CN105417820A - Separation recycling system of chloride radicals and sulfate radicals in high-salinity wastewater - Google Patents

Separation recycling system of chloride radicals and sulfate radicals in high-salinity wastewater Download PDF

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Publication number
CN105417820A
CN105417820A CN201510866873.5A CN201510866873A CN105417820A CN 105417820 A CN105417820 A CN 105417820A CN 201510866873 A CN201510866873 A CN 201510866873A CN 105417820 A CN105417820 A CN 105417820A
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electrodialysis
nanofiltration
reverse osmosis
separation
treatment
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CN105417820B (en
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吴雅琴
丁武龙
张高旗
朱圆圆
杨波
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HANGZHOU (LIGHTED TORCH) XIDOUMEN MEMBRANE CO Ltd
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HANGZHOU (LIGHTED TORCH) XIDOUMEN MEMBRANE CO Ltd
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • 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
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention discloses a separation recycling system of chloride radicals and sulfate radicals in high-salinity wastewater. The separation recycling system comprises a pretreatment system, a nanofiltration system, a reverse osmosis system, an electrodialysis system, a first aftertreatment system and a second aftertreatment system; the high-salinity wastewater enters the pretreatment system for pretreatment; after the pretreatment, the wastewater is subjected to nanofiltration treatment in the nanofiltration system; the thick water flowing out of the nanofiltration system enters the reverse osmosis system for reverse osmosis treatment; the thick water flowing out of the reverse osmosis system enters the first aftertreatment system for aftertreatment to obtain a product containing sulfate radicals; the water flowing out of the nanofiltration system enters a concentration chamber of the electrodialysis system for electrodialysis treatment; the fresh water from a desalting chamber of the electrodialysis system enters the reverse osmosis system for reverse osmosis treatment; and the thick water from the concentration chamber of the electrodialysis system enters the second aftertreatment system for aftertreatment to obtain a product containing chloride radicals. The separation recycling system disclosed by the invention brings relatively good social and economic benefits.

Description

The separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater
Technical field
The invention belongs to Industrial Waste Water Treatments field, relate to the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater.
Background technology
In short supply along with industrial expansion and water resources, the factory effluent that part industry produces contains higher salinity, as Cl -, SO 4 2-, Na +, Ca 2+plasma, its pollution concentration and quantity discharged present the trend of rising, therefore, have become one of focus of current wastewater treatment to the pure water reuse of high-salt wastewater process and inorganic salt recovery technology.
At present, it is extensive that film combined treatment high salinity waste water realizes zero-discharge technology Application comparison, but the inadequate system of integrated artistic, and the rate of recovery is not high, recovery inorganic salt purity is low, and system energy consumption is high.The high salinity zero discharge of industrial waste water technique that ZL201310311089.9 introduces, carry out electrodialysis process by filtering the concentrated solution repeatedly, the material after electrodialysis concentrates carries out evaporating and crystallization, but the salt that this technique obtains is carnallite does not have use value.
Therefore, from cleaner production, watering balance, resource reclaim angle system analysis combination membrane process feature, the comprehensive treating process of high salinity trade effluent is made to have good social and economic effects.
Summary of the invention
The object of the invention is to, for the above deficiency existed, provide the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater.
For this reason, the invention provides following solution:
A separation and recovery system for chlorine root and sulfate radical in high-salt wastewater, described separation and recovery system comprises pretreatment system, nanofiltration system, reverse osmosis system, electrodialysis system, the first after-treatment system and the second after-treatment system, high-salt wastewater enters pretreatment system and carries out pre-treatment, enter nanofiltration system after pretreatment and carry out nanofiltration process, enter reverse osmosis system from the dense water of nanofiltration system outflow and carry out reverse-osmosis treated, enter the first after-treatment system from the dense water of reverse osmosis system outflow and carry out the product that aftertreatment obtains containing sulfate radicals, the concentration compartments entering electrodialysis system from the product water of nanofiltration system outflow carries out electrodialysis process, the fresh water flowed out from the diluting compartment of electrodialysis system enters reverse osmosis system and carries out reverse-osmosis treated, the dense water flowed out from the concentration compartments of electrodialysis system enters the second after-treatment system and carries out the product that aftertreatment obtains chloride.Main containing sulfate ion in the dense water that nanofiltration system flows out, main containing chlorion in the product water that nanofiltration system flows out, the nanofiltration membrane of described nanofiltration system is used for by chlorion and retains sulfate ion.High-salt wastewater mentioned in context be saltiness higher than 1.5%wt, dissolvability solid amount is higher than the high salinity trade effluent of 15000mg/L.
Further, described first after-treatment system comprises freezing and crystallizing system and dehumidification system, enter freezing and crystallizing system from the dense water of reverse osmosis system outflow and carry out freezing and crystallizing, the mother liquor reuse of described freezing and crystallizing system carries out electrodialysis process to the diluting compartment of electrodialysis system, and the crystallization of described freezing and crystallizing system enters dehumidification system and carries out the product that drying obtains containing sulfate radicals.
Further, between the dense water out of reverse osmosis system and the entrance of freezing and crystallizing system, ozone oxidation system is set.
Further, described second after-treatment system comprises the second nanofiltration system and evaporation and crystallization system, enter the second nanofiltration system from the dense water of electrodialysis system outflow and carry out nanofiltration process, the diluting compartment entering electrodialysis system from the dense water of the second nanofiltration system outflow carries out electrodialysis process, enters evaporation and crystallization system carry out the product that evaporative crystallization obtains chloride from the product water of the second nanofiltration system outflow.
Further, described evaporation and crystallization system is one or more the combination in MVR evaporation and crystallization system, heterogeneous evaporation and crystallization system and membrane distillation system.
Further, described pretreatment system is one or more the combination in dosing melded system, ozone high grade oxidation system, activated carbon filtration system, ultrafiltration system and resin melded system.
Further, described electrodialysis system adopts a divalence to be separated electrodialytic membranes.
MVR be mechanical steam recompression technology ( mechanical vapor recompression) abbreviation, the secondary steam and energy thereof that utilize vapo(u)rization system self to produce, through vapour compressor compressed action, promote the heat content of secondary steam, lead into cooling tower, the cooling water circulation preheating material of cooling tower, so circulation provides heat energy to vapo(u)rization system, thus reduces a power-saving technology of the demand of the energy to external world.
The invention provides the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater, be separated electrodialytic membranes by a divalence and be separated chlorine root and sulfate radical; Concentrated the concentration that improve sulfate radical by reverse osmosis system, improve the purity of sulfate radical by freezing and crystallizing system; Concentration and the purity of chlorine root is improve by the second nanofiltration system concentrating and separating; The cost of the separation and recovery system provided is far below high-salinity wastewater zero-emission of the same trade and fully utilize cost and running cost, simultaneously, chlorine root and sulfate radical purity salt are all greater than 92% and meet industrial salt standard, therefore, in the high-salt wastewater provided, the separation and recovery system of chlorine root and sulfate radical has good social and economic effects.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater provided by the present invention;
In figure: 1-pretreatment system; 2-nanofiltration system; 3-reverse osmosis system; 4-electrodialysis system; 501-ozone oxidation system; 502-freezing and crystallizing system; 503-dehumidification system; 504-second nanofiltration system; 505-evaporation and crystallization system.
Embodiment
With reference to the drawings and specific embodiments, the present invention is described in detail further.
A separation and recovery system for chlorine root and sulfate radical in high-salt wastewater, described separation and recovery system comprises pretreatment system 1, nanofiltration system 2, reverse osmosis system 3, electrodialysis system 4, first after-treatment system and the second after-treatment system, high-salt wastewater enters pretreatment system 1 and carries out pre-treatment, enter nanofiltration system 2 after pretreatment and carry out nanofiltration process, enter reverse osmosis system 3 from the dense water of nanofiltration system 2 outflow and carry out reverse-osmosis treated, enter the first after-treatment system from the dense water of reverse osmosis system 3 outflow and carry out the product that aftertreatment obtains containing sulfate radicals, the concentration compartments entering electrodialysis system 4 from the product water of nanofiltration system 2 outflow carries out electrodialysis process, the fresh water flowed out from the diluting compartment of electrodialysis system 4 enters reverse osmosis system 3 and carries out reverse-osmosis treated, the dense water flowed out from the concentration compartments of electrodialysis system enters the second after-treatment system and carries out the product that aftertreatment obtains chloride.
Described first after-treatment system comprises freezing and crystallizing system 502 and dehumidification system 503, enter freezing and crystallizing system 502 from the dense water of reverse osmosis system 3 outflow and carry out freezing and crystallizing, the mother liquor reuse of described freezing and crystallizing system 502 carries out electrodialysis process to the diluting compartment of electrodialysis system 4, and the crystallization of described freezing and crystallizing system 502 enters dehumidification system 503 and carries out the product that drying obtains containing sulfate radicals.
Between the dense water out of reverse osmosis system 3 and the entrance of freezing and crystallizing system 502, ozone oxidation system 501 is set.
Described second after-treatment system comprises the second nanofiltration system 504 and evaporation and crystallization system 505, enter the second nanofiltration system 504 from the dense water of electrodialysis system 4 outflow and carry out nanofiltration process, the diluting compartment that the dense water flowed out from the second nanofiltration system 504 enters electrodialysis system 4 carries out electrodialysis process, and the water gone out from the second nanofiltration system miscarriage 504 enter evaporation and crystallization system 505 and carry out the product that evaporative crystallization obtains chloride.
Described evaporation and crystallization system 505 is one or more the combination in MVR evaporation and crystallization system, heterogeneous evaporation and crystallization system and membrane distillation system.
Described pretreatment system 2 is one or more the combination in dosing melded system, ozone high grade oxidation system, activated carbon filtration system, ultrafiltration system and resin melded system.
Described electrodialysis system 4 adopts a divalence to be separated electrodialytic membranes.
Particularly, following technique can be adopted:
With the treatment capacity of 360 tons per hour to each treatment unit design of whole technique and installation and debugging, finally carry out spot testing, certain high-salt wastewater carried out to the Separation and Recovery pilot plant test of sodium-chlor and sodium sulfate:
The saltiness 1%wt of certain factory's high-salt wastewater, COD cr160mg/L, suspended substance are less than 70mg/L, Ca 2+concentration is 360ppm, Mg 2+concentration is 35ppm, and the concentration of silicon is 50ppm, Cl -concentration is 1800ppm, SO 4 2-concentration is 2540ppm;
Pretreatment system, is undertaken adding the coagulating precipitation sofening treatment such as alkali, soda ash, flocculation agent and removes calcium ions and magnesium ions, water outlet Ca by the high-salt wastewater of 360m3/h 2+, Mg 2+concentration all lower than 50ppm, the concentration of silicon is lower than 5ppm; Dosing softens the waste water after clarification through ozone high grade oxidation and activated carbon filter, makes COD lower than 80ppm; Be less than 0.5NTU by ultrafiltration system turbidity again, and ensure water outlet Ca by cation bed, weak acid bed, degassing tower successively 2+, Mg 2+, CO 3 2-be less than 5ppm;
Through the high-salt wastewater of pretreatment system process, enter nanofiltration system, the dense water of separation is 117m3/h, containing NaCl concentration 0.3%wt, Na 2sO 4concentration is 1.1%wt; The dense water of nanofiltration system being passed into reverse osmosis system is separated concentrated, and the product water of reverse osmosis system carries out reuse, and the final concentrated stream amount of its reverse osmosis system is 15m3/h, is 2.7%wt, Na containing NaCl concentration 2sO 4concentration is 10%wt; Dense water is passed into ozone and reduce colourity, degraded COD; Enter the dry white crystal particle of dehumidification system after passing into freezing and crystallizing system and obtain Na 2sO 4purity is greater than 92%, and the mother liquor of freezing and crystallizing system is with NaCl concentration 2.9%wt, Na 2sO 4concentration is 4%wt, and pass into the diluting compartment desalination that a divalence is separated electrodialysis system, the fresh water that diluting compartment flows out is that 12m3/h contains NaCl concentration 1%wt, Na 2sO 4concentration is that 4%wt is back to reverse osmosis system and concentrates;
The product water of nanofiltration system passes into the concentration compartments that a divalence is separated electrodialysis system, and the dense water of electrodialysis system enters the second nanofiltration system and carries out nanofiltration separation, and the product water obtained is containing NaCl concentration 15%wt, SO 4 2-concentration is less than 0.15%wt, thus reclaims high-purity chloro root; Concentrate recirculation to one divalence of the second nanofiltration system is separated the diluting compartment of electrodialysis system.
Above-mentioned embodiment is used for explaining and the present invention is described; be only the preferred embodiments of the present invention; instead of limit the invention; in the protection domain of spirit of the present invention and claim; the any amendment made the present invention, equivalent replacement, improvement etc., all fall into protection scope of the present invention.

Claims (7)

1. the separation and recovery system of chlorine root and sulfate radical in high-salt wastewater, it is characterized in that, described separation and recovery system comprises pretreatment system, nanofiltration system, reverse osmosis system, electrodialysis system, the first after-treatment system and the second after-treatment system, high-salt wastewater enters pretreatment system and carries out pre-treatment, enter nanofiltration system after pretreatment and carry out nanofiltration process, enter reverse osmosis system from the dense water of nanofiltration system outflow and carry out reverse-osmosis treated, enter the first after-treatment system from the dense water of reverse osmosis system outflow and carry out the product that aftertreatment obtains containing sulfate radicals, the concentration compartments entering electrodialysis system from the product water of nanofiltration system outflow carries out electrodialysis process, the fresh water flowed out from the diluting compartment of electrodialysis system enters reverse osmosis system and carries out reverse-osmosis treated, the dense water flowed out from the concentration compartments of electrodialysis system enters the second after-treatment system and carries out the product that aftertreatment obtains chloride.
2. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater according to claim 1, it is characterized in that, described first after-treatment system comprises freezing and crystallizing system and dehumidification system, enter freezing and crystallizing system from the dense water of reverse osmosis system outflow and carry out freezing and crystallizing, the mother liquor reuse of described freezing and crystallizing system carries out electrodialysis process to the diluting compartment of electrodialysis system, and the crystallization of described freezing and crystallizing system enters dehumidification system and carries out the product that drying obtains containing sulfate radicals.
3. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater according to claim 2, is characterized in that, arrange ozone oxidation system between the dense water out of reverse osmosis system and the entrance of freezing and crystallizing system.
4. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater according to claim 1, it is characterized in that, described second after-treatment system comprises the second nanofiltration system and evaporation and crystallization system, enter the second nanofiltration system from the dense water of electrodialysis system outflow and carry out nanofiltration process, the diluting compartment entering electrodialysis system from the dense water of the second nanofiltration system outflow carries out electrodialysis process, enters evaporation and crystallization system carry out the product that evaporative crystallization obtains chloride from the product water of the second nanofiltration system outflow.
5. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater according to claim 4, it is characterized in that, described evaporation and crystallization system is one or more the combination in MVR evaporation and crystallization system, heterogeneous evaporation and crystallization system and membrane distillation system.
6. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater according to claim 1, it is characterized in that, described pretreatment system is one or more the combination in dosing melded system, ozone high grade oxidation system, activated carbon filtration system, ultrafiltration system and resin melded system.
7. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater according to claim 1, is characterized in that, described electrodialysis system adopts a divalence to be separated electrodialytic membranes.
CN201510866873.5A 2015-12-01 The separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater Active CN105417820B (en)

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CN106396232A (en) * 2016-11-17 2017-02-15 杭州水处理技术研究开发中心有限公司 Zero emission system and method for high-salinity printing and dyeing waste water
CN106430773A (en) * 2016-09-23 2017-02-22 内蒙古久科康瑞环保科技有限公司 Method for treating high-salt-concentration industrial wastewater at different ionic concentrations
CN107304090A (en) * 2016-04-21 2017-10-31 广州市心德实业有限公司 A kind of Resourceful treatment method for high-salinity wastewater of sodium chloride-containing and sodium sulphate
CN107777803A (en) * 2016-08-25 2018-03-09 中煤鄂尔多斯能源化工有限公司 The processing system and handling process of a kind of Technique of Coal Mine Drainage
CN108423903A (en) * 2018-02-27 2018-08-21 四川美富特水务有限责任公司 Dyeing waste water zero-discharge treatment system
CN108726769A (en) * 2017-04-24 2018-11-02 中国石油化工股份有限公司 A kind of advanced treatment and reclamation method of flue gas desulfurization liquid
CN108726772A (en) * 2017-04-24 2018-11-02 中国石油化工股份有限公司 A kind of advanced treatment and reclamation method of sodium alkali desulfurization liquid
CN109231252A (en) * 2018-08-27 2019-01-18 江苏天楹环保能源成套设备有限公司 SO is separated in plasma fume treatment high concentration salt water42-CaSO processed4Method and system
CN109502871A (en) * 2019-01-08 2019-03-22 山东蓝然环境科技有限公司 A kind of high-salinity wastewater zero-emission and divide salt resource utilization device
CN110407361A (en) * 2019-08-12 2019-11-05 济南上华科技有限公司 A kind of zero-emission of silica gel waste water and recycling treatment process and silica gel waste water treatment system
CN113968650A (en) * 2020-07-23 2022-01-25 中国石油化工股份有限公司 System and method for recycling wastewater generated in pseudoboehmite production
CN114133096A (en) * 2021-09-08 2022-03-04 浙江津膜环境科技有限公司 High-salinity wastewater recycling treatment method and system in metallurgical industry

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CN107304090A (en) * 2016-04-21 2017-10-31 广州市心德实业有限公司 A kind of Resourceful treatment method for high-salinity wastewater of sodium chloride-containing and sodium sulphate
CN106115740A (en) * 2016-06-13 2016-11-16 神华集团有限责任公司 A kind of salt extraction process and salt making system
CN106115740B (en) * 2016-06-13 2017-06-30 神华集团有限责任公司 A kind of salt extraction process and salt making system
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