CN106186550A - Sewage recycling Zero emission device and method - Google Patents

Sewage recycling Zero emission device and method Download PDF

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Publication number
CN106186550A
CN106186550A CN201610720100.0A CN201610720100A CN106186550A CN 106186550 A CN106186550 A CN 106186550A CN 201610720100 A CN201610720100 A CN 201610720100A CN 106186550 A CN106186550 A CN 106186550A
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water
sedimentation tank
carnallite
pond
pipeline
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CN201610720100.0A
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孟广祯
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Gelante Environmental Protection Engineering (beijing) Co Ltd
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Gelante Environmental Protection Engineering (beijing) Co Ltd
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Priority to CN201610720100.0A priority Critical patent/CN106186550A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00Halides of sodium, potassium or alkali metals in general
    • C01D3/04Chlorides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D9/00Nitrates of sodium, potassium or alkali metals in general
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/18Carbonates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/46Sulfates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00Compounds of magnesium
    • C01F5/14Magnesium hydroxide
    • C01F5/22Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
    • CCHEMISTRY; METALLURGY
    • 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048Purification of waste water by evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5281Installations for water purification using chemical agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F2001/007Processes including a sedimentation step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage

Abstract

The present invention relates to sewage recycling zero-discharge technology field.Sewage recycling Zero emission device, include flocculation sediment carnallite successively, add soda and obtain precipitation of calcium carbonate, add Caustic soda and obtain magnesium hydroxide, membrane filtration, pH value regulates, ion exchange softening, advanced oxidation, biomembrane biochemistry, film filter, nanofiltration, nanofiltration trap water is added lime cream and is obtained calcium sulfate, supernatant is back to carnallite sedimentation tank, nanofiltration concentrates again through the concentration of brine concentration device through water through reverse osmosis A, brine concentration device fresh water through reverse osmosis B concentrating return-flow to brine concentration device, the dense water of brine concentration device enters crystallizing evaporator, sodium chloride and sodium nitrate is respectively obtained again through thermal release and cold separation, crystalline mother solution major part reflow treatment, fraction drying and other treatment;Reverse osmosis produced water and distilled water reuse.The present invention has reclaimed the calcium carbonate of commercialization, magnesium hydroxide, calcium sulfate, sodium chloride, sodium nitrate salt and high-quality recycle-water, and solid waste discharge is few, and operating cost is low.

Description

Sewage recycling Zero emission device and method
Technical field
The present invention relates to technical field of sewage, relate to obtaining sewage disposal recycled water, and by salt main in water The liquid zero emission method of Crystallization Separation.
Background technology
Along with the aggravation of economical activities of mankind, water resource will become the bottleneck of economic development.Therefore increasing feelings Need under condition regeneration effluent becomes the recycled water that can substitute former water;Need to realize liquid zero emission under certain situation.
Common recycled water technology is the sewage after conventional biochemical processes or the relatively low sewage of other Organic Pollutions enters Row includes that flocculation sediment, ultrafiltration, reverse-osmosis treated, currently mainly problem are owing to before entering membranous system, organic pollution processes not Deeply, organic pollutants is still within higher level, and reverse osmosis is cleaned frequently, and reverse osmosis concentrated water can not reach discharge mark Accurate.
Liquid zero emission sewage water treatment method generally comprises sewage chemical and softens and flocculation sediment, ultrafiltration, reverse osmosis, dense water The devices such as reverse osmosis, brine concentration and evaporative crystallization, wherein saline brine concentration device includes that electrodialysis, steam mechanical compression are steamed Send out device, just permeate, Membrane Materials, high pressure reverse osmosis etc..Currently mainly problem is owing to before entering membranous system, organic pollution processes Not deeply so that reverse osmosis membrane needs frequent Chemical cleaning, also due to organic pollution processes not deeply before entering membranous system, In reverse osmosis concentrated water, content of organics is too high so that dense water evaporative crystallization runs difficulty, and evaporative crystallization obtains larger amount of carnallite Carnallite mixture with organic pollution.This carnallite mixture major part is dissolved in water, deals with improperly and can again result in environment dirt Dye;Therefore this Master Mix is further processed into the highest, even needs to process as dangerous waste product.
Chinese patent application (201510522599.X) emphasis solves Organic substance interference problem in sewage zero-discharge technique, But do not reclaim difficulty soluble salt so that chemical sludge amount is too high;Sodium sulfate is obtained so that evaporative crystallization processes by evaporative crystallization Amount increases, and the sodium sulfate crystal containing water of crystallization obtained is worth almost without reuse, adds processing cost.
In common sewage, dominant cation is sodium, calcium, magnesium, and Main Anions is chloride ion, sulfate radical, nitrate anion, carbonic acid Hydrogen radical.A small amount of potassium, fluorine, phosphate radical plasma.The purpose of this sewage recycling Zero emission device and processing method seeks to handle Cation main in water and anion all reclaim and resource, reduce solid waste total amount and operating cost simultaneously.
Summary of the invention
The invention solves the problems that recycled water technology reverse osmosis is cleaned frequently, reverse osmosis concentrated water can not reach the technology of discharge standard Problem;In liquid zero emission sewage water treatment method, reverse osmosis membrane needs frequent Chemical cleaning, and dense water evaporative crystallization runs difficulty, steams Send out crystallization acquisition is the mixture of larger amount of carnallite and organic pollution, and whole system is difficult for long-term stable operation, salt Recovery ratio is low, and chemical sludge amount is big, the problem that operating cost is high.
Disclose a kind of sewage recycling zero discharge treatment device to reach the object above present invention, include a flocculation successively Agent adding set, a flocculation aid adding set, a carnallite sedimentation tank, a soda adding set, a precipitation of calcium carbonate pond, a Caustic soda Adding set, a magnesium hydrate precipitate pond, an acid adding set, a cation exchanger, an oxidant adding set, an oxidation Catalyst, a biofilm reactor and an aerator, a film filter B, a nanofiltration membrane separation device, brine concentration device, evaporation knot Brilliant device, heat separator, cold separator, mother solution drying device;Also include for by the most miscellaneous for regenerating cation exchanger return of waste water The regenerating cation exchanger return of waste water pipeline of salt sedimentation tank, for by film filter B return of waste water to carnallite sedimentation tank Film filter B return of waste water pipeline, for processing the calcium sulfate precipitation pond of nanofiltration separation device trap water, for by nanofiltration separation device Trap water is back to the nanofiltration dense water concentrate recirculation pipeline in calcium sulfate precipitation pond, for adding stone in nanofiltration separation device trap water The lime cream adding set of ash;Return for calcium sulfate precipitation pond product water being back to the calcium sulfate precipitation pond product water of carnallite sedimentation tank Flow tube road, for by the reverse osmosis B concentrate recirculation pipeline of reverse osmosis isolation device B concentrate recirculation to brine concentration device, be used for portion Point crystalline mother solution be back to vaporizer mother liquor reflux crystallizer pipeline, for by partially crystallizable mother liquor reflux to carnallite sedimentation tank Mother liquor reflux carnallite sedimentation tank pipeline;Also include multiple precipitate pressure-filteration drying device, multiple film backwash and Chemical cleaning dress Put, at least one regenerating cation exchanger device, multiple elevator pump and automaton.
A film filter A is also included and for by film between described magnesium hydrate precipitate pond and described cation exchanger Filter A return of waste water is to the film filter A return of waste water pipeline of carnallite sedimentation tank.
A reverse osmosis isolation device A, this reverse osmosis is also included between described nanofiltration membrane separation device and described brine concentration device The dense water of separator A enters brine concentration device, and its fresh water is recycle-water.
The dilution pipeline of an interpolation recycle-water is also included between described cation exchanger and oxidation catalyst.
Described brine concentration device is electrodialysis plant, steam mechanical recompression evaporator, multi-effect evaporator, single effect evaporator In at least one.
Described crystallizing evaporator is steam mechanical recompression crystallizing evaporator, multiple-effect evaporation crystallizing evaporator, single-action crystallization At least one in crystallizing evaporator.
The most in order to achieve the above object, the present invention discloses and a kind of uses described sewage recycling zero discharge treatment device Sewage recycling Zero discharge treatment method, add flocculant and flocculation aid adding set including former water through flocculant adding apparatus The a small amount of indissoluble carnallite comprising phosphate and organic pollution adding flocculation aid generation precipitates in carnallite sedimentation tank, this indissoluble Carnallite forms solid waste;Carnallite sedimentation tank produces water and adds micro-excess soda (sodium carbonate) through soda adding set, generation Calcium carbonate precipitates in precipitation of calcium carbonate pond, obtains calcium carbonate;Precipitation of calcium carbonate pond is produced water and is added Caustic soda through Caustic soda adding set (sodium hydroxide), to pH=11-12, the magnesium hydroxide of generation precipitates in magnesium hydrate precipitate pond, obtains magnesium hydroxide;Hydrogen-oxygen Change magnesium precipitate pond product water adds acid for adjusting pH value through acid adding set and softens to 5-8, entrance cation exchanger, and cation is handed over Parallel operation regenerative wastewater is through regenerating cation exchanger return of waste water pipeline backflow carnallite sedimentation tank;Cation exchanger produces in water logical Peroxide agent adding set adds oxidant, enters oxidation catalyst, improves giving birth to of organic pollutant by oxidation reaction The property changed;Oxidation catalyst water outlet enters biofilm reactor, and the biochemical degradation reaction of organic pollution, biofilm reactor occur Producing water to filter through film filter B, film filter B filters the waste water produced and flows to carnallite through film filter B return of waste water back of pipeline Sedimentation tank;Film filter B produces water and enters nanofiltration separation device, and nanofiltration separation device trap water adds Calx through lime cream adding set Breast, the calcium sulfate of generation precipitates in calcium sulfate precipitation pond, obtains calcium sulfate, and water is produced through calcium sulfate precipitation pond in calcium sulfate precipitation pond Reflux line is back to carnallite sedimentation tank (1) nanofiltration separation device and enters brine concentration device through water;Brine concentration device fresh water is through anti- Infiltration B processes and obtains recycle-water, and the dense water of reverse osmosis B flow to brine concentration device through reverse osmosis B concentrate recirculation back of pipeline and enters water;Saline The dense water that concentrator produces enters crystallizing evaporator, and the steam that crystallizing evaporator produces obtains recycle-water through heat reclamation device, control Evaporation and concentration degree processed make sodium nitrate in crystallizing evaporator in hot mother liquor close to saturated, by this hot mother liquor through heat separator separate Obtain sodium chloride, the mother solution cooling that heat separator separates, causes sodium nitrate crystallization process, separates through cold separator, obtain nitric acid Sodium;The mother solution major part separated through cold separator is back to crystallizing evaporator continuation evaporation knot through mother liquor reflux crystallizer pipeline Crystalline substance, so circulates;When mother solution organic pollution and other impurity effect sodium chloride and sodium nitrate purity, partial mother liquid is through mother solution Backflow carnallite sedimentation tank back of pipeline flows to carnallite sedimentation tank, eliminates wherein most by carnallite sedimentation tank and subsequent technique thereof dirty Dye thing;In order to be further ensured that sodium chloride and sodium nitrate purity, fraction mother solution is dried through mother solution exsiccator, produces mother solution mummification Product.
Between described magnesium hydrate precipitate pond and described acid adding set, also include that a film filter A, film filter A produce Entering cation exchanger after water acid adding, film filter A waste water flows to carnallite precipitation through film filter A return of waste water back of pipeline Pond.
A reverse osmosis isolation device A, reverse osmosis isolation device A is had between described nanofiltration membrane separation device and described brine concentration device Fresh water is recycle-water, and the dense water of reverse osmosis isolation device A enters brine concentration device.
Repeat described interpolation oxidant and described biochemical degradation reacts at least one times.
Recycle-water is added, by salinity by dilution pipeline between described cation exchanger and described oxidation catalyst Regulation is to less than 2%.
It is stable that beneficial effects of the present invention includes degrading majority of organic pollutants, membranous system and vaporizer, returns Receive salt purity high;Calcium carbonate, magnesium hydroxide, calcium sulfate, sodium chloride, five kinds of salts of sodium nitrate are reclaimed, by common in former water Leading ion all reclaim, solid waste substantially reduces;Obtain high-quality recycle-water;Sulfate radical is precipitated, reduces dense salt Water evaporates, and reduces operating cost.
Accompanying drawing explanation
Fig. 1 sewage recycling treatment method schematic flow sheet.
Wherein: 1. carnallite sedimentation tank, 2. precipitation of calcium carbonate pond, 3. magnesium hydrate precipitate pond, 4. film filter A, 5. sun from Sub-exchanger, 6. oxidation catalyst, 7. biofilm reactor, 8. film filter B, 9. nanofiltration membrane separation device, 10. calcium sulfate precipitation Pond, 11. reverse osmosis membrane separator A, 12. brine concentration devices, 13. reverse osmosis concentration device B, 14. evaporated crystallization devices, 15. heat point From device, 16. cold separators, 17. mother solution drying devices;
110. film filter A return of waste water pipelines, 120. regenerating cation exchanger return of waste water pipelines, 130. membrane filtrations Device B return of waste water pipeline, 140. nanofiltration concentrate recirculation pipelines, water reflux line, 160. reverse osmosis B are produced in 150. calcium sulfate precipitation ponds Concentrate recirculation pipeline, 170. mother liquor reflux crystallizer pipelines, 180. mother liquor reflux carnallite sedimentation tank pipelines;
210. flocculant adding apparatus, 220. flocculation aid adding sets, 230. soda adding sets, 240. Caustic sodas add dress Put, 250. acid adding sets, 260. oxidant adding sets, 270. aerators, 280. lime cream adding sets;
300. former water, 310. recycled waters, 320. calcium carbonate, 330. magnesium hydroxide, 340. calcium sulfate, 350. sodium chloride, 360. sodium nitrate;
410. indissoluble carnallites, 420. mother solution mummification products.
Detailed description of the invention
As it is shown in figure 1, sewage recycling zero discharge treatment device, include a flocculant adding apparatus (210) successively, one help Solidifying agent adding set (220), a carnallite sedimentation tank (1), a soda adding set (230), a precipitation of calcium carbonate pond (2), a fire Alkali adding set (240), a magnesium hydrate precipitate pond (3), acid adding set (250), a cation exchanger (5), an oxygen Agent adding set (260), oxidation catalyst (6), a biofilm reactor (7) and an aerator (270), a film filter B (8), a nanofiltration membrane separation device (9), brine concentration device (12), evaporated crystallization device (14), heat separator (15), cold separator (16), mother solution drying device (17);Also include for cation exchanger (5) regenerative wastewater is back to carnallite sedimentation tank (1) Regenerating cation exchanger return of waste water pipeline (120), for by film filter B (8) return of waste water to carnallite sedimentation tank (1) Film filter B return of waste water pipeline (130), it is used for processing the calcium sulfate precipitation pond (10) of nanofiltration separation device (9) trap water, being used for Nanofiltration separation device (9) trap water is back to the nanofiltration dense water concentrate recirculation pipeline (140) in calcium sulfate precipitation pond (10), for Nanofiltration separation device (9) trap water is added the lime cream adding set (280) of Calx;For calcium sulfate precipitation pond (10) are produced water Water reflux line (150) is produced, for by dense for reverse osmosis isolation device B (13) in the calcium sulfate precipitation pond being back to carnallite sedimentation tank (1) Water is back to reverse osmosis B concentrate recirculation pipeline (160) of brine concentration device (12), is used for partially crystallizable mother liquor reflux to evaporation Mother liquor reflux crystallizer pipeline (170) of device, for partially crystallizable mother liquor reflux is miscellaneous to the mother liquor reflux of carnallite sedimentation tank (1) Salt sedimentation tank pipeline (180);Also include multiple precipitate pressure-filteration drying device, multiple film backwash and chemically-cleaning device, at least One regenerating cation exchanger device, multiple elevator pump and automaton.
In order to improve the regeneration period of cation exchanger, magnesium hydrate precipitate pond (3) and cation exchanger (5) it Between also include that a film filter A (4) and is for by the film filter of film filter A (4) return of waste water to carnallite sedimentation tank (1) A return of waste water pipeline (110).
Described film filter A (4) is in cross-current type intrinsic pressure tubular membrane filter, cross-current type intrinsic pressure capillary-pipe film filter At least one.Described film filter B is the one in all kinds of ultrafiltration or microfiltration.
When former water salinity is less than 2%, between nanofiltration membrane separation device (9) and brine concentration device (12), there is a reverse osmosis Separator A (11), this reverse osmosis isolation device A (11) dense water enters brine concentration device (12), and its fresh water is recycle-water (310).
When former water salinity is more than 2%, it is characterised in that between cation exchanger (5) and oxidation catalyst (6) There is the dilution pipeline (190) of interpolation recycle-water (310), salinity regulation is beneficial to subsequent bio film reaction between 1-2% The reaction efficiency of device (7).
Described oxidant is ozone, and oxidant adding set (260) is ozonator, ozone adds facility and ozone is urged Change bed.
Described oxidant is hydrogen peroxide, and oxidant adding set (260) is that facility is added in hydrogen peroxide metering.
Described brine concentration device (12) is electrodialysis (ED) device, steam mechanical recompression evaporator, multi-effect evaporator, list At least one in single-effect evaporator.
Described crystallizing evaporator is steam mechanical recompression crystallizing evaporator, multiple-effect evaporation crystallizing evaporator, single-action crystallization At least one in crystallizing evaporator.
Described mother solution exsiccator is the one in spray dryer, evaporation pond.
Use the sewage recycling Zero discharge treatment method of described sewage recycling zero discharge treatment device, including former water (300) comprising of flocculation aid generation is added through flocculant adding apparatus (210) interpolation flocculant and flocculation aid adding set (220) A small amount of indissoluble carnallite (410) of phosphate and organic pollution is precipitation, this indissoluble carnallite (410) shape in carnallite sedimentation tank (1) Become solid waste;Carnallite sedimentation tank (1) produces water and adds micro-excess soda (sodium carbonate) through soda adding set (230), generates Calcium carbonate (320) precipitation in precipitation of calcium carbonate pond (2), obtain calcium carbonate (320);Water is produced through fire in precipitation of calcium carbonate pond (2) Alkali adding set (240) adds Caustic soda (sodium hydroxide) and sinks at magnesium hydroxide to pH=11-12, the magnesium hydroxide (330) of generation In pond, shallow lake (3), precipitation, obtains magnesium hydroxide (330);Magnesium hydrate precipitate pond (3) is produced water and is adjusted through acid adding set (250) acid adding Joint pH value, to 5-8, enters cation exchanger (5) and softens, and cation exchanger (5) regenerative wastewater is through cation exchanger Regenerative wastewater reflux line (120) backflow carnallite sedimentation tank (1);Cation exchanger (5) produces in water and adds dress by oxidant Put (260) and add oxidant, enter oxidation catalyst (6), improved the biodegradability of organic pollutant by oxidation reaction;Oxygen Change catalyst (6) water outlet and enter biofilm reactor (7), the biochemical degradation reaction of organic pollution, biofilm reactor occur (7) producing water to filter through film filter B, film filter B filters the waste water produced and returns through film filter B return of waste water pipeline (130) Flow to carnallite sedimentation tank (1);Film filter B produces water and enters nanofiltration separation device (9), and nanofiltration separation device (9) trap water is through lime cream Adding set (280) adds lime cream, and the calcium sulfate (340) of generation is precipitation in calcium sulfate precipitation pond (10), obtains calcium sulfate (340), calcium sulfate precipitation pond (10) are produced water and are back to carnallite sedimentation tank (1), nanofiltration through calcium sulfate precipitation pond reflux line (150) Separator (9) enters brine concentration device (12) through water;Brine concentration device (12) fresh water processes through reverse osmosis B (13) and obtains reuse Water (310), reverse osmosis B (13) dense water is back to brine concentration device (12) through reverse osmosis B concentrate recirculation pipeline (160) and enters water;Salt The dense water that water concentrator (12) produces enters crystallizing evaporator (14), and the steam that crystallizing evaporator (14) produces is through heat reclamation device Obtain recycle-water (310), control evaporation and concentration degree make sodium nitrate in crystallizing evaporator (12) in hot mother liquor close to saturated, general This hot mother liquor, through heat separator (15) isolated sodium chloride (350), the mother solution cooling that heat separator (15) separates, causes nitric acid Sodium crystallization process, separates through cold separator (16), obtains sodium nitrate (360);Through the mother solution major part that cold separator (16) separates It is back to crystallizing evaporator (14) through mother liquor reflux crystallizer pipeline (170) and continues evaporative crystallization, so circulate;When mother solution is organic When pollutant and other impurity effect sodium chloride (350) and sodium nitrate (360) purity, partial mother liquid precipitates through mother liquor reflux carnallite Pond pipeline (180) is back to carnallite sedimentation tank (1), eliminates wherein most by carnallite sedimentation tank (1) and subsequent technique thereof dirty Dye thing;In order to be further ensured that sodium chloride (350) and sodium nitrate (360) purity, fraction mother solution is done through mother solution exsiccator (17) Dry, produce mother solution mummification product (420).
In order to improve the regeneration period of cation exchanger, magnesium hydrate precipitate pond (3) and acid adding set (250) it Between also include a film filter A (4), film filter A (4) to produce after water acid adding entering cation exchanger (5), film filter A (4) Waste water is back to carnallite sedimentation tank (1) through film filter A return of waste water pipeline (110).
When former water salinity is less than 2%, between nanofiltration membrane separation device (9) and brine concentration device (12), there is a reverse osmosis Separator A (11), reverse osmosis isolation device A (11) fresh water is recycle-water (310), and reverse osmosis isolation device A (11) dense water enters saline Concentrator (12).
When in former water, persistent organic pollutants content is higher, repeat to add oxidant and biochemical degradation reaction at least Secondary.
When former water salinity is more than 2%, by dilution pipeline between cation exchanger (5) and oxidation catalyst (190) add recycle-water (310), salinity regulation to less than 2% is beneficial to the reaction effect of subsequent bio membrane reactor (7) Rate.

Claims (11)

1. a sewage recycling zero discharge treatment device, it is characterised in that include successively a flocculant adding apparatus (210), one Flocculation aid adding set (220), a carnallite sedimentation tank (1), a soda adding set (230), a precipitation of calcium carbonate pond (2), one Caustic soda adding set (240), a magnesium hydrate precipitate pond (3), one acid adding set (250), a cation exchanger (5), one Oxidant adding set (260), oxidation catalyst (6), a biofilm reactor (7) and an aerator (270), a membrane filtration Device B (8), a nanofiltration membrane separation device (9), brine concentration device (12), evaporated crystallization device (14), heat separator (15), cold separation Device (16), mother solution drying device (17);Also include for cation exchanger (5) regenerative wastewater is back to carnallite sedimentation tank (1) Regenerating cation exchanger return of waste water pipeline (120), for by film filter B (8) return of waste water to carnallite sedimentation tank (1) Film filter B return of waste water pipeline (130), be used for processing the calcium sulfate precipitation pond (10) of nanofiltration separation device (9) trap water, use In nanofiltration separation device (9) trap water being back to the nanofiltration dense water concentrate recirculation pipeline (140) in calcium sulfate precipitation pond (10), it is used for The lime cream adding set (280) of Calx is added in nanofiltration separation device (9) trap water;For calcium sulfate precipitation pond (10) are produced Water is back to the calcium sulfate precipitation pond of carnallite sedimentation tank (1) and produces water reflux line (150), for by reverse osmosis isolation device B (13) Concentrate recirculation to brine concentration device (12) reverse osmosis B concentrate recirculation pipeline (160), for by partially crystallizable mother liquor reflux to steaming Send out mother liquor reflux crystallizer pipeline (170) of device, for by the mother liquor reflux of partially crystallizable mother liquor reflux to carnallite sedimentation tank (1) Carnallite sedimentation tank pipeline (180);Also include multiple precipitate pressure-filteration drying device, multiple film backwash and chemically-cleaning device, extremely A few regenerating cation exchanger device, multiple elevator pump and automaton.
Sewage recycling zero discharge treatment device the most according to claim 1, it is characterised in that in magnesium hydrate precipitate pond (3) and also include between cation exchanger (5) that a film filter A (4) and is for arriving film filter A (4) return of waste water Film filter A return of waste water pipeline (110) of carnallite sedimentation tank (1).
Sewage recycling zero discharge treatment device the most according to claim 1, it is characterised in that in nanofiltration membrane separation device (9) And having reverse osmosis isolation device A (11) between brine concentration device (12), this reverse osmosis isolation device A (11) dense water enters brine concentration Device (12), its fresh water is recycle-water (310).
Sewage recycling zero discharge treatment device the most according to claim 1, it is characterised in that exchange in described cation The dilution pipeline (190) of an interpolation recycle-water (310) is also included between device (5) and described oxidation catalyst (6).
Sewage recycling zero discharge treatment device the most according to claim 1, it is characterised in that described brine concentration device (12) it is at least one in electrodialysis (ED) device, steam mechanical recompression evaporator, multi-effect evaporator, single effect evaporator.
Sewage recycling zero discharge treatment device the most according to claim 1, it is characterised in that described crystallizing evaporator is At least one in steam mechanical recompression crystallizing evaporator, multiple-effect evaporation crystallizing evaporator, single-action crystallization and evaporation crystallizer.
7. a sewage recycling Zero discharge treatment method, it is characterised in that use the sewage money described in claim 1,4,5 or 6 Source zero discharge treatment device, adds flocculant and flocculation aid interpolation dress including former water (300) through flocculant adding apparatus (210) Put (220) and add a small amount of indissoluble carnallite (410) comprising phosphate and organic pollution of flocculation aid generation at carnallite sedimentation tank (1) precipitation in, this indissoluble carnallite (410) forms solid waste;Carnallite sedimentation tank (1) produces water through soda adding set (230) Adding micro-excess soda (sodium carbonate), the calcium carbonate (320) of generation is precipitation in precipitation of calcium carbonate pond (2), obtains calcium carbonate (320);Precipitation of calcium carbonate pond (2) is produced water and is added Caustic soda (sodium hydroxide) to pH=11-12, life through Caustic soda adding set (240) The magnesium hydroxide (330) become is precipitation in magnesium hydrate precipitate pond (3), obtains magnesium hydroxide (330);Magnesium hydrate precipitate pond (3) produce water and add acid for adjusting pH value to 5-8 through acid adding set (250), enter cation exchanger (5) and soften, cation Exchanger (5) regenerative wastewater is through regenerating cation exchanger return of waste water pipeline (120) backflow carnallite sedimentation tank (1);Cation Exchanger (5) produces in water and adds oxidant by oxidant adding set (260), enters oxidation catalyst (6), logical peroxidation The biodegradability of organic pollutant should be improved;Oxidation catalyst (6) water outlet enters biofilm reactor (7), and organic dirt occurs The biochemical degradation reaction of dye thing, biofilm reactor (7) produces water and filters through film filter B, and film filter B filters the waste water produced It is back to carnallite sedimentation tank (1) through film filter B return of waste water pipeline (130);Film filter B produces water and enters nanofiltration separation device (9), nanofiltration separation device (9) trap water adds lime cream through lime cream adding set (280), and the calcium sulfate (340) of generation is at sulfur Precipitation in acid calcium deposit pond (10), obtains calcium sulfate (340), and calcium sulfate precipitation pond (10) produce water through calcium sulfate precipitation pond return duct Road (150) is back to carnallite sedimentation tank (1), and nanofiltration separation device (9) enters brine concentration device (12) through water;Brine concentration device (12) fresh water processes through reverse osmosis B (13) and obtains recycle-water (310), and reverse osmosis B (13) dense water is through reverse osmosis B concentrate recirculation pipeline (160) it is back to brine concentration device (12) and enters water;The dense water that brine concentration device (12) produces enters crystallizing evaporator (14), evaporation The steam that crystallizer (14) produces obtains recycle-water (310) through heat reclamation device, controls evaporation and concentration degree and sodium nitrate is being steamed Send out in crystallizer (12) interior hot mother liquor close to saturated, by this hot mother liquor through heat separator (15) isolated sodium chloride (350), heat The mother solution cooling that separator (15) separates, causes sodium nitrate crystallization process, separates through cold separator (16), obtain sodium nitrate (360);The mother solution major part separated through cold separator (16) is back to crystallizing evaporator through mother liquor reflux crystallizer pipeline (170) (14) continue evaporative crystallization, so circulate;When mother solution organic pollution and other impurity effect sodium chloride (350) and sodium nitrates (360), during purity, partial mother liquid is back to carnallite sedimentation tank (1) through mother liquor reflux carnallite sedimentation tank pipeline (180), passes through carnallite Sedimentation tank (1) and subsequent technique thereof eliminate wherein most pollutant;In order to be further ensured that sodium chloride (350) and sodium nitrate (360) purity, fraction mother solution is dried through mother solution exsiccator (17), produces mother solution mummification product (420).
Sewage recycling Zero discharge treatment method the most according to claim 7, it is characterised in that sink at described magnesium hydroxide Also include that a film filter A (4), film filter A (4) produce water acid adding between pond, shallow lake (3) and described acid adding set (250) laggard Entering cation exchanger (5), film filter A (4) waste water is back to carnallite precipitation through film filter A return of waste water pipeline (110) Pond (1).
Sewage recycling Zero discharge treatment method the most according to claim 7, it is characterised in that at described nanofiltration membrane separation Reverse osmosis isolation device A (11), reverse osmosis isolation device A (11) fresh water is had to be back between device (9) and described brine concentration device (12) With water (310), reverse osmosis isolation device A (11) dense water enters brine concentration device (12).
10. according to the sewage recycling Zero discharge treatment method described in claim 7,8 or 9, it is characterised in that repeat to add oxygen Agent and biochemical degradation react at least one times.
11. according to the sewage recycling Zero discharge treatment method described in claim 7,8,9 or 10, it is characterised in that at described sun Add recycle-water (310) by dilution pipeline (190) between ion exchanger (5) and described oxidation catalyst, salinity is adjusted Joint is to less than 2%.
CN201610720100.0A 2016-08-25 2016-08-25 Sewage recycling Zero emission device and method Pending CN106186550A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107720782A (en) * 2017-10-20 2018-02-23 侯新春 A kind of technique and system for use in carrying for dividing salt preparing potassium sulfate from high-salt wastewater
CN109851107A (en) * 2019-03-22 2019-06-07 盛隆资源再生(无锡)有限公司 A method of Nacl effluent resource will be mixed using membrane technology

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107720782A (en) * 2017-10-20 2018-02-23 侯新春 A kind of technique and system for use in carrying for dividing salt preparing potassium sulfate from high-salt wastewater
CN109851107A (en) * 2019-03-22 2019-06-07 盛隆资源再生(无锡)有限公司 A method of Nacl effluent resource will be mixed using membrane technology

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