CN1702047A - Method of cooling water treatment and treatment chemical - Google Patents
Method of cooling water treatment and treatment chemical Download PDFInfo
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- CN1702047A CN1702047A CN 200510051761 CN200510051761A CN1702047A CN 1702047 A CN1702047 A CN 1702047A CN 200510051761 CN200510051761 CN 200510051761 CN 200510051761 A CN200510051761 A CN 200510051761A CN 1702047 A CN1702047 A CN 1702047A
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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
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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
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- 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
- C23F11/12—Oxygen-containing compounds
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- 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
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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
- 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
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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
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The product of the invention can simultaneously prevent the metal corrosion and scale fault in an open circulatory cooling water system. A calcium carbonate precipitation inhibitor and a calcium carbonate dispersant can be added into a cooling water so as to disperse calcium carbonate micro-particles in the cooling water, thus achieving a cooling water treatment method with an anticorrosive coating formed on the metal surface. Through making the calcium carbonate which acts with the metal corrosive part existing in the cooling water in advance in terms of dispersible micro-particles, the supply to the corrosive part is increased so that a calcium carbonate anticorrosive film is formed stably and definitely at an early time. On the other hand, through improving the disperse of the micro-particles to prevent the exceeding attachment of water scale, the barrier caused by the water scale can be prevented. In order to enable the formation and disperse of the calcium carbonate micro-particles, the calcium carbonate precipitation inhibitor which prevents the precipitation of the calcium carbonate and the calcium carbonate dispersant, which prevents, in a manner beyond the precipitation of the calcium carbonate precipitation inhibitor, the overgrowth of the calcium carbonate formed in a water which has a performance limit and is dispersed in terms of a granularity within a certain range, can be combined for use.
Description
Technical field
The present invention relates to be used for preventing simultaneously the metallic corrosion of open cycle cooling water system and the treatment process and the processing medicament of incrustation scale obstacle.
Background technology
The metal parts that is provided with in open cycle water coolant system, for example the interchanger of carbon steel, copper or copper alloy system and reactor, pipe arrangement are corroded because of contacting with water coolant, so generally apply by adding the rotproofing of medicament.
For example in order to suppress the corrosion of interchanger, reactor and pipe arrangement that carbon steel makes, the past is added the phosphorus compound of orthophosphoric acid salt, hexametaphosphate, hydroxy ethylene diphosphonic acid salt, phosphinylidyne butane tricarboxylate etc. in water coolant.And also separately add sometimes or and with zinc salt or dichromate and so on heavy metallic salt.But a large amount of uses of a large amount of uses, particularly heavy metallic salt of these phosphorus compounds or heavy metallic salt are because polluted water has the worry that causes the environment great effect, so pay attention to its processing or draining processing and the very big expense of needs.
On the other hand, anticorrosion for the copper and copper alloy material, though mainly using nitrogenous pyroles or phosphorus zinc is medicine, but in case with heavy addition the cooling-water drain of nitrogenous medicine or phosphorus in enclosed waters, the concentration of these materials rises in the waters, will form the problem that red tide etc. causes environmental disruption because of eutrophication.
Yet, for not containing scale inhibitor, calcium hardness and the high water system of magnesium basicity, people know: though the initial corrosion of carbon steel, in case be subjected to that to a certain degree corrosion is just difficult further corrodes.It is believed that this is because because of corrosion reaction makes oxygen reduction reaction activation on the metallic surface, produce hydroxide ion, the pH of metallic surface increases, therefore incrustation scale such as lime carbonate is separated out and is covered on the metallic surface, and institute is so that the oxygen supply amount reduces the cause that corrosion reaction as a result is suppressed.
But, incrustation scale adhering on the metallic surface, though can suppress corrosion reaction, the adhering to of a large amount of incrustation scales, owing to be obstructed because of heat transfer in interchanger or the reactor etc. efficient is reduced, it is bad to produce performance.And, in piping system,, incrustation scale narrows down because of making fluid passage, and cause the ejection pressure of pump to rise, the various obstacles of pipe arrangement obstruction and so on can appear under significant situation.
For preventing separating out of lime carbonate, it is effective adding phosphorus compound such as phosphonic acids or polyphosphoric acid or toxilic acid polymkeric substance, in the open loop cooling water system, add these compounds and generally can prevent separating out of lime carbonate, stop the influence (for example opening flat 9-174092 communique) of incrustation scale incrustation scale referring to the spy.But, lime carbonate to be separated out under the situation of the boundary that prevents performance above these compounds when the water quality of water system, lime carbonate is crystallization rapidly then, causes the incrustation scale obstacle.And used under the situation of phosphorus compound or zinc salt, because of the same generation obstacle of separating out of calcium phosphate or calcium zinc orthophosphate activated by thallium.Therefore, the water quality that these compounds energy structures are tried out is restricted, and the also restricted grade of its cycles of concentration upper limit has the restriction in the use.
Summary of the invention
The object of the invention is to provide a kind of can not cause the problems referred to above, can prevent simultaneously the corrosion of open cycle cooling water system medium carbon steel and metal control equipments such as copper, copper alloy, machine and incrustation scale obstacle water coolant treatment process and handle medicament.
The treatment process of water coolant of the present invention is the treatment process that prevents the water coolant of incrustation scale obstacle in the corrosion of metal that suppresses cooling water system, it is characterized in that in this water coolant, adding lime carbonate and separate out inhibitor and calcium carbonate dispersant, calcium carbonate microparticle is disperseed in this water coolant, on this metallic surface, generate the corrosion protection tunicle.
As mentioned above, in order to suppress corrosion of metal, though it is effective to form the method for lime carbonate corrosion protection tunicle on the surface of metal parts, but make calcium ion and carbonic acid ion in the water directly generate this lime carbonate corrosion protection tunicle, because its speed of response is slow, and for the corrosion at abundant inhibition metallic corrosion position its concentration deficiency, so and impracticable.In addition, depend on diffusion in water owing to supply with these ions to the metallic surface, thus be subjected to the influence of intrasystem flow velocity or concentration easily, stable and to generate tunicle reliably be difficult.
Among the present invention, by the lime carbonate that acts on the corrosion of metal position can be present in the water coolant with dispersible particulate form in advance, increase feed rate to corrosion location, lime carbonate corrosion protection tunicle is stablized and generation reliably in early days, prevent excessively adhering to of incrustation scale by improving its dispersiveness on the other hand, prevent the obstacle of incrustation scale.That is to say, prevent that for this fine calcium carbonate microparticle being formed and disperse, being used in combination lime carbonate from separating out the lime carbonate of usefulness and separating out and prevent agent and separate out and prevent that separating out of agent from preventing the dispersed calcium carbonate dispersant of the granularity with in the certain limit that the lime carbonate that produces in the water quality of performance limitations can not thickization surpassing this lime carbonate among the present invention.
Among the present invention, preferably in water coolant, add 1～100 mg/litre lime carbonate respectively and separate out inhibitor and calcium carbonate dispersant, make calcium carbonate microparticle simultaneously, make the saturation index of dissolved lime carbonate in the water coolant reach 1.2～3.5 with 5～100 mg/litre dispersive.
Separate out inhibitor as the lime carbonate that uses among the present invention, preferably one or more materials of from following (1) phosphonic acids based compound, following (2) carboxylic acid polyalcohol and following (3) carboxylic acid based copolymer, selecting.
(1) hydroxy ethylene dicarboxylic acid, 2-phosphinylidyne butane-1,2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-phosphinylidyne butane-1,2,3, at least a material in 4-tetracarboxylic acid and the phosphono fumaric acid,
(2) at least a material in polyacrylic acid, polymethyl acrylic acid, polymaleic acid, poly-methylene-succinic acid, polyacrylate, poly-methyl acrylate, polymaleic acid salt and the poly-itaconate,
(3) contain 50 moles of % above be selected from one or more carboxylic acid composition among the group who constitutes by vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid and salt thereof, and 5 moles of % above be selected from one or more the multipolymer of unsaturated hydrocarbons composition among the group who constitutes by 4～10 carbon atom alkenes, vinylbenzene and Dicyclopentadiene (DCPD).
And the calcium carbonate dispersant of using among the present invention, preferably one or more materials of from following (4) carboxylic acid based copolymer and following (5) non-ionic polyalcohol, selecting:
(4) contain above one or more the carboxylic acid composition who from vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid and their salt, selects of 30 moles of %, and 5 moles of % above from vinyl sulfonic acid, allyl sulphonic acid, styrene sulfonic acid, isoprene sulfonic acid, 3-allyloxy-2-hydroxy-propanesulfonic acid and their salt, select one or more contain the multipolymer of sulfonic unsaturated hydrocarbons composition
(5) at least a material in polyacrylamide, polyvinyl alcohol, polyoxyethylene glycol, polypropylene glycol and the ethylene glycol and 1,2-propylene glycol segmented copolymer.
Among the present invention, utilize calcium carbonate microparticle for preventing metallic corrosion and producing incrustation scale, for example preferred for this reason following method (i) or (ii) of adopting makes calcium carbonate microparticle separate out in water coolant and disperse.
(i) in described water coolant, add one or more materials of from calcium salt, hydrocarbonate, carbonate and alkali metal hydroxide, selecting it is contacted with air, described calcium carbonate microparticle is separated out and the dispersive method;
(ii) the water temperature with described water coolant rises, and described calcium carbonate microparticle is separated out and the dispersive method.
The processing medicament of water coolant of the present invention, it contains one or more lime carbonate that 5～95 weight % select from above-mentioned (1) phosphonic acids based compound, above-mentioned (2) carboxylic acid polyalcohol and above-mentioned (3) carboxylic acid based copolymer separates out inhibitor, and 5～95 one or more calcium carbonate dispersants of from above-mentioned (4) carboxylic acid based copolymer and above-mentioned (5) nonionic polymkeric substance, selecting of weight %, can be used in the treatment process of water coolant of the present invention.
Adopt treatment of cooling water method of the present invention and handle medicament, on the metallic surface in cooling water system, stably generate in early days and can not cause the incrustation scale obstacle, but but can give full play to the lime carbonate corrosion protection tunicle of the suitable thickness of anticorrosion ability, when suppressing this metallic corrosion, can prevent the obstacle of incrustation scale really.
Description of drawings
Fig. 1 is the system diagram of the intermittent type cooling water system evaluation experimental device summary used in expression embodiment and the reference examples.
Embodiment
Below describe the treatment process of water coolant of the present invention in detail and handle medicament.
In the treatment of cooling water method of the present invention, in water coolant, add lime carbonate and separate out inhibitor and calcium carbonate dispersant, calcium carbonate microparticle is dispersed in the water coolant, make and generate the corrosion protection tunicle on the metallic surface in the water system.
Separate out inhibitor as the lime carbonate that in water coolant, adds, though can use over material of using as the calcium carbonate water scale preventive agent etc., preferably enumerate one or more materials of from following (1) phosphonic acids based compound, following (2) carboxylic acid polyalcohol and following (3) carboxylic acid based copolymer, selecting.
(1) hydroxy ethylene dicarboxylic acid, 2-phosphinylidyne butane-1,2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-phosphinylidyne butane-1,2,3, at least a material in 4-tetracarboxylic acid and the phosphono fumaric acid,
(2) at least a material in polyacrylic acid, polymethyl acrylic acid, polymaleic acid, poly-methylene-succinic acid, polyacrylate, poly-methyl acrylate, polymaleic acid salt and the poly-itaconate.The molecular weight of these carboxylic acid polyalcohols preferred about 500～5000.
(3) contain 40 moles more than the %, one or more the carboxylic acid composition who from vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid and their salt, selects of preferred 50～90 moles of %, and 5 moles more than the %, the multipolymer of one or more unsaturated hydrocarbons compositions of selecting from unsaturated hydrocarbons compositions such as 4～10 carbon atom alkenes (for example iso-butylene, butylene, isoprene etc.), vinylbenzene and Dicyclopentadiene (DCPD) of preferred 10～50 moles of %.The molecular weight of these polymers of carboxylic acid is preferably about 1000～20000.
As calcium carbonate dispersant, the preferred material with a kind of like this functional group that uses when described functional group is adsorbed by carboxyl when lime carbonate, can make hydrophobic groupings such as charged hydrophilic radical such as alkylsulfonyl and ethers be orientated towards the outside, prevents between particle approaching; Described calcium carbonate dispersant for example can be enumerated one or more materials of selecting from the carboxylic acid based copolymer of following (4) and following (5) nonionic polymkeric substance.
(4) contain 30 moles more than the %, one or more the carboxylic acid composition who from vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid and their salt, selects of preferred 50～90 moles of %, and 5 moles more than the %, preferred 10～50 moles of % from vinyl sulfonic acid, allyl sulphonic acid, styrene sulfonic acid, isoprene sulfonic acid, 3-allyloxy-2-hydroxy-propanesulfonic acid and their salt etc., select one or more contain the multipolymer of sulfonic unsaturated hydrocarbons composition.The molecular weight of these carboxylic acid based copolymers preferred about 1000～20000.
(5) at least a material in polyacrylamide, polyvinyl alcohol, polyoxyethylene glycol, polypropylene glycol and the ethylene glycol and 1,2-propylene glycol segmented copolymer.The molecular weight of these non-ionic copolymers preferred about 5000～100000.
Lime carbonate in the water coolant is separated out the addition of inhibitor and calcium carbonate dispersant, as long as its addition is that to be enough to obtain abundant effect just passable, though the kind of the kind of the with medicament that makes, the water quality of process object water coolant and anticorrosion object metal and different, but generally be respectively 1～100 mg/litre, the total amount that preferred 5～50 mg/litre, lime carbonate are separated out inhibitor and calcium carbonate dispersant is about 10～100 mg/litre.It is in a single day very few that lime carbonate is separated out the addition of inhibitor and calcium carbonate dispersant, just can not obtain sufficient additive effect, and cross uneconomically at most, and the generation of calcium carbonate microparticle slowed down.In addition, particularly under the situation of phosphorus compound, not preferred owing to have the problem of separating out of calcium phosphate and draining to handle problems.
Among the present invention, the necessary dispersion amount of dispersed calcium carbonate microparticle in water coolant, different because of the water quality and the water temperature of the kind of cooling off anticorrosion object metal, process object water coolant, be generally about 1～1000 mg/litre, about preferred 5～100 mg/litre.Dispersive calcium carbonate microparticle quantity is in a single day very few in water coolant, just can not obtain enough preservative effects, and the worry of the incrustation scale of causing obstacle is arranged too much the time.
In addition, because the particle diameter of dispersive calcium carbonate microparticle is greater than 10 microns in the water coolant, during perhaps less than 0.01 micron, all be helpless to the formation of corrosion protection tunicle, so preferably contain 1～1000 mg/litre, especially preferably contain 5～100 mg/litre particle diameters below 10 microns, particularly 0.01～10 micron calcium carbonate microparticle.But also can in water, contain particle diameter less than 0.01 micron or greater than 10 microns lime carbonate.By and separate out inhibitor and calcium carbonate dispersant with lime carbonate, this calcium carbonate microparticle is generated.
For making the calcium carbonate microparticle that under the unlikely situation that causes the incrustation scale obstacle, exists abundant amount to suppress metallic corrosion, must make the water coolant of process object keep the supersaturation water of lime carbonate among the present invention.Therefore, should be set in more than the certain numerical value according to calcium hardness, M basicity and the pH etc. of water temperature water coolant.The degree of supersaturation of lime carbonate is high more in the water coolant, and the amount of separating out of lime carbonate is just many more, is used to disperse the consumption of the calcium carbonate dispersant of lime carbonate to increase, so should adjust in the economic scope.Under the too high situation of calcium carbonate hardness, can calcium carbonate hardness be adjusted in the suitable scope by using tenderizer.Otherwise under the low excessively situation of degree of supersaturation, then lime carbonate separate out quantity not sufficient, often can not obtain enough preservative effects.The degree of supersaturation of water coolant preferably is decided to be about 1.2～3.5 in saturation index.
For by water coolant being set on this degree of supersaturation, the predetermined amount calcium carbonate microparticle is disperseed, though can in water coolant, add pulverizers such as utilizing the whirlwind shredder with the lime carbonate coarse grain pulverize the calcium carbonate microparticle make, calcium oxide powder is broken into microgranular back, and contact the calcium carbonate microparticle that generates or industrial commercially available median size with the pyrocarbon acid gas be calcium carbonate microparticle about 0.1～5 micron, it is favourable making the method for calcium carbonate microparticle chemical calcium carbonate microparticle of separating out in water coolant below the employing like that.
(i) in water coolant, add calcium salts such as one or more calcium chloride, nitrocalcite, calcium hydroxide, and hydrocarbonate such as one or more Sodium Hydrogen Carbonates, potassium bicarbonate, heavy carbonic lithium, carbonate such as yellow soda ash, salt of wormwood, Quilonum Retard, and alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, it is contacted with air, make calcium carbonate microparticle separate out and disperse.
(ii) utilize interchanger that the temperature of water coolant is risen, reduce the solubleness of lime carbonate, make calcium carbonate microparticle separate out and disperse.
In the treatment of cooling water method of the present invention, can also separate out inhibitor and the calcium carbonate dispersant medicament that in common water treatment, uses in addition as required and with interpolation lime carbonate.For example, contain when the water body system under the situation of copper material, and if with azole series derivatives such as benzotriazole or tolyl-triazole, then can improve antiseptic property for copper material.But also can and use sterilant such as adding clorox.
The processing medicament of water coolant of the present invention comprises that the lime carbonate that the invention described above relates to separates out inhibitor and calcium carbonate dispersant.In the processing medicament of the present invention, described lime carbonate separates out inhibitor and calcium carbonate dispersant contains 5～95 weight % usually respectively, preferably contains 20～80 weight %.Processing medicament of the present invention both can have been separated out lime carbonate inhibitor and calcium carbonate dispersant in advance and mixed, and also can supply with lime carbonate respectively and separate out inhibitor and calcium carbonate dispersant.Separate out inhibitor and calcium carbonate dispersant various medicaments in addition but also can contain lime carbonate.
Embodiment
Below enumerate embodiment and reference examples the present invention is done more specifically explanation.
Embodiment 1～7 and reference examples 1～14
The intermittent type cooling water system evaluation experimental device that utilizes Fig. 1 to schematically illustrate has carried out the investigation test that preservative effect and incrustation scale in embodiment and the reference examples prevent effect.
The water quality of the process water that uses in the test is as shown in table 1 below.And used lime carbonate separates out inhibitor and calcium carbonate dispersant is as shown in table 2 below.
Table 1
The water quality of process water
| ??pH | ??7.4 |
| Specific conductivity (mS/m) | ??33 |
| M basicity (mg/Las CaCO 3) | ??80 |
| Total hardness (mg/Las CaCO 3) | ??120 |
| Calcium hardness (mg/Las CaCO 3) | ??80 |
| Silicon oxide (mg/L) | ??25 |
Table 2
Lime carbonate is separated out inhibitor
| ?A | Toxilic acid/vinylformic acid/styrol copolymer (mol ratio 60: 25: 15, molecular weight 10000) |
| ?B | Toxilic acid/isobutylene copolymers (mol ratio 1: 1, molecular weight 14000) |
| ?C | Polyacrylic acid (molecular weight 2000) |
| ?D | Polymaleic acid (molecular weight 600) |
| ?E | Amino Trimethylene Phosphonic Acid |
| ?F | The hydroxy ethylene phosphonic acids |
| ?G | 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid |
Calcium carbonate dispersant
| ?a | Polyvinyl alcohol (molecular weight 20000) |
| ?b | Polyoxyethylene glycol (molecular weight 12000) |
| ?c | Vinylformic acid/vinyl sulfonic acid multipolymer (mol ratio 75: 25, molecular weight 5000) |
| ?d | Vinylformic acid/allyl sulphonic acid multipolymer (mol ratio 70: 30, molecular weight 3000) |
| ?e | Vinylformic acid/styrene sulfonic acid multipolymer (mol ratio 80: 20, molecular weight 8000) |
| ?f | Vinylformic acid/3-propionyloxy-2-hydroxy-propanesulfonic acid multipolymer (mol ratio 80: 20, molecular weight 3000) |
| ?g | Vinylformic acid/hydroxyl-metacrylate/isoprene sulfonic acid copolymer (mol ratio 70: 10: 20, molecular weight 13000) |
In the evaluation experimental device of Fig. 1, utilize circulation pipe arrangement 2 to supply with recirculated cooling water to interchanger 3, return water and return cooling tower 1 by pipe arrangement 4 from cooling tower 1 with pump P1.The 5th, the importing pipe arrangement, the 6th of supplementary feed, the importing pipe arrangement, the 7th of aqueous sodium hypochlorite solution, the importing pipe arrangement, the 8th of medicament shown in the table 3, the pipe arrangement that flows has pump P2, P3, P4 and P5 respectively.Interchanger 3 is the steam heating tube water flowing interchanger that are provided with the carbon steel tubulation of 19 millimeters of three external diameters, 1500 millimeters of length, 2.3 millimeters of thickness, and not shown corrosometer is installed on this pipe.The 9th, the pipeline pipe arrangement has valve 9a.
The operating condition of this evaluation experimental device is as follows.
[operating condition]
Possess the water yield: 350 liters
Quantity of circulating water: 80 liters/minute (the cooling-tower circulating water amount that comprises heat exchange manifold)
The water yield flows: 4.5～9.5 liters/hour (by cycles of concentration)
Supplementary feed: process water
The supply water yield: 24～29 liters/hour (by cycles of concentration)
Flow velocity: 0.3 meter per second clock
Cycles of concentration: as shown in table 3
Heat exchanger entrance water temperature: 30 ℃
Heat exchanger exit water temperature: 50 ℃ (steam heating)
T:20 ℃ of water temperature temperature difference
The clorox addition: injection makes the water coolant concentration of residual chlorine reach 0.3～0.5 mg/litre continuously
Additive amount of medicament: added the medicament shown in the table 3 to add concentration shown in the table 3.
Above-mentioned running was carried out 30, had measured once/day corrosion speed (carbon steel) with corrosometer.The calcium hardness analysis is carried out once weekly in the water coolant, utilizes 0.1 micron millipore filter to filter water coolant, adopts volumetry to obtain the calcium hardness of filtrate.And the calcium hardness of strainer seizure part, after adding hydrochloric acid boils, use aas determination.
After running on the 30th, from interchanger, take out developmental tube, dry back every 20 centimetres with its cut-out, be used to estimate dirt settling and corrosion hole.The dirt settling of developmental tube takes off with metal brush, calculates the speed of adhering to of incrustation scale by its dry weight and pipe planimeter.And after taking off the chlorohydric acid pickling of the developmental tube utilization adding stopping agent behind the dirt settling, remove corrosion product.Utilize the degree of depth in hole on the hydrobarometer determination test tube-surface, obtain its maximum value.
With the calcium hardness of filtrate, filter the degree of depth of corrosion speed, corrosion hole of pipe in the calcium hardness of catching part, the interchanger and incrustation scale and adhere to speed and be shown among the table 3.Wherein the measured value of the calcium hardness of part is caught in the calcium hardness of corrosion speed, filtrate and filtration, adopts mean value during this period respectively.
And in table 3, also put down in writing the numerical value that multiply by cycles of concentration by the calcium hardness of supplementary feed (process water) in the lump, the difference of the calcium hardness sum of part is caught in the calcium hardness of deduction filtrate and filtration, as the index of incrustation scale tendency.
This moment, the lime carbonate saturation index that is dissolved in the water coolant was as shown in table 3, and the dispersive particle diameter is 0.1～10 micron a calcium carbonate microparticle amount in water coolant, filters the calcium hardness of catching part by 0.1 micron and is calculated as 0～30 mg/litre.
Table 3
| Example | Cooling water quality | Lime carbonate is separated out inhibitor | Calcium carbonate dispersant | Calcium hardness in the water coolant (mg/Las CaCO 3) | The saturation index of the calcium carbonate that dissolves in the cooling water | Evaluation effect | |||||||
| Kind | Concentration (mg/L) | Kind | Concentration (m g/ L) | 0.1 micron filtrate | 0.1 filtering, micron catches | Incrustation scale tendency * 4 | Corrosion speed (md d) | The corrosion hole degree of depth (mm/moon) | Incrustation scale adheres to speed (mg/c m 2/ month) | ||||
| Embodiment | ??1 | 3 times of condensed water of process water | ??A | ??30 | ??a | ??40 | ??210 | ??30 | ??0 | ??1.44 | ??2.3 | ??0.17 | ??4.7 |
| ??2 | ??B | ??5 | ??b | ??20 | ??230 | ??10 | ??0 | ??1.57 | ??3.4 | ??0.13 | ??2.8 | ||
| ??3 | ??C | ??10 | ??c | ??5 | ??230 | ??5 | ??5 | ??1.57 | ??3.9 | ??0.15 | ??3.4 | ||
| ??4 | 4 times of condensed water of process water | ??D | ??20 | ??d | ??20 | ??300 | ??15 | ??5 | ??1.96 | ??2.7 | ??0.21 | ??9.8 | |
| ??5 | ??E | ??6 | ??e | ??20 | ??315 | ??5 | ??0 | ??2.03 | ??2.3 | ??0.17 | ??3.6 | ||
| ??6 | ??F | ??6 | ??f | ??15 | ??310 | ??5 | ??5 | ??2.01 | ??1.8 | ??0.16 | ??2.1 | ||
| ??7 | 5 times of condensed water of process water | ??G | ??14 | ??g | ??25 | ??380 | ??15 | ??5 | ??2.31 | ??1.0 | ??0.20 | ??5.5 | |
| Reference examples | ??1 | 3 times of condensed water of process water | ??A | ??80 | ??213 | ??0 | ??27 | ??1.45 | ??16.0 | ??0.38 | ??4.3 | ||
| ??2 | ??B | ??20 | ??240 | ??0 | ??0 | ??1.63 | ??4.0 | ??0.25 | ??5.2 | ||||
| ??3 | ??C | ??20 | ??230 | ??5*1 | ??5 | ??1.60 | ??8.9 | ??0.47 | ??37.6 | ||||
| ??4 | 4 times of condensed water of process water | ??D | ??40 | ??310 | ??0 | ??10 | ??2.01 | ??7.2 | ??0.37 | ??38.0*3 | |||
| ??5 | ??E | ??30 | ??316 | ??0 | ??4 | ??2.04 | ??1.8 | ??0.30 | ??24.3*2 | ||||
| ??6 | ??F | ??20 | ??310 | ??0 | ??10 | ??2.01 | ??1.6 | ??0.28 | ??27.1*2 | ||||
| ??7 | 5 times of condensed water of process water | ??G | ??40 | ??376 | ??0 | ??24 | ??2.30 | ??1.9 | ??0.26 | ??11.7*3 | |||
| ??8 | 3 times of condensed water of process water | ??a | ??80 | ??155 | ??0 | ??85 | ??0.99 | ??60.5 | ??0.44 | ??38.0 | |||
| ??9 | ??b | ??40 | ??160 | ??0 | ??80 | ??1.04 | ??43.2 | ??0.52 | ??27.6 | ||||
| ??10 | ??c | ??20 | ??200 | ??0 | ??40 | ??1.37 | ??13.8 | ??0.34 | ??6.0 | ||||
| ??11 | 4 times of condensed water of process water | ??d | ??40 | ??250 | ??0 | ??70 | ??1.69 | ??14.6 | ??0.38 | ??4.2 | |||
| ??12 | ??e | ??30 | ??180 | ??0 | ??140 | ??1.21 | ??28.0 | ??0.42 | ??15.6 | ||||
| ??13 | ??f | ??30 | ??250 | ??0 | ??70 | ??1.69 | ??5.9 | ??0.36 | ??1.4 | ||||
| ??14 | 5 times of condensed water of process water | ??g | ??40 | ??230 | ??0 | ??170 | ??1.59 | ??8.3 | ??0.32 | ??2.3 | |||
* 1 strainer seizure thing is the gelling thing of polymkeric substance and calcium ion
* the main component of 2 dirt settlings is a calcium phosphate
* the main component of 3 dirt settlings is Magnesium Silicate q-agents
* the calcium hardness X cycles of concentration of 4 supplementary feed (process water)-(calcium hardness of filtrate+filtration catch calcium hardness)
Table 3 shows that employing the present invention can prevent corrosion of metal and incrustation scale obstacle in the cooling water system simultaneously.
Claims (7)
1. the treatment process of a water coolant in the corrosion of metal that suppresses cooling water system, prevents the incrustation scale obstacle, it is characterized in that,
In described water coolant, add lime carbonate and separate out inhibitor and calcium carbonate dispersant, calcium carbonate microparticle is disperseed in described water coolant, generate the corrosion protection tunicle in described metallic surface.
2. according to the described treatment of cooling water method of claim 1, it is characterized in that, in described water coolant, add the lime carbonate of 1～100 mg/litre respectively and separate out inhibitor and calcium carbonate dispersant, make described calcium carbonate microparticle with 5～100 mg/litre dispersive simultaneously, the saturation index that makes dissolved lime carbonate in described water coolant is 1.2～3.5.
3. according to claim 1 or 2 described treatment of cooling water methods, it is characterized in that, described lime carbonate separate out inhibitor be selected from by following (1) phosphonic acids based compound, following (2) carboxylic acid polyalcohol and following (3) carboxylic acid based copolymer form group in one or both or two or more:
(1) hydroxy ethylene diphosphonic acid, 2-phosphinylidyne butane-1,2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-phosphonic acids butane-1,2,3, at least a in 4-tetracarboxylic acid and the phosphono fumaric acid,
(2) at least a in polyacrylic acid, polymethyl acrylic acid, polymaleic acid, poly-methylene-succinic acid, polyacrylate, poly-methyl acrylate, polymaleic acid salt and the poly-itaconate,
(3) contain 40 moles of % or its above be selected from by vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid and their salt forms group in one or both or two or more carboxylic acid compositions; And 5 moles of % or its above be selected from by carbonatoms be 4～10 alkene, vinylbenzene and Dicyclopentadiene (DCPD) forms group in the multipolymer of one or both or two or more unsaturated hydrocarbons composition.
4. according to any described treatment of cooling water method in the claim 1～3, it is characterized in that, described calcium carbonate dispersant be from the group that following (4) carboxylic acid based copolymer and following (5) nonionic polymkeric substance are formed, select one or both or two or more:
(4) contain 30 moles of % or its above one or both or the two or more carboxylic acid compositions that from the group that vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid and their salt are formed, select; And above one or both or the two or more multipolymers that contains sulfonic unsaturated hydrocarbons composition from the group that vinyl sulfonic acid, allyl sulphonic acid, styrene sulfonic acid, isoprene sulfonic acid, 3-allyloxy-2-hydroxy-propanesulfonic acid and their salt constitute, selected of 5 moles of % or its
(5) at least a in polyacrylamide, polyvinyl alcohol, polyoxyethylene glycol, polypropylene glycol and the ethylene glycol and 1,2-propylene glycol segmented copolymer.
5. according to any described treatment of cooling water method in the claim 1～4, it is characterized in that, one or both that interpolation is selected from the group that calcium salt, hydrocarbonate, carbonate and alkali metal hydroxide constitute in described water coolant or two or more materials, by it is contacted with air, make described calcium carbonate microparticle separate out, disperse.
6. according to any described treatment of cooling water method in the claim 1～5, it is characterized in that, rise, separate out, disperse described calcium carbonate microparticle by the water temperature that makes described water coolant.
7. cooling water treatment agent, it is characterized in that one or both or the two or more lime carbonate selected that contain 5～95 weight % are separated out inhibitor from the group that following (1) phosphonic acids based compound, following (2) carboxylic acid polyalcohol and following (3) carboxylic acid based copolymer constitute; And one or both or the two or more calcium carbonate dispersants from the group that following (4) carboxylic acid based copolymer and following (5) nonionic polymkeric substance constitute, selected of 5～95 weight %:
(1) hydroxy ethylene dicarboxylic acid, 2-phosphinylidyne butane-1,2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-phosphinylidyne butane-1,2,3,4-tetracarboxylic acid, and at least a in the phosphono fumaric acid,
(2) polyacrylic acid, polymethyl acrylic acid, polymaleic acid, poly-methylene-succinic acid, polyacrylate, poly-methyl acrylate, polymaleic acid salt, and at least a in the poly-itaconate,
(3) contain 40 moles of % or its above one or both or the two or more carboxylic acid compositions that from the group that vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid and their salt are formed, select; What 5 moles of % or its were above is the multipolymer of one or both or the two or more unsaturated hydrocarbons composition selected the group that forms of 4～10 alkene, vinylbenzene and Dicyclopentadiene (DCPD) from carbonatoms,
(4) contain 30 moles of % or its above one or both or the two or more carboxylic acid compositions that from the group that vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid and their salt are formed, select; One or both or the two or more multipolymers that contains sulfonic unsaturated hydrocarbons composition that 5 moles of % or its are above selects from the group that vinyl sulfonic acid, allyl sulphonic acid, styrene sulfonic acid, isoprene sulfonic acid, 3-allyloxy-2-hydroxy-propanesulfonic acid and their salt are formed
(5) at least a material in polyacrylamide, polyvinyl alcohol, polyoxyethylene glycol, polypropylene glycol and the ethylene glycol and 1,2-propylene glycol segmented copolymer.
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| JP2004154821 | 2004-05-25 | ||
| JP2004154821 | 2004-05-25 |
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| CN1702047A true CN1702047A (en) | 2005-11-30 |
| CN100395199C CN100395199C (en) | 2008-06-18 |
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| CNB2005100517610A Expired - Fee Related CN100395199C (en) | 2004-05-25 | 2005-03-01 | Method of cooling water treatment and treatment chemical |
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|---|---|
| JP (1) | JP4725513B2 (en) |
| CN (1) | CN100395199C (en) |
| MY (1) | MY146543A (en) |
| TW (1) | TW200538405A (en) |
| WO (1) | WO2005116296A1 (en) |
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| CN104310606A (en) * | 2014-10-22 | 2015-01-28 | 山东华亚环保科技有限公司 | Corrosion inhibitor used for seawater concentration device |
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| CN105423591A (en) * | 2014-09-11 | 2016-03-23 | 株式会社日立制作所 | Working medium for absorption refrigerators, and absorption refrigerator using the same |
| CN105481116A (en) * | 2015-12-18 | 2016-04-13 | 宁波高新区夏远科技有限公司 | Circulating cooling water corrosion and scale inhibitor and preparation method thereof |
| CN113800653A (en) * | 2020-06-16 | 2021-12-17 | 中国石油化工集团有限公司 | Geothermal fluid scale inhibitor and preparation method and application thereof |
| CN114106788A (en) * | 2021-12-15 | 2022-03-01 | 湖南省希润弗高分子新材料有限公司 | Industrial circulating cooling liquid |
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| JP5128839B2 (en) * | 2007-03-30 | 2013-01-23 | 伯東株式会社 | Water treatment method for open circulation type cooling water system and water treatment agent for open circulation type cooling water system |
| KR100936378B1 (en) * | 2009-04-27 | 2010-01-13 | 에스엔유 프리시젼 주식회사 | Unit for supplying source and apparatus for depositioning thin film and method for depositioning thin film |
| CN101565660B (en) * | 2009-06-02 | 2011-08-17 | 董宇新 | Organic descaling composition, preparation method and application thereof |
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| JPS61118199A (en) * | 1984-11-14 | 1986-06-05 | Kurita Water Ind Ltd | Water-treating agent |
| JPH0730471B2 (en) * | 1987-12-29 | 1995-04-05 | 高砂熱学工業株式会社 | How to prevent corrosion of the piping system |
| JPH0231894A (en) * | 1988-07-22 | 1990-02-01 | Mitsubishi Gas Chem Co Inc | Agent for preventing scaling in cooling water system |
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- 2005-02-02 JP JP2006513807A patent/JP4725513B2/en active Active
- 2005-02-02 WO PCT/JP2005/001472 patent/WO2005116296A1/en active Application Filing
- 2005-03-01 CN CNB2005100517610A patent/CN100395199C/en not_active Expired - Fee Related
- 2005-03-08 TW TW094107049A patent/TW200538405A/en not_active IP Right Cessation
- 2005-04-22 MY MYPI20051786A patent/MY146543A/en unknown
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| CN113800653A (en) * | 2020-06-16 | 2021-12-17 | 中国石油化工集团有限公司 | Geothermal fluid scale inhibitor and preparation method and application thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI305765B (en) | 2009-02-01 |
| JPWO2005116296A1 (en) | 2008-04-03 |
| TW200538405A (en) | 2005-12-01 |
| CN100395199C (en) | 2008-06-18 |
| JP4725513B2 (en) | 2011-07-13 |
| MY146543A (en) | 2012-08-15 |
| WO2005116296A1 (en) | 2005-12-08 |
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