CN104379512B - ammonia treatment system - Google Patents
ammonia treatment system Download PDFInfo
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- CN104379512B CN104379512B CN201380025991.2A CN201380025991A CN104379512B CN 104379512 B CN104379512 B CN 104379512B CN 201380025991 A CN201380025991 A CN 201380025991A CN 104379512 B CN104379512 B CN 104379512B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
- C02F2201/4614—Current
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/14—NH3-N
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/29—Chlorine compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/40—Liquid flow rate
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
A kind of ammonia treatment system, it possesses：Boiler plant, for carrying out recuperation of heat；Ammonia injection unit, ammonia is injected to the water supply system in boiler plant；Ammonia concentration determination unit, is measured to the ammonia density for blowing water from water supply system or boiler plant；Flow measurement unit, measure blows the water of water；Water is blown in dump tank, receiving；Chloride ion feed unit, imports as the sodium-chloride water solution in chloride ion source to dump tank；Electrolytic cell, to being electrolysed comprising the treatment water for blowing water and sodium-chloride water solution；And control device, electric current and process time during control electrolysis.Control device is based on ammonia density and calculates required chlorine dose, and magnitude of current when controlling to be electrolysed with the water for blowing water.
Description
Technical field
The present invention relates to ammonia treatment system, more particularly to blowing the ammonia contained in water as the draining from boiler plant
Be electrolysed the ammonia treatment system for the treatment of.
The application advocate on May 25th, 2012 submit to Japanese patent application the 2012-119933rd and in January, 2013
The priority of the Japanese patent application the 2013-010251st submitted to for 23rd, their content is quoted in the application.
Background technology
For example in thermal power plant, the hydrazine used to remove the oxygen of the main cause as corrosion is be evaluated as " seeing
Observe the chemical substance of mutagenicity ", thus in recent years using safer deoxidier, do not use the water process of deoxidier.
As the deoxidier for not using hydrazine, it is known to (such as pH7~the pH9) for increasing the value of hydrogen ion exponent (pH)
Ammonia, but it is envisioned that due to using ammonia as deoxidier, the ammonia density of the draining from power plant can increase and (for example join from now on
According to non-patent literature 1).On the other hand, specified according to draining, reduction nitrogen is also required that, therefore desirable for being tackled as early as possible.
Following ammonia treatment system has been recorded in patent document 1：It is electrolysed by the draining discharged from power plant, by
Ammonolysis craft is determined the terminal of electrolysis by concentration of residual chlorine by this.
In addition, it is also known that decompose the ammonia treatment system of ammonia by chlorine treatment using reagents such as sodium hypochlorite.
Prior art literature
Patent document
Patent document 1：No. 4518826 publications of Japanese Patent No.
Non-patent literature
Non-patent literature 1：" the de- ヒ De ラ ジ Application へ Qu Group body in firepower プ ラ Application ト water process ", [online], Mitsubishi
Heavy industry skill reports Vol.46No.2 (2009), [retrieval of Heisei on March 30th, 24], website<URL:http://www.mhi.co.jp/ technology/review/pdf/462/462055.pdf>
The content of the invention
The invention problem to be solved
But, such as when processing the draining from boiler plant, the variation of the water, ammonia density of draining is big, example
Such as when the startup more than the water of water is blown, there is a problem of electrolysis treatment not in time.
In addition, it is necessary to be provided as the hypochlorous acid of strong basicity oxidant when carrying out ammonolysis craft using reagents such as sodium hypochlorite
The space of sodium tank etc., and be difficult to assemble into existing equipment.
The present invention provides a kind of ammonia treatment system for being arranged at boiler plant, even if the ammonia treatment system is in discharging of boiler
Variation it is big in the case of, it is also possible to suitably carry out ammonia electrolysis treatment.
Means for solving the problems
First method of the invention, ammonia treatment system has：Boiler plant, for carrying out recuperation of heat；Ammonia injection is single
Unit, ammonia is injected to the water supply system in the boiler plant；Ammonia concentration determination unit, to from the water supply system or the pot
The ammonia density for blowing water of furnace apparatus is measured；Flow measurement unit, determine described in blow the water of water；Dump tank, receives described
Blow water；Chloride ion feed unit, imports as the sodium-chloride water solution in chloride ion source to the dump tank；Electrolysis
Groove, to being electrolysed comprising the treatment water for blowing water and the sodium-chloride water solution；And control device, when controlling the electrolysis
Electric current and process time.The control device is based on the ammonia density and the water for blowing water calculates required chlorine dose, and
Magnitude of current during control electrolysis.
According to above-mentioned composition, water supply system based on boiler plant or blow the ammonia density of water and blow the water of water and control electricity
Solution.Therefore, even if in the case where the variation of discharging of boiler is big, it is also possible to meet the draining benchmark of ammonia density.
In above-mentioned ammonia treatment system, the residual chlorine measurement with the concentration of residual chlorine that the treatment water is determined in electrolysis
Unit, above-mentioned control device can determine the terminal of electrolysis according to the concentration of residual chlorine.
According to above-mentioned composition, by the index for terminating concentration of residual chlorine as electrolysis, thus, it is possible to more accurately control
The draining benchmark of the ammonia density of discharge.
In above-mentioned ammonia treatment system, the chloride ion concentration with the chloride ion concentration for determining the treatment water
Determination unit, above-mentioned control device can control described in the way of so that the chloride ion concentration reaches more than normal concentration
The import volume of sodium-chloride water solution.
According to above-mentioned composition, the chloride ion required for can stably ensuring electrolysis.
In above-mentioned ammonia treatment system, at least to treatment water can be set between the dump tank and electrolytic cell
The enrichment facility that the ammonia contained in point is concentrated.
According to above-mentioned composition, the ammonia for importeding into electrolytic cell is concentrated using enrichment facility, thus can reduce the chlorine of needs,
Therefore, it is possible to reduce the quantity delivered as the chloride ion of raw material.
Second method of the invention, ammonia treatment system possesses：Boiler plant, for carrying out recuperation of heat；Ammonia injection is single
Unit, ammonia is injected to the water supply system in the boiler plant；Ammonia concentration determination unit, to from the water supply system or the pot
The ammonia density for blowing water of furnace apparatus is measured；Flow measurement unit, determine described in blow the water of water；Electrolytic cell, possesses importing
As the chloride ion feed unit of the sodium-chloride water solution in chloride ion source, and electricity is carried out to the sodium-chloride water solution
Solution；Mixing channel, receives described to blow the treatment water of water and receiving from the electrolytic cell；And control device, control the electrolysis
When electric current and process time.The control device is based on the ammonia density and the water for blowing water calculates required chlorine dose,
And magnitude of current when controlling to be electrolysed.
According to above-mentioned composition, water supply system based on boiler plant or blow the ammonia density of water and blow the water of water and control electricity
Solution.Therefore, even if in the case where the variation of discharging of boiler is big, it is also possible to meet the draining benchmark of ammonia density.
Further, since sodium-chloride water solution is imported into electrolytic cell, therefore energy in the state of chloride ion concentration is high
Enough increase current density.
In above-mentioned ammonia treatment system, the residual chlorine measurement with the concentration of residual chlorine that the treatment water is determined in electrolysis
Unit, above-mentioned control device can determine the terminal of electrolysis according to the concentration of residual chlorine.
In above-mentioned ammonia treatment system, can possess：It is arranged on the desalter in the downstream of the mixing channel；With by profit
A part for the condensed water concentrated with the desalter is recycled as the condensed water that chloride ion source is supplied to electrolytic cell
Pipe arrangement.
According to above-mentioned composition, reclaim laggard from desalter by the chloride ion for being set as being fed into electrolytic cell
The composition of row supply, the supply cost thus, it is possible to reduce chloride ion.
Invention effect
According to above-mentioned ammonia treatment system, water supply system based on boiler plant or blow water ammonia density and blow the water of water come
Control electrolysis.Therefore, even if in the case where the variation of discharging of boiler is big, it is also possible to meet the draining benchmark of ammonia density.
Brief description of the drawings
Fig. 1 is the entirety of the combined cycle power stations for possessing the ammonia treatment system involved by first embodiment of the invention
System diagram.
Fig. 2 is the detailed system figure of the ammonia treatment system involved by first embodiment of the invention.
Fig. 3 is the detailed system figure of the ammonia treatment system involved by second embodiment of the present invention.
Fig. 4 is the detailed system figure of the ammonia treatment system involved by third embodiment of the present invention.
Fig. 5 is the detailed system figure of the ammonia treatment system involved by the 4th implementation method of the invention.
Fig. 6 is the detailed system figure of the ammonia treatment system involved by the 5th implementation method of the invention.
Fig. 7 is the detailed system figure of the ammonia treatment system involved by the 6th implementation method of the invention.
Fig. 8 is the detailed system figure of the ammonia treatment system involved by the 7th implementation method of the invention.
Fig. 9 is the detailed system figure of the ammonia treatment system involved by the 8th implementation method of the invention.
Figure 10 is the detailed system figure of the ammonia treatment system involved by the 9th implementation method of the invention.
Figure 11 is the detailed system figure of the ammonia treatment system involved by the tenth implementation method of the invention.
Specific embodiment
(first embodiment)
First embodiment of the invention is described in detail referring to the drawings.
As shown in figure 1, the ammonia treatment system 1 of present embodiment is arranged at the combined-circulation hair for possessing heat recovery boiler 3
Power plant 2.Combined cycle power stations 2 have：Heat recovery boiler 3 that gas turbine 4, the waste gas from gas turbine 4 are sent to,
Steam turbine 5, by the rotary driving force of gas turbine 4 and steam turbine 5 drive and the generator (not shown) that is generated electricity and
To the ammonia treatment system 1 that water is processed of blowing discharged from heat recovery boiler 3.
Heat recovery boiler 3 possesses：Hyperbaric heating unit 6, middle pressure heating unit 7 and low-pressure heating unit 8.In used heat
In recovery boiler 3, steam is produced by hyperbaric heating unit 6, middle pressure heating unit 7 and low-pressure heating unit 8, will produced
Steam deliver to steam turbine 5 and done work by steam turbine 5.The exhaust of steam turbine 5 is condensed and cold by condenser 9
It is solidifying, and import heat recovery boiler 3 using condenser pump 10.The condensed water condensed using condenser 9 is delivered to useless via feedwater line 11
Thimble-tube boiler 3.
Hyperbaric heating unit 6 has：High-pressure superheater 13, pressure cylinder high 14, high pressure evaporator 15 and high pressure section carbon device 16.
The water of pressure cylinder high 14 crosses thermal cycle in the high pressure evaporator 15 being configured in heat recovery boiler 3, is produced in pressure cylinder high 14 high
Pressure steam.The high steam produced in pressure cylinder high 14 was carried out by configuring the high-pressure superheater 13 in heat recovery boiler 3
Steam turbine 5 is directed to after heat.
Middle pressure heating unit 7 has：Middle pressure superheater 17, middle pressure cylinder 18, middle pressure evaporator 19 and middle pressure section carbon device 20.In
The water of pressure cylinder 18 crosses thermal cycle in the middle pressure evaporator 19 being configured in heat recovery boiler 3, is pressed in being produced in middle pressure cylinder 18
Steam.The middle pressure steam produced in middle pressure cylinder 18 is directed to reheater 21 by middle pressure superheater 17, is carried out in reheater 21
Steam turbine 5 is directed to after reheating.From the middle steam for pressing superheater 17 as high-temperature portion (burner, the oar of gas turbine 4
Leaf etc.) cooling purposes be directed to the side of gas turbine 4.
Low-pressure heating unit 8 has：Low-pressure superheater 23, low pressure cylinder 24, low pressure evaporator 25 and low pressure section carbon device 26.
The water of low pressure cylinder 24 crosses thermal cycle in the low pressure evaporator 25 being configured in heat recovery boiler 3, is produced in low pressure cylinder 24 low
Pressure steam.The low-pressure steam produced in low pressure cylinder 24 imported into steam turbine 5 by low-pressure superheater 23.
The condensed water 27 for carrying out condenser 9 is fed into low pressure cylinder 24 by degasser 28 and low pressure section carbon device 26.Low pressure
The outlet side of section carbon device 26 is provided with the feedwater line 29 being connected with pressure cylinder high 14 and middle pressure cylinder 18.By feedwater line 29, via high pressure
Feed pump 30 is fed water to pressure cylinder high 14, is fed water to middle pressure cylinder 18 via middle pressure feed pump 31.That is, concurrently to low pressure
Cylinder 24 and middle pressure cylinder 18 and pressure cylinder high 14 are fed water.Low pressure cylinder 24 is considered as the cylinder of low pressure side unit.Middle pressure cylinder 18 and high pressure
Cylinder 14 is considered as the cylinder of high pressure side unit.
It should be noted that the streamline between feedwater line 11 and feedwater line 29 is provided with circulation from low pressure section carbon device
The circulating pump 32 of 26 feedwater.
In addition, in the entrance side of degasser 28, a part for condensed water 27 returns to condenser 9, from after the branch of feedwater line 11,
A part of water returns to the side of degasser 28.Each machine in heat recovery boiler 3 is configured to an example, section carbon device, superheater
Number of units, configuration can suitably be changed according to performance of gas turbine 4 etc..
As the ammonia injection unit 34 of the ammonia that injection pH adjusting agent is provided with the feedwater line 11 of water supply system.Injected by ammonia
Unit 34, to the ammonia of feedwater injection ormal weight, makes the pH of the feedwater in low pressure cylinder 24 reach more than 9.0 as pH regulation purposes, and
And ammonia density is reached more than 0.5ppm.
In general, when the pH of feedwater is less than 9.0, it is possible to which corrosion, erosion occurs due to flowing.Therefore, low pressure is made
The pH of the feedwater in cylinder 24 is more than 9.0.The feedwater of the pressure less than pressure cylinder high 14 and middle pressure cylinder 18 of the feedwater in low pressure cylinder 24
Pressure, ammonia is easy to evaporation and pressure is more low is more easily mixed in gas phase side (being difficult to be mixed in liquid phase), therefore, i.e. gas phase and liquid
The value of the apportionment ratio of phase is high, therefore is more than 9.0 by the pH for making the feedwater in low pressure cylinder 24, thus enables that the He of pressure cylinder high 14
The pH of the feedwater of middle pressure cylinder 18 is the value higher than 9.0.
In addition, multiple ammonia that the ammonia density for determining feedwater is provided with the feedwater line 11 of the outlet side of condenser 9 are dense
Degree determines device 47,48,49.Specifically, ammonia concentration determination device 47 is on feedwater line 11, and be arranged at condenser pump 10 with
Between ammonia injection unit 34.Ammonia concentration determination device 48 is arranged between ammonia injection unit 34 and degasser 28.Ammonia density is surveyed
Determine device 49 to be arranged between degasser 28 and low pressure section carbon device 26.
On feedwater line 11, and branched out between condenser 9 and condenser pump 10 and blow line 35.It is for arranging to blow line 35
Go out in the combined cycle power stations 2 comprising heat recovery boiler 3 produce as containing ammonia draining the circuit for blowing water.
In addition, being provided with the flow rate-measuring device 53 for determining the water for blowing water in blowing line 35.By flow rate-measuring device 53
The water for blowing water for determining is sent to control device 41.
Ammonia treatment system 1 is connected with line 35 is blowed.Ammonia treatment system 1 is blown water and is imported with the dump tank of seawater by storage
36th, electrolytic processing apparatus 37, control device 41 are constituted.
Electrolytic processing apparatus 37 possess：It is imported with and blow following for the treatment water that water and seawater are constituted by what is flowed out from dump tank 36
Ring adjustment tank 38, it is imported with the adjustment electrolytic cell 39 of liquid and following for cyclic electrolysis treatment fluid for carrying out self-loopa adjustment tank 38
Ring pump 40, electrolytic processing apparatus 37 are the structures for making the electrolysis treatment fluid in electrolytic cell 39 after treatment be recycled to circulation adjustment tank 38
Into.
As shown in Fig. 2 being connected with dump tank 36 for the seawater that imports as chloride ion source, (chloride ion is dense
Degree：About 18,000mg/ liters) seawater lead-in wire 42 (chloride ion feed unit).Seawater is provided with seawater lead-in wire 42
Pump 46.The sea water pump 46 forms the composition for being capable of the control of controlled device 41.
As long as it should be noted that it is by liquid of the liquid comprising chloride ion that seawater lead-in wire 42 is imported
Can, however it is not limited to seawater.It for example can be the composition that sodium-chloride water solution is imported from seawater lead-in wire 42.So, by importing
Sodium-chloride water solution, it is also possible to corresponding with the facility for being difficult to obtain seawater.
In addition, being provided with circulation adjustment tank 38：The pH for determining the pH for the treatment of water determines device 43, determines the temperature for the treatment of water
The chloride ion concentration of the temperature measuring apparatus 51 of degree and the chloride ion concentration for determining treatment water determines device 44.
Electrolytic cell 39 has：At least one pair of electrode for being immersed in the treatment fluid in electrolytic cell 39 and it is connected with the electrode
Continuous-current plant 45.Between these electrodes, DC voltage is applied using continuous-current plant 45, thus carry out the place in groove
Manage the electrolysis of liquid.
In addition, electrolytic cell 39 is provided with the residual chlorine measurement device 52 of the concentration for determining the residual chlorine in electrolytic cell 39.It is residual
Chlorine measurement device 52 is stayed to be connected with control device 41.
Then, the effect to the ammonia treatment system 1 of present embodiment is illustrated.
First, to importing the water that blows containing ammonia in dump tank 36, and imported to the water that blows of storage by seawater lead-in wire 42
Seawater containing sodium chloride.
Then, by blowing water and seawater is constituted and treatment water containing chloride ion is supplied to electrolysis with fixing speed
Reason device 37.
Here, treatment water is fed into the circulation adjustment tank 38 of electrolytic processing apparatus 37, electrolytic cell 39 is then fed into.
In electrolytic cell 39, assigned voltage is applied between the electrode in electrolytic cell 39, electricity is supplied in the way of the current density for reaching regulation
Stream, in anode, chlorine (Cl is produced by the electrode reaction of formula (1)2)。
Cl-→Cl2+2e-…(1)
Then, the Cl for being produced in the treatment fluid in groove2Hypochlorous acid (HClO) is generated by the solution reaction of formula (2).
Cl2+H2O→HClO+H++Cl-…(2)
When there is ammonia in treatment water, there is solution reaction with hypochlorous acid, chloramines (NH is generated by formula (3), formula (4)2Cl、
NHCl2)。
NH3+HClO→NH2Cl+H2O…(3)
NH2Cl+HClO→NHCl2+H2O…(4)
Then, the chloramines of generation decomposes to nitrogen (N by the solution reaction of formula (5) in above-mentioned formula (3) and formula (4)2)。
NH2Cl+NHCl2→N2+3H++3Cl-…(5)
Control device 41 is based on the ammonia density determined by ammonia concentration determination device 47,48,49 and by flow rate-measuring device 53
What is determined blows the water of water to control continuous-current plant 45, so that when controlling current value and the treatment of electrolytic processing apparatus 37
Between.That is, control device 41 can the control by way of with the adaptable hypochlorous acid concentration of the water and ammonia density that reach with blow water
The electric current of supply unit processed, thus accurately carries out the ammonia treatment in ammonia treatment system 1.
It should be noted that ammonia concentration determination device can be to be arranged at the composition at 1, it is now, preferential closer to condensation
The setting position of the ammonia concentration determination device 47 of device 9.
Using the process time of the electrolysis treatment of electrolytic processing apparatus 37, in addition to ammonia density, also based on by residual chlorine measurement
The concentration controlled device 41 of the residual chlorine that device 52 is determined is controlled, and at the end for the treatment of, treatment water is released after suitably being collected.
Specifically, control device 41 is judged whether the concentration of residual chlorine reaches more than setting value.Then, it is based on
The testing setup for carrying out in advance can interpolate that out that ammonia density reaches the concentration of the residual chlorine below setting, reach the residual chlorine
Concentration setting value when stop electrolysis.Treatment water is released by residual chlorine processor (not shown).
That is, for the process time of the electrolysis set according to ammonia density, even if the feelings not reduced suitably in ammonia density
Under condition, can also extend process time until ammonia density is reached below setting.
In addition, the amount of seawater is controlled according to the measured value that pH determines device 43.That is, control device 41 is based on coming from pH
The input of device 43 is determined, sea water pump is controlled in the way of the pH for making the treatment water in circulation adjustment tank 38 reaches pH7~pH9
46, adjust the amount of seawater.
Similarly, the amount of seawater is controlled according to the measured value of temperature measuring apparatus 51.That is, control device 41 is so that place
The mode that the temperature of reason water reaches 20 DEG C~50 DEG C controls sea water pump 46, adjusts the amount of seawater.
Similarly, the amount of seawater is controlled based on the measured value that chloride ion concentration determines device 44.
That is, control device 41 is so that the mode that the chloride ion concentration for the treatment of water reaches 2, the 000mg/ liter above controls sea
Water pump 46, adjusts the amount of seawater.
According to above-mentioned implementation method, water supply system based on heat recovery boiler 3 or blow the ammonia density of water and blow the water of water
Measure to control electrolysis.Thus, even if in the case where the variation of discharging of boiler is big, it is also possible to meet the draining benchmark of ammonia density.
In addition, by the index for terminating the concentration of residual chlorine as electrolysis, can more accurately control the ammonia of discharge dense
Degree.
Further, since so that the mode that the chloride ion concentration for the treatment of water reaches 2, the 000mg/ liter above adjusts seawater
Import volume, therefore, it is possible to stably ensure the chloride ion required for electrolysis.
Further, since adjusting seawater in the way of the pH of the treatment water in electrolytic processing apparatus 37 is reached pH7~pH9
Import volume, therefore, it is possible to suppress the generation of chlorine, three chloramines, so as to efficiently carry out the decomposition of ammonia.
In addition, when the temperature for the treatment of water reaches a high temperature, the chlorine of generation becomes readily volatilized, but due to so that the temperature for the treatment of water
Degree reaches the import volume that 20 DEG C~50 DEG C of mode adjusts seawater, therefore, it is possible to the ammonia removing performance caused by the volatilization for preventing chlorine
Decline.
Further, since the space of sodium hypochlorite tank etc. need not be set, it is thus susceptible to be assembled into existing device.
(second embodiment)
Second embodiment of the present invention is described in detail referring to the drawings.
Fig. 3 is the detailed system figure of the ammonia treatment system involved by present embodiment.It should be noted that present embodiment
In, by with the difference of above-mentioned first embodiment centered on described, eliminate its explanation for identical part.
As shown in figure 3, the ammonia treatment system 1B of present embodiment by electrolytic processing apparatus 37B and blow line 35 connect and
Storage is blown the dump tank 36 of water, is imported with from the treatment water of the outflow of dump tank 36 and the treatment water from electrolytic processing apparatus 37B
Mixing channel 55 and control device 41 constitute.
It is connected with dump tank 36 for importing as the seawater lead-in wire 70 of the seawater in chloride ion source.Seawater is imported
Sea water pump 71 is provided with line 70.The sea water pump 71 forms the composition for being capable of the control of controlled device 41.In addition, on dump tank 36
It is provided with the temperature measuring apparatus 72 for determining the temperature for blowing water.
Electrolytic processing apparatus 37B possesses：The circulation adjustment tank 38B of seawater is imported with, is imported with and is carried out self-loopa adjustment tank 38B
Adjustment liquid electrolytic cell 39 and the circulating pump 40 for cyclic electrolysis treatment fluid.Electrolytic processing apparatus 37B is made in electrolytic cell
Electrolysis treatment fluid in 39 after treatment is recycled to the composition of circulation adjustment tank 38B.
It is connected with for importing as the seawater lead-in wire 42B of the seawater in chloride ion source on circulation adjustment tank 38B.Sea
Be provided with sea water pump 46 on water lead-in wire 42B, the sea water pump 46 can controlled device 41 control.
In addition, being provided with circulation adjustment tank 38B：The pH for determining the pH for the treatment of water determines device 43, determines treatment water
The chloride ion concentration of the temperature measuring apparatus 51 of temperature and the chloride ion concentration for determining treatment water determines device 44.
Then, the effect to the ammonia treatment system 1B of present embodiment is illustrated.
Seawater containing sodium chloride is imported directly into the circulation adjustment tank 38B of electrolytic processing apparatus 37B, generates hypochlorous acid
(HClO).It is imported into stored with the mixing channel 55 for blowing water containing hypochlorous treatment water, blows ammonia present in water and sent out with hypochlorous acid
Raw solution reaction, decomposes to nitrogen (N2)。
In addition, the amount for importeding into the seawater of dump tank 36 is controlled according to the measured value of temperature measuring apparatus 72.Control
Device 41 controls sea water pump 71 in the way of the temperature for making the treatment water in dump tank 36 is reached below 50 DEG C, adjustment seawater
Amount.
It is dense due to importing chloride ion to electrolytic cell in addition to the effect of first embodiment according to above-mentioned implementation method
Degree seawater high, therefore, it is possible to increase current density, can realize the densification of electrolytic processing apparatus 37B.
(the 3rd implementation method)
Third embodiment of the present invention is described in detail referring to the drawings.
Fig. 4 is the detailed system figure of the ammonia treatment system involved by present embodiment.It should be noted that present embodiment
In, by with the difference of above-mentioned first embodiment centered on recorded, eliminate its explanation for identical part.
As shown in figure 4, in the ammonia treatment system 1C of present embodiment, being set between dump tank 36 and electrolytic processing apparatus 37
Be equipped with by process water part or all in the enrichment facility 60 that is concentrated of the ammonia that contains.That is, from the discharge of dump tank 36
After the ammonia contained in treatment water is concentrated the concentration of device 60, electrolytic processing apparatus 37 are imported into.As enrichment facility 60, can adopt
With having used the inverse device for being impregnated with film, electrodialysis, capacitor desalination, ion exchange resin, water softener.
According to above-mentioned implementation method, carried out using enrichment facility 60 by the ammonia that will imported into electrolytic processing apparatus 37 dense
Contracting, the chlorine (with reference to formula (2)) required for thus can reducing, therefore, it is possible to reduce the quantity delivered as the chloride ion of raw material.
That is, chloride ion can be efficiently utilized in electrolytic cell 39, can be reduced from outside quantity delivered.
(the 4th implementation method)
The 4th implementation method of the invention is described in detail referring to the drawings.
Fig. 5 is the detailed system figure of the ammonia treatment system involved by present embodiment.It should be noted that present embodiment
In, by with the difference of the 3rd above-mentioned implementation method centered on recorded, eliminate its explanation for identical part.
As shown in figure 5, in the ammonia treatment system 1D of present embodiment, the ammonia generated when the ammonia in enrichment facility 60 is concentrated
The low draining of concentration mixes with the treatment water released from electrolytic processing apparatus 37.That is, set in the enrichment facility 60 of present embodiment
It is equipped with the drainpipe 61 of the low draining of discharge ammonia density.This is released from the draining of the discharge of drainpipe 61 with from electrolytic processing apparatus 37
Treatment water mixing.
According to above-mentioned implementation method, processed with from electrolysis by the low draining of the ammonia density for making to be generated in enrichment facility 60
The treatment water mixing that device 37 is released, thus, it is possible to the ammonia density of the treatment water released is remained below normal concentration.
(the 5th implementation method)
The 5th implementation method of the invention is described in detail referring to the drawings.
Fig. 6 is the detailed system figure of the ammonia treatment system involved by present embodiment.It should be noted that present embodiment
In, by with the difference of the 3rd above-mentioned implementation method centered on recorded, eliminate its explanation for identical part.
As shown in fig. 6, in the ammonia treatment system 1E of present embodiment, making the treatment water of electrolytic processing apparatus 37 in dump tank
Circulated between 36 and enrichment facility 60.That is, in the ammonia treatment system 1E of present embodiment, will be electrolysed, the treatment water after ammonia treatment
Returned to before enrichment facility 60 via treatment water circulation pipe arrangement 62, sodium chloride is recycled.
According to above-mentioned implementation method, the recycling of chloride ion can be realized, it is not necessary to from outside supply.
(the 6th implementation method)
The 6th implementation method of the invention is described in detail referring to the drawings.
Fig. 7 is the detailed system figure of the ammonia treatment system involved by present embodiment.It should be noted that present embodiment
In, by with the difference of above-mentioned second embodiment centered on recorded, eliminate its explanation for identical part.
As shown in fig. 7, in the ammonia treatment system 1F of present embodiment, concentration salinity is provided with the downstream of mixing channel 55
Desalter 63, be desalted device 63 concentrate after condensed water a part as chloride ion source be supplied to electrolysis process
Device 37B.Desalter 63 recycles pipe arrangement 64 to be connected with electrolytic processing apparatus 37B by condensed water.
In addition, discharged from the treatment water of the discharge of desalter 63 or as water is released, or as boiler feedwater, industry
Recycled with water, miscellaneous water.
As desalter 63, can using used it is inverse be impregnated with film, electrodialysis, capacitor desalination, ion exchange resin,
The device of water softener etc..
According to above-mentioned implementation method, by being set as being fed into the chloride ion of electrolytic processing apparatus 37B from desalination
The composition that device 63 is supplied after reclaiming, can reduce the supply cost of chloride ion.
(the 7th implementation method)
The 7th implementation method of the invention is described in detail referring to the drawings.
Fig. 8 is the detailed system figure of the ammonia treatment system involved by present embodiment.It should be noted that present embodiment
In, by with the difference of the 6th above-mentioned implementation method centered on recorded, eliminate its explanation for identical part.
As shown in figure 8, in the ammonia treatment system 1G of present embodiment, the upstream side of the mixing channel 55 on line 35 is blowed sets
It is equipped with the SS separators 65 for the SS (suspended solid) for processing water separate.That is, the ammonia treatment system 1G of present embodiment
It is to be supplied to after SS separation the composition of mixing channel 55 via blowing line 35 and import the treatment water containing ammonia.
As SS separators 65, can use and use filter screen, secondary filter film (MF) module, milipore filter (UF) mould
The device of block, sand filtering, sedimentation basin, cyclone hydraulic separators etc..
According to above-mentioned implementation method, separated by SS, SS compositions can be reduced to electrolytic processing apparatus 37B, desalter
63 inflow, can reduce electrolytic processing apparatus 37B, the risk of the damage of desalter 63.
(the 8th implementation method)
The 8th implementation method of the invention is described in detail referring to the drawings.
Fig. 9 is the detailed system figure of the ammonia treatment system involved by present embodiment.It should be noted that present embodiment
In, by with the difference of the 6th above-mentioned implementation method centered on recorded, eliminate its explanation for identical part.
As shown in figure 9, in the ammonia treatment system 1H of present embodiment, the upstream side of the mixing channel 55 on line 35 is blowed sets
It is equipped with the cooler 66 of cooling treatment water.
According to above-mentioned implementation method, the treatment of (such as 50 DEG C) high temperature (such as 80 DEG C) is cooled down by using cooler 66
Water, can reduce electrolytic processing apparatus 37B, the damage risk of desalter 63.
(the 9th implementation method)
The 9th implementation method of the invention is described in detail referring to the drawings.
Figure 10 is the detailed system figure of the ammonia treatment system involved by present embodiment.It should be noted that this embodiment party
In formula, by with the difference of the 6th above-mentioned implementation method centered on recorded, eliminate its explanation for identical part.
As shown in Figure 10, in the ammonia treatment system 1J of present embodiment, set between mixing channel 55 and desalter 63
There is removing residual chlorine (Cl2、ClO-) Cl removing devices 67.
As Cl removing devices 67, can be using the device that make use of activated carbon, air aeration, reducing agent supply etc..Make
It is reducing agent, sodium thiosulfate (Na can be used2S2O3), sodium hydrogensulfite (NaHSO3), sodium sulfite (Na2SO3) etc..
According to above-mentioned implementation method, by using Cl removing devices 67, residual chlorine is reduced and is decomposed into chloride ion,
Thus can prevent to be flowed into the residual chlorine of the treatment water of desalter 63, therefore, it is possible to prevent the damage of desalter 63.
(the tenth implementation method)
The tenth implementation method of the invention is described in detail referring to the drawings.
Figure 11 is the detailed system figure of the ammonia treatment system involved by present embodiment.It should be noted that this embodiment party
In formula, by with the difference of the 9th above-mentioned implementation method centered on recorded, eliminate its explanation for identical part.
As shown in figure 11, in the ammonia treatment system 1K of present embodiment, in the ammonia treatment system 1J of the 9th implementation method
The downstream (upstream side of desalter 63) of Cl removing devices 67 is provided with residual chlorine measurement device 68, according to by the residual chlorine
The concentration of residual chlorine of the measure of device 68 is determined to control Cl removing devices 67.
In addition, being provided with from Cl removing devices 67 in the downstream (upstream side of desalter 63) of Cl removing devices 67
The treatment water branch of discharge recycles the bypass pipe arrangement 69 of pipe arrangement 64 to the condensed water in the downstream of desalter 63.Removed from Cl
The treatment water of the discharge of device 67 is based on any that the instruction of control device 41 is directed in desalter 63 and bypass pipe arrangement 69
It is individual.Its switching is carried out by valve (not shown).
Specific control method to the ammonia treatment system 1J of present embodiment is illustrated.Control device 41 passes through residual chlorine
68 pairs, device is determined to be monitored from the concentration of residual chlorine of the treatment water of the discharge of mixing channel 55, and operate Cl removing devices 67 up to
Can't detect concentration of residual chlorine.Specifically, control reducing agent, the addition of activated carbon, air aeration amount.
When detecting concentration of residual chlorine, the stream for leading to desalter 63 is stopped with valve, treatment water is imported into bypass stream
69, it is branched off into condensed water and is recycled pipe arrangement 64.
According to above-mentioned implementation method, it is possible to increase using the removal rate of the residual chlorine of Cl removing devices 67.
It should be noted that technical scope of the invention is not limited to above-mentioned implementation method, master of the invention is not being departed from
Various changes can be carried out in the range of purport.For example, each implementation method described above be ammonia density by being arranged at feedwater line 11
The composition that is measured of ammonia concentration determination device, but it is also possible to be the composition that the ammonia density for blowing water is determined in line 35 is blowed.
In addition, as the method for the concentration for determining ammonia, however it is not limited to the measure based on ammonia concentration determination device, or
The composition that the water for blowing water of injection rate and water supply system from the ammonia from ammonia injection unit is speculated.
Industrial applicability
By above-mentioned ammonia treatment system, the water supply system of boiler plant can be based on or blown the ammonia density of water and blown the water of water
To control electrolysis.Therefore, even if in the case where the variation of discharging of boiler is big, it is also possible to meet the draining benchmark of ammonia density.
Label declaration
1 ammonia treatment system
2 combined cycle power stations
3 heat recovery boilers (boiler plant)
11 feedwater lines (water supply system)
34 ammonia injection units
35 blow line
36 dump tanks
37 electrolytic processing apparatus
38 circulation adjustment tanks
39 electrolytic cells
41 control devices
42nd, 42B seawater lead-in wire (chloride ion feed unit)
44 chloride ion concentrations determine device (chloride ion concentration determination unit)
45 continuous-current plants
46 sea water pumps
47 ammonia concentration determination devices (ammonia concentration determination unit)
48 ammonia concentration determination devices (ammonia concentration determination unit)
49 ammonia concentration determination devices (ammonia concentration determination unit)
52 residuals chlorine measurement device (residual chlorine determination unit)
53 flow rate-measuring devices (flow measurement unit)
55 mixing channels
60 enrichment facilities
63 desalters
64 condensed waters recycle pipe arrangement
Claims (6)
1. a kind of ammonia treatment system, it possesses：
Boiler plant, for carrying out recuperation of heat,
Ammonia injection unit, ammonia is injected to the water supply system in the boiler plant,
Ammonia concentration determination unit, is measured to the ammonia density for blowing water from the water supply system or the boiler plant,
Flow measurement unit, determine described in blow the water of water,
Dump tank, receive described in blow water,
Chloride ion feed unit, imports as the sodium-chloride water solution in chloride ion source to the dump tank,
Pump, is arranged at the chloride ion feed unit and controls the import volume of the sodium-chloride water solution,
Circulation adjustment tank, is imported with and blows the treatment that water and the sodium-chloride water solution are constituted by from described in dump tank outflow
Water,
Electrolytic cell, is imported with the treatment water from the circulation adjustment tank, and is electrolysed the treatment water,
Circulating pump, the electrolysis treatment fluid for making to be treated in the electrolytic cell is recycled to the circulation adjustment tank, and
Control device, electric current and process time during the control electrolysis,
It is provided with the circulation adjustment tank：The pH for determining the pH of the treatment water determines device, determines the temperature of the treatment water
The chloride ion concentration of the temperature measuring apparatus of degree and the chloride ion concentration for determining the treatment water determines device,
The control device is based on the ammonia density and the flow measurement unit that the ammonia concentration determination unit is measured to
The water of water is blown described in being measured to control the magnitude of current during electrolysis, and so that the chloride ion concentration
The chloride ion concentration for determining the treatment water that device is measured to reaches more than normal concentration and the pH for processing water
The pump is controlled for 7~9 mode.
2. ammonia treatment system as claimed in claim 1, the electrolytic cell has residual chlorine determination unit, the residual chlorine measurement
Unit determines the concentration of residual chlorine of the treatment water in electrolysis,
The control device determines the terminal of electrolysis according to the concentration of residual chlorine.
3. ammonia treatment system as claimed in claim 1 or 2, it is provided with to place between the dump tank and the electrolytic cell
The enrichment facility that the ammonia contained at least a portion for managing water is concentrated.
4. a kind of ammonia treatment system, it possesses：
Boiler plant, for carrying out recuperation of heat,
Ammonia injection unit, ammonia is injected to the water supply system in the boiler plant,
Ammonia concentration determination unit, is measured to the ammonia density for blowing water from the water supply system or the boiler plant,
Flow measurement unit, determine described in blow the water of water,
Chloride ion feed unit, imports as the sodium-chloride water solution in chloride ion source,
Pump, is arranged at the chloride ion feed unit and controls the import volume of the sodium-chloride water solution,
Circulation adjustment tank, is imported with the sodium-chloride water solution,
Electrolytic cell, is imported with the sodium-chloride water solution from the circulation adjustment tank, and the sodium-chloride water solution is electric
Solution,
Circulating pump, for the electrolysis treatment fluid treated in the electrolytic cell to be recycled into the circulation adjustment tank,
Mixing channel, receive it is described blow water and receive from the treatment water for circulating adjustment tank, and
Control device, electric current and process time during the control electrolysis,
It is provided with the circulation adjustment tank：The pH for determining the pH of the treatment water determines device, determines the temperature of the treatment water
The chloride ion concentration of the temperature measuring apparatus of degree and the chloride ion concentration for determining the treatment water determines device,
The ammonia density and the flow measurement unit that the control device is measured to based on the ammonia concentration determination unit are surveyed
It is fixed to the water for blowing water control the magnitude of current during electrolysis, and so that the chloride ion concentration is determined
The chloride ion concentration of the treatment water that device is measured to reach more than normal concentration and the treatment water pH for 7~
9 mode controls the pump.
5. ammonia treatment system as claimed in claim 4, the electrolytic cell has residual chlorine determination unit, the residual chlorine measurement
Unit determines the concentration of residual chlorine of the treatment water in electrolysis,
The control device determines the terminal of electrolysis according to the concentration of residual chlorine.
6. the ammonia treatment system as described in claim 4 or 5, it possesses：
Desalter, is arranged on the downstream of the mixing channel, and
Condensed water recycles a part for pipe arrangement, the condensed water that will be concentrated by the use of the desalter to be supplied as chloride ion source
It is given to the circulation adjustment tank.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-119933 | 2012-05-25 | ||
| JP2012119933 | 2012-05-25 | ||
| JP2013-010251 | 2013-01-23 | ||
| JP2013010251A JP6191070B2 (en) | 2012-05-25 | 2013-01-23 | Ammonia treatment system |
| PCT/JP2013/063663 WO2013176032A1 (en) | 2012-05-25 | 2013-05-16 | Ammonia treatment system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104379512A CN104379512A (en) | 2015-02-25 |
| CN104379512B true CN104379512B (en) | 2017-06-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380025991.2A Active CN104379512B (en) | 2012-05-25 | 2013-05-16 | ammonia treatment system |
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| Country | Link |
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| JP (1) | JP6191070B2 (en) |
| KR (1) | KR101757525B1 (en) |
| CN (1) | CN104379512B (en) |
| SG (1) | SG11201407526RA (en) |
| WO (1) | WO2013176032A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5700735B1 (en) * | 2014-08-28 | 2015-04-15 | 株式会社日立パワーソリューションズ | Water treatment apparatus and control method for water treatment apparatus |
| BR112017007253A2 (en) | 2014-10-10 | 2017-12-19 | Xogen Tech Inc | system and method for ammonia oxidation |
| JP6388124B2 (en) * | 2014-11-10 | 2018-09-12 | 三菱重工環境・化学エンジニアリング株式会社 | Electrolysis system |
| JP6331145B2 (en) * | 2014-11-26 | 2018-05-30 | 三菱重工環境・化学エンジニアリング株式会社 | Ammonia treatment system |
| JP2018508732A (en) * | 2015-01-23 | 2018-03-29 | シーメンス アクティエンゲゼルシャフト | Preheating untreated water in power plant equipment |
| WO2016167271A1 (en) * | 2015-04-17 | 2016-10-20 | 三菱重工環境・化学エンジニアリング株式会社 | Hypochlorous acid supply device and boiler waste-water treatment method |
| JP6383989B2 (en) | 2015-04-17 | 2018-09-05 | 三菱重工環境・化学エンジニアリング株式会社 | Hypochlorous acid supply device |
| JP7104591B2 (en) | 2018-09-07 | 2022-07-21 | 三菱重工業株式会社 | Hydrogen production system |
| KR101997846B1 (en) | 2018-10-08 | 2019-07-08 | 웅진코웨이엔텍 주식회사 | Ammonia removal system and method using membrane contactor |
| CN110078178A (en) * | 2019-05-10 | 2019-08-02 | 浙江浙能嘉华发电有限公司 | A kind of strong ammonia wastewater cyclic electrolysis treatment process and equipment |
| CN110204017B (en) * | 2019-05-16 | 2023-08-22 | 浙江浙能技术研究院有限公司 | Electrolytic treatment system and method for adjusting pH value of ammonia-containing wastewater |
| KR102155238B1 (en) | 2019-09-25 | 2020-09-11 | 코웨이엔텍 주식회사 | Ammonia removal system and method using membrane contactor for sewage reuse |
| KR102108512B1 (en) | 2019-09-25 | 2020-05-08 | 코웨이엔텍 주식회사 | Ammonia removal system and method using membrane contactor |
| WO2022051600A1 (en) | 2020-09-04 | 2022-03-10 | Buckman Laboratories International, Inc. | Predictive systems and methods for proactive intervention in chemical processes |
| CN113003786B (en) * | 2021-03-26 | 2022-04-01 | 马鞍山钢铁股份有限公司 | Combined treatment process for industrial gas dust removal water of CCPP unit |
| JP6940713B1 (en) * | 2021-05-18 | 2021-09-29 | 三菱重工環境・化学エンジニアリング株式会社 | Hydrogen production system |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20150013551A (en) | 2015-02-05 |
| CN104379512A (en) | 2015-02-25 |
| JP2014000563A (en) | 2014-01-09 |
| WO2013176032A1 (en) | 2013-11-28 |
| JP6191070B2 (en) | 2017-09-06 |
| KR101757525B1 (en) | 2017-07-12 |
| SG11201407526RA (en) | 2015-03-30 |
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