CN109437444A - Deposition vanadium mother liquid and wash water processing equipment for recycling and its method - Google Patents

Deposition vanadium mother liquid and wash water processing equipment for recycling and its method Download PDF

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CN109437444A
CN109437444A CN201811632251.6A CN201811632251A CN109437444A CN 109437444 A CN109437444 A CN 109437444A CN 201811632251 A CN201811632251 A CN 201811632251A CN 109437444 A CN109437444 A CN 109437444A
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water
high ammonia
nitrogen wastewater
precipitation
vanadium
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CN109437444B (en
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张博
戚可卓
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Jiangsu Zhuo Bo Environmental Protection Technology 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes

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

Abstract

The characteristics of deposition vanadium mother liquid of the present invention and wash water processing equipment for recycling and its method are the high ammonia nitrogen brine wastes for deposition vanadium mother liquid and wash water containing heavy metal ion, high strength ammonium-chloride, high concentration sodium chloride and a small amount of metavanadic acid root；To the Centrifuge filtrate of low concentration, first with electrolytic oxidation and ultrafiltration heavy-metal ion removal and suspended matter, reduce COD value, secondly resin adsorption metavanadic acid radical ion is utilized, recycle vanadium resource, concentration decrement and purification finally are carried out using reverse osmosis, concentrated water decrement goes subsequent evaporation, the production water reuse of purification；And to the precipitation high ammonia-nitrogen wastewater of high concentration, most of calcium ion is precipitated first with soda ash, utilize electrolytic oxidation and ultrafiltration heavy-metal ion removal and suspended matter, reduce COD value, secondly resin adsorption metavanadic acid radical ion is utilized, vanadium resource is recycled, finally isolates ammonium chloride and sodium chloride using evaporative crystallization, it is back to use vanadium extraction production, condensed water is also able to reuse；Deposition vanadium mother liquid and wash water recycling treatment are achieved the purpose that.

Description

Deposition vanadium mother liquid and wash water processing equipment for recycling and its method
Technical field
The present invention relates to deposition vanadium mother liquids and wash water processing equipment for recycling and its method, belong to Industrial Wastewater Treatment Technical field.
Background technique
Vanadium is a kind of transition elements, atomic number 23, atomic weight 50.9.Vanadium is that have body-centered cubic in silver grey non-ferrous metal Structure, 1890 ± 10 DEG C of fusing point, 3380 DEG C of boiling point.Vanadium possesses good physical property, stable chemical property and catalytic activity, It is widely used in the fields such as metallurgy, steel, chemical industry, building materials, dyestuff, battery.
It is vanadium titano-magnetite and bone coal in the primary raw material of China, vanadium extraction, and the bone coal reserves in China are very rich, extensively It is distributed in the ground such as Hunan, Hubei, Zhejiang, Jiangxi, Guangdong, Guangxi, Guizhou, Anhui, Henan, Shaanxi, Gansu.Vanadium master in bone coal To exist with trivalent, most process for extracting vanadium will first be oxidized to 5 valences, be dissolved out with sodium metavanadate, ammonium chloride precipitation is then utilized, Ammonium metavanadate is generated, vanadic anhydride can also be made with deamination.Currently, extracting vanadium from stone coal main technique has: low sodium roasts water logging work Skill, calcium salt baking acid immersion technique, is exempted to roast direct dilute sulfuric acid technique blank baking acid immersion technique.
Here the vanadium extraction of water logging technique, production process are as follows: " ore is crushed to 0 .25 mm or less are roasted mainly for low sodium → doping be uniformly mixed → molding balling-up → reverberatory furnace oxidizing roasting → defibrination water logging → separation of solid and liquid → ion exchange → Loaded resin desorption → stripping liquid removal of impurities → ammonium metavanadate precipitate/dehydration → deamination/vanadic anhydride product ".It is generated heavy Vanadium mother liquid (also referred to as precipitation high ammonia-nitrogen wastewater) and wash water (also referred to as Centrifuge filtrate) are a kind of containing heavy metal ion, high concentration The high ammonia nitrogen brine waste of ammonium chloride, high concentration sodium chloride and a small amount of metavanadic acid root, cannot such as be handled well, not only can be tight Heavily contaminated environment also wastes nitrogen and vanadium resource.The precipitation that existing part is generated for the roasting water logging technique vanadium extraction of low sodium at present is useless The patent of water handling reclamation, such as method of 201210130522.4 Leaching of Vanadium from Vanadium slag high-salt wastewater resource utilizations, main technique are " vanadium extraction high-salt wastewater adds alkali removing calcium and magnesium and metal impurities ion, alkali ammonia still process, acid absorption ammonia, evaporative crystallization is further added to go out ammonium Salt, deamination waste water re-evaporation crystallize out sodium salt, recycling condensing water "；He is using first ammonia still process, and then acid absorbs ammonia, evaporative crystallization Ammonium salt out, then distilled ammonia wastewater evaporative crystallization is gone out into sodium salt, there are 3 evaporation processes here, operating cost is too high, and unrecovered inclined vanadium Acid group, and waste vanadium resource.A kind of processing method of vanadium wastewater of another patent 201010574183.X, main technique are " vanadium wastewater add alkali removing heavy metals, improve pH by ammonium ion be converted into ammonia, ammonia nitrogen seperation film deamination, sulfuric acid absorption output sulphur ammonium, Reverse osmosis concentration goes out sodium sulphate, produces water reuse after deamination；First with film deamination, sulfuric acid absorption goes out sulphur ammonium, then sodium sulphate is concentrated out, Also unrecovered metavanadic acid root.It is desirable to develop a kind of new deposition vanadium mother liquid and wash water resource treatment technique.
Summary of the invention
Proposed by the present invention is a kind of deposition vanadium mother liquid and wash water processing equipment for recycling and its method, and purpose is intended to be directed to The deposition vanadium mother liquid (precipitation high ammonia-nitrogen wastewater) and wash water (Centrifuge filtrate) this one kind that low sodium roasting water logging vanadium extraction generates are containing a huge sum of money The high ammonia nitrogen brine waste for belonging to ion, high strength ammonium-chloride, high concentration sodium chloride and a small amount of metavanadic acid root, deals with improperly not only The problem of would seriously pollute the environment, also wasting nitrogen and vanadium resource.To the Centrifuge filtrate of low concentration, first with electrolytic oxidation with Ultrafiltration heavy-metal ion removal and suspended matter reduce COD value, secondly utilize resin adsorption metavanadic acid radical ion, recycle vanadium resource, Concentration decrement and purification finally are carried out using reverse osmosis, concentrated water decrement goes subsequent evaporation, the production water reuse of purification；Before processing, The COD value of Centrifuge filtrate is 50~100mg/L, V5+(vanadium ion) value is 10~60mg/L, TDS value be 10000~ 20000mg/L, after processing, COD value is 10~20mg/L, and the removal rate of COD reaches 80%, V5+(vanadium ion) value is 1~6mg/L, The rate of recovery of vanadium ion reaches 90%, and the TDS value of concentrated water is 50000~100000mg/L, concentrates 4~6.6 times, produces the TDS of water Value is 100~200mg/L, produces water desalination rate and reaches 99%；And to the precipitation high ammonia-nitrogen wastewater of high concentration, it is heavy first with soda ash Most of calcium ion and the heavy metal ion of forming sediment reduce COD using electrolytic oxidation and ultrafiltration heavy-metal ion removal and suspended matter Secondly value utilizes resin adsorption metavanadic acid radical ion, recycle vanadium resource, finally isolate ammonium chloride and chlorination using evaporative crystallization Sodium, is back to use vanadium extraction production, and condensed water is also able to reuse；Before processing, the Ca of precipitation high ammonia-nitrogen wastewater2+(calcium ion) value is 100 ~800mg/L, COD value are 500~1000mg/L, V5+(vanadium ion) value is 100~600mg/L, after processing, Ca2+(calcium ion) Value≤40mg/L, Ca2+The removal rate of (calcium ion) reaches 60~95%, and COD value is 60~150mg/L, and the removal rate of COD reaches 85~88%, V5+(vanadium ion) value is≤10mg/L, the rate of recovery >=90% of vanadium ion；Deposition vanadium mother liquid and wash water recycling are reached The purpose of processing.
Technical solution of the invention: deposition vanadium mother liquid and wash water processing equipment for recycling, structure include centrifugation machine filter Liquid pretreatment system PTS1, Centrifuge filtrate resins exchange system RS1, counter-infiltration system ROS, precipitation high ammonia-nitrogen wastewater pretreatment System PTS2, precipitation high ammonia-nitrogen wastewater resins exchange system RS2, evaporation and crystallization system VCS, vanadium stripping liquid storage send system VLS；Its Middle Centrifuge filtrate CMFL is connected to Centrifuge filtrate pretreatment system PTS1Water inlet, utilize Centrifuge filtrate pretreatment system PTS1The heavy metal ion in Centrifuge filtrate is removed, COD value is reduced to < 20mg/L；Centrifuge filtrate pretreatment system PTS1Backwash water out send out Centrifuge filtrate hyperfiltration reverse-rinsing drain SW to precipitation high ammonia-nitrogen wastewater pretreatment system PTS2It is anti- Wash water import, Centrifuge filtrate pretreatment system PTS1Water outlet and Centrifuge filtrate resins exchange system RS1Water inlet phase It connects, utilizes Centrifuge filtrate resins exchange system RS1Adsorb the metavanadic acid radical ion in Centrifuge filtrate, Centrifuge filtrate resin Exchange system RS1The storage of liquid outlet and vanadium stripping liquid send the 1# inlet of system VLS to connect, the storage of vanadium stripping liquid send system VLS's Liquid outlet sends out vanadium stripping liquid (sodium metavanadate) VL, goes to the precipitation pond of vanadium extraction production system to carry out precipitation again, reaches recycling vanadium The purpose of resource；Centrifuge filtrate resins exchange system RS1Water outlet connect with the water inlet of counter-infiltration system ROS, utilize Counter-infiltration system ROS will be pre-processed and decrement be concentrated with the Centrifuge filtrate after adsorption of vanadium, is concentrated 4~6.6 times, its TDS is concentrated To 50000~100000mg/L, to reduce the expense of subsequent evaporation crystallization；Send out reverse osmosis in the concentrated water outlet of counter-infiltration system ROS The 2# concentrated water import of saturating concentrated water ROCW to evaporation and crystallization system VCS, and counter-infiltration system ROS produces TDS≤200mg/L of water, it is full Sufficient reuse requirement, the water outlet of counter-infiltration system ROS send out recycle-water RUW；Precipitation high ammonia-nitrogen wastewater SVWW is connected to the high ammonia of precipitation Nitrogen waste water pretreatment system PTS21# water inlet, utilize precipitation high ammonia-nitrogen wastewater pretreatment system PTS2Remove the high ammonia nitrogen of precipitation COD value is reduced to≤150mg/L, Ca by the heavy metal ion in waste water2+(calcium ion) is reduced to≤40mg/L；The high ammonia of precipitation Nitrogen waste water pretreatment system PTS2Mud mouth send out mud cake SC, precipitation high ammonia-nitrogen wastewater pretreatment system PTS2Water outlet with Precipitation high ammonia-nitrogen wastewater resins exchange system RS2Water inlet connect, utilize precipitation high ammonia-nitrogen wastewater resins exchange system RS2It inhales Metavanadic acid radical ion in attached precipitation high ammonia-nitrogen wastewater, precipitation high ammonia-nitrogen wastewater resins exchange system RS2Liquid outlet and vanadium solution Imbibition storage send the 2# inlet of system VLS to connect；Precipitation high ammonia-nitrogen wastewater resins exchange system RS2Water outlet and evaporative crystallization The inlet of system VCS connects, will be by pre-processing and the precipitation high ammonia-nitrogen wastewater after adsorption of vanadium using evaporation and crystallization system VCS Evaporative crystallization simultaneously isolates the ammonium chloride of purity >=90% and the common salt of purity >=98%, all meets the reuse requirement to salt, Meanwhile evaporative crystallization generates TDS value≤200mg/L of condensed water, also meets reuse requirement；Evaporation and crystallization system VCS's goes out salt Mouth sends out crystal salt (ammonium chloride, common salt) Salt.As a result, deposition vanadium mother liquid and wash water processing equipment for recycling are by Centrifuge filtrate It is handled respectively with precipitation high ammonia-nitrogen wastewater, has not only recycled valuable metavanadic acid radical ion, recycled ammonium chloride, chlorination It receives, will also produce water and recycling condensing water has arrived in the production of vanadium extraction, achieved the purpose that deposition vanadium mother liquid and wash water recycling treatment.
Here, OH(hydroxy radical is generated for using electrolytic oxidation) and ClO?Strong oxidizers such as (hypochlorites) come Organic pollutant in oxidation reduces COD value.Its basic chemical equation is as follows:
2H2O → 2·OH + 2H+ + 2e?(1)
Organic matter+OH → CO2↑ + H2O (2)
Cl2 + H2O → ClO? + H+ + Cl?(3)
Organic matter+ClO- → CO2↑ + H2O (4)
Divide salt for evaporative crystallization thermal method, is the difference that sodium chloride Yu ammonium chloride saturated concentration and temperature relation is utilized, chlorination The solubility table of sodium and ammonium chloride is as follows:
The solubility table (unit: g/100ml) of sodium chloride and ammonium chloride
Can be clearly seen from table, the saturated concentration variation with temperature of sodium chloride is little, and the saturated concentration of ammonium chloride with The variation of temperature is very big, the difference that both can use, for example utilizes forced-circulation evaporation, in 100 DEG C of ceaselessly circulating and evaporatings Concentration, Crystallization Separation go out sodium chloride, and when ammonium chloride is close to when being saturated, using cooling to 20 DEG C~40 DEG C, Crystallization Separation goes out chlorination Then ammonium enters back into the evaporation and crystal process of next evaporation and concentration, Crystallization Separation, in this way, available sodium chloride purity >=98%, purity of ammonia chloride >=90%.
Deposition vanadium mother liquid and wash water recycling processing method, include the following steps:
1) by Centrifuge filtrate pretreatment system, by the heavy metal ion and suspended matter removal, COD value drop in Centrifuge filtrate As low as < 20mg/L；
2) by Centrifuge filtrate resins exchange system, the metavanadic acid root in Centrifuge filtrate is adsorbed, sodium metavanadate is desorbed, And send system to send precipitation pond back to using the storage of vanadium stripping liquid, so that vanadium resource is recycled, the rate of recovery >=90%；
3) by counter-infiltration system, the Centrifuge filtrate after pretreatment and adsorption of vanadium is subjected to concentration decrement and purification, concentration 4~ 6.6 times, its TDS is concentrated to 50000~100000mg/L, to reduce the expense of subsequent evaporation crystallization；The TDS of the production water of purification ≤ 200mg/L meets reuse requirement；
4) by precipitation high ammonia-nitrogen wastewater pretreatment system, by precipitation high ammonia-nitrogen wastewater heavy metal ion and suspended matter go It removes, and COD value is reduced to < 150mg/L, Ca2+Value is reduced to≤40mg/L；
5) by precipitation high ammonia-nitrogen wastewater resins exchange system, the metavanadic acid root in precipitation high ammonia-nitrogen wastewater is adsorbed, is desorbed Sodium metavanadate recycles vanadium resource, the rate of recovery >=90%；
6) by VCS indicate evaporation and crystallization system, be evaporated crystallization thermal method divide salt, isolate the ammonium chloride of purity >=90% with And the common salt of purity >=98%, evaporative crystallization generate TDS value≤200mg/L of condensed water, Yan Heshui has obtained reuse.
Advantages of the present invention, deposition vanadium mother liquid of the present invention and wash water processing equipment for recycling and its method are female for precipitation The high ammonia nitrogen saliferous of liquid and wash water containing heavy metal ion, high strength ammonium-chloride, high concentration sodium chloride and a small amount of metavanadic acid root is useless The characteristics of water；To the Centrifuge filtrate of low concentration, first with electrolytic oxidation and ultrafiltration heavy-metal ion removal and suspended matter, drop Low cod value, secondly utilize resin adsorption metavanadic acid radical ion, recycle vanadium resource, finally using it is reverse osmosis carry out concentration decrement with Purification, concentrated water decrement go subsequent evaporation, the production water reuse of purification；And to the precipitation high ammonia-nitrogen wastewater of high concentration, first with Soda ash precipitates most of calcium ion, using electrolytic oxidation and ultrafiltration heavy-metal ion removal and suspended matter, reduces COD value, secondly Using resin adsorption metavanadic acid radical ion, vanadium resource is recycled, finally isolates ammonium chloride and sodium chloride, reuse using evaporative crystallization It is produced to vanadium extraction, condensed water is also able to reuse；Deposition vanadium mother liquid and wash water recycling treatment are achieved the purpose that.
Detailed description of the invention
Attached drawing 1 is the general structure schematic diagram of deposition vanadium mother liquid Yu wash water processing equipment for recycling.
CMFL in attached drawing indicates that Centrifuge filtrate, RUW indicate that recycle-water, SVWW indicate precipitation high ammonia-nitrogen wastewater, Salt Indicate (ammonium chloride, common salt) crystal salt, VL indicates vanadium stripping liquid (sodium metavanadate), and ROCW indicates that reverse osmosis concentrated water, VCW indicate Evaporative crystallization condensate, SC indicate that mud cake, SW indicate the draining of Centrifuge filtrate hyperfiltration reverse-rinsing；PTS1Indicate Centrifuge filtrate pretreatment System, RS1Indicate Centrifuge filtrate resins exchange system, ROS indicates counter-infiltration system, PTS2Indicate that precipitation high ammonia-nitrogen wastewater is pre- Processing system, RS2Indicate precipitation high ammonia-nitrogen wastewater resins exchange system, VCS indicates evaporation and crystallization system, and VLS indicates vanadium desorption System is sent in liquid storage.
Attached drawing 2 is the Centrifuge filtrate pretreatment system structural schematic diagram of deposition vanadium mother liquid Yu wash water processing equipment for recycling.
CMFL in attached drawing indicates that Centrifuge filtrate, SW indicate the draining of Centrifuge filtrate hyperfiltration reverse-rinsing, PT1Out indicate from The water outlet of scheming filtrate pretreatment system；PTS1Indicate Centrifuge filtrate pretreatment system；T1Indicate Centrifuge filtrate case, EO1It indicates Centrifuge filtrate electrolytic oxidation apparatus, UF1Indicate Centrifuge filtrate ultrafiltration apparatus, T2Indicate ultrafiltration water producing tank, D1Indicate centrifuge Filtrate hydrochloric acid throwing device；P1Indicate Centrifuge filtrate booster pump, P2Indicate reverse osmosis water supply pump, P3Indicate that Centrifuge filtrate is super Filter backwashing pump.
Attached drawing 3 is the precipitation high ammonia-nitrogen wastewater pretreatment system structural representation of deposition vanadium mother liquid Yu wash water processing equipment for recycling Figure.
SVWW in attached drawing indicates that precipitation high ammonia-nitrogen wastewater, SC indicate that mud cake, SW indicate Centrifuge filtrate hyperfiltration reverse-rinsing row Water, PT2 Out indicates the water outlet of precipitation high ammonia-nitrogen wastewater pretreatment system；PTS2Indicate precipitation high ammonia-nitrogen wastewater pretreatment system；T3 Indicate that precipitation high ammonia-nitrogen wastewater case, ST indicate sedimentation basin, T4Indicate intermediate water tank, EO2Indicate precipitation high ammonia-nitrogen wastewater electrolytic oxidation Device, UF2Indicate precipitation high ammonia-nitrogen wastewater ultrafiltration apparatus, T5Indicate that high ammonia nitrogen concentrated water case, SD indicate sludge dewatering system, D2Table Show soda ash and coagulant dosage device, D3Indicate precipitation high ammonia-nitrogen wastewater hydrochloric acid throwing device；P5Indicate that precipitation high ammonia-nitrogen wastewater increases Press pump, P6Indicate intermediate delivery pump, P7Indicate VCS solution feed pump, P8Indicate precipitation high ammonia-nitrogen wastewater hyperfiltration reverse-rinsing pump, P9Indicate heavy Vanadium high ammonia-nitrogen wastewater pretreatment system reflux pump.
Attached drawing 4 is that system knot is sent in the resins exchange system of deposition vanadium mother liquid and wash water processing equipment for recycling and the storage of vanadium stripping liquid Structure schematic diagram.
RS in attached drawing1Indicate Centrifuge filtrate resins exchange system, RS2Indicate precipitation high ammonia-nitrogen wastewater resins exchange system System, VLS indicate that system is sent in the storage of vanadium stripping liquid；PT1Out indicates the water outlet of Centrifuge filtrate pretreatment system, PT2Out indicates that precipitation is high The water outlet of ammonia nitrogen waste water pretreatment system, RS1Out indicates the water outlet of Centrifuge filtrate resins exchange system, RS2Out indicates the high ammonia of precipitation The water outlet of nitrogen waste water resins exchange system, VL indicate vanadium stripping liquid (sodium metavanadate)；D4Indicate the sodium chloride and chlorine of Centrifuge filtrate Change ammonium throwing device, D5Indicate the sodium chloride and ammonium chloride throwing device of precipitation high ammonia-nitrogen wastewater, RST1Indicate Centrifuge filtrate tree Rouge adsorption tanks, RST2Indicate that precipitation high ammonia-nitrogen wastewater resin adsorption tank, VLT indicate that sodium metavanadate desorbs liquid case；P10Indicate inclined vanadium Sour sodium stripping liquid delivery pump.
Attached drawing 5 is counter-infiltration system and the evaporation and crystallization system structural representation of deposition vanadium mother liquid and wash water processing equipment for recycling Figure.
ROS in attached drawing indicates that counter-infiltration system, VCS indicate evaporation and crystallization system；RS1Out indicates Centrifuge filtrate tree The water outlet of Ester exchange system, RS2Out indicates the water outlet of precipitation high ammonia-nitrogen wastewater resins exchange system, and RUW indicates recycle-water, Salt table Show crystal salt (ammonium chloride, common salt), ROCW indicates that reverse osmosis concentrated water, VCW indicate evaporative crystallization condensate；D6Indicate that antisludging agent is thrown Feeder apparatus, SFF indicate that cartridge filter, RO indicate that reverse osmosis unit, VC indicate evaporated crystallization device, T6Indicate reuse water tank, T7 Indicate evaporative crystallization material feeding box；P11Indicate reverse osmosis high-pressure pump, P12Indicate reuse water pump, P13Indicate evaporative crystallization feed pump.
Attached drawing 6 is the water balance figure of deposition vanadium mother liquid and wash water processing equipment for recycling and its embodiment of the method.
Specific embodiment
Attached drawing 1, deposition vanadium mother liquid and wash water processing equipment for recycling are compareed, structure includes Centrifuge filtrate pretreatment system PTS1, Centrifuge filtrate resins exchange system RS1, counter-infiltration system ROS, precipitation high ammonia-nitrogen wastewater pretreatment system PTS2, precipitation High ammonia-nitrogen wastewater resins exchange system RS2, evaporation and crystallization system VCS, vanadium stripping liquid storage send system VLS；Wherein Centrifuge filtrate CMFL is connected to Centrifuge filtrate pretreatment system PTS1Water inlet, utilize Centrifuge filtrate pretreatment system PTS1Removal centrifugation COD value is reduced to < 20mg/L by the heavy metal ion in machine filter liquid；Centrifuge filtrate pretreatment system PTS1Backwash water go out Mouth sends out Centrifuge filtrate hyperfiltration reverse-rinsing and drains SW to precipitation high ammonia-nitrogen wastewater pretreatment system PTS2Backwash water inlet, centrifugation Machine filter liquid pretreatment system PTS1Water outlet and Centrifuge filtrate resins exchange system RS1Water inlet connect, utilize centrifuge Filtrate resins exchange system RS1Adsorb the metavanadic acid radical ion in Centrifuge filtrate, Centrifuge filtrate resins exchange system RS1's Liquid outlet send the 1# inlet of system VLS to connect with the storage of vanadium stripping liquid, and the storage of vanadium stripping liquid send the liquid outlet of system VLS to send out vanadium solution Imbibition (sodium metavanadate) VL, goes to the precipitation pond of vanadium extraction production system to carry out precipitation again, achievees the purpose that recycle vanadium resource；Centrifugation Machine filter liquid resins exchange system RS1Water outlet connect with the water inlet of counter-infiltration system ROS, utilize counter-infiltration system ROS will Decrement is concentrated in Centrifuge filtrate after pretreatment and adsorption of vanadium, is concentrated 4~6.6 times, its TDS is concentrated to 50000~ 100000mg/L, to reduce the expense of subsequent evaporation crystallization；Send out reverse osmosis concentrated water ROCW in the concentrated water outlet of counter-infiltration system ROS To the 2# concentrated water import of evaporation and crystallization system VCS, and counter-infiltration system ROS produces TDS≤200mg/L of water, meets reuse requirement, The water outlet of counter-infiltration system ROS sends out recycle-water RUW；Precipitation high ammonia-nitrogen wastewater SVWW is connected to the pretreatment of precipitation high ammonia-nitrogen wastewater System PTS21# water inlet, utilize precipitation high ammonia-nitrogen wastewater pretreatment system PTS2Remove the huge sum of money in precipitation high ammonia-nitrogen wastewater Belong to ion, COD value is reduced to≤150mg/L, Ca2+(calcium ion) is reduced to≤40mg/L；The pretreatment of precipitation high ammonia-nitrogen wastewater System PTS2Mud mouth send out mud cake SC, precipitation high ammonia-nitrogen wastewater pretreatment system PTS2Water outlet and the high ammonia nitrogen of precipitation it is useless Water-resin exchange system RS2Water inlet connect, utilize precipitation high ammonia-nitrogen wastewater resins exchange system RS2Adsorb the high ammonia nitrogen of precipitation Metavanadic acid radical ion in waste water, precipitation high ammonia-nitrogen wastewater resins exchange system RS2Liquid outlet and vanadium stripping liquid storage send system The 2# inlet of VLS connects；Precipitation high ammonia-nitrogen wastewater resins exchange system RS2Water outlet and evaporation and crystallization system VCS into Liquid mouth connects, will be by pre-processing with the precipitation high ammonia-nitrogen wastewater evaporative crystallization after adsorption of vanadium simultaneously using evaporation and crystallization system VCS The ammonium chloride of purity >=90% and the common salt of purity >=98% are isolated, the reuse requirement to salt is all met, meanwhile, evaporation knot Crystalline substance generates TDS value≤200mg/L of condensed water, also meets reuse requirement；The salt outlet of evaporation and crystallization system VCS sends out crystal salt (ammonium chloride, common salt) Salt.As a result, deposition vanadium mother liquid and wash water processing equipment for recycling are by Centrifuge filtrate and the high ammonia nitrogen of precipitation Waste water is handled respectively, has not only been recycled valuable metavanadic acid radical ion, has been recycled ammonium chloride, common salt, will also produce water with Recycling condensing water has arrived in the production of vanadium extraction, has achieved the purpose that deposition vanadium mother liquid and wash water recycling treatment.
Compare attached drawing 2, Centrifuge filtrate pretreatment system PTS1, structure includes Centrifuge filtrate case T1, Centrifuge filtrate Electrolytic oxidation apparatus EO1, Centrifuge filtrate ultrafiltration apparatus UF1, ultrafiltration water producing tank T2, Centrifuge filtrate hydrochloric acid throwing device D1, with And Centrifuge filtrate booster pump P1, reverse osmosis water supply pump P2, Centrifuge filtrate hyperfiltration reverse-rinsing pump P3；Wherein Centrifuge filtrate CMFL It is connected to Centrifuge filtrate case T1Water inlet, Centrifuge filtrate case T1Water outlet pass through Centrifuge filtrate booster pump P1With centrifugation Machine filter liquid electrolytic oxidation apparatus EO1Water inlet connect, Centrifuge filtrate hydrochloric acid throwing device D1Medicine outlet also with centrifugation machine filter Liquid electrolytic oxidation apparatus EO1Water inlet connect, Centrifuge filtrate electrolytic oxidation apparatus EO1Water outlet and Centrifuge filtrate it is super Filter device UF1Water inlet connect, Centrifuge filtrate ultrafiltration apparatus UF1Water outlet and ultrafiltration water producing tank T2Water inlet connect, Ultrafiltration water producing tank T2Backwash water out by Centrifuge filtrate hyperfiltration reverse-rinsing pump P3With Centrifuge filtrate ultrafiltration apparatus UF1It is anti- Wash water import connects, Centrifuge filtrate ultrafiltration apparatus UF1Backwash water out send out Centrifuge filtrate hyperfiltration reverse-rinsing drain SW, surpass Filter water producing tank T2Water outlet pass through reverse osmosis water supply pump P2It sends out Centrifuge filtrate pretreatment system and is discharged PT1out；Using from Scheming filtrate electrolytic oxidation apparatus EO1The strong oxidizers such as the hypochlorite and hydroxy radical of generation degrade COD, go removing heavy metals from Son, and utilize Centrifuge filtrate ultrafiltration apparatus UF1Part COD, suspended matter and heavy metal reactant are filtered out, COD value is reduced to ≤20mg/L。
Compare attached drawing 3, precipitation high ammonia-nitrogen wastewater pretreatment system PTS2, structure includes precipitation high ammonia-nitrogen wastewater case T3, it is heavy Shallow lake pond ST, intermediate water tank T4, precipitation high ammonia-nitrogen wastewater electrolytic oxidation apparatus EO2, precipitation high ammonia-nitrogen wastewater ultrafiltration apparatus UF2, high ammonia Nitrogen concentrated water case T5, sludge dewatering system SD, soda ash and coagulant dosage device D2, precipitation high ammonia-nitrogen wastewater hydrochloric acid throwing device D3, And precipitation high ammonia-nitrogen wastewater booster pump P5, intermediate delivery pump P6, evaporation and crystallization system solution feed pump P7, precipitation high ammonia-nitrogen wastewater it is super Filter backwashing pump P8, precipitation high ammonia-nitrogen wastewater pretreatment system reflux pump P9；Wherein precipitation high ammonia-nitrogen wastewater SVWW is connected to the high ammonia of precipitation Nitrogen waste water tank T3Water inlet, precipitation high ammonia-nitrogen wastewater case T3Water outlet pass through precipitation high ammonia-nitrogen wastewater booster pump P5With precipitating The water inlet of pond ST connects, soda ash and coagulant dosage device D2Medicine outlet also connect with the water inlet of sedimentation basin ST, precipitate The mud mouth of pond ST connects with the 1# mud inlet of sludge dewatering system SD, and it is de- that Centrifuge filtrate hyperfiltration reverse-rinsing draining SW is connected to sludge The 3# mud inlet of water system SD carries out filters pressing using sludge dewatering system SD, separates dry mud and filtrate, sludge dewatering system SD's Mud mouth sends out mud cake SC, and the liquid outlet of sludge dewatering system SD passes through precipitation high ammonia-nitrogen wastewater pretreatment system reflux pump P9It will Filtrate sends precipitation high ammonia-nitrogen wastewater case T back to3Inlet；The water outlet and intermediate water tank T of sedimentation basin ST4Water inlet connect, in Between water tank T4Water outlet pass through intermediate delivery pump P6With precipitation high ammonia-nitrogen wastewater electrolytic oxidation apparatus EO2Water inlet connect, sink Vanadium high ammonia-nitrogen wastewater hydrochloric acid throwing device D3Medicine outlet also with precipitation high ammonia-nitrogen wastewater electrolytic oxidation apparatus EO2Water inlet phase It connects, precipitation high ammonia-nitrogen wastewater electrolytic oxidation apparatus EO2Water outlet and precipitation high ammonia-nitrogen wastewater ultrafiltration apparatus UF2Water inlet phase It connects, precipitation high ammonia-nitrogen wastewater ultrafiltration apparatus UF2Water outlet and high ammonia nitrogen concentrated water case T5Water inlet connect, high ammonia nitrogen concentrated water case T5Backwash water out by precipitation high ammonia-nitrogen wastewater hyperfiltration reverse-rinsing pump P8With precipitation high ammonia-nitrogen wastewater ultrafiltration apparatus UF2Backwash Water inlet connects, precipitation high ammonia-nitrogen wastewater ultrafiltration apparatus UF2Backwash water row's mouth be connected to the 2# mud inlet of sludge dewatering system SD, High ammonia nitrogen concentrated water case T5Water outlet pass through evaporation and crystallization system solution feed pump P7Send out the water outlet of precipitation high ammonia-nitrogen wastewater pretreatment system PT2 out；Here it is reacted by soda ash with calcium ion and generates precipitation of calcium carbonate and heavy metal hydroxide precipitating, utilize hydrochloric acid It is neutrality by pH readjustment, and using electrolytic oxidation and ultra-filtration filters with heavy-metal ion removal, and COD value is reduced to≤ Calcium ion is reduced to≤40mg/L by 150mg/L.
Compare attached drawing 4, resins exchange system PTS1、PTS2System VLS is sent with the storage of vanadium stripping liquid, structure includes centrifuge Filtrate resin adsorption tank RST1, precipitation high ammonia-nitrogen wastewater resin adsorption tank RST2, sodium metavanadate desorb liquid case VLT, Centrifuge filtrate Sodium chloride and ammonium chloride throwing device D4, precipitation high ammonia-nitrogen wastewater sodium chloride and ammonium chloride throwing device D5, sodium metavanadate solution Imbibition delivery pump P10；Wherein Centrifuge filtrate pretreatment system is discharged PT1Out is connected to Centrifuge filtrate resin adsorption tank RST1's Water inlet, the sodium chloride and ammonium chloride throwing device D of Centrifuge filtrate4Medicine outlet and Centrifuge filtrate resin adsorption tank RST1 Feeding opening connect, Centrifuge filtrate resin adsorption tank RST1Liquid outlet and sodium metavanadate desorption liquid case VLT 1# inlet Connect, Centrifuge filtrate resin adsorption tank RST1Water outlet send out Centrifuge filtrate resins exchange system be discharged RS1out；Precipitation High ammonia-nitrogen wastewater pretreatment system is discharged PT2Out is connected to precipitation high ammonia-nitrogen wastewater resin adsorption tank RST2Water inlet, precipitation is high The sodium chloride and ammonium chloride throwing device D of ammonia nitrogen waste water5Medicine outlet and precipitation high ammonia-nitrogen wastewater resin adsorption tank RST2Into medicine Mouth connects, precipitation high ammonia-nitrogen wastewater resin adsorption tank RST2Liquid outlet and sodium metavanadate desorption liquid case VLT 2# inlet phase It connects, precipitation high ammonia-nitrogen wastewater resin adsorption tank RST2Water outlet send out precipitation high ammonia-nitrogen wastewater resins exchange system water outlet RS2out；The liquid outlet that sodium metavanadate desorbs liquid case VLT passes through sodium metavanadate stripping liquid delivery pump P10Send out vanadium stripping liquid (inclined vanadium Sour sodium) VL；Here, adsorb metavanadic acid root using large pore anion resin, after resin saturation, using sodium hydroxide and sodium chloride into Row desorption, obtains sodium metavanadate, then go precipitation, so that the vanadium resource being lost in waste water is recycled.
Attached drawing 5, counter-infiltration system ROS and evaporation and crystallization system VCS are compareed, structure includes cartridge filter SFF, reverse osmosis Saturating device RO, reuse water tank T6, evaporative crystallization material feeding box T7, evaporated crystallization device VC, scale inhibitor feeding device D6And reverse osmosis Saturating high-pressure pump P11, reuse water pump P12, evaporative crystallization feed pump P13；Wherein Centrifuge filtrate resins exchange system is discharged RS1out It is connected to the water inlet of cartridge filter SFF, scale inhibitor feeding device D6Medicine outlet be also connected to the water inlet of cartridge filter SFF Mouthful, the water outlet of cartridge filter SFF pumps P by reverse osmosis high-pressure11Connect with the water inlet of reverse osmosis unit RO, reverse osmosis dress The concentrated water outlet for setting RO connects with the 2# inlet of evaporated crystallization device VC, the production water out and reuse water tank of reverse osmosis unit RO T61# water inlet connect, reuse water tank T6Water outlet pass through reuse water pump P12Send out recycle-water RUW；Here with reverse osmosis Centrifuge filtrate is subjected to concentration decrement, to reduce evaporation capacity, to reduce evaporation operating cost, while purified production water is returned With；Precipitation high ammonia-nitrogen wastewater resins exchange system is discharged RS2Out is connected to evaporative crystallization material feeding box T71# inlet, evaporative crystallization Material feeding box T7Liquid outlet pass through evaporative crystallization feed pump P13Connect with the inlet of evaporated crystallization device VC, evaporated crystallization device Evaporative crystallization condensate VCW is connected to reuse water tank T by the water outlet of VC62# water inlet, the salt outlet of evaporated crystallization device VC send Crystal salt (ammonium chloride, common salt) Salt out.It realizes and handles precipitation high ammonia-nitrogen wastewater and Centrifuge filtrate, production water, which is back to use, to be mentioned The multiple production workshop sections of vanadium, ammonium chloride, sodium chloride also obtain reuse, while having recycled sodium metavanadate, have reached deposition vanadium mother liquid and have washed The purpose of recycling of water resource processing.
Deposition vanadium mother liquid and wash water recycling processing method, include the following steps:
1) by Centrifuge filtrate pretreatment system, by the heavy metal ion and suspended matter removal, COD value drop in Centrifuge filtrate As low as < 20mg/L；
2) by Centrifuge filtrate resins exchange system, the metavanadic acid root in Centrifuge filtrate is adsorbed, sodium metavanadate is desorbed, And send system to send precipitation pond back to using the storage of vanadium stripping liquid, so that vanadium resource is recycled, the rate of recovery >=90%；
3) by counter-infiltration system, the Centrifuge filtrate after pretreatment and adsorption of vanadium is subjected to concentration decrement and purification, concentration 4~ 6.6 times, its TDS is concentrated to 50000~100000mg/L, to reduce the expense of subsequent evaporation crystallization；The TDS of the production water of purification ≤ 200mg/L meets reuse requirement；
4) by precipitation high ammonia-nitrogen wastewater pretreatment system, by precipitation high ammonia-nitrogen wastewater heavy metal ion and suspended matter go It removes, and COD value is reduced to < 150mg/L, Ca2+Value is reduced to≤40mg/L；
5) by precipitation high ammonia-nitrogen wastewater resins exchange system, the metavanadic acid root in precipitation high ammonia-nitrogen wastewater is adsorbed, is desorbed Sodium metavanadate recycles vanadium resource, the rate of recovery >=90%；
6) by VCS indicate evaporation and crystallization system, be evaporated crystallization thermal method divide salt, isolate the ammonium chloride of purity >=90% with And the common salt of purity >=98%, evaporative crystallization generate TDS value≤200mg/L of condensed water, Yan Heshui has obtained reuse.
The step 1) specifically utilizes Centrifuge filtrate electrolytic oxidation apparatus by Centrifuge filtrate pretreatment system EO1The strong oxidizers such as the hypochlorite and hydroxy radical of generation degradation COD, heavy-metal ion removal, and utilize Centrifuge filtrate Ultrafiltration apparatus UF1Part COD, suspended matter and heavy metal reactant are filtered out, COD value is reduced to≤20mg/ from 50~100mg/L L。
The step 2 is by Centrifuge filtrate resins exchange system, specifically by the metavanadic acid root benefit in Centrifuge filtrate It is adsorbed with large pore anion resin, after resin saturation, is desorbed using sodium hydroxide and sodium chloride, desorb metavanadic acid Sodium, and send system to send precipitation pond back to using the storage of vanadium stripping liquid, so that vanadium resource is recycled, the rate of recovery >=90%.
Centrifuge filtrate after pretreatment and adsorption of vanadium is specifically utilized reverse osmosis by counter-infiltration system by the step 3) Row concentration decrement and purification are penetrated into, is concentrated 4~6.6 times, its TDS is concentrated to 50000 from 10000~20000mg/L~ 100000mg/L, to reduce the expense of subsequent evaporation crystallization；The TDS of the production water of purification is 100~200mg/L, meets reuse and wants It asks, produces multiple workshop sections that water is back to use vanadium extraction production.
The step 4) specifically reacts generation with calcium ion using soda ash by precipitation high ammonia-nitrogen wastewater pretreatment system Precipitation of calcium carbonate and heavy metal hydroxide precipitating, using hydrochloric acid by pH readjustment to be neutral, and utilize electrolytic oxidation and ultrafiltration COD value is reduced to 60~150mg/L from 500~1000mg/L with heavy-metal ion removal by filtering, by Ca2+Value from 100~ 800mg/L is reduced to≤40mg/L.
The step 5), specifically will be inclined in precipitation high ammonia-nitrogen wastewater by precipitation high ammonia-nitrogen wastewater resins exchange system Vanadic acid root is adsorbed using large pore anion resin, after resin saturation, is desorbed, is desorbed using sodium hydroxide and sodium chloride Sodium metavanadate out, and send system to send precipitation pond back to using the storage of vanadium stripping liquid, so that vanadium resource is recycled, the rate of recovery >=90%.
The step 6) indicates evaporation and crystallization system by VCS, specifically by the high ammonia of precipitation after pretreatment and adsorption of vanadium The reverse osmosis concentrated water of nitrogen waste water and Centrifuge filtrate is evaporated crystallization, and isolates the ammonium chloride and purity of purity >=90% >=98% common salt, evaporative crystallization generate TDS value≤200mg/L of condensed water, and common salt is roasted back to low sodium in vanadium extraction production The burn plus agglomerating process of salt, ammonium chloride return to multiple works in vanadium extraction production back to precipitation process in vanadium extraction production, condensed water Section.
Embodiment:
Certain Fan Ye company produces 600 tons of ammonium metavanadates per year using local Rock coal containing alum resource abundant, in the production of ammonium metavanadate Cheng Zhong, bone coal add sodium salt and water agglomerating through crushing, and carry out resin adsorption after sodium roasting, utilize sodium chloride and sodium hydroxide solution It inhales, stripping liquid adds ammonium chloride and forms ammonium metavanadate precipitate, finally utilizes washing, centrifuge separation output ammonium metavanadate product.This During a, deposition vanadium mother liquid (also referred to as precipitation high ammonia-nitrogen wastewater) and wash water (also referred to as Centrifuge filtrate) contain a higher huge sum of money Category, COD, TDS(are mainly ammonium chloride, sodium chloride), it is a kind of high ammonia-nitrogen wastewater, such as handles bad, discharge environmental pollution Seriously, and this project has carried out recycling treatment to it, while having recycled ammonium chloride, sodium chloride and recycle-water, achieved preferably Economic benefit and environmental benefit.
Design influent quality, water
Design water inlet has Centrifuge filtrate and precipitation high ammonia-nitrogen wastewater, and water quality indicator is as follows:
2. process flow
2.1 precipitation high ammonia-nitrogen sewage treatment systems
Vanadium wastewater → vanadium wastewater pond/elevator pump (soda ash, coagulant →)-→ sedimentation basin → intermediate water tank/UF elevator pump- (→ vanadium desorbs liquid case/desorption to → (hydrochloric acid →) electrolysis unit → ultrafiltration apparatus → (common salt, sodium hydroxide →) resin adsorption tank Liquid pump → precipitation pond) → high ammonia nitrogen concentrated water case/delivery pump → evaporated crystallization device (the RO fresh-water tank that → condensate goes to (2.2)) → chlorine Change ammonium, sodium chloride
Wherein:
Sludge from sedimentation tank, hyperfiltration reverse-rinsing draining → sludge-tank/sludge delivery pump → sludge dehydration device → sludge outward transport；
Pressing filtering liquid → vanadium wastewater pond that sludge treatment equipment generates.
2.2 Centrifuge filtrate processing systems
Centrifuge filtrate → Centrifuge filtrate pond/elevator pump (hydrochloric acid →)-→ electrolysis unit → ultrafiltration apparatus → ultrafiltration produces water Case/RO booster pump → (common salt, sodium hydroxide →) resin adsorption tank (→ stripping liquid goes the vanadium of (2.1) to desorb liquid case)-→ (antisludging agent →) cartridge filter/high-pressure pump → RO device (→ concentrated water drainage to high ammonia nitrogen concentrated water case) → RO fresh-water tank/fresh water returns With pumping → send to water spot
Wherein:
Hyperfiltration reverse-rinsing drains → goes the sludge-tank of (2.1).
Water balance
The water balance of Centrifuge filtrate and precipitation high ammonia-nitrogen wastewater processing item is referring to 6 deposition vanadium mother liquid of attached drawing and wash water recycling The water balance figure of processing unit and its embodiment of the method.
Description of the process
4.1 precipitation high ammonia-nitrogen sewage treatment systems
Precipitation high ammonia-nitrogen wastewater enters the storage of precipitation high ammonia-nitrogen wastewater pond, is pressurized through precipitation high ammonia-nitrogen wastewater elevator pump and enters precipitating Pond adds soda ash, coagulant in sedimentation basin water inlet, and the calcium ion in water forms calcium carbonate through chemical reaction, removes through precipitating, sinks The water outlet of shallow lake pond enters intermediate water tank, by entering electrolysis unit after the pressurization of UF elevator pump, after heavy-metal ion removal, fills into ultrafiltration It sets, goes oil removal, colloid, partial organic substances etc. through hyperfiltration treatment, ultrafiltration produces water and enters after resin adsorption tank adsorption of vanadium High ammonia nitrogen concentrated water case is pumped to evaporated crystallization device through conveying and is evaporated crystallization, separates ammonium chloride and sodium chloride using thermal method.
Clarifier sludge and hyperfiltration reverse-rinsing drain into sludge-tank, are sent by sludge delivery pump to sludge dehydration device, filters pressing Mud cake outward transport processing, pressing filtering liquid send back to vanadium wastewater pond reprocessing.
The condensate that evaporated crystallization device generates is sent to (Centrifuge filtrate processing system) RO water producing tank.
Resin container is desorbed using common salt, sodium hydroxide, is generated sodium metavanadate and is recycled to precipitation pond.
4.2 Centrifuge filtrate processing systems
Centrifuge filtrate enters the storage of Centrifuge filtrate pond, enters an electrolysis unit removal huge sum of money through the pressurization of Centrifuge filtrate elevator pump After belonging to ion, into ultrafiltration apparatus, oil removal, colloid, partial organic substances etc. are gone through hyperfiltration treatment, ultrafiltration produces water and enters ultrafiltration Water producing tank, is introduced into resin adsorption tank absorption metavanadic acid root after the pressurization of RO booster pump, and ion exchange tail water enters security personnel's filtering Device, then enter the desalination of RO device, concentration through high-pressure pump pressurization, RO fresh water enters RO fresh-water tank, after the pressurization of fresh water reuse water pump It send to water spot (TDS≤250mg/L).RO concentrated water enters (precipitation high ammonia-nitrogen sewage treatment system) high ammonia nitrogen concentrated water case, It carries out further evaporation and divides salt.Ultrafiltration is drained into (precipitation high ammonia-nitrogen sewage treatment system) sludge-tank, is further dehydrated Processing.It after ion exchange resin adsorption saturation, is eluted using NaCl and NaOH, recycles sodium metavanadate.
System main design parameters
5.1 civil engineerings:
5.2 capital equipments:

Claims (10)

1. deposition vanadium mother liquid and wash water processing equipment for recycling, it is characterized in that including Centrifuge filtrate pretreatment system (PTS1), centrifugation Machine filter liquid resins exchange system (RS1), counter-infiltration system (ROS), precipitation high ammonia-nitrogen wastewater pretreatment system (PTS2), precipitation it is high Ammonia nitrogen waste water resins exchange system (RS2), evaporation and crystallization system (VCS), vanadium stripping liquid storage send system (VLS)；Wherein centrifuge Filtrate (CMFL) is connected to Centrifuge filtrate pretreatment system (PTS1) water inlet, utilize Centrifuge filtrate pretreatment system (PTS1) removal Centrifuge filtrate in heavy metal ion, COD value is reduced to < 20mg/L；Centrifuge filtrate pretreatment system (PTS1) backwash water out send out Centrifuge filtrate hyperfiltration reverse-rinsing draining (SW) to precipitation high ammonia-nitrogen wastewater pretreatment system (PTS2) backwash water inlet, Centrifuge filtrate pretreatment system (PTS1) water outlet and Centrifuge filtrate resins exchange system (RS1) water inlet connect, utilize Centrifuge filtrate resins exchange system (RS1) absorption Centrifuge filtrate in metavanadic acid root from Son, Centrifuge filtrate resins exchange system (RS1) the storage of liquid outlet and vanadium stripping liquid send the 1# inlet of system (VLS) to connect, The storage of vanadium stripping liquid send the liquid outlet of system (VLS) to send out vanadium stripping liquid (VL), and the precipitation pond of vanadium extraction production system is gone to carry out again Precipitation achievees the purpose that recycle vanadium resource；Centrifuge filtrate resins exchange system (RS1) water outlet and counter-infiltration system (ROS) water inlet connects, and will be pre-processed using counter-infiltration system (ROS) and decrement is concentrated with the Centrifuge filtrate after adsorption of vanadium, 4~6.6 times of concentration, is concentrated to 50000~100000mg/L for its TDS, to reduce the expense of subsequent evaporation crystallization；Reverse osmosis system The 2# concentrated water import of reverse osmosis concentrated water (ROCW) to evaporation and crystallization system (VCS) is sent out in the concentrated water outlet of system (ROS), and reverse osmosis System (ROS) produces TDS≤200mg/L of water, meets reuse requirement, and the water outlet of counter-infiltration system (ROS) sends out recycle-water (RUW)；Precipitation high ammonia-nitrogen wastewater (SVWW) is connected to precipitation high ammonia-nitrogen wastewater pretreatment system (PTS2) 1# water inlet, using heavy Vanadium high ammonia-nitrogen wastewater pretreatment system (PTS2) heavy metal ion in removal precipitation high ammonia-nitrogen wastewater, COD value is reduced to≤ 150mg/L、Ca2+(calcium ion) is reduced to≤40mg/L；Precipitation high ammonia-nitrogen wastewater pretreatment system (PTS2) mud mouth send out Mud cake (SC), precipitation high ammonia-nitrogen wastewater pretreatment system (PTS2) water outlet and precipitation high ammonia-nitrogen wastewater resins exchange system (RS2) water inlet connect, utilize precipitation high ammonia-nitrogen wastewater resins exchange system (RS2) absorption precipitation high ammonia-nitrogen wastewater in it is inclined Vanadic acid radical ion, precipitation high ammonia-nitrogen wastewater resins exchange system (RS2) liquid outlet and the storage of vanadium stripping liquid send the 2# of system (VLS) Inlet connects；Precipitation high ammonia-nitrogen wastewater resins exchange system (RS2) water outlet and evaporation and crystallization system (VCS) inlet Connect, by the precipitation high ammonia-nitrogen wastewater evaporative crystallization after pretreatment and adsorption of vanadium and is divided using evaporation and crystallization system (VCS) The ammonium chloride of purity >=90% and the common salt of purity >=98% are separated out, the reuse requirement to salt is all met；Evaporation and crystallization system (VCS) salt outlet sends out crystal salt.
2. deposition vanadium mother liquid according to claim 1 and wash water processing equipment for recycling, it is characterized in that the centrifugation machine filter Liquid pretreatment system (PTS1), structure includes Centrifuge filtrate case (T1), Centrifuge filtrate electrolytic oxidation apparatus (EO1), centrifugation Machine filter liquid ultrafiltration apparatus (UF1), ultrafiltration water producing tank (T2), Centrifuge filtrate hydrochloric acid throwing device (D1) and Centrifuge filtrate increasing Press pump (P1), reverse osmosis water supply pump (P2), Centrifuge filtrate hyperfiltration reverse-rinsing pump (P3)；Wherein Centrifuge filtrate (CMFL) be connected to from Scheming filtrate box (T1) water inlet, Centrifuge filtrate case (T1) water outlet pass through Centrifuge filtrate booster pump (P1) and centrifugation Machine filter liquid electrolytic oxidation apparatus (EO1) water inlet connect, Centrifuge filtrate hydrochloric acid throwing device (D1) medicine outlet also with centrifugation Machine filter liquid electrolytic oxidation apparatus (EO1) water inlet connect, Centrifuge filtrate electrolytic oxidation apparatus (EO1) water outlet and centrifugation Machine filter liquid ultrafiltration apparatus (UF1) water inlet connect, Centrifuge filtrate ultrafiltration apparatus (UF1) water outlet and ultrafiltration water producing tank (T2) water inlet connect, ultrafiltration water producing tank (T2) backwash water out by Centrifuge filtrate hyperfiltration reverse-rinsing pump (P3) and centrifugation Machine filter liquid ultrafiltration apparatus (UF1) backwash water inlet connect, Centrifuge filtrate ultrafiltration apparatus (UF1) backwash water out send out from Scheming filtrate hyperfiltration reverse-rinsing drains (SW), ultrafiltration water producing tank (T2) water outlet pass through reverse osmosis water supply pump (P2) send out centrifuge Filtrate pretreatment system is discharged (PT1Out)；Utilize Centrifuge filtrate electrolytic oxidation apparatus (EO1) generate hypochlorite and hydroxyl from By the strong oxidizers such as base degradation COD, heavy-metal ion removal, and utilize Centrifuge filtrate ultrafiltration apparatus (UF1) filter out part COD value is reduced to≤20mg/L by COD, suspended matter and heavy metal reactant.
3. deposition vanadium mother liquid according to claim 1 and wash water processing equipment for recycling, it is characterized in that the high ammonia of the precipitation Nitrogen waste water pretreatment system (PTS2), structure includes precipitation high ammonia-nitrogen wastewater case (T3), sedimentation basin ST, intermediate water tank (T4), it is heavy Vanadium high ammonia-nitrogen wastewater electrolytic oxidation apparatus (EO2), precipitation high ammonia-nitrogen wastewater ultrafiltration apparatus (UF2), high ammonia nitrogen concentrated water case (T5), it is dirty Mud dewatering system SD, soda ash and coagulant dosage device (D2), precipitation high ammonia-nitrogen wastewater hydrochloric acid throwing device (D3) and precipitation High ammonia-nitrogen wastewater booster pump (P5), intermediate delivery pump (P6), evaporation and crystallization system solution feed pump (P7), precipitation high ammonia-nitrogen wastewater ultrafiltration Backwashing pump (P8), precipitation high ammonia-nitrogen wastewater pretreatment system reflux pump (P9)；Wherein precipitation high ammonia-nitrogen wastewater (SVWW) is connected to precipitation High ammonia-nitrogen wastewater case (T3) water inlet, precipitation high ammonia-nitrogen wastewater case (T3) water outlet pass through precipitation high ammonia-nitrogen wastewater booster pump (P5) connect with the water inlet of sedimentation basin (ST), soda ash and coagulant dosage device (D2) medicine outlet also with sedimentation basin (ST) Water inlet connects, and the mud mouth of sedimentation basin (ST) connects with the 1# mud inlet of sludge dewatering system (SD), Centrifuge filtrate ultrafiltration Backwash draining (SW) is connected to the 3# mud inlet of sludge dewatering system (SD), carries out filters pressing using sludge dewatering system (SD), separates The mud mouth of dry mud and filtrate, sludge dewatering system (SD) sends out mud cake (SC), and the liquid outlet of sludge dewatering system (SD) passes through Precipitation high ammonia-nitrogen wastewater pretreatment system reflux pump (P9) send filtrate back to precipitation high ammonia-nitrogen wastewater case (T3) inlet；Precipitating The water outlet and intermediate water tank (T in pond (ST)4) water inlet connect, intermediate water tank (T4) water outlet pass through intermediate delivery pump (P6) and precipitation high ammonia-nitrogen wastewater electrolytic oxidation apparatus (EO2) water inlet connect, precipitation high ammonia-nitrogen wastewater hydrochloric acid throwing device (D3) medicine outlet also with precipitation high ammonia-nitrogen wastewater electrolytic oxidation apparatus (EO2) water inlet connect, precipitation high ammonia-nitrogen wastewater electrolysis Oxidation unit (EO2) water outlet and precipitation high ammonia-nitrogen wastewater ultrafiltration apparatus (UF2) water inlet connect, precipitation high ammonia-nitrogen wastewater Ultrafiltration apparatus (UF2) water outlet and high ammonia nitrogen concentrated water case (T5) water inlet connect, high ammonia nitrogen concentrated water case (T5) backwash water go out Mouth pumps (P by precipitation high ammonia-nitrogen wastewater hyperfiltration reverse-rinsing8) and precipitation high ammonia-nitrogen wastewater ultrafiltration apparatus (UF2) backwash water inlet phase It connects, precipitation high ammonia-nitrogen wastewater ultrafiltration apparatus (UF2) backwash water row's mouth be connected to the 2# mud inlet of sludge dewatering system (SD), high ammonia Nitrogen concentrated water case (T5) water outlet pass through evaporation and crystallization system solution feed pump (P7) send out the water outlet of precipitation high ammonia-nitrogen wastewater pretreatment system (PT2 Out)；Here it is reacted by soda ash with calcium ion and generates precipitation of calcium carbonate and heavy metal hydroxide precipitating, utilize salt PH readjustment is neutrality by acid, and using electrolytic oxidation and ultra-filtration filters with heavy-metal ion removal, and COD value is reduced to≤ Calcium ion is reduced to≤40mg/L by 150mg/L.
4. deposition vanadium mother liquid according to claim 1 and wash water processing equipment for recycling, it is characterized in that the centrifugation machine filter Liquid resins exchange system (RS1), precipitation high ammonia-nitrogen wastewater resins exchange system (RS2) stored up with vanadium stripping liquid and give system (VLS), Structure includes Centrifuge filtrate resin adsorption tank (RST1), precipitation high ammonia-nitrogen wastewater resin adsorption tank (RST2), sodium metavanadate desorption Liquid case (VLT), the sodium chloride of Centrifuge filtrate and ammonium chloride throwing device (D4), the sodium chloride of precipitation high ammonia-nitrogen wastewater and chlorination Ammonium throwing device (D5), sodium metavanadate stripping liquid delivery pump (P10)；Wherein Centrifuge filtrate pretreatment system is discharged (PT1Out) It is connected to Centrifuge filtrate resin adsorption tank (RST1) water inlet, the sodium chloride of Centrifuge filtrate and ammonium chloride throwing device (D4) Medicine outlet and Centrifuge filtrate resin adsorption tank (RST1) feeding opening connect, Centrifuge filtrate resin adsorption tank (RST1) Liquid outlet connects with the 1# inlet of sodium metavanadate desorption liquid case (VLT), Centrifuge filtrate resin adsorption tank (RST1) water outlet Mouth sends out Centrifuge filtrate resins exchange system and is discharged (RS1Out)；Precipitation high ammonia-nitrogen wastewater pretreatment system is discharged (PT2Out) It is connected to precipitation high ammonia-nitrogen wastewater resin adsorption tank (RST2) water inlet, sodium chloride and the ammonium chloride of precipitation high ammonia-nitrogen wastewater adds Device (D5) medicine outlet and precipitation high ammonia-nitrogen wastewater resin adsorption tank (RST2) feeding opening connect, precipitation high ammonia-nitrogen wastewater tree Rouge adsorption tanks (RST2) the 2# inlet of liquid outlet and sodium metavanadate desorption liquid case (VLT) connect, precipitation high ammonia-nitrogen wastewater tree Rouge adsorption tanks (RST2) water outlet send out precipitation high ammonia-nitrogen wastewater resins exchange system be discharged (RS2Out)；Sodium metavanadate desorption The liquid outlet of liquid case (VLT) passes through sodium metavanadate stripping liquid delivery pump (P10) send out vanadium stripping liquid (VL)；Here, macropore yin is utilized Ion exchange resin is adsorbed metavanadic acid root and is desorbed using sodium hydroxide and sodium chloride after resin is saturated, obtain sodium metavanadate, then Precipitation is gone, so that the vanadium resource being lost in waste water is recycled.
5. deposition vanadium mother liquid according to claim 1 and wash water processing equipment for recycling, it is characterized in that the reverse osmosis system Unite (ROS) and evaporation and crystallization system (VCS), and structure includes cartridge filter (SFF), reverse osmosis unit (RO), reuse water tank (T6), evaporative crystallization material feeding box (T7), evaporated crystallization device (VC), scale inhibitor feeding device (D6) and reverse osmosis high-pressure pump (P11), reuse water pump (P12), evaporative crystallization feed pump (P13)；Wherein Centrifuge filtrate resins exchange system is discharged (RS1Out) It is connected to the water inlet of cartridge filter (SFF), scale inhibitor feeding device (D6) medicine outlet be also connected to cartridge filter (SFF) The water outlet of water inlet, cartridge filter (SFF) pumps (P by reverse osmosis high-pressure11) water inlet phase with reverse osmosis unit (RO) It connects, the concentrated water outlet of reverse osmosis unit (RO) connects with the 2# inlet of evaporated crystallization device (VC), reverse osmosis unit (RO) Produce water out and reuse water tank (T6) 1# water inlet connect, reuse water tank (T6) water outlet pass through reuse water pump (P12) send out Recycle-water (RUW)；Centrifuge filtrate is subjected to concentration decrement here with reverse osmosis, to reduce evaporation capacity, to reduce evaporation fortune Row expense, while purified production water reuse；Precipitation high ammonia-nitrogen wastewater resins exchange system is discharged (RS2Out) it is connected to evaporation knot Brilliant material feeding box (T7) 1# inlet, evaporative crystallization material feeding box T7Liquid outlet pass through evaporative crystallization feed pump (P13) tied with evaporation The inlet of brilliant device (VC) connects, and evaporative crystallization condensate (VCW) is connected to recycle-water by the water outlet of evaporated crystallization device (VC) Case (T6) 2# water inlet, the salt outlet of evaporated crystallization device (VC) sends out crystal salt；Realize by precipitation high ammonia-nitrogen wastewater with from The processing of scheming filtrate produces water and is back to use the multiple production workshop sections of vanadium extraction, and ammonium chloride, sodium chloride also obtain reuse, while having recycled partially Sodium vanadate has achieved the purpose that deposition vanadium mother liquid and wash water recycling treatment.
6. deposition vanadium mother liquid and wash water recycling processing method, it is characterized in that including the following steps:
1) by Centrifuge filtrate pretreatment system, by the heavy metal ion and suspended matter removal, COD value drop in Centrifuge filtrate As low as < 20mg/L；
2) by Centrifuge filtrate resins exchange system, the metavanadic acid root in Centrifuge filtrate is adsorbed, sodium metavanadate is desorbed, And send system to send precipitation pond back to using the storage of vanadium stripping liquid, so that vanadium resource is recycled, the rate of recovery >=90%；
3) by counter-infiltration system, the Centrifuge filtrate after pretreatment and adsorption of vanadium is subjected to concentration decrement and purification, concentration 4~ 6.6 times, its TDS is concentrated to 50000~100000mg/L, to reduce the expense of subsequent evaporation crystallization；The TDS of the production water of purification ≤ 200mg/L meets reuse requirement；
4) by precipitation high ammonia-nitrogen wastewater pretreatment system, by precipitation high ammonia-nitrogen wastewater heavy metal ion and suspended matter go It removes, and COD value is reduced to < 150mg/L, Ca2+Value is reduced to≤40mg/L；
5) by precipitation high ammonia-nitrogen wastewater resins exchange system, the metavanadic acid root in precipitation high ammonia-nitrogen wastewater is adsorbed, is desorbed Sodium metavanadate recycles vanadium resource, the rate of recovery >=90%；
6) crystallization thermal method is evaporated by evaporation and crystallization system (VCS) and divides salt, isolate the ammonium chloride of purity >=90% and pure The common salt of degree >=98%, evaporative crystallization generate TDS value≤200mg/L of condensed water, and Yan Heshui has obtained reuse.
7. deposition vanadium mother liquid according to claim 6 and wash water recycling processing method, it is characterized in that the step 1) is logical Centrifuge filtrate pretreatment system is crossed, Centrifuge filtrate electrolytic oxidation apparatus (EO is specifically utilized1) generate hypochlorite and The strong oxidizers such as hydroxy radical degradation COD, heavy-metal ion removal, and utilize Centrifuge filtrate ultrafiltration apparatus (UF1) filter out portion Divide COD, suspended matter and heavy metal reactant, COD value is reduced to≤20mg/L from 50~100mg/L；The step 2) is logical Centrifuge filtrate resins exchange system is crossed, specifically carries out the metavanadic acid root in Centrifuge filtrate using large pore anion resin Absorption is desorbed after resin is saturated using sodium hydroxide and sodium chloride, desorbs sodium metavanadate, and store up using vanadium stripping liquid System is sent to send precipitation pond back to, so that vanadium resource is recycled, the rate of recovery >=90%.
8. deposition vanadium mother liquid according to claim 6 and wash water recycling processing method, it is characterized in that the step 3) is logical It crosses counter-infiltration system, the Centrifuge filtrate after pretreatment and adsorption of vanadium is specifically utilized into the reverse osmosis concentration decrement and net of carrying out Change, is concentrated 4~6.6 times, its TDS is concentrated to 50000~100000mg/L from 10000~20000mg/L, to reduce subsequent steaming Send out the expense of crystallization；The TDS of the production water of purification is 100~200mg/L, meets reuse requirement, produces water and is back to use vanadium extraction production Multiple workshop sections；The step 4) is specifically reacted using soda ash with calcium ion by precipitation high ammonia-nitrogen wastewater pretreatment system Generate precipitation of calcium carbonate and heavy metal hydroxide precipitating, using hydrochloric acid by pH readjustment for neutrality, and using electrolytic oxidation with COD value is reduced to 60~150mg/L from 500~1000mg/L with heavy-metal ion removal by ultra-filtration filters, by Ca2+Value from 100~800mg/L is reduced to≤40mg/L.
9. deposition vanadium mother liquid according to claim 6 and wash water recycling processing method, it is characterized in that the step 5) is logical Precipitation high ammonia-nitrogen wastewater resins exchange system is crossed, the metavanadic acid root in precipitation high ammonia-nitrogen wastewater is specifically utilized into large pore anion Resin is adsorbed, and after resin saturation, is desorbed using sodium hydroxide and sodium chloride, desorbs sodium metavanadate, and utilize vanadium Stripping liquid storage send system to send precipitation pond back to, so that vanadium resource is recycled, the rate of recovery >=90%.
10. deposition vanadium mother liquid according to claim 6 and wash water recycling processing method, it is characterized in that the step 6) is logical Pervaporation crystal system (VCS), specifically by pretreatment and adsorption of vanadium after precipitation high ammonia-nitrogen wastewater and Centrifuge filtrate it is anti- Infiltration concentrated water is evaporated crystallization, and isolates the ammonium chloride of purity >=90% and the common salt of purity >=98%, evaporative crystallization TDS value≤200mg/L of condensed water is generated, common salt adds the agglomerating process of salt, chlorination back to sodium roasting low in vanadium extraction production Ammonium returns to multiple workshop sections in vanadium extraction production back to precipitation process in vanadium extraction production, condensed water.
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