CN1225415C - Water-treatment agent for steam-boiler device - Google Patents

Water-treatment agent for steam-boiler device Download PDF

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Publication number
CN1225415C
CN1225415C CN 02128549 CN02128549A CN1225415C CN 1225415 C CN1225415 C CN 1225415C CN 02128549 CN02128549 CN 02128549 CN 02128549 A CN02128549 A CN 02128549A CN 1225415 C CN1225415 C CN 1225415C
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acid
water
feedwater
salt
steam
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CN 02128549
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CN1405100A (en
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若狭晓
中岛纯一
久米隆成
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Miura Co Ltd
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Miura Co Ltd
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  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

To realize a water treating agent suppressing corrosion of a metal and suppressing the generation of a scale. A water treating agent is to suppress adhesion of a scale to the water tube of a steam boiler device and corrosion of the water tube, and contains an organic polybasic acid oxide, a pH controlling agent, an oxygen scavenger, and a chelating agent.

Description

Water-treatment agent for steam-boiler device
Technical field
The present invention relates to water-treatment agent for steam-boiler device, especially suppress the incrustation scale of steam-boiler device water pipe is adhered to and water pipe corrosive water conditioner.
Background technology
Supply water to steam boiler, heat, the steam-boiler device of consequent steam supply load device, water pipe in the steam-boiler device and the feedwater pipe arrangement that feeds water to steam boiler mainly use steel pipe.Therefore, steam-boiler device is accompanied by long-play, produces corrosion in steam boiler and in the feedwater pipe arrangement, or adheres to incrustation scale.
Here, corrosion can be understood as usually, and incorrect (when pH departed from OK range, for example, feedwater was lower than 11) of harmful ion such as the dissolved oxygen that is contained in feedwater, chlorion and feedwater pH value caused.The corrosive form roughly is divided into 2 classes.That is, general corrosion (uniform corrosion) is characterized in that, with metal that feedwater or feedwater contact on evenly carry out, cause the metal attenuate, but it is slower to carry out velocity ratio.Otherwise, local corrosion is that the privileged site at metal partly causes concentrated corrosive nature, is the poroid corrosion of carrying out from the contact surface one side direction another side with water or feedwater (pitting), but it is very fast to carry out speed, metal is produced fatal breakage at short notice, and this is its feature.
On the other hand, adhering to of incrustation scale, be calcium ion, magnesium ion, iron ion and the zine ion etc. that are contained in the feedwater, with reactions such as silicon-dioxide contained in the same feedwater and carbonic acid ions, generate water-fast compound, produce in view of the above, perhaps in steam boiler, feedwater is concentrated superfluously to be caused.
Above-mentioned corrosion and incrustation scale adhere to, and make the lost of life of steam-boiler device, and the thermal conductivity of steam boiler is reduced, and are the reasons that hinders steady running.Therefore, in steam-boiler device, usually use feedwater, suppress above-mentioned corrosion and incrustation scale and adhere to through deoxidation treatment and water softening processing, yet, the reason that corrosion and incrustation scale adhere to is many-sided, and the corrosive scene also is many-sided, so, the soft water that only uses the process deoxidation treatment is difficult to effectively suppress adhering to of corrosion and incrustation scale as feedwater.
Therefore, above-mentioned steam-boiler device usually in order to suppress to corrode and the adhering to of incrustation scale, adopts various water conditioners.As an example of this water conditioner, the spy opens flat 4-232286 communique and proposes with organic multicomponent acid or its salt, reductibility carbohydrate and the alkali metal hydroxide boiler feed water agent composition as principal constituent.This water conditioner is that required composition is dissolved in the aqueous solution in the water, can inject feedwater.Be injected into the water conditioner of feedwater, can be suppressed in the feedwater pipe arrangement and the corrosion in the steam boiler.In addition, the ion in organic multicomponent acid and the feedwater forms coordination compound, can suppress adhering to of incrustation scale.
Summary of the invention
Though above-mentioned water conditioner can fully suppress the generation of the incrustation scale that is made of hardness and silicon-dioxide, the incrustation scale that might be able to not suppress to be made of hardness and carbonic acid generates.
The objective of the invention is to realize a kind ofly can suppress corrosion of metal, and can suppress the water conditioner of the generation of incrustation scale again.
The present invention suppresses incrustation scale to the adhering to and water pipe corrosive water conditioner of steam-boiler device water pipe, contains organic multicomponent acid compound, pH regulator agent, reductor and sequestrant.
Here, the organic multicomponent acid compound for example is at least a kind of compound selecting from organic multicomponent acid such as succsinic acid, oxysuccinic acid, tartrate, citric acid and isocitric acid.In addition, the organic multicomponent acid compound both can be that the form of acid also can be the form of salt.
And the pH regulator agent for example is at least a kind that selects from alkali metal hydroxide and silicate.In addition, reductor for example, is at least a kind that selects from reductibility carbohydrate, sulphite, saccharosonic acid and salt thereof, xitix and salt thereof.And, sequestrant, for example is at least a kind that selects from the multipolymer of the salt of polyacrylic acid, polyacrylate, polymaleic acid, polymaleic acid salt, phospho acid, phosphinocarboxylic acid's (acid of ホ ス Off ィ ノ カ Le ボ Application), ethylenediamine tetraacetic acid (EDTA), edetate, triacetamide, triacetamide and vinylformic acid and acrylamide.
The simple declaration of accompanying drawing
Fig. 1 is the graphic representation of the calcium solubleness when using water conditioner in the many water quality of silicon-dioxide.
Fig. 2 is the graphic representation of the calcium solubleness when using water conditioner in the many water quality of carbonate composition.
Fig. 3 is the graphic representation of the pitting degree of depth when adopting water conditioner.
The working of an invention scheme
Water conditioner of the present invention is to be used for suppressing incrustation scale to the adhering to and water pipe corrosive water conditioner of steam-boiler device water pipe, contains organic multicomponent acid compound, pH regulator agent, reductor and sequestrant.
The organic multicomponent acid compound is to form the solidity to corrosion epithelium at the inner peripheral surface of metal system pipe arrangement, simultaneously, suppresses the compound of the generation of the incrustation scale that is made of hardness and silicon-dioxide, is the organic compound with 2 above carboxyls.This organic compound preferably also contains 1~8 carbon atom except that the carbon of carboxyl.Organic multicomponent acid compound as such can adopt organic multicomponent acid.As this organic multicomponent acid, for example, can enumerate the polyprotonic acid that succsinic acid, oxysuccinic acid, fumaric acid and tartrate etc. have 2 carboxyls, and the polyprotonic acid with the citric acid of 3 carboxyls and isocitric acid etc.Such organic multicomponent acid both can have been distinguished use separately, also can more than 2 kinds and use.
In addition, the organic multicomponent acid compound also can be the salt of above-mentioned organic multicomponent acid.As the salt of organic multicomponent acid, for example, can enumerate the metal-salt of organic multicomponent acid.Concrete an alkali metal salts such as the sodium salt that can enumerate above-mentioned organic multicomponent acid, sylvite and lithium salts, and alkali earth metal salts such as calcium salt and magnesium salts etc.At this, the salt of organic multicomponent acid can be that the part of carboxyl forms salt, also can be whole formation salt of carboxyl.In addition, the salt of such organic multicomponent acid both can have been distinguished separately and use, and also can more than 2 kinds and use.
Again, the organic multicomponent acid compound can be the mixture of above-mentioned organic multicomponent acid and above-mentioned organic multicomponent hydrochlorate.This mixture both can contain the organic multicomponent acid more than 2 kinds, also can contain the organic multicomponent hydrochlorate more than 2 kinds.
At this, as the organic multicomponent acid compound, solubleness height and suppress an alkali metal salt of the high organic multicomponent acid of function that incrustation scale takes place in water preferably.
In water conditioner of the present invention, it is preferred that the ratio of organic multicomponent acid compound is set in 1~30 quality % usually, more preferably 5~25 quality %.The ratio of organic multicomponent acid compound is during less than 1 quality %, the inhibit feature of the generation of formation function that might above-mentioned epithelium and the incrustation scale that is made of hardness and silicon-dioxide is difficult to bring into play fully, and is difficult to bring into play the inhibition effect that required inhibition corrosive effect and incrustation scale take place.Otherwise during greater than 30 quality %, when making water conditioner, it is difficult that material dissolution might become.
The pH regulator agent is that the pH of feedwater is transferred to certain limit (for example, the feedwater administrative standard that provides among the JIS B 8223, concrete pH11.0~11.8), suppresses the conditioning agent of metallic corrosion in view of the above.As the pH regulator agent,, use the conditioning agent that improves pH or suppress the too high conditioning agent of pH according to the characteristic of feedwater.As the former, alkali metal hydroxides such as employing lithium hydroxide, sodium hydroxide and potassium hydroxide etc. are preferred.On the other hand, as the latter, silicate such as employing water glass or potassium silicate etc. are preferred.In addition, as the latter's example, also can adopt phosphoric acid salt, but consider from the viewpoint of the eutrophication that prevents to be caused by draining, strict control is used.
In water conditioner of the present invention, the ratio of pH regulator agent, it is preferred being set in 1~30 quality % usually, more preferably 1~20 quality %.When the ratio of pH regulator agent during less than 1 quality %, the pH regulator effect might diminish.Otherwise when greater than 30 quality %, when making water conditioner, it is difficult that material dissolution might become.
Reductor is to be used for chemistry to remove contained dissolved oxygen in the water, suppresses to result from the corrosion of dissolved oxygen, the material of particularly more effective inhibition pitting.At this,, for example, can enumerate sulphite such as reductibility carbohydrate, S-WAT and potassium sulfite, xitix and salt thereof, saccharosonic acid and salt thereof etc. such as glucose and dextrin as used reductor.In these reductors, the reductibility carbohydrate is preferred.The reductibility carbohydrate when heating with the alkali metal hydroxide that uses as the pH regulator agent, can effectively be removed the dissolved oxygen in the water and suppresses corrosion.In addition, the reductibility carbohydrate is as sulphite, can not become the corrosive speedup factor with the reaction product of oxygen, compares with saccharosonic acid with xitix, and the normal processing cost of unit oxygen reduces.
In water conditioner of the present invention, the ratio of reductor, it is preferred being set in 0.5~30 quality % usually, more preferably 1.0~20 quality %.When the ratio of reductor during less than 0.5 quality %, the effect of reductor might reduce.Otherwise when greater than 30 quality %, material dissolution may become difficult when making water conditioner.
Sequestrant is by handle and the relevant ion chelating of generation incrustation scale, improves the solubleness of this ion in water, thereby suppresses the material of the generation of incrustation scale.Here as used sequestrant, except that above-mentioned organic multicomponent acid compound, for example, can enumerate the salt of polyacrylic acid, polyacrylate, polymaleic acid, polymaleic acid salt, phospho acid, phosphinocarboxylic acid, ethylenediamine tetraacetic acid (EDTA), edetate, triacetamide, triacetamide and the multipolymer of vinylformic acid and acrylamide etc.In these sequestrants, edetate is preferred.Edetate has more the bonding force of intensive and hardness components than carbonic acid ion, therefore can suppress the generation of the incrustation scale that is made of hardness and carbonic acid effectively.
In water conditioner of the present invention, it is preferred that the ratio of sequestrant is set in 0.1~30 quality % usually, more preferably 0.1~15 quality %.When the ratio of sequestrant during less than 0.1 quality %, the effect that suppresses incrustation scale might diminish.Otherwise when greater than 30 quality %, when making water conditioner, being dissolved with of raw material may become difficult.
Water conditioner of the present invention is in order to suppress incrustation scale adhering to and the corrosion of water pipe and being used the steam-boiler device water pipe.More particularly, for example, in steam-boiler device, adhere to incrustation scale, and suppress the corrosion of feedwater pipe arrangement, steam boiler water pipe etc. and use in order to be suppressed on the hardwares such as feedwater pipe arrangement to steam boiler feedwater, steam boiler water pipe.
Adopt water conditioner of the present invention, be suppressed on feedwater pipe arrangement, the steam boiler water pipe etc. and adhere to incrustation scale, and when suppressing the corrosion of feedwater pipe arrangement, steam boiler water pipe etc., to the feedwater pipe arrangement injection agent of steam boiler.To feedwater pipe arrangement injection agent water conditioner, in the feedwater pipe arrangement, mix the back and supply with steam boiler.Therefore, the organic multicomponent acid in the water conditioner at the feedwater pipe arrangement and the first-class formation epithelium of water pipe of steam-boiler device, thereby suppresses corrosion, and, thereby react the generation that suppresses incrustation scale with the hardness components in the feedwater.In addition, the pH regulator agent in the water conditioner suppresses corrosion by the pH that regulates feedwater, and the dissolved oxygen reaction in reductor and the feedwater can suppress the generation of pitting.In addition, the sequestrant in the water conditioner since than the carbonic acid ion in the feedwater preferentially with hardness components reaction, thereby can suppress the generation of the incrustation scale that constitutes by hardness and carbonic acid.
At this, water conditioner of the present invention is with respect to the injection rate of above-mentioned feedwater pipe arrangement, and it is preferred setting usually that water conditioner total concn in the feedwater reaches about 50~500mg/L for, more preferably about 100~250mg/L.
Embodiment
In distilled water, add Trisodium Citrate as the organic multicomponent acid compound, as the sodium hydroxide of pH regulator agent, as the glucose of reductor and as the ethylenediamine tetraacetic acid (EDTA) of sequestrant, stir, this stirs and continued about 1 hour.In view of the above, can obtain the purpose water conditioner.At this, various compositions contained in this water conditioner are shown in Table 1.
Comparative example
In distilled water, add Trisodium Citrate as the organic multicomponent acid compound, as the sodium hydroxide of pH regulator agent and as the glucose of reductor, stir, this stirs and continued about 1 hour.Thus, obtain the purpose water conditioner.At this, various compositions contained in this water conditioner are shown in Table 1.
Table 1
Composition Embodiment Comparative example
Trisodium citrate dihydrate 15 15
Sodium hydroxide 5 5
Glucose 5 5
Disodium ethylene diamine tetraacetate 5 -
Distilled water 70 75
(unit: quality %)
Estimate 1
To the water conditioner that embodiment and comparative example obtain respectively, estimate the incrustation scale that constitutes by hardness and silicon-dioxide and generate inhibition.Here, the dwarf boiler to steam output 500kg/ hour, the soft water of the water conditioner of 100mg/L has been added in supply, and the degree of enrichment of feedwater is 10 times, pressure 5kg/cm 2Steam make the operation of this dwarf boiler while recurring.At this moment, this dwarf boiler is through after 48 hours, the calcium solubleness in the investigation feedwater.The results are shown in Fig. 1.At this, the soft water that is used to feed water, use be that the Ai Yuan county is eased out the soft water of making after city's tap water is handled.This water quality is as follows.
PH:11.2 (feedwater)
Silicon-dioxide: 60mg/L (feedwater)
M basicity: 30mg-CaCo 3/ L (feedwater)
Hardness: 1mg-CaCO 3/ L (feedwater)
Estimate 2
To the water conditioner that embodiment and comparative example obtain respectively, the incrustation scale of estimating by hardness and carbonic acid generates inhibition.Here, be soft water from the water conditioner that has added 100mg/L to steam output 500kg/ hour dwarf boiler that supply with, 10 times of the degree of enrichment of feedwater recur pressure 5kg/cm Yi Bian make 2Steam make the operation of this dwarf boiler on one side.At this moment, investigate this dwarf boiler through the calcium ion solubleness in the feedwater after 48 hours.The results are shown in Fig. 2.Here, giving subaqueous soft water is that the Ai Yuan county is eased out that city's tap water is handled and the soft water that makes.Its water quality is as follows.
pH: 10.5
Silicon-dioxide: 5mg/L (feedwater)
M basicity: 120mg-CaCo 3/ L (feedwater)
Hardness: 1mg-CaCO 3/ L (feedwater)
From Fig. 1 and Fig. 2 as can be known, the water conditioner of embodiment is compared with the water conditioner of comparative example, and the solubleness of calcium ion increases a lot.That is, the calcium ion components of separating out as incrustation scale, owing to can increase with the amount that solubilised state is present in the feedwater, so can suppress the generation of incrustation scale.That is, the water conditioner of embodiment, no matter which side all can effectively suppress for incrustation scale that is made of hardness and silicon-dioxide and the incrustation scale that is made of hardness and carbonic acid.
Estimate 3
The water conditioner that embodiment and comparative example are obtained is respectively estimated it and is suppressed corrodibility.Here, supply with the soft water that has added the 100mg/L water conditioner to steam output 500kg/ hour dwarf boiler, the degree of enrichment of feedwater is 10 times, recurs pressure 3kg/cm Yi Bian make 2Steam make the operation of this dwarf boiler on one side.At this moment, the test piece of mild steel system is immersed in the feedwater of this dwarf boiler, investigation is through the pitting degree of depth after 48 hours.It the results are shown in Fig. 3.Here, the soft water that is used to feed water, employing be the tap water that the Ai Yuan county eases out the city to be handled and the soft water made.Its water quality is as follows.
PH:11.0 (feedwater)
Silicon-dioxide: 17mg/L (feedwater)
M basicity: 200mg-CaCo 3/ L (feedwater)
Chlorion: 400mg/L (feedwater)
As shown in Figure 3, the inhibition corrodibility of embodiment can be brought into play and the equal effect of the inhibition corrodibility of comparative example.
As mentioned above, water conditioner of the present invention with to water conditioner compare, can bring into play and suppress the incrustation scale generative nature, and can bring into play equal inhibition corrodibility.
The effect of invention
As mentioned above, corrosion of metal can be suppressed according to the present invention, and the generation of incrustation scale can be suppressed.

Claims (1)

1. water-treatment agent for steam-boiler device,
At least a kind that selects in the compound group that contains the organic multicomponent acid compound group that is made up of succsinic acid, oxysuccinic acid, tartrate, citric acid and isocitric acid and be made up of the salt of compound in this compound group is 1-30 quality %,
As the pH regulator agent, at least a kind that selects from alkali metal hydroxide and silicate is 1-30 quality %,
As reductor, at least a kind that selects from reductibility carbohydrate, sulphite, saccharosonic acid and salt thereof, xitix and salt thereof is 0.5-30 quality %,
As sequestrant, at least a kind that selects from the multipolymer of the salt of polyacrylic acid, polyacrylate, polymaleic acid, polymaleic acid salt, phospho acid, phosphinocarboxylic acid, ethylenediamine tetraacetic acid (EDTA), edetate, triacetamide, triacetamide and vinylformic acid and acrylamide is 0.1-30 quality %
Surplus is a water.
CN 02128549 2001-08-09 2002-08-09 Water-treatment agent for steam-boiler device Expired - Fee Related CN1225415C (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP241551/01 2001-08-09
JP241551/2001 2001-08-09
JP2001241551 2001-08-09
JP8121/02 2002-01-17
JP8121/2002 2002-01-17
JP2002008121A JP2003120904A (en) 2001-08-09 2002-01-17 Water treating agent for steam boiler device

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CN1405100A CN1405100A (en) 2003-03-26
CN1225415C true CN1225415C (en) 2005-11-02

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