CN107108280B - Electrolysis system - Google Patents

Electrolysis system Download PDF

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Publication number
CN107108280B
CN107108280B CN201580060429.2A CN201580060429A CN107108280B CN 107108280 B CN107108280 B CN 107108280B CN 201580060429 A CN201580060429 A CN 201580060429A CN 107108280 B CN107108280 B CN 107108280B
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seawater
line
water
nitrogen
electrolysis
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CN107108280A (en
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高波宏幸
三田村章弘
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Mitsubishi Heavy Industries Environmental and Chemical Engineering Co Ltd
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Mitsubishi Heavy Industries Environmental and Chemical Engineering Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/50Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/58Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/586Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing ammoniacal nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/70Treatment of water, waste water, or sewage by reduction

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The present invention provides an electrolysis system, comprising: a seawater line through which seawater introduced into the facility flows; a nitrogen treatment tank into which nitrogen-containing wastewater discharged from the facility is introduced; an electrolysis device for electrically decomposing seawater or brine to generate electrolyzed water having hypochlorous acid; an injection line that injects electrolysis-treated water into a seawater line; and a branch line branching from the injection line to inject the electrolyzed processing water into the nitrogen processing tank.

Description

Electrolysis system
Technical Field
The present invention relates to an electrolysis system having an electrolysis apparatus for electrically decomposing seawater or brine to generate electrolyzed water containing hypochlorous acid.
The present application claims priority based on japanese patent application No. 2014-228012, filed on 10/11/2014, and the contents thereof are incorporated herein by reference.
Background
In thermal power plants, nuclear power plants, and the like that use a large amount of seawater, the adhesion and propagation of algae and shellfish to parts of the plants that come into contact with seawater, such as intake ports, piping, condensers, and various coolers, has been a problem.
In order to solve this problem, a device for preventing marine organism adhesion has been proposed in which natural seawater is electrolyzed to generate sodium hypochlorite (chlorine or sodium hypochlorite), and electrolyzed water containing sodium hypochlorite is injected into a water intake port to suppress the adhesion of marine organisms (see, for example, patent document 1).
In order to remove oxygen, which is an important factor for corrosion of a water supply system in the above-described facility, a deoxidation method is known in which ammonia having an increased pH (hydrogen ion index) (for example, pH7 to pH10.5) is injected. However, if ammonia is used as the deoxidizer, the ammonia concentration of the wastewater discharged from the facility will increase in the future. On the other hand, nitrogen reduction is also sought by drainage restriction, and it is desired to respond to this as quickly as possible.
Patent document 2 describes an ammoniacal nitrogen removal apparatus for decomposing ammonia by chlorine treatment using a sodium hypochlorite salt obtained by electrolyzing seawater.
Prior art documents
Patent document
Patent document 1: japanese laid-open patent publication No. 10-85750
Patent document 2: japanese patent laid-open No. 2014-563
Disclosure of Invention
Problems to be solved by the invention
However, in facilities such as thermal power plants that extract a large amount of seawater and discharge wastewater containing ammonia nitrogen such as boiler wastewater, it is necessary to separately provide a marine organism adhesion preventing device and an ammonia nitrogen removing device.
That is, the marine organism adhesion preventing device has a method of controlling the flow rate of electrolytic water to be injected and the concentration of hypochlorous acid contained in the electrolytic water, in addition to the control of making the flow rate of electrolytic water to be injected constant and changing the concentration of hypochlorous acid contained in the electrolytic water. On the other hand, in the ammoniacal nitrogen removal apparatus, the operation control is performed by changing the injection amount of the electrolyzed water while keeping the concentration of hypochlorous acid constant.
Therefore, it is difficult to perform both the treatment for preventing the adhesion of marine organisms and the treatment for removing ammonia nitrogen by simply using one seawater electrolysis apparatus.
The purpose of the present invention is to provide an electrolysis system that can suppress the adhesion of marine organisms at a water intake and remove nitrogen components contained in nitrogen-containing wastewater discharged from an apparatus using one electrolysis device.
Means for solving the problems
According to a first aspect of the present invention, an electrolysis system is characterized by comprising: a seawater line through which seawater introduced into the facility flows; a nitrogen treatment tank into which nitrogen-containing wastewater discharged from the facility is introduced; an electrolysis device for electrically decomposing seawater or brine to generate electrolyzed water having hypochlorous acid; an injection line that injects the electrolytically-treated water into the seawater line; and a branch line branching from the injection line to inject the electrolytic treatment water into the nitrogen treatment tank.
According to the above configuration, adhesion of marine organisms on the sea water pipeline can be suppressed and nitrogen components contained in the nitrogen-containing wastewater discharged from the facility can be removed by using one electrolysis apparatus.
In the above electrolysis system, the following configuration may be adopted: the electrolytic treatment apparatus includes a control device for adjusting the flow rate of the electrolytic treatment water introduced from the branch line based on the hypochlorous acid amount of the electrolytic treatment water generated by the electrolysis device.
According to the above configuration, the amount of hypochlorous acid supplied to the nitrogen treatment tank and the amount of hypochlorous acid injected into the seawater line can be kept constant.
In the above electrolysis system, the system may further include a circulation flow path through which the seawater circulates, the electrolysis device may be configured to decompose the seawater in the middle of the circulation flow path, and the control device may be configured to retain the nitrogen-containing wastewater in the nitrogen treatment tank until the hypochlorous acid amount of the electrolyzed processing water flowing out of the circulation flow path reaches a predetermined amount.
According to the above configuration, the nitrogen-containing wastewater that has been insufficiently treated with nitrogen can be prevented from being discharged to the outside of the system.
Effects of the invention
According to the present invention, it is possible to remove nitrogen components contained in nitrogen-containing wastewater discharged from an apparatus while suppressing the adhesion of marine organisms at a water intake by using one electrolysis device.
Drawings
FIG. 1 is a schematic configuration diagram of an electrolysis system according to a first embodiment of the present invention.
FIG. 2 is a schematic configuration diagram of an electrolysis system according to a second embodiment of the present invention.
Fig. 3 is a schematic configuration diagram of an electrolysis system according to a modification of the second embodiment of the present invention.
Detailed Description
(first embodiment)
An electrolytic system 1 according to a first embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic configuration diagram of an electrolysis system 1 according to a first embodiment of the present invention. As shown in fig. 1, the electrolysis system 1 is a system mainly including a combined cycle power plant P including a heat recovery boiler B, a seawater electrolysis device 2, and a control device (not shown).
The combined cycle power plant P (hereinafter, referred to as plant P) has: a gas turbine (not shown); an exhaust heat recovery boiler B (hereinafter referred to as boiler B) to which exhaust gas from the gas turbine is supplied; a steam turbine (not shown); and a generator (not shown) that is driven by the rotational driving force of the gas turbine and the steam turbine to generate electric power.
Seawater M taken out from a water intake 4 of a seawater line 3 is introduced into the plant P. The seawater M is discharged after being used for purposes such as cooling. For example, boiler water of the boiler B contains ammonia as a deoxidizer for removing oxygen which is an important factor of corrosion. Therefore, the boiler waste water W discharged from the boiler B contains ammonia (NH)3) Ammonium ion (NH)4 +) And ammonia nitrogen-containing wastewater containing ammonia nitrogen. The boiler drain water W is stored in the drain tank 6 and then introduced into the nitrogen treatment tank 7. The boiler drain water W is nitrogen-removed in the nitrogen treatment tank 7 and then discharged via the waste water line 22.
The electrolysis system 1 includes a seawater supply pump 8 and a seawater electrolysis device 2 for electrically decomposing seawater M introduced by the seawater supply pump 8. The seawater supply pump 8 may be a structure for drawing seawater M directly from the ocean or a structure for drawing seawater M from the seawater line 3.
The seawater supply pump 8 and the seawater electrolysis apparatus 2 are connected by a seawater supply line 12. The seawater supply line 12 is provided with a first flow rate sensor 13 for measuring the flow rate of seawater M and a first flow rate adjustment valve 14 for adjusting the flow rate of seawater M. The seawater supply line 12 may be provided with a filter for preventing the entry of foreign matter that prevents electrolysis.
The seawater electrolysis apparatus 2 has an electrolysis bath 9 and a DC power supply 10. The seawater electrolysis apparatus 2 is an apparatus for generating electrolyzed water E containing sodium hypochlorite (chlorine, sodium hypochlorite) by electrolyzing seawater M. The electrolytic cell 9 has a plurality of electrodes (not shown).
The dc power supply device 10 is a device for supplying a current for the electrolysis of the seawater M, and may be configured to include a dc power supply and a constant current control circuit, for example. The dc power supply is a power supply that outputs dc power, and may be configured to rectify ac power output from an ac power supply into dc power and output the dc power.
The seawater electrolytic apparatus 2 of the present embodiment is a one-through (one-through) system in which seawater M is passed through the electrolytic bath 9 only once.
The electrolyzed processing water E generated in the seawater electrolysis apparatus 2 is injected into the intake port 4 of the seawater line 3 through the injection line 15. The electrolyzed processing water E (sodium hypochlorite) is injected into the intake port 4, whereby adhesion of marine organisms to the intake port 4 can be suppressed. That is, the seawater electrolytic device 2 of the present embodiment functions as a marine organism adhesion preventing device.
The injection line 15 is provided with a hypochlorous acid concentration sensor 19 for measuring the hypochlorous acid concentration of the electrolyzed processing water E flowing through the injection line 15.
A branch line 16 for introducing the electrolyzed processing water E into the nitrogen treatment tank 7 is branched from an injection line 15 connecting the seawater electrolysis apparatus 2 and the intake 4. That is, the electrolyzed processing water E generated in the seawater electrolysis apparatus 2 is introduced into the nitrogen treatment tank 7 through the branch line 16 branched from the injection line 15, and is mixed with the boiler drain water W.
The branch line 16 is provided with a second flow rate sensor 17 for measuring the flow rate of the electrolyzed processing water E and a second flow rate adjustment valve 18 for adjusting the flow rate of the electrolyzed processing water E.
The nitrogen treatment tank 7 is provided with a pH measuring device 20 for measuring the pH (hydrogen ion index) of the treated water comprising the boiler drain water W and the electrolyzed treated water E in the nitrogen treatment tank 7, and a pH adjusting device 21 for adjusting the pH of the treated water in the nitrogen treatment tank 7.
Boiler wastewater W and electrolyzed water E are introduced into the nitrogen treatment tank 7, and ammonia and hypochlorous acid present in the boiler wastewater W are decomposed into nitrogen gas (N) by solution reaction2). That is, the seawater electrolytic device 2 of the present embodiment functions as an ammonia nitrogen removal device.
A method of controlling the electrolysis system 1 of the present embodiment will be described.
The control device controls the dc power supply device 10 of the seawater electrolysis device 2 based on the amount of hypochlorous acid required at the intake port 4 (hereinafter referred to as a first hypochlorous acid amount). The control device calculates the first hypochlorous acid amount using the flow rate of the seawater M measured by the first flow rate sensor 13 and the hypochlorous acid concentration measured by the hypochlorous acid concentration sensor 19. The control device adjusts the hypochlorous acid concentration of the generated electrolyzed processing water E by controlling the DC power supply device 10 based on the calculated first hypochlorous acid amount.
Here, the hypochlorous acid amount required at the intake port 4 is a necessary minimum amount such that hypochlorous acid is almost consumed at the intake port 4 and is hardly discharged. The amount of the first hypochlorous acid was calculated at predetermined time intervals by a predetermined method. The amount of the first chloric acid is not constant but varies.
The control device adjusts the hypochlorous acid concentration of the electrolyzed processing water E according to the first hypochlorous acid amount.
On the other hand, the controller calculates the amount of hypochlorous acid per unit time (hereinafter, referred to as a second hypochlorous acid amount) required in the nitrogen treatment tank 7. The amount of the second chloric acid is approximately constant.
The control device adjusts the flow rate (hereinafter referred to as the second flow rate) of the electrolyzed processing water E2 introduced into the nitrogen treatment tank 7 through the branch line 16 based on the calculated second chloric acid amount and the hypochlorous acid concentration measured by the hypochlorous acid concentration sensor 19. The second flow rate can be calculated from the second hypochlorous acid amount and the hypochlorous acid amount concentration.
Specifically, the controller measures the flow rate of the branch line 16 by the second flow rate sensor 17 and adjusts the control of the second flow rate adjustment valve 18 so that the measured flow rate becomes the second flow rate.
The control device performs control for adjusting the flow rate of the seawater M introduced through the seawater supply line 12 in order to compensate for the flow rate of the electrolyzed processing water E1 flowing through the injection line 15 (hereinafter, referred to as a first flow rate) that decreases due to the second flow rate. That is, when the flow rate of the seawater M is FM, the flow rate of the electrolyzed water E flowing through the injection line 15 is F1, and the flow rate of the electrolyzed water E flowing through the branch line 16 is F2, the flow rate of the introduced seawater M is increased so that FM becomes F1+ F2.
Specifically, the controller measures the flow rate of the seawater supply line 12 by the first flow rate sensor 13 and adjusts the control of the first flow rate adjustment valve 14 so that the measured flow rate becomes the calculated flow rate of the seawater M.
In the nitrogen treatment tank 7, a pH adjusting agent is added and adjusted by a pH adjusting device 21 so that the pH of the treatment water in the nitrogen treatment tank 7 becomes a predetermined pH, based on the pH measured by the pH measuring device 20.
According to the above embodiment, the use of one seawater electrolysis apparatus 2 can remove nitrogen components contained in the nitrogen-containing wastewater discharged from the facility P while suppressing the adhesion of marine organisms at the intake 4.
Further, by adjusting the flow rate of the electrolyzed processing water E2 introduced from the branch line 16 based on the hypochlorous acid amount of the electrolyzed processing water E generated by the seawater electrolysis apparatus 2, the hypochlorous acid amount supplied to the nitrogen treatment tank 7 and the hypochlorous acid amount injected into the seawater line 3 can be kept constant.
(second embodiment)
An electrolytic system 1B according to a second embodiment of the present invention will be described with reference to the drawings. In the present embodiment, differences from the first embodiment described above will be mainly described, and descriptions of the same parts will be omitted.
The seawater electrolysis device 2 of the electrolysis system 1B of the present embodiment includes a circulation flow path 24 for circulating the electrolyzed water E (seawater M). The seawater electrolysis device 2 is disposed to electrolyze the seawater M in the middle of the circulation flow path 24. That is, the seawater electrolytic apparatus 2 of the present embodiment adopts the following reuse method: the hypochlorous acid concentration of the electrolyzed water E is gradually increased by circulating the seawater M through the circulation flow path 24.
A return line 27 for returning the wastewater flowing through the wastewater line 22 to the drain tank 6 is branched from the wastewater line 22 of the electrolysis system 1B of the present embodiment.
A method of controlling the electrolysis system 1B of the present embodiment will be described.
When the seawater M is introduced into the circulation flow path 24, the seawater M is gradually electrolyzed while circulating in the circulation flow path 24 until the electrolyzed water E having a predetermined hypochlorous acid concentration is obtained. That is, when the seawater electrolytic apparatus 2 is set up, a predetermined time is required until the hypochlorous acid concentration becomes a concentration determined based on the first hypochlorous acid amount after the setting of the electrolytic system 1B is changed.
The control device controls the return of the wastewater discharged from the nitrogen treatment tank 7 to the drain tank 6 through the return line 27 until the hypochlorous acid amount in the electrolyzed processing water E flowing out of the circulation flow path 24 reaches a predetermined amount by operating the valves 28 provided in the wastewater line 22 and the return line. That is, the wastewater insufficiently treated with nitrogen is controlled to be retained in the nitrogen treatment tank 7.
When the hypochlorous acid amount in the electrolyzed processing water E reaches a predetermined amount, the same control as that of the electrolysis system 1 of the first embodiment is performed.
The method of retaining the wastewater in the nitrogen treatment tank 7 is not limited to this. For example, the nitrogen treatment tank 7 may be made sufficiently large without providing the return line 27. In this configuration, the valve 29 on the wastewater line 22 is closed, so that wastewater can be retained in the nitrogen treatment tank 7.
According to the above embodiment, when the seawater electrolytic apparatus 2 is set up and when the setting of the electrolytic system 1B is changed, the wastewater is retained in the nitrogen treatment tank 7, whereby the nitrogen-containing wastewater that has been insufficiently treated by nitrogen can be prevented from being discharged to the outside of the system.
In other words, according to the above embodiment, not only in the seawater electrolytic device 2 of the one-pass type in which the seawater M is passed through the electrolytic bath 9 only once as shown in the first embodiment, but also in the reuse type in which the scale prevention effect in the electrolytic bath 9 is excellent, both the treatment for preventing the adhesion of marine organisms and the removal of ammonia nitrogen can be performed.
(modification of the second embodiment)
An electrolytic system 1C according to a modification of the second embodiment will be described.
As shown in fig. 3, the injection line 15 of the present modification is provided with a third flow sensor 25 for measuring the flow rate of the electrolyzed processing water E flowing through the injection line 15, and a third flow rate adjustment valve 26 for adjusting the flow rate of the electrolyzed processing water E1. That is, the electrolysis system 1 of the present modification is a system capable of adjusting the flow rate of the electrolyzed processed water E1 while adjusting the concentration of the electrolyzed processed water E1 of the electrolyzed processed water E1 flowing through the injection line 15.
The control device of the present modification performs control of returning the wastewater discharged from the nitrogen treatment tank 7 to the drain tank 6 via the return line 27 until the hypochlorous acid amount of the electrolyzed processing water E flowing out of the circulation flow path 24 reaches a predetermined amount by operating the valves 28 and 29 provided in the wastewater line 22 and the return line 27, as in the control device of the second embodiment.
According to the above modification, even when the flow rate of the injection line 15 or the concentration of the electrolyzed processing water E is changed, both the prevention of the adhesion of marine organisms and the removal of ammonia nitrogen can be performed.
Although the embodiments of the present invention have been described in detail with reference to the drawings, the configurations and combinations thereof in the embodiments are merely examples, and additions, deletions, substitutions, and other modifications of the configurations may be made without departing from the scope of the present invention. The present invention is not limited by the embodiments, but is limited only by the scope of the claims.
For example, in the above embodiments, the seawater M is introduced into the seawater electrolysis apparatus 2, but the seawater M may be introduced into the seawater electrolysis apparatusThe brine is introduced into the seawater electrolysis apparatus 2. That is, the liquid introduced into the seawater electrolysis apparatus 2 contains chloride ions (Cl) as in the case of the seawater M-) And (4) finishing.
Description of reference numerals:
1. 1B, 1C: an electrolysis system; 2: a seawater electrolysis apparatus (electrolysis apparatus); 3: a seawater pipeline; 4: a water intake; 6: a drain tank; 7: a nitrogen treatment tank; 8: a seawater supply pump; 9: an electrolytic cell; 10: a direct current power supply device; 12: a seawater supply line; 13: a first flow sensor; 14: a first flow rate adjustment valve; 15: an injection line; 16: a branch line; 17: a second flow sensor; 18: second flow rate adjustment valve: 19: a hypochlorous acid concentration sensor; 20: pH measurement device: 21: a pH adjusting device; 22: a waste water line; 24: a circulation flow path; 25: a third flow sensor; 26: a third flow rate adjustment valve; 27: a return line; b: a boiler; E. e1, E2: electrolyzing the treated water; m: seawater; p: equipment; w: boiler drainage (nitrogen-containing drainage).

Claims (1)

1. An electrolysis system, wherein,
the electrolysis system has:
a seawater line that introduces seawater taken out of the ocean toward the facility;
a nitrogen treatment tank into which nitrogen-containing wastewater discharged from the facility is introduced;
an electrolysis device that electrically decomposes seawater drawn from the seawater line or seawater drawn from the ocean to generate electrolyzed treated water having hypochlorous acid;
an injection line that injects the electrolytically-treated water into the seawater line;
a branch line branching from the injection line to inject the electrolytic treatment water into the nitrogen treatment tank;
a control device for adjusting the flow rate of the electrolyzed processing water introduced from the branch line into the nitrogen processing tank based on the hypochlorous acid amount of the electrolyzed processing water generated by the electrolysis device;
a circulation flow path that branches from the injection line at a position upstream of a branching point of the branch line, and that introduces and circulates the electrolyzed water discharged from the electrolysis device to a downstream side of the electrolysis device to an upstream side of the electrolysis device;
a waste water line that discharges waste water in the nitrogen treatment tank; and
a return line that returns the wastewater flowing in the wastewater line to a line between the plant and the nitrogen treatment tank,
the control device returns the wastewater through the return line to retain the nitrogen-containing wastewater until the hypochlorous acid amount of the electrolyzed processing water in the injection line reaches a predetermined amount.
CN201580060429.2A 2014-11-10 2015-11-06 Electrolysis system Active CN107108280B (en)

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PCT/JP2015/081322 WO2016076225A1 (en) 2014-11-10 2015-11-06 Electrolysis system

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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
CN111977862A (en) * 2020-08-13 2020-11-24 浙江浙能嘉华发电有限公司 Equipment and method for preparing industrial bactericide by utilizing tail-end wastewater of thermal power plant

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KR101967077B1 (en) 2019-04-08
SG11201703655RA (en) 2017-06-29
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TWI585240B (en) 2017-06-01
TW201623693A (en) 2016-07-01

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