CN1473137A - Multifunctional water-treating composition and method of water-treating using the same - Google Patents

Multifunctional water-treating composition and method of water-treating using the same Download PDF

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CN1473137A
CN1473137A CNA018184197A CN01818419A CN1473137A CN 1473137 A CN1473137 A CN 1473137A CN A018184197 A CNA018184197 A CN A018184197A CN 01818419 A CN01818419 A CN 01818419A CN 1473137 A CN1473137 A CN 1473137A
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water treatment
chemical formula
treatment compositions
nitrate
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CN1280213C (en
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韩淳宗
金真万
崔东镇
崔起昇
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TSK water Co., Ltd.
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SK Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/26—Phosphorus; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • 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
    • C02F2303/04—Disinfection
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Inorganic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

In order to provide a water-treating compositon which has a superior stability during storage or the use and simultaneously prevents the corrosion, the scale formation and the growth of microorganism in a colling water, the present invention provides a multifunctional water-treating composition comprising at least one component selected from a group consisting of a mixture including azole compound and carboxylate, orthophosphate salt and zinc salt; a microorganism growth inhibitor; a scale formation inhibitor; an organic phosphonate; and nitrate.

Description

The water treatment method of multifunctional water treatment compositions and use said composition
Technical field
The present invention relates to the water treatment method of multifunctional water treatment compositions and use said composition.More particularly, the present invention relates to water treatment composition, said composition has excellent stability in storing and using, and can be suppressed at burn into fouling and the microorganism growth that takes place in the open loop cooling water system simultaneously.
Technical background
In the open loop cooling water system, with the temperature of cooling tower device control water coolant.Because air always flows into the water temperature control system with cooling tower, this system just is called the open loop cooling water system so.In the recirculation of water coolant, because evaporation of water, the various mineral substance that contain in the water are concentrated.According to method of wastewater treatment, the various phenomenons that influence cooling operation are arranged.These phenomenons can range burn into fouling and microorganism problem substantially.
Briefly, corrosion is meant and forms rust on metallic substance.Usually obtain metal by the refining oxide compound, therefore, it has the performance of the very strong oxidation state of returning the thermodynamics stable state.So, very natural can corrode in the open loop cooling water system.
The settling that causes by metallic corrosion, or various divalent-metal ions combine and fouling with the negative ionization compound in the water.Along with the temperature rising of water coolant, the solubleness of metal-salt reduces.Therefore, owing to heat for example refrigerator or the heat exchanger of open loop cooling water system, in the local fouling easily of relatively-high temperature state.If excessive fouling, then possible blocking pipe also reduces heat transfer efficiency, and this will cause the over-drastic energy consumption.
Microorganism such as bacterium, fungi, liver moss etc. can grow finely according to envrionment conditions or be bad.Unfortunately, the environment of cooling tower comprises that water temperature, pH, dissolved oxygen content, content of mineral substances and daylight provide most suitable condition for microbial growth.If the microorganism that grows in this proper environment condenses each other and is attached on the filler of cooling tower, they disturb flowing of water and air, and this causes the reduction of cooling efficiency.The microorganism mud that is attached in cooling tower on the filler is called sludge.If partial corrosion attached to the surface of metallic conduit, may take place owing to microorganism in this sludge.
Find that easily burn into fouling and sludge are present in the various industrial equipmentss with flowing water pipeline, comprise the heat exchanger of refrigerating unit.In this case, have serious problem, comprise reduction, infectation of bacteria, environmental pollution of shortening, the heat transfer efficiency in design of Cooling System life-span etc., cause enormous economic loss thus.
In order to overcome the problems referred to above, various water treatment compositions have been developed as a rule.Yet for water treatment, conventional water treating method uses corrosion inhibitor, scale inhibitor and microbial inhibitor respectively.So, only the problem that solves burn into fouling and microorganism growth simultaneously with chemical composition is impossible.For example, conventional water treating method suppresses fouling by introducing scale inhibitor, suppresses microorganism growth by introducing microbial inhibitor then.As the example of water treatment composition, comprise that azole compounds and phosphatic water treatment composition are disclosed in United States Patent (USP) 4,134,959 with this single effect.United States Patent (USP) 5,227,133 public uses comprise the treatment of cooling water method of zinc salt, molybdenum salt and phosphate composition in addition, and United States Patent (USP) 5,156,665 openly prevents the method for microorganism growth.
Yet, not too produce effect aspect the microorganism growth preventing for preventing to corrode, and not too produce effect aspect corrosion and the fouling preventing for the water treatment composition that prevents microorganism growth with the water treatment composition of fouling.Therefore, the use of conventional water treatment composition is restricted, and the user must inject suitable water treatment composition according to condition of water quality.The reason of developing corrosion inhibitor, scale inhibitor and microbial inhibitor respectively is, because if all their mix and form composition, the stability of product is just by variation so, and because the intermiscibility that lacks between each component forms precipitation.In addition, can not give full play to the possible effect of each component.
Summary of the invention
In order to address the above problem, as the result of research in several years, the inventor has researched and developed a kind of water treatment composition, and it is being stored and between the usage period good stability is being arranged, and in the open loop cooling water system, can solve the problem of relevant burn into fouling and microorganism growth simultaneously.
Therefore, the present invention seeks to the method that water treatment composition is provided and uses said composition to carry out water treatment for cooling tower, compare with conventional water treatment composition, said composition can suppress burn into fouling and microorganism growth simultaneously, and easy to use.
Another object of the present invention provides water treatment composition and utilizes the method for said composition water treatment, and excellent intermiscibility is arranged between each component of said composition, in the stability of storing or the said composition product has excellence between the usage period.
In order to achieve the above object, the multifunctional water treatment compositions of homogeneous is provided, and it comprises a kind of component of mixture that comprises azole compounds, carboxylate salt, orthophosphoric acid salt and zinc salt that is selected from, microorganism growth inhibitor at least, scale inhibitor, organic phosphonate and nitrate.Preferably, as the microorganism growth inhibitor, use acrylic ester polymer with the 3-isothiazolinone as scale inhibitor.In water treatment composition, also preferred, the amount of microorganism growth inhibitor is between 0.05 to 15wt%, the amount of scale inhibitor is between 0.5 to 50wt%, the amount of above-mentioned organic phosphonate is between 0.2 to 30wt%, wherein this amount is an organic phosphonate ionic amount, and the amount of nitrate is between 0.02 to 20wt%, and wherein this amount is the amount of nitrate ion.
If use orthophosphoric acid salt and/or zinc salt, preferably to measure be 0.1～30wt% for orthophosphoric acid salt and/or zinc salt so, and wherein this amount is orthophosphate ions and/or zinc salt ionic total amount.If use the mixture that comprises azole compounds and carboxylate salt, the amount of so preferred azole compounds is 0.01～10wt%, and the amount that reaches carboxylate salt is 0.2～40wt%, and wherein this amount is the amount of carboxylate compounds.
In addition, the present invention also provides a kind of water treatment method that is used to prevent burn into fouling and microorganism growth, this method comprises introduces the step that the multifunctional water treatment compositions enters cooling water system, described composition comprises a kind of component that is selected from the mixture that contains azole compounds, carboxylate salt, orthophosphoric acid salt and zinc salt at least, the microorganism growth inhibitor, scale inhibitor, organic phosphonate and nitrate.Detailed Description Of The Invention
The present invention is below described in more detail.
According to the present invention,, can use conventional microorganism growth inhibitor as the microorganism growth inhibitor that in water treatment composition, uses.Yet, the 3-isothiazolinone of following Chemical formula 1 is preferably as the microorganism growth inhibitor, this is because it and the other good intermiscibility of compound, for example scale inhibitor, organic phosphonate, azole compounds, carboxylate salt, orthophosphoric acid salt and zinc salt, it has excellent growth inhibitory effect to various microorganisms, and the long-term inhibition activity that continues.
[Chemical formula 1]
Figure A0181841900091
In Chemical formula 1, R 0Represent hydrogen atom or chlorine atom.
Specifically, more preferably use 2-methyl-4-isothiazolones-3-ketone, wherein R in Chemical formula 1 0Be hydrogen atom, or 5-chloro-2-methyl-4-isothiazolones-3-ketone, wherein R in Chemical formula 1 0It is the chlorine atom.The weight ratio of mixture of most preferably using 2-methyl-4-isothiazolones-3-ketone and 5-chloro-2-methyl-4-isothiazolones-3-ketone is 1: 20～20: 1 a mixture.In water treatment composition of the present invention, the amount of the 3-isothiazolinone of Chemical formula 1 is preferably 0.05～15wt% in the water treatment composition total amount.If the amount of 3-isothiazolinone is lower than 0.05wt%, sterilization effect reduces, if the amount of 3-isothiazolinone is higher than 15wt%, sterilization effect improves, but its composition is uneconomic.
According to the present invention,, can use conventional scale inhibitor as the scale inhibitor that in water treatment composition, uses.Yet, the acrylic ester polymer of following Chemical formula 2 is preferably scale inhibitor, this is owing to its intermiscibility with other compound excellence, for example microorganism growth inhibitor, organic phosphonate, azole compounds, carboxylate salt, orthophosphoric acid salt and zinc salt, and since the divalent metal salt excellence prevent the fouling effect.
[Chemical formula 2]
In above Chemical formula 2, l, m, n can be identical or different, is 0～1000 integer.R represents hydrogen atom, methyl or carboxyl, and when R is carboxyl, it can with contiguous carbonyl in conjunction with forming anhydro ring.R 1And R 8Can be identical or different, each represents hydrogen atom, alkyl, hydroxyl or phosphono.R 2And R 3Can be identical or different, each represents the alkyl of hydrogen atom or C1-C2.R 4Represent hydrogen atom, C1-C5 alkyl, and R 5Represent C1-C8 alkyl or C8-C10 aralkyl.X and Y can be identical or different, and each represents hydrogen atom, C1-C5 alkyl or C1-C5 hydroxyalkyl.In addition, R 0Comprise one or more groups that are selected from following chemical formula 3,4 and 5.
[chemical formula 3]
Figure A0181841900102
[chemical formula 4]
[chemical formula 5]
Figure A0181841900111
In above chemical formula, R 6And R 12Can be identical or different, represent hydrogen atom, C1-C2 alkyl separately, R 13And R 14Can be identical or different, represent the group of hydrogen atom, C1-C8 alkyl, C6-C8 cycloalkyl, benzyl or following chemical formula 6 separately.R 7Represent the group of C1-C6 alkyl, C6-C10 aralkyl or following chemical formula 6.
[chemical formula 6]
In chemical formula 6, i is 1,2 or 3, R 9Represent hydrogen atom or C1-C2 alkyl, R 10Represent hydrogen atom or C1-C6 alkyl.
In the water treatment composition of the present invention, the amount of preferred acrylic ester polymer is 0.5～50wt%.If the amount of acrylic ester polymer is lower than 0.5wt%, the ability that suppresses fouling reduces, if the amount of acrylic ester polymer is higher than 50wt%, so that the raising of the ability of fouling, but its composition is uneconomic.
For improving the intermiscibility between the component and preventing that corrosive performance, water treatment composition of the present invention from further comprising at least a component that is selected from the mixture that comprises azole compounds, carboxylate salt, orthophosphoric acid salt and zinc salt.
For azole compounds, preferably use benzotriazole, tolyl-triazole, mercaptobenzothiazole or its mixture, more preferably use benzotriazole.For carboxylate salt, the preferred use has 3 carboxylate salt or its mixtures to twelve carbon atom, more preferably uses Citrate trianion.Preferably, the amount of azole compounds is 0.01～10wt%, more preferably 0.05～8wt% in water treatment composition.If the amount of azole compounds is lower than 0.01wt%, can not carry out anticorrosionly effectively, if the amount of azole compounds is higher than 10wt%, be uneconomical economically.Preferably, the amount of carboxylate salt is 0.2～40wt%, and wherein this measures the amount into carboxylate compounds, and preferred amount is 0.5～30wt%.If it is anticorrosion that the amount of carboxylate compounds less than 0.2wt%, can not be carried out effectively, if the amount of carboxylate compounds is higher than 40wt%, uneconomical economically.
For orthophosphoric acid salt, preferably use monobasic orthophosphoric acid salt, binary orthophosphoric acid salt, ternary orthophosphoric acid salt, phosphoric acid or its mixture, more preferably use phosphoric acid.For zinc salt, preferably use zinc chloride, zinc sulfate, zinc nitrate or its mixture.In water treatment composition, the amount of preferred orthophosphoric acid salt and/or zinc salt is 0.1～30wt%, and wherein this amount is ionic total amount, the i.e. total amount of ortho-phosphoric acid ion and zine ion separately.More preferably, the amount of zine ion is 0.1～20wt%, and ortho-phosphoric acid ionic amount is 0.5～30wt%.If the amount of zine ion is lower than 0.1wt%, can not carry out anticorrosionly effectively, if the amount of zine ion is higher than 20wt%, when as sewage discharge, will produce harmful effect to fish and shellfish.If ortho-phosphoric acid ionic amount is lower than 0.5wt%, can not carry out effectively anticorrosion, and if ortho-phosphoric acid ionic amount be higher than 30wt%, will cause the calcium phosphate fouling.
For organic phosphonate of the present invention, preferably use hydroxy ethylene diphosphonic acid, hydroxy phosphinylidyne yl carboxylic acid, Amino Trimethylene Phosphonic Acid, phosphinylidyne butane tricarboxylic acid, ethylenediamine tetramethylene phosphonic acid or its mixture.Preferably, the amount of organic phosphonate is 0.2～30wt% in water treatment composition, and wherein this amount is an organic phospho acid ionic amount.If organic phospho acid ionic amount is lower than 0.2wt%, can not carry out corrosion protection and scale inhibition effectively, and if organic phospho acid ionic amount be higher than 30wt%, uneconomical economically.
The nitrate that the present invention uses has improved the intermiscibility between microorganism growth inhibitor, scale inhibitor, organic phosphonate, azole compounds and the carboxylate salt, has also improved package stability.For nitrate, can use magnesium nitrate, cupric nitrate etc.Preferably, in water treatment composition of the present invention, the amount of nitrate is 0.02～20wt%, and wherein this amount is the amount of nitrate ion.If the amount of nitrate ion is less than 0.02wt%, the resistance to corrosion of product and package stability variation, if it is the amount of nitrate ion is higher than 20wt%, uneconomical economically.
Preferably, water treatment composition of the present invention is introduced in the water coolant, so that the concentration of said composition is 1ppm～500 000ppm.Water treatment composition of the present invention is used for suppressing to occur in various industrial flow waterpipes effectively, as fouling in cooling tower and the heat exchanger and corrosion.Therefore, water treatment composition of the present invention is preferred for open loop cooling water system or various flowing water cooling system.Wherein, water treatment composition of the present invention more preferably is used to corrode with microorganism growth and causes the more open loop cooling water system of serious problems.
The invention provides following embodiment for illustrating better, but can not think and any limitation of the invention.[embodiment 1-3 and comparative example 1-3]
In water, dissolve water treatment composition, described composition comprises azole compounds, carboxylate salt, orthophosphoric acid salt, zinc salt, acrylate copolymer, organic phosphonate, isothiazolinone or nitrate, thereby the amount of active principle is listed in shown in table 1 and 2 (embodiment 1-9) and the table 3 and 4 (comparative example 1-6) in the test water sample.Carry out anticorrosion, scale inhibition, suppress the test of microorganism growth.
[table 1] in water treatment procedure, each group component of present composition dissolved (embodiment 1-3)
Component Amount (ppm)
Experiment 1 Experiment 2 Experiment 3
Azole compounds ????0.5 ????1 ????2
Carboxylate salt ????5 ????7.5 ????10
Acrylate copolymer ????5 ????7.5 ????10
Organic phosphonate, ????4 ????7 ????10
Isothiazolinone, ????1.5 ????2.0 ????2.5
Nitrate ion ????2.5 ????4 ????6.5
[table 2] in water treatment procedure, each group component of present composition dissolved (embodiment 4-9)
Component Amount (ppm)
Experiment 4 Experiment 5 Experiment 6 Experiment 7 Experiment 8 Experiment 9
Phosphate ion ????8 ???6 ???4 ???0 ??0 ????0
Zine ion ????0 ???0 ???0 ???2 ??2.5 ????3
Acrylic ester polymer ????5 ???7.5 ???10 ???5 ??7.5 ????10
Organic phosphonate ????4 ???6 ???8 ???4 ??6 ????8
Isothiazolinone, ????1.5 ???2.0 ???2.5 ???1.5 ??2.0 ????2.5
Nitrate ion ????2.5 ???4 ???6.5 ???2.5 ??4 ????6.5
[table 3] in water treatment procedure, each group component of conventional composition dissolved (comparative example 1-3)
Component Amount (ppm)
The contrast experiment 1 The contrast experiment 2 The contrast experiment 3
Azole compounds ????0 ????0 ????1
Carboxylate salt ????0 ????2.5 ????0
Acrylic ester polymer ????0 ????0 ????0
Organic phosphonate ????0 ????0 ????2
Isothiazolinone ????0 ????0.8 ????0
Nitrate ion ????0 ????6.5 ????6.5
[table 4] in water treatment procedure, each group component of conventional composition dissolved (comparative example 4-6)
Component Amount (ppm)
The contrast experiment 4 The contrast experiment 5 The contrast experiment 6
Positive phosphorus acid ion ????8 ????0 ????0
Zine ion ????0 ????0 ????2
Acrylic ester polymer, ????0 ????0 ????0
Organic phosphonate ????0 ????2 ????0
Isothiazolinone, ????0.8 ????0 ????0.8
Nitrate ion ????6.5 ????6.5 ????6.5
In table 1～4, organic phosphonate representation hydroxy ethylidene diphosphonic acid [the product HEDP of LONZA company limited], with acrylic ester polymer be that Belclenece 400 (FMC Corp.'s product) and isothiazolinone are SKYBIO WG (SK chemical industry company limited product).The azole compounds that uses is a benzotriazole, and the carboxylate salt of use is a citric acid.Use the salt that produces orthophosphoric acid salt, zine ion, nitrate ion, phosphoric acid, zinc chloride and magnesium nitrate respectively.Corrosion test
Carry out corrosion test with the rotation corrosion test instrument.Be test corrosion of carbon steel speed, the air of 170 rev/mins of rotating speeds, 10 ml/min inject and 30 ℃ condition under, rotation carbon steel specimen.Has in the water sample of character shown in the following table 5 concentration of component of conventional water treatment composition shown in the concentration of component of the water treatment composition of the present invention shown in the maintenance table 1 and 2 and table 3 and 4.Dipping carbon steel 5 days.Weightlessness according to carbon steel is measured erosion rate [mdd, mg/ (dm 2Day)], the results are shown in Table 6.
The water sample that uses in [table 5] corrosion test
Character Water
????#1 ????#2 ????#3
???PH ???????????7.5～8.0
Calcium hardness (ppm) ????100 ????200 ????300
M-basicity (ppm) ????80 ????100 ????120
Total hardness (ppm) ????120 ????240 ????360
Chlorion (ppm) ????80 ????160 ????240
Regulate water sample pH value with 0.1N aqueous sodium hydroxide solution and 0.05N aqueous sulfuric acid.Regulate calcium hardness, M-basicity, magnesium hardness and amount of chloride ions with calcium chloride, sodium bicarbonate, sal epsom and sodium-chlor respectively.Total hardness represent calcium hardness and magnesium hardness and.
The corrosion test result of [table 6] embodiment 1-9 and comparative example 1-6
Component Erosion rate (mdd)
Water #1 Water #2 Water #3
Embodiment 1 ????7.68 ????8.25 ????9.43
Embodiment 2 ????5.35 ????6.10 ????7.89
Embodiment 3 ????3.73 ????4.82 ????5.43
Embodiment 4 ????4.86 ????6.35 ????7.53
Embodiment 5 ????4.98 ????6.21 ????6.08
Embodiment 6 ????5.96 ????7.52 ????7.43
Embodiment 7 ????4.56 ????4.72 ????4.64
Embodiment 8 ????3.86 ????4.08 ????4.21
Embodiment 9 ????3.08 ????2.86 ????3.27
The comparative example 1 ????312.39 ????212.29 ????167.06
The comparative example 2 ????287.12 ????198.34 ????161.18
The comparative example 3 ????33.28 ????42.37 ????58.06
The comparative example 4 ????20.08 ????27.48 ????18.86
The comparative example 5 ????35.36 ????45.03 ????67.94
The comparative example 6 ????20.08 ????27.48 ????18.86
*mdd＝mg/(dm 2·day)
As shown in table 6, the antiseptic power of embodiment 1～3 composition greatly is better than comparative example 1～3 ability.And the antiseptic power of embodiment 4～9 compositions greatly is better than comprising respectively the comparative example's 4～6 of orthophosphoric acid salt, zinc salt or organic phosphonate ability.So, the multifunctional water treatment compositions of homogeneous of the present invention is stable under admixture, and has good anticorrosion character.The scale inhibition test
Sealing test solution securely, and placed 24 hours at 75 ℃.Filter test soln with 0.45 μ m strainer, then by measuring Hardness Determination scale inhibitor efficient.In the water sample that character shown in the following table 7 is arranged, keep the concentration of component of water treatment composition of the present invention shown in the table 1 and 2 and the concentration of component of the conventional water treatment composition shown in table 3 and 4.Calculate scale inhibitor efficient with following mathematical expression 1, the results are shown in table 8.
[mathematical expression 1]
Scale inhibitor efficient (%)=Ce/Ct * 100
In mathematical expression 7, water sample total hardness before the Ct representative test, Ce representative test back water sample total hardness.
The water sample that [table 7] uses in the scale inhibition test
Character Water
????#1 ????#2 ????#3
Calcium hardness (ppm) ????100 ????200 ????300
M-basicity (ppm) ????100 ????200 ????300
Chlorion (ppm) ????80 ????160 ????240
At the water sample of table 7, regulate calcium hardness with calcium chloride, regulate M-basicity and chlorion with sodium bicarbonate and sodium-chlor respectively.
The scale inhibition test result of [table 8] embodiment 1-9 and comparative example 1-6
Component Scale inhibition efficient (%)
Water #1 Water #2 Water #3
Embodiment 1 ????100 ????98 ????95
Embodiment 2 ????100 ????100 ????100
Embodiment 3 ????100 ????100 ????100
Embodiment 4 ????98 ????98 ????95
Embodiment 5 ????100 ????100 ????98
Embodiment 6 ????100 ????100 ????100
Embodiment 7 ????100 ????100 ????98
Embodiment 8 ????100 ????100 ????100
Embodiment 9 ????100 ????100 ????100
The comparative example 1 ????90 ????63 ????33
The comparative example 2 ????88 ????68 ????45
The comparative example 3 ????93 ????78 ????67
The comparative example 4 ????86 ????58 ????29
The comparative example 5 ????93 ????78 ????67
The comparative example 6 ????86 ????58 ????29
As shown in the table 8, be better than the efficient of comparative example 1-6 according to the scale inhibition efficient of embodiment of the invention 1-9.Microorganism suppresses test
Under the air injection condition of 30 ℃, 170 rev/mins and 10 ml/min, the solution that will comprise 8 kinds of microorganisms introduces that (8 kinds of microorganisms are: angry enterobacteria ATCC13048 in the sample, intestinal bacteria ATCC 11229, micrococcus flavus ATCC 9341, Pseudomonas aeruginosa ATCC 15442, Cray Bai Shi pneumobacillus ATCC 1560, edidermis staphylococcus A TCC, streptococcus aureus ATCC 6538, Bacillus subtilus ATCC 6984).Two days later, the concentration of measuring microorganism reduces.At this moment, obtain 10 6The microbial solution of CFU/ml concentration, and introduce and to have in the water sample of character shown in the table 9, microorganism concn is 10 like this 5CFU/ml.In addition in water sample, keep the concentration of component of conventional water treatment composition shown in the concentration of component of water treatment composition of the present invention shown in the table 1 and 2 and table 3 and 4.The microorganism concn that following table 10 is listed measurement reduces.
The water sample that [table 9] uses in microorganism growth suppresses to test
Character Water
????#1 ????#2 ????#3
????pH ?????????????7.5～8.0
Calcium hardness (ppm) ????100 ????200 ????300
M-basicity (ppm) ????80 ????100 ????120
Total hardness (ppm) ????120 ????240 ????360
Chlorion (ppm) ????80 ????160 ????240
Initial microbe number (CFU/ml) ????10 5 ????10 5 ????10 5
The microorganism growth of [table 10] embodiment 1-9 and comparative example 1-6 suppresses test result
Component Microbe population (CFU/ml)
Water #1 Water #2 Water #3
Embodiment 1 ????10 1 ????10 2
Embodiment 2 ????0 ????0 ????10 1
Embodiment 3 ????0 ????0 ????0
Embodiment 4 ????10 1 ????10 2 ????10 2
Embodiment 5 ????0 ????10 1 ????10 1
Embodiment 6 ????0 ????0 ????0
Embodiment 7 ????10 1 ????10 2 ????10 2
Embodiment 8 ????0 ????10 1 ????10 1
Embodiment 9 ????0 ????0 ????0
The comparative example 1 ????10 7 ????10 8 ????10 8
The comparative example 2 ????10 3 ????10 4 ????10 4
The comparative example 3 ????10 7 ????10 8 ????10 8
The comparative example 4 ????10 3 ????10 4 ????10 4
The comparative example 5 ????10 7 ????10 8 ????10 8
The comparative example 6 ????10 3 ????10 4 ????10 4
*CFU/ml=colony forms units per ml
As shown in table 10, with respect to using the microorganism growth inhibitor respectively, or make the situation of the microorganism growth inhibitor that contains other material, if use water treatment composition of the present invention, the microorganism inhibiting rate is very high.Therefore clearly under admixture, water treatment composition of the present invention is stable, and better microorganism growth retarding effect is arranged.
In a word, to open recirculating cooling water system, water treatment composition of the present invention can improve the function of anti-corrosion of metal, fouling and microorganism growth simultaneously, and in the stability of storing or have between the usage period excellence.
Water treatment composition of the present invention has the long-term fungicidal effectiveness that continues, and in the cooling water system of open loop, its sterilization effect to all microorganisms is very effective.In addition, said composition can prevent the anodic reaction and the cathodic reaction of corrosion reaction.Therefore, said composition can be reduced in the corrosion that the metallic surface takes place effectively.Therefore in addition, the crystalline structure of acrylate copolymer and the fouling of organic phosphonate correctability divalent metal salt, scale inhibition effectively.So water treatment composition of the present invention improves the performance of anti-corrosion of metal, fouling and microorganism growth simultaneously.

Claims (14)

1. multifunctional water treatment compositions comprises:
At least a component that is selected from the mixture that comprises azole compounds, carboxylate salt, orthophosphoric acid salt and zinc salt;
The microorganism growth inhibitor;
Scale inhibitor;
Organic phosphonate; With
Nitrate.
2. require 1 multifunctional water treatment compositions as the right profit, its microorganism growth inhibitor is the 3-isothiazolinone, and scale inhibitor is an acrylic ester polymer.
3. multifunctional water treatment compositions as claimed in claim 2, wherein the 3-isothiazolinone is the compound of being represented by following Chemical formula 1, acrylic ester polymer is the polymkeric substance of being represented by following Chemical formula 2,
[Chemical formula 1]
Figure A0181841900021
[Chemical formula 2]
Figure A0181841900022
In Chemical formula 1, R 0Represent hydrogen atom or chlorine atom, in Chemical formula 21, m, n can be identical or different, is 0～1000 integer, and R represents hydrogen atom, methyl or carboxyl, and when R was carboxyl, it can combine with contiguous carbonyl and form anhydro ring, R 1And R 8Can be identical or different, each represents hydrogen atom, alkyl, hydroxyl or phosphono, R 2And R 3Can be identical or different, each represents hydrogen atom or C1-C2 alkyl, R 4Represent hydrogen atom or C1-C5 alkyl, and R 5Represent C1-C8 alkyl or C8-C10 aralkyl, X and Y can be identical or different, and each represents hydrogen atom or C1-C5 alkyl or C1-C5 hydroxyalkyl, R 0Comprise one or more groups that are selected from following chemical formula 3,4 and 5,
[chemical formula 3]
Figure A0181841900031
[chemical formula 4]
Figure A0181841900032
[chemical formula 5]
Figure A0181841900033
In above chemical formula, R 6And R 12Can be identical or different, each represents hydrogen atom or C1-C2 alkyl, R 13And R 14Can be identical or different, each represents the group of hydrogen atom, C1-C8 alkyl, C6-C8 cycloalkyl, benzyl or following chemical formula 6, R 7Represent the group of C1-C6 alkyl, C6-C10 aralkyl or following chemical formula 6,
[chemical formula 6]
Figure A0181841900034
In chemical formula 6, i is 1,2 or 3, R 9Represent hydrogen atom or C1-C2 alkyl, and R 10Represent hydrogen atom or C1-C6 alkyl.
4. multifunctional water treatment compositions as claimed in claim 3, wherein the 3-isothiazolinone is that 2-methyl-4-isothiazolones-3-ketone and 5-chloro-2-methyl-4-isothiazolones-3-ketone are with 1: 20～20: 1 mixture of weight ratio of mixture.
5. multifunctional water treatment compositions as claimed in claim 1, wherein azole compounds is benzotriazole, tolyl-triazole or mercaptobenzothiazole.
6. multifunctional water treatment compositions as claimed in claim 1, wherein carboxylate salt is at least a compound that is selected from the carboxylate salt with 3～12 carbon.
7. multifunctional water treatment compositions as claimed in claim 1, wherein orthophosphoric acid salt is a phosphoric acid.
8. multifunctional water treatment compositions as claimed in claim 1, wherein zinc salt is at least a compound that is selected from zinc chloride, zinc sulfate and zinc nitrate.
9. multifunctional water treatment compositions as claimed in claim 1, wherein organic phosphonate is at least a hydroxy ethylene diphosphonic acid, hydroxy phosphinylidyne yl carboxylic acid, Amino Trimethylene Phosphonic Acid, phosphinylidyne butane tricarboxylic acid and the ethylenediamine tetramethylene phosphonic acid of being selected from.
10. multifunctional water treatment compositions as claimed in claim 1, wherein nitrate is at least a compound that is selected from magnesium nitrate and cupric nitrate.
11. multifunctional water treatment compositions as claimed in claim 1, wherein the amount of microorganism growth inhibitor is 0.05～15wt%, the amount of scale inhibitor is 0.5～50wt%, the amount of organic phosphonate is 0.2～30wt%, wherein this amount is an organic phospho acid ionic amount, and the amount of azole compounds is 0.01～10wt%, and the amount of carboxylate salt is 0.2～40wt%, the amount of nitrate is 0.02～20wt%, and wherein this amount is the amount of nitrate ion.
12. multifunctional water treatment compositions as claimed in claim 1, wherein the amount of microorganism growth inhibitor is 0.05～15wt%, the amount of scale inhibitor is 0.5～50wt%, the amount of organic phosphonate is 0.2～30wt%, wherein this amount is an organic phospho acid ionic amount, and the amount of orthophosphoric acid salt and/or zinc salt is 0.1～30wt%, and wherein this amount is the total amount of ortho-phosphoric acid ion and zine ion, the amount that reaches nitrate is 0.02～20wt%, and wherein this amount is the amount of nitrate ion.
13. a water treatment method comprises the step of the multifunctional water treatment compositions being introduced cooling water system, described composition comprises at least a component that is selected from the mixture that contains azole compounds, carboxylate salt, orthophosphoric acid salt and zinc salt; The microorganism growth inhibitor; Scale inhibitor; Organic phosphonate and nitrate.
14. as the water treatment method of claim 13, the concentrations of water treatment compositions of wherein introducing cooling water system is 1ppm～500,000ppm.
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