CN109437463B - Advanced treatment and recycling device for stone coal blank roasting vanadium extraction high-salt wastewater and using method - Google Patents

Advanced treatment and recycling device for stone coal blank roasting vanadium extraction high-salt wastewater and using method Download PDF

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CN109437463B
CN109437463B CN201811632206.0A CN201811632206A CN109437463B CN 109437463 B CN109437463 B CN 109437463B CN 201811632206 A CN201811632206 A CN 201811632206A CN 109437463 B CN109437463 B CN 109437463B
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CN109437463A (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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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/38Treatment of water, waste water, or sewage by centrifugal separation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2303/22Eliminating or preventing deposits, scale removal, scale prevention
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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Abstract

Aiming at the characteristics of strong acidity, high-salt wastewater containing a large amount of iron, aluminum, sulfate radicals, other heavy metal ions and a small amount of metavanadate generated by a blank roasting sulfuric acid silicon-inhibiting water vanadium extraction process, the invention firstly passes the vanadium-extracting high-salt wastewater through a pretreatment system, a large amount of lime is added to improve the pH value of the wastewater, and neutralization, precipitation, oxidation and membrane filtration are utilized to remove heavy metal ions and partial sulfate ions, so that COD, suspended matters and TDS are reduced; secondly, concentrating and reducing the wastewater by using reverse osmosis and ultrahigh-pressure reverse osmosis through a concentration treatment system; finally, evaporating and crystallizing out crystallization salt through an evaporation and crystallization system; the condensate of the reverse osmosis water production, the ultrahigh pressure reverse osmosis water production and the evaporative crystallization system meets the requirement of reuse water, and is reused in the vanadium extraction production section, thereby achieving the purpose of advanced treatment and reuse of the stone coal blank roasting vanadium extraction high-salt wastewater.

Description

Advanced treatment and recycling device for stone coal blank roasting vanadium extraction high-salt wastewater and using method
Technical Field
The invention relates to a stone coal blank roasting vanadium extraction high-salt wastewater advanced treatment recycling device and a use method thereof, 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, and then precipitate the vanadium by using ammonium chloride to generate ammonium metavanadate, so that the vanadium pentoxide can be prepared by deamination. 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 blank roasting sulfuric acid silicon-inhibiting water leaching vanadium extraction process comprises the following production processes: crushing and grinding, blank roasting, sulfuric acid silicon inhibition, leaching and filtering, ion exchange, purifying and washing, and vanadium precipitation and drying, wherein the product is ammonium metavanadate. Two kinds of wastewater are mainly generated in the process, wherein one is vanadium precipitation mother liquor, and the wastewater is high ammonia nitrogen wastewater; the second is the resin adsorption residual liquid of ion exchange, which is high-salt waste water with strong acidity, containing a large amount of iron, aluminum, sulfate radical, other heavy metal ions and a small amount of metavanadate, and has great harm to the environment. At present, a technology for treating high-salt wastewater which is generated by a novel blank roasting sulfuric acid silicon-inhibiting water leaching vanadium extraction process and contains a large amount of iron, aluminum, sulfate radicals, other heavy metal ions and a small amount of metavanadate is not available, and a partially similar patent is available for treating stone coal vanadium-extracting high-salt wastewater, for example, a 201210110313.3 comprehensive treatment method for stone coal vanadium-extracting salt-containing wastewater, and the main technology is that 'stone coal vanadium-extracting salt-containing wastewater, inverted electrodialysis for desalination, reduced pressure membrane distillation for concentration, crystallization and salt-burning, and electroosmosis for fresh water production and condensate water recycling'; 200910273138.8A recycling treatment method of stone coal vanadium-extracting high-salinity heavy metal-rich wastewater mainly comprises the steps of adding lime, sodium carbonate, PAC and PAM into the vanadium-extracting high-salinity heavy metal-rich wastewater for coagulating sedimentation, using a filter cake obtained by filter pressing bottom mud as a building admixture, desalting supernatant by electrodialysis, evaporating and crystallizing concentrated water, and recycling produced industrial salt, fresh water and condensate into stone coal vanadium-extracting process; the method is characterized in that the high-salt wastewater generated by extracting vanadium through a low-sodium roasting water leaching process is reused by utilizing electrodialysis desalination and concentrated water evaporative crystallization, and sodium chloride is recycled at the same time, but metavanadate is not recycled. And the electrodialysis energy consumption is larger, the water quality of produced water is lower than reverse osmosis, and the method has a plurality of defects. The advanced treatment and recycling technology of high-salt wastewater which is generated by the novel blank roasting sulfuric acid silicon-inhibiting water leaching vanadium extraction technology and contains a large amount of iron, aluminum, sulfate radicals, other heavy metal ions and a small amount of metavanadate needs to be developed.
Disclosure of Invention
The invention provides a stone coal blank roasting vanadium-extracting high-salt wastewater advanced treatment and recycling device and a use method thereof, and aims to treat wastewater to meet the requirement of reuse water, recycle the wastewater to a vanadium-extracting production section and fulfill the aim of advanced treatment and recycling of stone coal blank roasting vanadium-extracting high-salt wastewater, aiming at the characteristics of strong acidity, high-salt wastewater containing a large amount of iron, aluminum, sulfate radicals, other heavy metal ions and a small amount of metavanadate generated by a novel blank roasting sulfuric acid silicon-inhibiting water leaching vanadium-extracting process, and the defect that the environment is seriously polluted and precious vanadium resources are wasted if the treatment is poor.
The technical solution of the invention is as follows: the advanced treatment recycling device for stone coal blank roasting vanadium extraction high-salt wastewater structurally comprises a pretreatment system PTS, a concentration treatment system CTS, an evaporative crystallization system VCS and a recycled water storage and delivery system RCWT; wherein the resin adsorption residual liquid TW is connected to the water inlet of the pretreatment system PTS, the water outlet of the pretreatment system PTS is connected with the water inlet of the concentration treatment system CTS, the mud outlet of the pretreatment system PTS sends out mud cake SC, and the liquid outlet of the pretreatment system PTS sends out desorbed sodium metavanadate solution NaVO 3 The method comprises the steps of carrying out a first treatment on the surface of the The PTS of the preprocessing system not only promotesThe pH value of the wastewater removes heavy metal ions and part of sulfate ions, more importantly, the metavanadate in the wastewater is further recovered, and vanadium resources are more effectively utilized; the liquid outlet of the concentrating treatment system CTS is connected with the liquid inlet of the evaporative crystallization system VCS, and the water outlet of the concentrating treatment system CTS is connected with the water inlet 1# of the reuse water storage and delivery system RCWT; concentrating and reducing the wastewater by using a CTS (clear to treat) system to produce concentrated water, so that the subsequent evaporative crystallization system can conveniently evaporate crystalline salt, and meanwhile, the produced fresh water meets the recycling requirement; the Salt outlet of the evaporative crystallization system VCS is used for delivering crystallized Salt, and the condensate outlet of the evaporative crystallization system VCS is connected with the No. 2 water inlet of the recycled water storage and delivery system RCWT; the VCS of the evaporative crystallization system is subjected to evaporative crystallization to produce crystalline salt, and meanwhile, the produced condensed water also meets the recycling requirement; the water outlet of the reuse water storage and delivery system RCWT sends out reuse water RCW, and the reuse water RCW is reused in different sections of vanadium extraction production, so that the purpose of advanced treatment and reuse of the stone coal blank roasting vanadium extraction high-salt wastewater is achieved.
Aiming at the characteristic of high silicon content of stone coal, the blank roasting sulfuric acid silicon-inhibiting water leaching vanadium extraction process has the advantages that silicon is mostly present in stone coal in the form of metasilicate, and a large amount of silicon is dissolved out during water leaching, so that the vanadium extraction efficiency is affected; in the production, metasilicate is converted into SiO by adding sulfuric acid 2 And is remained in slag to achieve the purpose of inhibiting silicon; but sulfuric acid dissolves out a large amount of metal ions such as aluminum, iron and the like in stone coal, metavanadate is leached out during water leaching, a large amount of heavy metal ions are leached out, in the vanadium extraction process, resin adsorbs metavanadate to generate strong acid, high-salt wastewater containing a large amount of iron, aluminum, sulfate radicals, other heavy metal ions and a small amount of metavanadate is resin adsorption residual liquid, a large amount of lime is required to be added for the treatment to neutralize sulfuric acid to form saturated calcium sulfate so as to remove sulfate radicals, and meanwhile, the residual hydroxyl and the metal ions in the wastewater are combined into indissolvable metal hydroxide precipitate so as to achieve the purposes of improving the pH value, removing the heavy metal ions and partially removing the sulfate radicals, and simultaneously, the TDS value of the wastewater is reduced, and the subsequent concentration, reduction and evaporation crystallization are facilitated.
The main chemical reaction equation is as follows:
CaO + H 2 O = Ca 2+ + 2OH -
Ca 2+ + SO 4 2- = CaSO 4 ↓ ②
Fe 3+ + 3OH - = Fe(OH) 3 ↓ ③
Al 3+ + 3OH - = Al(OH) 3 ↓ ④
Me 2+ + 2OH - = Me(OH) 2 ↓ ⑤
in the formula (2), the saturated concentration of calcium sulfate is 2600ppm at normal temperature, and in the formula (5), me represents a divalent metal ion.
The advanced treatment and recycling method for the stone coal blank roasting vanadium extraction high-salt wastewater comprises the following steps:
1) Neutralizing and precipitating the resin adsorption residual liquid by using a large amount of lime through the front part of the pretreatment system, and carrying out advanced oxidation and membrane filtration to raise the pH value of the wastewater to 6-8, simultaneously removing heavy metal ions and part of sulfate ions, reducing COD and suspended matter content, and reducing TDS to 8000-12000 ppm;
2) The metavanadate in the wastewater is adsorbed and recovered by utilizing the resin through the rear part of the pretreatment system, so that vanadium resources are effectively recovered and utilized;
3) The pretreated effluent is concentrated and reduced by a concentration treatment system by using a reverse osmosis technology, and is concentrated for 10-15 times, and TDS is concentrated to 120000 ~ 150000ppm, so that the crystallization salt is evaporated from a subsequent evaporation crystallization system, and fresh water is produced, and the TDS is less than 200ppm and meets the recycling requirement;
4) The concentrated water of the concentration treatment system passes through an evaporation crystallization system to evaporate and crystallize crystallization salt, and condensate water is produced at the same time, and the TDS is less than 200ppm to meet the recycling requirement;
5) The produced water of the concentration treatment system and the condensed water of the evaporation crystallization system are collected as reuse water, and are stored and returned to different sections of vanadium extraction production through a reuse water storage and delivery system, so that the purpose of advanced treatment and reuse of the stone coal blank roasting vanadium extraction high-salt wastewater is achieved.
The invention has the beneficial effects that: aiming at the characteristics of strong acidity, high salt wastewater containing a large amount of iron, aluminum, sulfate radicals, other heavy metal ions and a small amount of metavanadate generated by a novel blank roasting sulfuric acid silicon-inhibiting water vanadium extraction process, firstly, the vanadium-extracting high salt wastewater passes through a pretreatment system, a large amount of lime is added to improve the pH value of the wastewater, and neutralization, precipitation, oxidation and membrane filtration are utilized to remove heavy metal ions and partial sulfate ions, so that COD, suspended matters and TDS are reduced; secondly, concentrating and reducing the wastewater by using reverse osmosis and ultrahigh-pressure reverse osmosis through a concentration treatment system; finally, evaporating and crystallizing out crystallization salt through an evaporation and crystallization system; the condensate of the reverse osmosis water production, the ultrahigh pressure reverse osmosis water production and the evaporative crystallization system meets the requirement of reuse water, and is reused in the vanadium extraction production section, thereby achieving the purpose of advanced treatment and reuse of the stone coal blank roasting vanadium extraction high-salt wastewater.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a stone coal blank roasting vanadium extraction high-salt wastewater advanced treatment recycling device.
FIG. 2 is a schematic diagram of the pretreatment system of the advanced treatment and recycling device for stone coal blank roasting vanadium extraction high-salt wastewater.
FIG. 3 is a schematic diagram of the structure of the concentrating system of the device for advanced treatment and recycling of high-salt wastewater from stone coal blank roasting vanadium extraction and the recycling water storage and delivery system.
FIG. 4 is a process flow diagram of an embodiment of a device and method for deeply treating and recycling high-salt wastewater generated in stone coal blank roasting vanadium extraction.
FIG. 5 is a water balance diagram of a stone coal blank roasting vanadium extraction high-salt wastewater advanced treatment recycling device and a method embodiment thereof.
TW in the figure means resin adsorption raffinate, salt means crystalline Salt and NaVO 3 The desorbed sodium metavanadate solution, the SC mud cake and the RCW recycled water (reverse osmosis produced water and evaporative crystal condensate); PTS represents pretreatment system, CTS represents concentration treatment system, VCS represents evaporative crystallization system, and RCWT represents recycled water storage and delivery system.
PTS represents a preprocessing system; TW represents resin adsorption residual liquid, SC represents mud cake and NaVO 3 Indicating desorbed sodium metavanadate solution, PToutIndicating the effluent of the pretreatment system; t (T) 1 Indicating a residual liquid water tank T 2 Representing an intermediate water tank T 3 Indicating ultrafiltration water producing tank T 4 Representing a sodium metavanadate solution tank; d (D) 1 Indicating lime adding device D 2 Represents sodium carbonate, coagulant aid adding device and D 3 Indicating the powder active carbon adding device D 4 Represents a bactericide adding device D 5 Representing a sodium hydroxide desorbent adding device; NR (NR) 1 Represents a primary neutralization reaction tank, ST 1 Represents a first-stage sedimentation tank, NR 2 Represents a secondary neutralization reaction tank, ST 2 Representing a secondary sedimentation tank, AOD representing an advanced oxidation device, HT representing a digestion tank, MSD representing a membrane separation device, RET representing an adsorption resin tank, SD representing a sludge dewatering device; p (P) 1 Representing a raffinate lift pump, P 2 Representing an intermediate water pump, P 3 Represents an ultrafiltration suction pump, P 4 Representing reverse osmosis booster pump, P 5 Represents ultrafiltration backwash pump, P 6 Represents a first-stage sedimentation tank dredge pump, P 7 Represents a sludge pump and P of a secondary sedimentation tank 8 A sodium metavanadate solution delivery pump is shown.
CTS stands for concentrate processing system, RCWT stands for reuse water storage and delivery system; PTout represents pretreatment system effluent, RCW represents reuse water and Salt represents crystalline Salt; t (T) 5 Represents reverse osmosis concentrated water tank T 6 Representing an ultrahigh pressure reverse osmosis concentrated water tank (also a liquid supply tank of an evaporative crystallization system) and T 7 Representing a reuse water tank; d (D) 6 Means that the scale inhibitor and the reducing agent are added into the device D 7 Representing a scale inhibitor adding device; SAF (software as a function of time) 1 Indicating reverse osmosis cartridge filter, RO indicating reverse osmosis device, SAF 2 Representing an ultra-high pressure reverse osmosis cartridge filter, UHPRO representing an ultra-high pressure reverse osmosis device, and VCS representing an evaporative crystallization system; p (P) 9 Representing a reverse osmosis high pressure pump, P 10 Representing ultra-high pressure reverse osmosis booster pump, P 11 Representing ultra-high pressure reverse osmosis plunger pump, P 12 Represents the liquid supply pump and P of the evaporative crystallization system 13 Representing a reuse water pump.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings
As shown in figure 1, the stone coal blank roasting vanadium extraction high-salt wastewater advanced treatment recycling device structurally comprises a pretreatment system PTS, a concentration treatment system CTS, an evaporative crystallization system VCS and a recycled water storage and delivery system RCWT; wherein the resin adsorption residual liquid TW is connected to the water inlet of the pretreatment system PTS, the water outlet of the pretreatment system PTS is connected with the water inlet of the concentration treatment system CTS, the mud outlet of the pretreatment system PTS sends out mud cake SC, and the liquid outlet of the pretreatment system PTS sends out desorbed sodium metavanadate solution NaVO 3 The method comprises the steps of carrying out a first treatment on the surface of the The PTS of the pretreatment system not only improves the pH value of the wastewater and removes heavy metal ions and part of sulfate ions, but also more importantly, further recovers metavanadate in the wastewater and more effectively utilizes vanadium resources; the liquid outlet of the concentrating treatment system CTS is connected with the liquid inlet of the evaporative crystallization system VCS, and the water outlet of the concentrating treatment system CTS is connected with the water inlet 1# of the reuse water storage and delivery system RCWT; concentrating and reducing the wastewater by using a CTS (clear to treat) system to produce concentrated water, so that the subsequent evaporative crystallization system can conveniently evaporate crystalline salt, and meanwhile, the produced fresh water meets the recycling requirement; the Salt outlet of the evaporative crystallization system VCS is used for delivering crystallized Salt, and the condensate outlet of the evaporative crystallization system VCS is connected with the No. 2 water inlet of the recycled water storage and delivery system RCWT; the VCS of the evaporative crystallization system is subjected to evaporative crystallization to produce crystalline salt, and meanwhile, the produced condensed water also meets the recycling requirement; the water outlet of the reuse water storage and delivery system RCWT sends out reuse water RCW, and the reuse water RCW is reused in different sections of vanadium extraction production, so that the purpose of advanced treatment and reuse of the stone coal blank roasting vanadium extraction high-salt wastewater is achieved.
The pretreatment system PTS of the stone coal blank roasting vanadium extraction high-salt wastewater advanced treatment recycling device structurally comprises a residual liquid water tank T1, a primary neutralization reaction tank NR1, a primary sedimentation tank ST1, a secondary neutralization reaction tank NR2, a secondary sedimentation tank ST2, an intermediate water tank T2, a high-grade oxidation device AOD, a digestion tank HT, a membrane separation device MSD, an ultrafiltration water production tank T3, an adsorption resin tank RET, a sodium metavanadate solution tank T4, a sludge dewatering device SD, a lime feeding device D1, sodium carbonate, a coagulant aid feeding device D2, a powder activated carbon feeding device D3, a bactericide feeding device D4, a sodium hydroxide desorber feeding device D5, a residual liquid lifting pump P1, an intermediate water pump P2, an ultrafiltration suction pump P3, a reverse osmosis booster pump P4, an ultrafiltration backwash pump P5, a primary sedimentation tank sludge pump P6, a secondary sedimentation tank sludge pump P7 and a sodium metavanadate solution conveying pump P8. The resin adsorption residual liquid TW is connected to a water inlet of a residual liquid water tank T1, a water outlet of the residual liquid water tank T1 is connected with a water inlet of a primary neutralization reaction tank NR1 through a residual liquid lifting pump P1, a medicine outlet of a lime feeding device D1 is connected with a medicine inlet of the primary neutralization reaction tank NR1, a water outlet of the primary neutralization reaction tank NR1 is connected with a water inlet of a primary sedimentation tank ST1, a mud outlet of the primary sedimentation tank ST1 is connected with a 1# mud inlet of a mud dewatering device SD through a primary sedimentation tank mud pump P6, a water outlet of the primary sedimentation tank ST1 is connected with a water inlet of a secondary neutralization reaction tank NR2, a medicine outlet of a sodium carbonate, coagulant aid feeding device D2 is connected with a medicine inlet of a secondary neutralization reaction tank NR2, a water outlet of the secondary neutralization reaction tank NR2 is connected with a 2 mud inlet of a secondary sedimentation tank ST2, a mud outlet of the secondary sedimentation tank ST2 is connected with a 2# mud inlet of the mud dewatering device SD through a secondary sedimentation tank mud pump P7, and a liquid outlet of the mud dewatering device SD is connected with a mud cake pressing filter liquor T1 to a mud inlet of the mud outlet of the mud dewatering device SC; the water outlet of the secondary sedimentation tank ST2 is connected with the water inlet of the middle water tank T2, the water outlet of the middle water tank T2 is connected with the water inlet of the advanced oxidation device AOD through the middle water pump P2, the water outlet of the advanced oxidation device AOD is connected with the water inlet of the digestion tank HT, the medicine outlet of the powder activated carbon adding device D3 is connected with the medicine inlet of the digestion tank HT, the water outlet of the digestion tank HT is connected with the water inlet of the membrane separation device MSD, and the medicine outlet of the bactericide adding device D4 is connected with the medicine inlet of the membrane separation device MSD; the water outlet of the membrane separation device MSD is connected with the water inlet of the ultrafiltration water producing tank T3 through an ultrafiltration suction pump P3, the backwash water outlet of the ultrafiltration water producing tank T3 is connected with the backwash water inlet of the membrane separation device MSD through an ultrafiltration backwash pump P5, and the backwash water outlet of the membrane separation device MSD is connected with the No. 3 mud inlet of the mud dewatering device SD; the water outlet of the ultrafiltration water producing tank T3 is connected with the water inlet of the adsorption resin tank RET through a reverse osmosis booster pump P4, the liquid outlet of the sodium hydroxide desorbing agent adding device D5 is connected with the liquid inlet of the adsorption resin tank RET, the liquid outlet of the adsorption resin tank RET is connected with the liquid inlet of the sodium metavanadate solution tank T4, and the liquid outlet of the sodium metavanadate solution tank T4 is used for sending out desorbed sodium metavanadate solution NaVO3 through a sodium metavanadate solution delivery pump P8; the outlet of the adsorption resin tank RET sends out the pretreatment system outlet PTout.
Referring to fig. 3, the stone coal blank roasting vanadium extraction high-salt wastewater advanced treatment recycling device concentration system CTS and the recycled water storage system RCWT structurally comprise a reverse osmosis cartridge filter SAF1, a reverse osmosis cartridge filter represented by RO, a reverse osmosis concentrated water tank T5, an ultrahigh pressure reverse osmosis cartridge filter SAF2, an ultrahigh pressure reverse osmosis device UHPRO, an ultrahigh pressure reverse osmosis concentrated water tank T6 (also an evaporation crystallization system liquid supply tank), an evaporation crystallization system VCS, a recycling water tank T7, a scale inhibitor and reducing agent adding device D6, a scale inhibitor adding device D7, a reverse osmosis high-pressure pump P9, an ultrahigh pressure reverse osmosis booster pump P10, an ultrahigh pressure reverse osmosis plunger pump P11, an evaporation crystallization system liquid supply pump P12 and a recycling water pump P13. Wherein the pretreatment system water PTout is connected to the water inlet of a reverse osmosis cartridge filter SAF1, the drug outlet of a scale inhibitor and reducing agent adding device D6 is also connected to the water inlet of the reverse osmosis cartridge filter SAF1, the water outlet of the reverse osmosis cartridge filter SAF1 is connected with the water inlet of a reverse osmosis device RO through a reverse osmosis high-pressure pump P9, the concentrated water outlet of the reverse osmosis device RO is connected with the water inlet of a reverse osmosis concentrated water tank T5, the water outlet of the reverse osmosis concentrated water tank T5 is connected to the water inlet of an ultrahigh pressure reverse osmosis cartridge filter SAF2 through an ultrahigh pressure reverse osmosis booster pump P10, the drug outlet of the scale inhibitor adding device D7 is also connected to the water inlet of the ultrahigh pressure reverse osmosis cartridge filter SAF2, and the water outlet of the ultrahigh pressure reverse osmosis cartridge filter SAF2 is connected with the water inlet of an ultrahigh pressure reverse osmosis device UHPRO through an ultrahigh pressure reverse osmosis plunger pump P11; the water outlet of the reverse osmosis device RO and the water outlet of the ultra-high pressure reverse osmosis device UHPRO are connected to the No. 1 water inlet of the reuse water tank T7, and the water outlet of the reuse water tank T7 sends out reuse water RCW through a reuse water pump P13; the concentrated water outlet of the ultra-high pressure reverse osmosis device UHPRO is connected with an ultra-high pressure reverse osmosis concentrated water tank T6, the ultra-high pressure reverse osmosis concentrated water tank T6 (also a liquid supply tank of an evaporative crystallization system) is connected to the liquid inlet of an evaporative crystallization system VCS through a liquid supply pump P12 of the evaporative crystallization system, the condensed water outlet of the evaporative crystallization system VCS is connected to a No. 2 water inlet of a recycling water tank T7, and a Salt outlet of the evaporative crystallization system VCS sends out crystallization Salt.
The advanced treatment and recycling method for the stone coal blank roasting vanadium extraction high-salt wastewater comprises the following steps:
1) Neutralizing and precipitating the resin adsorption residual liquid by using a large amount of lime through the front part of the pretreatment system, and carrying out advanced oxidation and membrane filtration to raise the pH value of the wastewater to 6-8, simultaneously removing heavy metal ions and part of sulfate ions, reducing COD and suspended matter content, and reducing TDS to 8000-12000 ppm;
2) The metavanadate in the wastewater is adsorbed and recovered by utilizing the resin through the rear part of the pretreatment system, so that vanadium resources are effectively recovered and utilized;
3) The pretreated effluent is concentrated and reduced by a concentration treatment system by using a reverse osmosis technology, and is concentrated for 10-15 times, and TDS is concentrated to 120000 ~ 150000ppm, so that the crystallization salt is evaporated from a subsequent evaporation crystallization system, and fresh water is produced, and the TDS is less than 200ppm and meets the recycling requirement;
4) The concentrated water of the concentration treatment system passes through an evaporation crystallization system to evaporate and crystallize crystallization salt, and condensate water is produced at the same time, and the TDS is less than 200ppm and meets the recycling requirement;
5) The produced water of the concentration treatment system and the condensed water of the evaporation crystallization system are collected as reuse water, and are stored and returned to different sections of vanadium extraction production through a reuse water storage and delivery system, so that the purpose of advanced treatment and reuse of the stone coal blank roasting vanadium extraction high-salt wastewater is achieved.
The method comprises the steps of 1) sequentially passing through a residual liquid water tank, a residual liquid lifting pump, a primary neutralization reaction tank, a primary sedimentation tank, a secondary neutralization reaction tank, a secondary sedimentation tank, an intermediate water pump, a high-grade oxidation device, a digestion tank, a membrane separation device and an ultrafiltration suction pump through the front part of a pretreatment system until reaching an ultrafiltration water production tank, neutralizing and precipitating by adding a large amount of lime into the primary neutralization reaction tank, neutralizing and precipitating by adding sodium carbonate, a coagulant and a coagulant aid into the secondary neutralization reaction tank, adsorbing and filtering by adding powdered activated carbon into the digestion tank, protecting an ultrafiltration membrane by adding a bactericide into the membrane separation device, finally reducing COD by utilizing high-grade oxidation, further filtering and removing suspended matters by utilizing the ultrafiltration membrane, finally increasing the pH value of wastewater from 1-2 to 6-8, removing heavy metal ions by utilizing a large amount of hydroxide ions and metal ions in water, and reducing most of sulfate ions from 50000-8000 ppm to 8000-00 ppm by utilizing the low solubility characteristic of calcium sulfate at normal temperature; the ultrafiltration membrane is backwashed regularly, flux is guaranteed, the ultrafiltration backwashed drain water and the sludge discharged from the primary and secondary sedimentation tanks are dehydrated by a sludge dehydration device, and filtrate is returned to be treated and the sludge is transported outwards.
Step 2) delivering the effluent of the ultrafiltration water producing tank into an adsorption resin tank through the rear part of the pretreatment system, specifically through a reverse osmosis booster pump, and adsorbing metavanadate in the wastewater by using macroporous anion exchange resin, wherein the water after the metavanadate is adsorbed is the effluent of the whole pretreatment system; after resin adsorption saturation, desorbing sodium metavanadate from an adsorption resin tank by using a 5-15% sodium hydroxide desorbing agent, and storing and returning the sodium metavanadate solution to a vanadium precipitation tank by using a sodium metavanadate solution tank and a sodium metavanadate solution delivery pump, so that vanadium resources are effectively recycled.
The pretreated effluent in the step 3) passes through a concentration treatment system, specifically, the effluent of the pretreatment system sequentially passes through a reverse osmosis cartridge filter, a reverse osmosis high-pressure pump, a reverse osmosis device RO, a reverse osmosis concentrated water tank, an ultrahigh pressure reverse osmosis booster pump, an ultrahigh pressure reverse osmosis cartridge filter, an ultrahigh pressure reverse osmosis device, an ultrahigh pressure reverse osmosis concentrated water tank and an evaporation crystallization system liquid supply pump to pump the concentrated water of the ultrahigh pressure reverse osmosis device; the reverse osmosis device is protected by a scale inhibitor, a reducing agent and a reverse osmosis cartridge filter, the waste water is primarily concentrated by 5-6 times, and the TDS of the waste water is concentrated from 8000-12000 ppm to 48000-60000 ppm; the ultra-high pressure reverse osmosis is protected by an ultra-high pressure reverse osmosis cartridge filter of a scale inhibitor, and the reverse osmosis concentrated water is further concentrated for 2 to 2.5 times, and the TDS of the reverse osmosis concentrated water is concentrated from 48000 to 60000ppm to 120000 ~ 150000ppm; the whole system concentrates the wastewater by 10-15 times so as to facilitate the subsequent evaporative crystallization system to evaporate the crystalline salt, and meanwhile, fresh water is produced, and the TDS is less than 200ppm so as to meet the requirement of reuse water.
The concentrated water of the concentration treatment system in the step 4) passes through an evaporation crystallization system, particularly the concentration of the concentrated water of ultrahigh-pressure reverse osmosis is 120000 ~ 150000ppm, and the concentrated water is subjected to evaporation crystallization by a heat exchanger, a crystallization separator, a liquid accumulation tank, a forced circulation pump, a discharge pump, a centrifugal machine and the like in the evaporation crystallization system to separate out crystallization salt, and meanwhile, condensed water is produced, wherein the TDS is less than 200ppm, and the requirement of reuse water is also met.
And 5) collecting the produced water of the concentration treatment system and the condensed water of the evaporation crystallization system as reuse water, collecting the produced water of the reverse osmosis of the concentration treatment system, the produced water of the ultrahigh-pressure reverse osmosis and the condensed water of the evaporation crystallization system into a reuse water tank for storage through a reuse water pump, and returning the water to different sections of vanadium extraction production, thereby achieving the purpose of advanced treatment and reuse of the stone coal blank roasting vanadium extraction high-salt wastewater.
Example 1
In the process of extracting vanadium from vanadium-containing stone coal, a mining development finite responsibility company firstly uses a circulating fluidized bed decarburization boiler to decarburize stone coal ore in advance to generate electricity, then uses a tunnel kiln blank roasting process to oxidize 3-valent vanadium into 5-valent vanadium, and uses sulfuric acid to inhibit silicon, water leaching, resin vanadium absorption, sodium hydroxide and sodium chloride desorption to obtain sodium metavanadate, and finally uses ammonium chloride to precipitate vanadium to obtain ammonium metavanadate products, so as to avoid sintering phenomenon caused by high heat value of stone coal. The stone coal vanadium extraction belt waste heat power generation project uses 50 ten thousand tons of stone coal, 3 kilotons of stone coal vanadium extraction is carried out annually, and the power generation is 1.75 hundred million degrees, so that good economic benefit is obtained.
In the vanadium extraction production, various waste water can be generated, the waste water is considered to be subjected to quality division multiplexing as much as possible, the waste water discharge is reduced, 2 kinds of waste water are mainly discharged into a waste water treatment station for treatment and recycling, firstly, high ammonia nitrogen mother liquor (ammonium metavanadate-containing washing water) for vanadium precipitation contains high-concentration ammonium chloride and sodium chloride, and the ammonium chloride and the sodium chloride can be respectively recovered by utilizing evaporation crystallization. The second is resin adsorption residual liquid (including power plant circulating sewage and part of resin regeneration washing water), which is high-salt waste water with strong acidity, containing a large amount of iron, aluminum, sulfate radical, other heavy metal ions and a small amount of metavanadate, and the following is a treatment and recycling engineering design of the resin adsorption residual liquid only listed in the corresponding technology of the patent.
Design the quality and quantity of water
The water inlet (resin adsorption raffinate) water amount was designed to be 2880T/D (120T/H). The water quality index is as follows:
after being treated by adopting a lime and soda chemical precipitation method, the water quantity is about 112t/h, and the water quality is as follows:
here, the heavy metals and part of the sulfate are removed by chemical precipitation, and the heavy metals remain in trace amounts. The following concentration, resin adsorption and evaporative crystallization are all designed according to the water quality.
Process flow for wastewater treatment
The technological process of the advanced treatment and recycling of the resin adsorption residual liquid is shown in the technological process of the embodiment of the device and the method for the advanced treatment and recycling of the stone coal blank roasting vanadium extraction wastewater in the figure 4.
In the figure, resin adsorption residual liquid (comprising air cooling drainage of a power plant and part of resin regeneration washing water) enters a regulating tank to carry out balanced regulation on water quality, a lifting pump is utilized to enter a first-stage reaction tank, a large amount of lime is used to neutralize sulfuric acid, the pH value is increased, calcium sulfate is saturated and crystallized, metal ions and hydroxyl ions are formed into hydroxide at the same time, a booster pump and a concentrating and squeezing integrated machine are utilized to remove part of heavy metal ions, filtrate enters a 1# middle water tank, the filtrate is conveyed into a second-stage reaction tank through the lifting pump, then sodium carbonate is added to remove excessive calcium ions through the booster pump and the concentrating and squeezing integrated machine, filtrate enters a 2# middle water tank, the filtrate is conveyed into a one-step purifier through the lifting pump to be further (through adding coagulant) coagulated, precipitated and purified, and sludge of the one-step purifier is conveyed out through a sludge conveyor, and a small amount of sludge discharged from the one-step purifier is returned to the regulating tank; the effluent of the one-step purifier enters an electrolysis and digestion device for electrolytic oxidation to reduce COD, powder activated carbon is added for adsorption and filtration assistance, suspended matters are further removed by a membrane separation device and a suction water pump to purify water quality, backwash water of the membrane separation device returns to a No. 2 middle water tank, produced water of the membrane separation device enters a water production tank of the membrane separation device, the produced water enters a high-pressure RO device for preliminary concentration through a high-pressure RO booster pump, (a reducing agent and a scale inhibitor) cartridge filter and a high-pressure pump, TDS in wastewater is increased from 10158ppm to 55978ppm, concentrated water of the high-pressure RO device enters a high-pressure RO concentrated water tank, the concentrated water enters the ultrahigh-pressure RO device through an ultrahigh-pressure RO booster pump, (a scale inhibitor) cartridge filter and a plunger pump for deep concentration and decrement, TDS in the wastewater is further increased from 55978ppm to 139885ppm, the produced water enters an evaporation crystallization feed box, and the produced water enters an evaporation crystallization system through an evaporation crystallization feed centrifuge for separation of impurity salt; the water produced by the high-pressure RO device and the ultrahigh-pressure RO device and condensed water of the evaporative crystallization system are collected into a recycling water pool, and are pumped back to the production section for recycling through a recycling water pump.
Water balance diagram
The water balance diagram of the resin adsorption residual liquid (including the circulating sewage of a power plant and part of resin regeneration washing water) treatment and recycling system is shown in the water balance diagram of the stone coal blank roasting vanadium extraction wastewater advanced treatment and recycling device and the method embodiment of the device in figure 5.
4. Main design parameters of system
(1) Civil engineering:
sequence number Name of the name Specification of specification Unit (B) Quantity of Structural design
1 Absorption raffinate equalizing basin V=400M 3 Seat base 1 FRP with steel concrete lining
2 1# and 2# middle water pool V=100M 3 Seat base 2 FRP with steel concrete lining
3 Membrane separation device water producing pool V=150M 3 Seat base 1 FRP with steel concrete lining
4 Reuse pool V=400M 3 Seat base 1 FRP with steel concrete lining
5 Wastewater treatment plant 80m×40m×10m Seat base 1 Light steel and steel concrete
6 Evaporation crystallization factory building 40m×15m×24m Seat base 1 Light steel and steel concrete
The wastewater treatment workshop comprises a vanadium precipitation mother liquor treatment system, and the evaporation crystallization workshop comprises an ammonium chloride and sodium chloride evaporation crystallization salt separation system of the vanadium precipitation mother liquor.
(2) The main equipment comprises:
sequence number Device name Specification and model Material of material Unit (B) Quantity of
Two (II) Membrane separation system
1 Electrolysis device Q=45m 3 1 for/h, 3 SS316L Cover 4
2 Digestion device Q=45m 3 1 for/h, 3 SS316L Cover 4
3 Membrane separation device and corollary equipment Net water yield q=37.5 m 3 1 preparation of the catalyst is used for 1 preparation, and comprises a pump, a fan and an adder Medicine device, chemical cleaning device and the like Membrane PVDF Cover 4
4 Powder active carbon adding device Matched with Cover 1
5 Compressed air storage tank for instrument V=2m 3 Matched safety valve, blow-down valve and the like Q345R Bench 1
/>
Sequence number Device name Specification and model Material of material Unit (B) Quantity of
Five kinds of Evaporation crystallization system The feeding amount is 10t/h, TDS is 14 percent, and the feeding box and the feeding are included Pump, heat exchanger, crystallization separator, condensate tank, liquid storage tank, Forced circulation pump, discharge pump, vapor compressor unit and centrifugal machine Etc. matched with instrument, electric and automatic control of evaporating crystallization system Connect with the concentrated solution Titanium alloy for contact part Gold, SS2507 Cover 1
Six kinds of Online meter Matched with Cover 1
Seven pieces of Mounting material Matched with Batch of materials 1
Eight (eight) Electrical system Matched with Cover 1
Nine pieces Other systems Matched lighting, heating, ventilation, water supply and drainage, communication and the like Cover 1

Claims (6)

1. The application method of the stone coal blank roasting vanadium-extracting high-salt wastewater advanced treatment and reuse device is characterized in that the stone coal blank roasting vanadium-extracting high-salt wastewater advanced treatment and reuse device comprises a pretreatment system (PTS), a Concentration Treatment System (CTS), an evaporative crystallization system (VCS) and a reuse water storage and delivery system (RCWT); the resin adsorption residual liquid (TW) is connected to a water inlet of a pretreatment system (PTS), a water outlet of the pretreatment system (PTS) is connected with a water inlet of a Concentration Treatment System (CTS), a mud outlet of the pretreatment system (PTS) sends out mud cakes (SC), and a liquid outlet of the pretreatment system (PTS) sends out desorbed sodium metavanadate solution; the liquid outlet of the Concentration Treatment System (CTS) is connected with the liquid inlet of the evaporative crystallization system (VCS), and the water outlet of the Concentration Treatment System (CTS) is connected with the 1 st water inlet of the recycled water storage and delivery system (RCWT); the Salt outlet of the evaporative crystallization system (VCS) is used for delivering crystalline Salt (Salt), and the condensate outlet of the evaporative crystallization system (VCS) is connected with the 2 nd water inlet of the recycled water storage and delivery system (RCWT); delivering reuse water (RCW) from a water outlet of a reuse water storage and delivery system (RCWT) to different sections of vanadium extraction production;
the pretreatment system (PTS) comprises a residual liquid water tank (T) 1 ) First order neutralization reaction tank (NR) 1 ) Primary Sedimentation Tank (ST) 1 ) Two-stage neutralization reaction tank (NR) 2 ) Two-stage Sedimentation Tank (ST) 2 ) Intermediate water tank (T) 2 ) Advanced Oxidation Device (AOD), digestion tank (HT), membrane Separation Device (MSD), ultrafiltration water production tank (T) 3 ) Adsorption treeFat tank (RET), sodium metavanadate solution tank (T) 4 ) A sludge dewatering device (SD) and a lime adding device (D) 1 ) Sodium carbonate, coagulant aid adding device (D) 2 ) Powder active carbon adding device (D) 3 ) Bactericide adding device (D) 4 ) Sodium hydroxide desorbent adding device (D) 5 ) And a raffinate lift pump (P) 1 ) Intermediate water pump (P) 2 ) Ultrafiltration suction pump (P) 3 ) Reverse osmosis booster pump (P) 4 ) Ultrafiltration backwash pump (P) 5 ) Sludge pump of primary sedimentation tank (P) 6 ) Sludge pump (P) of secondary sedimentation tank 7 ) Sodium metavanadate solution delivery pump (P) 8 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein the resin adsorption raffinate (TW) is connected to the raffinate tank (T) 1 ) Is a residual liquid water tank (T) 1 ) Through the residual liquid lifting pump (P) 1 ) With a primary neutralization reaction tank (NR) 1 ) Is connected with the water inlet of the lime feeding device (D) 1 ) And a primary neutralization reaction tank (NR) 1 ) Is connected with the medicine inlet of the first-stage neutralization reaction tank (NR) 1 ) Is connected with the first-stage Sedimentation Tank (ST) 1 ) Is connected with the water inlet of the first-stage Sedimentation Tank (ST) 1 ) The mud outlet of the (B) is communicated with a mud pump (P) of the primary sedimentation tank 6 ) Is connected with the 1 ST mud inlet of the sludge dewatering device (SD), and a first-stage sedimentation tank (ST 1 ) And a secondary neutralization reaction tank (NR) 2 ) Is connected with the water inlet of the device (D) 2 ) And a second neutralization reaction tank (NR) 2 ) Is connected with the medicine inlet of the second-stage neutralization reaction tank (NR) 2 ) Is connected with a secondary Sedimentation Tank (ST) 2 ) Is connected with the water inlet of the secondary Sedimentation Tank (ST) 2 ) The mud outlet of the (B) is communicated with a mud pump (P) 7 ) Is connected with the 2 nd mud inlet of the sludge dewatering device (SD), the liquid outlet of the sludge dewatering device (SD) connects the pressed filtrate to the residual liquid water tank (T) 1 ) A mud cake (SC) is sent out from a mud outlet of the mud dewatering device (SD); secondary Sedimentation Tank (ST) 2 ) Is connected with the middle water tank (T) 2 ) Is advanced by (a)The water gap is connected, the middle water tank (T) 2 ) Through the water outlet of the middle water pump (P) 2 ) Is connected with the water inlet of the Advanced Oxidation Device (AOD), the water outlet of the Advanced Oxidation Device (AOD) is connected with the water inlet of the digestion box (HT), and the powdered activated carbon adding device (D) 3 ) The medicine outlet of the digestion box (HT) is connected with the medicine inlet of the digestion box (HT), the water outlet of the digestion box (HT) is connected with the water inlet of the Membrane Separation Device (MSD), and the bactericide adding device (D) 4 ) The medicine outlet of the Membrane Separation Device (MSD) is connected with the medicine inlet of the Membrane Separation Device (MSD); the water outlet of the Membrane Separation Device (MSD) passes through an ultrafiltration suction pump (P) 3 ) With ultrafiltration water producing tank (T) 3 ) Is connected with the water inlet of the ultrafiltration water producing tank (T) 3 ) Is passed through an ultrafiltration backwash pump (P) 5 ) The water inlet and the water outlet of the Membrane Separation Device (MSD) are connected with the 3 rd mud inlet of the mud dewatering device (SD); ultrafiltrating water producing tank (T) 3 ) Is passed through reverse osmosis booster pump (P) 4 ) Connected with the water inlet of the adsorption resin tank (RET), and a sodium hydroxide desorbent adding device (D) 5 ) The liquid outlet of the adsorption resin tank (RET) is connected with the liquid inlet of the adsorption resin tank (RET), and the liquid outlet of the adsorption resin tank (RET) is connected with the sodium metavanadate solution tank (T) 4 ) Is connected with the liquid inlet of the sodium metavanadate solution tank (T) 4 ) The liquid outlet of the solution is communicated with a sodium metavanadate solution delivery pump (P) 8 ) Delivering the desorbed sodium metavanadate solution; a water outlet of the adsorption resin tank (RET) sends out pretreatment system effluent (PTout);
the Concentrating Treatment System (CTS) and the recycled water storage and delivery system (RCWT) comprise reverse osmosis cartridge filters (SAF) 1 ) Reverse osmosis device (RO), reverse osmosis concentrate tank (T) 5 ) Ultra-high pressure reverse osmosis cartridge filter (SAF) 2 ) Ultra-high pressure reverse osmosis device (UHPRO), ultra-high pressure reverse osmosis concentrate tank (T) 6 ) Evaporating crystallization system (VCS), recycling water tank (T) 7 ) Scale inhibitor and reducing agent adding device (D 6 ) Scale inhibitor adding device (D) 7 ) And a reverse osmosis high-pressure pump (P 9 ) Super high pressure reverse osmosis booster pump (P) 10 ) Ultra-high pressure reverse osmosis plunger pump (P) 11 ) Liquid supply pump (P) of evaporative crystallization system 12 ) Water pump for reuse (P) 13 ) Wherein the pretreatment system effluent (PTout) is connected to a reverse osmosis cartridge filter (SAF) 1 ) Is provided with a water inlet of a device (D) 6 ) The drug outlet of (2) is also connected with a reverse osmosis cartridge filter (SAF) 1 ) Is a water inlet of a reverse osmosis cartridge filter (SAF) 1 ) Is passed through the reverse osmosis high-pressure pump (P) 9 ) 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 reverse osmosis concentrated water tank (T) 5 ) Is connected with the water inlet of the reverse osmosis concentrated water tank (T) 5 ) Is passed through the water outlet of the ultra-high pressure reverse osmosis booster pump (P) 10 ) Is connected to an ultra-high pressure reverse osmosis cartridge filter (SAF) 2 ) Is provided with a scale inhibitor adding device (D) 7 ) The drug outlet of (2) is also connected with an ultra-high pressure reverse osmosis cartridge filter (SAF) 2 ) Is a water inlet of an ultra-high pressure reverse osmosis cartridge filter (SAF) 2 ) Is passed through the ultra-high pressure reverse osmosis plunger pump (P) 11 ) Is connected with a water inlet of an ultra-high pressure reverse osmosis device (UHPRO); the water outlet of the reverse osmosis device (RO) and the water outlet of the ultra-high pressure reverse osmosis device (UHPRO) are connected to the reuse water tank (T) 7 ) Is used as the 1 st water inlet of the water tank (T) 7 ) Through the water outlet of the recycling water pump (P) 13 ) Delivering recycled water (RCW); concentrated water outlet of ultra-high pressure reverse osmosis device (UHPRO) and ultra-high pressure reverse osmosis concentrated water tank (T) 6 ) Connecting, ultra-high pressure reverse osmosis concentrated water tank (T) 6 ) Liquid supply pump (P) through evaporative crystallization system 12 ) Is connected to the liquid inlet of the evaporative crystallization system (VCS), and the condensed water outlet of the evaporative crystallization system (VCS) is connected to the recycling water tank (T) 7 ) A 2 nd water inlet of the evaporative crystallization system (VCS) for delivering crystalline Salt (Salt);
the method comprises the following steps:
1) Neutralizing and precipitating the resin adsorption residual liquid by using a large amount of lime through the front part of the pretreatment system, and carrying out advanced oxidation and membrane filtration to raise the pH value of the wastewater to 6-8, simultaneously removing heavy metal ions and part of sulfate ions, reducing COD and suspended matter content, and reducing TDS to 8000-12000 ppm;
2) The metavanadate in the wastewater is adsorbed and recovered by utilizing the resin through the rear part of the pretreatment system, so that vanadium resources are effectively recovered and utilized;
3) The pretreated effluent is concentrated and reduced by a concentration treatment system by using a reverse osmosis technology, and is concentrated for 10-15 times, and TDS is concentrated to 120000 ~ 150000ppm, so that the crystallization salt is evaporated from a subsequent evaporation crystallization system, and fresh water is produced, and the TDS is less than 200ppm and meets the recycling requirement;
4) The concentrated water of the concentration treatment system passes through an evaporation crystallization system to evaporate and crystallize crystallization salt, and condensate water is produced at the same time, and the TDS is less than 200ppm and meets the recycling requirement;
5) The produced water of the concentration treatment system and the condensed water of the evaporation crystallization system are collected as reuse water, and are stored and returned to different sections of vanadium extraction production through a reuse water storage and delivery system, so that the purpose of advanced treatment and reuse of the stone coal blank roasting vanadium extraction high-salt wastewater is achieved.
2. The method for using the stone coal blank roasting vanadium-extracting high-salt wastewater advanced treatment recycling device according to claim 1, wherein the step 1) is characterized in that through the front part of a pretreatment system, particularly resin adsorption residual liquid, sequentially passes through a residual liquid water tank, a residual liquid lifting pump, a first neutralization reaction tank, a first sedimentation tank, a second neutralization reaction tank, a second sedimentation tank, a middle water pump, a high-grade oxidation device, a digestion tank, a membrane separation device and an ultrafiltration suction pump until an ultrafiltration water production tank, a large amount of lime is added into the first neutralization reaction tank for neutralization and precipitation, sodium carbonate, a coagulant and a coagulant aid are added into the second neutralization reaction tank for neutralization and precipitation, powder activated carbon is added into the digestion tank for adsorption and filtration assistance, a bactericide is added into the membrane separation device for protecting an ultrafiltration membrane, COD is finally reduced by using the high-grade oxidation, suspended matters are further filtered by the ultrafiltration membrane, the pH value of the wastewater is finally increased from 1-2 to 6-8, a large amount of root ions and metal ions in the water form solid metal hydroxide, and the solid sulfate ions are removed by using the high amount of root ions and the metal ions are removed from the sulfate radical ions to the low-soluble sulfate at the low temperature of 8000 ppm to the low temperature of 12000ppm; the ultrafiltration membrane is backwashed regularly, flux is guaranteed, the ultrafiltration backwashed drain water and the sludge discharged from the primary and secondary sedimentation tanks are dehydrated by a sludge dehydration device, and filtrate is returned to be treated and the sludge is transported outwards.
3. The method for using the stone coal blank roasting vanadium-extracting high-salt wastewater advanced treatment recycling device according to claim 1, wherein the step 2) is characterized in that the effluent of the ultrafiltration water producing tank is pressurized and sent into an adsorption resin tank through a reverse osmosis booster pump through the rear part of a pretreatment system, metavanadate in the wastewater is adsorbed by using macroporous anion exchange resin, and the water after the metavanadate is the effluent of the whole pretreatment system; after resin adsorption saturation, desorbing sodium metavanadate from an adsorption resin tank by using a 5-15% sodium hydroxide desorbing agent, and storing and returning the sodium metavanadate solution to a vanadium precipitation tank by using a sodium metavanadate solution tank and a sodium metavanadate solution delivery pump, so that vanadium resources are effectively recycled.
4. The method for using the stone coal blank roasting vanadium-extracting high-salt wastewater advanced treatment recycling device is characterized in that the pretreated effluent in the step 3) passes through a concentration treatment system, and particularly the pretreated effluent sequentially passes through a reverse osmosis cartridge filter, a reverse osmosis high-pressure pump, a reverse osmosis device, a reverse osmosis concentrated water tank, an ultrahigh pressure reverse osmosis booster pump, an ultrahigh pressure reverse osmosis cartridge filter, an ultrahigh pressure reverse osmosis plunger pump, an ultrahigh pressure reverse osmosis device, an ultrahigh pressure reverse osmosis concentrated water tank and an evaporation crystallization system liquid supply pump to pump the concentrated water of the ultrahigh pressure reverse osmosis device; the reverse osmosis device is protected by a scale inhibitor, a reducing agent and a reverse osmosis cartridge filter, the waste water is primarily concentrated by 5-6 times, and the TDS of the waste water is concentrated from 8000-12000 ppm to 48000-60000 ppm; the ultra-high pressure reverse osmosis is protected by a scale inhibitor and an ultra-high pressure reverse osmosis cartridge filter, and the reverse osmosis concentrated water is further concentrated for 2 to 2.5 times, and the TDS is concentrated from 48000 to 60000ppm to 120000 ~ 150000ppm; the whole system concentrates the wastewater by 10-15 times so as to facilitate the subsequent evaporative crystallization system to evaporate the crystalline salt, and meanwhile, fresh water is produced, and the TDS is less than 200ppm so as to meet the requirement of reuse water.
5. The method for using the stone coal blank roasting vanadium extraction high-salt wastewater advanced treatment recycling device according to claim 1, wherein the concentrated water of the concentrating treatment system in the step 4) passes through an evaporative crystallization system, particularly the concentrated water of ultrahigh pressure reverse osmosis, the concentration is 120000 ~ 150000ppm, the crystallization salt is separated by evaporative crystallization through a heat exchanger, a crystallization separator, a liquid storage tank, a forced circulation pump, a discharge pump and a centrifugal machine in the evaporative crystallization system, meanwhile, condensed water is produced, and the TDS is less than 200ppm and meets the requirement of the recycled water.
6. The method for using the stone coal blank roasting vanadium-extracting high-salt wastewater advanced treatment recycling device according to claim 1, wherein the water produced by the concentrating treatment system and the condensed water of the evaporating crystallization system in step 5) are collected as recycled water, and the recycled water is stored by a recycled water storage and delivery system, particularly the water produced by reverse osmosis of the concentrating treatment system, the water produced by reverse osmosis of ultrahigh pressure and the condensed water of the evaporating crystallization system are collected into a recycling water tank and are recycled to different sections of vanadium extraction production by a recycled water pump, so that the purpose of advanced treatment and recycling of the stone coal blank roasting vanadium-extracting high-salt wastewater is achieved.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112679014A (en) * 2020-12-14 2021-04-20 江苏卓博环保科技有限公司 Power plant concentrated wastewater zero-emission treatment device and treatment method
CN112707563A (en) * 2020-12-14 2021-04-27 江苏卓博环保科技有限公司 Membrane method recycling treatment device and treatment method for copper smelting high-salinity wastewater
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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101054630A (en) * 2007-05-28 2007-10-17 德物华经济信息研究院有限公司 Integrated treatment method for the three wastes generated form method of extracting vanadium pentoxide from stone-like coal navajoite
CN101062783A (en) * 2006-04-30 2007-10-31 邱宏麒 Environment-friendly type technique for vanadium extraction of stone coal
CN101629249A (en) * 2009-08-11 2010-01-20 紫金矿业集团股份有限公司 Comprehensive treatment method of three wastes in extracting vanadium from stone coal navajoite
CN101709390A (en) * 2009-12-15 2010-05-19 武汉科技大学 On-line circulation method for process for extracting vanadium from stone coal
CN102642970A (en) * 2012-04-28 2012-08-22 河北钢铁股份有限公司承德分公司 Method for recycling waste water with high salinity by extracting vanadium from vanadium slag
CN103420520A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Processing method of vanadium-containing aluminum-containing wastewater
CN103880218A (en) * 2014-03-27 2014-06-25 湖南大学 Complete cycle technology of vanadium smelting wastewater
CN105645439A (en) * 2016-01-30 2016-06-08 内蒙古久科康瑞环保科技有限公司 System for preparing potassium sulfate from high-salt-content industrial wastewater and technology of system
CN105695738A (en) * 2016-03-25 2016-06-22 武汉科技大学 Deironing method for vanadium-bearing stone coal lixivium
CN105907964A (en) * 2016-04-28 2016-08-31 河南理工大学 Method for separating vanadium, scandium and iron in acid solution
CN107827302A (en) * 2017-09-26 2018-03-23 上海晶宇环境工程股份有限公司 Vanadium-containing water technique of zero discharge and its special purpose device
CN108285239A (en) * 2018-04-11 2018-07-17 攀钢集团攀枝花钢铁研究院有限公司 A kind of process for treating waste liquor and system
CN109437444A (en) * 2018-12-29 2019-03-08 江苏卓博环保科技有限公司 Deposition vanadium mother liquid and wash water processing equipment for recycling and its method
CN209368011U (en) * 2018-12-29 2019-09-10 江苏卓博环保科技有限公司 Deposition vanadium mother liquid and wash water processing equipment for recycling
CN209412003U (en) * 2018-12-29 2019-09-20 江苏卓博环保科技有限公司 Coal calcination vanadium extraction high-salt wastewater advanced treatment and reclamation device
CN210313799U (en) * 2018-12-29 2020-04-14 江苏卓博环保科技有限公司 Resin adsorption tail water treatment recycling device for ammonium metavanadate production

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017010437A1 (en) * 2015-07-15 2017-01-19 国立大学法人群馬大学 Vanadium recovery method, method for producing electrolytic solution for redox flow batteries, vanadium recovery device, and device for producing electrolytic solution for redox flow batteries

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101062783A (en) * 2006-04-30 2007-10-31 邱宏麒 Environment-friendly type technique for vanadium extraction of stone coal
CN101054630A (en) * 2007-05-28 2007-10-17 德物华经济信息研究院有限公司 Integrated treatment method for the three wastes generated form method of extracting vanadium pentoxide from stone-like coal navajoite
CN101629249A (en) * 2009-08-11 2010-01-20 紫金矿业集团股份有限公司 Comprehensive treatment method of three wastes in extracting vanadium from stone coal navajoite
CN101709390A (en) * 2009-12-15 2010-05-19 武汉科技大学 On-line circulation method for process for extracting vanadium from stone coal
CN102642970A (en) * 2012-04-28 2012-08-22 河北钢铁股份有限公司承德分公司 Method for recycling waste water with high salinity by extracting vanadium from vanadium slag
CN103420520A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Processing method of vanadium-containing aluminum-containing wastewater
CN103880218A (en) * 2014-03-27 2014-06-25 湖南大学 Complete cycle technology of vanadium smelting wastewater
CN105645439A (en) * 2016-01-30 2016-06-08 内蒙古久科康瑞环保科技有限公司 System for preparing potassium sulfate from high-salt-content industrial wastewater and technology of system
CN105695738A (en) * 2016-03-25 2016-06-22 武汉科技大学 Deironing method for vanadium-bearing stone coal lixivium
CN105907964A (en) * 2016-04-28 2016-08-31 河南理工大学 Method for separating vanadium, scandium and iron in acid solution
CN107827302A (en) * 2017-09-26 2018-03-23 上海晶宇环境工程股份有限公司 Vanadium-containing water technique of zero discharge and its special purpose device
CN108285239A (en) * 2018-04-11 2018-07-17 攀钢集团攀枝花钢铁研究院有限公司 A kind of process for treating waste liquor and system
CN109437444A (en) * 2018-12-29 2019-03-08 江苏卓博环保科技有限公司 Deposition vanadium mother liquid and wash water processing equipment for recycling and its method
CN209368011U (en) * 2018-12-29 2019-09-10 江苏卓博环保科技有限公司 Deposition vanadium mother liquid and wash water processing equipment for recycling
CN209412003U (en) * 2018-12-29 2019-09-20 江苏卓博环保科技有限公司 Coal calcination vanadium extraction high-salt wastewater advanced treatment and reclamation device
CN210313799U (en) * 2018-12-29 2020-04-14 江苏卓博环保科技有限公司 Resin adsorption tail water treatment recycling device for ammonium metavanadate production

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张传宝.石煤提钒离子交换尾水处理及有价金属分离回收.《中国优秀硕士学位论文全文数据库-工程科技I辑》.2014,(第2014年第3期),第2、15页. *

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