JPWO2019065415A1 - Method for inhibiting corrosion of copper-based materials - Google Patents

Abstract

This is a method for inhibiting corrosion of a copper-based material in which a film-forming amine is added to a water system of a boiler using a copper-based material.

Description

  The present invention relates to a method for inhibiting corrosion of a copper-based material. Specifically, the present invention relates to a method for suppressing corrosion of a copper-based material by ammonia by using a film-forming amine alone or in combination with a neutralizing amine.

  Metal members of boilers and other steam generator cans and water supply pipes (hereinafter simply referred to as “boilers”), such as copper or copper alloy heat exchangers and pipes, should be in contact with cooling water. Due to corrosion. Therefore, many technological developments that suppress corrosion have been performed. For example, Patent Document 1 discloses a specific N-monosubstituted alkylenediamine as a corrosion inhibitor for metal pipes containing copper, and Patent Document 2 discloses fats and oils. An emulsified emulsion is disclosed.

Incidentally, one of the corrosion factors is pH. The pH adjustment of boiler water is performed by maintaining the pH of boiler water in a predetermined alkaline range by injecting a pH adjusting agent into boiler feed water or the like. As the pH adjuster, solid substances such as NaOH and KOH, sodium phosphate and potassium phosphate, and volatile substances such as volatile amine and ammonia are used.
When ammonia is used to adjust the pH of boiler feedwater, ammonia and non-condensable gas (especially oxygen) concentrate in the water droplets of condensed water in the vicinity of the air extraction section in the condenser. In the vicinity of the baffle, a phenomenon of severe corrosion (ammonia attack) occurs in a groove shape. Thus, as a countermeasure against ammonia attack, there are an increasing number of cases in which amine is applied as a substitute for ammonia.
As a countermeasure against ammonia attack, a part of the condensate is sprayed in the vicinity of the air extraction part in the condenser where ammonia attack is likely to occur, and the ammonia stays in the gap between the narrow tube of the double condenser and the baffle plate. There has been proposed a method of washing away (see, for example, Patent Document 3).

Japanese Patent No. 6134921 JP 2013-19042 A JP 2013-190166 A

However, since amine is an organic substance, when it exists for a long time in an environment of high temperature and high pressure, there is a drawback that a part of it is thermally decomposed to produce ammonia. For this reason, in the conventional technology, although the number of cases of ammonia attack in the condenser has been reduced, it has not completely disappeared.
Moreover, although patent document 1 presupposes that it is a seawater type | system | group, although it is calling for the corrosion suppression of the copper-type material by an amine-type corrosion inhibitor, in patent document 2, it is copper type | system | group by applying fats and oils to a corrosion inhibitor. The corrosion of the material is suppressed. As described above, none of the documents describes the use of an amine-based corrosion inhibitor to suppress the ammonia attack of a copper-based material, and there is room for further improvement in the method for inhibiting the corrosion of a copper-based material using an amine-based corrosion inhibitor. Yes.

  Then, this invention makes it a subject to provide the corrosion suppression method of the copper-type material which can suppress an ammonia attack.

As a result of repeated studies to solve the above problems, the present inventors have found that application of a film-forming amine reduces the corrosion of a copper-based material due to ammonia attack.
That is, the present invention is as follows.

1. A method for inhibiting corrosion of a copper-based material, wherein a film-forming amine is added to an aqueous system containing ammonia of a boiler using a copper-based material.
2. The method for inhibiting corrosion of a copper-based material according to 1 above, wherein the concentration of the film-forming amine added is adjusted according to the ammonia concentration and the copper elution amount.
3. The method for inhibiting corrosion of a copper-based material according to 1 or 2 above, wherein two or more kinds of the film-forming amine are added.
4). The method for inhibiting corrosion of a copper-based material according to any one of 1 to 3, wherein a neutralizing amine is further added to the aqueous system containing ammonia.
5. The method for inhibiting corrosion of a copper-based material according to any one of 1 to 4, wherein the water system is not a seawater system.
6). The method for inhibiting corrosion of a copper-based material according to any one of 1 to 5 above, wherein the addition of the film-forming amine is spray addition performed toward a thin tube.

  ADVANTAGE OF THE INVENTION According to this invention, the corrosion control method which becomes possible [performing the corrosion suppression of the copper-type material by ammonia attack effectively] during the normal driving | operation of a boiler can be provided.

It is a figure which shows the evaluation apparatus used in the Example of this invention. It is a graph of the elution amount of copper with respect to pH which shows the evaluation result of the Example of this invention.

The present invention is an invention relating to a method for inhibiting corrosion of a copper-based material in which a film-forming amine is added to an aqueous system containing ammonia of a boiler using a copper-based material.
[Boiler using copper-based material]
As the copper-based material, not only a condenser thin tube but also a material used for a feed water heater or a feed pump impeller can be targeted.
Moreover, the target material of the corrosion inhibiting method of the present invention may include not only a copper-based material but also an aluminum-based material. In addition, it is known in “J., Power Plant Chemistry 2014, 16 (6), 361” that a film-forming amine applied in the prior art reduces corrosion of an aluminum-based material.

[Water system]
The water quality of the aqueous system to which the corrosion inhibiting method of the present invention is applied is not particularly limited, but ion exchange water or the like can be used, and preferably degassed ion exchange water or the like can be suitably applied in the aqueous system. . Moreover, it is preferable that a water system is not a seawater system.
The aqueous dissolved oxygen concentration is preferably 500 μg / L or less, more preferably 100 μg / L or less, and still more preferably 70 μg / L or less, from the viewpoint of effectively suppressing boiler corrosion. The dissolved oxygen concentration can be adjusted, for example, by degassing the feed water.

[Film-forming amine]
Examples of the film-forming amine used in the present invention include those represented by the following general formula (1).
R ¹ — [NH (R ² ) —] _n —NH ₂ (1)
In formula (1), R ¹ represents a long chain alkyl group having 12 to 18 carbon atoms, and R ² represents an alkyl group having 1 to 4 carbon atoms. n is an integer of 0-7. The alkyl group for R ¹ may be linear or branched, but is preferably linear, and may be saturated or unsaturated, but is preferably an unsaturated alkyl group.
Specific examples of film-forming amines include long-chain alkylamines such as octadecylamine and N-octadecenylpropane-1,3-diamine. Only 1 type may be used for a film-forming amine and it may use 2 or more types together.

The corrosion inhibiting method of the present invention can adjust the additive concentration of the film-forming amine in accordance with the ammonia concentration and copper elution amount described later.
Moreover, you may change the addition density | concentration of film-forming amine according to ammonia concentration. For example, when the pH of the feed water is 9.4, which is the upper limit of JIS (when the low pressure feed water heater is a copper alloy and the high pressure feed water heater is made of steel pipe), the ammonia concentration in the feed water is 100 at the condenser air extraction unit. It is concentrated to 500 times (cited reference: The ASME Hnadbook on Water Technology for Thermal Power System, p976 (1989)). Since it is difficult to predict the concentration of ammonia in the condenser air extractor with an actual boiler, the concentration of copper detected in the condensate does not actually increase due to changes in the amount of medicinal amine injection. It is necessary to confirm that there is no thinning due to typical eddy current testing.
Thus, the calculation of the formula for calculating the coating amine injection amount can be adjusted for each site within the technical scope of those skilled in the art. In addition to the ammonia concentration, the fluctuation factors of the film-forming amine addition concentration include dissolved oxygen concentration, coexisting amine, flow rate, water temperature, flow rate, and the like.

  As described above, the addition concentration of the film-forming amine may be set as appropriate, but it is usually in the range of about 0.01 to 10 mg / L, particularly 0.1 to 1 mg / L with respect to the amount of water supply. If the addition amount is 0.01 mg / L or more, the corrosive effect by the film-forming amine can be sufficiently obtained, and if it is 10 mg / L or less, there is no possibility that sticky deposits are generated in the system.

  In addition, the film-forming amines to be applied are blended with those with different volatilities and adsorption amounts (for example, refer to “J., Power Plant Chemistry 2014, 16 (5), 284”), so that a wide range of condensers can be used more quickly. It can be spread through tubules. Therefore, two or more kinds of film-forming amines may be added to the boiler water system. For example, a combination of octadecylamine and N-octadecenylpropane-1,3-diamine is preferable.

[Neutralizing amine]
In the corrosion inhibiting method of the present invention, the film-forming amine may be used in combination with a neutralizing amine. Examples of neutralizing amines include monoethanolamine (MEA), cyclohexylamine (CHA), morpholine (MOR), diethylethanolamine (DEEA), monoisopropanolamine (MIPA), 3-methoxypropylamine (MOPA), 2 -Neutralizing amines (volatile amines) such as amino-2-methyl-1-propanol (AMP) and diglycolamine (DGA) can be used. Only one type of neutralizing amine may be used, or two or more types may be used in combination.

[PH adjuster]
The corrosion suppression method of the present invention has an effect of suppressing ammonia attack by ammonia used for pH adjustment, and ammonia is contained in the water system of the boiler. Therefore, ammonia is used as the pH adjuster in the aqueous system of the present invention, but the pH may be adjusted with ammonia derived from the thermal decomposition of the oxygen scavenger.
A pH adjuster may use only 1 type of ammonia, and may use ammonia and 1 or more types of other pH adjusters together. Examples of pH adjusters that can be used in combination with ammonia include potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate.
The ammonia concentration is not generally specified as long as it can be adjusted to a desired pH, but the concentration in the feed water is usually about 0.1 to 1,000 mg / L, preferably 1 to 500 mg / L.
Moreover, the corrosion suppression method of the present invention is an aqueous system having a pH of usually about 8.5 to 10.3, preferably 9.0 to 9.4, from the viewpoint of forming a protective film on a copper-based material and suppressing corrosion. Can be suitably applied.

[Oxygen scavenger]
In the corrosion inhibiting method of the present invention, the film-forming amine may be used in combination with an oxygen scavenger. As the oxygen scavenger, hydrazine derivatives such as hydrazine and carbohydrazide can be used. In addition, as non-hydrazine-based oxygen absorbers, hydroquinone, 1-aminopyrrolidine, 1-amino-4-methylpiperazine, N, N-diethylhydroxylamine, isopropylhydroxylamine, erythorbic acid or a salt thereof, ascorbic acid or a salt thereof, etc. Can also be used. Only one oxygen scavenger may be used, or two or more oxygen scavengers may be used in combination.

[Other additives]
As long as the object of the present invention is not impaired, a conventional component of a corrosion inhibitor and other auxiliary additive components may be added as necessary. Examples of other additives include various solubilizers, sequestering agents, scale inhibitors, scale removers, and antifreeze agents.

[Addition method, etc.]
In the method for inhibiting corrosion according to the present invention, two or more kinds of each component are added to the same place in the above-described film-forming amine, and optional components such as neutralizing amine, pH adjuster, oxygen scavenger and the like. When doing, it may mix and add beforehand and may add each separately. Moreover, it can add continuously or intermittently.
Further, the addition of the film-forming amine may be spray addition performed toward the narrow tube. Similarly, when the above-mentioned optional component is used in addition to the film-forming amine, the drug containing the film-forming amine can be sprayed and added to the capillary tube.
By spray-adding the film-forming amine toward the capillary tube, the copper-based material capillary tube in the vicinity of the air extraction portion where ammonia attack is likely to occur can be directly coated with the film-forming amine. Direct contact with can be prevented. Further, spraying the above-mentioned film-forming amine is limited to a portion where ammonia attack is likely to occur, such as a thin tube of a copper-based material, so that it is economically efficient and efficient corrosion inhibition is possible.
The method of spray addition is not particularly limited. For example, it can spray on the target location (a thin tube etc.) in vapor | steam using a spray nozzle. The spray addition may be either continuous or intermittent, but from the viewpoint of adsorption / desorption of the drug containing the film-forming amine, it is preferable that the spray addition is a continuous spray addition capable of maintaining a constant concentration in the aqueous system. .
The water temperature in the aqueous system is usually about 0 to 70 ° C, preferably 40 to 60 ° C.
The flow rate of the aqueous system is usually about 0.1 to 3.0 m / s.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

<Experimental conditions>
An evaluation apparatus as shown in FIG. 1 was produced as a verification method for a method of significantly reducing corrosion when ammonia and a copper-based material coexist by applying a film-forming amine.
In the test, ion-exchanged water degassed so that the dissolved oxygen concentration in the evaluation part was 100 μg / L was used, and a test liquid whose pH was adjusted with ammonia was abbreviated as “FFA” in Table 1 and FIG. Is added to the stainless steel tube B and heated to 50 ° C. in the stainless steel preheating tank 2, and then introduced into the copper tube A having a length of 1 m, which becomes the evaluation part, and is added to the 50 ° C. water tank 1. The amount of metallic copper that was circulated and eluted here was measured with an inductively coupled plasma (ICP) emission spectrometer.
In Table 1 and FIG. 2, N-octadecenylpropane-1,3-diamine (manufactured by Akzo Nobel, product name “Duomeen (registered trademark) OL”) was used as FFA.

<Results and discussion>
As test results, copper elution amount (μg / L), ammonia concentration (mg / L), and pH value are shown in Table 1. Moreover, the graph of the copper elution amount with respect to pH from the obtained test result is shown in FIG.
From Table 1 and FIG. 2, it can be seen that the elution of copper is greatly suppressed by application of the film-forming amine even in the region of pH 10.3 or more where the elution amount of copper rapidly increases in the blank. Specifically, it was confirmed that when the pH was about 10.5, the copper elution amount could be reduced to about 1/5 that of the blank. That is, it was confirmed that ammonia attack can be suppressed even in a place where ammonia is concentrated, such as an air extraction part of a condenser.

A: Copper tube B: Stainless steel tube 1: Evaluation part water tank (50 ° C.)
2: Stainless steel preheating tank (50 ° C)
3: Water tank with heater 4: Thermocouple (thermometer)
P: Pump DO: Dissolved oxygen measuring device

1. A copper-based material corrosion-inhibiting method of adding a film-forming amine to a water-based water-containing ammonia system using a copper-based material ,
Depending on the amount of elution of ammonia concentration and copper, it adjusts the addition concentration of the coating amine, corrosion inhibiting method for a copper-based material.
2 . 2. The method for inhibiting corrosion of a copper-based material according to 1 above, wherein two or more kinds of the film-forming amine are added.
3 . 3. The method for inhibiting corrosion of a copper-based material according to 1 or 2 , wherein a neutralizing amine is further added to the aqueous system containing ammonia.
4 . 4. The method for inhibiting corrosion of a copper-based material according to any one of 1 to 3 , wherein the aqueous system is not a seawater system.
5 . The method for inhibiting corrosion of a copper-based material according to any one of 1 to 4 above, wherein the addition of the film-forming amine is spray addition performed toward a thin tube.

Claims (6)

  A method for inhibiting corrosion of a copper-based material, wherein a film-forming amine is added to an aqueous system containing ammonia of a boiler using a copper-based material.   The method for inhibiting corrosion of a copper-based material according to claim 1, wherein an addition concentration of the film-forming amine is adjusted according to an ammonia concentration and an elution amount of copper.   The method for inhibiting corrosion of a copper-based material according to claim 1 or 2, wherein two or more kinds of the film-forming amine are added.   The method for inhibiting corrosion of a copper-based material according to any one of claims 1 to 3, wherein a neutralizing amine is further added to the aqueous system containing ammonia.   The method for inhibiting corrosion of a copper-based material according to any one of claims 1 to 4, wherein the aqueous system is not a seawater system. The method for inhibiting corrosion of a copper-based material according to any one of claims 1 to 5, wherein the addition of the film-forming amine is spray addition performed toward a thin tube.

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