WO2024037041A1 - Système et procédé de traitement des eaux usées de désulfuration - Google Patents

Système et procédé de traitement des eaux usées de désulfuration Download PDF

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WO2024037041A1
WO2024037041A1 PCT/CN2023/091495 CN2023091495W WO2024037041A1 WO 2024037041 A1 WO2024037041 A1 WO 2024037041A1 CN 2023091495 W CN2023091495 W CN 2023091495W WO 2024037041 A1 WO2024037041 A1 WO 2024037041A1
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hydrogen
desulfurization wastewater
gas
deoxygenation
liquid
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PCT/CN2023/091495
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English (en)
Chinese (zh)
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张利平
孙振新
廖海燕
袁野
杜庶铭
张秩鸣
马俯波
房臣昌
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国家能源集团新能源技术研究院有限公司
济南欧瑞实业有限公司
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Publication of WO2024037041A1 publication Critical patent/WO2024037041A1/fr

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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047Pressure swing adsorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/8671Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/508Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
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    • C01B3/56Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/01Electrolytic cells characterised by shape or form
    • C25B9/015Cylindrical cells
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D45/00Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
    • B01D45/12Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
    • B01D45/16Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces generated by the winding course of the gas stream, the centrifugal forces being generated solely or partly by mechanical means, e.g. fixed swirl vanes
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    • 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
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    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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    • C02F2103/18Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents

Definitions

  • the present invention relates to the technical field of desulfurization wastewater treatment, and in particular to a desulfurization wastewater treatment system and method.
  • wet desulfurization wastewater generally adopts a drug-added flocculation and sedimentation process. After most of the divalent ions are removed through flocculation and sedimentation, the pH value is adjusted by adding acid/alkali before being discharged into the receiving water body. With the gradual improvement of the country's environmental protection requirements, more and more production companies require zero discharge of pollutants.
  • desulfurization wastewater contains a large amount of chloride ions and sodium ions. In order to meet the zero discharge requirements, an evaporation process is generally used.
  • the desulfurization wastewater evaporation process means that after the desulfurization wastewater is pretreated, the water in the desulfurization wastewater is evaporated to dryness by heating to achieve zero discharge of desulfurization wastewater.
  • the conventional process route of this technology is: pretreatment + membrane concentration + evaporation crystallization ( MVR or MED), the evaporation process can achieve zero discharge of desulfurization wastewater, and there are already successful engineering cases.
  • MVR or MED membrane concentration + evaporation crystallization
  • this method has the following shortcomings: due to the use of membrane concentration and evaporation crystallization processes, the entire system occupies a large area, and this The investment cost and operating cost of this process are high; moreover, the salt produced by evaporation and crystallization is generally miscellaneous salt, which is difficult to reuse and difficult to process. There is still the discharge of pollutants, but it has changed from waste water to solid waste.
  • the purpose of the present invention is to provide a new desulfurization wastewater treatment system in order to overcome the problems existing in the existing desulfurization wastewater treatment system such as large system footprint, high process investment costs, high operating costs, and difficulty in processing miscellaneous salts generated during the evaporation process. Systems and methods.
  • the present invention provides a desulfurization wastewater treatment system, which system includes:
  • a pretreatment device used to pretreat desulfurization wastewater to remove divalent ions in the desulfurization wastewater
  • Electrolysis device for electrolysis of pretreated desulfurization wastewater
  • a gas-liquid separation device used for gas-liquid separation of the gas-liquid mixture produced in the electrolysis device
  • a dechlorination device used to dechlorinate the hydrogen separated in the gas-liquid separation device
  • a hydrogen pressurizing device for pressurizing, cooling and drying dechlorinated hydrogen
  • Hydrogen deoxygenation device is used to deoxygenate hydrogen after pressurization, cooling and drying.
  • the pretreatment device includes a pH adjustment box, a reaction box, a flocculation box, a sedimentation box and a multi-media filter connected in sequence.
  • the pH value adjustment box includes a box, a mixer, an acid solution dosing device, an alkali solution dosing device and a pH detector.
  • the main liquid inlet end of the mixer is connected to the desulfurization wastewater inlet, and the mixing
  • the auxiliary liquid inlet end of the device is connected to the acid solution dosing device and the alkali solution dosing device
  • the pH detector is arranged between the outlet of the mixer and the liquid inlet of the box.
  • the sedimentation tank includes a box body, a central liquid inlet pipe and an overflow weir.
  • the lower outlet of the central liquid inlet pipe is 10-30cm away from the bottom of the tank body.
  • the overflow weir is arranged around the tank. The upper part of the inner wall of the body.
  • the upper edge of the overflow weir has a zigzag structure.
  • the filter material filled inside the multi-media filter is one or any combination of at least two of quartz sand, activated carbon and anthracite.
  • the electrolytic cell used in the electrolysis device is a plate electrode tube electrolytic cell, a plate mesh electrode plate electrolytic cell or a concentric tube electrolytic cell.
  • the system further includes an acid cleaning device for cleaning the scaling generated during the operation of the electrolysis device.
  • the hydrogen deoxygenation device includes a primary hydrogen deoxygenation unit and a secondary hydrogen deoxygenation unit.
  • the primary hydrogen deoxygenation unit uses a gas separation membrane for deoxidation
  • the secondary hydrogen deoxygenation unit uses a palladium catalyst for deoxidation.
  • the hydrogen deoxygenation device further includes a tertiary hydrogen deoxygenation unit arranged behind the secondary hydrogen deoxygenation unit, and the tertiary hydrogen deoxygenation unit uses a temperature swing and pressure swing adsorption device for deoxygenation.
  • the invention also provides a method for treating desulfurization wastewater, which method includes the following steps:
  • the deoxidation process includes:
  • a temperature swing and pressure swing adsorption device can be used for three deoxygenations.
  • the desulfurization wastewater is pretreated, and most of the divalent ions are removed through flocculation and precipitation.
  • the remaining ones in the water body are basically sodium ions and chloride ions, and then electrolysis can Convert chloride ions into sodium hypochlorite, which can be used for factory disinfection.
  • the hydrogen generated during the electrolysis process is dechlorinated, pressurized, cooled, dried, and deoxygenated to obtain pure hydrogen. Therefore, when desulfurization wastewater is treated according to the technical solution of the present invention, the overall process will not produce any waste, and the entire system will occupy a small area, and the process investment cost and operating cost will be low.
  • FIG. 1 is a schematic diagram of the desulfurization wastewater treatment system according to the present invention.
  • Figure 2 is a schematic diagram of the pretreatment device in the desulfurization wastewater treatment system of the present invention.
  • FIG. 3 is a flow chart of the desulfurization wastewater treatment method according to the present invention.
  • the desulfurization wastewater treatment system of the present invention includes a pretreatment device, an electrolysis device, a gas-liquid separation device, a dechlorination device, a hydrogen pressurization device and a hydrogen deoxygenation device connected in sequence.
  • the pretreatment device is used to pretreat the desulfurization wastewater to remove divalent ions in the desulfurization wastewater.
  • the pretreatment device includes a pH value adjustment box, a reaction box, a flocculation box, a sedimentation box and a multi-media filter connected in sequence.
  • the pH value adjustment box includes a box, a mixer, an acid solution dosing device, an alkali solution dosing device and a pH detector.
  • the main liquid inlet end of the mixer is connected to the desulfurization wastewater inlet
  • the auxiliary liquid inlet end of the mixer is connected to the acid liquid dosing device and the alkali liquid dosing device
  • the pH detector is installed on the mixing between the outlet of the mixer and the liquid inlet of the box.
  • the pH detector is disposed at the connection between the mixer and the box.
  • the acid liquid dosing device includes an acid liquid metering pump, the inlet of the acid liquid dosing device is connected to the acid liquid storage tank, and the acid liquid is injected into the mixer through the acid liquid metering pump.
  • the liquid reducing dosing device includes an alkali metering pump, and the inlet connection of the alkali dosing device It is connected to the alkali liquid storage tank, and the alkali liquid is injected into the mixer through the alkali liquid metering pump.
  • the mixer may be selected from static mixers, dynamic agitation mixers and pipe mixers.
  • the reaction box includes a chemical dosing metering pump.
  • the medicine added by the medicine adding metering pump can be sodium carbonate, sodium hydroxide, etc., and the medicine adding metering pump is correspondingly connected to the respective liquid storage tank.
  • the flocculation box includes a flocculant dosing metering pump.
  • the flocculant dosing metering pump is connected to the flocculant storage tank.
  • the flocculant used can be a conventional choice in this field, for example, it can be polyaluminum chloride, ferric chloride, ferrous sulfate, alum and aluminum sulfate. At least one.
  • the sedimentation tank includes a box, a liquid inlet central pipe and an overflow weir.
  • the lower outlet of the liquid inlet central pipe is 10-30cm away from the bottom of the box, so
  • the overflow weir is arranged around the upper part of the inner wall of the box.
  • the structural form of the upper edge of the overflow weir is not particularly limited.
  • the upper edge of the overflow weir has a zigzag structure. This zigzag structure overcomes the surface tension of water and promotes uniform water flow.
  • the zigzag shape forming the upper edge of the overflow weir may be square, semicircular, triangular, etc.
  • the multi-media filter includes a tank body and filter material filled in the tank body.
  • the tank body may be made of fiberglass, carbon steel lined with plastic, or other materials.
  • the filter material filled inside the multi-media filter is preferably one or any combination of at least two of quartz sand, activated carbon and anthracite.
  • the electrolysis device is used to treat pre-treated The desulfurization wastewater is electrolyzed to generate sodium hypochlorite solution and hydrogen gas.
  • the electrolysis device includes an electrolysis tank and a power supply.
  • the electrolytic cell is preferably a plate electrode tube electrolytic cell, a plate mesh electrode plate electrolytic cell or a concentric tube electrolytic cell.
  • the power supply may adopt a high-frequency steady-current switching voltage or a silicon-controlled rectified power supply.
  • the electrolytic tank and the power supply are preferably connected through cables or copper bars.
  • the system further includes an acid cleaning device for cleaning the scaling generated during the operation of the electrolysis device.
  • the pickling device includes a pickling tank, an acid unloading pump, a pickling pump and an acid mist absorber.
  • the pickling tank can use a PE material tank, a glass fiber reinforced plastic tank, or a steel-lined rubber tank.
  • the acid unloading pump can be a magnetic pump or a centrifugal pump.
  • the pickling pump can be a magnetic pump or a centrifugal pump.
  • the inside of the acid mist absorber can be filled with fillers such as Raschig rings and filled with sodium hydroxide solution.
  • the inlet of the acid unloading pump is connected to the pickling solution tank, and the outlet of the acid unloading pump is connected to the pickling tank.
  • the inlet of the pickling pump is connected to the pickling tank, the outlet of the pickling pump is connected to the inlet of the electrolytic tank, and the pickling solution outlet of the electrolytic tank is connected to the pickling tank.
  • the inlet of the acid mist absorber is connected with the gas phase outlet at the top of the pickling tank.
  • the gas-liquid separation device is used to separate the gas-liquid mixture generated in the electrolysis device.
  • the inlet of the gas-liquid separation device is connected to the outlet of the electrolytic cell of the electrolysis device, the liquid outlet of the gas-liquid separation device is connected to the sodium hypochlorite solution storage tank, and the gas outlet of the gas-liquid separation device is connected to the dechlorination device. connected to the air inlet.
  • the interior of the gas-liquid separation device is a spiral structure, and the liquid entering the gas-liquid separation device is centrifuged along the spiral structure of the gas-liquid separation device. Movement to achieve centrifugal separation of gas and liquid, and separate them into sodium hypochlorite solution as a liquid phase and hydrogen as a gas phase.
  • the dechlorination device is used to dechlorinate the hydrogen separated in the gas-liquid separation device.
  • the dechlorination device includes a dechlorination tower, an alkali tank and an alkali pump.
  • the dechlorination tower adopts a barrel-shaped tank, and spray pipes are evenly distributed inside the dechlorination tower;
  • the alkali tank can be made of a material resistant to sodium hypochlorite corrosion;
  • the alkali pump can be a stainless steel centrifugal pump .
  • the inlet of the alkali liquid pump is connected to the alkali liquid tank, and the outlet of the alkali liquid pump is connected to the spray pipe inside the dechlorination tower.
  • the hydrogen pressurizing device is used to pressurize, cool and dry the dechlorinated hydrogen.
  • the hydrogen pressurizing device may use a hydrogen compressor or a gas booster pump.
  • the inlet of the hydrogen pressurizing device is connected with the gas outlet of the dechlorination device.
  • the gas pressurizing device also includes a hydrogen cooling and drying device, which can be cooled by a gas air cooler or a cold dryer.
  • the hydrogen deoxygenation device is used to deoxygenate the hydrogen gas that has been pressurized, cooled and dried.
  • the hydrogen deoxygenation device includes a primary hydrogen deoxygenation unit, a secondary hydrogen deoxygenation unit and an optional tertiary hydrogen deoxygenation unit, wherein the primary hydrogen deoxygenation unit uses a gas separation membrane to deoxygenate, separate hydrogen and Oxygen, the inlet of the primary hydrogen deoxygenation unit is connected to the outlet of the hydrogen pressurizing device; the secondary hydrogen deoxygenation unit uses a palladium catalyst for deoxidation, and the inlet of the secondary hydrogen deoxygenation unit is connected to the outlet of the primary hydrogen deoxygenation unit.
  • the outlets are connected; the tertiary hydrogen deoxygenation unit uses a temperature swing and pressure swing adsorption device for deoxygenation, and the inlet of the tertiary hydrogen deoxygenation unit is connected to the outlet of the secondary hydrogen deoxygenation unit.
  • the invention also provides a desulfurization wastewater treatment method, as shown in Figure 3.
  • the method includes the following steps:
  • the desulfurization wastewater treatment method is implemented using the desulfurization wastewater treatment system described above.
  • the deoxygenation process includes:
  • a temperature swing and pressure swing adsorption device can be used for three deoxygenations.
  • sodium hypochlorite solution and relatively pure hydrogen product can be obtained, and the entire process will not produce any waste waste.
  • the shedding wastewater used in the following examples contains chloride ions 18g/L, sodium ions 11.4g/L, sulfate ions 0.2g/L, calcium ions 0.2g/L and magnesium ions 0.05g/L.
  • the desulfurization wastewater treatment system used in this embodiment includes a pretreatment device, an electrolysis device, a gas-liquid separation device, a dechlorination device, a hydrogen pressurization device and a hydrogen deoxygenation device connected in sequence, as well as a device for A pickling device for cleaning the electrolytic device, wherein the pretreatment device includes a pH adjustment box, a reaction box, a flocculation box, a sedimentation box and a multi-media filter connected in sequence.
  • the pH value adjustment box includes a box, a mixer, an acid solution dosing device, an alkali solution dosing device and a pH detector.
  • the main liquid inlet end of the mixer is connected to the desulfurization wastewater inlet, and the auxiliary end of the mixer is connected to the desulfurization wastewater inlet.
  • the liquid inlet end is connected to the acid solution dosing device and the alkali solution dosing device, and the pH detector is arranged at the connection between the mixer and the box.
  • the sedimentation tank includes a box body, a liquid inlet central pipe and an overflow weir.
  • the lower outlet of the liquid inlet central pipe is 10-30cm away from the bottom of the box.
  • the overflow weir is arranged around the inner wall of the box. In the upper part, the upper edge of the overflow weir has a zigzag structure.
  • the multi-media filter includes a tank body and filter material filled in the tank body.
  • the filter material is quartz sand.
  • the electrolysis device includes an electrolytic cell and a power supply, wherein the electrolytic cell is a plate electrode tube electrolytic cell.
  • the pickling device includes a pickling tank, an acid unloading pump, a pickling pump and an acid mist absorber.
  • the inlet of the pump is connected to the pickling solution tank, the outlet of the acid unloading pump is connected to the pickling tank, the inlet of the pickling pump is connected to the pickling tank, and the outlet of the pickling pump is connected to the pickling tank.
  • the inlet of the electrolytic tank is connected, the pickling solution outlet of the electrolytic tank is connected with the pickling tank, and the inlet of the acid mist absorber is connected with the gas phase outlet on the top of the pickling tank.
  • the inlet of the gas-liquid separation device is connected to the outlet of the electrolytic cell of the electrolysis device, the liquid outlet of the gas-liquid separation device is connected to the sodium hypochlorite solution storage tank, and the gas outlet of the gas-liquid separation device is connected to the dechlorination device. connected to the air inlet.
  • the dechlorination device includes a dechlorination tower, an alkali tank and an alkali pump. Spray pipes are evenly distributed inside the dechlorination tower.
  • the inlet of the alkali pump is connected to the alkali tank.
  • the alkali tank The outlet of the pump is connected to the spray pipe inside the dechlorination tower.
  • the hydrogen pressurizing device adopts a hydrogen compressor, and the inlet of the hydrogen pressurizing device is connected to the gas outlet of the dechlorination device.
  • the hydrogen deoxygenation device includes a primary hydrogen deoxygenation unit, a secondary hydrogen deoxygenation unit and a tertiary hydrogen deoxygenation unit.
  • the primary hydrogen deoxygenation unit uses a gas separation membrane to deoxygenate and separate hydrogen and oxygen.
  • the inlet of the primary hydrogen deoxygenation unit is connected to The outlet of the hydrogen pressurizing device is connected; the hydrogen secondary deoxygenation unit uses a palladium catalyst for deoxygenation, and the inlet of the hydrogen secondary deoxygenation unit is connected to the outlet of the hydrogen primary deoxygenation unit; the hydrogen tertiary deoxygenation unit adopts variable temperature
  • the pressure swing adsorption device performs deoxygenation, and the inlet of the tertiary hydrogen deoxygenation unit is connected to the outlet of the secondary hydrogen deoxygenation unit.
  • the process of desulfurization wastewater treatment is: inject the desulfurization wastewater into the above-mentioned desulfurization wastewater treatment system for treatment.
  • the pretreatment device add flocculant polyaluminum chloride (purchased from Jinan Jiayang Chemical Co., Ltd., in which Al 2 O 3 ⁇ 28%), to remove divalent ions in the desulfurization wastewater through flocculation and precipitation; then, the pretreated desulfurization wastewater is electrolyzed in an electrolysis device to generate a gas-liquid mixture containing sodium hypochlorite solution and hydrogen.
  • the gas-liquid mixture is separated into a sodium hypochlorite solution as a liquid phase and hydrogen as a gas phase; secondly, the separated hydrogen is dechlorinated to remove trace amounts of chlorine entrained in the hydrogen. ; Subsequently, the hydrogen after dechlorination is pressurized, cooled and dried; then, the hydrogen after pressurized, cooled and dried is deoxygenated three times.
  • the purity of the hydrogen prepared according to this method is 99.999%, the concentration of the sodium hypochlorite solution is 8g/L, and the amount of hydrogen produced is 1800L per cubic meter of desulfurization wastewater.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne un système et un procédé de traitement des eaux usées de désulfuration. Le système de traitement des eaux usées de désulfuration comprend un dispositif de prétraitement utilisé pour prétraiter les eaux usées de désulfuration, de manière à éliminer les ions divalents contenus dans celles-ci ; un dispositif d'électrolyse utilisé pour électrolyser les eaux usées de désulfuration prétraitées ; un dispositif de séparation gaz-liquide utilisé pour effectuer une séparation gaz-liquide sur un mélange gaz-liquide généré par le dispositif d'électrolyse ; un dispositif de déchloration utilisé pour déchlorer l'hydrogène séparé par le dispositif de séparation gaz-liquide ; un dispositif de mise sous pression de l'hydrogène utilisé pour effectuer une mise sous pression et un séchage par refroidissement de l'hydrogène déchloré ; et un dispositif de désoxydation de l'hydrogène utilisé pour désoxyder l'hydrogène soumis à la mise sous pression et au séchage par refroidissement. La présente invention permet de traiter les eaux usées de désulfuration et de produire une solution d'hypochlorite de sodium et de l'hydrogène ; l'ensemble du processus ne génère ni ne rejette de déchets.
PCT/CN2023/091495 2022-08-19 2023-04-28 Système et procédé de traitement des eaux usées de désulfuration WO2024037041A1 (fr)

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CN105314773A (zh) * 2014-07-10 2016-02-10 王辛平 一种湿法脱硫废水回收利用方法及其装置
CN205099427U (zh) * 2015-11-06 2016-03-23 山东大学 利用电解电渗析处理湿法脱硫系统中氯离子的系统
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