CN110963585B - Non-phosphorus composite corrosion inhibitor and application thereof in low hard water - Google Patents
Non-phosphorus composite corrosion inhibitor and application thereof in low hard water Download PDFInfo
- Publication number
- CN110963585B CN110963585B CN201811140584.7A CN201811140584A CN110963585B CN 110963585 B CN110963585 B CN 110963585B CN 201811140584 A CN201811140584 A CN 201811140584A CN 110963585 B CN110963585 B CN 110963585B
- Authority
- CN
- China
- Prior art keywords
- gluconate
- phosphorus
- corrosion inhibitor
- triethanolamine
- condensation reaction
- 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
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
- C02F5/12—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
-
- 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
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 a phosphorus-free composite corrosion inhibitor for circulating cooling water, and discloses a phosphorus-free composite corrosion inhibitor and application thereof in low hard water. The phosphorus-free composite corrosion inhibitor comprises a condensation reaction product of gluconate and triethanolamine, sodium tartrate, a copolymer containing sulfonic acid groups and zinc salts, wherein the weight ratio of the condensation reaction product of gluconate and triethanolamine to the sodium tartrate to the copolymer containing sulfonic acid groups to the zinc salts is 1:0.5-3:0.16-5:0.04-1.25, and the weight of the zinc salts is calculated by zinc ions; wherein the gluconate is sodium gluconate and/or potassium gluconate. The phosphorus-free composite corrosion inhibitor prepared by adopting the proportion is suitable for corrosion inhibition treatment of low-hardness circulating cooling water.
Description
Technical Field
The invention relates to a phosphorus-free composite corrosion inhibitor for circulating cooling water, in particular to a phosphorus-free composite corrosion inhibitor and application thereof in low hard water.
Background
Among the industrial water consumption, cooling water accounts for a large proportion. Decades ago, China mostly adopts a direct-current cooling water system, and great waste is caused to water resources. In recent years, circulating cooling water systems have been widely popularized in various industries because of their obvious water saving effects. However, this is accompanied by the problem of corrosion and fouling of cooling equipment in recirculating cooling water systems.
The addition of corrosion inhibitors to circulating water systems is an effective way to control corrosion. The phosphorus water treatment agent has no toxicity, low price and better corrosion inhibition performance, and accounts for more than 70-80% of the prior water treatment agent, but the discharge of phosphorus easily causes water eutrophication and seriously affects the ecological environment. In this regard, international calls for phosphorus limitation and inhibition have become increasingly high, and the European Union, the United states, Japan, and the like have made regulations that set the total phosphorus emission mass concentration to be less than or equal to 1.0 mg/L. In order to realize sustainable water resource management, the application of inorganic phosphorus and organic phosphorus series medicaments is bound to be limited, and the development and application of the high-efficiency environment-friendly phosphorus-free water treatment agent is undoubtedly a necessary trend for the development of the water treatment industry in the 21 st century.
CN107522301A discloses a corrosion inhibitor and corrosion inhibitor composition, a preparation method thereof, application thereof in inhibiting water corrosion and a treatment method of circulating water, wherein the composition of the corrosion inhibitor and zinc salt has a certain corrosion inhibition effect in specific water quality, but the dosage is higher.
The low-hardness circulating water has low hardness and alkalinity, and belongs to water quality easy to corrode. The existing corrosion inhibitor cannot carry out corrosion inhibition treatment on low-hardness circulating cooling water in a targeted manner.
Disclosure of Invention
The invention aims to solve the problem that the corrosion inhibitor in the prior art cannot specifically inhibit corrosion of low hard water, and provides a phosphorus-free composite corrosion inhibitor particularly suitable for low hard water and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a phosphorus-free composite corrosion inhibitor, which includes a condensation reaction product of gluconate and triethanolamine, sodium tartrate, a copolymer containing sulfonic acid groups, and a zinc salt, wherein the weight ratio of the condensation reaction product of gluconate and triethanolamine, sodium tartrate, copolymer containing sulfonic acid groups, and zinc salt is 1:0.5-3:0.16-5:0.04-1.25, and the weight of the zinc salt is calculated by zinc ions; wherein the gluconate is sodium gluconate and/or potassium gluconate.
The invention also provides an application of the phosphorus-free composite corrosion inhibitor in treating circulating cooling water.
The phosphorus-free composite corrosion inhibitor prepared by the invention does not contain phosphorus and meets the requirement of environmental protection. The condensation reaction product of gluconate and triethanolamine, sodium tartrate and zinc salt have synergistic effect, and can be used for corrosion inhibition treatment of low-hardness circulating cooling water; the copolymer containing sulfonic acid group can stabilize zinc salt in circulating water and prevent calcium carbonate scale and suspended matter from depositing. In addition, the phosphorus-free composite corrosion inhibitor can be matched with azole heterocyclic compounds, and has a corrosion inhibition effect on copper materials. By adopting the technical scheme, the corrosion inhibitor can achieve a good corrosion inhibition effect on low hard water under the conditions of less components of a water treatment agent and low using amount (especially the using amount of a condensation reaction product of gluconate and triethanolamine), 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, which comprises a condensation reaction product of gluconate and triethanolamine, sodium tartrate, a copolymer containing sulfonic acid groups and zinc salts, wherein the weight ratio of the condensation reaction product of gluconate and triethanolamine to the sodium tartrate to the copolymer containing sulfonic acid groups to the zinc salts is 1:0.5-3:0.16-5:0.04-1.25, and the weight of the zinc salts is calculated by zinc ions; wherein the gluconate is sodium gluconate and/or potassium gluconate.
In the invention, a condensation reaction product of gluconate (sodium gluconate and/or potassium gluconate in the invention) and triethanolamine is prepared according to the following method: the gluconate and triethanolamine are subjected to condensation reaction under the action of acid catalysis, and the gluconate and the triethanolamine are directly contacted in water for reaction to generate the product. The condensation reaction refers to dehydration condensation reaction of carboxyl in gluconate and hydroxyl in triethanolamine.
Preferably, the molar ratio of triethanolamine to gluconate is (0.15-6):1, preferably (0.3-3):1, and the acid catalyst is preferably sulfuric acid and/or nitric acid. The molar ratio of the catalyst to the gluconate calculated by hydrogen ions is (0.2-6) to 1, preferably (0.8-4) to 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 under heating conditions of 100 ℃ and 180 ℃, and the contacting time is 2-10 hours.
Preferably, the molecular weight distribution of the condensation reaction product of gluconate and triethanolamine is in the range of 300-700, more preferably 327-683.
The corrosion inhibitor is a mixture of a condensation reaction product of gluconate and triethanolamine, sodium tartrate, a copolymer containing sulfonic acid groups and zinc salt, does not contain phosphorus, has broad spectrum, can be used for treating the corrosion problem of cooling facilities in a circulating cooling water system, and is suitable for various materials except copper materials. The condensation reaction product of the gluconate and the triethanolamine, the sodium tartrate and the zinc salt synergistically have a good corrosion inhibition effect, and the sulfonic acid group-containing copolymer has the effects of stabilizing zinc ions in circulating cooling water and preventing calcium carbonate scale and suspended matters from depositing on the inner wall of a cooling facility.
When the condensation reaction product of the gluconate and the triethanolamine, the sodium tartrate, the copolymer containing sulfonic acid groups and the zinc salt are mixed according to the weight ratio, the mixture can be used for treating low-hardness circulating cooling water (namely low-hardness water). In the invention, the low hard water means that the sum of the calcium ion content and the total alkalinity in the water supplement of the circulating cooling water is less than or equal to 100mg/L, preferably 45-100 mg/L; wherein the calcium ion content and total alkalinity are both CaCO3And (6) counting. The water quality determination method refers to the analysis and test method of cooling water (1993, published by the information center of the general petrochemical plant in Anqing) compiled by the Ministry of production and development of the general petrochemical company of China.
Preferably, the weight ratio of the condensation reaction product of the gluconate and the triethanolamine, the sodium tartrate, the sulfonic acid group-containing copolymer and the zinc salt is 1:0.5-3:0.33-4.1: 0.083-1.1.
When the condensation reaction product of the gluconate and the triethanolamine, the sodium tartrate, the copolymer containing sulfonic acid groups and the zinc salt are mixed according to the proportion, the corrosion inhibition effect on the low-hardness circulating cooling water is better.
Preferably, the sulfonic acid group-containing copolymer is selected from the group consisting of a copolymer of acrylic acid with 2-acrylamido-2-methylpropanesulfonic acid, a terpolymer of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and hydroxypropyl acrylate, a binary copolymer of acrylic acid and sulfonate, a carboxylate-sulfonate-nonionic terpolymer, a copolymer of acrylic acid and styrenesulfonic acid, a copolymer of acrylic acid ester and styrenesulfonic acid, a copolymer of acrylic acid and allylsulfonic acid, a copolymer of acrylic acid and vinylsulfonic acid, a copolymer of acrylic acid and 2-methyl-2' -acrylamidopropanesulfonic acid, acrylic acid, at least one of a terpolymer of acrylamide and 2-methyl-2 '-acrylamidopropanesulfonic acid, and a terpolymer of acrylic acid, an acrylic ester, and 2-methyl-2' -acrylamidopropanesulfonic acid.
Preferably, the acrylate is C1-8 acrylate, and more preferably, the acrylate is at least one of methyl acrylate, ethyl acrylate and hydroxypropyl acrylate.
The limiting viscosity of the sulfonic acid group-containing copolymer at 30 ℃ is usually from 0.07 to 0.08dL/g, or the dynamic viscosity of the sulfonic acid group-containing copolymer at 25 ℃ is usually from 100 to 500 cps.
The sulfonic acid group-containing copolymer is selected, so that on one hand, the sulfonic acid group-containing copolymer can be uniformly mixed with other components in the raw material, on the other hand, zinc ions in water can be stabilized, and the calcium carbonate scale and the scale deposition of suspended matters on the inner wall of a cooling facility can be effectively relieved.
Preferably, the zinc salt is selected from water soluble zinc salts, more preferably zinc sulfate and/or zinc chloride.
The choice of zinc salt in the present invention is not particularly limited as long as it is soluble in water and can be uniformly mixed with other components in the solution.
The phosphorus-free composite corrosion inhibitor also contains a heterocyclic compound, preferably, the weight ratio of the condensation reaction product of the gluconate and the triethanolamine to the heterocyclic compound is 1:0.0417-0.75, and more preferably 1: 0.1-0.75.
Preferably, the heterocyclic compound is selected from mercaptobenzothiazole and/or benzotriazole.
The phosphorus-free composite corrosion inhibitor disclosed by the invention is matched with the azole heterocyclic compound, can be used for copper materials in a targeted manner, and is suitable for corrosion inhibition treatment of low-hardness circulating cooling water. The azole heterocyclic compound is preferably mercaptobenzothiazole (2-mercaptobenzothiazole) and/or benzotriazole, and is matched with the phosphorus-free composite corrosion inhibitor according to the proportion, so that the azole heterocyclic compound is effectively used for corrosion inhibition treatment of copper materials.
According to a preferred embodiment of the present invention, the phosphorus-free composite corrosion inhibitor consists 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 invention provides an application of the phosphorus-free composite corrosion inhibitor in treating circulating cooling water; preferably, the sum of the calcium ion content and the total alkalinity in the water supplement of the circulating cooling water is less than or equal to 100mg/L, and more preferably 45-100 mg/L; the addition amount of the phosphorus-free composite corrosion inhibitor enables the concentrations of a condensation reaction product of gluconate and triethanolamine, sodium tartrate, a copolymer containing sulfonic groups, zinc salt and a heterocyclic compound in circulating cooling water to be 2-12mg/L, 4.5-6mg/L, 2-8mg/L, 0.5-2.5mg/L and 0.5-1.5mg/L respectively, wherein the concentration of the zinc salt is calculated by zinc ions.
Preferably, Ca in the water supplement of the circulating cooling water2+The content of (A) is 15-40mg/L, and the total alkalinity is 30-60 mg/L.
The corrosion inhibitor prepared by the invention can be used for specifically carrying out corrosion inhibition treatment on low-hardness water, and effectively inhibiting the corrosion of low-hardness circulating cooling water on cooling facilities. When the corrosion inhibitor is used for carrying out corrosion inhibition treatment on low hard water, the pH value of the low hard water does not need to be adjusted.
By combining the components, excellent corrosion inhibition effect can be obtained under the condition of low consumption of a condensation reaction product of gluconate and triethanolamine. Wherein, the dosage of the non-phosphorus composite corrosion inhibitor ensures that the concentration of a condensation reaction product of gluconate and triethanolamine in circulating cooling water is 2-12mg/L, and the total dosage of each component is not higher than 30mg/L (preferably 12-23 mg/L).
The present invention will be described in detail below by way of examples.
In the following examples, the method for measuring water quality was described in "analysis and test method of cooling water" written by Ministry of production and Ministry of development of general petrochemical industries of China (1993, published by the information center of the Ministry of petrochemical industries, Anqing).
The corrosion inhibition performance evaluation of the corrosion inhibitor is carried out according to the following method: fixing 20# high-quality carbon steel/brass test piece on a coupon instrument, putting the test piece into test water (water obtained by concentrating test raw water by 5 times) added with a corrosion inhibitor, keeping the temperature at 45 +/-1 ℃, keeping the rotating speed at 75rpm, rotating for 72 hours, recording the weight of the test piece before and after the test, and calculating the average corrosion speed.
The average corrosion rate is calculated by the formula: f ═ C × Δ W)/(a × T × ρ)
C, calculating constant, when mm/a (millimeter/year) is taken as unit, C is 8.76 multiplied by 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)。
The molecular weights of the condensation reaction product of sodium gluconate and triethanolamine, the condensation reaction product of potassium gluconate and triethanolamine, the condensation reaction product of trisodium citrate and triisopropanolamine, the condensation reaction product of sodium gluconate and triisopropanolamine, and the condensation reaction product of trisodium citrate and triethanolamine were determined by mass spectrometry in a scanning mode of FTMS-p ESI Full ms [100-1000 ].
In the following examples, copolymers of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (AA/AMPS copolymers), and copolymers of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and hydroxypropyl acrylate (AA/AMPS/HPA copolymers) were obtained from the company, Strong Rockwell industries, Ltd;
acrylic acid-sulfonate copolymer (TH-2000), carboxylate-sulfonate-nonionic copolymer (TH-3100) available from Shandongtai and Water treatment science, Inc.;
sodium gluconate and potassium gluconate were obtained from Bailingwei science & technology Ltd, triethanolamine, triisopropanolamine and sodium tartrate were obtained from Beijing chemical Agents, concentrated sulfuric acid and concentrated nitric acid were obtained from Tianjin Guangfu Fine chemical research institute, trisodium citrate, mercaptobenzothiazole, ZnSO4·7H2O and ZnCl2Purchased from the national pharmaceutical group chemical agents limited.
The water quality of the test raw water used for the treatment of the phosphorus-free composite corrosion inhibitor prepared in each of the following examples is shown in table 1.
TABLE 1
| Quality of water | Ca2+ | Total alkalinity | Cl- | SO4 2- | pH | Electrical conductivity of |
| Quality of water 1 | 17 | 33 | 12 | 35 | 7.4 | 82 |
| Quality of water 2 | 35 | 58 | 26 | 48 | 7.5 | 177 |
Note: pH is nothing, conductivity is μ s/cm, the rest is mg/L, Ca2+CaCO for total alkalinity3The same applies below. Ca2+This represents the calcium hardness, as follows. The measurement method of each parameter is as follows: ca2+: reference standard GB/T6910-2006; total alkalinity: reference standard GB/T15451-2006; cl-: reference standard GB/T15453-2008; SO (SO)4 2-: reference standard GB/T14642-2009; pH value: reference standard GB/T6920-; conductivity: reference is made to the standard GB/T6908-2008.
The test water in the following examples is water concentrated 5 times as much as the test raw water in table 1.
Preparation example 1
Preparing a condensation reaction product of sodium gluconate and triethanolamine: 32.7g (0.15mol) of sodium gluconate, 14.9g (0.1mol) of triethanolamine and 100mL of water were placed in a four-necked flask equipped with a stirrer, a distillation apparatus and a thermometer, and stirring was started to sufficiently dissolve and mix the sodium gluconate and the triethanolamine. Then 5g (0.05mol) of concentrated sulfuric acid is added at the temperature of 20 ℃, oil bath (dimethyl silicon oil) is heated to 130 ℃ for reaction for 6h, the distilled water amount is 40g, the residual liquid is cooled to obtain the condensation reaction product of the sodium gluconate and the triethanolamine, the solid content is 40 weight percent through measurement, and the molecular weight is distributed in the range of 327 and 683.
Preparation example 2
Preparing a condensation reaction product of sodium gluconate and triethanolamine: 32.7g (0.15mol) of sodium gluconate and 134.1g (0.9 m) of sodium gluconate were placed in a four-necked flask equipped with a stirrer, a distillation apparatus and a thermometerol) triethanolamine and 100mL water, and stirring to fully dissolve and mix the sodium gluconate and the triethanolamine. Thereafter, 45g (containing H) were added at 20 ℃2SO40.45mol) of concentrated sulfuric acid, heating the mixture to 130 ℃ in an oil bath (dimethyl silicon oil), reacting for 6 hours, wherein the distilled water amount is 50g, and the residual liquid is cooled to obtain a condensation reaction product of sodium gluconate and triethanolamine, wherein the solid content is 59.6 weight percent and the molecular weight is 327 through determination.
Preparation example 3
Preparing a condensation reaction product of potassium gluconate and triethanolamine: in a four-necked flask equipped with a stirrer, a distillation apparatus and a thermometer, 23.4g (0.1mol) of potassium gluconate, 2.3g (0.015mol) of triethanolamine and 100mL of water were placed, and stirring was turned on to sufficiently dissolve and mix the potassium gluconate and the triethanolamine. Thereafter, 3.15g (containing HNO) were added at 20 deg.C30.034mol) of concentrated nitric acid, heating the mixture in an oil bath (dimethyl silicone oil) to 110 ℃, reacting for 2 hours, wherein the distilled water amount is 25g, and cooling the residual liquid to obtain a condensation reaction product of potassium gluconate and triethanolamine, wherein the solid content is 22.8 percent by weight through measurement, and the molecular weight is distributed in the range of 327 and 683.
Preparation example 4
Preparation of condensation reaction product of trisodium citrate with triisopropanolamine: in a four-necked flask equipped with a stirrer, a distillation apparatus and a thermometer, 38.4g (0.15mol) of trisodium citrate, 19.3g (0.1mol) of triisopropanolamine and 100mL of water were placed, and stirring was started to sufficiently dissolve and mix the trisodium citrate and triisopropanolamine. 9.3g of concentrated nitric acid (containing HNO) was added at room temperature (20 ℃ C.)30.1 mol). Heating the heating bath (heating medium is dimethyl silicone oil) with the flask to 180 ℃, reacting for 6 hours, wherein the distilled water amount is 55g, and the residual liquid is cooled to obtain a condensation reaction product of trisodium citrate and triisopropanolamine, wherein the solid content is 44.2 weight percent and the molecular weight is distributed in the range of 365-.
Preparation example 5
Preparation of condensation reaction product of sodium gluconate and triisopropanolamine: 32.7g (0.15mol) of sodium gluconate, 19.3g (0.1mol) of triisopropanolamine and100mL of water is stirred to fully dissolve and mix the sodium gluconate and the triisopropanolamine. 9.3g of concentrated nitric acid (containing HNO) was added at room temperature (20 ℃ C.)30.1 mol). Heating the heating bath (heating medium is dimethyl silicone oil) with the flask to 180 ℃, reacting for 6 hours, wherein the distilled water amount is 50g, and the residual liquid is cooled to obtain a condensation reaction product of sodium gluconate and triisopropanolamine, wherein the solid content is 44.5 weight percent and the molecular weight is distributed in the range of 365-.
Preparation example 6
Preparation of condensation reaction product of trisodium citrate with triethanolamine: a four-necked flask equipped with a stirrer, a distillation apparatus and a thermometer was charged with 38.4g (0.15mol) of trisodium citrate, 14.9g (0.1mol) of triethanolamine and 100mL of water, and stirring was started to sufficiently dissolve and mix the trisodium citrate and triethanolamine. 9.3g of concentrated nitric acid (containing HNO) was added at room temperature (20 ℃ C.)30.1 mol). Heating the heating bath (heating medium is dimethyl silicone oil) with the flask to 180 ℃, reacting for 6 hours, wherein the distilled water amount is 50g, and the residual liquid is cooled to obtain a condensation reaction product of trisodium citrate and triethanolamine, wherein the solid content is 44.0 weight percent and the molecular weight is distributed in the range of 365-.
Example 1
This example was used to prepare a phosphorus-free composite corrosion inhibitor:
5g of a condensation reaction product of sodium gluconate having a solids content of 40% by weight and triethanolamine (prepared according to preparation example 1), 6g of sodium tartrate, 26.7g of an AA/AMPS copolymer having a solids content of 30% by weight (limiting viscosity at 30 ℃ of 0.075dl/g, weight ratio AA/AMPS: 70/30), and 8.8g of ZnSO4·7H2And O, adding 53.5g of water, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into test water according to the concentration of 100mg/L, a condensation reaction product of sodium gluconate and triethanolamine, sodium tartrate, AA/AMPS copolymer and Zn in the water2+The effective concentrations of (A) are 2mg/L, 6mg/L, 8mg/L and 2mg/L respectively.
Example 2
The preparation process of example 1 is followed, with the difference that the phosphorus-free composite corrosion inhibitor has different component contents.
12.5g of a condensation reaction product of sodium gluconate having a solids content of 40% by weight and triethanolamine (prepared according to preparation example 1), 4.5g of sodium tartrate, 6.7g of an AA/AMPS/HPA copolymer having a solids content of 30% by weight (limiting viscosity number at 30 ℃ C. of 0.075dl/g, weight ratio AA/AMPS/HPA: 60/20/20), 2.2g of ZnSO4·7H2And O, adding 74.1g of water, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, a condensation reaction product of sodium gluconate and triethanolamine, sodium tartrate, AA/AMPS/HPA copolymer and Zn in the water2+The effective concentrations of (A) are 5mg/L, 4.5mg/L, 2mg/L and 0.5mg/L respectively.
Example 3
The preparation process of example 1 is followed, with the difference that the phosphorus-free composite corrosion inhibitor has different component contents.
30g of condensation reaction product of sodium gluconate with a solid content of 40 wt% and triethanolamine (prepared according to preparation example 1), 6g of sodium tartrate and 8.9g of TH-2000 with a solid content of 45 wt% (density (20 ℃) is more than or equal to 1.15g cm-3Dynamic viscosity (25 ℃ C.) of 100-500cps), 2.1g of ZnCl2Adding 53g of water, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, a condensation reaction product of sodium gluconate and triethanolamine, sodium tartrate, TH-2000 and Zn in the water2+The effective concentrations of (A) are 12mg/L, 6mg/L, 4mg/L and 1mg/L respectively.
Example 4
The preparation process of example 1 is followed, with the difference that the phosphorus-free composite corrosion inhibitor has different component contents.
17.5g of a condensation reaction product of sodium gluconate having a solid content of 40% by weight and triethanolamine (prepared according to preparation example 1), 4.7g of sodium tartrate, 11.1g of TH-3100 having a solid content of 45% by weight (density (20 ℃) of not less than 1.15g cm)-3Dynamic viscosity (25 ℃) of 100-300cps) and 4.8g of ZnCl2Adding 61.9And (5) shaking the mixture evenly with water to obtain 100g of the medicament required to be prepared.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, a condensation reaction product of sodium gluconate and triethanolamine, sodium tartrate, TH-3100 and Zn are added into the test water2+The effective concentrations of (A) are 7mg/L, 4.7mg/L, 5mg/L and 2.3mg/L respectively.
Example 5
The preparation process of example 1 is followed, with the difference that the phosphorus-free composite corrosion inhibitor has different component contents.
22.5g of a condensation reaction product of sodium gluconate having a solids content of 40% by weight and triethanolamine (prepared according to preparation example 1), 5.5g of sodium tartrate, 10g of an AA/AMPS copolymer having a solids content of 30% by weight (limiting viscosity at 30 ℃ of 0.075dl/g, weight ratio AA/AMPS: 70/30), and 6.7g of TH-2000 having a solids content of 45% by weight (density at 20 ℃), in the form of a powder, is not less than 1.15 g/cm-3Dynamic viscosity (25 ℃) of 100-500cps) and 6.6g of ZnSO4·7H2And O, adding 48.7g of water, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, a condensation reaction product of sodium gluconate and triethanolamine, sodium tartrate, AA/AMPS copolymer, TH-2000 and Zn in the water2+The effective concentrations of (A) are 9mg/L, 5.5mg/L, 3mg/L and 1.5mg/L, respectively.
Example 6
The preparation process of example 1 was followed except that the condensation reaction product of sodium gluconate prepared in preparation example 2 and triethanolamine was used.
3.3g of a condensation reaction product of sodium gluconate with a solids content of 59.6% by weight and triethanolamine (prepared according to preparation example 2), 6g of sodium tartrate, 26.7g of an AA/AMPS copolymer with a solids content of 30% by weight (limiting viscosity number at 30 ℃ of 0.075dl/g, weight ratio AA/AMPS: 70/30), 8.8g of ZnSO4·7H2And O, adding 55.2g of water, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into test water according to the concentration of 100mg/L, the sodium gluconate and the triethanolamine in the water are condensedThe resultant, sodium tartrate, AA/AMPS copolymer and Zn2+The effective concentrations of (A) are 2mg/L, 6mg/L, 8mg/L and 2mg/L respectively.
Example 7
The preparation process of example 1 was followed except that the condensation reaction product of potassium gluconate and triethanolamine prepared in preparation example 3 was used.
8.8g of a condensation reaction product of potassium gluconate with 22.8% by weight solids content and triethanolamine (prepared according to preparation 3), 6g of sodium tartrate, 26.7g of an AA/AMPS copolymer with 30% by weight solids content (limiting viscosity number at 30 ℃ of 0.075dl/g, weight ratio AA/AMPS: 70/30), 8.8g of ZnSO4·7H2And O, adding 49.7g of water, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into test water according to the concentration of 100mg/L, a condensation reaction product of potassium gluconate and triethanolamine, sodium tartrate, AA/AMPS copolymer and Zn in the water2+The effective concentrations of (A) are 2mg/L, 6mg/L, 8mg/L and 2mg/L respectively.
Example 8
The preparation method of the corrosion inhibitor for copper materials in the embodiment 1 is characterized in that: 1.0g of mercaptobenzothiazole and 52.5g of water are added into the raw materials to prepare the composite corrosion inhibitor, and the test piece material used in the rotating coupon corrosion test is brass.
When the prepared medicament is added into test water according to the concentration of 100mg/L, a condensation reaction product of sodium gluconate and triethanolamine, sodium tartrate, AA/AMPS copolymer and Zn in the water2+And the effective concentrations of mercaptobenzothiazole were 2mg/L, 6mg/L, 8mg/L, 2mg/L and 1mg/L, respectively.
Comparative example 1
The process of example 1 is followed with the difference that the condensation reaction product of sodium gluconate and triethanolamine is not added.
6g of sodium tartrate, 26.7g of an AA/AMPS copolymer with a solids content of 30% by weight (limiting viscosity number at 30 ℃ of 0.075dl/g, weight ratio AA/AMPS: 70/30), and 8.8g of ZnSO were weighed out4·7H2O, adding 58.5g of water, and shaking up to obtain the required preparation100g of the prepared medicament.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, the sodium tartrate, the AA/AMPS copolymer and the Zn are added into the test water2+The effective concentrations of (A) are respectively 6mg/L, 8mg/L and 2 mg/L.
Comparative example 2
The procedure of example 2 was followed except that sodium tartrate was not added.
12.5g of a condensation reaction product of sodium gluconate and triethanolamine having a solids content of 40% by weight, 6.7g of an AA/AMPS/HPA copolymer having a solids content of 30% by weight (limiting viscosity at 30 ℃ of 0.075dl/g, weight ratio AA/AMPS/HPA: 60/20/20), and 2.2g of ZnSO4·7H2And O, adding 78.6g of water, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, a condensation reaction product of sodium gluconate and triethanolamine, AA/AMPS/HPA copolymer and Zn in the water2+The effective concentrations of (A) are 5mg/L, 2mg/L and 0.5mg/L respectively.
Comparative example 3
The process of example 3 was followed except that the sulfonic acid group-containing copolymer was added in a small amount.
30g of condensation reaction product of sodium gluconate with solid content of 40 wt% and triethanolamine, 6g of sodium tartrate and 1.1g of TH-2000 (density (20 ℃) with solid content of 45 wt% is more than or equal to 1.15g cm-3Dynamic viscosity (25 ℃) of 100-500cps) and 2.1g ZnCl2Adding 60.8g of water, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, a condensation reaction product of sodium gluconate and triethanolamine, sodium tartrate, TH-2000 and Zn in the water2+The effective concentrations of (A) are 12mg/L, 6mg/L, 0.5mg/L and 1mg/L respectively.
Comparative example 4
The procedure is as in example 4, except that no zinc salt is added.
17.5g of condensation reaction product of sodium gluconate with the solid content of 40 percent and triethanolamine,4.7g of sodium tartrate, 11.1g of TH-3100 (density (20 ℃) not less than 1.15g cm) with a solid content of 45 wt%-3And the dynamic viscosity (25 ℃) is 100-300cps), 66.7g of water is added and shaken evenly, and 100g of the medicament required to be prepared is obtained.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, the condensation reaction product of sodium gluconate and triethanolamine, sodium tartrate and TH-3100 have effective concentrations of 7mg/L, 4.7mg/L and 5mg/L respectively.
Comparative example 5
The procedure of example 4 was followed except that the amounts of sodium tartrate, sulfonic acid group-containing copolymer and zinc salt were decreased.
17.5g of a condensation reaction product of sodium gluconate having a solid content of 40% by weight and triethanolamine (prepared according to preparation example 1), 2.1g of sodium tartrate, 1.56g of TH-3100 having a solid content of 45% by weight (density (20 ℃) of not less than 1.15g cm)-3Dynamic viscosity (25 ℃ C.) of 100-300cps) and 0.3g of ZnCl278.54g of water is added and shaken up to obtain 100g of the medicament required to be prepared.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, a condensation reaction product of sodium gluconate and triethanolamine, sodium tartrate, TH-3100 and Zn are added into the test water2+The effective concentrations of (A) are 7mg/L, 2.1mg/L, 0.7mg/L and 0.14mg/L, respectively.
Comparative example 6
The process according to example 4, with the difference that: sodium tartrate was replaced with trisodium citrate.
Comparative example 7
The process according to example 4, with the difference that: the condensation reaction product of sodium gluconate and triethanolamine was replaced with the condensation reaction product of trisodium citrate and triisopropanolamine prepared in preparation example 4.
15.8g of a condensation reaction product of trisodium citrate having a solid content of 44.2% by weight and triisopropanolamine (prepared according to preparation example 4), 4.7g of sodium tartrate, 11.1g of TH-3100 having a solid content of 45% by weight (having a density of not less than 1.15 g/cm (20 ℃ C.))-3Dynamic viscosity (25 ℃) of 100-300cps) and 4.8g of ZnCl2Adding 63.6And (5) shaking the mixture evenly with water to obtain 100g of the medicament required to be prepared.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, a condensation reaction product of trisodium citrate and triisopropanolamine, sodium tartrate, TH-3100 and Zn are added into the test water2+The effective concentrations of (A) are 7mg/L, 4.7mg/L, 5mg/L and 2.3mg/L respectively.
Comparative example 8
The process according to example 4, with the difference that: the condensation reaction product of sodium gluconate and tri-isopropanolamine prepared in preparation example 5 is used to replace the condensation reaction product of sodium gluconate and triethanolamine.
15.7g of a condensation reaction product of sodium gluconate having a solid content of 44.5% by weight and triisopropanolamine (prepared according to preparation example 5), 4.7g of sodium tartrate, and 11.1g of TH-3100 having a solid content of 45% by weight (having a density of not less than 1.15 g/cm (20 ℃ C.))-3Dynamic viscosity (25 ℃) of 100-300cps) and 4.8g of ZnCl2Adding 63.7g of water, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, a condensation reaction product of sodium gluconate and triisopropanolamine, sodium tartrate, TH-3100 and Zn are added into the test water2+The effective concentrations of (A) are 7mg/L, 4.7mg/L, 5mg/L and 2.3mg/L respectively.
Comparative example 9
The process according to example 4, with the difference that: the condensation reaction product of sodium gluconate and triethanolamine was replaced with the condensation reaction product of trisodium citrate and triethanolamine prepared in preparation example 6.
15.9g of a condensation reaction product of trisodium citrate having a solids content of 44.0% by weight and triethanolamine (prepared in accordance with preparation example 6), 4.7g of sodium tartrate, 11.1g of TH-3100 having a solids content of 45% by weight (having a density of not less than 1.15 g/cm (20 ℃))-3Dynamic viscosity (25 ℃) of 100-300cps) and 4.8g of ZnCl2Adding 63.5g of water, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into test water according to the medicament concentration of 100mg/L, the condensation of trisodium citrate and triethanolamine in the waterReaction product, sodium tartrate, TH-3100 and Zn2+The effective concentrations of (A) are 7mg/L, 4.7mg/L, 5mg/L and 2.3mg/L respectively.
Comparative example 10
37.5g of a condensation reaction product of sodium gluconate having a solids content of 40% by weight and triethanolamine (prepared according to preparation example 1) and 8.8g of ZnSO were weighed out4·7H2And O, adding 53.7g of water, and shaking up to obtain 100g of the required prepared medicament.
When the prepared medicament is added into test water according to the concentration of 100mg/L, the condensation reaction product of sodium gluconate and triethanolamine and Zn in the water2+The effective concentrations of (A) are 15mg/L and 2mg/L respectively.
The corrosion inhibiting effects of the corrosion inhibitors prepared in examples 1-8 and comparative examples 1-10 above are shown in Table 2.
TABLE 2
Table 2 (continuation)
As can be seen from the results in Table 2, the phosphorus-free composite corrosion inhibitor prepared by the raw materials and the mixture ratio of the invention is suitable for the treatment of the circulating cooling water with low hardness. As shown in comparative examples 1 and 2, if the condensation reaction product of sodium gluconate and triethanolamine is not added or sodium tartrate is not added, the corrosion inhibitor finally prepared is used in a cooling system, the corrosion rate is increased, and the treatment of the circulating cooling water with low hardness is not facilitated. As shown in comparative example 3, if the amount of the sulfonic acid group-containing copolymer is reduced, the corrosion inhibitor obtained when used in a cooling system will be corroded at a higher rate, which is disadvantageous for the treatment of circulating cooling water having low hardness. As shown in comparative example 4, if zinc salt is not added in the raw materials, the corrosion inhibitor prepared by the method has higher corrosion speed when being used in a cooling system, and is not suitable for the treatment of circulating cooling water with low hardness.
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 (15)
1. A phosphorus-free composite corrosion inhibitor is characterized by comprising a condensation reaction product of gluconate and triethanolamine, sodium tartrate, a copolymer containing sulfonic acid groups and zinc salts, wherein the weight ratio of the condensation reaction product of the gluconate to the triethanolamine to the sodium tartrate to the copolymer containing sulfonic acid groups to the zinc salts is 1:0.5-3:0.16-5:0.04-1.25, and the weight of the zinc salts is calculated by zinc ions; wherein the gluconate is sodium gluconate and/or potassium gluconate.
2. The phosphorus-free composite corrosion inhibitor according to claim 1, wherein the weight ratio of the condensation reaction product of gluconate and triethanolamine, sodium tartrate, the copolymer containing sulfonic acid groups and the zinc salt is 1:0.5-3:0.33-4.1: 0.083-1.1.
3. The phosphorus-free composite corrosion inhibitor as claimed in claim 1 or 2, wherein the molar ratio of gluconate to triethanolamine in the condensation reaction product of gluconate and triethanolamine is 1:0.15-6, and the molecular weight distribution of the condensation reaction product of gluconate and triethanolamine is in the range of 300-.
4. The phosphorus-free composite corrosion inhibitor according to claim 1 or 2, wherein the sulfonic acid group-containing copolymer is selected from the group consisting of a copolymer of acrylic acid with 2-acrylamide-2-methylpropanesulfonic acid, a terpolymer of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and hydroxypropyl acrylate, a binary copolymer of acrylic acid and sulfonate, a carboxylate-sulfonate-nonionic terpolymer, a copolymer of acrylic acid and styrene sulfonic acid, a copolymer of acrylic acid and allyl sulfonic acid, a copolymer of acrylic acid and vinyl sulfonic acid, a copolymer of acrylic acid and 2-methyl-2 '-acrylamidopropanesulfonic acid, a terpolymer of acrylic acid, acrylamide and 2-methyl-2' -acrylamidopropanesulfonic acid, at least one of a terpolymer of acrylic acid, an acrylate, and 2-methyl-2' -acrylamidopropanesulfonic acid.
5. The phosphorus-free composite corrosion inhibitor according to claim 4, wherein the acrylate is C1-8 acrylate.
6. The phosphorus-free composite corrosion inhibitor according to claim 5, wherein the acrylate is at least one of methyl acrylate, ethyl acrylate and hydroxypropyl acrylate.
7. The phosphorus-free composite corrosion inhibitor according to claim 1 or 2, wherein the zinc salt is selected from water-soluble zinc salts.
8. The phosphorus-free composite corrosion inhibitor of claim 7, wherein the zinc salt is selected from zinc sulfate and/or zinc chloride.
9. The phosphorus-free composite corrosion inhibitor according to claim 1 or 2, wherein the phosphorus-free composite corrosion inhibitor further comprises a heterocyclic compound.
10. The phosphorus-free composite corrosion inhibitor according to claim 9, wherein the weight ratio of the condensation reaction product of gluconate and triethanolamine to the heterocyclic compound is 1: 0.0417-0.75.
11. The phosphorus-free composite corrosion inhibitor according to claim 10, wherein the weight ratio of the condensation reaction product of gluconate and triethanolamine to the heterocyclic compound is 1: 0.1-0.75.
12. The phosphorus-free composite corrosion inhibitor according to claim 9, wherein the heterocyclic compound is selected from mercaptobenzothiazole and/or benzotriazole.
13. Use of the phosphorus-free composite corrosion inhibitor according to any one of claims 1 to 12 for treating recirculated cooling water.
14. The use of claim 13, wherein the sum of the calcium ion content and the total alkalinity in the make-up water of the circulating cooling water is less than or equal to 100 mg/L; the addition amount of the phosphorus-free composite corrosion inhibitor enables the concentrations of a condensation reaction product of gluconate and triethanolamine, sodium tartrate, a copolymer containing sulfonic groups, zinc salt and a heterocyclic compound in circulating cooling water to be 2-12mg/L, 4.5-6mg/L, 2-8mg/L, 0.5-2.5mg/L and 0.5-1.5mg/L respectively, wherein the concentration of the zinc salt is calculated by zinc ions.
15. Use according to claim 14, wherein the sum of the calcium ion content and the total alkalinity in the make-up water of the recirculating cooling water is 45-100 mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811140584.7A CN110963585B (en) | 2018-09-28 | 2018-09-28 | Non-phosphorus composite corrosion inhibitor and application thereof in low hard water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811140584.7A CN110963585B (en) | 2018-09-28 | 2018-09-28 | Non-phosphorus composite corrosion inhibitor and application thereof in low hard water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110963585A CN110963585A (en) | 2020-04-07 |
| CN110963585B true CN110963585B (en) | 2021-09-21 |
Family
ID=70026891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811140584.7A Active CN110963585B (en) | 2018-09-28 | 2018-09-28 | Non-phosphorus composite corrosion inhibitor and application thereof in low hard water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110963585B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426337B (en) * | 2020-09-27 | 2024-02-13 | 中国石油化工股份有限公司 | Phosphorus-free composite corrosion inhibitor and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621362A (en) * | 2003-11-26 | 2005-06-01 | 北京燕化兴业技术开发公司 | Non-phosphorus compound scale and corrosion inhibitor for treatment of circulating cooling water |
| CN102351328A (en) * | 2011-09-16 | 2012-02-15 | 天津若泽化学技术有限公司 | Green total organic carbon steel scale and corrosion inhibitor for circulating cooling water system |
| JP2014502310A (en) * | 2010-11-11 | 2014-01-30 | リバートツプ・リニユーワブルズ | Corrosion inhibiting composition |
| CN103570153A (en) * | 2012-07-24 | 2014-02-12 | 中国石油化工股份有限公司 | Method of recycling reclaimed water for recirculating cooling water system |
| CN103771596A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Phosphorus-free composite scale and corrosion inhibitor, applications thereof, and processing method for circulating water |
| CN104556428A (en) * | 2013-10-14 | 2015-04-29 | 中国石油化工股份有限公司 | Composition for corrosion inhibition and scale inhibition and application of composition |
| CN107304077A (en) * | 2016-04-20 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of corrosion-mitigation scale-inhibition sterilization composition and its application |
| CN107522301A (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 |
-
2018
- 2018-09-28 CN CN201811140584.7A patent/CN110963585B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621362A (en) * | 2003-11-26 | 2005-06-01 | 北京燕化兴业技术开发公司 | Non-phosphorus compound scale and corrosion inhibitor for treatment of circulating cooling water |
| JP2014502310A (en) * | 2010-11-11 | 2014-01-30 | リバートツプ・リニユーワブルズ | Corrosion inhibiting composition |
| CN102351328A (en) * | 2011-09-16 | 2012-02-15 | 天津若泽化学技术有限公司 | Green total organic carbon steel scale and corrosion inhibitor for circulating cooling water system |
| CN103570153A (en) * | 2012-07-24 | 2014-02-12 | 中国石油化工股份有限公司 | Method of recycling reclaimed water for recirculating cooling water system |
| CN103771596A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Phosphorus-free composite scale and corrosion inhibitor, applications thereof, and processing method for circulating water |
| CN104556428A (en) * | 2013-10-14 | 2015-04-29 | 中国石油化工股份有限公司 | Composition for corrosion inhibition and scale inhibition and application of composition |
| CN107304077A (en) * | 2016-04-20 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of corrosion-mitigation scale-inhibition sterilization composition and its application |
| CN107522301A (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110963585A (en) | 2020-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1236373A (en) | Method of controlling iron induced fouling in water systems | |
| CN107522301B (en) | Use of corrosion inhibitors or corrosion inhibitor compositions for inhibiting water corrosion | |
| CN109110933B (en) | Low-phosphorus scale and corrosion inhibitor and preparation method thereof | |
| CN109748400B (en) | Phosphorus-free composite corrosion and scale inhibitor, application thereof and treatment method of circulating cooling water | |
| CN111072165B (en) | Composite scale and corrosion inhibitor and application thereof in low hard water | |
| CN110963585B (en) | Non-phosphorus composite corrosion inhibitor and application thereof in low hard water | |
| CN109748402B (en) | Low-phosphorus composite corrosion and scale inhibitor, application thereof and treatment method of circulating cooling water | |
| CN107304077B (en) | Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof | |
| CN109748401B (en) | Method for treating circulating cooling water | |
| CN111072164B (en) | Composite scale and corrosion inhibitor and application thereof in medium and hard water | |
| CN114426337B (en) | Phosphorus-free composite corrosion inhibitor and application thereof | |
| CN110963588B (en) | Non-phosphorus composite corrosion inhibitor and application thereof in medium and hard water | |
| CN110963587B (en) | Non-phosphorus composite corrosion inhibitor and application thereof in high hard water | |
| CN107304079B (en) | Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof | |
| CN86107456A (en) | Stablizing of iron in the aqueous systems | |
| CN111039422B (en) | Composite scale and corrosion inhibitor suitable for high-hardness water and application thereof | |
| CN110963586B (en) | Phosphorus-free composite corrosion inhibitor suitable for low-hardness water and application thereof | |
| CN111072163B (en) | Composite scale and corrosion inhibitor and application thereof in high hard water | |
| CN114426340B (en) | Low-temperature scale and corrosion inhibitor and scale and corrosion inhibition method for circulating cooling water | |
| CN110963583B (en) | Phosphorus-free composite corrosion inhibitor suitable for high-hardness water 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 | |
| CN107698041A (en) | A kind of recirculating cooling water system corrosion inhibiting and descaling agent using desalinization water as moisturizing | |
| CN110963584B (en) | Phosphorus-free composite corrosion inhibitor suitable for natural pH operation and application thereof | |
| CN114426342B (en) | Scale and corrosion inhibitor and application thereof |
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 |