composite corrosion and scale inhibitor after adjusting the pH value of the circulating cooling water containing sulfur to 8-9, and can obtain better corrosion and scale inhibition effects. The method can effectively inhibit the corrosion of sulfide in the sulfur-containing circulating cooling water to the water cooling equipment without using a large amount of medicaments and fresh water, and can effectively reduce the operation cost.
Description
Technical Field
The invention relates to the field of corrosion of circulating cooling water containing sulfur, in particular to a composite corrosion and scale inhibitor containing urotropine, application thereof and a method for inhibiting corrosion of circulating cooling water containing sulfur.
Background
In recent years, processing of highly corrosive crude oil containing high sulfur content in an oil refinery causes corrosion perforation of equipment, and a phenomenon of leakage of materials into circulating water occurs. Sulfides in crude oil can be divided into inorganic sulfur and organic sulfur, wherein the organic sulfur comprises mercaptan, thioether, disulfide, polysulfide, cyclic sulfide, thiophene and the like; the inorganic sulfur mainly comprises elemental sulfur and H2And S. These substances can directly corrode metals, and if corrosion perforation causes leakage of materials, the leaked materials can enter the circulating cooling water, causing serious deterioration of the quality of the circulating cooling water. Especially H2S gas can form sulfur ions (S) after entering the circulating cooling water2-) The sulfur ions not only can act with the surface of the metal, but also can act with a corrosion and scale inhibitor or a bactericide in the circulating cooling water, so that a series of problems of serious corrosion or standard exceeding of microorganisms and the like are caused to a water body. These problems will aggravate the corrosion of the equipment for cooling and exchanging the circulating cooling water, and further aggravate the leakage degree of the material, and form a vicious circle. At present, the treatment measures of the oil refinery for the circulating cooling water containing the sulfide ions are mainly two types: the first is to add a large amount of corrosion and scale inhibitor to increase the corrosion and scale inhibition effect; the second is bulk blowdown and fresh water make-up to reduce the sulphide concentration in the recycle water. Although the measures have certain effect, the dosage of the medicament is large, the fresh water consumption and the sewage discharge are greatly increased, and the operation cost of the circulating water system is increased.
CN1958848A discloses a method for inhibiting corrosion of cooling water containing sulfur circulation, which comprises controlling the alkalinity of sulfur-containing circulation water calculated by calcium carbonate to be 250-350mg/L, then adding composite corrosion inhibitor into the circulating cooling water, the adding amount is 5-40 times of the mass concentration of the discharged sulfur ions in the circulating water, the composite corrosion inhibitor contains 2-24 wt% of organic corrosion inhibitor selected from one or two or more of hydroxyethylidene diphosphonic acid, hydroxyphosphinoacetic acid, amino trimethylene phosphonic acid, ethylene diamine tetramethylene phosphonic acid, 2-phosphino-1, 2, 4-tricarboxylic acid-butane and potassium salt, sodium salt, polyhydric alcohol phosphate and polyether alcohol amine phosphate, the method can control the corrosion rate to be below 0.075mm/a by matching with the operation under the condition of not changing the original medicament adding of the circulating water field. The composite corrosion inhibitor is an organic phosphonic acid medicament, the corrosion and scale inhibition formula on the market at present is mainly an organic phosphine formula, and the composite corrosion inhibitor is added with the organic phosphine medicament under the condition of adding the original medicament, which aims to achieve the purpose of reducing corrosion by improving the adding concentration of the corrosion and scale inhibitor.
CN103420493A discloses a method for treating circulating cooling water containing sulfur ions, which comprises: mixing and contacting circulating cooling water containing sulfur ions with a precipitator and a corrosion and scale inhibitor, wherein the precipitator can form precipitates with the sulfur ions, the corrosion and scale inhibitor is at least one selected from vanadate, organic phosphonic acid, organic polymer and water-soluble zinc salt, and the precipitator is copper sulfate. The method adopts copper salt as a precipitator, has certain effect, but promotes carbon steel corrosion when copper ions in the circulating water exceed 0.1mg/L, and in practical application, the concentration of sulfur ions leaked from the circulating water is changed, and the adding amount of the copper ions is difficult to accurately control.
Therefore, a composite corrosion and scale inhibitor and a novel method for inhibiting the corrosion of circulating cooling water containing sulfur are needed at present, and the corrosion of sulfides on a water cooler can be effectively inhibited without a large amount of medicaments or a large amount of pollution discharge and fresh water supplement.
Disclosure of Invention
The invention aims to solve the problems of high operating cost caused by large consumption of corrosion and scale inhibitor, large fresh water consumption and large discharge capacity in the process of inhibiting the corrosion of the circulating cooling water containing sulfur in the prior art, and provides a novel composite corrosion and scale inhibitor containing urotropine and a method for inhibiting the corrosion of the circulating cooling water containing sulfur.
In order to achieve the above object, the present invention provides a urotropine-containing composite corrosion and scale inhibitor, which comprises zinc salt, hydroxyethylidene diphosphonic acid (HEDP), 2-hydroxyphosphonoacetic acid (HPAA), sulfonate copolymer and urotropine, wherein the weight ratio of the zinc salt, the HEDP, the HPAA, the sulfonate copolymer and the urotropine is 1:2-5:2-5:4-10:125-250, and the weight of the zinc salt is calculated by zinc ions.
The invention also provides an application of the composite corrosion and scale inhibitor in inhibiting the corrosion of circulating cooling water containing sulfur.
In a third aspect, the present invention provides a method for inhibiting corrosion of circulating cooling water containing sulfur, the method comprising:
(1) adding alkaline substances to ensure that the pH value of the circulating cooling water containing sulfur is 8-9;
(2) adding the composite corrosion and scale inhibitor.
Through the technical scheme, the corrosion of the sulfur-containing circulating cooling water to the water cooling equipment can be effectively inhibited under the condition of not using a large amount of medicaments and fresh water, and the operation cost is reduced.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a composite corrosion and scale inhibitor containing urotropine, which comprises zinc salt, HEDP, HPAA, sulfonate copolymer and urotropine, wherein the weight ratio of the zinc salt to the HEDP to the HPAA to the sulfonate copolymer to the urotropine is 1:2-5:2-5:4-10:125-250, and the weight of the zinc salt is calculated by zinc ions. The phosphorus content in the composite corrosion and scale inhibitor is below 1.5 percent by weight.
According to the present invention, the zinc salt, HEDP, HPAA and urotropin are all commercially available. Wherein, the zinc salt is an inorganic salt which can be dissolved in water and provide zinc ions. Preferably, the zinc salt is selected from zinc sulphate and/or zinc chloride.
According to the present invention, the sulfonate copolymer is commercially available. Preferably, the sulfonate copolymer comprises a structural unit provided by acrylic acid, a structural unit provided by 2-methyl-2 '-acrylamidopropanesulfonic acid, and optionally a structural unit provided by other monomers, the other monomers being at least one of acrylamide, methyl acrylate, and maleic acid, the molar percentage of the structural unit provided by the 2-methyl-2' -acrylamidopropanesulfonic acid is 10 to 30% based on the total amount of the sulfonate copolymer, and the sulfonate copolymer has an ultimate viscosity of 0.065 to 0.085 dL/g.
More preferably, the sulfonate copolymer is selected from at least one of a copolymer of acrylic acid and 2-methyl-2 '-acrylamidopropanesulfonic acid, a copolymer of acrylic acid, acrylamide and 2-methyl-2' -acrylamidopropanesulfonic acid, a copolymer of acrylic acid, hydroxypropyl acrylate and 2-methyl-2 '-acrylamidopropanesulfonic acid, and a copolymer of acrylic acid, maleic acid and 2-methyl-2' -acrylamidopropanesulfonic acid.
Because the circulating cooling water containing sulfur is generally acidic, in order to make the composite corrosion and scale inhibitor better suitable for the circulating cooling water containing sulfur, the composite corrosion and scale inhibitor preferably contains an independent alkaline substance.
Preferably, the alkaline substance is at least one selected from sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
According to a preferred embodiment of the invention, the composite corrosion and scale inhibitor consists of the components.
The invention provides an application of the composite corrosion and scale inhibitor in inhibiting corrosion of circulating cooling water containing sulfur.
After entering the circulating cooling water, the sulfide exists in the form of sulfide ions. According to the invention, preferably, the content of sulfur ions in the circulating cooling water containing sulfur is 0.25-1 mg/L.
According to the invention, the adding concentration of the composite corrosion and scale inhibitor can be properly adjusted according to the content of sulfur ions in the sulfur-containing circulating cooling water. Preferably, the total adding concentration of the zinc salt, the hydroxyethylidene diphosphonic acid, the 2-hydroxyphosphonoacetic acid, the sulfonate copolymer and the urotropin is 300-500mg/L of water.
In a third aspect, the present invention provides a method for inhibiting corrosion of circulating cooling water containing sulfur, the method comprising:
(1) adding alkaline substances to ensure that the pH value of the circulating cooling water containing sulfur is 8-9;
(2) adding the composite corrosion and scale inhibitor.
According to the present invention, the alkaline substance is not particularly required as long as the pH adjusting action can be achieved. Preferably, the alkaline substance is at least one selected from sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
According to the invention, the adding concentration of the composite corrosion and scale inhibitor can be properly adjusted according to the content of sulfur ions in the sulfur-containing circulating cooling water. Preferably, the total adding concentration of the zinc salt, the hydroxyethylidene diphosphonic acid, the 2-hydroxyphosphonoacetic acid, the sulfonate copolymer and the urotropin is 300-500mg/L of water.
According to the invention, the method can be applied to circulating cooling water with different sulfur ion contents. Preferably, the content of sulfur ions in the circulating cooling water containing sulfur is 0.25-1mg/L, Ca2+The content of (1) is 200-500mg/L, the total alkalinity is 200-500mg/L, and Cl-The content of (A) is 20-700mg/L, SO4 2-The content of (b) is 50-500mg/L, the conductivity is 500-3000 mu s/cm, and the pH is 7-8.5.
The present invention will be described in detail below by way of examples. The starting materials used are all commercially available unless otherwise specified.
In the following examples, the actual sulfur leakage was simulated by adding sodium sulfide to the test raw water, and the quality of the test raw water is shown in table 1.
TABLE 1
| Ca2+ | Total alkalinity | Cl- | SO4 2- | Electrical conductivity of | pH | |
| Test raw Water 1 | 253 | 214 | 28 | 85 | 568 | 7.5 |
| Test raw Water 2 | 430 | 475 | 436 | 420 | 2360 | 8.2 |
Note: pH is nothing, conductivity is mus/cm, the rest is mg/L, Ca2+CaCO for total alkalinity3The same applies below.
In Table 1, Ca2+According to the national standard GB/T6910-Water analysis method, calcium determination, and complex titration method; the total alkalinity is measured according to the national standard GB/T15451-2006 determination of alkalinity of industrial circulating cooling water, total alkali and phenolphthalein; cl-Measured according to the standard GB/T15453-2008; SO (SO)4 2-Determined according to standard GB/T14642-; the conductivity is determined according to the standard GB/T6908-2008; the pH value was determined according to the standard GB/T6920-1986.
The rotary coupon corrosion test method comprises the following steps:
will 20#Fixing the carbon steel test piece on a coupon instrument, placing the test piece in test water, keeping the constant temperature at 45 +/-1 ℃, keeping the rotating speed at 75r/min for 72 hours, recording the weight of the test piece before and after the test, and calculating the average corrosion rate.
The average corrosion rate is calculated by the formula:
F＝(C×△W)/(A×T×ρ)
c: the constants were calculated, in mm/a, such that C is 8.76 × 107；
Δ W: corrosion weight loss (g) of the test piece;
a: area of test piece (cm)2)；
T: corrosion test time (h);
ρ: density of the test piece material (kg/m 3).
The test method for calcium carbonate scale resistance comprises the following steps:
adding test raw water into a volumetric flask, adding sodium sulfide, a composite corrosion and scale inhibitor and other substances according to the embodiment and the comparative example, standing for 10 hours in a constant-temperature water bath at the temperature of 80 +/-1 ℃ after constant volume, sampling and analyzing the residual Ca in the water after cooling2+And simultaneously making blank samples, and calculating the scale inhibition rate.
Scale inhibition rate ═ C-C0)/(C1－C0)×100％
C: ca after test of test solution added with water treatment agent2+Concentration of (g/L);
C0: ca after blank test without water treatment agent2+Concentration of (g/L);
C1: ca in prepared test solution before test2+(iii) concentration (mg/L).
Example 1
Test water was obtained by adding sodium sulfide to test raw water 1 so that the concentration of sulfide ions was 0.5 mg/L. Adding sodium carbonate to adjust the pH value to 8.2, and then adding 400mg/L of a composite corrosion and scale inhibitor, wherein the composite corrosion and scale inhibitor comprises the following components: zinc sulfate (as zinc ion) a copolymer of HEDP HPAA acrylic acid and 2-methyl-2' -acrylamidopropanesulfonic acid (70 and 30 mole percent of each monomer, respectively, and an ultimate viscosity of 0.071dL/g, available from shandongtai and water processing technologies, co., ltd., hereafter, the same) with urotropin 1:4:4:7:150 (weight ratio). A rotary hanging piece corrosion test and a calcium carbonate scale resistance test are carried out, the corrosion rate is 0.040mm/a, and the scale inhibition rate is 98.7%.
Example 2
Test water was obtained by adding sodium sulfide to test raw water 1 so that the concentration of sulfide ions was 0.5 mg/L. Adding sodium hydroxide to adjust the pH value to 8.5, and then adding 320mg/L of a composite corrosion and scale inhibitor, wherein the composite corrosion and scale inhibitor comprises the following components: zinc chloride (calculated as zinc ions) a copolymer of HEDP: HPAA: acrylic acid, acrylamide, and 2-methyl-2' -acrylamidopropanesulfonic acid (70%, 15%, and 15% mole percent of the tri-monomers, respectively, and an ultimate viscosity of 0.068dL/g, available from shandongtai and water processing technologies co., ltd., same, below) urotropin 1:2.2:4.8:4.5:130 (by weight). A rotary coupon corrosion test and a calcium carbonate scale resistance test are carried out, the corrosion rate is 0.045mm/a, and the scale inhibition rate is 99.2%.
Example 3
Test water was obtained by adding sodium sulfide to test raw water 1 so that the concentration of sulfide ions was 0.5 mg/L. Adding sodium hydroxide and sodium carbonate to adjust the pH value to 8.8, and then adding 480mg/L of a composite corrosion and scale inhibitor, wherein the composite corrosion and scale inhibitor comprises the following components: zinc sulfate (calculated as zinc ions) a copolymer of HEDP HPAA acrylic acid, hydroxypropyl acrylate and 2-methyl-2' -acrylamidopropanesulfonic acid (70, 15 and 15 mole percent of the tri-monomers, respectively, and an ultimate viscosity of 0.070dL/g, available from shandongtai and water processing technologies, ltd.) urotropin 1:4.8:2.2:8:240 (by weight). A rotary hanging piece corrosion test and a calcium carbonate scale resistance test are carried out, the corrosion rate is 0.039mm/a, and the scale inhibition rate is 99.0%.
Example 4
Test water was obtained by adding sodium sulfide to test raw water 1 so that the concentration of sulfide ions was 0.5 mg/L. Adding sodium carbonate to adjust the pH value to 8.6, and then adding 350mg/L of a composite corrosion and scale inhibitor, wherein the composite corrosion and scale inhibitor comprises the following components: zinc sulfate (as zinc ion) a copolymer of HEDP HPAA acrylic acid, maleic acid, and 2-methyl-2' -acrylamidopropanesulfonic acid (70, 15, and 15 mole percent of the tri-monomers, respectively, and an ultimate viscosity of 0.080dL/g, available from shandongtai and water processing technologies co., ltd.) urotropin 1:4:4:9.5:175 (by weight). A rotary hanging piece corrosion test and a calcium carbonate scale resistance test are carried out, the corrosion rate is 0.037mm/a, and the scale inhibition rate is 98.8%.
Example 5
The test was conducted in accordance with the method of example 1 except that the concentration of sulfur ions was 0.25mg/L, the corrosion rate was measured to be 0.030mm/a, and the scale inhibition rate was 98.8%.
Example 6
The test was conducted in accordance with the method of example 1 except that the concentration of sulfur ions was 1mg/L, the corrosion rate was 0.048mm/a and the scale inhibition rate was 98.2%.
Example 7
A test was conducted in the same manner as in example 1 except that the copolymer of acrylic acid and 2-methyl-2' -acrylamidopropanesulfonic acid was replaced with a copolymer of acrylic acid and styrenesulfonic acid (the molar percentages of the two monomers were 70% and 30%, respectively, and the limiting viscosity was 0.080dL/g), and it was found that the corrosion rate was 0.069mm/a and the scale inhibition rate was 96.8%.
Example 8
The test was carried out in the same manner as in example 1 except that the test raw water 1 was replaced with the test raw water 2, and found that the corrosion rate was 0.035mm/a and the scale inhibition rate was 97.5%.
Comparative example 1
The test was carried out as in example 1 except that the pH of the test water was not adjusted, that the pH was naturally 7.5, that the corrosion rate was 0.142mm/a and that the scale inhibition rate was 99.0%.
Comparative example 2
The test was carried out according to the method of example 2, except that the composition of the composite corrosion and scale inhibitor used was: zinc chloride (in terms of zinc ion) HEDP HPAA copolymer of acrylic acid, acrylamide and 2-methyl-2' -acrylamidopropanesulfonic acid urotropine 1:2.2:4.8:4.5:270 (weight ratio), corrosion rate was found to be 0.136mm/a, and scale inhibition rate was found to be 85.0%.
Comparative example 3
The test was carried out according to the method of example 2, except that the composition of the composite corrosion and scale inhibitor used was: zinc chloride (in terms of zinc ion), HEDP, HPAA, a copolymer of acrylic acid, acrylamide, and 2-methyl-2' -acrylamidopropanesulfonic acid, urotropine, 1:1.5:1.5:11:130 (weight ratio), corrosion rate of 0.177mm/a, and scale inhibition rate of 83.5%.
Comparative example 4
The test was carried out in the same manner as in example 1 except that the composite corrosion and scale inhibitor used contained no HEDP and HPAA, and it was found that the corrosion rate was 1.012mm/a and the scale inhibition rate was 78.0%.
Comparative example 5
The test was carried out in the same manner as in example 1 except that the composite corrosion and scale inhibitor used was not a copolymer of acrylic acid and 2-methyl-2' -acrylamidopropanesulfonic acid, and it was found that the corrosion rate was 0.857mm/a and the scale inhibition rate was 76.5%.
Comparative example 6
The test was carried out in accordance with the procedure of example 1, except that the composite corrosion and scale inhibitor used contained no urotropin, and that the corrosion rate was 0.096mm/a and the scale inhibition rate was 98.5%.
Comparative example 7
The test was conducted in accordance with the procedure of example 1 except that the composite corrosion and scale inhibitor used had zinc sulfate replaced with copper sulfate (in mass terms of copper ions), and found that the corrosion rate was 1.770mm/a and the scale inhibition rate was 98.8%.
Comparative example 8
The experiment was carried out in the same manner as in example 1 except that HEDP in the composite corrosion and scale inhibitor used was replaced with 2-phosphono-1, 2, 4-tricarboxylic acid to measure a corrosion rate of 0.081mm/a and a scale inhibition rate of 99.0%.
Comparative example 9
The test was carried out in accordance with the procedure of example 1 except that HPAA in the composite corrosion and scale inhibitor used was replaced with amino trimethylene phosphonic acid, and it was found that the corrosion rate was 0.090mm/a and the scale inhibition rate was 97.8%.
As can be seen from the above examples and comparative examples, the urotropine-containing composite corrosion and scale inhibitor provided by the invention is prepared by compounding high-concentration urotropine with zinc salt, HEDP, HPAA and sulfonate copolymer, and the weight ratio is limited to 1:2-5:2-5:4-10:125-250, so that the urotropine-containing composite corrosion and scale inhibitor can play a synergistic effect and has good corrosion and scale inhibition effects. Under the condition of proper pH (pH is 8-9), the composite corrosion and scale inhibitor with proper concentration (300-500mg/L) is added, so that the effect of better inhibiting the circulating cooling water containing sulfur from corroding water cooling equipment can be realized.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. The composite corrosion and scale inhibitor containing the urotropine is characterized by comprising zinc salt, hydroxyethylidene diphosphonic acid, 2-hydroxyphosphonoacetic acid, a sulfonate copolymer and urotropine, wherein the weight ratio of the zinc salt to the hydroxyethylidene diphosphonic acid to the 2-hydroxyphosphonoacetic acid to the sulfonate copolymer to the urotropine is 1:2-5:2-5:4-10:125-250, and the weight of the zinc salt is calculated by zinc ions.
2. The composite corrosion and scale inhibitor according to claim 1, wherein the zinc salt is selected from zinc sulfate and/or zinc chloride.
3. The composite corrosion and scale inhibitor according to claim 1, wherein the sulfonate copolymer comprises structural units provided by acrylic acid, structural units provided by 2-methyl-2 '-acrylamidopropanesulfonic acid, and optionally structural units provided by other monomers, the other monomers are at least one of acrylamide, methyl acrylate, and maleic acid, the mole percentage of the structural units provided by the 2-methyl-2' -acrylamidopropanesulfonic acid is 10 to 30% based on the total amount of the sulfonate copolymer, and the sulfonate copolymer has an ultimate viscosity of 0.065 to 0.085 dL/g.
4. The composite corrosion and scale inhibitor according to claim 1, wherein the sulfonate copolymer is selected from at least one of a copolymer of acrylic acid and 2-methyl-2 '-acrylamidopropanesulfonic acid, a copolymer of acrylic acid, acrylamide and 2-methyl-2' -acrylamidopropanesulfonic acid, a copolymer of acrylic acid, hydroxypropyl acrylate and 2-methyl-2 '-acrylamidopropanesulfonic acid, and a copolymer of acrylic acid, maleic acid and 2-methyl-2' -acrylamidopropanesulfonic acid.
5. The composite corrosion and scale inhibitor according to claim 1, wherein the composite corrosion and scale inhibitor further comprises an independent basic substance.
6. The composite corrosion and scale inhibitor according to claim 5, wherein the alkaline substance is at least one selected from sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
7. The use of the composite corrosion and scale inhibitor of any one of claims 1 to 6 for inhibiting the corrosion of circulating cooling water containing sulfur.
8. The use of claim 7, wherein the content of sulfur ions in the circulating cooling water containing sulfur is 0.25-1 mg/L.
9. The use as claimed in claim 7, wherein the total concentration of the zinc salt, hydroxyethylidene diphosphonic acid, 2-hydroxyphosphonoacetic acid, sulfonate copolymer and urotropin is 300-500 mg/L.
10. A method for inhibiting corrosion in circulating cooling water containing sulfur, the method comprising:
(1) adding alkaline substances to ensure that the pH value of the circulating cooling water containing sulfur is 8-9;
(2) adding the composite corrosion and scale inhibitor of any one of claims 1 to 4.
11. The method of claim 10, wherein the alkaline substance is selected from at least one of sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide.
12. The method as claimed in claim 10, wherein the zinc salt, hydroxyethylidene diphosphonic acid, 2-hydroxyphosphonoacetic acid, sulfonate copolymer and urotropin are added at a total concentration of 300-500 mg/L.
13. The method as claimed in any one of claims 10 to 12, wherein the content of sulfur ions in the circulating cooling water containing sulfur is 0.25 to 1 mg/L.
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| CN201810885329.9A CN110803785B (en) | 2018-08-06 | 2018-08-06 | Composite corrosion and scale inhibitor containing urotropine, application thereof and method for inhibiting corrosion of circulating cooling water containing sulfur |
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| CN201810885329.9A CN110803785B (en) | 2018-08-06 | 2018-08-06 | Composite corrosion and scale inhibitor containing urotropine, application thereof and method for inhibiting corrosion of circulating cooling water containing sulfur |
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1293119A1 (en) * | 1985-02-06 | 1987-02-28 | Ленинградское Электромашиностроительное Объединение "Электросила" Им.С.М.Кирова | Method of preventing formation of copper deposits in water cooling systems of electrical machine windings |
| CN1258649A (en) * | 1998-12-25 | 2000-07-05 | 北京燕山石油化工公司研究院 | Recompounded multielement antisludging corrosion inhibitor |
| CN1854092A (en) * | 2005-04-25 | 2006-11-01 | 上海万森水处理有限公司 | Corrosion-proofing and antisludging method of boiler |
| CN1854090A (en) * | 2005-04-25 | 2006-11-01 | 上海万森水处理有限公司 | Antioxidant corrosion-proofing and antisludging agent of boiler |
| CN101638273A (en) * | 2009-08-28 | 2010-02-03 | 张振海 | High-efficiency corrosion-mitigation scale-inhibition water saving agent for boiler |
| CN102515373A (en) * | 2011-12-16 | 2012-06-27 | 蓝星环境工程有限公司 | Green corrosion and scale inhibitor for hot-water boiler |
| CN103030228A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Circulating water treatment method adopting deionized water as supplement water |
| CN104724838A (en) * | 2015-03-18 | 2015-06-24 | 北京蓝星清洗有限公司 | Low-phosphorus corrosion/scale inhibitor for circulating cooling water |
| CN104891684A (en) * | 2015-05-25 | 2015-09-09 | 山东英联化学科技有限公司 | Phosphorus-free composite corrosion and scale inhibitor for bitter circulating water and preparation method thereof |
| CN106191876A (en) * | 2016-08-30 | 2016-12-07 | 湖北省兴发磷化工研究院有限公司 | A kind of Cleaning and Passivation method of heat-exchange system equipment |
| CN106242087A (en) * | 2016-08-22 | 2016-12-21 | 山东鑫泰水处理技术有限公司 | A kind of environment-friendly type anti-incrustation corrosion inhibitor XT 619B |
| CN106745837A (en) * | 2015-11-20 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of method for processing circulating cooling water containing sulfur |
| CN107973417A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | The corrosion-proofing and antisludging method and oil production method of composite slow-corrosion scale resistor, oil field water |
-
2018
- 2018-08-06 CN CN201810885329.9A patent/CN110803785B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1293119A1 (en) * | 1985-02-06 | 1987-02-28 | Ленинградское Электромашиностроительное Объединение "Электросила" Им.С.М.Кирова | Method of preventing formation of copper deposits in water cooling systems of electrical machine windings |
| CN1258649A (en) * | 1998-12-25 | 2000-07-05 | 北京燕山石油化工公司研究院 | Recompounded multielement antisludging corrosion inhibitor |
| CN1854092A (en) * | 2005-04-25 | 2006-11-01 | 上海万森水处理有限公司 | Corrosion-proofing and antisludging method of boiler |
| CN1854090A (en) * | 2005-04-25 | 2006-11-01 | 上海万森水处理有限公司 | Antioxidant corrosion-proofing and antisludging agent of boiler |
| CN101638273A (en) * | 2009-08-28 | 2010-02-03 | 张振海 | High-efficiency corrosion-mitigation scale-inhibition water saving agent for boiler |
| CN103030228A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Circulating water treatment method adopting deionized water as supplement water |
| CN102515373A (en) * | 2011-12-16 | 2012-06-27 | 蓝星环境工程有限公司 | Green corrosion and scale inhibitor for hot-water boiler |
| CN104724838A (en) * | 2015-03-18 | 2015-06-24 | 北京蓝星清洗有限公司 | Low-phosphorus corrosion/scale inhibitor for circulating cooling water |
| CN104891684A (en) * | 2015-05-25 | 2015-09-09 | 山东英联化学科技有限公司 | Phosphorus-free composite corrosion and scale inhibitor for bitter circulating water and preparation method thereof |
| CN106745837A (en) * | 2015-11-20 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of method for processing circulating cooling water containing sulfur |
| CN106242087A (en) * | 2016-08-22 | 2016-12-21 | 山东鑫泰水处理技术有限公司 | A kind of environment-friendly type anti-incrustation corrosion inhibitor XT 619B |
| CN106191876A (en) * | 2016-08-30 | 2016-12-07 | 湖北省兴发磷化工研究院有限公司 | A kind of Cleaning and Passivation method of heat-exchange system equipment |
| CN107973417A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | The corrosion-proofing and antisludging method and oil production method of composite slow-corrosion scale resistor, oil field water |
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