JP2012196655A - Scale inhibitor and method of preventing scale - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a scale inhibitor and a method of preventing scale which has a high deposition suppression effect on all the scale components of hard components, silica and iron, and which has a more excellent scale preventing effect than the conventional ones.SOLUTION: A first high molecular compound (low-molecular polymer component) having a carboxy group and having 1.0×10-1.0×10mass-average molecular weight, and a second high molecular compound (high-molecular polymer component) having a carboxy group and having 2.0×10-7.0×10mass-average molecular weight are at least added to a high temperature water system such as a boiler water system.

Description

  The present invention relates to a scale inhibitor and a scale prevention method. More specifically, the present invention relates to a scale inhibitor and a scale prevention method used in high-temperature water systems such as boilers and steam generators.

  In recent years, in order to reduce energy costs, the number of water systems that operate at a high concentration by reducing the amount of water blown out of the system is increasing. In such an aqueous system, scale components such as calcium, magnesium, silica, and iron in water also have a high concentration. Therefore, these components may be scaled and deposited, which may cause a decrease in thermal efficiency or blockage. .

  In particular, in boiler water systems, the scale components brought into the boiler can scale and adhere to the heat transfer surface with a high heat load, which causes expansion, bending, rupture, and a decrease in thermal efficiency due to overheating of the steel material. . In addition, adhesion of the scale to the heat transfer surface causes heat transfer inhibition and energy loss, leading to an increase in fuel cost.

  For this reason, in a high-temperature water system such as a boiler water system, in order to prevent the adhesion of scales, calcium and magnesium, which are hardness components in raw water, are removed by a water softener and water softened is used as water supply. In addition, by adding a scale inhibitor, a water treatment method that suppresses adhesion of the scale components brought into the can into the system and discharges these components out of the system by blowing is also performed.

  Here, the “scale inhibitor” suppresses the precipitation of scale components brought into the aqueous system, and conventionally, phosphates such as trisodium phosphate and sodium tripolyphosphate, or polyacrylates, etc. The high molecular compound is used.

  For example, in a boiler water system, a boiler in which phosphonic acid or a salt thereof and an unsaturated carboxylic acid polymer are added as a scale inhibitor together with at least one natural product corrosion inhibitor among tannins, lignins and sugars. A water treatment method has been proposed (see Patent Document 1). In the treatment method described in Patent Document 1, three types of chemicals are used in combination to prevent calcium carbonate, calcium phosphate, and iron hydroxide scales.

  In addition, it is obtained by aqueous solution polymerization of one or more monomers of maleic acid, maleic anhydride, phthalic acid and itaconic acid and other water-soluble monomers for the purpose of suppressing the adhesion of calcium carbonate scale. Further, a scale inhibitor containing a copolymer having a number average molecular weight of 400 to 1000 or a salt thereof has also been proposed (see Patent Document 2).

  Furthermore, a scale inhibitor containing at least a polyacrylate having a molecular weight of 20000 to 70000 has been proposed for use in steam generating equipment (see Patent Document 3). Since the scale inhibitor described in Patent Document 3 exhibits excellent effects on hardness components such as calcium and magnesium and silica, high-concentration operation is possible, and energy costs can be reduced.

  On the other hand, in order to prevent corrosion and blockage of the spray nozzle, a treatment method has been proposed in which a scale inhibitor is added together with a chlorine agent to a direct cooling water system for a hot rolling process (see Patent Document 4). In the treatment method described in Patent Document 4, an organic phosphonic acid, an organic phosphinic acid compound, or a water-soluble acrylic acid copolymer having a molecular weight of about 1000 to 10,000 is used as a scale inhibitor.

JP-A-6-108274 JP 2001-252692 A JP 2010-172816 A JP-A-8-155529

  However, the conventional techniques described above have the following problems. That is, the conventional scale inhibitor composed of a single component has a problem that the effect on the scale component of any one of the hardness component, silica, and iron is inferior. For example, in the case of polyacrylate, as shown in the comparative example of Patent Document 1, when used alone, iron-based scales such as iron hydroxide are prevented compared to scales derived from hardness components and silica. The effect is low.

  In this way, if an aqueous component contains a component with a low scale inhibitor effect, not only the component with the low effect scales, but also other components are involved when scaling, so other components It will also reduce the effect on. As a method for solving this problem, it is conceivable to use a plurality of drugs having different effects as in the method described in Patent Document 1, but for example, when tannin, lignin or saccharide is used in combination, boiler water is colored. There is a problem of doing. The coloring of boiler water becomes a problem at the time of drainage, or the steam drain is colored by carrying over, whereby the steam heating target is also colored and the quality is deteriorated.

  Therefore, the main object of the present invention is to provide a scale inhibitor and a scale prevention method that have a high precipitation suppression effect on all the scale components of the hardness component, silica, and iron, and that have a superior scale prevention effect than conventional. To do.

  In order to solve the above-mentioned problems, the present inventor has conducted extensive experimental research. As a result, the performance of a polymer compound containing a carboxyl group differs depending on the molecular weight. The present inventors have found that the dispersibility is excellent and have reached the present invention.

That is, the scale inhibitor according to the present invention is a scale inhibitor for high-temperature water systems, has a carboxyl group, and has a mass average molecular weight of 1.0 × 10 ^{3 to} 1.0 × 10 ^4. It contains at least a polymer compound and a second polymer compound having a carboxyl group and having a mass average molecular weight of 2.0 × 10 ^{4 to} 7.0 × 10 ⁴ .
Here, the “high-temperature water system” is a water system in which the water temperature in the system becomes a high temperature of 40 to 250 ° C., such as a boiler, a hot water boiler, a steam generator, and a cooling water system.
In the present invention, the dispersibility of iron is particularly improved by the first polymer compound, and the dispersibility of the hardness component and silica is particularly improved by the second polymer compound. In this way, by dispersing all the scale components without any inferiority, it is possible to prevent a component having a low scale prevention effect from being scaled by involving other components. As a result, even when a hardness component, silica, and iron coexist in the aqueous system, a high scale prevention effect is obtained.
In this scale inhibitor, for example, a polyacrylate can be used as the first polymer compound and / or the second polymer compound.

The scale prevention method according to the present invention includes a first polymer compound having at least a carboxyl group and having a mass average molecular weight of 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ in a high-temperature water system, and a carboxyl group. And a second polymer compound having a mass average molecular weight of 2.0 × 10 ^{4 to} 7.0 × 10 ⁴ is added.
In this scale prevention method, the addition concentration of the first polymer compound and the second polymer compound can be 1 to 500 mg / L, respectively.
Further, a polyacrylate may be used as the first polymer compound and / or the second polymer compound.

  According to the present invention, since the low molecular weight carboxyl group-containing polymer compound and the high molecular weight carboxyl group-containing polymer compound are used in combination, even when the hardness component, silica and iron coexist in the aqueous system, it is excellent. Scale prevention effect is obtained.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the embodiments described below.

(First embodiment)
First, the scale inhibitor according to the first embodiment of the present invention will be described. The scale inhibitor of the present embodiment prevents scale generation in high-temperature water systems such as boilers and steam generators, and contains at least two kinds of carboxyl group-containing polymer compounds having different molecular weights.

[High molecular weight polymer component (Mw: 2.0 × 10 ^{4 to} 7.0 × 10 ⁴ )]
Among the two types of carboxyl group-containing polymer compounds contained in the scale inhibitor of the present embodiment, the “high molecular weight polymer component” has a mass average molecular weight (Mw) of 2.0 × 10 ^{4 to} 7.0 × 10. ⁴ carboxyl group-containing polymer compound. The carboxyl group-containing polymer compound having a molecular weight within this range is excellent in hardness components such as calcium and magnesium and dispersibility of silica, and has an effect of preventing them from being scaled.

  However, since this high molecular weight polymer component has lower iron dispersibility than the hardness component and silica, when used alone in an aqueous system containing a large amount of iron, a sufficient scale prevention effect cannot be obtained. Furthermore, since other components are also involved when iron is scaled, the scale prevention effect of the entire system may be reduced.

Moreover, when a carboxyl group-containing polymer compound having a mass average molecular weight (Mw) of less than 2.0 × 10 ⁴ or more than 7.0 × 10 ⁴ is used as the high molecular weight polymer component, the hardness component and the dispersibility of silica are reduced. Therefore, a sufficient scale prevention effect cannot be obtained. Furthermore, when a carboxyl group-containing polymer compound having a mass average molecular weight (Mw) exceeding 7.0 × 10 ⁴ is used under low temperature conditions such as a cooling water system, the scale dispersion effect may be reduced due to gelation.

  On the other hand, examples of the carboxyl group-containing polymer compound used as the high molecular weight polymer component include acrylic acid or a salt thereof, methacrylic acid or a salt thereof, itaconic acid or a salt thereof, maleic acid or a salt thereof, fumaric acid or a salt thereof. And a polymer or copolymer as a monomer unit. Among these carboxyl group-containing polymer compounds, it is preferable to use a polyacrylate from the viewpoint of the hardness component and the dispersibility of silica. In particular, when sodium polyacrylate is used, a higher scale prevention effect is obtained. It is done.

[Low molecular weight polymer component (Mw: 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ )]
On the other hand, the “low molecular weight polymer component” is a carboxyl group-containing polymer compound having a mass average molecular weight (Mw) of 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ . A carboxyl group-containing polymer compound having a molecular weight in this range is excellent in iron dispersibility and has an effect of suppressing the generation of iron scale.

  However, this low molecular weight polymer component has low hardness component and dispersibility of silica, so when used alone, these scaling cannot be sufficiently suppressed. It will become.

Further, when a carboxyl group-containing polymer compound having a mass average molecular weight (Mw) exceeding 1.0 × 10 ⁴ is used as the low molecular weight polymer component, the effect of iron dispersion cannot be sufficiently obtained. Furthermore, since the inside of the steam generating facility is subjected to high temperature and high pressure, the molecular weight of the polymer may be reduced due to thermal decomposition. For this reason, when a carboxyl group-containing polymer compound having a mass average molecular weight (Mw) of less than 1.0 × 10 ³ is used for the low molecular weight polymer component, the dispersibility of iron decreases due to the decrease in the molecular weight, and the iron scale inhibiting effect is exhibited. It becomes insufficient.

  On the other hand, examples of the carboxyl group-containing polymer used as the low molecular weight polymer component include acrylic acid or a salt thereof, methacrylic acid or a salt thereof, itaconic acid or a salt thereof, maleic acid or a salt thereof, fumaric acid or a salt thereof. And a polymer or copolymer as a monomer unit. Among these carboxyl group-containing polymer compounds, it is preferable to use a polyacrylate from the viewpoint of iron dispersibility. In particular, when sodium polyacrylate is used, a higher scale prevention effect can be obtained.

[Other ingredients]
In addition to the above-described components, the scale inhibitor of this embodiment can also contain an alkali agent, an oxygen scavenger, an anticorrosive agent, and the like.

  The alkaline agent has an effect of preventing corrosion of the water supply system and suppressing slime of the water supply system. The kind of alkali agent blended in the scale inhibitor of the present embodiment is not particularly limited, and one or more alkalis that can be used for aqueous treatment can be appropriately selected and used. . Specific examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, etc. Among them, sodium hydroxide and potassium hydroxide, etc. from the viewpoint of preventing corrosion of the water supply piping and suppressing slime in the water supply system The caustic alkali is preferred.

  Further, the oxygen scavenger has an effect of reducing dissolved oxygen in the aqueous system and suppressing the degradation of the carboxylic acid-containing polymer compound over time. The kind of oxygen scavenger to be blended in the scale inhibitor of the present embodiment is not particularly limited as long as it has an action of reducing dissolved oxygen in the aqueous system, and one or more kinds thereof are used. It can be appropriately selected and used.

  Specifically, hydrazine, sulfite or a salt thereof, bisulfite or a salt thereof, a tannin-based substance, polyhydric phenols such as gallic acid produced by blending tannin and an alkali, a reaction product of saccharides, sugar and alkali, glucone Aldonic acids or salts thereof such as acids or salts thereof, α-glucoheptonic acid or salts thereof, erythorbic acid or salts thereof, ascorbic acid or salts thereof, N- such as 1-aminopyrrolidine and 1-amino-4-methylpiperazine Examples include heterocyclic compounds having a substituted amino group, hydroxyamines such as diethylhydroxylamine and isopropylhydroxylamine, and carbohydrazide.

  Among these oxygen scavengers, erythorbic acid or a salt thereof, ascorbic acid or a salt thereof is preferable because it is highly safe, has little coloration in can water, and has a high effect of inhibiting the degradation of polyacrylate.

  The anticorrosive is added for the purpose of preventing corrosion of the water supply system and the high temperature water system. The kind of anticorrosive agent mix | blended with the scale inhibitor of this embodiment is not specifically limited, What is necessary is just to be able to acquire the corrosion prevention effect in a water supply system and a high temperature water system, 1 type (s) or 2 or more types. It can be appropriately selected and used.

  Specifically, organic acids such as citric acid, succinic acid, tartaric acid, malic acid and aldonic acid or salts thereof can be used. Here, the aldonic acid salt includes all hydroxy monocarboxylates formed by oxidation of only the aldehyde group of aldose, such as gluconic acid, α-glucoheptonic acid, mannonic acid, mannoheptonic acid, galactonic acid and galactoheptone. Examples thereof include sodium salt, potassium salt, amine salt and ammonium salt of acid. Among these anticorrosive agents, citric acid, succinic acid, gluconic acid, α-glucoheptonic acid or a salt thereof is preferable from the viewpoint of corrosion prevention effect.

As described in detail above, the scale inhibitor of the present embodiment is a carboxyl having a mass average molecular weight (Mw) of 2.0 × 10 ^{4 to} 7.0 × 10 ⁴ with particularly excellent hardness components and dispersibility of silica. Group-containing polymer compound (high molecular weight polymer component) and a carboxyl group-containing polymer compound having a mass average molecular weight (Mw) of 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ , which is particularly excellent in iron dispersibility ( Since the low molecular weight polymer component) is used in combination, an excellent scale prevention effect is obtained for all scale components.

  Thereby, since the component with a low scale prevention effect can prevent other components from being involved in scaling, a high scale prevention effect can be obtained even when the hardness component, silica, and iron coexist in the aqueous system. The scale inhibitor of this embodiment is particularly effective for a high-temperature water system in which these scale components are present in high concentrations.

  And the scale inhibitor of this embodiment not only protects the equipment by keeping the heat transfer surface clean, but also works well in aqueous systems where the scale component is highly concentrated. It is possible to recover thermal energy by recovering the drain containing water, and the energy cost can be reduced. Furthermore, the scale inhibitor of this embodiment does not cause a problem due to coloring of boiler water unless it is used in combination with tannin, lignin, saccharides and the like.

(Second Embodiment)
Next, a scale prevention method according to the second embodiment of the present invention will be described. The scale prevention method of this embodiment uses the scale inhibitor of the first embodiment described above to prevent high temperature aqueous scale. Then, at least the carboxyl group-containing polymer compound (high molecular weight polymer component) having a mass average molecular weight (Mw) of 2.0 × 10 ^{4 to} 7.0 × 10 ⁴ and a mass average molecular weight (Mw) ) Is added from 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ carboxyl group-containing polymerized compound (low molecular weight polymer component).

[High molecular weight polymer component added]
The addition amount of the high molecular weight polymer component can be appropriately set according to the scale component contained in the water system to be treated, particularly the hardness component and the concentration of silica, and is, for example, 1 to 500 mg / L. desirable. In addition, when the addition amount of the high molecular weight polymer component is less than 1 mg / L, the scale prevention effect may be insufficient. When the addition amount exceeds 500 mg / L, the economic efficiency is inferior, and the high-temperature water system tends to foam. There may be a concern about the occurrence of carry-over.

[Low molecular weight polymer component addition]
On the other hand, the addition amount of the low molecular weight polymer component can be appropriately set according to the concentration of the scale component contained in the aqueous system to be treated, particularly iron, but is preferably 1 to 500 mg / L. In addition, when the addition amount of the low molecular weight polymer component is less than 1 mg / L, the scale prevention effect may be insufficient. When the addition amount exceeds 500 mg / L, the economic efficiency is inferior, and the high-temperature water system tends to foam. There may be a concern about the occurrence of carry-over.

  These high molecular weight polymer component and low molecular weight polymer component can be premixed, but may be individually added to the aqueous system. Moreover, the addition position is not particularly limited, and for example, it is added to a water supply tank, makeup water, condensate, a water supply line in which these are mixed, or added directly into a boiler can. Is possible.

  On the other hand, when an alkali agent is added together with a high molecular weight polymer component and a low molecular weight polymer component, the addition amount is not particularly limited, and the alkali from water treatment chemicals such as the quality of feed water and a canning agent used together. The amount can be appropriately set according to the balance with the generation amount and the polyacrylate concentration.

  Similarly, when adding an oxygen scavenger, the addition amount is not particularly limited, and can be appropriately set according to the concentration of the carboxyl group-containing polymer compound added to the aqueous system. In the scale prevention method of the present embodiment, an oxygen scavenger is added in accordance with the dissolved oxygen concentration in the feed water so that the oxygen scavenger component remains in the boiler water of the boiler or steam generation facility. It is preferable.

  Further, when the anticorrosive agent is added, the addition amount is not particularly limited, and can be appropriately set according to the quality of the feed water, the concentration factor of the high-temperature water system, or the like.

As described above in detail, the scale prevention method of the present embodiment includes a carboxyl group-containing polymer compound (high molecular weight polymer component) having a mass average molecular weight (Mw) of 2.0 × 10 ^{4 to} 7.0 × 10 ^4. , Since a carboxyl group-containing polymer compound (low molecular weight polymer component) having a mass average molecular weight (Mw) of 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ is used in combination, the hardness component, silica and Even when iron coexists, an excellent scale prevention effect can be obtained.

  The configuration and effects other than those described above in the scale prevention method of the present embodiment are the same as those of the first embodiment described above.

  Moreover, the scale prevention method of this embodiment can be applied to an aqueous system in which scale adhesion occurs such as a boiler, and can be applied to all types of water supply. Furthermore, when it applies to a boiler water system, the kind of boiler is not specifically limited, It can apply to all boilers, such as a special circulation boiler, a water pipe boiler, a round boiler, and a waste heat recovery boiler.

  Hereinafter, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention. In this example, a boiler test was conducted using the scale inhibitor of Examples 1 to 12 prepared within the scope of the present invention and the scale inhibitor of Comparative Examples 1 to 9 deviating from the scope of the present invention. The scale prevention effect was compared. At that time, the polymer compounds used for the scale inhibitor are shown in Table 1 below.

The test conditions were pressure: 0.7 MPa, evaporation amount: 8 L / hour, test time: 48 hours, and the blow amount was appropriately adjusted so that the concentration rate was 10 times or 20 times. The water supply is mixed with Nogicho water and its softened water so that the Ca hardness is 15 mg CaCO ₃ / L, the Mg hardness is 7 mg CaCO ₃ / L, the silica is 25 mg SiO ₂ / L, and the M alkalinity is 30 mg CaCO ₃ / L). In addition, iron hydroxide was added as iron to 3 mgFe / L.

Then, the water supply line of a boiler, each scale inhibitor of Examples and Comparative Examples, was added a predetermined amount, after the boiler was operated for 48 hours, taken out a heat transfer tube (stainless steel, the surface area 200 cm ² 3 present) . Next, scraping off the attached scale, measuring the amount of scale attached, and from the total amount of scale components (hardness component, silica, iron) brought in from the water supply and the amount of scale attached, the scale discharge rate (%) Asked. The results are summarized in Table 2 below.

As shown in Table 2 above, a carboxyl group-containing polymer compound having a mass average molecular weight of 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ and a mass average molecular weight of 2.0 × 10 ^{4 to} 7.0 × 10. scale inhibitor of examples 1 to 12 using a combination of carboxyl group-containing polymer compound ^4, scale inhibitor of Comparative example 1～3,5～7,9 using these alone, and molecular weight of the present invention Compared with the scale inhibitor of Comparative Examples 4 and 8 using a carboxyl group-containing polymer compound that deviates from the above range, these scale components could be effectively discharged in the boiler water system in which the hardness component, silica and iron coexist.

  Thereby, it was confirmed that the scale inhibitor of Examples 1-12 has the scale prevention effect superior to the scale inhibitor of Comparative Examples 1-9. In addition, as shown in Example 10 and Comparative Example 9, the scale inhibitor of the present invention has an excellent scale prevention effect compared to conventional scale inhibitors even in highly concentrated operation with a reduced blow amount. It was confirmed that

  Next, as a reference example of the present invention, high molecular compounds having different structures or molecular weights were used to evaluate the iron dispersion effect. At that time, the test solution was prepared by simulating high-temperature water quality and adjusted to pH: 11.8, chloride ion: 300 mg / L, sulfate ion: 300 mg / L, iron hydroxide: 20 mg Fe / L did. A predetermined amount of an evaluation base material (polymer compound) shown in Table 3 below was added to 1.0 L of this test solution, and the mixture was treated in an autoclave (volume: 1.5 L) at a pressure of 1.0 MPa for 20 hours. After heating, the sample was stirred well, transferred to a 100 mL colorimetric tube, allowed to stand for 24 hours, and the supernatant was collected. And the dispersion rate of iron was calculated | required from the light absorbency (650 nm) after completion | finish of a heating and 24 hours still standing. The results are summarized in Table 4 below.

As shown in Table 4 above, the carboxyl group-containing polymer compound having a mass average molecular weight of 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ is more water than the carboxyl group-containing polymer compound having a higher molecular weight. It was confirmed that the iron oxide dispersion effect was excellent. Among them, in particular, a polyacrylate having a mass average molecular weight of 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ was excellent in iron dispersibility.

Claims (5)

An anti-scale agent for high-temperature water systems,
A first polymer compound having a carboxyl group and having a mass average molecular weight of 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ;
A second polymer compound having a carboxyl group and having a mass average molecular weight of 2.0 × 10 ^{4 to} 7.0 × 10 ⁴ ;
Scale inhibitor containing at least   The scale inhibitor according to claim 1, wherein the first polymer compound and / or the second polymer compound is a polyacrylate. At least in the high temperature water system
A first polymer compound having a carboxyl group and having a mass average molecular weight of 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ;
A second polymer compound having a carboxyl group and having a mass average molecular weight of 2.0 × 10 ^{4 to} 7.0 × 10 ⁴ ;
Adding scale prevention method.   The scale prevention method according to claim 3, wherein the addition concentration of the first polymer compound and the second polymer compound is 1 to 500 mg / L, respectively.   The scale prevention method according to claim 3 or 4, wherein the first polymer compound and / or the second polymer compound is a polyacrylate.