CN101151400A - Water treatment and method of water treatment - Google Patents
Water treatment and method of water treatment Download PDFInfo
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- CN101151400A CN101151400A CNA200680010488XA CN200680010488A CN101151400A CN 101151400 A CN101151400 A CN 101151400A CN A200680010488X A CNA200680010488X A CN A200680010488XA CN 200680010488 A CN200680010488 A CN 200680010488A CN 101151400 A CN101151400 A CN 101151400A
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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
- C23F11/18—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 inorganic inhibitors
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved 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
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
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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
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
- F24H9/00—Details
- F24H9/0005—Details for water heaters
- F24H9/0042—Cleaning arrangements
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
A water treatment for preventing the heat transfer surface of a boiler tube from general or local corrosion and attaining excellent heat transfer characteristics, which is composed of water as the main component, a film forming agent for forming a film on the heat transfer surface of a boiler tube, a deoxidizing agent, a scale inhibitor, and a pH regulator. By pouring this water treatment into boiler feeding, the prevention of a boiler tube from corrosion and the inhibition of scaling can be attained with good balance. According to the invention, a film for preventing the heat transfer surface of a boiler tube from corrosion is formed from the film forming agent; the oxygen dissolved in boiler feeding is removed with the deoxidizing agent; the scaling on the heat transfer surface of a boiler tube is inhibited with the scale inhibitor; and the pH of boiler feeding is regulated, whereby the heat transfer surface of a boiler tube can be prevented from general or local corrosion and excellent heat transfer characteristics can be attained.
Description
Technical field
The present invention relates to water conditioner and water treatment method, particularly, can obtain the water conditioner of excellent heat transfer characteristic and the water treatment method that uses this water conditioner in general corrosion that prevents the boiler water tube heat-transfer surface and local corrosive while.
Background technology
Boiler is used as heating, generating is extensive use of with the equal energy source supply arrangement, is the device that generates steam.The inner surface (heat-transfer surface of boiler water tube) that produces the water pipe of steam in the boiler is in high temperature and high pressure environment, supply with compositions such as calcium contained in the water (oiler feed) of boiler and be attached to (fouling) on this heat-transfer surface with the form of incrustation scale, this heat-transfer surface also can be corroded by oiler feed.
If incrustation scale is attached to heat-transfer surface, this incrustation scale hinders the transmission of heat, makes heat transfer characteristic reductions such as boiler efficiency.In addition, if heat-transfer surface is corroded, because this corrosion makes the boiler water tube breakage, because of the breakage of this boiler water tube may make the running of boiler stop.
Therefore, in the past in order to prevent the fouling or the corrosion of (inhibition) this boiler water tube heat-transfer surface, in oiler feed, add reagent such as scale inhibitor, pH regulator agent as water conditioner.But water conditioner in the past is for the fouling that prevents the boiler water tube heat-transfer surface or prevents to corrode and use respectively, simultaneously and balance prevent from the boiler water tube fouling of heat-transfer surface well and prevent to corrode to be difficult to.
That is, add water conditioner for the fouling that prevents heat-transfer surface in oiler feed, even can prevent the fouling of heat-transfer surface, the corrosion of anti-antipriming pipe heat-transfer surface is also insufficient.And in oiler feed, add water conditioner for the corrosion that prevents heat-transfer surface, even can prevent the corrosion of heat-transfer surface, prevent that the fouling of heat-transfer surface is still insufficient.
Therefore, the corrosion of the heat-transfer surface that produces for the influence that suppresses owing to moisture and the generation of incrustation scale, as can be simultaneously and balance prevent fouling of heat-transfer surface well and prevent that corrosive water conditioner, someone from having proposed the water conditioner (with reference to TOHKEMY 2003-159597 communique) that is made of the material that contains silicon-dioxide and pH regulator agent, scale inhibitor.
Water conditioner in the TOHKEMY 2003-159597 communique is in order to prevent the corrosion of boiler water tube heat-transfer surface, by silica composition and pH regulator agent, on heat-transfer surface, formed and be used to prevent corrosive silicon dioxide layer and iron hydroxide layer (for example alkali formula ironic hydroxide).But, if the thickness of silicon dioxide layer that forms and iron hydroxide layer is not enough, then can't bring into play corrosion-resisting function on heat-transfer surface, therefore also have the corrosive situation takes place on the heat-transfer surface.
If heat-transfer surface is covered by this corrosion product,, therefore the problem of the heat transfer characteristic variation of boiler is arranged because the thermal conductivity of corrosion product is little.In addition, heat-transfer surface can't be covered equably when whole, on heat-transfer surface, local corrosion (pitting) can be produced at this silicon dioxide layer and iron hydroxide layer.Heat-transfer surface is then produced the hole of once through boiler water pipe by local corrosion, the problem of being leaked in the stove of boiler by this hole occurs.
Summary of the invention
The object of the present invention is to provide the general corrosion and the local burn into that prevent the boiler water tube heat-transfer surface can obtain the water conditioner of excellent heat transfer characteristic and the water treatment method that uses this water conditioner simultaneously.
Purpose of the present invention realizes that by a kind of water conditioner this water conditioner is characterised in that: as main component, be engaged in the film forming membrane-forming agent of shape, reductor, scale inhibitor, pH regulator agent on the heat-transfer surface of boiler water tube with water in above-mentioned water.
Adopt above-mentioned formation, on the heat-transfer surface of boiler water tube, form and to suppress the corrosive film by membrane-forming agent; Dissolved oxygen in the oiler feed is removed by reductor; And the fouling of boiler water tube heat-transfer surface is prevented by scale inhibitor; The pH of oiler feed has also carried out pH regulator; Therefore the general corrosion and the local corrosion of boiler water tube heat-transfer surface can be prevented, excellent heat transfer characteristic can be obtained simultaneously.
Above-mentioned membrane-forming agent contains at least a or multiple in silicon-dioxide, water glass, potassium silicate, ortho-silicate, the polysilicate.
Adopt above-mentioned formation, then can on the heat-transfer surface of boiler water tube, suppress the corrosive film by as at least a or multiple formation the in the silicon-dioxide of membrane-forming agent, water glass, potassium silicate, ortho-silicate, the polysilicate, therefore the general corrosion and the local corrosion of boiler water tube heat-transfer surface can be further prevented, excellent heat transfer characteristic can be obtained simultaneously.
Above-mentioned reductor contains at least a or multiple in vitamins C and salt, tannin, carbohydrate reductor, saccharosonic acid and salt thereof, the sulphite.
Here, reductor uses vitamins C and salt thereof etc., is owing to can remove the oxygen that is dissolved in the oiler feed by strong reducing power, and does not have the toxicity of hydrazine.The oiler feed of having removed dissolved oxygen reduces for the corrosive nature of boiler water tube heat-transfer surface.
Adopt above-mentioned formation, at least a or the multiple nontoxic reductors such as reductor that dissolved oxygen in the oiler feed is contained in vitamins C and salt thereof, tannin, carbohydrate reductor, saccharosonic acid and salt thereof, the sulphite are removed, therefore the general corrosion and the local corrosion of boiler water tube heat-transfer surface can be further prevented, excellent heat transfer characteristic can be obtained simultaneously.
Above-mentioned scale inhibitor contains at least a or multiple in citric acid, ethylenediamine tetraacetic acid (EDTA) and salt thereof, polyacrylic acid and salt thereof, polymaleic acid and the salt thereof.
Here, using scale inhibitor is because it can prevent that incrustation scale is attached to the heat-transfer surface of boiler water tube (fouling).That is, when this scale inhibitor used citric acid, ethylenediamine tetraacetic acid (EDTA) and salt thereof, contained calcium ion or magnesium ion can't be attached to the heat-transfer surface of boiler water tube with the form of incrustation scale by this scale inhibitor chelating in the oiler feed.In addition, when this scale inhibitor used polyacrylic acid, polymaleic acid etc., the growth of the incrustation scale nucleus that is formed by calcium ion or magnesium ion was hindered, and can't be attached to the heat-transfer surface of boiler water tube with the form of incrustation scale.
Adopt above-mentioned formation, at least a or multiple scale inhibitor that the fouling of boiler water tube heat-transfer surface is contained in citric acid, ethylenediamine tetraacetic acid (EDTA) and salt thereof, polyacrylic acid and salt thereof, polymaleic acid and the salt thereof prevents.Like this, because the fouling of boiler water tube heat-transfer surface is prevented that by scale inhibitor-ethylenediamine tetraacetic acid (EDTA) and salt etc. thereof can prevent the general corrosion and the local corrosion of boiler water tube heat-transfer surface, the while can obtain more excellent heat transfer characteristic.
Above-mentioned pH regulator agent contains at least a or multiple in the alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide.
Here, adopt this pH regulator agent, be for the corrosion that prevents the boiler water tube heat-transfer surface with the pH regulator of oiler feed to an alkaline side.
Adopt above-mentioned formation, pH regulator is carried out at least a or multiple pH regulator agent of the pH of oiler feed in containing alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide.Like this,, the general corrosion and the local corrosion of boiler water tube heat-transfer surface can be prevented, excellent heat transfer characteristic can be obtained simultaneously because the pH of oiler feed carries out pH regulator through pH regulator agent such as sodium hydroxide.
Target of the present invention realizes that by a kind of water treatment method this water treatment method is characterised in that and comprises following steps: the step that above-mentioned water conditioner is adjusted to normality; Detection is dissolved in the step to silica concentration in the water pot and dissolved oxygen content; To supplying with the step that above-mentioned amount of giving the above-mentioned water conditioner of water pot is controlled.
By adopting above-mentioned formation, when silica concentration in the oiler feed or dissolved oxygen content change, for being combined with on the heat-transfer surface of the boiler water tube film forming membrane-forming agent of shape, reductor, scale inhibitor, pH regulator agent and being adjusted to the water conditioner of normality, can supply with the amount of giving water pot according to above-mentioned change control.Thus, even silica concentration in the oiler feed or dissolved oxygen content change, also water conditioner can be adjusted to normality, control according to above-mentioned change carried out concentration adjustment water conditioner to giving the feed rate of water pot, the general corrosion and the local corrosion of boiler water tube heat-transfer surface can be prevented thus, excellent heat transfer characteristic can be obtained simultaneously.
The accompanying drawing summary
Fig. 1 is the signal pie graph of the steam boiler plant of the embodiment of the invention 2.
The best mode that carries out an invention
The present invention realizes by the water conditioner of following formation: as main component, be engaged in the film forming membrane-forming agent of shape, reductor, scale inhibitor, pH regulator agent on the boiler water tube heat-transfer surface with water in above-mentioned water.
In this water conditioner, membrane-forming agent uses at least a or multiple of known materials such as silicon-dioxide (silicic anhydride), water glass, potassium silicate, ortho-silicate, polysilicate.This membrane-forming agent is adsorbed on the heat-transfer surface of boiler water tube, forms film, covers the heat-transfer surface of boiler water tube with this film.The film that forms with this membrane-forming agent is by covering the heat-transfer surface of boiler water tube, and the function on performance blocking layer (shielding layer) plays the effect of corrosion protection film, and therefore, the corrosion of the boiler water tube heat-transfer surface that is covered by this protective membrane is suppressed.
The reductor that uses with this membrane-forming agent uses at least a or multiple of vitamins C and salt, tannin, carbohydrate reductor, saccharosonic acid and known material such as salt, sulphite thereof.This reductor does not have the such toxicity of hydrazine, can remove the oxygen that is dissolved in the oiler feed.Be dissolved in oxygen in the oiler feed as oxygenant, have the effect of corrosion boiler water tube heat-transfer surface.Therefore, remove the oxygen that is dissolved in the oiler feed by reductor, then the oxidant concentration in the oiler feed reduces, and has therefore prevented the general corrosion of boiler water tube heat-transfer surface.In addition, remove the oxygen that is dissolved in the oiler feed, then on the heat-transfer surface of boiler water tube, the ununiformity of oxygen concn reduces, and therefore is difficult to form the deep or light battery of oxygen, has also prevented the local corrosion of boiler water tube heat-transfer surface.Here, the water conditioner with embodiment of the present invention is prevented following being elaborated of situation of the local corrosion of boiler water tube heat-transfer surface.
Usually, can suppress the corrosive film if form on the heat-transfer surface of boiler water tube, the material (for example carbon steel) that then uses on this boiler water tube heat-transfer surface is difficult to be corroded by oiler feed.The film that forms on this boiler water tube heat-transfer surface for example is the surface that silica composition is adsorbed on carbon steel, forms the film of alkali formula ironic hydroxide on the surface of carbon steel.But the surface of this boiler water tube heat-transfer surface can exist because of hindering film forming factor and cause the insufficient part of film forming (film defect part).Suppressing this film forming factor has variously, for example exist to suppress film forming chloride ion in the oiler feed, owing to the surface inhomogeneity that the surface segregation that contained sulphur (sulfide) waits in the carbon steel causes, flow into the inhomogeneous density unevenness that causes membrane-forming agent of oiler feed flow velocity in the boiler water tube and spare etc.This occurs and suppress film forming factor, then there be membrane portions (intact membrane portions) and the inadequate part of this film forming (film defect part) that is formed by silicon-dioxide or iron hydroxide in the surface of boiler water tube heat-transfer surface, intact membrane portions and film defect part form local element, and local corrosion can take place.
But local corrosions such as common known crevice corrosion or pitting (corrosion of metallic surface is not equably but corrosion that concentration of local ground takes place) are easily in the environment generation down that is difficult to take place general corrosion (corrosion that the metallic surface roughly takes place equably).General corrosion is roughly to take place equably on the metallic surface; therefore the metallic surface can be by local corrosion; and local corrosion is by passive film or protective membrane the corrosion integral body of metallic surface to be suppressed when (form intact film, suppress general corrosion), takes place at the film defect part easily.This be because: compare with intact membrane portions, the film defect part is corroded easily, is corroded to film defect part concentration of local.
Promptly, be owing to form local element between this film defect part and the intact membrane portions, this film defect part becomes the anode electrode (negative pole of battery of local element, oxidizing reaction takes place, and metal is dissolved, promptly is corroded), intact membrane portions becomes the cathode electrode (positive pole of battery of local element, reduction reaction takes place, and metal is not dissolved, promptly is not corroded).This local element forms the deep or light battery of oxygen, carries out cell reaction.The deep or light battery of known oxygen normally forms the ratio big more (Cell EMF is big) of intact membrane portions with the oxygen amount (concentration) that forms anodic film defect part of negative electrode, and then corrosion speed is fast more.Just mean on the contrary,, then can prevent (inhibition) because the local corrosion that the film defect part causes if can reduce the ratio of the oxygen amount (concentration) of intact membrane portions and film defect part.
Even the film of the boiler water tube heat-transfer surface that is formed by above-mentioned membrane-forming agent has formed the film defect part for some reason, owing to can reduce the oxygen amount (concentration) that is dissolved in the oiler feed by reductor, be difficult to form the deep or light battery of oxygen, therefore water conditioner of the present invention can prevent local corrosion.Promptly, the oxygen amount (concentration) that is dissolved in the oiler feed reduces, and the absolute magnitude of the oxygen amount (concentration) of then intact membrane portions reduces, and the ratio of the therefore intact membrane portions and the oxygen amount (concentration) of film defect part reduces, the electromotive force of the deep or light battery of oxygen reduces, and can prevent local corrosion.
In the water conditioner of the present invention, except that reductor, also be combined with scale inhibitor.This scale inhibitor uses at least a or multiple of known materials such as citric acid, ethylenediamine tetraacetic acid (EDTA) and salt thereof, polyacrylic acid, polymaleic acid.When scale inhibitor used citric acid, ethylenediamine tetraacetic acid (EDTA) and salt (EDTA-Na) thereof, contained calcium ion or magnesium ion were by this scale inhibitor chelating in the oiler feed, and incrustation scale is difficult to be attached on the heat-transfer surface of boiler water tube.When scale inhibitor used polyacrylic acid and salt, polymaleic acid and salt thereof etc., the growth of the nucleus of the incrustation scale that is formed by calcium ion or magnesium ion was hindered, and incrustation scale is difficult to be attached on the heat-transfer surface of boiler water tube.Like this, incrustation scale is difficult to be attached to the heat-transfer surface of boiler water tube, and boiler just can keep excellent heat transfer characteristic to turn round.
And this water conditioner also is combined with the pH regulator agent.At least a or multiple of known materials such as alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide used in the pH regulator agent.For preventing the corrosion of boiler water tube heat-transfer surface, this pH regulator agent with the pH regulator of oiler feed to an alkaline side.
Membrane-forming agent of the present invention, reductor, scale inhibitor, pH regulator agent can be with the forms of independent reagent, supply with the form that is dissolved in water, but consider that the adding (dosing) of water conditioner is bothersome, preferably make a kind of preparation of liquid.
[embodiment]
Below, exemplify embodiment 1-embodiment 3, be elaborated according to an embodiment of the water conditioner of table 1 pair embodiment of the present invention.
Table 1
| Embodiment | Comparative example | ||||
| 1 | 2 | 3 | 1 | 2 | |
| Water glass [g] | 1.26 | 5.46 | 9.66 | 0.04 | 21.5 |
| Vitamins C [g] | 2.5 | 5.0 | 7.5 | 0.0 | 0.0 |
| EDTA-2Na[g] | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Sodium hydroxide [g] | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 |
| Whether general corrosion is arranged | Do not have | Do not have | Do not have | Do not have | Do not have |
| Whether local corrosion is arranged | Have slightly | Do not have | Do not have | Have | Do not have |
| The maximum pitting degree of depth [μ m] | 80 | 33 | 2 | 130 | 2 |
| Whether there is incrustation scale to adhere to | Do not have | Do not have | Do not have | Do not have | Have |
| The Ca solubleness [mg/l] of feedwater | ≥10 | ≥10 | ≥10 | ≥10 | 8.2 |
(1) embodiment 1
The water conditioner of table 1 illustrated embodiment 1 be every 100g water conditioner total amount in pure water, amount fits in film, reductor, scale inhibitor, pH regulator agent gained according to the rules.Promptly, the water conditioner of embodiment 1 cooperate 1.26g water glass (with the pure medicine of light, special grade chemical) as membrane-forming agent, 2.5g vitamins C (L-xitix) (with the pure medicine of light, special grade chemical) as reductor, 0.4g EDTA-2Na (with the pure medicine of light, special grade chemical) as scale inhibitor, agent forms 4.0g sodium hydroxide (with the pure medicine of light, special grade chemical) as pH regulator, it is joined in the softening water, add 500mg in every premium on currency.Here, use water with the softening water manual shift gained of Osaka City as the softening water of oiler feed, water quality is: pH 7.5, perveance 25mS/m, M basicity 20mg/l-CaCO
3, hardness 1mg/l-CaCO
3Adopt the softening water that uses in the embodiment of this water conditioner and the comparative example to use the water that this Osaka City softening water is carried out the manual shift gained, omit content later on about this softening water.
(2) embodiment 2
The water conditioner of the water conditioner of embodiment 2 and embodiment 1 is same, be every 100g water conditioner total amount in pure water according to the rules amount fit in film, reductor, scale inhibitor, pH regulator agent gained.Promptly, the water conditioner of embodiment 2 cooperate 5.46g water glass (with the pure medicine of light, special grade chemical) as membrane-forming agent, 5.0g vitamins C (L-xitix) (with the pure medicine of light, special grade chemical) as reductor, 0.4g EDTA-2Na (with the pure medicine of light, special grade chemical) as scale inhibitor, agent forms 4.0g sodium hydroxide (with the pure medicine of light, special grade chemical) as pH regulator, it is joined in the softening water, add 500mg in every premium on currency.
(3) embodiment 3
The water conditioner of the water conditioner of embodiment 3 and embodiment 1 is same, be every 100g water conditioner total amount in pure water according to the rules amount fit in film, reductor, scale inhibitor, pH regulator agent gained.Promptly, the water conditioner of embodiment 3 cooperate the 9.66g water glass as membrane-forming agent, 7.5g vitamins C (L-xitix) (with the pure medicine of light, special grade chemical) as reductor, 0.4g EDTA-2Na (with the pure medicine of light, special grade chemical) as scale inhibitor, agent forms 4.0g sodium hydroxide (with the pure medicine of light, special grade chemical) as pH regulator, it is joined in the softening water, add 500mg in every premium on currency.
[comparative example]
(1) comparative example 1
The water conditioner of comparative example 1 be every 100g water conditioner total amount in pure water according to the rules amount fit in film, scale inhibitor, pH regulator agent gained.Promptly, the water conditioner of comparative example 1 cooperate 0.04g water glass (with the pure medicine of light, special grade chemical) as membrane-forming agent, 0.4gEDTA-2Na (with the pure medicine of light, special grade chemical) as scale inhibitor, agent forms 4.0g sodium hydroxide (with the pure medicine of light, special grade chemical) as pH regulator, it is joined in the softening water, add 500mg in every premium on currency.
(2) comparative example 2
The water conditioner of the water conditioner of comparative example 2 and comparative example 1 is same, be every 100g water conditioner total amount in pure water according to the rules amount fit in film, scale inhibitor, pH regulator agent gained.Promptly, the water conditioner of comparative example 2 cooperate 21.5g water glass (with the pure medicine of light, special grade chemical) as membrane-forming agent, 0.4g EDTA-2Na (with the pure medicine of light, special grade chemical) as scale inhibitor, agent forms 4.0g sodium hydroxide (with the pure medicine of light, special grade chemical) as pH regulator, it is joined in the softening water, add 500mg in every premium on currency.
[evaluation]
(1) test condition
Use and measure the oiler feed of having added the water conditioner shown in embodiment 1-3, the comparative example 1-2 according to the rules, incrustation scale attachment characteristic and corrosion on the boiler water tube heat-transfer surface are estimated.This incrustation scale attachment characteristic and corrosive are estimated use test and are carried out with one through boiler, to steam output is that 1.35kg/ hour test is supplied with according to the rules amount in one through boiler and added the softening water of the water conditioner shown in embodiment 1-3, the comparative example 1-2 as oiler feed, making it continuously produce pressure is the steam of 0.3MPa, and the discharge rate that makes oiler feed simultaneously is 10% to turn round.In order to make incrustation scale attachment characteristic and the corrosion evaluation evaluation of approaching actual boiler as much as possible on the boiler water tube heat-transfer surface, one through boiler continuous operation 48 hours are used in this test.Incrustation scale attachment characteristic on the boiler water tube heat-transfer surface is to gather feedwater (heated water in the boiler water tube) in boiler running beginning after 24 hours, measure the Ca concentration in the feedwater, estimate the solubleness of Ca, simultaneously finish the back and take out the boiler water tube of estimating usefulness with one through boiler, observe the heat-transfer surface of this boiler water tube and estimate by test running in 48 hours.The corrosion of boiler water tube heat-transfer surface is to observe above-mentioned evaluation to estimate with the heat-transfer surface of boiler water tube.
(2) evaluation of incrustation scale attachment characteristic
Incrustation scale attachment characteristic on the boiler water tube heat-transfer surface is estimated according to following order.
At first, carry out the collection of feedwater after 24 hours in the boiler entry into service, the Ca concentration of the feedwater of collection is measured by the ICP apparatus for analyzing luminosity, estimates Ca solubleness by the Ca concentration of this mensuration, estimates the incrustation scale attachment characteristic on the boiler water tube heat-transfer surface.Here, estimate the incrustation scale attachment characteristic by the evaluation of Ca solubleness, if be to be conceived to Ca precipitate into as incrustation scale on the heat-transfer surface of boiler water tube, then the Ca concentration of feedwater, be that Ca solubleness reduces and to carry out.Specifically, be that containing Ca concentration was 1.0 mg/l-CaCO when one through boiler was used in the running test under 10% the condition in the discharge rate of boiler
3If oiler feed on the boiler water tube heat-transfer surface, do not have Ca to separate out as incrustation scale, then the Ca solubleness of feedwater does not reduce, Ca concentration can be detected with the concentration that keeps about 10mg/l.And if the surface C a of boiler water tube heat-transfer surface separates out as incrustation scale, then the Ca solubleness of feedwater reduces, and the concentration of Ca is detected with the concentration lower than 10mg/l.
Below, the running of test with one through boiler ended in the boiler entry into service after 48 hours, take out boiler water tube in the boiler by this termination, and whether have Ca with the form of incrustation scale adhere to, estimate the incrustation scale attachment characteristic with magnifying glass if with the naked eye observing on this boiler water tube heat-transfer surface.The incrustation scale attachment characteristic also can use film thickness gauge, measures the thickness that is attached to the incrustation scale on the boiler water tube heat-transfer surface, is estimated by the thickness of incrustation scale.
Like this, in the table 1,, provided the Ca solubleness of feedwater with the form of the Ca concentration of boiler running beginning after 24 hours for the oiler feed of the water conditioner shown in amount interpolation embodiment 1-3, the comparative example 1-2 according to the rules.
According to the result shown in this table 1, to measure in the oiler feed of the water conditioner that has added embodiment 1-3 and comparative example 1 according to the rules, Ca solubleness is more than the 10mg/l.And measure according to the rules in the oiler feed of the water conditioner that has added comparative example 2, the solubleness of Ca is below the 10mg/l.In the water conditioner of comparative example 2, Ca solubleness is little, and this is that the silica composition in the water glass combines with hardness (Ca), is attached to thickly on the heat-transfer surface of boiler water tube because the concentration of oiler feed mesosilicic acid sodium is big.
(3) corrosion evaluation
The corrosion evaluation of boiler water tube heat-transfer surface carries out in the following order.At first, the boiler running was stopped after 48 hours,, remove descale by the water pipe surface by washing or pickling by taking out boiler water tube in this boiler that stops.Then, with the naked eye or visual observation such as the magnifying glass surface of having removed the boiler water tube of incrustation scale, check whether it has general corrosion.At last, for local corrosion, whether the surface of having removed the boiler water tube of incrustation scale by visual observations such as naked eyes or magnifying glasses pitting (also being pit) has taken place, and with the optical displacement instrumentation degree of depth at the position of pitting takes place surely, obtains the full depth of pitting.
Whether the heat-transfer surface that in the table 1 oiler feed of the water conditioner of the embodiment 1-3, the comparative example 1-2 that have added specified amount has been provided boiler water tube respectively has the full depth of general corrosion, local corrosion and pitting.
According to the result shown in the table 1, the oiler feed of having added the water conditioner of the embodiment 1-3 of specified amount and comparative example 2 can prevent the general corrosion and the local corrosion of boiler water tube heat-transfer surface.Though and the oiler feed of water conditioner of having added the comparative example 1 of specified amount has prevented general corrosion, fails to prevent the local corrosion of boiler water tube heat-transfer surface.
Show by above, water conditioner according to this embodiment 1-3, form on the boiler water tube heat-transfer surface by membrane-forming agent and can suppress the corrosive film, remove dissolved oxygen in the oiler feed, prevent that by scale inhibitor the pH of fouling, oiler feed of boiler water tube heat-transfer surface is through pH regulator again by reductor, the general corrosion and the local corrosion of boiler water tube heat-transfer surface can be prevented thus, excellent heat transfer characteristic can be obtained simultaneously.
Below, describe in steam boiler plant, using an embodiment of the water treatment method of water conditioner of the present invention according to Fig. 1.Fig. 1 represents that the signal of steam boiler plant constitutes.
Among Fig. 1, steam boiler plant 1 supplies with part 4 by feeding apparatus part 2, steam boiler 3, water conditioner and control section 5 constitutes.
If owing to have dissolved oxygen in the soft water, this oxygen is corroded the heat-transfer surface of boiler water tube easily, so de-gassing vessel 22 mainly is a device of removing the dissolved oxygen in the soft water in advance.De-gassing vessel 22 can adopt by gas separation membrane or heating and remove the device of deoxidation continuously and utilize decompression or hyperacoustic intermittent type device etc.Wherein, use can see through gas but not see through the device of the film-gas separation membrane of liquid, and its processing ease, stably continuous operation, cost are low, are preferred embodiment therefore.That is, the device of using gas separatory membrane makes through the softening water of handling (soft water) and flows through in the inboard of gas separation membrane, makes the outside of film be in vacuum state, is discharged to the outside of film in this soft water between the contained air penetrating film, can make the soft water degassing.
During the soft water that has been removed dissolved oxygen in this de-gassing vessel 22 is stored in to water pot 23.Store the oiler feed of supplying with steam boilers 3 for water pot 23, and have the silica concentration in mensurations, the detection oiler feed or the test section 24 of dissolved oxygen content.The steam water of condensation after heat exchange in load device (omitting diagram) that generates in the soft water of de-gassing vessel 22 degassing and steam boiler 3 is supplied with via water of condensation recycling pipeline (omitting diagram) should be to water pot 23.In addition, for agent treated is carried out in oiler feed, be stored in water conditioner in the water conditioner jar 41 described later by reagent supply pump P1, supply with to water pot 23 via water conditioner supply line W2.This water conditioner is the described water conditioner of the embodiment of the invention described above, as main component, is combined with the film forming membrane-forming agent of shape, reductor, scale inhibitor, pH regulator agent on the boiler water tube heat-transfer surface with water.Therefore, this water conditioner is supplied with oiler feed, can prevent the corrosion of boiler water tube heat-transfer surface or adhering to of incrustation scale.This oiler feed by service pump P2, via feedwater line W3 by supplying with steam boilers 3 for water pot 23.
Here, the silica concentration that detects in test section 24 is as concentration of silicon dioxide, measures and detects according to the yellow absorption photometry of the molybdenum of JIS K0101.In addition, dissolved oxygen content is measured and is detected according to the process water method of testing of JIS K0101.
Supply with in the steam boiler 3 of this oiler feed and generate steam, this steam is supplied with various load devices (omitting diagram) via vapour line S1.
The water treatment method of present embodiment is: in being stored in to the oiler feed in the water pot 23 when dissolved silica concentration or dissolved oxygen content change, according to above-mentioned change, supply with method to water pot 23 with being adjusted to normality in advance and being stored in water conditioner in the water conditioner jar 41.In this case, supply controls its feed rate according to the change of silica concentration or dissolved oxygen content for the water conditioner of water pot 23.The control of the feed rate of water conditioner can be passed through control section 5 described later, and the control water conditioner is supplied with the work output of the reagent supply pump P1 of part 4 and carried out.
Water conditioner is supplied with part 4 and is made of the water conditioner jar 41 of above-mentioned storage water conditioner, the reagent supply pump P1 that is supplied with to water pot 23 by water conditioner jar 41.Water conditioner jar 41 stores the water conditioner that is adjusted to normality in advance.
The change conditions of silica concentration or dissolved oxygen content is by detecting for silica concentration or dissolved oxygen content in the 24 pairs of oiler feeds in test section that have in the water pot 23 in the oiler feed, according to silica concentration or the dissolved oxygen content that detection obtains, judge by control section 5.
As shown in Figure 1, control section 5 is electrically connected with each instrument that constitutes feeding apparatus part 2 and water conditioner supply part 4.Specifically, test section 24 that has in control section 5 and the oiler feed jar 23 and reagent are supplied with part P1 and are electrically connected.
Control section 5 is with the form formation that is the logical circuit at center with the minicomputer, has the RAM52 of central processing unit CPU51, temporary storaging data, the ROM53 of storage processing program or the input/output interface 54 of the various signals of input and output.Control section 5 by the relevant information of test section 24 input silica concentrations or dissolved oxygen content, according to this information, is exported the control signal of reagent supply pump P1 work output as mentioned above, the work output of control reagent supply pump P1.
Increase if supply with the feed rate of the water conditioner of giving water pot 23, then incrustation scale is attached on the boiler water tube heat-transfer surface easily, the heat transfer characteristic variation, and therefore, the work output of control reagent supply pump P1 is in order to prevent this problem.On the other hand, the feed rate of supplying with the water conditioner of giving water pot 23 reduces, the then thickness attenuation of silicon dioxide layer that on the boiler water tube heat-transfer surface, forms or iron hydroxide layer, and the boiler water tube heat-transfer surface is by general corrosion, therefore, the work output of control reagent supply pump P1 also is in order to prevent this problem.In addition, the thickness distribution of silicon dioxide layer that forms on the boiler water tube heat-transfer surface or iron hydroxide layer is inhomogeneous, and then the boiler water tube heat-transfer surface is easily by local corrosion, and the work output of control reagent supply pump P1 is also in order to prevent this problem.
As mentioned above, water treatment method according to present embodiment, when silica concentration in the oiler feed or dissolved oxygen content change, for being combined with the film forming membrane-forming agent of shape, reductor, scale inhibitor, pH regulator agent on the heat-transfer surface of boiler water tube, and be adjusted to the water conditioner of normality, control by the water conditioner jar by the above-mentioned change of correspondence and to supply with amount to water pot, the general corrosion and the local corrosion of boiler water tube heat-transfer surface can be prevented, excellent heat transfer characteristic can be obtained simultaneously.
Claims (6)
1. water conditioner is characterized in that, this water conditioner as main component, is combined with the film forming membrane-forming agent of shape, reductor, scale inhibitor, pH regulator agent on the boiler water tube heat-transfer surface with water in above-mentioned water.
2. the water conditioner of claim 1 is characterized in that, above-mentioned membrane-forming agent contains at least a or multiple in silicon-dioxide, water glass, potassium silicate, ortho-silicate, the polysilicate.
3. claim 1 or 2 water conditioner is characterized in that, above-mentioned reductor contains at least a or multiple in vitamins C and salt, tannin, carbohydrate reductor, saccharosonic acid and salt thereof, the sulphite.
4. claim 1,2 or 3 water conditioner is characterized in that, above-mentioned scale inhibitor contains at least a or multiple in citric acid, ethylenediamine tetraacetic acid (EDTA) and salt thereof, polyacrylic acid and salt thereof, polymaleic acid and the salt thereof.
5. claim 1,2,3 or 4 water conditioner is characterized in that, above-mentioned pH regulator agent contains at least a or multiple in the alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide.
6. water treatment method is characterized in that, the method includes the steps of: the step that claim 1,2,3,4 or 5 water conditioner is adjusted to normality; Detection is dissolved in the step to silica concentration in the water pot and dissolved oxygen content; To supplying with the step that above-mentioned amount of giving the above-mentioned water conditioner of water pot is controlled.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP099551/2005 | 2005-03-30 | ||
| JP2005099551A JP2006274427A (en) | 2005-03-30 | 2005-03-30 | Water treating agent and water treatment method |
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| CN101151400A true CN101151400A (en) | 2008-03-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA200680010488XA Pending CN101151400A (en) | 2005-03-30 | 2006-03-20 | Water treatment and method of water treatment |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2006274427A (en) |
| KR (1) | KR20070116022A (en) |
| CN (1) | CN101151400A (en) |
| CA (1) | CA2603426A1 (en) |
| WO (1) | WO2006109546A1 (en) |
Cited By (9)
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| CN101846310A (en) * | 2009-03-25 | 2010-09-29 | 三浦工业株式会社 | Steam boiler apparatus and operating method therefor |
| CN102311177A (en) * | 2010-06-30 | 2012-01-11 | 三浦工业株式会社 | Method of operating steam boiler |
| CN103351031A (en) * | 2013-05-10 | 2013-10-16 | 湖北中烟工业有限责任公司 | Purification agent for prolonging use period of reconstituted tobacco production circulation water, and use method thereof |
| CN104628154A (en) * | 2013-11-09 | 2015-05-20 | 西安润达化工科技有限公司 | Boiler water treatment agent |
| CN107673489A (en) * | 2017-11-14 | 2018-02-09 | 昌邑市龙港无机硅有限公司 | A kind of recirculated water corrosion inhibiting and descaling agent |
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| TWI641798B (en) * | 2012-04-09 | 2018-11-21 | 美商奈寇公司 | Method and device for preventing corrosion in hot water systems |
| CN110952103A (en) * | 2019-12-06 | 2020-04-03 | 万华化学集团股份有限公司 | Carbon steel corrosion inhibitor for oxygen-containing salt water and preparation method thereof |
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| JP2003043028A (en) * | 2001-07-31 | 2003-02-13 | Miura Co Ltd | Method and apparatus for measuring constituent concentration |
| JP2003120904A (en) * | 2001-08-09 | 2003-04-23 | Miura Co Ltd | Water treating agent for steam boiler device |
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-
2005
- 2005-03-30 JP JP2005099551A patent/JP2006274427A/en not_active Withdrawn
-
2006
- 2006-03-20 CN CNA200680010488XA patent/CN101151400A/en active Pending
- 2006-03-20 CA CA002603426A patent/CA2603426A1/en not_active Abandoned
- 2006-03-20 WO PCT/JP2006/306064 patent/WO2006109546A1/en active Application Filing
- 2006-03-20 KR KR1020077022065A patent/KR20070116022A/en not_active Application Discontinuation
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| CN101846310A (en) * | 2009-03-25 | 2010-09-29 | 三浦工业株式会社 | Steam boiler apparatus and operating method therefor |
| CN102311177A (en) * | 2010-06-30 | 2012-01-11 | 三浦工业株式会社 | Method of operating steam boiler |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2006274427A (en) | 2006-10-12 |
| KR20070116022A (en) | 2007-12-06 |
| WO2006109546A1 (en) | 2006-10-19 |
| CA2603426A1 (en) | 2006-10-19 |
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