WO2013176032A1

WO2013176032A1 - Ammonia treatment system

Info

Publication number: WO2013176032A1
Application number: PCT/JP2013/063663
Authority: WO
Inventors: 水谷　洋; 達也松村; 浅野　昌道; 鵜飼　展行; 竹内　和久; 勇作那須
Original assignee: 三菱重工環境・化学エンジニアリング株式会社
Priority date: 2012-05-25
Filing date: 2013-05-16
Publication date: 2013-11-28
Also published as: CN104379512B; KR101757525B1; CN104379512A; SG11201407526RA; JP2014000563A; JP6191070B2; KR20150013551A

Abstract

An ammonia treatment system comprises: a boiler facility for collecting heat; an ammonia injection means for injecting ammonia into a water supply system arranged in the boiler facility; an ammonia concentration measurement means for measuring the concentration of ammonia in blow water coming from the water supply system or the boiler facility; a flow volume measurement means for measuring the volume of the blow water; a receiving vessel for receiving the blow water therein; a chloride ion supply means for introducing an aqueous sodium chloride solution as a chloride ion source into the receiving vessel; an electrolysis vessel for electrolyzing a treated aqueous solution comprising the blow water and the aqueous sodium chloride solution; and a control device for controlling an electric current to be applied in the electrolysis and a treatment time period. In the control device, the necessary chloride amount is calculated on the basis of the concentration of ammonia and the volume of the blow water to control the amount of an electric current to be applied in the electrolysis.

Description

Ammonia treatment system

The present invention relates to an ammonia treatment system, and more particularly to an ammonia treatment system that electrolyzes ammonia contained in blow water that is drainage from boiler equipment.
This application claims priority to Japanese Patent Application No. 2012-119933 filed on May 25, 2012 and Japanese Patent Application No. 2013-010251 filed on January 23, 2013. , The contents of which are incorporated herein.

For example, hydrazine used to remove oxygen that causes corrosion in thermal power plants has been evaluated as a "chemical substance with recognized mutagenicity". Adoption of water treatment without agents and oxygen scavengers is in progress.
As an oxygen scavenger that does not use hydrazine, ammonia with a high hydrogen ion index (pH) (for example, pH 7 to pH 9) is known. However, by using ammonia as the oxygen scavenger, wastewater from the plant can be reduced in the future. It is assumed that the ammonia concentration becomes high (see, for example, Non-Patent Document 1). On the other hand, reduction of nitrogen is also required by the drainage regulations, and an immediate response is desired.

Patent Document 1 describes an ammonia treatment system for decomposing ammonia by electrolyzing waste water discharged from a power plant, and determining the end point of electrolysis from the residual chlorine concentration.
In addition, an ammonia treatment system that decomposes ammonia by chlorine treatment using a chemical such as sodium hypochlorite is also known.

Japanese Patent No. 4518826

However, for example, when waste water from a boiler facility is treated, there is a problem that the amount of waste water and ammonia concentration vary greatly, and, for example, at the time of start-up where the amount of blow water is large, electrolytic treatment is not in time.
In addition, in the case of ammonia decomposition using chemicals such as sodium hypochlorite, a space for installing a sodium hypochlorite tank or the like, which is a strong alkali oxidizing agent, is required, and it has been difficult to incorporate it into existing facilities.

The present invention provides an ammonia treatment system provided in a boiler facility, which can appropriately perform an electrolysis treatment of ammonia even when the fluctuation of boiler drainage is large.

According to the first aspect of the present invention, an ammonia treatment system includes: boiler equipment for heat recovery; ammonia injection means for injecting ammonia into a water supply system in the boiler equipment; and the water supply system or the boiler equipment. Ammonia concentration measuring means for measuring the ammonia concentration of blow water, a flow rate measuring means for measuring the amount of blow water, a receiving tank for receiving the blow water, and an aqueous sodium chloride solution as a chloride ion source introduced into the receiving tank A chloride ion supplying means, an electrolytic cell for electrolyzing the treated water composed of the blow water and the sodium chloride aqueous solution, and a control device for controlling a current and a treatment time during the electrolysis. The control device calculates a required chlorine amount based on the ammonia concentration and the amount of blow water, and controls a current amount during electrolysis.

According to the above configuration, the electrolysis is controlled based on the feed water system of the boiler facility or the ammonia concentration of the blow water and the amount of the blow water. For this reason, even when the fluctuation | variation of boiler waste_water | drain is large, the waste_water | drain standard of ammonia concentration can be satisfied.

The ammonia treatment system may have a residual chlorine measuring means for measuring the residual chlorine concentration of the treated water during electrolysis, and the control device may determine the end point of electrolysis according to the residual chlorine concentration.

According to the above configuration, the drainage standard of the discharged ammonia concentration can be more accurately controlled by using the residual chlorine concentration as an indicator of the end of electrolysis.

The ammonia treatment system has a chloride ion concentration measuring means for measuring a chloride ion concentration of the treated water, and the control device is configured so that the chloride ion concentration is equal to or higher than a predetermined concentration. The amount of introduction may be controlled.
According to the said structure, the chloride ion required for electrolysis can be ensured stably.

In the ammonia treatment system, a concentrating device for concentrating ammonia contained in at least a part of the treated water may be provided between the receiving tank and the electrolytic cell.

According to the above configuration, the required chlorine is reduced by concentrating the ammonia introduced into the electrolytic cell by the concentrator, so that the supply amount of chloride ions as a raw material can be reduced.

According to the second aspect of the present invention, an ammonia treatment system includes: boiler equipment for heat recovery; ammonia injection means for injecting ammonia into a water supply system in the boiler equipment; and the water supply system or the boiler equipment. Ammonia concentration measuring means for measuring the ammonia concentration of blow water, a flow rate measuring means for measuring the amount of water in the blow water, and a chloride ion supply means for introducing a sodium chloride aqueous solution as a chloride ion source, An electrolyzer that electrolyzes water, a mixing tank that receives the blow water and the treated water from the electrolyzer, and a control device that controls the current and the treatment time during the electrolysis. The control device calculates a required chlorine amount based on the ammonia concentration and the amount of blow water, and controls a current amount during electrolysis.

According to the said structure, electrolysis is controlled based on the ammonia density | concentration of blower water supply system or blow water, and the amount of blow water. For this reason, even when the fluctuation | variation of boiler waste_water | drain is large, the waste_water | drain standard of ammonia concentration can be satisfied.
Further, since the sodium chloride aqueous solution is introduced into the electrolytic cell in a state where the chloride ion concentration is high, the current density can be increased.

The ammonia treatment system has a chloride ion concentration measuring means for measuring a chloride ion concentration of the treated water, and the control device is configured so that the chloride ion concentration is equal to or higher than a predetermined concentration. The amount of introduction may be controlled.

In the ammonia treatment system, a desalinator provided on the downstream side of the mixing tank, and a concentrated water reuse pipe for supplying a part of the concentrated water concentrated by the desalter as a chloride ion source to the electrolytic cell And may be provided.

According to the above configuration, the supply cost of chloride ions can be reduced by the configuration in which the chloride ions supplied to the electrolytic cell are recovered and supplied from the desalting apparatus.

According to the above-described ammonia treatment system, electrolysis is controlled based on the feedwater system of the boiler facility or the ammonia concentration of blow water and the amount of blow water. For this reason, even when the fluctuation | variation of boiler waste_water | drain is large, the waste_water | drain standard of ammonia concentration can be satisfied.

It is a whole system diagram of a combined cycle power plant provided with an ammonia treatment system concerning a first embodiment of the present invention. 1 is a detailed system diagram of an ammonia treatment system according to a first embodiment of the present invention. It is a detailed systematic diagram of the ammonia processing system which concerns on 2nd embodiment of this invention. It is a detailed systematic diagram of the ammonia processing system which concerns on 3rd embodiment of this invention. It is a detailed systematic diagram of the ammonia processing system which concerns on 4th embodiment of this invention. It is a detailed systematic diagram of the ammonia processing system which concerns on 5th embodiment of this invention. It is a detailed systematic diagram of the ammonia processing system which concerns on 6th embodiment of this invention. It is a detailed systematic diagram of the ammonia processing system which concerns on 7th embodiment of this invention. It is a detailed systematic diagram of the ammonia processing system which concerns on 8th embodiment of this invention. It is a detailed systematic diagram of the ammonia processing system which concerns on 9th embodiment of this invention. It is a detailed systematic diagram of the ammonia processing system which concerns on 10th embodiment of this invention.

(First embodiment)
Hereinafter, a first embodiment of the present invention will be described in detail with reference to the drawings.
As shown in FIG. 1, an ammonia treatment system 1 according to this embodiment is provided in a combined cycle power plant 2 having an exhaust heat recovery boiler 3. The combined cycle power plant 2 is driven by the rotational driving force of the gas turbine 4, the exhaust heat recovery boiler 3 to which the exhaust gas from the gas turbine 4 is sent, the steam turbine 5, and the gas turbine 4 and the steam turbine 5 to generate power. And an ammonia treatment system 1 that performs a treatment of blow water discharged from the exhaust heat recovery boiler 3.

The exhaust heat recovery boiler 3 is provided with a high pressure heating unit 6, an intermediate pressure heating unit 7, and a low pressure heating unit 8. In the exhaust heat recovery boiler 3, steam is generated via the high-pressure heating unit 6, the intermediate-pressure heating unit 7, and the low-pressure heating unit 8, and the generated steam is sent to the steam turbine 5 so as to work on the steam turbine 5. It has become. Exhaust gas from the steam turbine 5 is condensed and condensed in a condenser 9, and is introduced into an exhaust heat recovery boiler 3 by a condensate pump 10. Condensate condensed in the condenser 9 is sent to the exhaust heat recovery boiler 3 through the water supply line 11.

The high pressure heating unit 6 includes a high pressure superheater 13, a high pressure drum 14, a high pressure evaporator 15, and a high pressure economizer 16. The water in the high-pressure drum 14 is superheated and circulated in a high-pressure evaporator 15 disposed in the exhaust heat recovery boiler 3 to generate high-pressure steam in the high-pressure drum 14. The high-pressure steam generated in the high-pressure drum 14 is superheated by the high-pressure superheater 13 disposed in the exhaust heat recovery boiler 3 and introduced into the steam turbine 5.

The intermediate pressure heating unit 7 includes an intermediate pressure superheater 17, an intermediate pressure drum 18, an intermediate pressure evaporator 19, and an intermediate pressure economizer 20. The water in the intermediate pressure drum 18 is superheated and circulated in an intermediate pressure evaporator 19 disposed in the exhaust heat recovery boiler 3 to generate intermediate pressure steam in the intermediate pressure drum 18. The intermediate pressure steam generated in the intermediate pressure drum 18 is introduced into the reheater 21 through the intermediate pressure superheater 17, reheated by the reheater 21, and introduced into the steam turbine 5. The steam from the intermediate pressure superheater 17 is introduced to the gas turbine 4 side for cooling the high temperature portion (combustor, blades, etc.) of the gas turbine 4.

The low pressure heating unit 8 includes a low pressure superheater 23, a low pressure drum 24, a low pressure evaporator 25, and a low pressure economizer 26. Water in the low-pressure drum 24 is superheated and circulated in a low-pressure evaporator 25 disposed in the exhaust heat recovery boiler 3 to generate low-pressure steam in the low-pressure drum 24. The low pressure steam generated in the low pressure drum 24 is introduced into the steam turbine 5 through the low pressure superheater 23.

Condensate 27 from the condenser 9 is supplied to the low pressure drum 24 through a deaerator 28 and a low pressure economizer 26. A water supply line 29 connected to the high pressure drum 14 and the intermediate pressure drum 18 is provided on the outlet side of the low pressure economizer 26. From the water supply line 29, water is supplied to the high pressure drum 14 via the high pressure water supply pump 30, and water is supplied to the intermediate pressure drum 18 via the intermediate pressure water supply pump 31. That is, water is supplied to the low-pressure drum 24, the intermediate-pressure drum 18 and the high-pressure drum 14 in parallel. The low pressure drum 24 is a drum of the low pressure side unit. The intermediate pressure drum 18 and the high pressure drum 14 are drums of the high pressure side unit.
A circulation pump 32 that circulates water supplied from the low-pressure economizer 26 is provided in a line between the water supply line 11 and the water supply line 29.

Further, a part of the condensate 27 is returned to the condenser 9 on the inlet side of the deaerator 28, and a part of the water is returned to the deaerator 28 side by branching from the water supply line 11. The arrangement of each device in the exhaust heat recovery boiler 3 is an example, and the number and arrangement of the economizers and superheaters are appropriately changed depending on the performance of the gas turbine 4 and the like.

A water supply line 11 serving as a water supply system is provided with ammonia injection means 34 for injecting ammonia as a pH adjusting agent. A predetermined amount of ammonia is injected from the ammonia injection means 34 into the feed water for pH adjustment so that the pH of the feed water in the low-pressure drum 24 is 9.0 or more and the ammonia concentration is 0.5 ppm or more.

Generally, if the pH of the feed water is less than 9.0, there is a concern that erosion and corrosion (corrosion and erosion) due to flow may occur. For this reason, the pH of the feed water in the low-pressure drum 24 is set to 9.0 or more. The pressure of the feed water in the low-pressure drum 24 is lower than the pressure of the feed water in the high-pressure drum 14 and the intermediate-pressure drum 18, and ammonia is more likely to evaporate and is easier to mix on the gas phase side (lower in the liquid phase). Since the distribution ratio between the gas phase and the liquid phase is high, the pH of the feed water in the low-pressure drum 24 is set to 9.0 or higher so that the pH of the feed water in the high-pressure drum 14 and the intermediate-pressure drum 18 is 9.0. Can also be high.

Also, a plurality of ammonia

concentration measuring devices

47, 48, and 49 for measuring the ammonia concentration of the feed water are installed on the water supply line 11 on the outlet side of the condenser 9. Specifically, the ammonia concentration measuring device 47 is installed on the water supply line 11 and between the condensate pump 10 and the ammonia injection means 34. The ammonia concentration measuring device 48 is installed between the ammonia injection means 34 and the deaerator 28. The ammonia concentration measuring device 49 is installed between the deaerator 28 and the low pressure economizer 26.

A blow line 35 is branched from the condenser 9 and the condensate pump 10 on the water supply line 11. The blow line 35 is a line for discharging blow water which is ammonia-containing waste water generated in the combined cycle power plant 2 including the exhaust heat recovery boiler 3.

The blow line 35 is provided with a flow rate measuring device 53 for measuring the amount of blow water. The amount of blow water measured by the flow rate measuring device 53 is transmitted to the control device 41.

The ammonia treatment system 1 is connected to the blow line 35. The ammonia treatment system 1 includes a receiving tank 36 in which blow water is stored and seawater is introduced, an electrolytic treatment device 37, and a control device 41.
The electrolytic treatment apparatus 37 includes a circulation adjustment tank 38 into which treated water consisting of blow water and seawater flowing out from the receiving tank 36 is introduced, an electrolytic tank 39 into which adjustment liquid from the circulation adjustment tank 38 is introduced, and an electrolytic treatment liquid. And a circulation pump 40 for circulating the electrolyte, and the electrolytic treatment liquid treated in the electrolytic bath 39 is circulated to the circulation adjusting bath 38.

As shown in FIG. 2, a seawater introduction line 42 (chloride ion supply means) for introducing seawater (chloride ion concentration: about 18,000 mg / liter) as a chloride ion source is connected to the receiving tank 36. Has been. The seawater introduction line 42 is provided with a seawater pump 46. The seawater pump 46 is configured to be controllable by the control device 41.

Note that the liquid introduced through the seawater introduction line 42 is not limited to seawater as long as the liquid contains chloride ions. For example, a configuration in which an aqueous sodium chloride solution is introduced from the seawater introduction line 42 may be adopted. In this way, by introducing the sodium chloride aqueous solution, it is possible to cope with facilities where seawater intake is difficult.

The circulation adjusting tank 38 includes a pH measuring device 43 that measures the pH of the treated water, a temperature measuring device 51 that measures the temperature of the treated water, and a chloride ion concentration measurement that measures the chloride ion concentration of the treated water. A device 44 is provided.

The electrolytic cell 39 has at least a pair of electrodes immersed in the treatment liquid in the electrolytic cell 39 and a DC power supply device 45 connected to the electrodes. By applying a DC voltage between these electrodes by a DC power supply device 45, the treatment liquid in the tank is electrolyzed.
The electrolytic cell 39 is provided with a residual chlorine measuring device 52 that measures the concentration of residual chlorine in the electrolytic cell 39. The residual chlorine measuring device 52 is connected to the control device 41.

Next, the operation of the ammonia processing system 1 of the present embodiment will be described.
First, blow water containing ammonia is introduced into the receiving tank 36, and seawater containing sodium chloride is introduced into the stored blow water via the seawater introduction line 42.

Next, treated water comprising blow water and seawater and containing chloride ions is supplied to the electrolytic treatment apparatus 37 at a predetermined rate.
Here, the treated water is supplied to the circulation adjusting tank 38 of the electrolytic treatment apparatus 37 and then supplied to the electrolytic tank 39. In the electrolytic cell 39, a predetermined voltage is applied between the electrodes in the electrolytic cell 39, and a current is supplied so as to obtain a predetermined current density. At the anode, chlorine (Cl ₂ ) is generated by the electrode reaction of Formula (1). appear.
Cl ⁻ → Cl ₂ + 2e ⁻ (1)

Further, Cl ₂ generated in the treatment liquid in the tank generates hypochlorous acid (HClO) by the solution reaction of formula (2).
Cl ₂ + H ₂ O → HClO + H ⁺ + Cl ⁻ (2)

When ammonia is present in the treated water, it undergoes a solution reaction with hypochlorous acid to produce chloroamine (NH ₂ Cl, NHCl ₂ ) according to formulas (3) and (4).
NH ₃ + HClO → NH ₂ Cl + H ₂ O (3)
NH ₂ Cl + HClO → NHCl ₂ + H ₂ O (4)

Furthermore, the chloroamine produced in the above formulas (3) and (4) is decomposed to nitrogen gas (N ₂ ) by the solution reaction of formula (5).
NH ₂ Cl + NHCl ₂ → N ₂ + 3H ⁺ + 3Cl ⁻ (5)

The control device 41 controls the DC power supply device 45 on the basis of the ammonia concentration measured by the ammonia

concentration measuring devices

47, 48, and 49 and the amount of blow water measured by the flow rate measuring device 53 to control the electrolytic treatment device 37. The current value and processing time are controlled. That is, the control device 41 performs the ammonia treatment in the ammonia treatment system 1 with high accuracy by controlling the current of the power supply device so that the concentration of hypochlorous acid is adapted to the amount of blow water and the ammonia concentration. Can do.
The ammonia concentration measuring device may be installed in one place, and in that case, the installation location of the ammonia concentration measuring device 47 closer to the condenser 9 is given priority.

The treatment time of the electrolytic treatment by the electrolytic treatment device 37 is controlled by the control device 41 on the basis of the concentration of residual chlorine measured by the residual chlorine measuring device 52 in addition to the ammonia concentration. Released.
Specifically, the control device 41 determines whether the concentration of residual chlorine is equal to or higher than a set value. Then, based on a test performed in advance, a residual chlorine concentration at which it can be determined that the ammonia concentration has become a predetermined value or less is set, and when the residual chlorine concentration reaches a set value, the electrolysis is stopped. The treated water is discharged through a residual chlorinator (not shown).
That is, in the electrolysis treatment time set according to the ammonia concentration, even when the ammonia concentration does not fall appropriately, the treatment time is extended until the ammonia concentration becomes a predetermined value or less.

The amount of seawater is controlled according to the measured value of the pH measuring device 43. That is, the control device 41 adjusts the amount of seawater by controlling the seawater pump 46 based on the input from the pH measuring device 43 so that the pH of the treated water in the circulation adjusting tank 38 becomes pH 7 to pH 9.
Similarly, the amount of seawater is controlled according to the measured value of the temperature measuring device 51. That is, the control device 41 controls the seawater pump 46 to adjust the amount of seawater so that the temperature of the treated water is 20 ° C. to 50 ° C.
Similarly, the amount of seawater is controlled based on the measured value of the chloride ion concentration measuring device 44.
That is, the control device 41 adjusts the amount of seawater by controlling the seawater pump 46 so that the chloride ion concentration of the treated water becomes 2,000 mg / liter or more.

According to the above embodiment, the electrolysis is controlled based on the feed water system of the exhaust heat recovery boiler 3 or the ammonia concentration of blow water and the amount of blow water. Thereby, even when the fluctuation | variation of boiler waste_water | drain is large, the waste_water | drain standard of ammonia concentration can be satisfied.

Moreover, the ammonia concentration discharged | emitted can be controlled more correctly by making the density | concentration of a residual chlorine into the parameter | index of completion | finish of electrolysis.
In addition, since the amount of seawater introduced is adjusted so that the chloride ion concentration of the treated water is 2,000 mg / liter or more, chloride ions necessary for electrolysis can be secured stably.

Further, since the introduction amount of seawater is adjusted so that the pH of the treated water in the electrolytic treatment apparatus 37 is pH 7 to pH 9, generation of chlorine gas and trichloramine can be suppressed, and decomposition of ammonia is efficiently performed. Can proceed.

In addition, when the temperature of the treated water is high, the generated chlorine is likely to volatilize, but the amount of seawater introduced is adjusted so that the temperature of the treated water is 20 ° C to 50 ° C. Reduction in removal performance can be prevented.
Furthermore, since a space for installing a sodium hypochlorite tank or the like is not required, it can be easily incorporated into existing facilities.

(Second embodiment)
Hereinafter, a second embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 3 is a detailed system diagram of the ammonia treatment system according to the present embodiment. In the present embodiment, differences from the first embodiment described above will be mainly described, and description of similar parts will be omitted.

As shown in FIG. 3, the ammonia treatment system 1 B of the present embodiment is connected to the electrolytic treatment apparatus 37 B and the blow line 35, a receiving tank 36 in which blow water is stored, and a process that flows out of the receiving tank 36. It comprises a mixing tank 55 into which water and treated water from the electrolytic treatment device 37B are introduced, and a control device 41.
A seawater introduction line 70 for introducing seawater as a chloride ion source is connected to the receiving tank 36. The seawater introduction line 70 is provided with a seawater pump 71. The seawater pump 71 is configured to be controllable by the control device 41. Further, the receiving tank 36 is provided with a temperature measuring device 72 for measuring the temperature of blow water.

The electrolytic treatment apparatus 37B includes a circulation adjustment tank 38B into which seawater is introduced, an electrolytic tank 39 into which the adjustment liquid from the circulation adjustment tank 38B is introduced, and a circulation pump 40 for circulating the electrolytic treatment liquid. The electrolytic treatment apparatus 37B is configured to circulate the electrolytic treatment liquid treated in the electrolytic bath 39 to the circulation adjustment bath 38B.

The seawater introduction line 42B for introducing seawater as a chloride ion source is connected to the circulation adjustment tank 38B. The seawater introduction line 42 B is provided with a seawater pump 46, and the seawater pump 46 can be controlled by the control device 41.

The circulation adjusting tank 38B includes a pH measuring device 43 that measures the pH of the treated water, a temperature measuring device 51 that measures the temperature of the treated water, and a chloride ion concentration measurement that measures the chloride ion concentration of the treated water. A device 44 is provided.

Next, the effect | action of the ammonia processing system 1B of this embodiment is demonstrated.
Seawater containing sodium chloride is directly introduced into the circulation adjustment tank 38B of the electrolytic treatment apparatus 37B to generate hypochlorous acid (HClO). Treated water containing hypochlorous acid is introduced into a mixing tank 55 in which blow water is stored, and ammonia and hypochlorous acid present in the blow water undergo a solution reaction to be decomposed into nitrogen gas (N ₂ ). The
Further, the amount of seawater introduced into the receiving tank 36 is controlled according to the measured value of the temperature measuring device 72. The control device 41 controls the seawater pump 71 to adjust the amount of seawater so that the temperature of the treated water in the receiving tank 36 is 50 ° C. or less.

According to the above embodiment, in addition to the effects of the first embodiment, seawater with a high chloride ion concentration is introduced into the electrolytic cell, so that the current density can be increased, and the electrolytic treatment apparatus 37B can be made compact. Can be planned.

(Third embodiment)
Hereinafter, a third embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 4 is a detailed system diagram of the ammonia treatment system according to this embodiment. In the present embodiment, differences from the first embodiment described above will be mainly described, and description of similar parts will be omitted.

As shown in FIG. 4, in the ammonia treatment system 1 C of the present embodiment, a concentrator 60 that concentrates ammonia contained in part or all of the treated water is provided between the receiving tank 36 and the electrolytic treatment device 37. Yes. That is, ammonia contained in the treated water discharged from the receiving tank 36 is concentrated by the concentrating device 60 and then introduced into the electrolytic processing device 37. As the concentration device 60, a device using a reverse osmosis membrane, electrodialysis, capacitor desalting, ion exchange resin, and water softener can be employed.

According to the above embodiment, the ammonia introduced into the electrolytic treatment device 37 is concentrated by the concentration device 60, so that the required chlorine (refer to the formula (2)) is reduced. The supply amount of ions can be reduced. That is, since chloride ions can be efficiently used in the electrolytic cell 39, the supply amount from the outside can be reduced.

(Fourth embodiment)
Hereinafter, a fourth embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 5 is a detailed system diagram of the ammonia treatment system according to the present embodiment. In this embodiment, the difference from the above-described third embodiment will be mainly described, and the description of the same parts will be omitted.

As shown in FIG. 5, in the ammonia treatment system 1 D of the present embodiment, wastewater having a low ammonia concentration generated during concentration of ammonia in the concentration device 60 is mixed with treated water discharged from the electrolytic treatment device 37. That is, the concentration device 60 of the present embodiment is provided with a drain pipe 61 that discharges waste water having a low ammonia concentration. Waste water discharged from the drain pipe 61 is mixed with treated water discharged from the electrolytic treatment apparatus 37.

According to the above embodiment, the wastewater having a low ammonia concentration produced by the concentrator 60 is mixed with the treated water discharged from the electrolytic treatment device 37, whereby the ammonia concentration of the discharged treated water is reduced to a predetermined concentration or less. Can keep.

(Fifth embodiment)
Hereinafter, a fifth embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 6 is a detailed system diagram of the ammonia treatment system according to the present embodiment. In this embodiment, the difference from the above-described third embodiment will be mainly described, and the description of the same parts will be omitted.

As shown in FIG. 6, in the ammonia treatment system 1E of the present embodiment, the treated water of the electrolytic treatment device 37 is circulated between the receiving tank 36 and the concentration device 60. That is, the ammonia treatment system 1E of this embodiment returns the electrolyzed and ammonia-treated treated water to the front of the concentrating device 60 via the treated water circulation pipe 62, and circulates and uses sodium chloride.

According to the above embodiment, chloride ions can be recycled, and no external supply is required.

(Sixth embodiment)
Hereinafter, a sixth embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 7 is a detailed system diagram of the ammonia treatment system according to the present embodiment. In the present embodiment, differences from the second embodiment described above will be mainly described, and description of similar parts will be omitted.

As shown in FIG. 7, in the ammonia processing system 1 F of the present embodiment, a desalinator 63 for concentrating salt is provided on the downstream side of the mixing tank 55, and a part of the concentrated water concentrated by the desalter 63 is electrolyzed. It supplies to the processing apparatus 37B as a chloride ion source. The desalting apparatus 63 and the electrolytic treatment apparatus 37 B are connected by a concentrated water reuse pipe 64.
Moreover, the treated water discharged | emitted from the desalination apparatus 63 is discharged | emitted as discharge water, or reused as boiler feed water, industrial water, and miscellaneous water.
As the desalting device 63, a device using a reverse osmosis membrane, electrodialysis, capacitor desalting, ion exchange resin, water softener, or the like can be used.

According to the above-described embodiment, the supply of chloride ions can be reduced by recovering and supplying chloride ions supplied to the electrolytic treatment apparatus 37B from the desalting apparatus 63.

(Seventh embodiment)
Hereinafter, a seventh embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 8 is a detailed system diagram of the ammonia treatment system according to the present embodiment. In this embodiment, the difference from the above-described sixth embodiment will be mainly described, and the description of the same parts will be omitted.

As shown in FIG. 8, in the ammonia processing system 1G of the present embodiment, an SS separation device 65 that separates SS (floating matter) of treated water is provided on the upstream side of the mixing tank 55 on the blow line 35. That is, the ammonia treatment system 1G of the present embodiment is configured to supply the mixing tank 55 after the SS separation of the treated water containing ammonia introduced through the blow line 35 is performed.

As the SS separator 65, an apparatus using a strainer, a microfiltration membrane (MF) module, an ultrafiltration membrane (UF) module, a sand filtration, a sedimentation basin, a liquid cyclone, or the like can be employed.

According to the above embodiment, the SS separation reduces the inflow of SS into the electrolytic treatment device 37B and the desalination device 63, and the risk of damage to the electrolytic treatment device 37B and the desalination device 63 can be reduced.

(Eighth embodiment)
Hereinafter, an eighth embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 9 is a detailed system diagram of the ammonia treatment system according to this embodiment. In this embodiment, the difference from the above-described sixth embodiment will be mainly described, and the description of the same parts will be omitted.

As shown in FIG. 9, in the ammonia treatment system 1H of the present embodiment, a cooler 66 for cooling the treated water is provided on the upstream side of the mixing tank 55 on the blow line 35.

According to the above embodiment, the risk of damage to the electrolytic treatment apparatus 37B and the desalination apparatus 63 can be reduced by cooling (for example, 50 ° C.) the high-temperature (for example, 80 ° C.) treated water by the cooler 66. .

(Ninth embodiment)
Hereinafter, a ninth embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 10 is a detailed system diagram of the ammonia treatment system according to this embodiment. In this embodiment, the difference from the above-described sixth embodiment will be mainly described, and the description of the same parts will be omitted.

As shown in FIG. 10, the ammonia treatment system 1J of the present embodiment is provided with a Cl removal device 67 for removing residual chlorine (Cl ₂ , ClO ⁻ ) between the mixing tank 55 and the desalting device 63. Yes.
As the Cl removing device 67, a device using activated carbon, air aeration, reducing agent supply, or the like can be employed. As the reducing agent, sodium thiosulfate (Na ₂ S ₂ O ₃ ), sodium hydrogen sulfite (NaHSO ₃ ), sodium sulfite (Na ₂ SO ₃ ) and the like can be employed.

According to the above embodiment, the residual chlorine is reduced and decomposed into chloride ions by the Cl removing device 67, so that residual chlorine in the treated water flowing into the desalting device 63 is blocked. Can prevent damage.

(Tenth embodiment)
Hereinafter, a tenth embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 11 is a detailed system diagram of the ammonia treatment system according to the present embodiment. In the present embodiment, the differences from the above-described ninth embodiment will be mainly described, and description of similar parts will be omitted.

As shown in FIG. 11, in the ammonia treatment system 1K of the present embodiment, the residual chlorine measuring device 68 is provided downstream of the Cl removal device 67 (upstream of the desalting device 63) of the ammonia treatment system 1J of the ninth embodiment. The Cl removing device 67 is controlled according to the residual chlorine concentration measured by the residual chlorine measuring device 68.
Further, on the downstream side of the Cl removal device 67 (upstream side of the desalination device 63), a bypass that bypasses the treated water discharged from the Cl removal device 67 to the concentrated water reuse pipe 64 on the downstream side of the desalination device 63. A pipe 69 is provided. The treated water discharged from the Cl removal device 67 is introduced into either the desalting device 63 or the bypass pipe 69 according to a command from the control device 41. This switching is performed by a valve (not shown).

A specific control method of the ammonia treatment system 1J of the present embodiment will be described. The control device 41 monitors the residual chlorine concentration of the treated water discharged from the mixing tank 55 by the residual chlorine measuring device 68 and operates the Cl removal device 67 so that the residual chlorine concentration is not detected. Specifically, the amount of reducing agent / activated carbon added and the amount of air aeration are controlled.
When the residual chlorine concentration is detected, the flow path to the desalting apparatus 63 is shut off by a valve, the treated water is introduced into the bypass flow path 69, and bypassed to the concentrated water reuse pipe 64.

According to the above embodiment, the removal rate of residual chlorine by the Cl removal device 67 can be improved.

The technical scope of the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention. For example, in each embodiment described above, the ammonia concentration is measured by the ammonia concentration measuring device provided in the water supply line 11, but the ammonia concentration may be measured by the blow line 35. .

Further, the means for measuring the concentration of ammonia is not limited to the measurement by the ammonia concentration measuring device, but may be configured to be estimated from the amount of ammonia injected from the ammonia injection means and the amount of blow water in the water supply system.

1 Ammonia treatment system 2 Combined cycle power plant 3 Waste heat recovery boiler (boiler equipment)
11 Water supply line (water supply system)
34 Ammonia injection means 35 Blow line 36 Receiving tank 37 Electrolytic treatment apparatus 38 Circulation adjustment tank 39 Electrolytic tank 41

Control apparatus

42, 42B Seawater introduction line (chloride ion supply means)
44 Chloride ion concentration measuring device (chloride ion concentration measuring means)
45 DC power supply 46 Seawater pump 47 Ammonia concentration measuring device (ammonia concentration measuring means)
48 Ammonia concentration measuring device (Ammonia concentration measuring means)
49 Ammonia concentration measuring device (ammonia concentration measuring means)
52 Residual chlorine measuring device (Residual chlorine measuring means)
53 Flow rate measuring device (flow rate measuring means)
55 Mixing tank 60 Concentrator 63 Desalinator 64 Concentrated water reuse pipe

Claims

Boiler equipment for heat recovery;
Ammonia injection means for injecting ammonia into the water supply system in the boiler facility;
Ammonia concentration measuring means for measuring ammonia concentration of blow water from the water supply system or the boiler facility;
Flow rate measuring means for measuring the amount of blow water,
A receiving tank for receiving the blow water;
Chloride ion supply means for introducing a sodium chloride aqueous solution as a chloride ion source into the receiving tank;
An electrolytic cell for electrolyzing the treated water comprising the blow water and the sodium chloride aqueous solution;
A controller for controlling the current during the electrolysis and the processing time,
The control device calculates a necessary chlorine amount based on the ammonia concentration and the amount of blow water, and controls the amount of current during electrolysis.
Having residual chlorine measuring means for measuring the residual chlorine concentration of the treated water during electrolysis,
The ammonia processing system according to claim 1, wherein the control device determines an end point of electrolysis based on the residual chlorine concentration.
Having a chloride ion concentration measuring means for measuring the chloride ion concentration of the treated water;
The ammonia processing system according to claim 1 or 2, wherein the control device controls an introduction amount of the sodium chloride aqueous solution so that the chloride ion concentration is equal to or higher than a predetermined concentration.
The ammonia treatment system according to any one of claims 1 to 3, wherein a concentrating device for concentrating ammonia contained in at least a part of the treated water is provided between the receiving tank and the electrolytic cell.
Boiler equipment for heat recovery;
Ammonia injection means for injecting ammonia into the water supply system in the boiler facility;
Ammonia concentration measuring means for measuring ammonia concentration of blow water from the water supply system or the boiler facility;
Flow rate measuring means for measuring the amount of blow water,
An electrolytic cell comprising a chloride ion supply means for introducing a sodium chloride aqueous solution as a chloride ion source, and electrolyzing the sodium chloride aqueous solution;
A mixing tank that receives the blow water and receives treated water from the electrolytic cell;
A controller for controlling the current during the electrolysis and the processing time,
The control device calculates a necessary chlorine amount based on the ammonia concentration and the amount of blow water, and controls the amount of current during electrolysis.
Having residual chlorine measuring means for measuring the residual chlorine concentration of the treated water during electrolysis,
The ammonia processing system according to claim 5, wherein the controller determines an end point of electrolysis based on the residual chlorine concentration.
Having a chloride ion concentration measuring means for measuring the chloride ion concentration of the treated water;
The ammonia processing system according to claim 5 or 6, wherein the control device controls an introduction amount of the sodium chloride aqueous solution so that the chloride ion concentration is equal to or higher than a predetermined concentration.
A desalting apparatus provided on the downstream side of the mixing tank;
The ammonia treatment according to any one of claims 5 to 7, further comprising: a concentrated water reuse pipe that supplies a part of the concentrated water concentrated by the desalting apparatus to the electrolytic cell as a chloride ion source. system.