CN110963583B - Phosphorus-free composite corrosion inhibitor suitable for high-hardness water and application thereof - Google Patents

Phosphorus-free composite corrosion inhibitor suitable for high-hardness water and application thereof Download PDF

Info

Publication number
CN110963583B
CN110963583B CN201811140632.2A CN201811140632A CN110963583B CN 110963583 B CN110963583 B CN 110963583B CN 201811140632 A CN201811140632 A CN 201811140632A CN 110963583 B CN110963583 B CN 110963583B
Authority
CN
China
Prior art keywords
phosphorus
condensation reaction
corrosion inhibitor
reaction product
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811140632.2A
Other languages
Chinese (zh)
Other versions
CN110963583A (en
Inventor
任志峰
张化冰
魏新
刘金香
常磊
杨玉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201811140632.2A priority Critical patent/CN110963583B/en
Publication of CN110963583A publication Critical patent/CN110963583A/en
Application granted granted Critical
Publication of CN110963583B publication Critical patent/CN110963583B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/105—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances combined with inorganic substances
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

The invention relates to the field of circulating cooling water treatment, and discloses a phosphorus-free composite corrosion inhibitor suitable for high hard water and application thereof, wherein the phosphorus-free composite corrosion inhibitor contains a condensation reaction product, ascorbic acid, a sulfonate copolymer and a zinc salt, wherein the condensation reaction product comprises the following components in parts by weight: ascorbic acid: sulfonate copolymer: zinc salt is 1:0.6-2.5.4-5:0.05-1.25, wherein the condensation reaction product is a condensation reaction product of sodium gluconate and aspartic acid and/or a condensation reaction product of potassium gluconate and aspartic acid; the weight of the zinc salt is calculated as zinc ion. The phosphorus-free composite corrosion inhibitor provided by the invention has a synergistic effect among components, has a good corrosion inhibition effect, is few in component and low in dosage, and is particularly suitable for high-hardness and high-alkali circulating cooling water treatment with the sum of the calcium hardness and the total alkalinity of make-up water being 300-700 mg/L.

Description

Phosphorus-free composite corrosion inhibitor suitable for high-hardness water and application thereof
Technical Field
The invention relates to the field of circulating cooling water treatment, in particular to a phosphorus-free composite corrosion inhibitor suitable for high-hardness water and application thereof in circulating cooling water treatment.
Background
The supply and demand conditions of the circulating cooling water have great influence on water use, drainage and water saving of the whole industrial enterprise, but the problem of scaling and candle corrosion of cooling facilities in the circulating cooling water system is brought along. In a circulating cooling water system, adding a corrosion inhibitor is one of the most important methods for preventing the corrosion of circulating cooling water equipment. Along with the gradual improvement of the environmental protection regulations in China, the direct discharge standards of water pollutants have new requirements in recent years, wherein GB 31570-2015 'emission standards of petroleum refining industry pollutants' and GB 31571-2015 'requirements of emission standards of petrochemical industry pollutants' require that the total phosphorus of water discharged by enterprises is less than or equal to 1.0mg/L, the total zinc is less than or equal to 2.0mg/L and the total phosphorus of a special discharge area is limited to 0.5mg/L from 7 months and 1 day in 2017; the local standard of Beijing requires that COD is less than or equal to 30mg/L, total phosphorus is less than or equal to 0.3mg/L, and total zinc is less than or equal to 1.5 mg/L.
As the environmental protection standard is increasingly strict, the problem that the total phosphorus of the discharged sewage of most petrochemical enterprises exceeds the standard according to the new standard is solved. The circulating water which is used as a main source of phosphorus is treated by a source, the phosphorus content of the scale and corrosion inhibitor is controlled to be most economical and effective, the clean production concept is met, and the non-phosphorization or near-non-phosphorization of the scale and corrosion inhibitor is urgent. At present, the phosphorus-free corrosion inhibitor with excellent performance can be selected with small scope, and over 30 years, and the novel phosphorus-free corrosion inhibitor is always in active research and exploration.
CN107522300A discloses a non-phosphorus corrosion inhibitor and corrosion inhibitor composition, a preparation method thereof, application of the composition in inhibiting water corrosion and a treatment method of circulating water, wherein the corrosion inhibitor and zinc salt composition has good corrosion inhibition effect in specific water quality, the dosage of the corrosion inhibitor is 10-20mg/L, and the dosage is higher.
Therefore, the development and application of the phosphorus-free corrosion inhibitor, the few components of the composite corrosion inhibitor and the low-quantification application become the research focus of the circulating cooling water treatment.
Disclosure of Invention
The invention aims to overcome the problem of large consumption of the phosphorus-free corrosion inhibitor in the prior art, and provides a phosphorus-free composite corrosion inhibitor and application thereof in circulating cooling water treatment.
In order to achieve the above objects, a first aspect of the present invention provides a phosphorus-free composite corrosion inhibitor suitable for high hard water, comprising a condensation reaction product, ascorbic acid, a sulfonate copolymer, and a zinc salt, wherein the condensation reaction product: ascorbic acid: sulfonate copolymer: zinc salt is 1:0.6-2.5:0.4-5:0.05-1.25 (weight ratio), wherein the condensation reaction product is a condensation reaction product of sodium gluconate and aspartic acid and/or a condensation reaction product of potassium gluconate and aspartic acid; the weight of the zinc salt is calculated as zinc ion.
The invention also provides an application of the phosphorus-free composite corrosion inhibitor in cooling water treatment.
By adopting the technical scheme, a good corrosion inhibition effect can be achieved under the conditions of less components of the water treatment agent and low consumption (especially the consumption of condensation reaction products), the current increasingly severe pollutant discharge requirement can be met, and the 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 phosphorus-free composite corrosion inhibitor suitable for high hard water, which contains a condensation reaction product, ascorbic acid, a sulfonate copolymer and a zinc salt, wherein the condensation reaction product is as follows: ascorbic acid: sulfonate copolymer: zinc salt is 1:0.6-2.5:0.4-5:0.05-1.25 (weight ratio), wherein the weight of zinc salt is calculated by zinc ion.
In the invention, the condensation reaction product is a condensation reaction product of sodium gluconate and aspartic acid and/or a condensation reaction product of potassium gluconate and aspartic acid.
Preferably, the condensation reaction product: ascorbic acid: sulfonate copolymer: zinc salt is 1:0.6-2.5:0.69-4: 0.09-0.53.
According to the invention, the condensation reaction product can be produced by reacting sodium gluconate or potassium gluconate with aspartic acid in water by direct contact under condensation reaction conditions in the presence of a catalyst. The condensation reaction refers to dehydration condensation reaction between carboxyl in sodium gluconate or potassium gluconate and carboxyl hydroxyl in aspartic acid. Preferably, the molar ratio of the aspartic acid to the sodium gluconate or potassium gluconate is (0.5-8): 1. The catalyst is preferably an acid catalyst, more preferably the catalyst is selected from sulfuric acid and/or nitric acid, preferably the molar ratio of the catalyst to the sodium gluconate or potassium gluconate calculated on hydrogen ion is (0.4-6): 1. Preferably, the conditions of the condensation reaction include: the contacting is carried out at a temperature sufficient to distill off water, preferably the contacting is carried out in a heating bath at 100-. Preferably, the condensation reaction product has a molecular weight distribution of 300-600.
According to the present invention, the sulfonate copolymer (or sulfonic acid group-containing copolymer) is commercially available, and preferably, the sulfonate copolymer is a binary copolymer and/or a ternary copolymer. Preferably, the sulfonate copolymer is selected from at least one of a copolymer of acrylic acid ester and styrene sulfonic acid, a copolymer of acrylic acid and allylsulfonic acid, a copolymer of acrylic acid and 2-methyl-2 '-acrylamidopropanesulfonic acid, a copolymer of acrylic acid, acrylic acid ester and 2-methyl-2' -acrylamidopropanesulfonic acid, a copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (AA/AMPS), a copolymer of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and hydroxypropyl acrylate (AA/AMPS/HPA), an acrylic acid-sulfonate copolymer (TH-2000), and a carboxylate-sulfonate-nonionic copolymer (TH-3100). More preferably, the acrylate is at least one of methyl acrylate, ethyl acrylate, and hydroxypropyl acrylate. The limiting viscosity of the sulfonate copolymer at 30 ℃ is usually from 0.065 to 0.085dL/g, or the kinetic viscosity of the sulfonate copolymer at 25 ℃ is usually 100-500 cps.
According to the present invention, both the ascorbic acid and the zinc salt are 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 invention, in order to make the phosphorus-free composite corrosion inhibitor suitable for copper material circulating cooling water equipment, preferably, the phosphorus-free composite corrosion inhibitor also contains heterocyclic compounds; more preferably, the heterocyclic compound is at least one selected from mercaptobenzothiazole (2-mercaptobenzothiazole), benzotriazole and methylbenzotriazole.
Preferably, the condensation reaction product: heterocyclic compounds ═ 1:0.05 to 0.75 (by weight), more preferably, the condensation reaction product: the heterocyclic compound is 0.1 to 0.6.
According to a preferred embodiment of the present invention, the phosphorus-free composite corrosion inhibitor is composed of the above components. The individual ingredients may be provided in the form of a solution or suspension, but the amounts or amounts are on a dry basis (solids content).
The phosphorus-free composite corrosion inhibitor is particularly suitable for inhibiting high-hardness water, namely the corrosion of circulating cooling water with the sum of the calcium hardness and the total alkalinity of make-up water of 300-700 mg/L.
The invention also provides the application of the phosphorus-free composite corrosion inhibitor in circulating cooling water treatment.
The circulating cooling water in the invention can continuously supplement fresh water (make-up water) during the use process, and preferably is high-hardness and high-alkaline water with the sum of the calcium hardness and the total alkalinity of the make-up water being 300-700mg/L, and the pH value of the circulating cooling water is controlled to be between 7.8 and 8.5.
The composite corrosion inhibitor is suitable for treating the circulating cooling water with the pH value within the range. It will be appreciated by those skilled in the art that when the pH does not meet the above values, an acid (e.g., sulfuric acid and/or nitric acid) may be used for adjustment.
Preferably, Ca is added to the makeup water of the circulating cooling water2+The content of (b) is 150-300mg/L, and the total alkalinity is 150-400 mg/L.
By combining the components, excellent corrosion inhibition effect can be obtained under the condition of low consumption of the condensation reaction product, therefore, the non-phosphorus composite corrosion inhibitor is preferably added in an amount that the concentration of the condensation reaction product in circulating cooling water is 2-10 mg/L.
Preferably, the concentration of ascorbic acid in the recirculating cooling water is from 4.5 to 6 mg/L.
Preferably, the concentration of the sulfonate copolymer in the recirculating cooling water is from 4 to 10 mg/L.
Preferably, the concentration of zinc salt (in terms of zinc ions) in the recirculating cooling water is from 0.5 to 2.5 mg/L.
Preferably, the concentration of the heterocyclic compound in the circulating cooling water is 0.5 to 1.5 mg/L.
The total amount of each component is not higher than 30mg/L (preferably 11.5-30 mg/L).
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, test raw water was concentrated 2 times to obtain test water, which was used as makeup water for simulated circulating cooling water.
The quality of the raw water is shown in Table 1
TABLE 1
Ca2+ Total alkalinity Cl- SO4 2- Electrical conductivity of pH
Test raw Water 1 150 250 350 380 1210 7.8
Test raw Water 2 260 330 78 120 765 8.1
Note: 1) pH is nothing, conductivity is ms/cm, the rest is mg/L, Ca2+CaCO for total alkalinity3The same applies below.
2)Ca2+This represents the calcium hardness, as follows.
In Table 1, Ca2+According to the national standard GB/T6910-; 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 test raw water 1 and the test raw water 2 were each concentrated by 2 times, and adjusted to pH 8.3 and 8.4 with sulfuric acid, respectively, to obtain test water 1 and test water 2.
The rotary coupon corrosion test method comprises the following steps:
will 20#Fixing the carbon steel/brass test piece on a hanging piece instrument, putting the test piece into test water, keeping the constant temperature at 45 +/-1 ℃, keeping the rotating speed at 75r/min for rotating for 72h, and recording the weight of the test piece before and after the testAnd 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 test piece Material (kg/m)3)。
In the following preparation examples, the molecular weight of the condensation reaction product of sodium gluconate and aspartic acid and the molecular weight of the condensation reaction product of potassium gluconate and aspartic acid were measured by mass spectrometry and scanning method was FTMS-p ESI Full ms [100-1000 ].
Preparation example 1
Preparation of condensation reaction product of sodium gluconate and aspartic acid
21.8g (0.1mol) of sodium gluconate (purchased from Bailingwei science and technology Co., Ltd., analytical purity, the same below), 26.6g (0.2mol) of aspartic acid (purchased from Aladdin reagent Co., Ltd., analytical purity, the same below) and 100mL of water were added to a four-necked flask equipped with a stirrer, a distillation apparatus and a thermometer, stirring was started to sufficiently dissolve and mix the sodium gluconate and the aspartic acid, and then concentrated sulfuric acid (purchased from Tianjin optochemical research institute, analytical purity, 98 wt% concentration, the same below) was added to 15g (containing H) of sodium gluconate (purchased from Theleph technology Co., Ltd., analytical purity, the same below) at room temperature (20 ℃ C.)2SO40.15 mol). The heating bath (heating medium is dimethyl silicone oil) with the flask inside is heated to 100 ℃ and reacted for 10 hours, the distilled water amount in the reaction process is 30g, and the residual liquid, namely the condensation reaction product of the sodium gluconate and the aspartic acid with the solid content of 29.5 weight percent, is measured, and the molecular weight distribution is in the range of 311-426.
Preparation example 2
Preparation of condensation reaction product of sodium gluconate and aspartic acid
10.9g (0.05mol) of sodium gluconate was placed in a four-necked flask equipped with a stirrer, a distillation apparatus and a thermometer16.6g (0.125mol) of aspartic acid and 100mL of water are stirred to fully dissolve and mix the sodium gluconate and the aspartic acid, and then concentrated sulfuric acid 7.5g (containing H) is added at room temperature (20℃)2SO40.075 mol). The heating bath (heating medium is dimethyl silicone oil) with the flask inside is heated to 140 ℃ and reacted for 6 hours, the distilled water amount in the reaction process is 45g, and the residual liquid, namely the condensation reaction product of the sodium gluconate and the aspartic acid with the solid content of 26.3 weight percent, is measured, and the molecular weight distribution is in the range of 311-426.
Preparation example 3
Preparation of condensation reaction product of potassium gluconate and aspartic acid
23.4g (0.1mol) of potassium gluconate (purchased from carbofuran technologies, Ltd., analytical purity), 13.3g (0.1mol) of aspartic acid and 100mL of water were placed in a four-necked flask equipped with a stirrer, a distillation apparatus and a thermometer, stirring was started to sufficiently dissolve and mix the potassium gluconate and the aspartic acid, and then 3.7g (containing HNO) of concentrated nitric acid (purchased from Yili fine chemical research institute, Beijing, analytical purity, 68 wt%) was added at room temperature (20 ℃ C.) to the flask30.04 mol). The heating bath (heating medium is dimethyl silicone oil) with the flask inside is heated to 180 ℃ and reacted for 6 hours, the distilled water amount in the reaction process is 55g, and the residual liquid, namely the condensation reaction product of potassium gluconate and aspartic acid with the solid content of 41.7 weight percent, is measured, and the molecular weight distribution is in the range of 311-426.
Preparation example 4
Preparation of condensation reaction product of trisodium citrate and alanine
A four-necked flask equipped with a stirrer, a distillation apparatus and a thermometer was charged with 29.4g (0.1mol) of trisodium citrate (available from national pharmaceutical group chemical Co., Ltd., analytical grade), 8.9g (0.1mol) of alanine (available from Alantin reagent Co., Ltd., analytical grade), and 100mL of water, and stirring was started to sufficiently dissolve and mix the trisodium citrate and alanine, and then 8g (containing H) of concentrated sulfuric acid was charged at room temperature (20 ℃ C.)2SO40.08 mol). Heating the heating bath (heating medium is dimethyl silicone oil) with the flask to 150 deg.C, reacting for 4 hr, and steamingThe water yield was 50g, and the residual liquid, i.e., the condensation reaction product of trisodium citrate and alanine having a solid content of 31.8% by weight, was determined to have a molecular weight distribution in the range of 263-358.
Example 1
7.2g of the condensation reaction product of potassium gluconate obtained in preparation example 3 and aspartic acid, 6g of ascorbic acid, 9.3g of TH-2000 (density (20 ℃ C.)) having a solid content of 43% by weight or more than 1.15g cm were weighed-3Dynamic viscosity (25 ℃ C.) of 100-500cps as obtained from Shandongtai and Water treatment technologies, Inc., 3.3g of ZnCl2Adding water and shaking up to obtain 100g of the phosphorus-free composite corrosion inhibitor required to be prepared, wherein the condensation reaction product of potassium gluconate and aspartic acid comprises ascorbic acid, TH-2000 and Zn2+1:2:1.34:0.53 (weight ratio).
The phosphorus-free composite corrosion inhibitor is respectively added into test water 1 and test water 2 according to the concentration of 100mg/L, so that the concentration of a condensation reaction product of potassium gluconate and aspartic acid in the test water 1 and the test water 2 is 3mg/L, and rotary hanging pieces (20) are respectively carried out in the test water 1 and the test water 2#Carbon steel) corrosion test.
Example 2
20.3g of the condensation reaction product of sodium gluconate and aspartic acid obtained in preparation example 1, 4.7g of ascorbic acid, 16.7g of a copolymer of acrylic acid, acrylamide and 2-methyl-2' -acrylamidopropanesulfonic acid having a solids content of 30% by weight (the weight ratio of the three monomers is 70/15/15, the limiting viscosity at 30 ℃ is 0.068dL/g, available from Qianglong industries, Ltd., the same applies hereinafter) and 8.8g of ZnSO4·7H2O, adding water and shaking up to obtain 100g of the phosphorus-free composite corrosion inhibitor, wherein the condensation reaction product of sodium gluconate and aspartic acid comprises ascorbic acid, acrylic acid, acrylamide and copolymer of 2-methyl-2' -acrylamide propane sulfonic acid and Zn2+1:0.78:0.83:0.33 (by weight).
The phosphorus-free composite corrosion inhibitor is respectively added into test water 1 and test water 2 according to the concentration of 100mg/L, so that the concentration of a condensation reaction product of sodium gluconate and aspartic acid in the test water 1 and the test water 2 is 6mg/L, and the concentration of the condensation reaction product is respectively measured in the test water 1 and the test water 2Spin-on slides (20) in Water 1 and test Water 2#Carbon steel) corrosion test.
Example 3
30.5g of the condensation product of sodium gluconate and aspartic acid obtained in preparation example 1, 5.8g of ascorbic acid, 33.3g of AA/AMPS/HPA with a solids content of 30% by weight (weight ratio of the three monomers: 60/20/20, limiting viscosity at 30 ℃ C. of 0.075dL/g, from Rockwell industries Ltd.) and 1.7g of ZnCl were weighed out2Adding water and shaking uniformly to obtain 100g of phosphorus-free composite corrosion inhibitor, wherein the condensation reaction product of sodium gluconate and aspartic acid comprises ascorbic acid, AA/AMPS/HPA and Zn2+1:0.644:1.11:0.09 (weight ratio).
The phosphorus-free composite corrosion inhibitor is respectively added into test water 1 and test water 2 according to the concentration of 100mg/L, so that the concentration of a condensation reaction product of sodium gluconate and aspartic acid in the test water 1 and the test water 2 is 9mg/L, and rotary hanging pieces (20) are respectively carried out in the test water 1 and the test water 2#Carbon steel) corrosion test.
Example 4
7.6g of the condensation product of sodium gluconate and aspartic acid obtained in preparation 2, 5g of ascorbic acid, 12.1g of AA/AMPS with a solids content of 33% by weight (the weight ratio of the two monomers is 70/30, the limiting viscosity at 30 ℃ is 0.075dL/g, commercially available from Luoyangong industries, Ltd.), 8.5g of a copolymer of acrylic acid and styrenesulfonic acid with a solids content of 47% (the weight ratio of the two monomers is 70/30, the limiting viscosity at 30 ℃ is 0.080dL/g, commercially available from Luoyangong industries, Ltd.), and 2.2g of ZnSO4·7H2O, adding water and shaking up to obtain 100g of the phosphorus-free composite corrosion inhibitor, wherein the condensation reaction product of sodium gluconate and aspartic acid comprises ascorbic acid, AA/AMPS, copolymer of acrylic acid and styrene sulfonic acid and Zn2+1:2.5:2:2:0.25 (weight ratio).
The phosphorus-free composite corrosion inhibitor is respectively added into test water 1 and test water 2 according to the concentration of 100mg/L, so that the concentration of a condensation reaction product of sodium gluconate and aspartic acid in the test water 1 and the test water 2 is 2mg/L, and rotary hanging pieces (20) are respectively carried out in the test water 1 and the test water 2#Carbon steel) corrosion test.
Example 5
13.6g of the condensation reaction product of sodium gluconate and aspartic acid obtained in preparation example 1, 5.5g of ascorbic acid, 18.2g of a copolymer of acrylic acid, hydroxypropyl acrylate and 2-methyl-2' -acrylamidopropanesulfonic acid having a solids content of 33% by weight (70/15/15 parts by weight of the three monomers, an intrinsic viscosity at 30 ℃ of 0.078dL/g, available from Luoyangong industries, Ltd.), and 3.8g of ZnCl were weighed out2Adding water and shaking uniformly to obtain 100g of phosphorus-free composite corrosion inhibitor, wherein the condensation reaction product of sodium gluconate and aspartic acid comprises ascorbic acid, acrylic acid, hydroxypropyl acrylate and 2-methyl-2' -acrylamide propane sulfonic acid copolymer Zn2+1:1.38:1.5:0.45 (weight ratio).
The phosphorus-free composite corrosion inhibitor is respectively added into test water 1 and test water 2 according to the concentration of 100mg/L, so that the concentration of a condensation reaction product of sodium gluconate and aspartic acid in the test water 1 and the test water 2 is 4mg/L, and rotary hanging pieces (20) are respectively carried out in the test water 1 and the test water 2#Carbon steel) corrosion test.
Example 6
27.1g of the condensation product of sodium gluconate and aspartic acid obtained in preparation example 1, 4.8g of ascorbic acid, 11.7g of a copolymer of acrylic acid and vinylsulfonic acid having a solids content of 47% by weight (weight ratio of the two monomers: 80/20, limiting viscosity at 30 ℃ C. of 0.075dL/g, from Rockwell industries, Ltd.), and 9.7g of ZnSO4·7H2O, adding water and shaking up to obtain 100g of the phosphorus-free composite corrosion inhibitor, wherein the condensation reaction product of the sodium gluconate and the aspartic acid comprises ascorbic acid, a copolymer of acrylic acid and ethylene sulfonic acid and Zn2+1:0.6:0.69:0.28 (weight ratio).
The phosphorus-free composite corrosion inhibitor is respectively added into test water 1 and test water 2 according to the concentration of 100mg/L, so that the concentration of a condensation reaction product of sodium gluconate and aspartic acid in the test water 1 and the test water 2 is 8mg/L, and rotary hanging pieces (20) are respectively carried out in the test water 1 and the test water 2#Carbon steel) corrosion test.
Example 7
33.9g of the condensation reaction product of sodium gluconate and aspartic acid obtained in preparation example 1, 6g of ascorbic acid, 25.7g of a copolymer of methyl acrylate and styrenesulfonic acid having a solids content of 35% by weight (70/30 weight ratio of the two monomers, 0.078dL/g limiting viscosity at 30 ℃ C., available from Luoyangong industries Co., Ltd.), and 5.2g of ZnCl were weighed out2Adding water and shaking up to obtain 100g of the phosphorus-free composite corrosion inhibitor, wherein the condensation reaction product of sodium gluconate and aspartic acid comprises ascorbic acid, a copolymer of methyl acrylate and styrene sulfonic acid and Zn2+＝1:0.6:0.9:0.25。
The phosphorus-free composite corrosion inhibitor is respectively added into test water 1 and test water 2 according to the concentration of 100mg/L, so that the concentration of a condensation reaction product of sodium gluconate and aspartic acid in the test water 1 and the test water 2 is 10mg/L, and rotary hanging pieces (20 mg/L) are respectively carried out in the test water 1 and the test water 2#Carbon steel) corrosion test.
Example 8
23.7g of the condensation reaction product of sodium gluconate and aspartic acid obtained in preparation example 1, 5.2g of ascorbic acid, 4.4g of TH-3100 (density (20 ℃) having a solid content of 45% by weight or more than 1.15g cm. cndot.) were weighed-3Dynamic viscosity (25 ℃ C.) of 100-300cps as obtained from Shandongtai and Water treatment Co., Ltd.), 13.5g of a copolymer of acrylic acid and allylsulfonic acid having a solid content of 37% (weight ratio of the two monomers: 80/20, limiting viscosity at 30 ℃ of 0.078dL/g as obtained from Luoyangong industries, Ltd.), 5.3g of ZnSO4·7H2O, adding water and shaking up to obtain 100g of the phosphorus-free composite corrosion inhibitor, wherein the condensation reaction product of sodium gluconate and aspartic acid comprises ascorbic acid, TH-3100, copolymer of acrylic acid and allyl sulfonic acid and Zn2+1:0.74:0.29:0.71:0.17 (by weight).
The phosphorus-free composite corrosion inhibitor is respectively added into test water 1 and test water 2 according to the concentration of 100mg/L, so that the concentration of a condensation reaction product of sodium gluconate and aspartic acid in the test water 1 and the test water 2 is 7mg/L, and rotary hanging pieces (20) are respectively carried out in the test water 1 and the test water 2#Carbon steel) corrosionAnd (4) testing.
Example 9
The test was carried out according to the method of example 2, except that 1g of mercaptobenzothiazole was also used for the formulation of the composite corrosion inhibitor and the material used for the spinpack corrosion test was brass.
Comparative example 1
The experiment was performed according to the method of example 1, except that the condensation reaction product of potassium gluconate and aspartic acid prepared in preparation example 1 was not added in the preparation of the phosphorus-free composite corrosion inhibitor.
Comparative example 2
A test was carried out as in example 2, except that 1.7g of a copolymer of acrylamide and 2-methyl-2 '-acrylamidopropanesulfonic acid having a solids content of 30% by weight were added to give a phosphorus-free composite corrosion inhibitor containing the condensation reaction product of sodium gluconate and aspartic acid ascorbic acid, copolymer of acrylic acid, acrylamide and 2-methyl-2' -acrylamidopropanesulfonic acid, Zn2+1:0.78:0.08:0.33 (by weight).
Comparative example 3
The experiment was performed in accordance with the method of example 6, except that ZnSO was not added during the preparation of the phosphorus-free composite corrosion inhibitor4·7H2O。
Comparative example 4
The test was performed according to the method of example 2, except that ascorbic acid was not added in the process of preparing the phosphorus-free composite corrosion inhibitor.
Comparative example 5
The experiment was performed according to the method of example 2, except that the copolymer of acrylic acid, acrylamide and 2-methyl-2' -acrylamidopropanesulfonic acid was not added during the preparation of the phosphorus-free composite corrosion inhibitor.
Comparative example 6
The experiment was performed according to the method of example 2, except that sodium citrate was used instead of ascorbic acid.
Comparative example 7
The experiment was carried out in the same manner as in example 2 except that 18.9g of the condensation reaction product of trisodium citrate and alanine obtained in preparation example 4 was used in place of the condensation reaction product of sodium gluconate and aspartic acid.
Comparative example 8
The test was carried out as in example 2, except that 1.5g of ascorbic acid was added to obtain a phosphorus-free composite corrosion inhibitor in which the product of the condensation reaction of sodium gluconate with aspartic acid, ascorbic acid, a copolymer of acrylic acid, acrylamide and 2-methyl-2' -acrylamidopropanesulfonic acid, Zn2+1:0.25:0.83:0.33 (by weight).
Comparative example 9
50.8g of the condensation reaction product of sodium gluconate obtained in preparation example 1 and aspartic acid, 8.8g of ZnSO4·7H2O, adding water and shaking up to obtain 100g of the phosphorus-free composite corrosion inhibitor, wherein the condensation reaction product of potassium gluconate and aspartic acid is Zn2+1:0.13 (weight ratio).
The phosphorus-free composite corrosion inhibitor is respectively added into test water 1 and test water 2 according to the concentration of 100mg/L, and condensation reaction products of sodium gluconate and aspartic acid and Zn are added into the water2+Respectively has an effective concentration of 15mg/L and 2mg/L, and is subjected to spin coating in test water 1 and test water 2 (20)#Carbon steel) corrosion test.
Comparative example 10
67.8g of the condensation reaction product of sodium gluconate obtained in preparation example 1 and aspartic acid, 8.8g of ZnSO were weighed out4·7H2O, adding water and shaking up to obtain 100g of the phosphorus-free composite corrosion inhibitor, wherein the condensation reaction product of potassium gluconate and aspartic acid is Zn2+1:0.1 (weight ratio).
The phosphorus-free composite corrosion inhibitor is respectively added into test water 1 and test water 2 according to the concentration of 100mg/L, and condensation reaction products of sodium gluconate and aspartic acid and Zn are added into the water2+Respectively has an effective concentration of 20mg/L and 2mg/L, and is subjected to spin coating in test water 1 and test water 2 (20)#Carbon steel) corrosion test.
The results of the spin corrosion tests of the above examples and comparative examples are shown in table 2.
TABLE 2
Figure GDA0001881215880000141
Figure GDA0001881215880000151
The results in table 2 show that the phosphorus-free composite corrosion inhibitor provided by the invention is prepared by compounding a condensation reaction product, ascorbic acid, a sulfonate copolymer and a zinc salt, and the weight ratio is limited to 1:0.6-2.5:0.4-5:0.05-1.25, so that the phosphorus-free composite corrosion inhibitor can play a synergistic effect, reduces the consumption of the condensation reaction product, and has a good corrosion inhibition effect. The phosphorus-free composite corrosion inhibitor provided by the invention has few components and low dosage, and is particularly suitable for high-hardness and high-alkali circulating cooling water treatment with the sum of the calcium hardness and the total alkalinity of supplementing water being 300-700 mg/L.
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. A phosphorus-free composite corrosion inhibitor suitable for high hard water is characterized by comprising a condensation reaction product, ascorbic acid, a sulfonate copolymer and a zinc salt, wherein the condensation reaction product comprises the following components in percentage by weight: ascorbic acid: sulfonate copolymer: the zinc salt is 1:0.6-2.5:0.4-5:0.05-1.25, wherein the condensation reaction product is a condensation reaction product of sodium gluconate and aspartic acid and/or a condensation reaction product of potassium gluconate and aspartic acid; the weight of the zinc salt is calculated as zinc ion.
2. The phosphorus-free composite corrosion inhibitor according to claim 1, wherein the condensation reaction product: ascorbic acid: sulfonate copolymer: zinc salt is 1:0.6-2.5:0.69-4: 0.09-0.53.
3. The phosphorus-free composite corrosion inhibitor according to claim 1 or 2, wherein the molecular weight distribution of the condensation reaction product is 300-600.
4. The phosphorus-free composite corrosion inhibitor according to claim 1 or 2, wherein the sulfonate copolymer is selected from at least one of a copolymer of acrylic acid ester and styrene sulfonic acid, a copolymer of acrylic acid and allyl sulfonic acid, a copolymer of acrylic acid and 2-methyl-2 '-acrylamidopropanesulfonic acid, a copolymer of acrylic acid, acrylic acid ester and 2-methyl-2' -acrylamidopropanesulfonic acid, a copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, a copolymer of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and hydroxypropyl acrylate, an acrylic acid-sulfonate copolymer, and a carboxylate-sulfonate-nonionic copolymer.
5. The phosphorus-free composite corrosion inhibitor according to claim 4, wherein the acrylate is at least one of methyl acrylate, ethyl acrylate and hydroxypropyl acrylate.
6. The phosphorus-free composite corrosion inhibitor according to claim 1 or 2, wherein the zinc salt is selected from zinc sulfate and/or zinc chloride.
7. The phosphorus-free composite corrosion inhibitor according to claim 1 or 2, wherein the phosphorus-free composite corrosion inhibitor further comprises a heterocyclic compound.
8. The phosphorus-free composite corrosion inhibitor according to claim 7, wherein the heterocyclic compound is at least one selected from mercaptobenzothiazole, benzotriazole and methylbenzotriazole.
9. The phosphorus-free composite corrosion inhibitor according to claim 7, wherein the condensation reaction product comprises, in weight ratios: the heterocyclic compound is 1: 0.05-0.75.
10. The phosphorus-free composite corrosion inhibitor according to claim 7, wherein the condensation reaction product comprises, in weight ratios: the heterocyclic compound is 1: 0.1-0.6.
11. The use of the phosphorus-free composite corrosion inhibitor of claims 1-10 in the treatment of circulating cooling water.
12. The use as claimed in claim 11, wherein the recirculated cooling water is high-hardness high-alkali water with the sum of calcium hardness and total alkalinity of the make-up water being 300-700mg/L, and the pH value of the recirculated cooling water is controlled between 7.8-8.5.
13. The use according to claim 11, wherein the concentration of the condensation reaction product, ascorbic acid, sulfonate copolymer, zinc salt, and heterocyclic compound in the circulating cooling water is 2-10mg/L, 4.5-6mg/L, 4-10mg/L, 0.5-2.5mg/L, and 0.5-1.5mg/L, respectively, wherein the concentration of zinc salt is calculated as zinc ion.
CN201811140632.2A 2018-09-28 2018-09-28 Phosphorus-free composite corrosion inhibitor suitable for high-hardness water and application thereof Active CN110963583B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811140632.2A CN110963583B (en) 2018-09-28 2018-09-28 Phosphorus-free composite corrosion inhibitor suitable for high-hardness water and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811140632.2A CN110963583B (en) 2018-09-28 2018-09-28 Phosphorus-free composite corrosion inhibitor suitable for high-hardness water and application thereof

Publications (2)

Publication Number Publication Date
CN110963583A CN110963583A (en) 2020-04-07
CN110963583B true CN110963583B (en) 2021-08-03

Family

ID=70026824

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811140632.2A Active CN110963583B (en) 2018-09-28 2018-09-28 Phosphorus-free composite corrosion inhibitor suitable for high-hardness water and application thereof

Country Status (1)

Country Link
CN (1) CN110963583B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102225809A (en) * 2011-04-08 2011-10-26 武汉理工大学 Ascorbic acid phosphorus-free corrosion and scale inhibitor, and preparation method thereof
CN105366823A (en) * 2014-08-29 2016-03-02 中国石油化工股份有限公司 Non-phosphorus corrosion and scale inhibitor composition, non-phosphorus corrosion and scale inhibitor, application of non-phosphorus corrosion and scale inhibitor and application of copolymer to corrosion inhibition
CN105800802A (en) * 2016-05-21 2016-07-27 中山市绿浪助剂有限公司 Composite type phosphorous-free corrosion and scale inhibitor
CN106430646A (en) * 2016-07-13 2017-02-22 中国神华能源股份有限公司 Strong corrosion water treatment method
US9845258B1 (en) * 2012-09-19 2017-12-19 Premier Magnesia, Llc Compositions and methods for treating wastewater
CN107522300A (en) * 2016-06-20 2017-12-29 中国石油化工股份有限公司 The processing method of corrosion inhibiter and composite corrosion inhibitor and preparation method thereof and its application and recirculated water in aqueous corrosion is suppressed

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102225809A (en) * 2011-04-08 2011-10-26 武汉理工大学 Ascorbic acid phosphorus-free corrosion and scale inhibitor, and preparation method thereof
US9845258B1 (en) * 2012-09-19 2017-12-19 Premier Magnesia, Llc Compositions and methods for treating wastewater
CN105366823A (en) * 2014-08-29 2016-03-02 中国石油化工股份有限公司 Non-phosphorus corrosion and scale inhibitor composition, non-phosphorus corrosion and scale inhibitor, application of non-phosphorus corrosion and scale inhibitor and application of copolymer to corrosion inhibition
CN105800802A (en) * 2016-05-21 2016-07-27 中山市绿浪助剂有限公司 Composite type phosphorous-free corrosion and scale inhibitor
CN107522300A (en) * 2016-06-20 2017-12-29 中国石油化工股份有限公司 The processing method of corrosion inhibiter and composite corrosion inhibitor and preparation method thereof and its application and recirculated water in aqueous corrosion is suppressed
CN106430646A (en) * 2016-07-13 2017-02-22 中国神华能源股份有限公司 Strong corrosion water treatment method

Also Published As

Publication number Publication date
CN110963583A (en) 2020-04-07

Similar Documents

Publication Publication Date Title
CN107522301B (en) Use of corrosion inhibitors or corrosion inhibitor compositions for inhibiting water corrosion
CN105800802B (en) A kind of compound phosphate-free corrosion inhibition antisludging agent
CN109748400B (en) Phosphorus-free composite corrosion and scale inhibitor, application thereof and treatment method of circulating cooling water
CN111471988A (en) Prefilming agent and preparation method thereof
CN1880244A (en) Composite water treating agent for central air conditioner cooling water
CN107304077B (en) Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof
CN110963586B (en) Phosphorus-free composite corrosion inhibitor suitable for low-hardness water and application thereof
CN109748401B (en) Method for treating circulating cooling water
CN110963583B (en) Phosphorus-free composite corrosion inhibitor suitable for high-hardness water and application thereof
CN111039422B (en) Composite scale and corrosion inhibitor suitable for high-hardness water and application thereof
CN111072165B (en) Composite scale and corrosion inhibitor and application thereof in low hard water
CN107304079B (en) Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof
CN110963584B (en) Phosphorus-free composite corrosion inhibitor suitable for natural pH operation and application thereof
CN114426337B (en) Phosphorus-free composite corrosion inhibitor and application thereof
CN110963585B (en) Non-phosphorus composite corrosion inhibitor and application thereof in low hard water
CN103936177B (en) Non-phosphorus corrosion and scale inhibitor for industrial cooling water system as well as preparation method and application thereof
CN111039425B (en) Composite scale and corrosion inhibitor suitable for natural pH operation and application thereof
CN111039424B (en) Composite scale and corrosion inhibitor suitable for low-hardness water and application thereof
CN100469715C (en) Composite water treating agent for industrial circulation cooling water
CN111072164B (en) Composite scale and corrosion inhibitor and application thereof in medium and hard water
CN114426340B (en) Low-temperature scale and corrosion inhibitor and scale and corrosion inhibition method for circulating cooling water
CN110963587B (en) Non-phosphorus composite corrosion inhibitor and application thereof in high hard water
CN107698041A (en) A kind of recirculating cooling water system corrosion inhibiting and descaling agent using desalinization water as moisturizing
CN114426336A (en) Corrosion inhibition method for low-temperature phosphorus-free corrosion inhibitor and circulating cooling water
CN110963588B (en) Non-phosphorus composite corrosion inhibitor and application thereof in medium and hard water

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant