CN109748407B - Method for treating circulating cooling water - Google Patents
Method for treating circulating cooling water Download PDFInfo
- Publication number
- CN109748407B CN109748407B CN201711070738.5A CN201711070738A CN109748407B CN 109748407 B CN109748407 B CN 109748407B CN 201711070738 A CN201711070738 A CN 201711070738A CN 109748407 B CN109748407 B CN 109748407B
- Authority
- CN
- China
- Prior art keywords
- corrosion
- copolymer
- low
- scale inhibitor
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
Abstract
The invention relates to circulating cooling waterThe corrosion and scale inhibition field, in particular to a treatment method of circulating cooling water, which comprises the steps of contacting the circulating cooling water with a low-phosphorus composite corrosion and scale inhibitor; the low-phosphorus composite corrosion and scale inhibitor contains hydrolyzed polymaleic anhydride, a compound A, a sulfonate copolymer, zinc salt and an optional copper corrosion inhibitor; the compound A is 2-phosphonobutane-1, 2, 4-tricarboxylic acid and/or polyaminopolyether methylene phosphonic acid; the circulating cooling water is high-hardness water with the sum of calcium hardness and total alkalinity being more than 900mg/L, and the pH value of the circulating cooling water is 7.3-8.5. The composite corrosion and scale inhibitor has excellent corrosion inhibition performance and can well stabilize Zn in water2+Ability to and CaCO3The corrosion and scale inhibitor has the advantages of less components and low dosage, and is particularly suitable for the treatment of circulating cooling water with the sum of calcium hardness and total alkalinity of more than 900 mg/L. And the composite corrosion and scale inhibitor has low phosphorus content and is green and environment-friendly.
Description
Technical Field
The invention relates to the field of corrosion and scale inhibition of circulating cooling water, in particular to a method for treating circulating cooling water by adopting low-phosphorus composite corrosion and scale inhibition.
Background
The circulating cooling water treatment mainly solves the problems of scaling, corrosion and microorganism hazard in a circulating water system. To achieve this goal, a water treatment formulation suitable for water quality conditions must be screened out. The common corrosion and scale inhibitor for domestic and foreign recirculated cooling water treatment is almost a phosphorus water treatment agent compound formula, although they are non-toxic, low-cost and have good corrosion and scale inhibition performance, after discharged into water, the water is easy to cause eutrophication and environmental pollution. With the improvement of global environmental protection and safety consciousness, phosphorus forbidden and limited measures are continuously taken in many countries and regions, and as far as the current limit standard for industrial enterprises in China is concerned, the total phosphorus emission (counted by P) is less than or equal to 1.0mg/L, the total zinc is less than or equal to 2.0mg/L and the chemical oxygen consumption is less than or equal to 60mg/L in the petrochemical industry pollutant emission standard GB 31570-2015; the total phosphorus of newly built plants is less than or equal to 0.3mg/L, the chemical oxygen consumption is less than or equal to 30mg/L, the total zinc is less than or equal to 1.0mg/L, the discharge requirements of phosphorus content and COD are very low, and the research and development of the corrosion and scale inhibitor without phosphorus and low phosphorus are bound to become the key research content of water treatment agents at home and abroad. Meanwhile, as the human beings enter a green age taking 'environmental protection, natural advocation and sustainable development promotion' as a core, green economy becomes the key point of the economic development strategy of the 21 st century. The method aims at environment, performance and economy, and designs and develops a low-phosphorus or phosphorus-free medicament which is easy to biodegrade and has high efficiency and a corresponding treatment scheme according to the principles and ideas of green chemistry and pollution prevention.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for treating circulating cooling water by adopting low-phosphorus composite corrosion and scale inhibitor, and the composite corrosion and scale inhibitor used in the method has the characteristics of less components, low phosphorus, low working concentration and environmental protection.
In order to achieve the above object, the present invention provides a method for treating recirculated cooling water, which comprises contacting recirculated cooling water with a low-phosphorous composite corrosion and scale inhibitor;
the low-phosphorus composite corrosion and scale inhibitor contains hydrolyzed polymaleic anhydride, a compound A, a sulfonate copolymer, zinc salt and an optional copper corrosion inhibitor; wherein the compound A is 2-phosphonobutane-1, 2, 4-tricarboxylic acid and/or polyaminopolyether methylene phosphonic acid;
wherein the circulating cooling water is high-hardness water with the sum of calcium hardness and total alkalinity of more than 900mg/L, and the pH value of the circulating cooling water is 7.3-8.5.
Preferably, the sulfonate copolymer is a disulfonate copolymer or a trisulfonate copolymer.
Preferably, the copper corrosion inhibitor is an azole compound.
Preferably, the low-phosphorus composite corrosion and scale inhibitor further contains water in an amount of 30 to 80 parts by weight based on 100 parts by weight of the low-phosphorus composite corrosion and scale inhibitor.
The composite corrosion and scale inhibitor used in the circulating cooling water treatment method has excellent corrosion inhibition performance and can well stabilize Zn in water2+Ability to and CaCO3The corrosion and scale inhibitor has the advantages of less components and lower dosage, and is particularly suitable for the circulating cooling water treatment of high-hardness water quality, such as the circulating cooling water treatment of high-hardness water with the sum of calcium hardness and total alkalinity of more than 900 mg/L. In addition, the composite corrosion and scale inhibitor used in the method has low phosphorus content, and belongs to an environment-friendly corrosion and scale inhibitor.
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 first aspect of the invention provides a method for treating circulating cooling water, which comprises the steps of contacting the circulating cooling water with a low-phosphorus composite corrosion and scale inhibitor;
the low-phosphorus composite corrosion and scale inhibitor contains hydrolyzed polymaleic anhydride, a compound A, a sulfonate copolymer, zinc salt and an optional copper corrosion inhibitor; wherein the compound A is 2-phosphonobutane-1, 2, 4-tricarboxylic acid and/or polyaminopolyether methylene phosphonic acid;
wherein the circulating cooling water is high-hardness water with the sum of calcium hardness and total alkalinity of more than 900mg/L, and the pH value of the circulating cooling water is 7.3-8.5.
Preferably, the low-phosphorus composite corrosion and scale inhibitor consists of hydrolyzed polymaleic anhydride, a compound A, a sulfonate copolymer, zinc salt and an optional copper corrosion inhibitor.
In the process of research, the inventor of the invention finds that phosphorus-free medicament is adopted to hydrolyze polymaleic anhydride (HPMA) and low-phosphorus medicament 2-phosphineThe acid butane-1, 2, 4-tricarboxylic acid (namely 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid and PBTCA) and/or polyamino polyether methylene Phosphonic Acid (PAPEMP) are compounded with the zinc salt and sulfonate copolymer, so that the corrosion and scale inhibition performance is good, other organic phosphine agents can be omitted, and the dosage of PBTCA and/or PAPEMP is low. The hydrolyzed polymaleic anhydride and the zinc salt can play a role in corrosion inhibition, and the sulfonate copolymer can play a role in stabilizing the zinc salt in the circulating water, so that the zinc salt can be well stabilized in the water to play a role in corrosion inhibition; PBTCA and PAPEMP play roles in inhibiting scale and dispersing and preventing CaCO3Deposition of scale and suspended matter. The components are compounded for use, and each component can play a good synergistic effect. When the method is applied to circulating water treatment, the harm of a common organic phosphine agent to the environment due to high phosphorus content can be reduced. Therefore, the green environment-friendly corrosion and scale inhibitor is developed and used for treating high-hardness water with the sum of calcium hardness and total alkalinity of more than 900mg/L and the pH value of 7.3-8.5, has low working concentration and also obtains good effect.
In the invention, the hydrolyzed polymaleic anhydride (HPMA) is orange viscous liquid, the relative density is 1.2(20 ℃), the general relative molecular weight is 400-800, the average relative molecular weight is about 600, and the hydrolyzed polymaleic anhydride is acidic, can be ionized, can be dissolved in water, and has the decomposition temperature of over 330 ℃.
In the present invention, the object of the present invention can be achieved by using the above-mentioned components in combination and applying them to the treatment of water having high hardness as described above, and the content of each component is not particularly required. Preferably, in order to further improve the corrosion and scale inhibition effect, the content of the compound A is 5-100 parts by weight, the content of the sulfonate copolymer is 20-500 parts by weight, and the zinc salt is Zn based on 100 parts by weight of hydrolyzed polymaleic anhydride2+The content is 10-125 weight portions, and the content of the optional copper corrosion inhibitor is 5-75 weight portions; more preferably, the content of the compound A is 5-35 parts by weight, the content of the sulfonate copolymer is 80-185 parts by weight, and the zinc salt is Zn relative to 100 parts by weight of hydrolyzed polymaleic anhydride2+The content is 15-40 weight portions, and the content of the optional copper corrosion inhibitor is 10-50 weight portions.
The type of the sulfonate copolymer is not particularly limited in the present invention, and in order to further improve the corrosion and scale inhibition effect, it is preferable that the sulfonate copolymer is a disulfonate copolymer or a trisulfonate copolymer, and it is further preferable that the sulfonate copolymer is selected from the group consisting of an acrylic acid/2-acrylamide-2-methylpropanesulfonic acid copolymer, an acrylic acid/2-acrylamide-2-methylpropanesulfonic acid/hydroxypropyl acrylate copolymer, an acrylic acid/acrylate/sulfonate copolymer, a carboxylate/sulfonate/nonionic copolymer, an acrylic acid/styrene sulfonic acid copolymer, an acrylate/styrene sulfonic acid copolymer, an acrylic acid/allyl sulfonic acid copolymer, an acrylic acid/vinyl sulfonic acid copolymer, an acrylic acid/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, a salt of a carboxylic acid/sulfonic acid/nonionic copolymer, an acrylic acid/, At least one of acrylic acid/acrylamide/2-methyl-2 ' -acrylamidopropanesulfonic acid copolymer, acrylic acid/maleic acid/2-methyl-2 ' -acrylamidopropanesulfonic acid copolymer, and acrylic acid/acrylate-2-methyl-2 ' -acrylamidopropanesulfonic acid copolymer.
In the invention. The zinc salt can be water-soluble zinc salt with corrosion inhibition performance (the solubility is more than or equal to 1g/100g water at 20 ℃) which is common in the field, and the type and the content of the zinc salt are not particularly limited. Preferably, the zinc salt is zinc sulfate and/or zinc chloride.
In one embodiment of the invention, the low-phosphorous composite corrosion and scale inhibitor contains a copper corrosion inhibitor. The copper corrosion inhibitor can be various heterocyclic compounds with copper corrosion inhibition performance commonly seen in the field. The kind and content thereof are not particularly limited. Preferably, the copper corrosion inhibitor is an azole corrosion inhibitor, preferably at least one selected from benzotriazole, methylbenzotriazole and mercaptobenzotriazol.
The components of the low-phosphorus composite corrosion and scale inhibitor used in the method can be stored independently or in a mixed manner.
In a preferred embodiment, the low-phosphorous composite corrosion and scale inhibitor used in the method of the present invention consists of the above components. The individual components are commercially available and may be provided in the form of a solution, but the contents or weights referred to in the present invention are each in terms of an effective concentration (content or weight of solute).
According to a specific embodiment of the invention, the low-phosphorus composite corrosion and scale inhibitor used in the method of the invention also contains water, and the components of the low-phosphorus corrosion and scale inhibitor can be dissolved in water according to a proportion to prepare a corrosion and scale inhibitor solution for standby, or can be matched with water when in use. Preferably, the water content is 30 to 80 parts by weight, more preferably 50 to 70 parts by weight, based on 100 parts by weight of the low-phosphorous composite corrosion and scale inhibitor.
In the treatment method of the circulating cooling water of the present invention, the amount of the low-phosphorous composite corrosion and scale inhibitor is not particularly limited as long as the corrosion and scale inhibition effect on the cooling equipment is achieved. Preferably, the composite corrosion and scale inhibitor is used in an amount such that the concentration of the hydrolyzed polymaleic anhydride in the circulating cooling water is 2-10mg/L (for example, 2mg/L, 4mg/L, 6mg/L, 8mg/L, 10mg/L), the concentration of the compound A is 0.5-2mg/L (for example, 0.5mg/L, 0.8mg/L, 1mg/L, 1.2mg/L, 1.5mg/L, 2mg/L), the concentration of the sulfonate copolymer is 2-10mg/L (for example, 2mg/L, 4mg/L, 6mg/L, 8mg/L, 10mg/L), and Zn is used as the additive2+The concentration of zinc salt is 1-2.5mg/L (e.g., 1.0mg/L, 1.2mg/L, 1.5mg/L, 1.8mg/L, 2.0mg/L, 2.2mg/L, 2.5mg/L), and the concentration of copper corrosion inhibitor is optionally 0.5-1.5mg/L (e.g., 0.5mg/L, 0.8mg/L, 1.0mg/L, 1.2mg/L, 1.5 mg/L).
In the circulating cooling water treatment method provided by the invention, the components of the low-phosphorus corrosion and scale inhibitor can cooperate with each other, so that the corrosivity of high-hardness water can be effectively relieved under the condition of low consumption of the components, and Zn in the water can be well stabilized2+Ability of (C) and resistance of CaCO3The scale effect is obvious. Therefore, the low-phosphorus composite corrosion and scale inhibitor can obtain excellent corrosion and scale inhibition effects without using phosphorus-containing components.
In practical application, the low-phosphorus composite corrosion and scale inhibitor can be prepared before use, for example, the components are mixed according to the formula and then added into circulating cooling water; the components can also be added directly to the recirculating cooling water in accordance with the foregoing formulation without a mixing step. When directly added, the order of addition of the respective components is not particularly limited. In addition, the components can be mixed with water to be fully dissolved and then added into circulating cooling water.
In order to control the growth of microorganisms in the circulating cooling water, a bactericide can be added into the circulating cooling water when the circulating cooling water is treated, the bactericide can be added simultaneously or not simultaneously with the components of the low-phosphorus composite corrosion and scale inhibitor, and the type and the using amount of the bactericide used are well known to those skilled in the art and are not described again.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples,
hydrolyzed polymaleic anhydride (HPMA), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTCA), polyaminopolyether methylenephosphonic acid (PAPEMP), acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer (AA/AMPS), acrylic acid/acrylate/sulfonate copolymer (TH-2000), acrylic acid/2-acrylamide-2-methylpropanesulfonic acid/hydroxypropyl acrylate copolymer (AA/AMPS/HPA), acrylic acid/acrylamide/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, acrylic acid/vinylsulfonic acid copolymer, acrylic acid/styrenesulfonic acid copolymer, acrylic acid/styrene sulfonic acid copolymer, acrylic acid, Acrylate/styrene sulfonic acid copolymer, acrylic acid/allyl sulfonic acid copolymer, carboxylate-sulfonate-nonionic copolymer (TH-3100), all available from Tai and Water treatment, Inc., Shandong province.
The water quality of the test water is shown in Table 1. Wherein Ca2+And total alkalinity are all as CaCO3In which Ca is counted2+Representing calcium hardness. 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.
TABLE 1
| Quality of water | Ca2+(mg/l) | Total alkalinity (mg/l) | Cl-(mg/l) | PH | Conductivity (μ s/cm) |
| Test Water 1 | 256 | 345 | 78 | 7.9 | 1018 |
| Test Water 2 | 1050 | 160 | 221 | - | 1902 |
Determination of calcium carbonate Scale inhibition Properties
The calcium carbonate scale inhibition performance test is to determine the scale inhibition performance of the water treatment medicament composition according to the method of GB/T16632-2008 'determination of scale inhibition performance of water treatment agent-calcium carbonate deposition method'. The specific process is as follows:
to Ca2+Adding the reagent into test water with the concentration of 600mg/L and the alkalinity of 600mg/L, preserving the heat for 10 hours in a constant-temperature water bath at the temperature of 80 +/-1 ℃, sampling and analyzing the residual Ca in the water after cooling2+And simultaneously making blank samples, and calculating the scale inhibition rate.
The scale inhibition rate calculation formula is as follows:
c: actually measured Ca2+Concentration of (2)
C0: ca of blank2+Concentration of (2)
Determination of Corrosion inhibition Performance
The rotating hanging piece corrosion test is to measure the corrosion inhibition performance of the water treatment medicament composition according to the method of GB/T18175-. The specific process is as follows:
fixing a No. 20 high-quality carbon steel test piece on a coupon instrument, putting the test piece into test water 2 added with a corrosion and scale inhibitor, keeping the temperature at 45 +/-1 ℃, keeping the rotating speed at 75rpm 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 ═ CxDeltaW/A × T × ρ
C: the constants were calculated, and when mm/a (mm/year) is used, C is 8.76 × 107
Δ W: corrosion weight loss of test piece (gram)
A: area of test piece (cm)2)
T: corrosion test time (hours)
ρ: density of test piece material (kg/m)3)
Dynamic simulation test
The dynamic simulation test is to determine the effect of the water treatment medicament composition of the invention on simulating the water treatment of a circulating water field according to the method of HG/T2160-2008 cooling water dynamic simulation test method. The specific process is as follows:
in order to simulate the circulating water field condition, a dynamic simulation test is carried out. Annual corrosion rate B (mm/a) and adhesion rate mcm (mg/cm)3) The evaluation is carried out according to the following specific calculation formula:
the annual corrosion rate is calculated by the formula:
K：3.65×106
g: mass (g) reduced after tube corrosion
T: time of test run (d)
A: corrosion area of test tube (cm)2)
D: metal density (g/cm)3)
Adhesion rate calculation formula: mcm is 7.2 × 105(W1-W2)/A·t
W1: weight of test tube after test, g;
W2: weight of tube after washing, g;
a: internal surface area, cm, of test tube before test2；
t: test time, h.
Stabilization of zinc salt properties
Preparing Ca from distilled water2+The concentration is 250 mg.L-1Alkalinity of 250 mg.L-1，Zn2+Is 5 mg.L-1And 1g/L of sodium tetraborate as test water, adding a low-phosphorus corrosion and scale inhibitor, standing for 10 hours in a constant-temperature water bath at the temperature of 80 +/-1 ℃, sampling and analyzing residual Zn in the water2+And (4) simultaneously making blank samples, and calculating the zinc resistance rate.
The zinc resistance rate calculation formula is as follows: the zinc resistance rate is (C-C0)/(C1-C0). times.100%
C: actually measured Zn2+Concentration of (2)
C0: zn of blank2+Concentration of (2)
C1: zn in raw water2+Concentration of (2)
The higher the zinc inhibition rate, the better the stability of the zinc salt in water, which indicates that the performance of stabilizing the zinc salt is better.
Total phosphorus determination
See HG/T3540 & 2011 determination of total phosphate content in industrial circulating cooling water
Chemical oxygen consumption determination
See DL/T502.23-2006 section 23 of method for steam analysis in thermal power plants: in the determination of chemical oxygen consumption (potassium dichromate method), the solution with COD less than or equal to 30mg/L can be tested by 0.025mol/L potassium dichromate solution.
Example 1
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 6.0g of HPMA with effective content of 50%, 2.0g of PBTCA with effective content of 50%, 10.0g of acrylic acid/styrene sulfonic acid copolymer with active component of 30%, 8.3g of acrylic ester/styrene sulfonic acid copolymer with active component of 30%, and 5.3g of ZnSO4·7H2And O, adding 68.4g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 1 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 1 is added into test water 1 (for inhibiting CaCO) according to the concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be between 8.3 +/-0.2), and measuring the CaCO resistance of the low-phosphorus corrosion and scale inhibitor 1 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Example 2
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 9.0g of HPMA with effective content of 50%, 2.4g of PAPEMP with effective content of 40%, 20.0g of AA/AMPS with active component of 30%, and 6.6g of ZnSO4·7H2And O, adding 62g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 2 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 2 is added into test water 1 (for inhibiting CaCO) according to the concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be between 8.3 +/-0.2), and measuring the CaCO resistance of the low-phosphorus corrosion and scale inhibitor 2 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Example 3
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 12.0g ofHPMA with effective content of 50%, PAPEMP with effective content of 40% 2.8g, AA/AMPS/HPA with active component of 45% 20.0g, and ZnSO with active component of 10.6g4·7H2And O, adding 54.6g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 3 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 3 is added into test water 1 (for inhibiting CaCO) according to the concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be between 8.0 +/-0.2), and measuring the CaCO resistance of the low-phosphorus corrosion and scale inhibitor 3 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Example 4
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 15.0g of HPMA with effective content of 50%, 3.6g of PBTCA with effective content of 50%, 16.7g of TH-2000 with active component of 45%, and 8.8g of ZnSO4·7H2And O, adding 55.9g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 4 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 4 is added into test water 1 (for inhibiting CaCO) according to the concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be 7.8 +/-0.2), and measuring the CaCO resistance of the low-phosphorus corrosion and scale inhibitor 4 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Example 5
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 18.0g of HPMA with effective content of 50%, 3.2g of PAPEMP with effective content of 40%, 18.9g of TH-3100 with active component of 45%, and 7.7g of ZnSO4·7H2And O, adding 52.2g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 5 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 5 is added into test water 1 (for inhibiting CaCO) according to the concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding dilute sulfuric acid after adding medicine to adjust the pH value of the solution to be 7.8 +/-0.2), and measuring according to the methodCaCO (calcium carbonate) of fixed low-phosphorus corrosion and scale inhibitor 53The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Example 6
Weighing 10.0g of HPMA with effective content of 50%, 1.6g of PBTCA with effective content of 50%, 6.7g of acrylic acid/vinyl sulfonic acid copolymer with active component of 30%, 8.3g of acrylic acid/2-methyl-2' -acrylamide propane sulfonic acid copolymer with active component of 30%, and 6.6g of ZnSO4·7H2And O, adding 66.8g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 6 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 6 is added into test water 1 (for inhibiting CaCO) according to the concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be 7.5 +/-0.2), and measuring the CaCO resistance of the low-phosphorus corrosion and scale inhibitor 6 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Example 7
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 13.0g of HPMA with effective content of 50%, 2.0g of PAPEMP with effective content of 40%, 11.7g of acrylic acid/acrylamide/2-methyl-2' -acrylamidopropanesulfonic acid copolymer with active component of 30%, and 9.7g of ZnSO4·7H2And O, adding 63.6g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 7 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 7 is added into test water 1 (for inhibiting CaCO) according to the concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be between 7.5 +/-0.2), and measuring the CaCO resistance of the low-phosphorus corrosion and scale inhibitor 7 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Example 8
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
17.0g of 50% effective HPMA, 1.2g of 50% effective PBTCA and 11.7g of acrylic acid/allyl alcohol with 30% active ingredient were weighed outSulfamic acid copolymer, 11.7g of acrylic acid/acrylic ester/2-methyl-2' -acrylamidopropanesulfonic acid copolymer having an active ingredient of 30%, 4.8g of ZnCl2Adding 53.6g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 8 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 8 is added into test water 1 (for inhibiting CaCO) according to the concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be 7.5 +/-0.2), and measuring the CaCO resistance of the low-phosphorus corrosion and scale inhibitor 8 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Example 9
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
The low-phosphorus corrosion and scale inhibitor 9 was formulated as in example 4, except that 2.2g of TH-2000 was used and the total amount of the low-phosphorus corrosion and scale inhibitor was made up to 100.0g with water. The prepared low-phosphorus corrosion and scale inhibitor 9 is added into test water 1 (for inhibiting CaCO) according to the concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be 7.8 +/-0.2), and measuring the CaCO resistance of the low-phosphorus corrosion and scale inhibitor 9 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Example 10
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
The low-phosphorous corrosion and scale inhibitor 10 was formulated as in example 5, except that the amount of papamp was 0.8g, and the total amount of the low-phosphorous corrosion and scale inhibitor was made up to 100.0g with water. The prepared low-phosphorus corrosion and scale inhibitor 10 is added into test water 1 (for inhibiting CaCO) according to the concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be 7.8 +/-0.2), and measuring the CaCO resistance of the low-phosphorus corrosion and scale inhibitor 10 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Comparative example 1
The comparative example is used for explaining the corrosion and scale inhibition performance of the reference low-phosphorus corrosion and scale inhibitor
The formulation of the low phosphorus corrosion and scale inhibitor D1 was carried out as in example 4, except that PBTCA was not added and the total amount of low phosphorus corrosion and scale inhibitor was made up to 100.0g with water. The prepared low-phosphorus corrosion and scale inhibitor D1 is added into test water 1 (for inhibiting CaCO) at a concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be 7.8 +/-0.2), and measuring the CaCO inhibition of the low-phosphorus corrosion and scale inhibitor D1 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Comparative example 2
The comparative example is used for explaining the corrosion and scale inhibition performance of the reference low-phosphorus corrosion and scale inhibitor
The low phosphorus corrosion and scale inhibitor D2 was formulated as in example 4, except that the zinc salt was not added and the total amount of low phosphorus corrosion and scale inhibitor was made up to 100.0g with water. The prepared low-phosphorus corrosion and scale inhibitor D2 is added into test water 1 (for inhibiting CaCO) at a concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be 7.8 +/-0.2), and measuring the CaCO inhibition of the low-phosphorus corrosion and scale inhibitor D2 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Comparative example 3
The comparative example is used for explaining the corrosion and scale inhibition performance of the reference low-phosphorus corrosion and scale inhibitor
The low phosphorous corrosion and scale inhibitor D3 was formulated as in example 4, except that the HPMA was replaced with an equal amount of polyaspartic acid. The prepared low-phosphorus corrosion and scale inhibitor D3 is added into test water 1 (for inhibiting CaCO) at a concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be 7.8 +/-0.2), and measuring the CaCO inhibition of the low-phosphorus corrosion and scale inhibitor D3 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
Comparative example 4
The comparative example is used for explaining the corrosion and scale inhibition performance of the reference low-phosphorus corrosion and scale inhibitor
The formulation of the low phosphorous corrosion and scale inhibitor D4 was carried out as in example 4, except that HPMA was replaced by an equal amount of a copolymer of maleic acid and acrylamide. The prepared low-phosphorus corrosion and scale inhibitor D4 is added into test water 1 (for inhibiting CaCO) at a concentration of 100mg/L3Scale test) and test water 2 (for corrosion inhibition test, adding diluted sulfuric acid after adding medicine to adjust the pH value of the solution to be 7.8 +/-0.2), and measuring the CaCO inhibition of the low-phosphorus corrosion and scale inhibitor D4 according to the method3The scale formation rate, corrosion rate and zinc inhibition rate are shown in Table 2.
TABLE 2
| Examples/comparative examples | Corrosion rate (mm. a-1) | CaCO-resistant3Fouling rate (%) | Zinc resistance (%) |
| Example 1 | 0.046 | 78.1 | 53.6 |
| Example 2 | 0.034 | 83.7 | 60.8 |
| Example 3 | 0.019 | 92.3 | 81.6 |
| Example 4 | 0.011 | 98.9 | 82.4 |
| Comparative example 1 | 0.384 | 49.3 | 76.1 |
| Comparative example 2 | 0.356 | 43.6 | 45.3 |
| Comparative example 3 | 0.101 | 64.9 | 65.5 |
| Comparative example 4 | 0.098 | 61.2 | 60.3 |
| Example 5 | 0.014 | 99.6 | 84.1 |
| Example 6 | 0.048 | 82.1 | 64.3 |
| Example 7 | 0.026 | 87.2 | 59.0 |
| Example 8 | 0.018 | 93.6 | 70.6 |
| Example 9 | 0.296 | 56.3 | 23.6 |
| Example 10 | 0.069 | 70.2 | 80.3 |
As can be seen from the data in Table 2, the low-phosphorus composite corrosion and scale inhibitor of the invention has good comprehensive performance, good corrosion inhibition performance and CaCO inhibition3Scale rate and stabilization of Zn in water2+The ability of the cell to perform.
Simulation experiment 1
To simulate the field, dynamic simulation tests were performed. The dynamic simulation test method is carried out according to the chemical industry standard HG/T2160-2008 of the people's republic of China, and the control parameters are as follows:
water quality: experimental Water 2 in Table 1
The concentration multiple is controlled by calcium hardness and total alkalinity value:
concentrating the A tower: 900-1200mg/L B column: 900-1200mg/L
Flow rate: 1.0m/s
Medicament: tower A: comparative example 1 low-phosphorus composite corrosion and scale inhibitor D2
Tower B: low-phosphorus composite corrosion and scale inhibitor 6 of example 4
Inlet temperature: temperature difference of 32. + -. 1 ℃: 10 deg.C
pH value control range: tower A: 7.8. + -. 0.2B column: 7.8 +/-0.2
The corrosion rate and tube adhesion rate are shown in table 3.
The results of the water quality index measured after the dynamic simulation test are shown in Table 4.
TABLE 3
TABLE 4
The corrosion speed of the carbon steel pipe wall of the open system is less than or equal to 0.075mm/a as specified in national standard GB 50050-2007 design Specification for Industrial circulating Cooling Water treatment 3.1.6; in the cooling water analysis and test method compiled by the production department and the development department of the general company of petrochemical industry, the laboratory small simulation test method stipulates that the corrosion speed of carbon steel is in a good grade between 0 and 0.028mm/a, in a good grade between 0.028 and 0.056mm/a and in an allowable grade between 0.056 and 0.070 mm/a; the adhesion speed is of the order of "good" at 0-6mcm, of "good" at 6-15mcm and of "permissible" at 15-20 mcm.
Therefore, when the sum of the calcium hardness and the total alkalinity is more than 900mg/L, the corrosion rate of the test tube is 0.019mm/a, the good-grade standard of the middle petrochemical industry is achieved, the adhesion rate is 3.8 mm, the good-grade standard is achieved, and the corrosion and scale inhibition effects of the low-phosphorus composite scale and corrosion inhibitor are better than those of the formula of the comparative example. And the results of measuring the total phosphorus and COD of the circulating water after 15 days of operation show that the total phosphorus is almost absent, the COD value is lower, and the total phosphorus and the COD value meet the requirements in the discharge standard GB31570-2015 of pollutants for the petrochemical industry, namely the total phosphorus discharge (measured by P) is less than or equal to 1.0mg/L, and the chemical oxygen consumption is less than or equal to 60 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 (12)
1. A treatment method of circulating cooling water is characterized by comprising the steps of contacting the circulating cooling water with a low-phosphorus composite corrosion and scale inhibitor or a low-phosphorus composite corrosion and scale inhibitor solution;
the low-phosphorus composite corrosion and scale inhibitor consists of hydrolyzed polymaleic anhydride, a compound A, a sulfonate copolymer and zinc salt; wherein the compound A is 2-phosphonobutane-1, 2, 4-tricarboxylic acid and/or polyaminopolyether methylene phosphonic acid;
the low-phosphorus composite corrosion and scale inhibitor solution consists of the low-phosphorus composite corrosion and scale inhibitor and water, wherein the content of the water is 30-80 parts by weight based on 100 parts by weight of the low-phosphorus composite corrosion and scale inhibitor;
wherein the circulating cooling water is high-hardness water with the sum of calcium hardness and total alkalinity of more than 900mg/L, and the pH value of the circulating cooling water is 7.3-8.5;
wherein, relative to 100 weight parts of hydrolyzed polymaleic anhydride, the content of the compound A is 5 to 35 weight parts, the content of the sulfonate copolymer is 80 to 185 weight parts, and the zinc salt is Zn2+The content is 15-40 weight portions.
2. The method of claim 1 wherein the sulfonate copolymer is a disulfonate copolymer or a trisulfonate copolymer.
3. The method of claim 2, wherein the sulfonate copolymer is selected from the group consisting of acrylic acid/2-acrylamido-2-methylpropanesulfonic acid copolymer, acrylic acid/2-acrylamido-2-methylpropanesulfonic acid/hydroxypropyl acrylate copolymer, acrylic acid/acrylate/sulfonate copolymer, carboxylate/sulfonate/nonionic copolymer, acrylic acid/styrenesulfonic acid copolymer, acrylate/styrenesulfonic acid copolymer, acrylic acid/allylsulfonic acid copolymer, acrylic acid/vinylsulfonic acid copolymer, acrylic acid/2-methyl-2 '-acrylamidopropanesulfonic acid copolymer, acrylic acid/acrylamide/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, and mixtures thereof, At least one of acrylic acid/maleic acid/2-methyl-2 '-acrylamidopropanesulfonic acid copolymer and acrylic acid/acrylate-2-methyl-2' -acrylamidopropanesulfonic acid copolymer.
4. The method according to any one of claims 1-3, wherein the zinc salt is selected from zinc sulphate and/or zinc chloride.
5. The method according to any one of claims 1 to 3, wherein the low-phosphorus composite corrosion and scale inhibitor or the low-phosphorus composite corrosion and scale inhibitor solution is used in an amount such that the concentration of hydrolyzed polymaleic anhydride in the circulating cooling water is 2 to 10mg/L, the concentration of compound A is 0.5 to 2mg/L, the concentration of sulfonate copolymer is 2 to 10mg/L, and Zn is used as per liter of the circulating cooling water2+The concentration of the zinc salt is 1-2.5 mg/L.
6. A treatment method of circulating cooling water is characterized by comprising the steps of contacting the circulating cooling water with a low-phosphorus composite corrosion and scale inhibitor or a low-phosphorus composite corrosion and scale inhibitor solution;
the low-phosphorus composite corrosion and scale inhibitor consists of hydrolyzed polymaleic anhydride, a compound A, a sulfonate copolymer, a zinc salt and a copper corrosion inhibitor; wherein the compound A is 2-phosphonobutane-1, 2, 4-tricarboxylic acid and/or polyaminopolyether methylene phosphonic acid;
the low-phosphorus composite corrosion and scale inhibitor solution consists of the low-phosphorus composite corrosion and scale inhibitor and water, wherein the content of the water is 30-80 parts by weight based on 100 parts by weight of the low-phosphorus composite corrosion and scale inhibitor;
wherein the circulating cooling water is high-hardness water with the sum of calcium hardness and total alkalinity of more than 900mg/L, and the pH value of the circulating cooling water is 7.3-8.5;
wherein, relative to 100 weight parts of hydrolyzed polymaleic anhydride, the content of the compound A is 5 to 35 weight parts, the content of the sulfonate copolymer is 80 to 185 weight parts, and the zinc salt is Zn2+The content is 15-40 weight portions, and the content of the copper corrosion inhibitor is 10-50 weight portions.
7. The method of claim 6 wherein the sulfonate copolymer is a disulfonate copolymer or a trisulfonate copolymer.
8. The method of claim 7, wherein the sulfonate copolymer is selected from the group consisting of acrylic acid/2-acrylamido-2-methylpropanesulfonic acid copolymer, acrylic acid/2-acrylamido-2-methylpropanesulfonic acid/hydroxypropyl acrylate copolymer, acrylic acid/acrylate/sulfonate copolymer, carboxylate/sulfonate/nonionic copolymer, acrylic acid/styrenesulfonic acid copolymer, acrylate/styrenesulfonic acid copolymer, acrylic acid/allylsulfonic acid copolymer, acrylic acid/vinylsulfonic acid copolymer, acrylic acid/2-methyl-2 '-acrylamidopropanesulfonic acid copolymer, acrylic acid/acrylamide/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, and mixtures thereof, At least one of acrylic acid/maleic acid/2-methyl-2 '-acrylamidopropanesulfonic acid copolymer and acrylic acid/acrylate-2-methyl-2' -acrylamidopropanesulfonic acid copolymer.
9. The method according to any one of claims 6-8, wherein the zinc salt is selected from zinc sulphate and/or zinc chloride.
10. The method according to any one of claims 6-8, wherein the copper corrosion inhibitor is an azole compound.
11. The method of claim 10, wherein the copper corrosion inhibitor is selected from at least one of benzotriazole, methylbenzotriazole, and mercaptobenzotriazol.
12. The method according to any one of claims 6 to 8 and 11, wherein the low-phosphorus composite corrosion and scale inhibitor or the low-phosphorus composite corrosion and scale inhibitor solution is used in an amount such that the concentration of hydrolyzed polymaleic anhydride, the concentration of compound a, the concentration of sulfonate copolymer, the concentration of zinc salt in Zn2+, and the concentration of copper corrosion inhibitor are respectively 2 to 10mg/L, 0.5 to 2mg/L, 0.5 to 1.5mg/L, and 0 to 10mg/L, respectively, in the circulating cooling water, per liter of circulating cooling water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711070738.5A CN109748407B (en) | 2017-11-03 | 2017-11-03 | Method for treating circulating cooling water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711070738.5A CN109748407B (en) | 2017-11-03 | 2017-11-03 | Method for treating circulating cooling water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109748407A CN109748407A (en) | 2019-05-14 |
| CN109748407B true CN109748407B (en) | 2020-12-18 |
Family
ID=66398612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711070738.5A Active CN109748407B (en) | 2017-11-03 | 2017-11-03 | Method for treating circulating cooling water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109748407B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0231894A (en) * | 1988-07-22 | 1990-02-01 | Mitsubishi Gas Chem Co Inc | Agent for preventing scaling in cooling water system |
| CN102674570A (en) * | 2011-03-15 | 2012-09-19 | 中国石油化工股份有限公司 | Composite low-phosphorus corrosion and scale inhibitor and application thereof |
| CN102718329A (en) * | 2012-06-28 | 2012-10-10 | 山东省泰和水处理有限公司 | Composite corrosion inhibition antisludging agent for ultralow rigidity circulation cooling water and preparation method thereof |
| CN106430648A (en) * | 2016-10-26 | 2017-02-22 | 国家开发投资公司 | Antisludging agent used in highly hard and high alkalinity water and preparing method and antisludging method thereof |
| CN106809962A (en) * | 2015-12-01 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of composite slow-corrosion scale resistor and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63231894A (en) * | 1987-03-18 | 1988-09-27 | 松下電工株式会社 | Divided heat-sensitive panel heater |
-
2017
- 2017-11-03 CN CN201711070738.5A patent/CN109748407B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0231894A (en) * | 1988-07-22 | 1990-02-01 | Mitsubishi Gas Chem Co Inc | Agent for preventing scaling in cooling water system |
| CN102674570A (en) * | 2011-03-15 | 2012-09-19 | 中国石油化工股份有限公司 | Composite low-phosphorus corrosion and scale inhibitor and application thereof |
| CN102718329A (en) * | 2012-06-28 | 2012-10-10 | 山东省泰和水处理有限公司 | Composite corrosion inhibition antisludging agent for ultralow rigidity circulation cooling water and preparation method thereof |
| CN106809962A (en) * | 2015-12-01 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of composite slow-corrosion scale resistor and its preparation method and application |
| CN106430648A (en) * | 2016-10-26 | 2017-02-22 | 国家开发投资公司 | Antisludging agent used in highly hard and high alkalinity water and preparing method and antisludging method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109748407A (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109748402B (en) | Low-phosphorus composite corrosion and scale inhibitor, application thereof and treatment method of circulating cooling water | |
| LeChevallier et al. | Examining the relationship between iron corrosion and the disinfection of biofilm bacteria | |
| CN102732892B (en) | Metal corrosion inhibitor composition, metal corrosion inhibitor thereof and application thereof | |
| CN109748400B (en) | Phosphorus-free composite corrosion and scale inhibitor, application thereof and treatment method of circulating cooling water | |
| CN106745847B (en) | Composite corrosion and scale inhibitor and preparation method thereof | |
| CN108623020A (en) | A kind of novel corrosion-retarding antisludging agent and the preparation method and application thereof | |
| CN109748401B (en) | Method for treating circulating cooling water | |
| CN105084561B (en) | Non-phosphorus scale and corrosion inhibitor containing fulvic acid and preparation method thereof | |
| CN112047498A (en) | Circulating water phosphorus-free corrosion and scale inhibitor and preparation method thereof | |
| CN104894566A (en) | Composite corrosion inhibitor for seawater circulation cooling system carbon steel material anticorrosion | |
| CN107304077B (en) | Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof | |
| CN111472006A (en) | Corrosion inhibition composition for carbon steel pipeline of nuclear power fire-fighting water system, cleaning composition and preparation method | |
| Peng et al. | Principal factors affecting microbiologically influenced corrosion of carbon steel | |
| CN109748406B (en) | Method for treating circulating cooling water | |
| CN109133386B (en) | Method for treating circulating cooling water | |
| CN101709473B (en) | High-temperature water-soluble corrosion inhibitor | |
| CN109748407B (en) | Method for treating circulating cooling water | |
| CN109294545A (en) | A kind of water solubility corrosion inhibitor for oil field and preparation method thereof | |
| CN111072165B (en) | Composite scale and corrosion inhibitor and application thereof in low hard water | |
| CN109748404B (en) | Method for treating circulating cooling water | |
| CN109133390B (en) | Method for treating circulating cooling water | |
| CN111039422B (en) | Composite scale and corrosion inhibitor suitable for high-hardness water and application thereof | |
| CN1631814A (en) | Scale removal method adapted for circulating and cooling water system | |
| CN111039424B (en) | Composite scale and corrosion inhibitor suitable for low-hardness water and application thereof | |
| CN111039425B (en) | Composite scale and corrosion inhibitor suitable for natural pH operation 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 |