CN116444085A - Waste lithium battery recycling wastewater treatment process and system - Google Patents
Waste lithium battery recycling wastewater treatment process and system Download PDFInfo
- Publication number
- CN116444085A CN116444085A CN202310487593.8A CN202310487593A CN116444085A CN 116444085 A CN116444085 A CN 116444085A CN 202310487593 A CN202310487593 A CN 202310487593A CN 116444085 A CN116444085 A CN 116444085A
- Authority
- CN
- China
- Prior art keywords
- tank
- oil
- lithium
- phosphorus
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 88
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002699 waste material Substances 0.000 title claims abstract description 37
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 12
- 238000004064 recycling Methods 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 238000001556 precipitation Methods 0.000 claims abstract description 46
- 239000002351 wastewater Substances 0.000 claims abstract description 45
- 238000000926 separation method Methods 0.000 claims abstract description 39
- 239000011574 phosphorus Substances 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 37
- 239000011737 fluorine Substances 0.000 claims abstract description 37
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001704 evaporation Methods 0.000 claims abstract description 31
- 230000008020 evaporation Effects 0.000 claims abstract description 27
- 238000011084 recovery Methods 0.000 claims abstract description 27
- 238000002485 combustion reaction Methods 0.000 claims abstract description 25
- 230000001105 regulatory effect Effects 0.000 claims abstract description 23
- 238000001728 nano-filtration Methods 0.000 claims abstract description 19
- 239000003345 natural gas Substances 0.000 claims abstract description 18
- 238000003825 pressing Methods 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000012452 mother liquor Substances 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 3
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 72
- 238000006115 defluorination reaction Methods 0.000 claims description 17
- 229910000831 Steel Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000010959 steel Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- -1 phosphorus ion Chemical class 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 11
- 238000000108 ultra-filtration Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011152 fibreglass Substances 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000011001 backwashing Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011211 glass fiber reinforced concrete Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001471 micro-filtration Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 2
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 claims 1
- 230000003750 conditioning effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 3
- 239000012065 filter cake Substances 0.000 description 7
- 239000003350 kerosene Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ZHQXROVTUTVPGO-UHFFFAOYSA-N [F].[P] Chemical compound [F].[P] ZHQXROVTUTVPGO-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
-
- 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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a waste lithium battery recovery wastewater treatment process and a waste lithium battery recovery wastewater treatment system, wherein the process comprises the following steps: (1) The water quality and the water quantity of the waste water recovered from the waste lithium batteries are regulated to be uniform, and oil-water separation is carried out to obtain an oily component and a water-based component; (2) Adding natural gas into oily components for combustion, recovering steam, purifying and then discharging combustion tail gas; (3) Nanofiltration of aqueous components, precipitation of lithium, solid-liquid separation and recovery of solid lithium salt; (4) Regulating the water quality of the liquid separated in the step (3) to be uniform, and recovering fluorine and phosphorus solids through primary phosphorus removal and fluorine removal, primary filter pressing and secondary filter pressing; (5) Filtering the liquid obtained in the step (4) to remove suspended matters, and evaporating and crystallizing to obtain a sodium sulfate product and recovered MVR evaporation mother liquor. According to the process, oil-water separation is carried out on waste lithium battery recycling wastewater, and separated oil and COD are subjected to integrated incineration and purification, so that the oil and the COD are thoroughly removed.
Description
Technical Field
The invention belongs to the technical field of wastewater recovery, and particularly relates to a waste lithium battery recovery wastewater treatment process and a waste lithium battery recovery wastewater treatment system.
Background
With the continuous development of new energy industry and the mass use of ion batteries, a large number of retired waste lithium batteries are generated, and the recycling industry of waste lithium batteries is developed. At present, the recycling of the waste lithium batteries is mainly based on a physical-fire and wet combined recovery process, and a large amount of lithium battery recovery wastewater such as lithium-precipitated liquid, extraction residual liquid, nickel-precipitated liquid and the like can be generated at the tail end of the process. Wherein the recovered wastewater is treated with alkali metal ions (including Li + 、Na + Etc.), fluoride ions, phosphate groups, SO 4 2- And acidic high-salt wastewater mainly containing sulfonated kerosene of which part contains an extractant, wherein the wastewater is difficult to treat, and the direct discharge of the wastewater can cause serious damage to the environment.
At present, most of treatment methods for waste lithium battery recovery wastewater remain in the theoretical research stage, and the wastewater mainly relates to removal of lithium ions, fluoride ions, phosphate radicals, oil components and COD (mainly extraction agents and sulfonated kerosene). The current wastewater treatment process mainly comprises the following steps:
1) Activated carbon adsorption and evaporation crystallization. After the waste lithium batteries are recycled through noble metal resources, oily organic matters such as kerosene, extractant and the like in the waste water can be removed through activated carbon adsorption; and directly evaporating and crystallizing the extracted wastewater to obtain sulfate. The treatment of the solid waste generated in the activated carbon activation regeneration and activation process in the method increases the process cost, and the adsorbed extractant and oil have no utilization value.
2) Membrane separation + evaporative crystallization. The method is to separate oil-containing wastewater and salt-containing wastewater by a membrane method, and evaporate and crystallize the salt-containing wastewater to obtain sulfate. According to the method, oil components (mainly an extracting agent and sulfonated kerosene) and salt-containing wastewater are separated through a membrane method, and the oil components separated out are not going because the extracting agent and the sulfonated kerosene have similar compatible reactions in use and have changed performances and cannot be directly recycled.
In summary, the two methods for removing COD have the following defects:
1)Li + the resources are not recycled.
2) The wastewater after COD removal is directly evaporated and crystallized without removing fluoride ions and phosphate radical, which can cause corrosion and scaling of an evaporation system and seriously affect continuous and stable operation of the evaporation system, and meanwhile, the quality of sodium sulfate salt can be affected when the fluoride ions and the phosphate radical enter into a crystallization salt system.
3) The adsorbed or separated oil is not completely removed, and secondary pollution exists.
Disclosure of Invention
The invention aims to solve the technical problems of treating and recycling MVR concentrated mother liquor, overcomes the defects and the shortcomings in the background art, and provides a ternary wastewater MVR evaporation mother liquor treatment process and a ternary wastewater MVR evaporation mother liquor treatment system.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a waste lithium battery recovery wastewater treatment process comprises the following steps:
(1) The water quality and the water quantity of the waste water recovered from the waste lithium batteries are regulated to be uniform, and oil-water separation is carried out to obtain an oily component and a water-based component;
(2) Adding natural gas into oily components for combustion, recovering steam, purifying and then discharging combustion tail gas;
(3) Nanofiltration of aqueous components, precipitation of lithium, solid-liquid separation and recovery of solid lithium salt;
(4) Regulating the water quality of the liquid separated in the step (3) to be uniform, and recovering fluorine and phosphorus solids through primary phosphorus removal and fluorine removal, primary filter pressing and secondary filter pressing;
(5) Filtering the liquid obtained in the step (4) to remove suspended matters, and evaporating and crystallizing to obtain a sodium sulfate product.
Preferably, in the waste lithium battery recovery wastewater, the concentration of lithium ions is not lower than 2000mg/L, the concentration of fluorine ions is not lower than 200mg/L, the concentration of phosphorus ions is not lower than 50mg/L, and the concentration of COD is not lower than 1000mg/L.
Preferably, in the step (1), primary oil-water separation and secondary oil-water separation are performed, wherein the primary oil-water separation adopts a physical sedimentation means, and the secondary oil-water separation adopts ultrafiltration and nanofiltration steps;
preferably, the combustion of the added natural gas in the step (2) is specifically: the oily components are lifted to an integrated burner through a pump, natural gas is added to support combustion, the combustion temperature reaches above 800 ℃, water in the integrated burner generates steam through high temperature combustion, and the steam is recovered and used as a heat source for evaporation and crystallization in the step (5).
According to the method, the oily components are recovered, on one hand, oil-water separation is carried out for a plurality of times, so that the oily components (extractant, sulfonated tar and the like) can be recovered and removed, and the influence of the components on the removal and recovery of other components is avoided; on the other hand, the tail gas after combustion possibly contains a small amount of organic matters and acid gases, and is discharged after being absorbed by the tail gas purifying device and reaching the standard, thereby being beneficial to environmental protection; finally, the heat value steam generated by the oil components after combustion can be sent to the subsequent evaporation step of the application and used as a double-effect evaporation heat source, so that energy is saved, the repeated and effective application of resources is realized, and the whole steps have the functions of fusion, penetration and synergistic effect.
Preferably, the lithium deposition in the step (3) adopts a lithium deposition agent, the lithium deposition agent comprises sodium carbonate and/or sodium phosphate, the primary and secondary dephosphorization and defluorination in the step (4) adopt a dephosphorization and defluorination agent, and the dephosphorization and defluorination agent comprises a calcium salt dephosphorization and defluorination agent or a composite cationic inorganic polymer flocculant with aluminum ions as cores.
Preferably, the adjusting in the steps (1) and (4) adopts at least one of physical means for residence, air stirring or mechanical stirring to adjust the water quantity and water quality. The water quantity and the water quality can be uniform through the adjustment of the adjusting tank, and suitable conditions are provided for the subsequent treatment process.
Under the same technical conception, the invention also provides a waste lithium battery recovery wastewater treatment system, which comprises an oil removal system, a lithium precipitation system, a primary secondary phosphorus and fluorine removal system and an evaporative crystallization system which are sequentially connected.
Preferably, the oil removal system comprises an oil removal adjusting tank, an oil removal tank, an ultra-filtration tank and a nanofiltration tank which are sequentially connected, wherein the oil removal tank and the nanofiltration tank are connected with an oil storage tank by adopting a pump, and the oil storage tank is sequentially connected with an integrated burner, a tail gas purification device and a discharge chimney; the integrated combustor comprises an RTO integrated incineration device; the integrated combustor is provided with a spray gun, a blower and a natural gas ignition device, wherein the spray gun and the natural gas ignition device respectively spray the waste oil and the natural gas in the oil storage tank into the combustor at the same time, and blow air through the blower to support combustion; the inner wall of the integrated combustor is provided with a water wall pipe, water circulates in the water wall pipe, and steam is generated through heating; the oil storage tank is connected to a spray gun of the integrated combustor through a pump and a conveying pipeline, and a filter is arranged on the conveying pipeline; the oil separation tank comprises a horizontal flow type oil separation tank or an air floating type oil separation tank, and the oil separation tank adopts a ceramic membrane.
The integrated burner provided by the invention has the advantages that the waste oil, the natural gas and the air are utilized for combustion supporting combustion, the combustion temperature can reach more than 800 ℃, the water in the water wall pipe is heated to generate steam, and the steam can be used in the double-effect evaporator of a subsequent device.
More preferably, the delivery conduit is provided with a Y-filter which prevents oily components from clogging the conduit during transport.
The optimized ultrafiltration and nanofiltration materials of the invention adopt ceramic membranes and the like, do not generate similar compatible reaction with organic matters such as extractant, sulfonated coal oil and the like, and cannot generate the following problemsCausing irreversible damage to the membrane. The tail gas purifying device of the invention should have the function of removing organic matters and SO 2 And the ability to treat acid gases.
Preferably, the lithium precipitation system comprises a nanofiltration tank, a lithium precipitation centrifuge and a lithium precipitation rear liquid regulating tank, wherein the lithium precipitation centrifuge is connected with the lithium precipitation tank and the lithium precipitation rear liquid regulating tank; the primary secondary phosphorus and fluorine removal system comprises a primary phosphorus and fluorine removal reaction tank, a primary filter press, a secondary phosphorus and fluorine removal reaction tank and a secondary filter press which are connected in sequence, wherein the primary filter press and the secondary filter press are plate-and-frame filter presses.
Preferably, the evaporative crystallization system comprises a precise filter and a double-effect evaporator which are sequentially connected, and the precise filter is connected with the activated carbon adsorption system; the precise filter comprises a microfiltration grade filter with automatic backwashing and/or without a backwashing device, the double-effect evaporator is connected with the integrated burner, and steam recovered from the integrated burner is used as an evaporation heat source.
Preferably, the oil separation adjusting tank and the lithium precipitation post-liquid adjusting tank comprise mechanical stirring equipment, and the mechanical stirring equipment comprises one or more of steel lining PPH, steel lining rubber or steel lining glass fiber reinforced plastic; the ultrafiltration tank, the nanofiltration tank, the lithium precipitation tank, the liquid regulation tank after lithium precipitation, the primary dephosphorization and defluorination reaction tank, the primary filter-pressing liquid tank, the secondary dephosphorization and defluorination reaction tank and the secondary filter-pressing liquid tank are made of one or more of PPH, glass fiber reinforced plastic, steel lining rubber, steel lining glass fiber reinforced plastic or concrete lining anti-corrosion coating.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the process, oil-water separation is carried out on waste lithium battery recycling wastewater, and separated oil and COD are subjected to integrated incineration and purification, so that the oil and the COD are thoroughly removed. Then extracting lithium to recover lithium resources, and performing double-effect evaporation after the procedures of phosphorus removal and fluorine removal to form primary sodium sulfate (sodium sulfate) for sale. Through the process, lithium resources in waste lithium battery recovery wastewater can be recovered, COD is thoroughly removed, and meanwhile, harmful impurities such as fluorine and phosphorus are removed, so that continuous and stable operation of an evaporation system is ensured, and the quality of byproduct sodium sulfate is improved.
(2) The wastewater recovery sequence of the present invention has advantages. Most of oily components in the wastewater float on the water surface and are easier to remove, and if the floating oil enters the subsequent process, the oil pollution of equipment can be caused, so that the oil removal is firstly carried out. The lithium removing agent can possibly introduce phosphate radical, the lithium is removed firstly and then the fluorine removing phosphorus is more reasonable, and in addition, the fluorine removing phosphorus can possibly adsorb a certain amount of lithium ions, so that double waste of lithium resources and the fluorine removing phosphorus is caused. In summary, the invention adopts the sequence of removing oil, removing lithium and removing phosphorus and fluorine, and considers the problems of impurity introduction and interference among the steps, thereby improving the recovery efficiency on the whole.
(3) The heat value steam generated by the oil components after combustion can be sent to the subsequent evaporation step of the application and used as a double-effect evaporation heat source, so that energy is saved, the repeated and effective application of resources is realized, and the whole steps have the functions of fusion, penetration and synergistic effect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of a waste lithium battery recovery wastewater treatment system.
In the figure: 1. an adjustment tank; 2. an oil separation tank; 3. a ultrafiltration tank; 4. a nanofiltration tank; 5. a lithium precipitation tank; 6. a lithium precipitation centrifuge; 7. a liquid regulating tank after lithium precipitation; 8. a first-stage dephosphorization defluorination reaction tank; 9. a first-stage filter press; 10. a liquid tank after primary filter pressing; 11. a secondary dephosphorization and defluorination reaction tank; 12. a second-stage filter press; 13. a liquid tank after secondary filter pressing; 14. a precision filter; 15. a double-effect evaporator; 21. an oil reservoir; 22. an integrated burner; 23. an exhaust gas purifying device; 24. and (5) discharging the chimney.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
as shown in FIG. 1, the process system adopted in the embodiment is a degreasing system, a lithium precipitation system, a primary secondary dephosphorization and defluorination system and an evaporative crystallization system which are connected in sequence.
The oil removal system comprises an oil removal regulating tank 1, an oil removal tank 2, an ultrafiltration tank 3 and a nanofiltration tank 4 which are sequentially connected, wherein the oil removal tank 2 and the nanofiltration tank 4 are connected with an oil storage tank 21 by adopting a pump, and the oil storage tank 21 is sequentially connected with an integrated combustor 22, a tail gas purifying device 23 and a discharge chimney 24; the integrated combustor 22 is an RTO integrated incinerator, natural gas is introduced as energy, and the oil separation tank 2 comprises a horizontal flow type oil separation tank or an air floating type oil separation tank, and the oil separation tank adopts a ceramic membrane.
The integrated burner 22 is provided with a waste oil spray gun and a natural gas ignition device, the waste oil spray gun and the natural gas ignition device are sprayed into the burner at the same time, combustion air is blown into the burner by adopting a blower, the inner wall of the integrated burner is provided with a water wall pipe, water is arranged in the pipe, steam can be generated after heating, and the generated steam can be used as a heat source of the double-effect evaporator 15.
The Y-shaped filter is arranged on the pipeline for conveying the oil to the burner, so that the blockage of the spray gun can be effectively prevented.
The lithium precipitation system comprises a lithium precipitation tank 5, a lithium precipitation centrifugal machine 6 and a lithium precipitation rear liquid regulating tank 7, wherein the lithium precipitation centrifugal machine 6 is connected with the lithium precipitation tank 5 and the lithium precipitation rear liquid regulating tank 7; the primary secondary phosphorus and fluorine removal system comprises a primary phosphorus and fluorine removal reaction tank 8, a primary filter press 9, a primary filter press rear liquid tank 10, a secondary phosphorus and fluorine removal reaction tank 11, a secondary filter press 12 and a secondary filter press rear liquid tank 13 which are sequentially connected, wherein the primary filter press 9 and the secondary filter press 12 are plate-and-frame filter presses.
The evaporative crystallization system comprises a precise filter 14 and a double-effect evaporator 15 which are sequentially connected, wherein the precise filter 14 is connected with the activated carbon adsorption system; the fine filter 14 comprises a microfiltration grade filter with automatic backwashing and/or without backwashing devices, and the double-effect evaporator 15 is connected with the integrated burner 22, and takes the steam recovered in the integrated burner 22 as a vaporization heat source.
The oil separation tank 2 and the lithium precipitation liquid regulating tank 7 comprise mechanical stirring equipment, and the mechanical stirring equipment comprises one or more of steel lining PPH, steel lining rubber or steel lining glass fiber reinforced plastic; the ultra-filtration tank 3, the nanofiltration tank 4, the lithium precipitation tank 5, the lithium precipitation rear liquid regulating tank 7, the primary dephosphorization and defluorination reaction tank 8, the primary filter-pressing rear liquid tank 10, the secondary dephosphorization and defluorination reaction tank 11 and the secondary filter-pressing rear liquid tank 13 are made of one or more of PPH, glass fiber reinforced plastic, steel lining rubber, steel lining glass fiber reinforced plastic or concrete lining anti-corrosion coating.
2000.0m of waste water recovered from a certain waste lithium battery 3 D, temperature about 30 ℃, li + About 3000mg/L, F + About 200mg/L, P 3+ About 50mg/L, COD about 1000mg/L, pH5-6, salt (sodium sulfate) about 18%.
The treatment process of the embodiment is as follows:
waste water (lithium precipitation liquid, nickel precipitation liquid and extraction residual liquid) from waste lithium batteries firstly enters the regulating tank, and the water quantity and the water quality can be uniform through stirring regulation of the regulating tank, so that suitable conditions are provided for the subsequent treatment process. The effluent of the regulating tank enters an oil separation tank, the physical sedimentation is carried out for one-time oil-water separation, and the separated oil (mainly containing extractant and sulfonated kerosene) enters an oil storage tank. The effluent of the oil separation tank is subjected to ultrafiltration and nanofiltration to further carry out secondary oil-water separation, the separated oil content also enters an oil storage tank, the oil content in the oil storage tank is lifted to an integrated combustor through a pump, natural gas is added to support combustion, the temperature in the combustor can reach more than 800 ℃, the heat value of the oil content is fully recovered to generate steam, and the steam is sent into double-effect evaporation to serve as evaporation heatA source. The tail gas after combustion possibly contains a small amount of organic matters and acid gas, and is discharged after being absorbed by a tail gas purifying device. Firstly adding sodium phosphate into nanofiltration water with qualified oil removal (COD reduced to below 50 mg/L) in a lithium precipitation tank to produce lithium phosphate precipitation, separating lithium phosphate products by a lithium precipitation centrifuge, recycling the separated lithium phosphate into a new material battery workshop, and collecting the supernatant liquid after the centrifuge contains Li + About 100mg/L, the wastewater enters a lithium-precipitation liquid regulating tank, a stirrer is arranged in the lithium-precipitation liquid regulating tank, the wastewater enters a first-stage dephosphorization and defluorination reaction tank after homogenizing the wastewater, aluminum ions are taken as core compound cationic inorganic polymeric flocculant is added, after the reaction is finished, the wastewater is pumped into a first-stage plate-and-frame filter press by a first-stage filter press feed pump, fluorine-phosphorus slag in the wastewater is trapped to form a filter cake, the water content of the filter cake is about 60% after the filter cake is pressed through a diaphragm, the filtrate automatically flows into a first-stage filter press liquid tank, the effluent of the liquid tank after the first-stage filter press is lifted to a second-stage dephosphorization and defluorination reaction tank by a pump, the dephosphorization and defluorination agent is added to react with fluorine in the wastewater to generate precipitation, the wastewater is pumped into a second-stage filter press by a second-press feed pump after the reaction is finished, the fluorine-phosphorus slag in the wastewater is trapped to form a filter cake by the second-stage filter press feed pump, and the water content of the filter cake after the filter cake is pressed by a diaphragm, and the filter cake formed by the first-stage press is transported out as general industrial solid waste. The filtrate of the second-stage plate-and-frame filter press automatically flows into a liquid tank after the second-stage filter pressing, wherein the fluorine content of the filtrate is less than 10mg/L, and the phosphorus content is less than 5mg/L. The filtrate after removing the fluorine and the phosphorus is trapped by a precision filter and then enters a pre-evaporation liquid tank, a stirrer is arranged in the pre-evaporation liquid tank, the pH value is adjusted back to 6-9 by adding 35% sodium hydroxide solution, and the adjusted-back wastewater is pumped into a double-effect evaporation system through a pump for evaporation and crystallization, so that sodium sulfate is sold.
The COD concentration in the waste lithium battery recovery wastewater is about 1000mg/L, and can be reduced to below 50mg/L after the treatment of the invention, and the COD removal rate is more than 95%.
The concentration of lithium ions in the waste lithium battery recovery wastewater is about 2000mg/L, the concentration of lithium ions can be reduced to below 100mg/L after the treatment of the invention, and the lithium recovery rate is more than 95%.
The concentration of fluoride ions in waste lithium battery recovery wastewater is about 200mg/L, and can be reduced to below 10mg/L after being treated by the method, and the fluoride removal rate is more than 95%.
The phosphorus concentration in the waste lithium battery recovery wastewater is about 50mg/L, and can be reduced to below 5mg/L after the treatment of the invention, and the phosphorus removal rate is more than 90%.
The waste lithium battery treated by the method is used for recycling waste water, oil content and COD are thoroughly decomposed and removed while the heat value is recovered, lithium resources in the waste water are recycled, and meanwhile, the waste water after impurities such as fluorine and phosphorus are removed can completely enter a double-effect evaporation system for evaporation and crystallization to obtain a sodium sulfate product.
Comparative example 1:
the water quality, treatment system and other operations were the same as in example 1, using a single defluorination process, the effluent measured about 30mg/L fluorine and about 10mg/L phosphorus.
Comparative example 2:
the water quality, the treatment system and the rest of the operation are the same as those of the example 1, no advanced catalytic oxidation is adopted, COD is not adsorbed by the activated carbon and is almost not removed, and the COD of the inlet water is measured to be about 1000mg/L, and the COD of the outlet water is measured to be about 950mg/L.
Claims (10)
1. The waste lithium battery recovery wastewater treatment process is characterized by comprising the following steps of:
(1) The water quality and the water quantity of the waste water recovered from the waste lithium batteries are regulated to be uniform, and oil-water separation is carried out to obtain an oily component and a water-based component;
(2) Adding natural gas into oily components for combustion, recovering steam, purifying and then discharging combustion tail gas;
(3) Nanofiltration of aqueous components, precipitation of lithium, solid-liquid separation and recovery of solid lithium salt;
(4) Regulating the water quality of the liquid separated in the step (3) to be uniform, and recovering fluorine and phosphorus solids through primary phosphorus removal and fluorine removal, primary filter pressing and secondary phosphorus removal and fluorine removal and secondary filter pressing;
(5) Filtering the liquid obtained in the step (4) to remove suspended matters, and evaporating and crystallizing to obtain a sodium sulfate product and recovered MVR evaporation mother liquor.
2. The treatment process according to claim 1, wherein the waste lithium battery recovery wastewater has a lithium ion concentration of not less than 2000mg/L, a fluorine ion concentration of not less than 200mg/L, a phosphorus ion concentration of not less than 50mg/L, and a COD concentration of not less than 1000mg/L.
3. The process of claim 1, wherein the oil-water separation of step (1) comprises a primary oil-water separation and a secondary oil-water separation, the primary oil-water separation using physical sedimentation means, the secondary oil-water separation using ultrafiltration and nanofiltration steps.
4. The process according to claim 1, wherein the combustion of the added natural gas in step (2) is in particular: the oily components are lifted to an integrated burner through a pump, natural gas is added to support combustion, the combustion temperature reaches above 800 ℃, water in the integrated burner generates steam through high temperature combustion, and the steam is recovered and used as a heat source for evaporation and crystallization in the step (5).
5. The treatment process of claim 1, wherein the lithium deposition in step (3) is performed by using a lithium deposition agent, the lithium deposition agent comprises sodium carbonate and/or sodium phosphate, the primary phosphorus and fluorine removal and the secondary phosphorus and fluorine removal in step (4) are performed by using a phosphorus and fluorine removal agent, and the phosphorus and fluorine removal agent comprises a calcium salt phosphorus and fluorine removal agent or a composite cationic inorganic polymeric flocculant with aluminum ions as cores. The fluorine content of the filtrate after the secondary filter pressing is less than 10mg/L, and the phosphorus content is less than 5mg/L.
6. The process of claim 1, wherein the conditioning of steps (1) and (4) is performed by at least one of physical means of residence, air agitation or mechanical agitation.
7. The process according to claim 1, wherein the filtering in step (5) is specifically: after the suspended substances in the filtrate are intercepted by a precision filter, 35 percent sodium hydroxide solution is added to adjust the pH value to 6-9, and then evaporation crystallization is carried out.
8. The waste lithium battery recovery wastewater treatment system is characterized by comprising an oil removal system, a lithium precipitation system, a primary phosphorus and fluorine removal system, a secondary phosphorus and fluorine removal system and an evaporation crystallization system which are sequentially connected;
the oil removal system comprises an oil removal adjusting tank (1), an oil removal tank (2), an ultrafiltration tank (3) and a nanofiltration tank (4) which are sequentially connected, wherein the oil removal tank (2) and the nanofiltration tank (4) are connected with an oil storage tank (21) by adopting a pump, and the oil storage tank (21) is sequentially connected with an integrated combustor (22), a tail gas purifying device (23) and a discharge chimney (24); the integrated burner (22) comprises an RTO integrated incineration device; the integrated combustor (22) is provided with a spray gun, a blower and a natural gas ignition device, wherein the spray gun and the natural gas ignition device respectively spray waste oil and natural gas in an oil storage tank (21) into the combustor at the same time, and blow air through the blower to support combustion; the inner wall of the integrated combustor (22) is provided with a water wall pipe, water circulates in the water wall pipe, and steam is generated through heating; the oil storage tank (21) is connected to a spray gun of the integrated combustor (22) through a pump and a conveying pipeline, and a filter is arranged on the conveying pipeline; the oil separation tank (2) comprises a horizontal flow type oil separation tank or an air floating type oil separation tank, and the oil separation tank adopts a ceramic membrane.
9. The processing system of claim 8, wherein the lithium precipitation system comprises a lithium precipitation tank (5), a lithium precipitation centrifuge (6) and a post-lithium precipitation liquid regulating tank (7), the lithium precipitation centrifuge (6) being connected to the lithium precipitation tank (5) and the post-lithium precipitation liquid regulating tank (7); the primary secondary phosphorus and fluorine removal system comprises a primary phosphorus and fluorine removal reaction tank (8), a primary filter press (9), a primary filter press back liquid tank (10), a secondary phosphorus and fluorine removal reaction tank (11), a secondary filter press (12) and a secondary filter press back liquid tank (13) which are connected in sequence, wherein the primary filter press (9) and the secondary filter press (12) are plate-and-frame filter presses.
10. The treatment system according to claim 8, characterized in that the evaporative crystallization system comprises a precision filter (14) and a double-effect evaporator (15) connected in sequence, the precision filter (14) being connected to an activated carbon adsorption system; the precise filter (14) comprises a microfiltration grade filter with automatic backwashing and/or without a backwashing device, the double-effect evaporator (15) is connected with the integrated combustor (22), steam recovered in the integrated combustor (22) is used as an evaporation heat source, mechanical stirring equipment is contained in the oil separation tank (2) and the lithium precipitation rear liquid regulating tank (7), and the mechanical stirring equipment comprises one or more of steel lining PPH, steel lining rubber or steel lining glass fiber reinforced plastic; the ultrafiltration tank (3), the nanofiltration tank (4), the lithium precipitation tank (5), the lithium precipitation rear liquid regulating tank (7), the primary dephosphorization and defluorination reaction tank (8), the primary filter-pressing rear liquid tank (10), the secondary dephosphorization and defluorination reaction tank (11) and the secondary filter-pressing rear liquid tank (13) are made of one or more of PPH, glass fiber reinforced plastic, steel lining rubber, steel lining glass fiber reinforced plastic or concrete lining anticorrosive coatings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310487593.8A CN116444085A (en) | 2023-04-28 | 2023-04-28 | Waste lithium battery recycling wastewater treatment process and system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310487593.8A CN116444085A (en) | 2023-04-28 | 2023-04-28 | Waste lithium battery recycling wastewater treatment process and system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116444085A true CN116444085A (en) | 2023-07-18 |
Family
ID=87120219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310487593.8A Pending CN116444085A (en) | 2023-04-28 | 2023-04-28 | Waste lithium battery recycling wastewater treatment process and system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116444085A (en) |
-
2023
- 2023-04-28 CN CN202310487593.8A patent/CN116444085A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2177478A1 (en) | Method and systems for processing waste water using zero process water discharge | |
| CN105254084A (en) | Desulfurization waste water bipolar membrane electrodialysis treatment method and device | |
| CN105948367A (en) | Novel desulfurization waste water zero discharging process and system | |
| CN113105138A (en) | Method and system for water washing dechlorination of waste incineration fly ash and evaporation mass-separation crystallization of water washing liquid | |
| CN212597897U (en) | Flying dust washing processing system | |
| CN111170520A (en) | Treatment process and treatment system for desulfurization wastewater | |
| CN111039492A (en) | Low-cost zero-discharge desulfurization wastewater treatment system and method | |
| CN212174704U (en) | Coal fired power plant wet flue gas desulfurization waste water decrement zero release processing system | |
| CN117185527A (en) | Chemical industry incineration flue gas high-ammonium salt spray wastewater recycling method and system for simultaneously recycling magnesium ammonium phosphate and ammonium sulfate | |
| CN111115661B (en) | Nitric acid wastewater treatment system and method | |
| CN105621775A (en) | Novel desulfurated wastewater zero-emission treatment device and method | |
| CN113173674A (en) | High-salinity concentrated water recycling treatment system and method | |
| CN112573720A (en) | Thermal power plant desulfurization wastewater zero-discharge system and method | |
| CN110937735A (en) | Coal-fired power plant desulfurization wastewater recycling treatment system and method | |
| CN116444085A (en) | Waste lithium battery recycling wastewater treatment process and system | |
| CN214693342U (en) | Mixed salt processing system of industrial salt that contains organic matter | |
| CN210559894U (en) | Zero release and resource utilization system of whole factory of power plant waste water | |
| CN115259518A (en) | System and method for treating percolate concentrated solution | |
| CN211546234U (en) | Desulfurization wastewater treatment system | |
| CN112225232A (en) | Mixed salt processing system of industrial salt that contains organic matter | |
| CN112441601A (en) | System and method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater | |
| CN105923707B (en) | A kind of desulfurization wastewater vibration membrane processing method and processing device | |
| CN214299718U (en) | Desulfurization wastewater treatment system | |
| CN1484556A (en) | Wet methd for treaving petroleum-originated combustion ash | |
| CN220812088U (en) | Wet flue gas desulfurization waste water zero release processing system in cement preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |