WO2016084754A1 - アンモニア処理システム - Google Patents

アンモニア処理システム Download PDF

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Publication number
WO2016084754A1
WO2016084754A1 PCT/JP2015/082777 JP2015082777W WO2016084754A1 WO 2016084754 A1 WO2016084754 A1 WO 2016084754A1 JP 2015082777 W JP2015082777 W JP 2015082777W WO 2016084754 A1 WO2016084754 A1 WO 2016084754A1
Authority
WO
WIPO (PCT)
Prior art keywords
boiler
drainage
line
seawater
storage tank
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/082777
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
宏幸 高波
勇作 那須
章弘 三田村
大暉 四條
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Heavy Industries Environmental and Chemical Engineering Co Ltd
Original Assignee
Mitsubishi Heavy Industries Environmental and Chemical Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Heavy Industries Environmental and Chemical Engineering Co Ltd filed Critical Mitsubishi Heavy Industries Environmental and Chemical Engineering Co Ltd
Priority to CN201580063882.9A priority Critical patent/CN107001076A/zh
Priority to SG11201704241YA priority patent/SG11201704241YA/en
Priority to KR1020177013814A priority patent/KR101967079B1/ko
Publication of WO2016084754A1 publication Critical patent/WO2016084754A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K9/00—Plants characterised by condensers arranged or modified to co-operate with the engines

Definitions

  • the present invention relates to an ammonia treatment system, and more particularly, to an ammonia treatment system for treating ammonia contained in boiler wastewater that is wastewater from boiler equipment.
  • This application claims priority about Japanese Patent Application No. 2014-238737 for which it applied on November 26, 2014, and uses the content here.
  • hydrazine is used to remove oxygen that causes corrosion. Since hydrazine is regarded as a “chemical substance with recognized mutagenicity”, the adoption of safer oxygen scavengers and water treatment without oxygen scavengers has been progressing in recent years.
  • an oxygen scavenger that does not use hydrazine ammonia having a high hydrogen ion exponent (pH) (for example, pH 7 to pH 10.5) is known.
  • PH hydrogen ion exponent
  • reduction of nitrogen is also required by the drainage regulations, and an immediate response is desired.
  • Patent Document 1 describes an ammonia treatment system that decomposes ammonia by chlorination using sodium hypochlorite (sodium hypochlorite) obtained by electrolyzing seawater.
  • sodium hypochlorite sodium hypochlorite
  • the capacity of the mixing tank is determined according to the reaction time of boiler wastewater and hypochlorous acid.
  • the reaction time between the boiler wastewater and hypochlorous acid becomes long, it is necessary to increase the capacity of the mixing tank.
  • An object of the present invention is to provide an ammonia treatment system that can shorten the reaction time between boiler wastewater and hypochlorous acid.
  • the ammonia treatment system includes a drainage line for supplying boiler wastewater to the mixing tank, a pH measuring device for measuring the pH of the boiler wastewater flowing through the drainage line, and the drainage line. And a pH adjusting device for adding a pH adjusting agent for adjusting the pH of the boiler wastewater to the boiler wastewater, and an electrolytic device for electrolyzing seawater or salt water to generate electrolytically treated water having hypochlorous acid. Based on the measured value of the pH measuring device, a supply line that is provided upstream from the junction of the drainage line and the mixing tank and that supplies hypochlorous acid generated by the electrolysis device to the boiler drainage And a control device for controlling the amount of the pH adjuster added.
  • the reaction time between the boiler wastewater and hypochlorous acid can be shortened by adding a pH adjuster to adjust the pH of the boiler wastewater.
  • the pH measuring device is disposed downstream of the pH adjusting device and at a position where the pH of the boiler wastewater adjusted by the pH adjusting agent added by the pH adjusting device is stable. May be.
  • the pH of the boiler wastewater can be measured more accurately by the pH measuring device.
  • adjustment of pH of boiler drainage by a pH adjustment device can be performed correctly.
  • the ammonia treatment system includes a storage tank that is provided upstream of the drainage line and stores the boiler drainage, and a storage tank pH measurement device that measures the pH of the boiler drainage stored in the storage tank.
  • the said control apparatus may control the amount of hypochlorous acid produced
  • the reaction time between boiler wastewater and hypochlorous acid can be shortened by adding a pH adjuster to adjust the pH of the boiler wastewater.
  • FIG. 1 is a schematic configuration diagram of a plant P having an ammonia treatment system 1 according to the first embodiment of the present invention.
  • the ammonia treatment system 1 is a system for treating boiler waste water W discharged from a combined cycle power plant P having an exhaust heat recovery boiler B.
  • the ammonia treatment system 1 includes a seawater electrolysis device 2 and a control device 8 as main components.
  • a combined cycle power plant P (hereinafter referred to as plant P) includes 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 sent, and a steam turbine. (Not shown) and a generator (not shown) that generates electric power by being driven by the rotational driving force of the gas turbine and the steam turbine.
  • Seawater M taken from the seawater intake 3 through the first seawater supply line 4 is introduced into the plant P. Seawater M is used for applications such as cooling.
  • the first seawater supply line 4 is provided with a seawater supply pump (not shown) that supplies the seawater M and a seawater flow rate adjustment valve (not shown) that adjusts the flow rate of the seawater M.
  • a seawater supply pump (not shown) that supplies the seawater M
  • a seawater flow rate adjustment valve (not shown) that adjusts the flow rate of the seawater M.
  • ammonia is used as an oxygen scavenger for removing oxygen that causes corrosion. Therefore, the boiler waste water W discharged from the boiler B is an ammonia nitrogen-containing waste water containing ammonia nitrogen such as ammonia (NH 3 ) and ammonium ions (NH 4 + ).
  • the boiler waste water W discharged from the boiler B is stored in the storage tank 5.
  • the storage tank 5 is provided with a dilution water introducing device 6 for introducing a temperature-reduced diluted water (industrial water supply) for reducing the temperature of the boiler waste water W into the storage tank 5.
  • the treated water in the storage tank 5 is managed below a predetermined temperature based on the temperature measured by a thermometer (not shown) that can measure the temperature of the treated water.
  • the storage tank 5 is provided with a storage tank pH measurement device 7 that measures the pH (hydrogen ion index) of the treated water in the storage tank 5.
  • a mixing tank 9 is provided on the downstream side of the storage tank 5.
  • the storage tank 5 and the mixing tank 9 are connected via a drainage line 10.
  • the boiler waste water W stored in the storage tank 5 and reduced in temperature is introduced into the mixing tank 9 through the drain line 10.
  • the boiler waste water W is discharged after being introduced into the mixing tank 9.
  • the drainage line 10 is provided with a drainage supply pump 16 that feeds the boiler drainage W stored in the storage tank 5 to the mixing tank 9.
  • the seawater electrolysis apparatus 2 is an apparatus that performs electrolysis of the seawater M introduced from the water intake 3 through the second seawater supply line 11.
  • the second seawater supply line 11 is provided with a seawater supply pump 14 that supplies the seawater M and a seawater flow rate adjustment valve 15 that adjusts the flow rate of the seawater M.
  • the seawater electrolysis apparatus 2 includes an electrolytic cell 12 and a DC power supply device 13.
  • the seawater electrolysis apparatus 2 is an apparatus that generates electrolyzed water E containing sodium hypochlorite (chlorine, sodium hypochlorite) by electrolyzing seawater M.
  • the electrolytic cell 12 has a plurality of electrodes (not shown).
  • the DC power supply device 13 is a device that supplies a current to be used for electrolysis of seawater M.
  • the DC power supply device 13 for example, a configuration including a DC power supply and a constant current control circuit can be employed.
  • the DC power source is a power source that outputs DC power.
  • the DC power supply may be configured to rectify and output AC power output from the AC power supply to DC, for example.
  • the seawater electrolysis apparatus 2 of the present embodiment is a one-through system in which the seawater M is passed through the electrolytic cell 12 only once.
  • a recycling method for circulating seawater may be adopted.
  • the downstream side of the electrolytic cell 12 (outlet of the electrolytic cell 12) and the upstream side of the electrolytic cell 12 (inlet of the electrolytic cell 12) are connected by a circulation channel to circulate seawater.
  • the seawater electrolysis device 2 may be of any type as long as it can generate hypochlorous acid using the seawater M.
  • the electrolyzed water E generated in the seawater electrolyzer 2 is introduced into the mixing tank 9 via the supply line 18 and mixed with the boiler waste water W.
  • a line mixer 21 that promotes mixing of the boiler wastewater W and the electrolytically treated water E is provided on the drainage line 10 and on the downstream side (mixing tank 9 side) of the junction 20 with the supply line 18. Yes.
  • Boiler waste water W and electrolytically treated water E are introduced into the mixing tank 9, and ammonia and hypochlorous acid present in the boiler waste water W undergo a solution reaction and are decomposed to nitrogen gas (N 2 ). That is, in the mixing tank 9, ammonia is processed and the boiler waste water W is in a state where it can be discharged.
  • a pH adjusting device 23 that adjusts the pH (hydrogen ion index) of the boiler drainage W that flows through the drainage line 10 in order from the upstream side, and a pH measurement device that measures the pH of the boiler drainage W. 24 is provided.
  • the pH adjusting device 23 and the pH measuring device 24 are provided on the upstream side of the junction 20 of the drain line 10 and the supply line 18. That is, the pH measuring device 24 is provided on the downstream side of the pH adjusting device 23, and the electrolytically treated water E is mixed on the downstream side of the pH measuring device 24.
  • the pH adjusting device 23 is a device that adjusts the pH of the boiler drainage W by adding a pH adjuster to the boiler drainage W flowing through the drainage line 10.
  • An acid or alkali agent such as hydrochloric acid is used as the pH adjuster.
  • the boiler waste water W of the present embodiment is often on the alkaline side, and hydrochloric acid is mainly added.
  • the pH measuring device 24 is installed sufficiently downstream of the pH adjusting device 23. Specifically, the pH measuring device 24 is arranged at a position where the pH adjusting agent added by the pH adjusting device 23 can be mixed with the boiler waste water W and can measure the pH of the boiler waste water W after reacting appropriately. . In other words, the pH measuring device 24 is disposed at a position where the pH of the boiler waste water W adjusted by the pH adjusting agent added by the pH adjusting device 23 is stabilized.
  • the pH adjusting device 23 is controlled to adjust the addition amount of the pH adjusting agent.
  • the control device 8 controls the pH adjusting device 23 so that hydrochloric acid is added to the boiler waste water W.
  • the boiler waste water W discharged from the boiler B is stored in the storage tank 5.
  • the pH of the boiler waste water W of this embodiment is around 10.5, indicating alkalinity.
  • the temperature-reduced diluted water is introduced into the storage tank 5.
  • the pH of the boiler waste water W in the storage tank 5 becomes 9.9, for example.
  • the boiler waste water W stored in the storage tank 5 is fed to the drain line 10 at a predetermined speed using the drain supply pump 16.
  • the control device 8 inputs a pH adjusting agent into the boiler waste water W using the pH adjusting device 23 based on the pH measured by the pH measuring device 24.
  • the control device 8 controls the pH adjusting device 23 so that the pH of the boiler waste water W becomes 7.5 to 9.5.
  • control device 8 calculates the required amount of hypochlorous acid based on the pH of the boiler waste water W measured by the storage tank pH measurement device 7 and determines the output current value of the DC power supply device 13. And the amount E of electrolytic treatment water required from the processing time etc. in the mixing tank 9 is determined.
  • the nitrogen concentration in the storage tank 5 is known by measuring the pH of the boiler waste water W.
  • the amount of hypochlorous acid with respect to the ammoniacal nitrogen concentration is also correlated, and the amount of hypochlorous acid increases or decreases in proportion to the current value of the DC power supply device 13. Therefore, it is possible to control the DC power supply 13 by measuring the pH of the boiler waste water W in the storage tank 5 and determine the amount of hypochlorous acid produced (ammonia nitrogen removal amount).
  • the ammonia contained in the boiler waste water W can be decomposed
  • reaction time between the boiler waste water W and hypochlorous acid can be shortened by adding a pH adjuster to adjust the pH of the boiler waste water W.
  • reaction time between the boiler waste water W and hypochlorous acid can be further shortened by adjusting the pH to the range of 7.5 to 9.5.
  • the pH adjuster added to the boiler waste water W is added on the upstream side of the merging portion 20 to which the electrolytically treated water E is supplied, so that it is not affected by the pH fluctuation caused by the electrolytically treated water E.
  • the pH of the boiler waste water W can be adjusted.
  • the ammonia treatment system 1 ⁇ / b> B of the present embodiment has an injection line 17 that injects the electrolytically treated water E generated by the seawater electrolysis apparatus 2 into the water inlet 3.
  • the electrolyzed water E sodium hypochlorite
  • the seawater electrolysis apparatus 2 of this embodiment has a function as a marine organism adhesion prevention apparatus.
  • a supply line 18 for supplying electrolytically treated water E to the mixing tank 9 is branched from an injection line 17 that connects the seawater electrolyzer 2 and the water intake 3. That is, the electrolytically treated water E generated by the seawater electrolyzer 2 is introduced into the mixing tank 9 through the supply line 18 branched from the injection line 17 and mixed with the boiler waste water W.
  • the supply line 18 is provided with a flow rate adjusting valve 19 that adjusts the flow rate of the electrolytically treated water E.
  • the control device 8 controls the amount of electrolytically treated water E (sodium hypochlorite) injected from the injection line 17 by adjusting the flow rate adjusting valve 19. Similar to the control device 8 of the first embodiment, the control device 8 calculates the required amount of hypochlorous acid based on the pH of the boiler waste water W measured by the storage tank pH measurement device 7, and the DC power supply device 13. Determine the output current value. And the amount E of electrolytic treatment water required from the processing time etc. in the mixing tank 9 is determined.
  • E sodium hypochlorite
  • the electrolytically treated water E generated by the seawater electrolysis apparatus 2 is injected into the intake 3 of the seawater M through the injection line 17.
  • the electrolyzed water E By injecting the electrolyzed water E into the water intake 3, adhesion of marine organisms to the water intake 3 can be suppressed.
  • the supply line 18 of the electrolytically treated water E according to the above embodiment is connected to the drainage line 10 through which the boiler drainage W flows, but the supply line 18 may be directly connected to the mixing tank 9.
  • the configuration in which the seawater M is introduced into the seawater electrolysis apparatus 2 is described, but the configuration in which saltwater is introduced into the seawater electrolysis apparatus 2 may be employed. That is, the liquid introduced into the seawater electrolysis apparatus 2 only needs to contain chlorine ions (Cl ⁇ ) like the seawater M.
  • a means for measuring pH, residual chlorine, water quality, etc. may be provided downstream of the mixing tank 9 or the mixing tank 9, and a line for returning the waste water to the storage tank 5 when the waste water does not meet the standard may be provided.
  • the reaction time between boiler wastewater and hypochlorous acid can be shortened by adding a pH adjuster to adjust the pH of the boiler wastewater.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (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)
  • Removal Of Specific Substances (AREA)
PCT/JP2015/082777 2014-11-26 2015-11-20 アンモニア処理システム Ceased WO2016084754A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201580063882.9A CN107001076A (zh) 2014-11-26 2015-11-20 氨处理系统
SG11201704241YA SG11201704241YA (en) 2014-11-26 2015-11-20 Ammonia processing system
KR1020177013814A KR101967079B1 (ko) 2014-11-26 2015-11-20 암모니아 처리 시스템

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-238637 2014-11-26
JP2014238637A JP6331145B2 (ja) 2014-11-26 2014-11-26 アンモニア処理システム

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WO2016084754A1 true WO2016084754A1 (ja) 2016-06-02

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PCT/JP2015/082777 Ceased WO2016084754A1 (ja) 2014-11-26 2015-11-20 アンモニア処理システム

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JP (1) JP6331145B2 (https=)
KR (1) KR101967079B1 (https=)
CN (1) CN107001076A (https=)
SG (1) SG11201704241YA (https=)
TW (1) TWI574921B (https=)
WO (1) WO2016084754A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016167271A1 (ja) * 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 次亜塩素酸供給装置及びボイラ排水の処理方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI648431B (zh) * 2018-01-03 2019-01-21 莊政霖 電解裝置
JP7123650B2 (ja) * 2018-06-18 2022-08-23 三菱重工業株式会社 復水設備、及びこれを備える蒸気タービンプラント
CN110204017B (zh) * 2019-05-16 2023-08-22 浙江浙能技术研究院有限公司 一种调节含氨废水pH值的电解处理系统及方法
JP6940713B1 (ja) * 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 水素製造システム

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US4137166A (en) * 1976-05-29 1979-01-30 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the purification of waste water containing ammonia and ammonium salts
JPH0975995A (ja) * 1995-09-19 1997-03-25 Hitachi Ltd 高濃度アンモニア態窒素の除去システム
US20030234224A1 (en) * 2002-04-19 2003-12-25 Hydro-Trace, Inc. Process for remediating ground water containing one or more nitrogen compounds
WO2005075355A2 (en) * 2004-02-10 2005-08-18 Kemira Oyj Process of removal of ammonium from waste water
JP2006006993A (ja) * 2004-06-22 2006-01-12 Miura Co Ltd 熱機器システム
JP2006297206A (ja) * 2005-04-15 2006-11-02 Mitsubishi Heavy Ind Ltd アンモニア性窒素含有廃水の電解処理方法及び装置
JP2007289841A (ja) * 2006-04-24 2007-11-08 Kurita Water Ind Ltd 石炭ガス化排水の処理方法及び処理装置
JP2014000563A (ja) * 2012-05-25 2014-01-09 Mitsubishi Heavy Industries Environmental & Chemical Engineering Co Ltd アンモニア処理システム

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CN201276469Y (zh) * 2008-03-25 2009-07-22 中国科学院广州地球化学研究所 一种折点氯化处理难生化处理氨氮废水装置
CN101570866B (zh) * 2009-01-15 2010-12-29 新汶矿业集团有限责任公司泰山盐化工分公司 全卤水离子膜电解制碱生产中去除铵的方法
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Publication number Priority date Publication date Assignee Title
US4137166A (en) * 1976-05-29 1979-01-30 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the purification of waste water containing ammonia and ammonium salts
JPH0975995A (ja) * 1995-09-19 1997-03-25 Hitachi Ltd 高濃度アンモニア態窒素の除去システム
US20030234224A1 (en) * 2002-04-19 2003-12-25 Hydro-Trace, Inc. Process for remediating ground water containing one or more nitrogen compounds
WO2005075355A2 (en) * 2004-02-10 2005-08-18 Kemira Oyj Process of removal of ammonium from waste water
JP2006006993A (ja) * 2004-06-22 2006-01-12 Miura Co Ltd 熱機器システム
JP2006297206A (ja) * 2005-04-15 2006-11-02 Mitsubishi Heavy Ind Ltd アンモニア性窒素含有廃水の電解処理方法及び装置
JP2007289841A (ja) * 2006-04-24 2007-11-08 Kurita Water Ind Ltd 石炭ガス化排水の処理方法及び処理装置
JP2014000563A (ja) * 2012-05-25 2014-01-09 Mitsubishi Heavy Industries Environmental & Chemical Engineering Co Ltd アンモニア処理システム

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016167271A1 (ja) * 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 次亜塩素酸供給装置及びボイラ排水の処理方法

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JP2016097387A (ja) 2016-05-30
SG11201704241YA (en) 2017-06-29
JP6331145B2 (ja) 2018-05-30
KR20170073657A (ko) 2017-06-28
TW201632468A (zh) 2016-09-16
TWI574921B (zh) 2017-03-21
CN107001076A (zh) 2017-08-01
KR101967079B1 (ko) 2019-04-08

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