WO2015122435A1 - 海水電解システム及び電解液注入方法 - Google Patents

海水電解システム及び電解液注入方法 Download PDF

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Publication number
WO2015122435A1
WO2015122435A1 PCT/JP2015/053767 JP2015053767W WO2015122435A1 WO 2015122435 A1 WO2015122435 A1 WO 2015122435A1 JP 2015053767 W JP2015053767 W JP 2015053767W WO 2015122435 A1 WO2015122435 A1 WO 2015122435A1
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Prior art keywords
seawater
line
flow rate
main
injection
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PCT/JP2015/053767
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English (en)
French (fr)
Japanese (ja)
Inventor
宏幸 高波
達也 松村
水谷　洋
Original Assignee
三菱重工環境・化学エンジニアリング株式会社
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Priority to CN201580006031.0A priority Critical patent/CN105939969B/zh
Priority to KR1020167020739A priority patent/KR101891906B1/ko
Publication of WO2015122435A1 publication Critical patent/WO2015122435A1/ja

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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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • 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
    • C02F2201/4611—Fluid flow
    • 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
    • C02F2201/46145—Fluid flow
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/046—Recirculation with an external loop

Definitions

  • the present invention relates to a seawater electrolysis system including a seawater electrolysis apparatus that generates sodium hypochlorite by electrolyzing seawater, and an electrolytic solution injection method.
  • a conventional seawater electrolysis system 101 includes a liquid receiving tank 6 that receives and reacts with seawater, a seawater electrolyzer 7 that electrolyzes seawater W to generate sodium hypochlorite, and seawater.
  • This is a recycling system having a recycling line 10 (circulation line) for circulating the electrolytically treated water E (electrolytic solution) generated in the electrolyzer 7.
  • the seawater electrolysis apparatus 7 has a configuration in which an anode and a cathode as electrodes are arranged in an electrolytic cell 8 forming a cylindrical body, and seawater W is circulated in the electrolytic cell 8. Since chloride ions and hydroxide ions exist in the seawater W, when current is passed between the anode and the cathode, chlorine is generated at the anode and sodium hydroxide is generated at the cathode. Then, by reacting chlorine and sodium hydroxide, sodium hypochlorite having an effect of suppressing adhesion of marine organisms is produced.
  • Main seawater M (intake seawater) that is seawater used in the plant P is introduced into the main seawater line 3 by a plurality of main seawater pumps 2.
  • Seawater W is supplied to the seawater electrolysis system 101 by the seawater supply pump 4.
  • the electrolytically treated water E containing sodium hypochlorite generated by the seawater electrolyzer 7 is introduced into the main seawater line 3 through the injection line 13.
  • the output of the DC power supply 9 of the seawater electrolysis device 7 with respect to the change amount.
  • the concentration of sodium hypochlorite in the infusion was adjusted by changing the current value. That is, as shown in line a of FIG. 4, the output current value C (A) of the DC power supply device 9 was adjusted at the point D when the number of main seawater pumps decreased.
  • the chlorine concentration LRTEC (mg / l) of the electrolytically treated water E in the recycle line 10 gradually decreases.
  • the flow rate CLSFR (m 3 / h) of the electrolyzed water E injected into the main seawater line 3 through the injection line 13 is constant as shown by the line c.
  • the chlorine concentration CCl of the electrolyzed water E that is the injection liquid becomes a set value corresponding to the output current value.
  • the chlorine concentration of the injected liquid cannot be instantaneously handled. There was a problem that the chlorine concentration in seawater at the injection point temporarily exceeded the set value.
  • the present invention aims to keep the chlorine concentration of the main seawater constant by adjusting the flow rate of the electrolyte containing chlorine introduced into the main seawater line in the recycle type seawater electrolysis system.
  • a seawater electrolysis system includes a recycle line through which seawater circulates, a seawater electrolyzer for electrolyzing seawater in the middle of the recycle line, and a part of the electrolyte from the recycle line.
  • An injection line that supplies the main seawater line through which the main seawater flows, and a flow rate adjusting valve that is provided in the injection line and adjusts the amount of electrolyte injected by the flow rate of the main seawater.
  • the flow rate of the electrolyte containing chlorine can be adjusted by providing the flow rate adjusting valve in the injection line.
  • the chlorine concentration of the main seawater can be kept constant.
  • the flow rate adjustment valve may be configured to reduce the electrolyte injection amount as the flow rate of the main seawater decreases.
  • Such a configuration can prevent chlorine from being excessively injected into the main seawater line when the flow rate of the main seawater decreases.
  • the seawater electrolysis system may include a branch line that branches a part of seawater of a seawater supply line that supplies seawater to the recycle line to the injection line. According to such a configuration, by introducing seawater into the injection line via the branch line, scale accumulation due to a decrease in the flow rate of the injection line can be prevented.
  • the seawater electrolysis system has a seawater branch flow rate adjustment valve that adjusts the flow rate of seawater flowing through the branch line, and the seawater branch flow rate adjustment valve increases the seawater branch flow rate as the flow rate of the main seawater decreases. Also good. According to such a configuration, it is possible to prevent scale accumulation due to a decrease in the flow rate of the injection line even when the amount of electrolyte injection decreases as the flow rate of the main seawater decreases.
  • the seawater branch flow rate adjustment valve may be configured to increase the seawater branch flow rate so that the flow velocity of the fluid flowing through the injection line is equal to or higher than a predetermined value. According to such a configuration, since the flow velocity of the fluid flowing through the injection line is ensured, scale deposition due to a decrease in the flow rate of the injection line can be prevented.
  • the flow rate of the main seawater may be detected by the number of main seawater pumps that supply seawater to the main seawater line. According to such a configuration, the flow rate of the main seawater can be detected more easily.
  • the main seawater flow rate may be detected by driving power of a main seawater pump that supplies seawater to the main seawater line. According to such a configuration, the flow rate of the main seawater can be detected more accurately.
  • the residual chlorine content of the wastewater from the main seawater line may be monitored, and the electrolyte injection amount may be reduced when the residual chlorine content exceeds a predetermined value. According to such a configuration, residual chlorine contained in the waste water can be reduced.
  • an electrolytic solution injection method includes a seawater supply step of supplying seawater to an annular recycle line, and electrolyzing the seawater in the middle of the recycle line so that the electrolyte is supplied to the recycle line. Circulate in the electrolyte solution, circulate the electrolyte solution through the injection line, inject the electrolyte solution into the main seawater line through which the main seawater flows, and inject the electrolyte solution according to the flow rate of the main seawater And an injection amount adjusting step for adjusting the amount.
  • the injection amount adjusting step may be configured to reduce the electrolyte injection amount with a decrease in the flow rate of the main seawater.
  • the electrolyte solution injection method may include a seawater branching step of supplying a part of the seawater supplied in the seawater supply step to the injection line.
  • the seawater branching step may be configured to increase the seawater branching flow rate with a decrease in the flow rate of the main seawater.
  • the seawater branch flow rate in the seawater branching step, may be increased so that the flow velocity of the fluid flowing through the injection line is equal to or higher than a predetermined value.
  • the flow rate of the main seawater may be detected by the number of main seawater pumps that supply seawater to the main seawater line.
  • the flow rate of the main seawater may be detected by driving power of a main seawater pump that supplies seawater to the main seawater line.
  • the electrolyte injection method in the injection amount adjustment step, the residual chlorine content of the waste water from the main seawater line is monitored, and the electrolyte injection amount when the residual chlorine content exceeds a predetermined value. It is good also as a structure which decreases.
  • the flow rate of the electrolyte solution containing chlorine can be adjusted by adjusting the flow rate of the fluid flowing through the injection line.
  • the chlorine concentration of the main seawater can be kept constant.
  • FIG. 1 is a schematic diagram showing an outline of a seawater electrolysis system 1 according to an embodiment of the present invention.
  • the seawater electrolysis system 1 takes seawater W from a main seawater line 3 which is a water intake channel through which the main seawater M circulates, electrolyzes the seawater W by a seawater electrolyzer 7, and then electrolyzes water E (electrolyte).
  • This is a system for injecting into the main seawater line 3.
  • the main seawater M of the main seawater line 3 is used by being introduced into a plant P such as a thermal power and nuclear power plant, a seawater desalination plant, a chemical plant, and a steelmaking plant.
  • This seawater electrolysis system 1 is an annular recycling line that circulates a seawater supply pump 4 for introducing seawater W necessary for electrolysis, a liquid receiving tank 6, a seawater electrolyzer 7, and electrolytically treated water E (seawater W). 10 (circulation flow path) and an injection line 13 for injecting the electrolyzed water E circulating through the recycle line 10 into the main seawater line 3.
  • Main seawater M is introduced into the main seawater line 3 by a plurality of main seawater pumps 2 (intake pumps).
  • the flow rate of the main seawater M introduced into the main seawater line 3 varies according to the number of operating main seawater pumps 2.
  • the recycling line 10 includes a first recycling line 11 and a second recycling line 12.
  • the seawater supply pump 4 may be configured to pump the seawater W from the main seawater line 3 or may be configured to pump the seawater W directly from the ocean.
  • the liquid receiving tank 6 is a tank that stores the electrolytically treated water E circulating in the system and the seawater W supplied from the seawater supply pump 4.
  • the seawater electrolyzer 7 electrolyzes the seawater W in the middle of the recycle line 10.
  • the seawater electrolyzer 7 has an electrolytic cell 8 and a DC power supply device 9.
  • the seawater electrolyzer 7 generates sodium hypochlorite (chlorine, sodium hypochlorite) by electrolyzing the seawater W.
  • the electrolytic bath 8 includes a plurality of electrodes (not shown), an inlet 15 for introducing the electrolytically treated water E into the electrolytic bath 8, and an outlet 16 for discharging the electrolytically treated water E from the inside of the electrolytic bath 8. ,have.
  • the DC power supply device 9 supplies a current for electrolysis of the seawater W.
  • the DC power supply device 9 for example, a configuration including a DC power supply and a constant current control circuit can be adopted.
  • the DC power source is a power source that outputs DC power, and may be configured to rectify and output AC power output from the AC power source to DC, for example.
  • the seawater supply pump 4 and the liquid receiving tank 6 are connected by a seawater supply line 5.
  • the seawater supply line 5 may be provided with a strainer for preventing entry of foreign substances that hinder electrolysis.
  • the liquid receiving tank 6 and the inlet 15 of the electrolytic tank 8 are connected by a first recycle line 11. That is, the electrolytically treated water E in the liquid receiving tank 6 is introduced into the electrolytic tank 8 through the first recycle line 11.
  • An injection pump 17 is provided on the first recycle line 11. The injection pump 17 supplies the electrolytically treated water E that circulates to the electrolytic cell 8 and transfers the electrolytically treated water E to the injection line 13.
  • the second recycle line 12 connects the outlet 16 of the electrolytic cell 8 and the liquid receiving tank 6. That is, the electrolytically treated water E generated by the seawater electrolyzer 7 is introduced into the liquid receiving tank 6 through the second recycle line 12.
  • An injection nozzle (not shown) is provided at the downstream end of the injection line 13. By providing the injection nozzle, sodium hypochlorite generated by the seawater electrolyzer 7 can be efficiently diffused into the main seawater line 3.
  • the flow rate sensor 18 is a sensor that detects the flow rate of the electrolytically treated water E flowing through the injection line 13.
  • the flow rate adjusting valve 19 is a valve provided on the downstream side of the flow rate sensor 18 in the injection line 13. The flow rate of the electrolytically treated water E flowing through the injection line 13 can be controlled using the flow rate adjusting valve 19 and the flow rate sensor 18.
  • a branch line 21 (backup line) for introducing the seawater W supplied by the seawater supply pump 4 directly into the injection line 13 is provided. That is, the seawater electrolysis system 1 of the present embodiment can branch directly to the injection line 13 without sending the seawater W flowing through the seawater supply line 5 to the liquid receiving tank 6.
  • a seawater branch flow rate adjustment valve 22 for adjusting the flow rate of the seawater W flowing through the branch line 21 is provided.
  • the main seawater line 3 is provided with a main seawater flow rate sensor 24 that detects the flow rate of the main seawater M flowing through the main seawater line 3.
  • a residual chlorine measuring device 25 that measures the concentration of residual chlorine is provided downstream of the main seawater line 3 into which the used main seawater M discharged from the plant P flows.
  • the seawater electrolysis system 1 also injects sodium hypochlorite (chlorine) contained in the electrolyzed water E and seawater W introduced into the main seawater line 3 based on the flow rate of the main seawater M flowing through the main seawater line 3.
  • a control device (not shown) that performs control to keep the rate constant is provided.
  • the control device has a function of adjusting the output current value of the DC power supply device 9 based on the flow rate of the main seawater M.
  • the control device reduces sodium hypochlorite generated in the seawater electrolyzer 7, thereby reducing the main seawater.
  • control is performed to increase sodium hypochlorite generated in the seawater electrolyzer 7.
  • control device has a function of controlling the flow rate (electrolyte injection amount) of the electrolytically treated water E flowing through the injection line 13 based on the flow rate of the main seawater M flowing through the main seawater line 3.
  • the control device adjusts the flow rate of the electrolytically treated water E by the flow rate adjusting valve 19 in order to keep the chlorine concentration in the main seawater M at the target value.
  • the control device detects the flow rate of the main seawater M based on the number of operating main seawater pumps 2 to adjust the output current value of the DC power supply device 9 and adjusts the flow rate of the electrolyzed water E flowing through the injection line 13. .
  • the control device adjusts the output current value and the flow rate of the electrolyzed water E when the number of operating main seawater pumps 2 fluctuates.
  • the control device has a function of increasing the flow rate of the seawater W flowing through the branch line 21 by operating the seawater branch flow rate adjustment valve 22 as the flow rate of the main seawater M decreases.
  • Main seawater M is introduced into the main seawater line 3 by the main seawater pump 2.
  • the main seawater M is introduced into the plant P and used, for example, for cooling the furnace.
  • a part of the seawater W flowing through the main seawater line 3 is introduced into the liquid receiving tank 6 through the seawater supply line 5.
  • the electrolytic solution circulation process the seawater W is introduced into the first recycling line 11, the electrolytic cell 8, and the second recycling line 12 and circulated.
  • seawater W is introduced into the electrolytic cell 8 via the first recycle line 11. Thereby, the electrode in the electrolytic cell 8 is immersed in the seawater W.
  • Electrolysis is performed on the seawater W when current flows through the seawater W between the electrodes. That is, at the anode, as shown in the following formula (1), electrons e are taken from chloride ions in the seawater W, oxidation occurs, and chlorine is generated. 2Cl ⁇ ⁇ Cl 2 + 2e ⁇ (1) On the other hand, at the cathode, as shown in the following equation (2), electrons are given to the water in the seawater W to cause reduction, and hydroxide ions and hydrogen gas are generated. 2H 2 O + 2e ⁇ ⁇ 2OH ⁇ + H 2 (2)
  • the hydroxide ions generated at the cathode react with sodium ions in the seawater W to generate sodium hydroxide.
  • sodium hypochlorite having an inhibitory effect on the adhesion of marine organisms is generated.
  • concentration of sodium hypochlorite is preferably 2,500 to 5,000 ppm because the chloride ion concentration of seawater W is increased to 30,000 to 40,000 mg / l.
  • the electrolyzed seawater W flows out from the outlet 16 of the electrolytic cell 8 together with hydrogen gas as electrolytically treated water E, and is stored in the liquid receiving tank 6 through the second recycling line 12.
  • the electrolytically treated water E stored in the liquid receiving tank 6 is introduced into the injection line 13 by the injection pump 17 and then injected into the main seawater line 3. That is, the electrolytically treated water E containing sodium hypochlorite is injected into the main seawater line 3 through the water injection line when the water injection pump is operated.
  • part of the seawater W flowing through the seawater supply line 5 is introduced into the injection line 13 via the branch line 21. That is, a part of the seawater W in the seawater supply line 5 is used as backup seawater that supplements the flow rate of the electrolytically treated water E flowing through the injection line 13 without being supplied to the liquid receiving tank 6.
  • the control device adjusts the output current value of the DC power supply device 9 according to the flow rate of the main seawater M. Specifically, as shown in line a of FIG. 2, at time D when the number of main seawater pumps 2 decreases, the current value C so as to decrease sodium hypochlorite generated in the seawater electrolyzer 7. (A) is controlled. As a result, the chlorine concentration LRTEC (mg / l) of the electrolytically treated water E in the liquid receiving tank 6 (in the recycle line 10) gradually decreases as shown by the line b in FIG. That is, the chlorine concentration does not decrease rapidly.
  • the control device adjusts the flow rate of the electrolytically treated water E flowing through the injection line 13 according to the flow rate of the main seawater M. Specifically, as shown in the line c in FIG. 2, when the number of the main seawater pumps 2 decreases, the flow rate CLSFR (of the electrolyzed water E introduced into the main seawater line 3 through the injection line 13 at the time point D.
  • the flow rate adjustment valve 19 is controlled so that m 3 / h) decreases. That is, since the chlorine concentration of the electrolyzed water E circulating in the recycle line 10 cannot cope with a rapid decrease in the flow rate of the main seawater M, the control device throttles the flow rate of the electrolyzed water E flowing through the injection line 13.
  • the control device increases the flow rate of the seawater W flowing through the branch line 21 so as to compensate for the flow rate of the electrolyzed water E that has been reduced by the decrease in the flow rate of the main seawater M. .
  • the injection flow rate IFR (m 3 / h) becomes substantially constant as shown by the line e in FIG.
  • the flow rate of the seawater W flowing through the injection line 13 does not need to be substantially constant, and the flow rate of the fluid may be 0.7 m / s or more.
  • the control device monitors the residual chlorine content detected by the residual chlorine measuring device 25, and reduces the injection amount of the electrolyte when the residual chlorine content becomes a predetermined value or more.
  • the flow rate of the electrolytically treated water E containing sodium hypochlorite can be adjusted by providing the flow rate adjusting valve 19 in the injection line 13. Thereby, the chlorine concentration of the main seawater M can be kept constant.
  • the seawater branch flow rate adjusting valve 22 increases the seawater branch flow rate as the flow rate of the main seawater M decreases, the flow rate of the injection line 13 even when the electrolyte injection amount decreases as the flow rate of the main seawater M decreases. Scale accumulation due to the decrease can be prevented.
  • seawater branch flow rate adjustment valve 22 increases the seawater branch flow rate so that the flow rate of the fluid flowing through the injection line 13 is equal to or higher than a predetermined value, the flow rate of the fluid flowing through the injection line 13 is ensured. Scale accumulation due to a decrease in the flow rate of the line 13 can be prevented.
  • the flow rate of the main seawater M can be detected more easily.
  • residual chlorine contained in the wastewater can be reduced.
  • the seawater branch flow rate adjustment valve 22 provided in the branch line 21 can adjust the flow rate of the seawater W flowing through the branch line 21, but is not limited thereto.
  • a configuration may be adopted in which a constant flow valve is provided in the branch line 21 and the constant flow seawater W is introduced into the injection line 13 through the branch line 21.
  • the flow rate of the main seawater M may be detected by the driving power of the main seawater pump 2 instead of the number of operating main seawater pumps 2. Thereby, the flow volume of the main seawater M can be detected more correctly. Further, the flow rate of the main seawater M may be detected by the main seawater flow rate sensor 24.
  • the flow rate of the electrolyte solution containing chlorine can be adjusted by adjusting the flow rate of the fluid flowing through the injection line.
  • the chlorine concentration of the main seawater can be kept constant.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Hydrology & Water Resources (AREA)
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  • Environmental & Geological Engineering (AREA)
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  • Treatment Of Water By Oxidation Or Reduction (AREA)
PCT/JP2015/053767 2014-02-13 2015-02-12 海水電解システム及び電解液注入方法 WO2015122435A1 (ja)

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CN201580006031.0A CN105939969B (zh) 2014-02-13 2015-02-12 海水电解***以及电解液注入方法
KR1020167020739A KR101891906B1 (ko) 2014-02-13 2015-02-12 해수 전해 시스템 및 전해액 주입 방법

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CN116395898A (zh) * 2023-04-28 2023-07-07 青岛华丰伟业电力科技工程有限公司 一种海水淡化厂自动启停控制***

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CN108358284A (zh) * 2017-12-29 2018-08-03 中国船舶重工集团公司第七二五研究所 一种自动控制运行的海水管路电解防污装置及方法
JP7083452B2 (ja) * 2018-08-28 2022-06-13 中国電力株式会社 塩素強化注入運転装置および方法
KR102374891B1 (ko) * 2021-06-14 2022-03-15 김을환 살균수 생성 장치 제어 방법

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CN116395898A (zh) * 2023-04-28 2023-07-07 青岛华丰伟业电力科技工程有限公司 一种海水淡化厂自动启停控制***
CN116395898B (zh) * 2023-04-28 2024-01-16 青岛华丰伟业电力科技工程有限公司 一种海水淡化厂自动启停控制***

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KR20160103119A (ko) 2016-08-31
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