CN109437444B - Recycling treatment device and method for vanadium precipitation mother liquor and washing water - Google Patents

Recycling treatment device and method for vanadium precipitation mother liquor and washing water Download PDF

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CN109437444B
CN109437444B CN201811632251.6A CN201811632251A CN109437444B CN 109437444 B CN109437444 B CN 109437444B CN 201811632251 A CN201811632251 A CN 201811632251A CN 109437444 B CN109437444 B CN 109437444B
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vanadium
ammonia nitrogen
water
high ammonia
nitrogen wastewater
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CN109437444A (en
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张博
戚可卓
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Jiangsu Zhuobo 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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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
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Abstract

The invention relates to a device and a method for recycling vanadium precipitation mother liquor and washing water, which aim at the characteristics of high ammonia nitrogen and salt-containing wastewater containing heavy metal ions, high-concentration ammonium chloride, high-concentration sodium chloride and a small amount of metavanadate in the vanadium precipitation mother liquor and washing water; for the low-concentration centrifuge filtrate, firstly, removing heavy metal ions and suspended matters by electrolytic oxidation and ultrafiltration to reduce COD value, secondly, adsorbing metavanadate ions by using resin to recover vanadium resources, and finally, concentrating, reducing and purifying by using reverse osmosis, reducing the concentrated water to carry out subsequent evaporation, and recycling the purified produced water; for high-concentration vanadium-precipitating high-ammonia-nitrogen wastewater, firstly, most of calcium ions are precipitated by utilizing sodium carbonate, heavy metal ions and suspended matters are removed by utilizing electrolytic oxidation and ultrafiltration, the COD value is reduced, secondly, metavanadate ions are adsorbed by utilizing resin, vanadium resources are recovered, finally, ammonium chloride and sodium chloride are separated by utilizing evaporation crystallization and are recycled to vanadium extraction production, and condensed water is also recycled; the purpose of recycling the vanadium precipitation mother liquor and washing water is achieved.

Description

Recycling treatment device and method for vanadium precipitation mother liquor and washing water
Technical Field
The invention relates to a device and a method for recycling vanadium precipitation mother liquor and washing water, belonging to the technical field of industrial wastewater treatment.
Background
Vanadium is a transition element with an atomic number of 23 and an atomic weight of 50.9. Vanadium is a silver gray metal with a body centered cubic structure, melting point 1890+ -10deg.C and boiling point 3380deg.C. Vanadium has good physical properties, stable chemical properties and catalytic activity, and is widely used in the fields of metallurgy, steel, chemical industry, building materials, dyes, batteries and the like.
In China, vanadium is extracted from vanadium titano-magnetite and stone coal, but stone coal reserves in China are very abundant and widely distributed in Hunan, hubei, zhejiang, jiangxi, guangdong, guangxi, guizhou, anhui, henan, shanxi, gansu and other places. Vanadium in stone coal exists mainly in 3 valence, most vanadium extraction processes are to oxidize the vanadium into 5 valence, dissolve out the vanadium by sodium metavanadate, then precipitate vanadium by using ammonium chloride to generate ammonium metavanadate, and also can be deaminized to prepare vanadium pentoxide. At present, the main process for extracting vanadium from stone coal comprises the following steps: low sodium roasting water leaching process, blank roasting acid leaching process, calcium salt roasting acid leaching process and roasting-free direct dilute acid leaching process.
The method mainly aims at extracting vanadium by a low-sodium roasting water leaching process, and comprises the following production processes: crushing ore to below 0.25 and mm, adding additives, mixing uniformly, molding into balls, oxidizing and roasting in a reverberatory furnace, pulping and leaching, solid-liquid separation, ion exchange, loading resin desorption, desorption liquid impurity removal, ammonium metavanadate precipitation/dehydration and deamination/vanadium pentoxide product. The generated vanadium precipitation mother liquor (also called vanadium precipitation high ammonia nitrogen wastewater) and washing water (also called centrifuge filtrate) are high ammonia nitrogen salt-containing wastewater containing heavy metal ions, high-concentration ammonium chloride, high-concentration sodium chloride and a small amount of metavanadate, and if the wastewater cannot be well treated, the wastewater not only can seriously pollute the environment, but also wastes nitrogen and vanadium resources. At present, a part of the patent for treating and recycling the vanadium precipitation wastewater generated by extracting vanadium through a low-sodium roasting water leaching process, such as a method for recycling the high-salt wastewater generated by extracting vanadium from 201210130522.4 vanadium slag, mainly comprises the steps of adding alkali into the high-salt wastewater for removing calcium and magnesium and metal impurity ions, further adding alkali for ammonia distillation, absorbing ammonia gas by acid, evaporating for crystallizing ammonium salt, evaporating for crystallizing sodium salt from deamination wastewater, and recycling condensed water; the method adopts the steps of firstly evaporating ammonia, then absorbing ammonia by acid, evaporating and crystallizing ammonium salt, and evaporating and crystallizing ammonia-evaporating wastewater to obtain sodium salt, wherein the method has 3 evaporation processes, has high operation cost, does not recycle metavanadate, and wastes vanadium resources. Another patent 201010574183.X is a treatment method of vanadium precipitation wastewater, which mainly comprises the steps of adding alkali into the vanadium precipitation wastewater to remove heavy metals, improving pH to convert ammonium ions into ammonia, deaminizing an ammonia nitrogen separation membrane, absorbing sulfuric acid to produce ammonium sulfate, concentrating the ammonia sulfate by reverse osmosis after deamination to obtain sodium sulfate, and recycling produced water; firstly deaminizing by using a membrane, absorbing ammonium sulfate by sulfuric acid, concentrating to obtain sodium sulfate, and not recovering metavanadate. At present, a new vanadium precipitation mother liquor and washing water recycling treatment technology needs to be developed.
Disclosure of Invention
The invention provides a device and a method for recycling vanadium precipitation mother liquor and washing water, and aims at low-sodium roasting waterThe heavy metal ion, high concentration ammonium chloride, high concentration sodium chloride and small amount of metavanadate high ammonia nitrogen containing wastewater, which is vanadium precipitation mother liquor (vanadium precipitation high ammonia nitrogen wastewater) and washing water (centrifuge filtrate) generated by leaching vanadium, are seriously polluted by improper treatment, and the problems of nitrogen and vanadium resource waste are solved. For the low-concentration centrifuge filtrate, firstly, removing heavy metal ions and suspended matters by electrolytic oxidation and ultrafiltration to reduce COD value, secondly, adsorbing metavanadate ions by using resin to recover vanadium resources, and finally, concentrating, reducing and purifying by using reverse osmosis, reducing the concentrated water to carry out subsequent evaporation, and recycling the purified produced water; before treatment, the COD value of the filter liquor of the centrifugal machine is 50-100 mg/L, V 5+ The (vanadium ion) value is 10-60 mg/L, TDS value is 10000-20000 mg/L, the COD value is 10-20 mg/L after treatment, the removal rate of COD reaches 80%, V 5+ The (vanadium ion) value is 1-6 mg/L, the recovery rate of vanadium ion reaches 90%, the TDS value of concentrated water is 50000-100000 mg/L, the concentration is 4-6.6 times, the TDS value of produced water is 100-200 mg/L, and the desalination rate of produced water reaches 99%; for high-concentration vanadium-precipitating high ammonia nitrogen wastewater, firstly, most calcium ions and heavy metal ions are precipitated by utilizing sodium carbonate, the heavy metal ions and suspended matters are removed by utilizing electrolytic oxidation and ultrafiltration, the COD value is reduced, secondly, metavanadate ions are adsorbed by utilizing resin, vanadium resources are recovered, finally, ammonium chloride and sodium chloride are separated by utilizing evaporation crystallization and are recycled to vanadium extraction production, and condensed water is recycled; ca of vanadium precipitation high ammonia nitrogen wastewater before treatment 2+ The (calcium ion) value is 100-800 mg/L, COD value is 500-1000 mg/L, V 5+ (vanadium ion) value is 100-600 mg/L, and after treatment, ca 2+ The (calcium ion) value is less than or equal to 40mg/L, ca 2+ The removal rate of (calcium ions) reaches 60 to 95 percent, the COD value is 60 to 150mg/L, the removal rate of COD reaches 85 to 88 percent, V 5+ The (vanadium ion) value is less than or equal to 10mg/L, and the recovery rate of the vanadium ion is more than or equal to 90 percent; the purpose of recycling the vanadium precipitation mother liquor and washing water is achieved.
The technical solution of the invention is as follows: the recycling treatment device for vanadium precipitation mother liquor and washing water structurally comprises a centrifugal machine filtrate pretreatment system PTS 1 Centrifuge filtrate resin exchange system RS 1 ROS, precipitating vanadium in reverse osmosis systemPTS (PTS) of high ammonia nitrogen wastewater pretreatment system 2 Resin exchange system RS for vanadium precipitation high ammonia nitrogen wastewater 2 The system comprises an evaporation crystallization system VCS and a vanadium desorption solution storage and delivery system VLS; wherein the centrifuge filtrate CMFL is connected to a centrifuge filtrate pretreatment system PTS 1 By using a centrifugal machine filtrate pretreatment system PTS 1 Heavy metal ions in the filter liquor of the centrifugal machine are removed, and the COD value is reduced to less than 20mg/L; centrifuge filtrate pretreatment system PTS 1 Sending out the ultrafiltered backwash drain SW of the centrifugal filter liquor from the backwash water outlet of the (B) to a PTS of a vanadium precipitation high ammonia nitrogen wastewater pretreatment system 2 Is arranged in the centrifuge filtrate pretreatment system PTS 1 Is connected with a centrifugal machine filtrate resin exchange system RS 1 Is connected with the water inlet of a filter liquor resin exchange system RS of a centrifugal machine 1 Adsorb metavanadate ion in centrifuge filtrate, centrifuge filtrate resin exchange system RS 1 The liquid outlet of the vanadium desorption liquid storage and delivery system VLS is connected with the No. 1 liquid inlet of the vanadium desorption liquid storage and delivery system VLS, the liquid outlet of the vanadium desorption liquid storage and delivery system VLS is used for delivering vanadium desorption liquid (sodium metavanadate) VL, and vanadium is precipitated again in a vanadium precipitation tank of a vanadium extraction production system, so that the purpose of recovering vanadium resources is achieved; centrifuge filtrate resin exchange system RS 1 The water outlet of the centrifugal machine filtrate after pretreatment and vanadium adsorption is concentrated and reduced by 4 to 6.6 times by utilizing the reverse osmosis system ROS, and the TDS is concentrated to 50000 to 100000mg/L so as to reduce the cost of subsequent evaporation and crystallization; the concentrated water outlet of the ROS (reactive oxygen species) of the reverse osmosis system sends out reverse osmosis concentrated water ROCW to the 2# concentrated water inlet of the VCS of the evaporative crystallization system, the TDS (total dissolved solids) of the water produced by the ROS of the reverse osmosis system is less than or equal to 200mg/L, the recycling requirement is met, and the water outlet of the ROS of the reverse osmosis system sends out recycled water RUW; the SVWW of the vanadium-precipitation high ammonia nitrogen wastewater is connected to a PTS of the vanadium-precipitation high ammonia nitrogen wastewater pretreatment system 2 1# water inlet of (1), utilize heavy vanadium high ammonia nitrogen wastewater pretreatment system PTS 2 Heavy metal ions in the vanadium-precipitating high ammonia nitrogen wastewater are removed, and the COD value is reduced to be less than or equal to 150mg/L, ca 2+ (calcium ions) is reduced to less than or equal to 40mg/L; PTS (PTS) of vanadium precipitation high ammonia nitrogen wastewater pretreatment system 2 Delivering mud cake SC from mud outlet of the system, and precipitating vanadium and high ammonia nitrogen wastewater pretreatment system PTS 2 Is connected with a water outlet of a vanadium precipitation high ammonia nitrogen wastewater resin exchange system RS 2 Is connected with the water inlet of the high ammonia nitrogen wastewater resin exchange system RS by utilizing vanadium precipitation 2 Adsorbing metavanadate ions in vanadium-precipitation high-ammonia-nitrogen wastewater, and adsorbing resin exchange system RS of vanadium-precipitation high-ammonia-nitrogen wastewater 2 The liquid outlet of the (2) is connected with the liquid inlet of the VLS; resin exchange system RS for vanadium precipitation high ammonia nitrogen wastewater 2 The water outlet of the wastewater with high ammonia nitrogen content, which is pretreated and adsorbed with vanadium, is evaporated and crystallized by the evaporating and crystallizing system VCS to separate ammonium chloride with purity more than or equal to 90% and sodium chloride with purity more than or equal to 98%, which meet the recycling requirement of salt, and the TDS value of condensed water produced by evaporating and crystallizing is less than or equal to 200mg/L, which also meets the recycling requirement; the Salt outlet of the VCS of the evaporative crystallization system sends out crystallized Salt (ammonium chloride, sodium chloride) Salt. As a result, the vanadium precipitation mother liquor and the washing water recycling treatment device respectively treat the filtrate of the centrifugal machine and the high ammonia nitrogen wastewater of the vanadium precipitation, thereby not only recovering precious metavanadate ions and recycling ammonium chloride and sodium chloride, but also recycling produced water and condensed water into the production of extracting vanadium, and achieving the purpose of recycling the vanadium precipitation mother liquor and the washing water.
Here, the production of OH (hydroxyl radical) and ClO by electrolytic oxidation is aimed at － And (2) oxidizing the organic pollutants in the wastewater by a strong oxidant such as hypochlorite and the like to reduce the COD value. The basic chemical equation is as follows:
2H 2 O → 2·OH + 2H + + 2e － （1）
organic + & OH & gtCO 2 ↑ + H 2 O （2）
Cl 2 + H 2 O → ClO － + H + + Cl － （3）
Organic + ClO - → CO 2 ↑ + H 2 O （4）
Aiming at salt separation by an evaporation crystallization heat method, the difference of the relationship between saturated concentration and temperature of sodium chloride and ammonium chloride is utilized, and the solubility of the sodium chloride and the ammonium chloride is shown as follows:
solubility meter of sodium chloride and ammonium chloride (unit: g/100 ml)
As is clear from the table, the saturated concentration of sodium chloride does not change much with temperature, but the saturated concentration of ammonium chloride changes much with temperature, so that the difference of the two can be utilized, for example, forced circulation evaporation is utilized, continuous circulation evaporation concentration is carried out at 100 ℃, sodium chloride is separated by crystallization, when the ammonium chloride is close to saturation, the ammonium chloride is separated by crystallization by cooling to 20-40 ℃, and then the next evaporation concentration and crystallization separation evaporation crystallization process is carried out, so that the purity of the obtained sodium chloride is more than or equal to 98%, and the purity of the ammonium chloride is more than or equal to 90%.
The method for recycling the vanadium precipitation mother liquor and the washing water comprises the following steps:
1) Removing heavy metal ions and suspended matters in the filter liquor of the centrifugal machine through a filter liquor pretreatment system of the centrifugal machine, and reducing the COD value to less than 20mg/L;
2) Adsorbing and desorbing sodium metavanadate from the filtrate of the centrifugal machine by using a resin exchange system of the filtrate of the centrifugal machine, and sending the sodium metavanadate back to a vanadium precipitation tank by using a vanadium desorption liquid storage and delivery system, so that vanadium resources are recovered, and the recovery rate is more than or equal to 90%;
3) Concentrating, reducing and purifying the pretreated and vanadium-adsorbed centrifugal filtrate by a reverse osmosis system for 4-6.6 times, and concentrating the TDS to 50000-100000 mg/L to reduce the cost of subsequent evaporation and crystallization; the TDS of the purified produced water is less than or equal to 200mg/L, and the recycling requirement is met;
4) Heavy metal ions and suspended matters in the vanadium-precipitating high ammonia-nitrogen wastewater are removed through the vanadium-precipitating high ammonia-nitrogen wastewater pretreatment system, and the COD value is reduced to less than 150mg/L, ca 2+ The value is reduced to be less than or equal to 40mg/L;
5) Adsorbing metavanadate in the vanadium-precipitation high ammonia nitrogen wastewater by a resin exchange system, desorbing sodium metavanadate, and recovering vanadium resources, wherein the recovery rate is more than or equal to 90%;
6) The VCS represents an evaporative crystallization system, and the salt is separated by an evaporative crystallization thermal method, so that ammonium chloride with the purity of more than or equal to 90% and sodium chloride with the purity of more than or equal to 98% are separated, and the TDS value of condensate water produced by evaporative crystallization is less than or equal to 200mg/L, so that both the salt and water are recycled.
The invention has the advantages that the device and the method for recycling the vanadium precipitation mother liquor and the washing water are aimed at the characteristics of the high ammonia nitrogen salt-containing wastewater containing heavy metal ions, high-concentration ammonium chloride, high-concentration sodium chloride and a small amount of metavanadate; for the low-concentration centrifuge filtrate, firstly, removing heavy metal ions and suspended matters by electrolytic oxidation and ultrafiltration to reduce COD value, secondly, adsorbing metavanadate ions by using resin to recover vanadium resources, and finally, concentrating, reducing and purifying by using reverse osmosis, reducing the concentrated water to carry out subsequent evaporation, and recycling the purified produced water; for high-concentration vanadium-precipitating high-ammonia-nitrogen wastewater, firstly, most of calcium ions are precipitated by utilizing sodium carbonate, heavy metal ions and suspended matters are removed by utilizing electrolytic oxidation and ultrafiltration, the COD value is reduced, secondly, metavanadate ions are adsorbed by utilizing resin, vanadium resources are recovered, finally, ammonium chloride and sodium chloride are separated by utilizing evaporation crystallization and are recycled to vanadium extraction production, and condensed water is also recycled; the purpose of recycling the vanadium precipitation mother liquor and washing water is achieved.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a vanadium precipitation mother liquor and washing water recycling treatment device.
In the drawing, CMFL represents centrifuge filtrate, RUW represents reuse water, SVWW represents vanadium precipitation high ammonia nitrogen wastewater, salt represents (ammonium chloride and sodium chloride) crystal Salt, VL represents vanadium desorption liquid (sodium metavanadate), ROCW represents reverse osmosis concentrated water, VCW represents evaporation crystal condensate, SC represents mud cake, SW represents ultrafiltration backwash drainage of the centrifuge filtrate; PTS (presentation time System) 1 Representing a centrifuge filtrate pretreatment system, RS 1 Represents the centrifuge filtrate resin exchange system, ROS represents the reverse osmosis system, PTS 2 Represents a vanadium precipitation high ammonia nitrogen wastewater pretreatment system, RS 2 The method is characterized in that the method is used for representing a vanadium precipitation high ammonia nitrogen wastewater resin exchange system, VCS represents an evaporative crystallization system, and VLS represents a vanadium desorption solution storage and delivery system.
FIG. 2 is a schematic diagram of a centrifugal machine filtrate pretreatment system of a vanadium precipitation mother liquor and washing water recycling treatment device.
In the drawing, CMFL represents the filter liquor of the centrifugal machine, SW represents the ultrafiltration backwash drain of the filter liquor of the centrifugal machine, PT 1 out represents the effluent of the centrifuge filtrate pretreatment system; PTS (presentation time System) 1 Representing a centrifuge filtrate pretreatment system; t (T) 1 Represents the filtrate tank of the centrifuge, EO 1 Represents the electrolytic oxidation device of the filter liquor of the centrifugal machine, UF 1 Represents a centrifugal machine filtrate ultrafiltration device T 2 Represents an ultrafiltration water producing tank D 1 Representing a device for adding hydrochloric acid into the filtrate of the centrifugal machine; p (P) 1 Represents a centrifugal machine filtrate booster pump, P 2 Represents a reverse osmosis water supply pump, P 3 Showing the ultrafiltration backwash pump of the centrifuge filtrate.
FIG. 3 is a schematic diagram of a vanadium precipitation high ammonia nitrogen wastewater pretreatment system of a vanadium precipitation mother liquor and washing water recycling treatment device.
SVWW in the drawing represents vanadium precipitation high ammonia nitrogen wastewater, SC represents mud cake, SW represents ultrafiltration backwash drainage of centrifuge filtrate, PT 2 out represents effluent of the vanadium precipitation high ammonia nitrogen wastewater pretreatment system; PTS (presentation time System) 2 Representing a vanadium precipitation high ammonia nitrogen wastewater pretreatment system; t (T) 3 ST represents a sedimentation tank, T represents a high ammonia nitrogen wastewater tank 4 Represents an intermediate tank, EO 2 Represents an electrolytic oxidation device for vanadium precipitation high ammonia nitrogen wastewater, UF 2 Represents an ultrafiltration device for vanadium precipitation and high ammonia nitrogen wastewater, T 5 Represents a high ammonia nitrogen concentrated water tank, SD represents a sludge dewatering system, D 2 Indicating soda ash and coagulant adding device D 3 Represents a hydrochloric acid adding device for vanadium precipitation high ammonia nitrogen wastewater; p (P) 5 P represents a booster pump for vanadium precipitation high ammonia nitrogen wastewater 6 Represents an intermediate transfer pump, P 7 Representing VCS fluid supply pump, P 8 Represents an ultrafiltration backwash pump of vanadium precipitation high ammonia nitrogen wastewater, P 9 Represents a reflux pump of a vanadium precipitation high ammonia nitrogen wastewater pretreatment system.
FIG. 4 is a schematic diagram of the resin exchange system and the vanadium desorption solution storage and delivery system of the vanadium precipitation mother liquor and washing water recycling treatment device.
RS in the accompanying drawings 1 Representing a centrifuge filtrate resin exchange system, RS 2 The VLS represents a vanadium desorption solution storage and delivery system; PT (PT) 1 out represents the centrifuge filtratePretreatment system effluent, PT 2 out represents effluent of vanadium precipitation high ammonia nitrogen wastewater pretreatment system, RS 1 out represents the effluent of the centrifugal machine filtrate resin exchange system, RS 2 out represents effluent of a resin exchange system of the vanadium precipitation high ammonia nitrogen wastewater, and VL represents vanadium desorption liquid (sodium metavanadate); d (D) 4 Sodium chloride and ammonium chloride feeding device for representing filtrate of centrifugal machine, D 5 Sodium chloride and ammonium chloride feeding device for vanadium precipitation high ammonia nitrogen wastewater and RST 1 RST represents the filtrate resin adsorption tank of the centrifuge 2 The VLT represents a sodium metavanadate desorption solution tank; p (P) 10 Represents a sodium metavanadate desorption solution delivery pump.
FIG. 5 is a schematic diagram of the reverse osmosis system and the evaporative crystallization system of the vanadium precipitation mother liquor and washing water recycling treatment device.
ROS in the figures represent reverse osmosis systems, VCS represents evaporative crystallization systems; RS (Reed-Solomon) 1 out represents the effluent of the centrifugal machine filtrate resin exchange system, RS 2 out represents effluent of a vanadium precipitation high ammonia nitrogen wastewater resin exchange system, RUW represents reuse water, salt represents crystal Salt (ammonium chloride and sodium chloride), ROCW represents reverse osmosis concentrated water, and VCW represents evaporation crystal condensate; d (D) 6 The scale inhibitor adding device, the SFF, the security filter, the RO, the reverse osmosis device, the VC, the evaporating and crystallizing device and the T are shown in the specification 6 Indicating a reuse water tank T 7 Representing an evaporative crystallization feed box; p (P) 11 Represents a reverse osmosis high-pressure pump, P 12 Represents a recycling water pump, P 13 Indicating an evaporative crystallization feed pump.
FIG. 6 is a water balance diagram of an embodiment of a device for recycling vanadium precipitation mother liquor and washing water.
Detailed Description
Referring to fig. 1, the recycling treatment device for vanadium precipitation mother liquor and washing water structurally comprises a centrifugal machine filtrate pretreatment system PTS 1 Centrifuge filtrate resin exchange system RS 1 ROS (reactive oxygen species) and vanadium precipitation high ammonia nitrogen wastewater pretreatment system PTS (PTS) of reverse osmosis system 2 Resin exchange system RS for vanadium precipitation high ammonia nitrogen wastewater 2 The system comprises an evaporation crystallization system VCS and a vanadium desorption solution storage and delivery system VLS; wherein the centrifuge filtersThe liquid CMFL is connected to a centrifuge filtrate pretreatment system PTS 1 By using a centrifugal machine filtrate pretreatment system PTS 1 Heavy metal ions in the filter liquor of the centrifugal machine are removed, and the COD value is reduced to less than 20mg/L; centrifuge filtrate pretreatment system PTS 1 Sending out the ultrafiltered backwash drain SW of the centrifugal filter liquor from the backwash water outlet of the (B) to a PTS of a vanadium precipitation high ammonia nitrogen wastewater pretreatment system 2 Is arranged in the centrifuge filtrate pretreatment system PTS 1 Is connected with a centrifugal machine filtrate resin exchange system RS 1 Is connected with the water inlet of a filter liquor resin exchange system RS of a centrifugal machine 1 Adsorb metavanadate ion in centrifuge filtrate, centrifuge filtrate resin exchange system RS 1 The liquid outlet of the vanadium desorption liquid storage and delivery system VLS is connected with the No. 1 liquid inlet of the vanadium desorption liquid storage and delivery system VLS, the liquid outlet of the vanadium desorption liquid storage and delivery system VLS is used for delivering vanadium desorption liquid (sodium metavanadate) VL, and vanadium is precipitated again in a vanadium precipitation tank of a vanadium extraction production system, so that the purpose of recovering vanadium resources is achieved; centrifuge filtrate resin exchange system RS 1 The water outlet of the centrifugal machine filtrate after pretreatment and vanadium adsorption is concentrated and reduced by 4 to 6.6 times by utilizing the reverse osmosis system ROS, and the TDS is concentrated to 50000 to 100000mg/L so as to reduce the cost of subsequent evaporation and crystallization; the concentrated water outlet of the ROS (reactive oxygen species) of the reverse osmosis system sends out reverse osmosis concentrated water ROCW to the 2# concentrated water inlet of the VCS of the evaporative crystallization system, the TDS (total dissolved solids) of the water produced by the ROS of the reverse osmosis system is less than or equal to 200mg/L, the recycling requirement is met, and the water outlet of the ROS of the reverse osmosis system sends out recycled water RUW; the SVWW of the vanadium-precipitation high ammonia nitrogen wastewater is connected to a PTS of the vanadium-precipitation high ammonia nitrogen wastewater pretreatment system 2 1# water inlet of (1), utilize heavy vanadium high ammonia nitrogen wastewater pretreatment system PTS 2 Heavy metal ions in the vanadium-precipitating high ammonia nitrogen wastewater are removed, and the COD value is reduced to be less than or equal to 150mg/L, ca 2+ (calcium ions) is reduced to less than or equal to 40mg/L; PTS (PTS) of vanadium precipitation high ammonia nitrogen wastewater pretreatment system 2 Delivering mud cake SC from mud outlet of the system, and precipitating vanadium and high ammonia nitrogen wastewater pretreatment system PTS 2 Is connected with a water outlet of a vanadium precipitation high ammonia nitrogen wastewater resin exchange system RS 2 Is connected with the water inlet of the high ammonia nitrogen wastewater resin exchange system RS by utilizing vanadium precipitation 2 Resin exchange system for absorbing metavanadate ions in vanadium-precipitation high-ammonia-nitrogen wastewaterRS 2 The liquid outlet of the (2) is connected with the liquid inlet of the VLS; resin exchange system RS for vanadium precipitation high ammonia nitrogen wastewater 2 The water outlet of the wastewater with high ammonia nitrogen content, which is pretreated and adsorbed with vanadium, is evaporated and crystallized by the evaporating and crystallizing system VCS to separate ammonium chloride with purity more than or equal to 90% and sodium chloride with purity more than or equal to 98%, which meet the recycling requirement of salt, and the TDS value of condensed water produced by evaporating and crystallizing is less than or equal to 200mg/L, which also meets the recycling requirement; the Salt outlet of the VCS of the evaporative crystallization system sends out crystallized Salt (ammonium chloride, sodium chloride) Salt. As a result, the vanadium precipitation mother liquor and the washing water recycling treatment device respectively treat the filtrate of the centrifugal machine and the high ammonia nitrogen wastewater of the vanadium precipitation, thereby not only recovering precious metavanadate ions and recycling ammonium chloride and sodium chloride, but also recycling produced water and condensed water into the production of extracting vanadium, and achieving the purpose of recycling the vanadium precipitation mother liquor and the washing water.
Referring to FIG. 2, centrifuge filtrate pretreatment System PTS 1 The structure of the filter tank comprises a filter tank T of a centrifugal machine 1 EO (ethylene oxide) electrolytic oxidation device for filtrate of centrifugal machine 1 UF of centrifugal machine filtrate ultrafiltration device 1 Ultrafiltration water producing tank T 2 Centrifuge filtrate hydrochloric acid adding device D 1 And centrifuge filtrate booster pump P 1 Reverse osmosis water supply pump P 2 Ultrafiltration backwash pump P for centrifugal filter liquor 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the centrifuge filtrate CMFL is connected to a centrifuge filtrate tank T 1 Is provided with a water inlet of a centrifugal machine filtrate tank T 1 Is passed through a centrifugal filter liquor booster pump P 1 EO electrolytic oxidation device with centrifuge filtrate 1 Is connected with the water inlet of the centrifuge filtrate hydrochloric acid adding device D 1 The drug outlet of (2) is also connected with EO of the filter liquor electrolytic oxidation device of the centrifugal machine 1 Is connected with the water inlet of the electrolytic oxidation device EO for the filtrate of the centrifugal machine 1 UF of the water outlet of the centrifuge filtrate ultrafiltration device 1 Is connected with the water inlet of the UF of the filter liquor ultrafiltration device of the centrifugal machine 1 Is provided with a water outlet and an ultrafiltration water producing tank T 2 Is connected with the water inlet of the ultrafiltration water producing tank T 2 Is ultrafiltered and backwashed by a centrifuge filtrate through a backwashed water outlet of a centrifuge 3 UF ultrafiltration device for filtrate of centrifugal machine 1 Is of (2)Water inlet is connected, and centrifugal machine filtrate ultrafiltration device UF 1 The backwash water outlet of the (B) is sent out of the ultrafiltration backwash drainage SW of the filter liquor of the centrifugal machine, and the ultrafiltration water producing tank T 2 Through the reverse osmosis water supply pump P 2 Effluent PT of filtrate pretreatment system of centrifugal machine 1 out; EO electrolytic oxidation device using centrifuge filtrate 1 The generated hypochlorite and hydroxyl free radical and other strong oxidants degrade COD, remove heavy metal ions, and ultrafilter UF by using the filter liquor of a centrifuge 1 Filtering out partial COD, suspended matters and heavy metal reactant and reducing the COD value to less than or equal to 20mg/L.
Referring to fig. 3, a PTS (PTS) system for pretreating vanadium precipitation high ammonia nitrogen wastewater 2 The structure of the high ammonia nitrogen wastewater tank T comprises a vanadium precipitation high ammonia nitrogen wastewater tank T 3 A sedimentation tank ST and an intermediate water tank T 4 EO (ethylene oxide) electrolytic oxidation device for vanadium precipitation high ammonia nitrogen wastewater 2 UF (UF) ultrafiltration device for vanadium precipitation high ammonia nitrogen wastewater 2 High ammonia nitrogen concentrated water tank T 5 Device D for adding sodium carbonate and coagulant into sludge dewatering system SD and sodium carbonate and coagulant 2 Device D for adding hydrochloric acid into vanadium precipitation high ammonia nitrogen wastewater 3 And vanadium precipitation high ammonia nitrogen wastewater booster pump P 5 Intermediate transfer pump P 6 Liquid supply pump P of evaporative crystallization system 7 Ultrafiltration backwash pump P for vanadium precipitation high ammonia nitrogen wastewater 8 Reflux pump P of vanadium precipitation high ammonia nitrogen wastewater pretreatment system 9 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the vanadium precipitation high ammonia nitrogen wastewater SVWW is connected to the vanadium precipitation high ammonia nitrogen wastewater tank T 3 Is a water inlet of a vanadium precipitation high ammonia nitrogen waste water tank T 3 Is passed through vanadium precipitation high ammonia nitrogen wastewater booster pump P 5 Connected with the water inlet of the sedimentation tank ST, and the soda ash and coagulant adding device D 2 The medicine outlet of the sedimentation tank is also connected with the water inlet of the sedimentation tank ST, the mud outlet of the sedimentation tank ST is connected with the 1# mud inlet of the sludge dewatering system SD, the ultrafiltration backwash drainage SW of the centrifugal machine filtrate is connected to the 3# mud inlet of the sludge dewatering system SD, the sludge dewatering system SD is utilized for filter pressing, dry mud and filtrate are separated, the mud cake SC is sent out from the mud outlet of the sludge dewatering system SD, and the liquid outlet of the sludge dewatering system SD passes through the reflux pump P of the vanadium precipitation high ammonia nitrogen wastewater pretreatment system 9 Sending filtrate back to vanadium high ammonia nitrogen waste water tank T 3 Is provided with a liquid inlet; the water outlet of the sedimentation tank ST and the middle water tank T 4 Is connected with the water inlet of the water tank,intermediate water tank T 4 Through the middle delivery pump P 6 EO (ethylene oxide) electrolytic oxidation device for vanadium precipitation high ammonia nitrogen wastewater 2 Is connected with a water inlet of the device D for adding hydrochloric acid into the vanadium-precipitating high ammonia nitrogen wastewater 3 The drug outlet of the (E) is also connected with EO of the vanadium precipitation high ammonia nitrogen wastewater electrolytic oxidation device 2 Is connected with the water inlet of the electrolytic oxidation device EO for the vanadium-precipitating high ammonia nitrogen wastewater 2 UF (UF) ultrafiltration device for water outlet and vanadium precipitation high ammonia nitrogen wastewater 2 Is connected with the water inlet of the UF ultrafiltration device for the vanadium precipitation high ammonia nitrogen wastewater 2 Is provided with a water outlet and a high ammonia nitrogen concentration water tank T 5 Is connected with the water inlet of the high ammonia nitrogen concentrated water tank T 5 Is ultrafiltered and backwashed by a backwashed water outlet of the high ammonia nitrogen wastewater through vanadium precipitation 8 UF (UF) ultrafiltration device for vanadium-precipitating high ammonia nitrogen wastewater 2 UF of ultrafiltration device for vanadium-precipitating high ammonia nitrogen wastewater with the backwash water inlet connected 2 The backwash water discharge port of the sewage treatment system is connected to a No. 2 sludge inlet of a sludge dewatering system SD, and a high ammonia nitrogen concentrated water tank T 5 The water outlet of the (B) is communicated with a liquid supply pump P of an evaporation crystallization system 7 Effluent PT of pretreatment system for delivering vanadium-precipitating high ammonia nitrogen wastewater 2 out; the method comprises the steps of generating calcium carbonate precipitate and heavy metal hydroxide precipitate through the reaction of sodium carbonate and calcium ions, adjusting the pH to be neutral by using hydrochloric acid, removing heavy metal ions by using electrolytic oxidation and ultrafiltration filtration, reducing the COD value to be less than or equal to 150mg/L, and reducing the calcium ions to be less than or equal to 40mg/L.
Referring to FIG. 4, the resin exchange system PTS 1 、PTS 2 The structure of the system comprises a centrifugal machine filtrate resin adsorption tank RST, and a vanadium desorption liquid storage and delivery system VLS 1 RST (RST) of vanadium precipitation high ammonia nitrogen wastewater resin adsorption tank 2 Sodium chloride and ammonium chloride feeding device D for sodium metavanadate desorption tank VLT and centrifuge filtrate 4 Sodium chloride and ammonium chloride feeding device D for vanadium precipitation high ammonia nitrogen wastewater 5 Sodium metavanadate desorption liquid delivery pump P 10 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the effluent PT of the centrifuge filtrate pretreatment system 1 out is connected with a filter liquor resin adsorption tank RST of the centrifugal machine 1 Sodium chloride and ammonium chloride adding device D for filtrate of centrifugal machine 4 Is arranged at the drug outlet of the filter liquid resin adsorption tank RST of the centrifugal machine 1 Is connected with the medicine inlet of the filter liquor resin adsorption tank RST of the centrifugal machine 1 Is provided with a liquid outlet1# liquid inlet of sodium metavanadate desorption liquid tank VLT is connected, and centrifuge filtrate resin adsorption tank RST 1 Is sent out of the water outlet RS of the filter liquor resin exchange system of the centrifugal machine 1 out; effluent PT of vanadium precipitation high ammonia nitrogen wastewater pretreatment system 2 out is connected to vanadium precipitation high ammonia nitrogen wastewater resin adsorption tank RST 2 Sodium chloride and ammonium chloride adding device D for vanadium precipitation high ammonia nitrogen wastewater 5 RST of chemical outlet and vanadium precipitation high ammonia nitrogen wastewater resin adsorption tank 2 Is connected with the chemical inlet of the resin adsorption tank RST for precipitating vanadium and high ammonia nitrogen wastewater 2 The liquid outlet of the (2) is connected with the liquid inlet of the 2# liquid inlet of the sodium metavanadate desorption liquid tank VLT, and the vanadium precipitation high ammonia nitrogen wastewater resin adsorption tank RST 2 Is sent out from a water outlet RS of a vanadium precipitation high ammonia nitrogen wastewater resin exchange system 2 out; the liquid outlet of the sodium metavanadate desorption liquid tank VLT passes through a sodium metavanadate desorption liquid delivery pump P 10 Delivering a vanadium desorption solution (sodium metavanadate) VL; here, the metavanadate is adsorbed by using macroporous anion resin, and after the resin is saturated, sodium hydroxide and sodium chloride are used for desorption to obtain sodium metavanadate, and vanadium is removed, so that the vanadium resources lost in the wastewater are recovered.
Referring to FIG. 5, the structure of the RO system ROS and the VCS comprises a cartridge filter SFF, a RO device RO and a recycling water tank T 6 Feeding box T for evaporative crystallization 7 VC, scale inhibitor adding device D of evaporative crystallization device 6 And a reverse osmosis high-pressure pump P 11 Water pump P for reuse 12 Feed pump P for evaporative crystallization 13 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the centrifuge filtrate resin exchange system effluent RS 1 out is connected to the water inlet of the cartridge filter SFF, and the scale inhibitor adding device D 6 The medicine outlet of the cartridge filter SFF is also connected with the water inlet of the cartridge filter SFF, and the water outlet of the cartridge filter SFF passes through the reverse osmosis high-pressure pump P 11 The water inlet of the reverse osmosis device RO is connected with the concentrated water outlet of the reverse osmosis device RO is connected with the No. 2 liquid inlet of the evaporative crystallization device VC, and the water outlet of the reverse osmosis device RO is connected with the recycling water tank T 6 The No. 1 water inlet of (C) is connected with the water recycling tank T 6 Through the water outlet of the reuse water pump P 12 Delivering reuse water RUW; the centrifuge filtrate is concentrated and reduced by reverse osmosis toThe evaporation capacity is reduced, so that the evaporation operation cost is reduced, and meanwhile, the purified produced water is recycled; effluent RS of vanadium precipitation high ammonia nitrogen wastewater resin exchange system 2 out is connected to an evaporation crystallization feeding box T 7 No. 1 liquid inlet of (C), evaporation crystallization feeding box T 7 Through the evaporation crystallization feeding pump P 13 Is connected with a liquid inlet of an evaporative crystallization device VC, a water outlet of the evaporative crystallization device VC connects evaporative crystallization condensate VCW to a recycling water tank T 6 The Salt outlet of the evaporative crystallization device VC sends out crystallized Salt (ammonium chloride, sodium chloride) Salt. The method realizes the treatment of vanadium precipitation high ammonia nitrogen wastewater and the filtrate of a centrifugal machine, the produced water is recycled to a plurality of production sections for extracting vanadium, the ammonium chloride and sodium chloride are also recycled, and meanwhile, the sodium metavanadate is recovered, thereby achieving the purpose of recycling the vanadium precipitation mother liquor and washing water.
The method for recycling the vanadium precipitation mother liquor and the washing water comprises the following steps:
1) Removing heavy metal ions and suspended matters in the filter liquor of the centrifugal machine through a filter liquor pretreatment system of the centrifugal machine, and reducing the COD value to less than 20mg/L;
2) Adsorbing and desorbing sodium metavanadate from the filtrate of the centrifugal machine by using a resin exchange system of the filtrate of the centrifugal machine, and sending the sodium metavanadate back to a vanadium precipitation tank by using a vanadium desorption liquid storage and delivery system, so that vanadium resources are recovered, and the recovery rate is more than or equal to 90%;
3) Concentrating, reducing and purifying the pretreated and vanadium-adsorbed centrifugal filtrate by a reverse osmosis system for 4-6.6 times, and concentrating the TDS to 50000-100000 mg/L to reduce the cost of subsequent evaporation and crystallization; the TDS of the purified produced water is less than or equal to 200mg/L, and the recycling requirement is met;
4) Heavy metal ions and suspended matters in the vanadium-precipitating high ammonia-nitrogen wastewater are removed through the vanadium-precipitating high ammonia-nitrogen wastewater pretreatment system, and the COD value is reduced to less than 150mg/L, ca 2+ The value is reduced to be less than or equal to 40mg/L;
5) Adsorbing metavanadate in the vanadium-precipitation high ammonia nitrogen wastewater by a resin exchange system, desorbing sodium metavanadate, and recovering vanadium resources, wherein the recovery rate is more than or equal to 90%;
6) The VCS represents an evaporative crystallization system, and the salt is separated by an evaporative crystallization thermal method, so that ammonium chloride with the purity of more than or equal to 90% and sodium chloride with the purity of more than or equal to 98% are separated, and the TDS value of condensate water produced by evaporative crystallization is less than or equal to 200mg/L, so that both the salt and water are recycled.
The step 1) is performed by a centrifuge filtrate pretreatment system, in particular to an EO electrolytic oxidation device by utilizing the centrifuge filtrate 1 The generated hypochlorite and hydroxyl free radical and other strong oxidants degrade COD, remove heavy metal ions, and ultrafilter UF by using the filter liquor of a centrifuge 1 Filtering out partial COD, suspended matters and heavy metal reactant and reducing the COD value from 50-100 mg/L to less than or equal to 20mg/L.
And 2) adsorbing metavanadate in the centrifugal filtrate by using macroporous anion resin through a centrifugal filtrate resin exchange system, desorbing sodium metavanadate by using sodium hydroxide and sodium chloride after the resin is saturated, and sending the desorbed sodium metavanadate back to a vanadium precipitation tank by using a vanadium desorption liquid storage and delivery system, so that vanadium resources are recovered, and the recovery rate is more than or equal to 90%.
The step 3) is carried out concentration, decrement and purification by reverse osmosis on the centrifuge filtrate after pretreatment and vanadium adsorption by a reverse osmosis system, wherein the concentration is 4-6.6 times, and the TDS is concentrated from 10000-20000 mg/L to 50000-100000 mg/L so as to reduce the cost of subsequent evaporation and crystallization; the TDS of the purified produced water is 100-200 mg/L, the recycling requirement is met, and the produced water is recycled to a plurality of working sections of vanadium extraction production.
The step 4) is carried out by a vanadium precipitation high ammonia nitrogen wastewater pretreatment system, specifically, calcium carbonate precipitation and heavy metal hydroxide precipitation are generated by utilizing the reaction of sodium carbonate and calcium ions, the pH value is adjusted back to be neutral by utilizing hydrochloric acid, the heavy metal ions are removed by utilizing electrolytic oxidation and ultrafiltration filtration, the COD value is reduced from 500-1000 mg/L to 60-150 mg/L, and Ca is added into the wastewater pretreatment system by utilizing the reaction of sodium carbonate and calcium ions 2+ The value is reduced from 100 to 800mg/L to less than or equal to 40mg/L.
And 5) adsorbing metavanadate in the vanadium-precipitating high ammonia nitrogen wastewater by using macroporous anion resin through a vanadium-precipitating high ammonia nitrogen wastewater resin exchange system, desorbing sodium metavanadate by using sodium hydroxide and sodium chloride after the resin is saturated, and sending the desorbed sodium metavanadate back to a vanadium-precipitating tank by using a vanadium desorption liquid storage and delivery system, so that vanadium resources are recovered, and the recovery rate is more than or equal to 90%.
Step 6) represents an evaporative crystallization system through VCS, specifically, the pretreated and vanadium-absorbed high ammonia nitrogen wastewater and reverse osmosis concentrated water of the centrifugal machine filtrate are subjected to evaporative crystallization, ammonium chloride with the purity of more than or equal to 90% and sodium chloride with the purity of more than or equal to 98% are separated, the evaporative crystallization produces condensate water with the TDS value of less than or equal to 200mg/L, the sodium chloride is returned to a salt agglomerating process of low-sodium roasting in the vanadium extraction production, the ammonium chloride is returned to a vanadium precipitation process in the vanadium extraction production, and the condensate water is returned to a plurality of working sections in the vanadium extraction production.
Examples:
in the production process of ammonium metavanadate, stone coal is crushed, sodium salt and water are added into the stone coal to form clusters, sodium roasting is carried out on the stone coal, resin adsorption is carried out, sodium chloride and sodium hydroxide are used for desorption, ammonium chloride is added into desorption liquid to form ammonium metavanadate precipitate, and finally water washing and centrifugal separation are used for producing ammonium metavanadate products. In the process, the vanadium precipitation mother liquor (also called vanadium precipitation high ammonia nitrogen wastewater) and washing water (also called centrifuge filtrate) contain higher heavy metals, COD and TDS (mainly ammonium chloride and sodium chloride), and are high ammonia nitrogen wastewater, such as poor treatment, serious environmental pollution caused by discharge, and the project carries out recycling treatment on the high ammonia nitrogen wastewater, and simultaneously recovers the ammonium chloride, the sodium chloride and the reuse water, thereby obtaining better economic benefit and environmental benefit.
Design the quality and quantity of water
The design of the inflow water has centrifuge filtrate and vanadium precipitation high ammonia nitrogen wastewater, and the water quality index is as follows:
2. process flow
2.1 vanadium precipitation high ammonia nitrogen wastewater treatment system
Vanadium precipitation wastewater- & gt vanadium precipitation wastewater pool/lift pump (soda, coagulant- & gt sedimentation tank- & gt intermediate water tank/UF lift pump- & gt electrolytic device- & gt ultrafiltration device- & gt sodium chloride and sodium hydroxide- & gt resin adsorption tank- & gt vanadium desorption liquid tank/desorption liquid pump- & gt vanadium precipitation tank- & gt high ammonia nitrogen concentration water tank/delivery pump- & gt evaporation crystallization device- & gt RO fresh water tank of condensate removal (2.2) - & gt ammonium chloride and sodium chloride
Wherein:
sludge discharge in a sedimentation tank, ultrafiltration backwash water discharge, a sludge tank/a sludge conveying pump, a sludge dewatering device and sludge outward transportation;
and the filter pressing liquid generated by the sludge treatment device is a vanadium precipitation wastewater pool.
2.2 centrifuge filtrate treatment System
Centrifuge filtrate- & gt centrifuge filtrate tank/lift pump (hydrochloric acid- & gt electrolyzer- & gt ultrafiltration device- & gt ultrafiltration water producing tank/RO booster pump- & gt resin adsorption tank- & gt desorption liquid removal (2.1) vanadium desorption tank- & gt security filter/high pressure pump- & gt RO device- & gt concentrated water discharge to high ammonia nitrogen concentrated water tank- & gt RO fresh water tank/fresh water recycling pump- & gt water use point
Wherein:
ultrafiltration backwash drainage to go to the sludge tank of (2.1).
Water balance
The water balance of the centrifugal machine filtrate and the vanadium precipitation high ammonia nitrogen wastewater treatment project is shown in a water balance diagram of the vanadium precipitation mother liquor and washing water recycling treatment device and the method embodiment of the device in the figure 6.
Description of the Process
4.1 vanadium precipitation high ammonia nitrogen wastewater treatment system
The method comprises the steps of enabling the vanadium-precipitating high ammonia nitrogen wastewater to enter a vanadium-precipitating high ammonia nitrogen wastewater pool for storage, pressurizing the vanadium-precipitating high ammonia nitrogen wastewater by a vanadium-precipitating high ammonia nitrogen wastewater lifting pump, adding sodium carbonate and a coagulant into the water entering the sedimentation pool, forming calcium carbonate by chemical reaction of calcium ions in the water, removing the calcium carbonate by precipitation, enabling the water discharged from the sedimentation pool to enter an intermediate water tank, pressurizing the intermediate water by a UF lifting pump, entering an electrolysis device, removing heavy metal ions, entering an ultrafiltration device, removing suspended matters, colloid, part of organic matters and the like by ultrafiltration treatment, enabling ultrafiltration produced water to enter a high ammonia nitrogen concentrated water tank after vanadium is adsorbed by a resin adsorption tank, and enabling the ultrafiltration produced water to enter an evaporation crystallization device for evaporation crystallization by a conveying pump, and separating ammonium chloride and sodium chloride by a thermal method.
The sludge in the sedimentation tank and ultrafiltration backwash water are discharged to a sludge tank, and are sent to a sludge dewatering device by a sludge conveying pump, the filter-pressed mud cakes are transported to the outside for treatment, and the pressed filtrate is sent back to a vanadium precipitation wastewater tank for retreatment.
The condensate produced by the evaporative crystallization device is sent to an RO water producing tank (of the centrifuge filtrate processing system).
The resin tank is desorbed by sodium chloride and sodium hydroxide, and sodium metavanadate is produced and recycled to the vanadium precipitation tank.
4.2 centrifuge filtrate treatment system
The centrifugal machine filtrate enters a centrifugal machine filtrate tank for storage, is pressurized by a centrifugal machine filtrate lifting pump, enters an electrolysis device for removing heavy metal ions, enters an ultrafiltration device for ultrafiltration treatment for removing suspended matters, colloid, partial organic matters and the like, ultrafiltered produced water enters an ultrafiltration produced water tank, is pressurized by an RO booster pump, firstly enters a resin adsorption tank for absorbing metavanadate, the ion exchange tail water enters a security filter, is pressurized by a high-pressure pump, enters an RO device for desalination and concentration, and RO fresh water enters an RO fresh water tank, is pressurized by a fresh water recycling water pump and is sent to a water consumption point (TDS is less than or equal to 250 mg/L). And the RO concentrated water enters a high ammonia nitrogen concentrated water tank (of a vanadium precipitation high ammonia nitrogen wastewater treatment system) for further evaporation and salt separation. The ultrafiltration drainage water enters a sludge tank (of a vanadium precipitation high ammonia nitrogen wastewater treatment system) for further dehydration treatment. And (3) eluting with NaCl and NaOH after the ion exchange resin is adsorbed and saturated, and recovering sodium metavanadate.
Main design parameters of system
5.1 civil engineering:
5.2 main equipment:
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Claims (8)

1. the vanadium precipitation mother liquor and washing water recycling treatment device is characterized by comprising a centrifugal machine filtrate pretreatment system (PTS) 1 ) Centrifuge filtrate resin exchange system (RS) 1 ) Reverse Osmosis System (ROS), vanadium precipitation high ammonia nitrogen wastewater pretreatment system (PTS) 2 ) Resin exchange system (RS) of vanadium precipitation high ammonia nitrogen wastewater 2 ) A Vapor Crystallization System (VCS), a vanadium desorption liquid storage system (VLS); wherein the centrifuge filtrate (CMFL) is connected to a centrifuge filtrate pretreatment system (PTS) 1 ) Using a centrifuge filtrate pretreatment system (PTS) 1 ) Heavy metal ions in the filter liquor of the centrifugal machine are removed, and the COD value is reduced to less than 20mg/L; centrifuge filtrate pretreatment system (PTS) 1 ) Sending out the ultrafiltered backwash wastewater (SW) of the filter liquor of the centrifugal machine to a vanadium precipitation high ammonia nitrogen wastewater pretreatment system (PTS) 2 ) Is provided, and a centrifuge filtrate pretreatment system (PTS) 1 ) Is connected with the centrifugal machine filtrate resin exchange system（RS 1 ) Is connected with the water inlet of the filter liquor resin exchange system (RS) 1 ) Adsorb metavanadate ions in the centrifuge filtrate, and the centrifuge filtrate resin exchange system (RS 1 ) The liquid outlet of the vanadium desorption liquid storage and delivery system (VLS) is connected with the liquid inlet 1# of the vanadium desorption liquid storage and delivery system (VLS), the liquid outlet of the vanadium desorption liquid storage and delivery system (VLS) is used for delivering vanadium desorption liquid (VL), and vanadium is precipitated again in a vanadium precipitation tank of the vanadium extraction production system, so that the purpose of recovering vanadium resources is achieved; centrifuge filtrate resin exchange system (RS) 1 ) The water outlet of the centrifugal machine is connected with the water inlet of a Reverse Osmosis System (ROS), the centrifugal machine filtrate after pretreatment and vanadium adsorption is concentrated and reduced by 4 to 6.6 times by utilizing the ROS, and the TDS is concentrated to 50000 to 100000mg/L so as to reduce the cost of subsequent evaporation and crystallization; the concentrated water outlet of the Reverse Osmosis System (ROS) sends out Reverse Osmosis Concentrated Water (ROCW) to the 2# concentrated water inlet of the evaporative crystallization system (VCS), the TDS of the water produced by the Reverse Osmosis System (ROS) is less than or equal to 200mg/L, the recycling requirement is met, and the water outlet of the Reverse Osmosis System (ROS) sends out recycled water (RUW); the vanadium precipitation high ammonia nitrogen wastewater (SVWW) is connected to a vanadium precipitation high ammonia nitrogen wastewater pretreatment system (PTS) 2 ) 1# water inlet of (1), utilize heavy vanadium high ammonia nitrogen wastewater pretreatment system (PTS) 2 ) Heavy metal ions in the vanadium-precipitating high ammonia nitrogen wastewater are removed, and the COD value is reduced to be less than or equal to 150mg/L, ca 2+ (calcium ions) is reduced to less than or equal to 40mg/L; vanadium precipitation high ammonia nitrogen wastewater pretreatment system (PTS) 2 ) Delivering mud cake (SC) from mud outlet of the device, and precipitating vanadium and high ammonia nitrogen wastewater pretreatment system (PTS) 2 ) Is connected with a high ammonia nitrogen wastewater resin exchange system (RS) 2 ) Is connected with the water inlet of the high ammonia nitrogen wastewater resin exchange system (RS) 2 ) Adsorb metavanadate ions in high ammonia nitrogen wastewater of heavy vanadium, heavy vanadium high ammonia nitrogen wastewater resin exchange system (RS 2 ) The liquid outlet of the (2) is connected with a liquid inlet of a vanadium desorption liquid storage and delivery system (VLS); vanadium precipitation high ammonia nitrogen wastewater resin exchange system (RS) 2 ) The water outlet of the (C) is connected with the liquid inlet of an evaporative crystallization system (VCS), and the evaporative crystallization system (VCS) is utilized to evaporate and crystallize the vanadium-precipitating high ammonia nitrogen wastewater after pretreatment and vanadium adsorption, and separate ammonium chloride with the purity of more than or equal to 90 percentAnd sodium chloride with purity more than or equal to 98 percent, which all meet the recycling requirement of salt; a salt outlet of the evaporative crystallization system (VCS) is used for delivering crystallized salt;
the centrifuge filtrate pretreatment system (PTS) 1 ) The structure comprises a centrifuge filtrate tank (T) 1 ) Electrolytic oxidation device of centrifuge filtrate (EO) 1 ) UF filter of centrifuge (UF) 1 ) Ultrafiltration water producing tank (T) 2 ) Centrifuge filtrate hydrochloric acid adding device (D) 1 ) And centrifuge filtrate booster pump (P) 1 ) Reverse osmosis water supply pump (P) 2 ) Ultrafiltration backwash pump (P) for centrifugal filter liquor 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein the centrifuge filtrate (CMFL) is connected to a centrifuge filtrate tank (T) 1 ) Is a water inlet of a centrifuge filtrate tank (T) 1 ) Is passed through the filter liquor booster pump (P) 1 ) Electrolytic oxidation device (EO) 1 ) Is connected with the water inlet of the filter liquid hydrochloric acid adding device (D) 1 ) The drug outlet of (2) is also connected with a centrifuge filtrate electrolytic oxidation device (EO) 1 ) Is connected with the water inlet of the filter liquor electrolytic oxidation device (EO) 1 ) Is connected with the filter ultrafiltration device (UF) 1 ) Is connected with the water inlet of the filter liquor ultrafiltration device (UF of the centrifugal machine 1 ) Is connected with the ultrafiltration water producing tank (T) 2 ) Is connected with the water inlet of the ultrafiltration water producing tank (T) 2 ) Is ultrafiltered and backwashed by a centrifuge filtrate backwash pump (P) 3 ) UF ultrafiltration device with centrifuge filtrate (UF) 1 ) Is connected with the backwash water inlet of the filter liquor ultrafiltration device (UF 1 ) Is sent out of a backwash water outlet of the filter liquor of the centrifugal machine, ultrafiltered backwash water is drained (SW), and an ultrafiltered water producing tank (T) 2 ) Through the reverse osmosis water supply pump (P) 2 ) Effluent (PT) of the centrifuge filtrate pretreatment system 1 out); electrolytic oxidation device (EO) using centrifuge filtrate 1 ) The generated hypochlorite and hydroxyl radical and other strong oxidants degrade COD, remove heavy metal ions, and utilize a centrifuge filtrate ultrafiltration device (UF 1 ) Filtering out partial COD, suspended matters and heavy metal reactant and reducing the COD value to less than or equal to 20mg/L.
2. The recycling treatment device of vanadium precipitation mother liquor and washing water according to claim 1, characterized in that the vanadium precipitation high ammonia nitrogen wastewater pretreatment system (PTS) 2 ) The structure of the device comprises a vanadium precipitation high ammonia nitrogen waste water tank (T) 3 ) The sedimentation tank ST, the middle water tank (T) 4 ) Electrolytic oxidation device (EO) for vanadium precipitation high ammonia nitrogen wastewater 2 ) UF (UF) ultrafiltration device for vanadium precipitation high ammonia nitrogen wastewater 2 ) High ammonia nitrogen concentrated water tank (T) 5 ) SD, sodium carbonate and coagulant adding device (D) 2 ) Adding device (D) of hydrochloric acid of vanadium precipitation high ammonia nitrogen wastewater 3 ) And vanadium precipitation high ammonia nitrogen wastewater booster pump (P) 5 ) Intermediate transfer pump (P) 6 ) Liquid supply pump (P) of evaporative crystallization system 7 ) Ultrafiltration backwash pump (P) for vanadium precipitation high ammonia nitrogen wastewater 8 ) Reflux pump (P) of vanadium precipitation high ammonia nitrogen wastewater pretreatment system 9 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein the vanadium precipitation high ammonia nitrogen wastewater (SVWW) is connected to a vanadium precipitation high ammonia nitrogen wastewater tank (T) 3 ) Is a water inlet of a vanadium precipitation high ammonia nitrogen waste water tank (T) 3 ) Is passed through vanadium precipitation high ammonia nitrogen wastewater booster pump (P) 5 ) Is connected with the water inlet of the Sedimentation Tank (ST), and the sodium carbonate and coagulant adding device (D 2 ) The medicine outlet of the Sedimentation Tank (ST) is also connected with the water inlet of the Sedimentation Tank (ST), the mud outlet of the Sedimentation Tank (ST) is connected with the 1# mud inlet of the sludge dewatering System (SD), the ultrafiltration backwash drain (SW) of the centrifugal machine filtrate is connected to the 3# mud inlet of the sludge dewatering System (SD), the sludge dewatering System (SD) is utilized for filter pressing, dry mud and filtrate are separated, the mud outlet of the sludge dewatering System (SD) is used for delivering mud cakes (SC), and the liquid outlet of the sludge dewatering System (SD) is provided with a reflux pump (P) of the vanadium precipitation high ammonia nitrogen wastewater pretreatment system 9 ) Sending the filtrate back to vanadium high ammonia nitrogen waste water tank (T) 3 ) Is provided with a liquid inlet; the water outlet of the Sedimentation Tank (ST) and the middle water tank (T) 4 ) Is connected with the water inlet of the middle water tank (T) 4 ) Through the middle delivery pump (P) 6 ) Electrolytic oxidation device (EO) for high ammonia nitrogen wastewater with vanadium precipitation 2 ) Is connected with the water inlet of the device (D) 3 ) The medicine outlet of (2)Electrolytic oxidation device (EO) for high ammonia nitrogen wastewater with vanadium precipitation 2 ) Is connected with the water inlet of the high ammonia nitrogen wastewater electrolytic oxidation device (EO) 2 ) UF (UF) ultrafiltration device for water outlet and vanadium precipitation high ammonia nitrogen wastewater 2 ) Is connected with the water inlet of the ultrafiltration device (UF) 2 ) Is connected with the water outlet of the high ammonia nitrogen concentrated water tank (T) 5 ) Is connected with the water inlet of the high ammonia nitrogen concentrated water tank (T) 5 ) The backwash water outlet of the high ammonia nitrogen wastewater ultrafiltration backwash pump (P) through vanadium precipitation 8 ) UF ultrafiltration device for vanadium precipitation high ammonia nitrogen wastewater 2 ) Is connected with the backwash water inlet of the high ammonia nitrogen wastewater ultrafiltration device (UF) 2 ) The backwash water outlet of the sewage treatment device is connected to a No. 2 mud inlet of a mud dewatering System (SD), and a high ammonia nitrogen concentrated water tank (T) 5 ) Is fed to a liquid pump (P) through an evaporation crystallization system 7 ) Effluent (PT) of effluent vanadium precipitation high ammonia nitrogen wastewater pretreatment system 2 out); the method comprises the steps of generating calcium carbonate precipitate and heavy metal hydroxide precipitate through the reaction of sodium carbonate and calcium ions, adjusting the pH to be neutral by using hydrochloric acid, removing heavy metal ions by using electrolytic oxidation and ultrafiltration filtration, reducing the COD value to be less than or equal to 150mg/L, and reducing the calcium ions to be less than or equal to 40mg/L.
3. The recycling treatment device for vanadium precipitation mother liquor and washing water according to claim 1, characterized in that the centrifuge filtrate resin exchange system (RS 1 ) Resin exchange system (RS) of vanadium precipitation high ammonia nitrogen wastewater 2 ) And vanadium desorption solution storage and delivery system (VLS) which comprises a centrifuge filtrate resin adsorption tank (RST) 1 ) High ammonia nitrogen wastewater resin adsorption tank (RST) for vanadium precipitation 2 ) Sodium metavanadate desorption solution tank (VLT), sodium chloride and ammonium chloride adding device (D) of centrifuge filtrate 4 ) Sodium chloride and ammonium chloride adding device (D) of vanadium precipitation high ammonia nitrogen wastewater 5 ) Sodium metavanadate desorption liquid delivery pump (P) 10 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein the centrifuge filtrate pretreatment system effluent (PT 1 out) is connected to a centrifuge filtrate resin adsorption tank (RST) 1 ) Sodium chloride and ammonium chloride adding device (D) 4 ) Is provided with a medicine outlet and a centrifugal machineFiltrate resin adsorption tank (RST) 1 ) Is connected with the medicine inlet of the centrifuge filtrate resin adsorption tank (RST) 1 ) The liquid outlet of the centrifuge filtrate resin adsorption tank (RST) is connected with the 1# liquid inlet of a sodium metavanadate desorption tank (VLT) 1 ) Is sent out of the water outlet of the filter liquor resin exchange system of the centrifugal machine (RS) 1 out); effluent (PT) of vanadium precipitation high ammonia nitrogen wastewater pretreatment system 2 out) is connected to a vanadium precipitation high ammonia nitrogen wastewater resin adsorption tank (RST) 2 ) Sodium chloride and ammonium chloride adding device (D) 5 ) Is arranged at the drug outlet and is used for precipitating vanadium and high ammonia nitrogen wastewater resin adsorption tank (RST) 2 ) Is connected with the medicine inlet of the high ammonia nitrogen wastewater resin adsorption tank (RST) 2 ) The liquid outlet of the (2) is connected with the liquid inlet of a sodium metavanadate desorption tank (VLT), and the vanadium precipitation high ammonia nitrogen wastewater resin adsorption tank (RST) 2 ) Is sent out from the water outlet of the resin exchange system (RS) 2 out); the liquid outlet of the sodium metavanadate desorption liquid tank (VLT) passes through a sodium metavanadate desorption liquid delivery pump (P) 10 ) Delivering vanadium desorption liquid (VL); here, the metavanadate is adsorbed by using macroporous anion resin, and after the resin is saturated, sodium hydroxide and sodium chloride are used for desorption to obtain sodium metavanadate, and vanadium is removed, so that the vanadium resources lost in the wastewater are recovered.
4. The recycling treatment device of vanadium precipitation mother liquor and washing water according to claim 1, characterized in that the Reverse Osmosis System (ROS) and evaporative crystallization system (VCS) comprises a cartridge filter (SFF), a reverse osmosis device (RO) and a recycling water tank (T) 6 ) Evaporation crystallization feeding box (T) 7 ) An evaporative crystallization device (VC) and a scale inhibitor adding device (D) 6 ) And a reverse osmosis high-pressure pump (P 11 ) Water pump for reuse (P) 12 ) Feed pump for evaporative crystallization (P) 13 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein the centrifuge filtrate resin exchange system effluent (RS) 1 out) is connected to the water inlet of the security filter (SFF), and the scale inhibitor adding device (D) 6 ) The medicine outlet of (2) is also connected with the water inlet of a security filter (SFF), and is securedThe water outlet of the filter (SFF) is connected with a reverse osmosis high-pressure pump (P) 11 ) Is connected with a water inlet of a reverse osmosis device (RO), a concentrated water outlet of the reverse osmosis device (RO) is connected with a No. 2 liquid inlet of an evaporative crystallization device (VC), and a water outlet of the reverse osmosis device (RO) is connected with a recycling water tank (T) 6 ) The No. 1 water inlet of (C) is connected with the reuse water tank (T) 6 ) Through the water outlet of the recycling water pump (P) 12 ) Delivering reuse water (RUW); the reverse osmosis is utilized to concentrate and decrement the filter liquor of the centrifugal machine so as to reduce the evaporation capacity, reduce the evaporation operation cost and recycle the purified produced water; effluent (RS) of vanadium precipitation high ammonia nitrogen wastewater resin exchange system 2 out) is connected to an evaporation crystallization feeding box (T) 7 ) No. 1 liquid inlet of (C), evaporation crystallization feeding box T 7 Through the liquid outlet of the evaporative crystallization feeding pump (P) 13 ) Is connected with a liquid inlet of an evaporative crystallization device (VC), a water outlet of the evaporative crystallization device (VC) connects evaporative crystallization condensate (VCW) to a recycling water tank (T) 6 ) A No. 2 water inlet of the evaporative crystallization device (VC) is used for delivering crystallized salt; the method realizes the treatment of vanadium precipitation high ammonia nitrogen wastewater and the filtrate of a centrifugal machine, the produced water is recycled to a plurality of production sections for extracting vanadium, the ammonium chloride and sodium chloride are also recycled, and meanwhile, the sodium metavanadate is recovered, thereby achieving the purpose of recycling the vanadium precipitation mother liquor and washing water.
5. The method for processing the vanadium precipitation mother liquor and the washing water recycling device according to any one of claims 1 to 4, which is characterized by comprising the following steps:
1) Removing heavy metal ions and suspended matters in the filter liquor of the centrifugal machine through a filter liquor pretreatment system of the centrifugal machine, and reducing the COD value to less than 20mg/L;
2) Adsorbing and desorbing sodium metavanadate from the filtrate of the centrifugal machine by using a resin exchange system of the filtrate of the centrifugal machine, and sending the sodium metavanadate back to a vanadium precipitation tank by using a vanadium desorption liquid storage and delivery system, so that vanadium resources are recovered, and the recovery rate is more than or equal to 90%;
3) Concentrating, reducing and purifying the pretreated and vanadium-adsorbed centrifugal filtrate by a reverse osmosis system for 4-6.6 times, and concentrating the TDS to 50000-100000 mg/L to reduce the cost of subsequent evaporation and crystallization; the TDS of the purified produced water is less than or equal to 200mg/L, and the recycling requirement is met;
4) Heavy metal ions and suspended matters in the vanadium-precipitating high ammonia-nitrogen wastewater are removed through the vanadium-precipitating high ammonia-nitrogen wastewater pretreatment system, and the COD value is reduced to less than 150mg/L, ca 2+ The value is reduced to be less than or equal to 40mg/L;
5) Adsorbing metavanadate in the vanadium-precipitation high ammonia nitrogen wastewater by a resin exchange system, desorbing sodium metavanadate, and recovering vanadium resources, wherein the recovery rate is more than or equal to 90%;
6) Separating salt by an evaporation crystallization system (VCS) through an evaporation crystallization thermal method, separating ammonium chloride with purity more than or equal to 90% and sodium chloride with purity more than or equal to 98%, wherein the TDS value of condensate water produced by evaporation crystallization is less than or equal to 200mg/L, and both salt and water are recycled;
step 6) is performed with evaporative crystallization through an evaporative crystallization system (VCS), specifically, the pretreated and vanadium-absorbed high ammonia nitrogen wastewater and reverse osmosis concentrated water of a centrifuge filtrate are subjected to evaporative crystallization, ammonium chloride with the purity of more than or equal to 90% and sodium chloride with the purity of more than or equal to 98% are separated, the TDS value of condensate water produced by the evaporative crystallization is less than or equal to 200mg/L, the sodium chloride is returned to a salt agglomerating process of low-sodium roasting in the vanadium extraction production, the ammonium chloride is returned to a vanadium precipitation process in the vanadium extraction production, and the condensate water is returned to a plurality of working sections in the vanadium extraction production.
6. The method of claim 5, wherein said step 1) comprises passing through a centrifuge filtrate pretreatment system, in particular, using a centrifuge filtrate electrolytic oxidation device (EO 1 ) The generated hypochlorite and hydroxyl radical and other strong oxidants degrade COD, remove heavy metal ions, and utilize a centrifuge filtrate ultrafiltration device (UF 1 ) Filtering out partial COD, suspended matters and heavy metal reactants, and reducing the COD value from 50-100 mg/L to less than or equal to 20mg/L; the step 2) is carried out by a centrifugal filter liquor resin exchange system, specifically, metavanadate in centrifugal filter liquor is adsorbed by macroporous anion resin, after the resin is saturated, sodium hydroxide and sodium chloride are used for desorption, sodium metavanadate is desorbed, andthe vanadium desorption liquid is returned to the vanadium precipitation tank by utilizing a vanadium desorption liquid storage and delivery system, so that vanadium resources are recovered, and the recovery rate is more than or equal to 90 percent.
7. The method for processing the vanadium precipitation mother liquor and the washing water recycling treatment device according to claim 5, wherein the step 3) is characterized in that the method comprises the steps of concentrating, reducing and purifying the pretreated and vanadium-adsorbed centrifuge filtrate by reverse osmosis for 4-6.6 times, and concentrating the TDS of the filtrate from 10000-20000 mg/L to 50000-100000 mg/L so as to reduce the cost of subsequent evaporation and crystallization; the TDS of the purified produced water is 100-200 mg/L, the recycling requirement is met, and the produced water is recycled to a plurality of working sections of vanadium extraction production; step 4) generating calcium carbonate sediment and heavy metal hydroxide sediment by utilizing a vanadium precipitation high ammonia nitrogen wastewater pretreatment system, namely, utilizing sodium carbonate to react with calcium ions, utilizing hydrochloric acid to adjust pH to be neutral, utilizing electrolytic oxidation and ultrafiltration filtration to remove heavy metal ions, reducing COD value from 500-1000 mg/L to 60-150 mg/L, and utilizing Ca to adjust the pH to be neutral 2+ The value is reduced from 100 to 800mg/L to less than or equal to 40mg/L.
8. The method for treating vanadium precipitation mother liquor and washing water recycling treatment device according to claim 5, wherein the step 5) is characterized in that through a vanadium precipitation high ammonia nitrogen wastewater resin exchange system, in particular, metavanadate in the vanadium precipitation high ammonia nitrogen wastewater is adsorbed by using macroporous anion resin, after the resin is saturated, sodium hydroxide and sodium chloride are used for desorption, sodium metavanadate is desorbed, and a vanadium desorption solution storage and delivery system is used for delivering the vanadium to a vanadium precipitation tank, so that vanadium resources are recovered, and the recovery rate is more than or equal to 90%.
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