CN105906128A - Method and system for recovering sodium chloride from high salinity wastewater - Google Patents

Method and system for recovering sodium chloride from high salinity wastewater Download PDF

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Publication number
CN105906128A
CN105906128A CN201610406418.1A CN201610406418A CN105906128A CN 105906128 A CN105906128 A CN 105906128A CN 201610406418 A CN201610406418 A CN 201610406418A CN 105906128 A CN105906128 A CN 105906128A
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China
Prior art keywords
unit
containing wastewater
sodium chloride
high slat
clear liquid
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CN201610406418.1A
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Chinese (zh)
Inventor
王建国
孙家喜
孙烨
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Shuangliang Eco Energy Systems Co Ltd
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Shuangliang Eco Energy Systems Co Ltd
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Priority to CN201610406418.1A priority Critical patent/CN105906128A/en
Publication of CN105906128A publication Critical patent/CN105906128A/en
Pending legal-status Critical Current

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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
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C01D3/06—Preparation by working up brines; seawater or spent lyes
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/444—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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness
    • C02F5/06—Softening water by precipitation of the hardness using calcium compounds

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

Abstract

The invention relates to a system for recovering sodium chloride from high salinity wastewater. The system is composed of a purifying unit, a nano-filtering unit, a reduction unit and an evaporation and crystallization unit. Calcium, magnesium, silicon oxide and matter prone to scaling and COD type organic matter are removed from high salinity wastewater through the purifying unit, the product enters the nano-filtering unit to be separated so that one stream of monovalent ion clear liquid and the other stream of thick liquid can be generated, the thick liquid returns to the purifying unit, monovalent ion clear liquid enters the reduction unit to be further concentrated, recovery water is generated for reuse, obtained concentrated liquid enters the evaporation and crystallization unit to be evaporated and crystallized and separated to obtain industrial sodium chloride, condensate water is reused, and a small amount of discharged mother solution returns to the purifying unit. Sodium chloride and other inorganic salt in high salinity wastewater are effectively separated and recovered, and meanwhile obtained recovered water can completely meet the reuse requirement.

Description

A kind of method and system reclaiming sodium chloride from high slat-containing wastewater
Technical field
The present invention relates to a kind of high slat-containing wastewater processing method, be specifically related to a kind of system reclaiming sodium chloride from high slat-containing wastewater.
Background technology
From the high strong brine of the industry discharges such as petrochemical industry, Coal Chemical Industry, power plant, oilfield exploitation through evaporative crystallization zero discharge treatment, the carnallite finally obtained carries out landfill disposal generally as solid waste, there is certain risk of environmental pollution, and recovery utilization rate is the highest.
In order to improve the sewage disposal later stage, the classification recycling of carnallite, it it is the development trend of high-salt sewage process, by above-mentioned high strong brine evaporative crystallization zero discharge treatment, and during the course the higher sodium chloride of value is separated and recovered, it is met the sodium chloride of industrial level, while solving solid waste disposal, obtains economic benefit, reduce the operating cost of high slat-containing wastewater zero-emission, the large-scale application of wastewater zero discharge is played an important role.
Summary of the invention
The technical problem to be solved is to provide a kind of method and system reclaiming sodium chloride from high slat-containing wastewater for above-mentioned prior art.
The present invention solves the technical scheme that the problems referred to above are used: a kind of system reclaiming sodium chloride from high slat-containing wastewater, including set gradually
Clean unit: remove calcium, magnesium, the easy scale forming matter of silicon oxide and COD type organic in high slat-containing wastewater；
Nano-filtration unit: purifying high slat-containing wastewater, obtain monovalent ion clear liquid and dope, dope is through loop foldback clean unit；
Minimizing unit: concentrate monovalent ion clear liquid to concentrated solution, producing can the recycle-water of reuse；
Evaporative crystallization unit: to concentrated solution evaporative crystallization isolated industrial chlorinations sodium, recycling condensing water, a small amount of mother solution of outer row is back to clean unit.
Preferably, described minimizing unit is the disc tube reverse osmosis (dt-ro) DTRO used, or pole-reversing electroosmosis EDR, or the combination of aforementioned upgrading unit.
Preferably, described evaporative crystallization unit is to use the outer crystalline texture for steam, or the crystalline texture of mechanical vapor-compression, and crystallizer uses forced circulation crystallizer, or draft tube baffle crystallizer.
It is a further object of the present invention to provide the method reclaiming sodium chloride from high slat-containing wastewater, including following operation,
Purify: remove calcium, magnesium, the easy scale forming matter of silicon oxide and COD type organic in high slat-containing wastewater；
Nanofiltration: high slat-containing wastewater produces one monovalent ion clear liquid and another strand of dope by nanofiltration separation after purifying, and dope is back to cleaning procedure；
Minimizing: the monovalent ion clear liquid obtaining nanofiltration separation concentrates, is concentrated into TDS and reaches the concentrated solution of more than 90000mg/L, gained recycle-water reuse；
Evaporative crystallization: to concentrated solution evaporative crystallization isolated industrial chlorinations sodium, recycling condensing water, a small amount of mother solution of outer row is back to cleaning procedure.
Preferably, cleaning procedure uses Calx+soda, or Caustic soda+soda, or Calx+flue gas, or calcium chloride+soda, or any one combination with activated carbon aforementioned removes the easy scale forming matter of the calcium in high slat-containing wastewater, magnesium and silicon oxide, heavy metal substance and COD type organic, then using micro-filtrate membrane filtration separation brine sludge and clear liquid, clear liquid enters next step nanofiltration operation.
Preferably, minimizing is through disc tube reverse osmosis (dt-ro) DTRO, or pole-reversing electroosmosis EDR, or the combination concentration of aforementioned upgrading unit.
Further, evaporative crystallization unit uses the outer crystallization mode for steam, or mechanical vapor-compression crystallization mode, and crystallizer uses forced circulation crystallizer, or draft tube baffle crystallizer.
Compared with prior art, it is an advantage of the current invention that: sodium chloride in high slat-containing wastewater and other inorganic salts are efficiently separated and reclaimed, and the recycle-water obtained during concurrently separating fully meets reuse requirement.Obtaining economic benefit while solving solid waste disposal, reduce the operating cost of high slat-containing wastewater zero-emission, the large-scale application for wastewater zero discharge has dissemination.
Accompanying drawing explanation
Fig. 1 is the structural representation reclaiming sodium chloride system in the embodiment of the present invention from high slat-containing wastewater.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
As it is shown in figure 1, the system reclaiming sodium chloride from high slat-containing wastewater in the present embodiment, specifically by clean unit, nano-filtration unit, minimizing unit, evaporative crystallization unit forms.High slat-containing wastewater removes easily scale forming matter and the COD type organic such as deliming, magnesium, silicon oxide through clean unit, separate subsequently into nano-filtration unit and produce one monovalent ion clear liquid and another strand of dope, dope is back to clean unit, monovalent ion clear liquid enters minimizing unit and concentrates further, produce recycle-water reuse, gained concentrated solution enters evaporative crystallization unit and is evaporated crystallization isolated industrial chlorinations sodium, and recycling condensing water, a small amount of mother solution of outer row is back to clean unit.
The disc tube reverse osmosis (dt-ro) DTRO that minimizing unit can use, or pole-reversing electroosmosis EDR, or the combination of aforementioned upgrading unit.
Evaporative crystallization unit can use the outer crystalline texture for steam, or the crystalline texture of mechanical vapor-compression, and crystallizer uses forced circulation crystallizer, or draft tube baffle crystallizer.
Embodiment 1
The method reclaiming sodium chloride from high slat-containing wastewater based on said system, arranging brine waste TDS outside certain Coal Chemical Industry reverse osmosis is 25000 mg/L, this waste water is after calcium chloride+soda+active carbon purifying, the clear liquid that solid-liquid separation obtains enters nano-filtration unit and isolates one monovalent ion clear liquid and one dope, the TDS of monovalent ion clear liquid be the TDS of 10000 mg/L and dope be 40000 mg/L, dope is back to clean unit, clear liquid entrance minimizing DTRO unit is concentrated into TDS and reaches the concentrated solution of 90000 mg/L, gained recycle-water reuse；Dope enters evaporative crystallization unit, and Crystallization Separation goes out to meet the sodium chloride of GB/T 5462-2003 II grade standard, Condensate reuse.
Embodiment 2
The method reclaiming sodium chloride from high slat-containing wastewater based on said system, arranging brine waste TDS outside certain Coal Chemical Industry reverse osmosis is 30000 mg/L, this waste water is after Calx+stack gas cleaning, the clear liquid that solid-liquid separation obtains enters nano-filtration unit and isolates one monovalent ion clear liquid and one dope, the TDS of monovalent ion clear liquid be the TDS of 15000 mg/L and dope be 50000 mg/L, dope is back to clean unit, clear liquid enters minimizing DTRO unit and is concentrated into the concentrated solution that TDS is 120000 mg/L, gained recycle-water reuse；Dope enters evaporative crystallization unit, and Crystallization Separation goes out to meet the sodium chloride of GB/T 5462-2003 II grade standard, Condensate reuse.
In addition to the implementation, present invention additionally comprises the technical scheme that other embodiments, all employing equivalents or equivalence substitute mode are formed, all should fall within the scope of the hereto appended claims.

Claims (7)

1. the system reclaiming sodium chloride from high slat-containing wastewater, it is characterised in that: include setting gradually
Clean unit: remove calcium, magnesium, the easy scale forming matter of silicon oxide and COD type organic in high slat-containing wastewater；
Nano-filtration unit: purifying high slat-containing wastewater, obtain monovalent ion clear liquid and dope, dope is through loop foldback clean unit；
Minimizing unit: concentrate monovalent ion clear liquid to concentrated solution, producing can the recycle-water of reuse；
Evaporative crystallization unit: to concentrated solution evaporative crystallization isolated industrial chlorinations sodium, recycling condensing water, a small amount of mother solution of outer row is back to clean unit.
The system reclaiming sodium chloride from high slat-containing wastewater the most according to claim 1, it is characterised in that: described minimizing unit is the disc tube reverse osmosis (dt-ro) DTRO used, or pole-reversing electroosmosis EDR, or the combination of aforementioned upgrading unit.
The system reclaiming sodium chloride from high slat-containing wastewater the most according to claim 1, it is characterized in that: described evaporative crystallization unit is to use the outer crystalline texture for steam, or the crystalline texture of mechanical vapor-compression, crystallizer uses forced circulation crystallizer, or draft tube baffle crystallizer.
4. the method reclaiming sodium chloride from high slat-containing wastewater, it is characterised in that: include following operation,
Purify: remove calcium, magnesium, the easy scale forming matter of silicon oxide and COD type organic in high slat-containing wastewater；
Nanofiltration: high slat-containing wastewater produces one monovalent ion clear liquid and another strand of dope by nanofiltration separation after purifying, and dope is back to cleaning procedure；
Minimizing: the monovalent ion clear liquid obtaining nanofiltration separation concentrates, is concentrated into TDS and reaches the concentrated solution of more than 90000mg/L, gained recycle-water reuse；
Evaporative crystallization: to concentrated solution evaporative crystallization isolated industrial chlorinations sodium, recycling condensing water, a small amount of mother solution of outer row is back to cleaning procedure.
The method reclaiming sodium chloride from high slat-containing wastewater the most according to claim 4, it is characterized in that: cleaning procedure uses Calx+soda, or Caustic soda+soda, or Calx+flue gas, or calcium chloride+soda, or any one combination with activated carbon aforementioned removes the easy scale forming matter of the calcium in high slat-containing wastewater, magnesium and silicon oxide, heavy metal substance and COD type organic, then using micro-filtrate membrane filtration separation brine sludge and clear liquid, clear liquid enters next step nanofiltration operation.
The method reclaiming sodium chloride from high slat-containing wastewater the most according to claim 4, it is characterised in that: minimizing is through disc tube reverse osmosis (dt-ro) DTRO, or pole-reversing electroosmosis EDR, or the combination concentration of aforementioned upgrading unit.
The method reclaiming sodium chloride from high slat-containing wastewater the most according to claim 4, it is characterised in that: evaporative crystallization unit uses the outer crystallization mode for steam, or mechanical vapor-compression crystallization mode, and crystallizer uses forced circulation crystallizer, or draft tube baffle crystallizer.
CN201610406418.1A 2016-06-12 2016-06-12 Method and system for recovering sodium chloride from high salinity wastewater Pending CN105906128A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106746128A (en) * 2017-01-17 2017-05-31 武汉致衡环境安全工程技术有限公司 Flue gas desulfurization waste-water is classified dual treatment method and system
CN107055862A (en) * 2017-01-20 2017-08-18 苏州新能环境技术股份有限公司 A kind of multistage continuous precipitation concentration point salt process
CN109437445A (en) * 2019-01-02 2019-03-08 利尔化学股份有限公司 The method that high-salt wastewater recycling recycles
CN109956604A (en) * 2017-12-22 2019-07-02 神华集团有限责任公司 Separate the method and system of monovalent salt and divalent salts in brine waste
CN110183023A (en) * 2019-06-21 2019-08-30 无锡中天固废处置有限公司 A method of recycling sodium chloride from the waste water containing DMAC, polyurethane
CN110451706A (en) * 2019-05-13 2019-11-15 上海晶宇环境工程股份有限公司 The separating technology and special equipment of high-enriched organics and salt during strong brine zero-emission
CN110818021A (en) * 2018-08-10 2020-02-21 王宇 Method for separating monovalent ions and multivalent ions in water
CN112707552A (en) * 2020-12-28 2021-04-27 赛恩斯环保股份有限公司 Method for removing calcium from high-salt and high-calcium wastewater
CN114920399A (en) * 2022-06-07 2022-08-19 安尔达技术(北京)有限责任公司 Comprehensive utilization treatment method for high-salinity wastewater

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EP1614660A1 (en) * 2004-07-09 2006-01-11 Saline Water Conversion Corporation, Riyadh - Olia Fully integrated NF-thermal seawater desalination process and equipment therefor
CN102329036A (en) * 2011-09-06 2012-01-25 江苏中圣高科技产业有限公司 High-efficiency method for recovery treatment of saliferous wastewater under zero emission through residual heat utilization
CN105565573A (en) * 2016-02-05 2016-05-11 大唐环境产业集团股份有限公司 Device and method for desulfurization waste water zero discharge treatment
CN205856230U (en) * 2016-06-12 2017-01-04 双良节能系统股份有限公司 A kind of system reclaiming sodium chloride from high slat-containing wastewater

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1614660A1 (en) * 2004-07-09 2006-01-11 Saline Water Conversion Corporation, Riyadh - Olia Fully integrated NF-thermal seawater desalination process and equipment therefor
CN102329036A (en) * 2011-09-06 2012-01-25 江苏中圣高科技产业有限公司 High-efficiency method for recovery treatment of saliferous wastewater under zero emission through residual heat utilization
CN105565573A (en) * 2016-02-05 2016-05-11 大唐环境产业集团股份有限公司 Device and method for desulfurization waste water zero discharge treatment
CN205856230U (en) * 2016-06-12 2017-01-04 双良节能系统股份有限公司 A kind of system reclaiming sodium chloride from high slat-containing wastewater

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106746128A (en) * 2017-01-17 2017-05-31 武汉致衡环境安全工程技术有限公司 Flue gas desulfurization waste-water is classified dual treatment method and system
CN106746128B (en) * 2017-01-17 2023-08-08 武汉致衡环境安全工程技术有限公司 Method and system for classifying and treating flue gas desulfurization wastewater
CN107055862A (en) * 2017-01-20 2017-08-18 苏州新能环境技术股份有限公司 A kind of multistage continuous precipitation concentration point salt process
CN109956604A (en) * 2017-12-22 2019-07-02 神华集团有限责任公司 Separate the method and system of monovalent salt and divalent salts in brine waste
CN110818021A (en) * 2018-08-10 2020-02-21 王宇 Method for separating monovalent ions and multivalent ions in water
CN109437445B (en) * 2019-01-02 2022-03-15 利尔化学股份有限公司 Method for recycling high-salinity wastewater
CN109437445A (en) * 2019-01-02 2019-03-08 利尔化学股份有限公司 The method that high-salt wastewater recycling recycles
CN110451706A (en) * 2019-05-13 2019-11-15 上海晶宇环境工程股份有限公司 The separating technology and special equipment of high-enriched organics and salt during strong brine zero-emission
CN110451706B (en) * 2019-05-13 2023-10-27 上海晶宇环境工程股份有限公司 Separation process of high-concentration organic matters and salt in zero-emission process of strong brine and special equipment
CN110183023A (en) * 2019-06-21 2019-08-30 无锡中天固废处置有限公司 A method of recycling sodium chloride from the waste water containing DMAC, polyurethane
CN110183023B (en) * 2019-06-21 2021-07-20 无锡中天固废处置有限公司 Method for recovering sodium chloride from wastewater containing DMAC (dimethylacetamide) and polyurethane
CN112707552A (en) * 2020-12-28 2021-04-27 赛恩斯环保股份有限公司 Method for removing calcium from high-salt and high-calcium wastewater
CN114920399A (en) * 2022-06-07 2022-08-19 安尔达技术(北京)有限责任公司 Comprehensive utilization treatment method for high-salinity wastewater

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