SG184694A1 - Method of preventing metal corrosion in cooling water system - Google Patents
Method of preventing metal corrosion in cooling water system Download PDFInfo
- Publication number
- SG184694A1 SG184694A1 SG2012023255A SG2012023255A SG184694A1 SG 184694 A1 SG184694 A1 SG 184694A1 SG 2012023255 A SG2012023255 A SG 2012023255A SG 2012023255 A SG2012023255 A SG 2012023255A SG 184694 A1 SG184694 A1 SG 184694A1
- Authority
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- Singapore
- Prior art keywords
- water system
- copolymer
- cooling water
- zinc
- metal corrosion
- Prior art date
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- 239000000498 cooling water Substances 0.000 title claims abstract description 51
- 238000005260 corrosion Methods 0.000 title claims abstract description 43
- 230000007797 corrosion Effects 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 30
- 230000003405 preventing effect Effects 0.000 title claims description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 76
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 21
- 238000011282 treatment Methods 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 17
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 17
- 239000011976 maleic acid Substances 0.000 claims abstract description 17
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000001174 sulfone group Chemical group 0.000 claims abstract description 13
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 150000003457 sulfones Chemical group 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- CLHYKAZPWIRRRD-UHFFFAOYSA-N 1-hydroxypropane-1-sulfonic acid Chemical compound CCC(O)S(O)(=O)=O CLHYKAZPWIRRRD-UHFFFAOYSA-N 0.000 claims 1
- FKOZPUORKCHONH-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid Chemical compound CC(C)CS(O)(=O)=O FKOZPUORKCHONH-UHFFFAOYSA-N 0.000 claims 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical group CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- -1 azole compound Chemical class 0.000 description 1
- BOOMOFPAGCSKKE-UHFFFAOYSA-N butane-2-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCC(C)S(O)(=O)=O BOOMOFPAGCSKKE-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- VMXUWOKSQNHOCA-UKTHLTGXSA-N ranitidine Chemical compound [O-][N+](=O)\C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-UKTHLTGXSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
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
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/105—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances combined with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
To effectively inhibit corrosion of a metal member in a cooling water system in which a non-phosphorus, zinc treatment is performed. The following components (A), (B), and (C) are caused to be present in a cooling water system in which a non-phosphorus, zinc treatment is performed. (A) A copolymer of acrylic acid and a sulfone group-containing monomer, in which, preferably, the sulfone group-containing monomer is 2-acrylamide-2-methylpropanesulfonic acid and/or 3-allyloxy-2-hydroxypropanesulfonic acid, the molecular weight is 500 to 50,000, and the molar ratio of acrylic acid to the sulfone group-containing monomer is 7:3 to 9:1. (B) A copolymer of maleic acid and isobutylene, in which, preferably, the molecular weight is 10,000 to 50,000, and the molar ratio of maleic acid to isobutylene is 5:5 to 8:2. (C) A zinc compound.Representative Drawing: Fig. 2
Description
METHOD OF PREVENTING METAL CORROSION IN COOLING WATER SYSTEM
[0001]
The present invention relates to a method of preventing corrosion of a metal member in a cooling water system in which phosphorus cannot be used because of environmental regulations or the like and zinc is used as a corrosion- preventing component in the case where water treatment is performed in the cooling water system.
[0002]
Metal corrosion in cooling water systems can cause serious economic problems, such as a decrease in production efficiency and emergency shutdown of plants. Accordingly, various methods have been proposed to prevent corrosion of metals in cooling water systems. As a method of preventing metal corrosion, high-concentration addition of phosphorus and zinc is generally performed.
However, with the recent tightening of environmental regulations, there has been an increase in the number of cases where phosphorus cannot be used in cooling water systems. As countermeasures against this, various non- phosphorus, non-zinc treatments and non-phosphorus, zinc treatments have been performed. However, the corrosion-
I i preventing effects of these treatments are insufficient compared with phosphorus and zinc treatments in many cases.
[0003]
Regarding the copolymers used in the present invention, the following reports have been made available. However, none of them is related to the use of copolymers in cooling water systems in which a non-phosphorus, zinc treatment is performed.
[0004]
Patent Literature 1 describes a method of preventing metal corrosion using a copolymer of a carboxyl group- containing monomer and a sulfone group-containing monomer, a copolymer of maleic acid and an alkene, and an azole compound in combinaticn in a cooling water system in which a non-phosphorus, non-zinc treatment is performed. However,
Patent Literature 1 dces nct specifically describe the case where a zinc compound is used tcgether with copolymers. f0005]
Patent Literatures 2 and 3 describe the corrosion- preventing effects of a copolymer, such as a terpolymer of acrylic acid/acrylamide methylpropanesulfonic acid/isobutylene, or silica scale-inhibiting effects in a ccoling water system in which a non-phosphorus, non-zinc treatment 1s performed. However, Patent Literatures 2 and 3 do not relate to a combination of polymers and a zinc ,
compound being used tcgether. [Patent Literature] [Patent Literature 1] W02005/123981 [Patent Literature 2] Japanese Patent Publication 7- 268666 A [Patent Literature 3] Japanese Patent 3055815
Object and Summary of Invention
[0006]
It is an object of the present invention to provide a method of preventing metal corrosion in a cooling water system, which is a method of effectively inhibiting corrosion of a metal member in a cocling water system in which a non-phosphorus, zinc treatment is performed.
[0007]
The present inventors have performed thorough studies in order to solve the problem described above, and have found that, by using two types of copolymers having a specific functional group exhibiting a metal corrosion- preventing effect and a zinc compound in combination, the corrosion-preventing effect is markedly improved compared with the case where a treatment is performed using any one of the components alone.
[0008]
The present invention has been achieved on the basis of the finding described above. A method of preventing metal corrosion in a cooling water system according to the present invention (claim 1), which is a method of preventing corrosion of a metal member in a cooling water system in which a non-phosphorus, zinc treatment is performed, includes causing the following components (A), (B}, and (C) to be present in the water system: (A) a copolymer of acrylic acid and a sulfone group- containing monomer (hereinafter described as the "copolymer (A)"), (B) a copolymer of maleic acid and isobutylene (hereinafter described as the "copolymer (B)"), and (C) a zinc compound.
[0009] : In the method of preventing metal corrosion in a cooling water system of the present invention, according to
Claim 1, the sulfone group-containing monomer of the copolymer (A) may be Z-acrylamide-Z-methylpropanesulfonic acid and/or 3-allyloxy-2-hydroxypropanesulfonic acid.
[0010]
In the method of preventing metal corrosion in a cooling water system of the present invention, according to
Claim 1 cr 2, the molecular weight of the copolymer (A) may be 500 to 50,000, and the molar ratio of acrylic acid to the sulfone group-~containing monomer may be 7:3 to 9:1. : [0011] - 4 - i
In the method of preventing metal corrosion in a cooling water system of the present invention, according to any one of Claims 1 to 3, the molecular weight of the copolymer (B) may be 10,000 to 50,000, and the molar ratio of maleic acid to isobutylene may be 5:5 to 8:2.
[0012]
In the method of preventing metal corrosion in a cooling water system of the present invention, according to any one of Claims 1 to 4, the zinc compound may be zinc chloride and/or zinc sulfate.
[0013]
In the method of preventing metal corrosion in a cooling water system of the present invention, according to any one of Claims 1 to 5, the copolymer (A) and the copolymer (B) may be added in the amcunt cf 5 to 50 mg-solid content/L in total relative to the blow water amount of the water system.
[0014]
In the method of preventing metal corrosion in a cooling water system of the present invention, according to any one of Claims 1 to 6, the zinc compound may be added in the amount of 0.5 mg/L or more relative to the blow water amount of the water system.
[0015]
In the method of preventing metal corrosion in a cooling water system of the present invention, according tc any one of Claims 1 to 7, the calcium hardness of the water system may be 100 to 1,000 mg-CaC0O3;/L, and the concentration of corrosive ions (total of the concentration of chloride ions and the concentration of sulfate ions) may be 2,000 mg/L or less.
Advantageous Effects of Invention [001g]
According to the present invention, by using the copclymer (A), the copolymer (B), and the zinc compound in combination, corrosion of a metal member in a cooling water system in which a non-phosphorus, zinc treatment is performed can be effectively inhibited. That is, according to the present invention, while the anode reaction of a corroding portion is inhibited by carboxyl groups contained in the copolymer (A) and the copolymer (B), the cathode reaction is inhibited by the zinc compound, and furthermore, the zinc compound can be maintained in water by the action of sulfone groups of the copolymer (B), thus providing a very good effect of synergizing corrosion-preventing effects.
[0017]
In particular, by using predetermined amounts of the copolymer (A) and the copolymer (B) and by maintaining the concentration of the zinc compound in the water system at a required concentration, it is possible to fully enhance the corrosion-preventing effect in the non-phosphorus, zinc treatment even in a water system having high hardness under highly saline conditions.
Consequently, the present invention realizes an environmental load reduction treatment with an enhanced corrosion-preventing effect for a metal member in a cooling water system.
[0018]
Fig. 1 is a flow diagram illustrating a testing apparatus used in Examples 1 and 2 and Comparative Examples 1 to 6.
Fig. 2 is a graph showing the results of Examples 1 and 2 and Comparative Examples 1 to 6.
Fig. 3 is a flow diagram illustrating a testing apparatus used in Examples 3 and 4 and Comparative Examples 7 and 8.
[0019]
Embodiments cof a method of preventing metal corrosion in a cooling water system according to the present invention will be described in detail below.
[6020]
In the present invention, by causing the following components (A), (B), and (C) to be present in a cooling water system in which a non-phosphorus, zinc treatment is performed, corrosion of a metal member in the water system is inhibited: (A) a copolymer of acrylic acid and a sulfone group- containing monomer (hereinafter described as the "copolymer (A)"), (B) a copolymer of maleic acid and isobutylene {hereinafter described as the "copelymer {(B)"), and (C) a zinc compound.
[0021]
The copolymer (A) is a copolymer of acrylic acid and a sulfone group-containing monomer, and the sulfone group- containing monomer of the copolymer (A) is not particularly limited as long as it contains sulfone groups. As a preferable sulfone group-containing monomer, 2-acrylamide-2Z- methylpropanesulfonic acid and/or 3-allyloxy-2- hydroxypropanesulfonic acid may be mentioned.
[0022]
The molar ratio of acrylic acid to the sulfone group- containing monomer in the copolymer (A) is preferably 7:3 to 9:1 from the standpoint of obtaining the action of carboxyl groups of acrylic acid and the action of sulfone groups of the sulfone group-containing monomer in a well-balanced manner.
[0023]
When the molecular weight of the copolymer (A) is excessively small, the effect of inhibiting calcium carbonate scales decreases. When the molecular weight of the copolymer (A) is excessively large, gelation with calcium occurs. Therefore, the molecular weight of the copolymer (A) is preferably 500 to 50,000, and in particular, 5,000 to 20,000.
[0024]
As the copolymer (A), two or more types of copolymers having different molar ratios of acrylic acid to the sulfone group-containing monomer or different molecular weights may be used.
[0025]
On the other hand, the copolymer (B} is a copolymer of maleic acid and isobutylene, and the molar ratio of maleic acid to isobutylene in the copolymer (B) is preferably 5:5 to 8:2, and in particular, 1:1, from the standpoint of obtaining the action of carboxyl groups of maleic acid and the hydrophobic action of iscbutylene in a well-balanced manner.
[0026]
When the molecular weight of the copolymer (B) is excessively small, the effect of inhibiting calcium carbonate scales decreases. When the molecular weight of the copolymer {(B) is excessively large, gelation with calcium cccurs. Therefore, the molecular weight of the copolymer (B) is preferably 10,000 to 50,000, and in particular, 30,000 to 50,000.
[0027]
As the copolymer (B), two or more types of copolymers having different molar ratios of maleic acid to isobutylene or different molecular weights may be used.
[0028]
The zinc compound is not particularly limited, but one or two or more zinc compounds, such as zinc chloride and zinc sulfate, may be used.
[0029]
In the present invention, the amount of the copolymer (A) to be added to the water system is 3 to 25 mg-solid content/L relative to the blow water amount, and the amount of the copolymer (B) to be added to the water system is 3 to mg-solid content/L relative to the blow water amount.
The total amount of the copolymer (A) and the copolymer (B) to be added is preferably 5 to 50 mg-solid content/L relative to the blow water amount. Regarding the addition amount ratio of the copolymer (A) to the copolymer (B), in order to obtain the synergetic effect of the combined use thereof, the addition amount ratio by weight of the copolymer {A) tc the copolymer {B) is preferably 1:0.5 to 1:2.
[0030]
Furthermore, preferably, the zinc compound is added at a zinc concentration of 0.5 mg/L or mere, and in particular, about 0.5 to 3 mg/L, relative to the blow water amount of the water system.
[0031]
Note that the addition amount relative to the blow water amount is usually equal to the standard control concentration in the cooling water system.
[0032]
In the present invention, two or three of the copolymer (A), the copolymer (B), and the zinc compound may be mixed in advance and the resulting mixture may be added to the cooling water system, or each of these components may be added separately to the cooling water system. Although the point of addition is not particularly limited, addition is usually made fo a cooling water tank in the cooling water system.
[0033]
In the method of preventing metal corrosion in a cooling water system of the present invention, a very excellent corrosion-preventing effect is obtained by combined use of the copolymer (A), the copolymer (B), and the zinc compound. Therefore, the corrosion-preventing effect is effectively exhibited even in a water system naving a high corrosion tendency, such as a water system having a high calcium hardness or a water system having a high concentration of corrosive ions. As the water quality of the cooling water system to which the present invention is applied, preferably, the calcium hardness is 100 to 1,000 mg-CaCO3/L, and the concentration of corrosive ions (total of the concentration of chloride ions and the concentration of sulfate ions) is 2,000 mg/L or less.
Examples and Comparative Examples
[0034]
The present invention will be described more specifically on the basis of examples.
[0035]
In Examples and Comparative Examples below, the followings were used as the copolymer (A) and the copolymer {B): <Copolymer (A}>
Copolymer of acrylic acid (AA) and 2-acrylamide-2- methylpropanesulfonic acid (AMPS), molecular weight: 10,000, molar ratio of AA to AMPS: 8:2 (hereinafter abbreviated as "AR/AMPS')
Copolymer of acrylic acid (AA) and 3=-allyloxy-2- hydroxypropanesulfonic acid (HAPS), molecular weight: 10,000, molar ratio of AA to HAPS: 8:2 (hereinafter abbreviated as "AA/HAPS")
<Copolymer (B):>
Copolymer of maleic acid (MA) and iscbutylene (IB), molecular weight: 40,000, molar ratic of MA to IB: 1:1 (hereinafter abbreviated as "MA/IB")
As the zinc compound, zinc sulfate was used.
Furthermore, for comparison, a homopolymer of maleic acid {molecular weight: 500, hereinafter abbreviated as "MA") was used. [Examples 1 and 2, Comparative Examples 1 to 6] [003¢]
Using a testing apparatus illustrated in Fig. 1, testing was performed in accordance with the procedure described below.
[0037]
A 5 wt% aquecus sodium bicarbonate solution was used in order to adjust the M-alkalinity, polymers shown in Table 1 were used, a 10 wt% aqueous calcium chloride solution was used in order to adjust the calcium hardness, a 10 wt% aqueous sodium chloride solution was used in order to adjust the chloride ion concentration, and an aqueous sodium sulfate solution was used in order to adjust the sulfate ion concentration. Furthermore, sulfuric acid was used for pH adjustment, and a 10 wt% aqueous zinc sulfate sclution was used as the zinc compound solution. These components were added to pure water to prepare synthetic water having the water quality described below.
[0038] <Synthetic water quality>
M-alkalinity: 200 mg/L as CaCOjz
Polymer concentration: concentration shown in Table 1
Calcium hardness: 500 mg/L as CaCOjz
Chloride ion concentration: 500 mg/L
Sulfate ion concentration: 500 mg/L
Zinc concentration: 2 mg/L pH: 8.6 [0G39] [Table 1]
Polymer concentration (mg—sclid content/L)
AA/AMPS | AA/HAPS | MA/IB a | ws | - [ws | os eamer| | am us | = | 5
Comparative 125 375 5
Example 1
Comparative 375 125 5
Example 2
Comparative 3.75 195 5
Example 3
Comparative 5
Example 4
Comparative 5
Example 5
Comparative 5
Example 6
[0040]
The synthetic water was placed in a mother liquid tank 1, and the synthetic water in the mother liquid tank 1 was transferred to a test tank (retained water amount 50 L) 2.
The synthetic water was circulated in the apparatus from the test tank 2 using a pump 3 at a flow rate of 0.5 m/sec, and the water was made to overflow such that the residence time was 80 hours. A carbon steel tube 4 and a corrosion sensor were installed in the circulation system, and the corrosion rate (mdd) was measured with the corrosion sensor 5.
The test period was set at seven days.
The results are shown in Fig. 2.
[0041]
As is evident from Fig. 2, in the cooling water system having high hardness and high salinity, by combining the copolymer (A) with the copolymer (B), the corrosion rate at the time of combined use of zinc is significantly decreased, and a markedly excellent corrosion-preventing effect is obtained compared with the case where another polymer is used. [Examples 3 and 4, Comparative Examples 6 and 7]
[0042]
Concentrated industrial water was produced using a testing apparatus illustrated in Fig. 3, and used as test water having the water quality shown in Table 2, and a test was carried out.
In Fig. 3, reference numeral 11 designates a cooling tower, reference numeral 12 designates a cooling water tank, reference numerals 13A and 13B each designate a test piece column, reference numerals 14A and 14B each designate a heat exchanger, reference numerals 152A and 15B each designate an electric heater, reference numerals 16A and 16B each designate a heat-transfer tube, reference numerals P;, Pa, and P3; each designate a chemical feed pump, reference numeral Ps, designates a blow pump, and reference numeral Py designates a circulation pump. The cecoling water in the cooling water tank 12 is circulated by the circulation pump
Ps into a circulating water system provided with the test piece columns 13A and 13B and into a circulating water system provided with the heat exchangers 14A and 14B. The circulating cooling water on the heat exchangers 14A and 14B side. is cooled with the cooling tower 11, and then returned to the cooling water tank 12. - le -
[0043] [Table 2]
Gatun trtvess nf onooco) | am
[0044]
Using the chemical feed pumps P; to Pj, the polymers shown in Table 3 were added into the cooling water tank 12 at the concentrations shown in Table 3, and an aqueous zinc sulfate soclution was added such that the zinc concentration in the water system was 2 mg/L.
[0045]
Subsequently, the test water was circulated using the circulation pump Ps, and then thermal load was applied in the heat exchangers 14A and 14B. The test was carried out under the two conditions described below. Under each condition, the corrosion rate of the test pieces in the test piece columns 13A and 13B and the pitting corrosion depth in the heat-transfer tubes 16A and 16B after the test were measured. The test period was set at 14 days.
Condition I: flow rate 0.5 m/sec
AT = 10°C (heat transfer amount = 46,000 kcal/m?-hr)
Condition II: flow rate 0.25 m/sec
AT = 5°C {heat transfer amount = 13,000 kcal/m°- hr)
The flow rate means the flow rate of circulating cooling water flowing through the test piece columns 13a and 13B and the heat—-transfer tubes 106A and 16B, and AT is the difference between the heat exchanger outlet temperature and the inlet temperature of circulating cooling water flowing through the heat-transfer tubes 16A and 16B.
[0046]
The results are shown in Table 4.
[0047] [Table 3] [ee [eet concentration
Covet | | 0 [0 [|e comromn | 2 | ss [| we | - [ws
[0048] [Table 4] ... Flow rate Heat transfer ore Corrosion
Test Condition (0.5m/s) « er) depth [fae (mm)
Cees | 1 | om | ww | ow | a
EYE I TT I CT
Comer | 1 | om | ww | ow | wm
Example 7
Cm] 5 oe | ow [ow | wo
[0049]
As 1s evident from Table 4, by adding the copolymer (A) and the copolymer (B) into a cooling water system in which a non-phosphorus, zinc treatment is performed, not only metal corrosion but also pitting corrosion can be effectively inhibited even under high hardness and high salinity conditions.
[0050] 1: mother liguid tank 2: test tank 3: circulation pump 4: carbon steel tube 5: «corrosion sensor 11: cooling tower 12: cooling water tank
134A, 13B: test plece celumn 14A, 14B: heat exchanger 15a, 13B: electric heater 106A, 16B: heat-transfer tube
Claims (1)
- CLAIMS 1 A method of preventing metal corrosion in a cooling water system, which is a method of preventing corrosion of a metal member in a cooling water system in which a non- phosphorus, zinc treatment is performed, the method comprising causing the following components (A), (B), and (C) to be present in the water system: (A) a copolymer of acrylic acid and a sulfone group- containing monomer (hereinafter described as the "copolymer A)", (B) a copolymer of maleic acid and isobutylene (hereinafter described as the "copolymer (B)"), and : (C} a zinc compound. | Bh 2 The method of preventing metal corrosion in a cooling water system according to Claim 1, wherein the sulfone group-containing monomer of the copolymer (A) is 2- acrylamide~2-methylpropanesulfonic acid and/or 3-allyloxy-2- : hydroxypropanesulfonic acid. 3 The method of preventing metal corrosion in a cooling water system according to Claim 1 or 2, wherein the molecular weight of the copolymer (A) is 500 to 50,000, and the molar ratio of acrylic acid to the sulfone group-containing monomer is 7:3 to 9:1. - or 4 The method of preventing metal corrosion in a cooling water system according to any one of Claims 1 to 3, wherein the molecular weight of the copolymer (B) is 10,000 to 50,000, and the molar ratio of maleic acid to isobutylene is 5:5 to 8:2. The method of preventing metal corrosion in a cooling water system according to any one of Claims 1 to 4, wherein the zinc compound is zinc chloride and/or zinc sulfate. 6 The method of preventing metal corrosion in a cooling water system according to any one of Claims 1 to 5, wherein the copolymer (A) and the copolymer (B) are added in the amount of 5 to 50 mg-solid content/L in total relative to the blow water amount of the water system. 7 The method of preventing metal corrosion in a cooling water system according to any one of Claims 1 to 6, wherein the zinc compound is added in the amount of 0.5 mg/L or more relative to the blow water amount of the water system. 8 The method of preventing metal corrosion in a cooling water system according to any one of Claims 1 to 7, wherein the calcium hardness of the water system is 100 to 1,000 mg- CaCOs;/L, and the concentration of corrosive ions (total of the concentration of chloride ions and the concentration of sulfate ions) is 2,000 mg/L or less.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011074615A JP5803207B2 (en) | 2011-03-30 | 2011-03-30 | Cooling water metal anticorrosion treatment method |
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| SG184694A1 true SG184694A1 (en) | 2012-10-30 |
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| SG2012023255A SG184694A1 (en) | 2011-03-30 | 2012-03-29 | Method of preventing metal corrosion in cooling water system |
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| JP (1) | JP5803207B2 (en) |
| CN (1) | CN102732897B (en) |
| SG (1) | SG184694A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160167997A1 (en) * | 2013-07-25 | 2016-06-16 | Kurita Water Industries Ltd. | Method for treating cooling water system |
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| JP6444105B2 (en) * | 2014-09-17 | 2018-12-26 | 株式会社日本触媒 | Metal corrosion inhibitor for polycarboxylic acid aqueous solution, metal corrosion inhibitor aqueous solution composition, and method for inhibiting metal corrosion of polycarboxylic acid aqueous solution |
| CN111439854A (en) * | 2020-05-25 | 2020-07-24 | 嘉兴天兴环保技术有限公司 | Non-phosphorus scale inhibition and dispersion agent for sewage treatment and preparation method thereof |
| JP7363875B2 (en) | 2021-10-18 | 2023-10-18 | 栗田工業株式会社 | Water-based metal corrosion protection treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61118199A (en) * | 1984-11-14 | 1986-06-05 | Kurita Water Ind Ltd | Water-treating agent |
| NZ226331A (en) * | 1987-10-05 | 1991-08-27 | Calgon Corp | Method of inhibiting corrosion of metallic surfaces in aqueous systems using acrylic polymers and zinc ions; compositions therefor |
| CA2042341C (en) * | 1990-05-23 | 2001-06-12 | Judy H. Bardsley | Silica scale inhibition |
| JP3932829B2 (en) * | 2001-05-17 | 2007-06-20 | 栗田工業株式会社 | Scale adhesion prevention method |
| DE60321938D1 (en) * | 2002-05-22 | 2008-08-14 | Kurita Water Ind Ltd | COMPOSITION FOR SLIME PREVENTION AND PROCESS FOR SLIME PREVENTION |
| JP2004107782A (en) * | 2002-09-20 | 2004-04-08 | Kurita Water Ind Ltd | Corrosion prevention method |
| CN1837097A (en) * | 2005-03-23 | 2006-09-27 | 上海万森水处理有限公司 | Composite dirt dispersion agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160167997A1 (en) * | 2013-07-25 | 2016-06-16 | Kurita Water Industries Ltd. | Method for treating cooling water system |
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|---|---|
| JP2012207279A (en) | 2012-10-25 |
| CN102732897A (en) | 2012-10-17 |
| JP5803207B2 (en) | 2015-11-04 |
| CN102732897B (en) | 2016-05-04 |
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