CN113371907A - Method for treating nickel electrolysis high-salinity wastewater by using flash steam - Google Patents
Method for treating nickel electrolysis high-salinity wastewater by using flash steam Download PDFInfo
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- CN113371907A CN113371907A CN202110626018.2A CN202110626018A CN113371907A CN 113371907 A CN113371907 A CN 113371907A CN 202110626018 A CN202110626018 A CN 202110626018A CN 113371907 A CN113371907 A CN 113371907A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000002351 wastewater Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 41
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000004073 vulcanization Methods 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000002386 leaching Methods 0.000 claims abstract description 5
- 239000002893 slag Substances 0.000 claims abstract description 5
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000701 coagulant Substances 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000013505 freshwater Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 12
- 239000012528 membrane Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- -1 nickel and the like Chemical class 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/06—Flash evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/16—Treatment of water, waste water, or sewage by heating by distillation or evaporation using waste heat from other processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2001/007—Processes including a sedimentation step
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- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The invention provides a method for treating nickel electrolysis high-salinity wastewater by using flash steam, which comprises the following steps: (1) the method comprises the steps of (1) pressurizing and leaching ore pulp flash steam from electrodeposited nickel, adding the flash steam into a low-temperature evaporator to serve as a heat source, (2) adjusting the pH value of nickel electrolysis high-salt wastewater, adding the wastewater into the low-temperature evaporator, concentrating and reducing to generate concentrated water, (3) adding the concentrated water into a vulcanization and weight removal device to perform vulcanization and weight removal reaction, precipitating and filtering to obtain a nickel-containing heavy metal filter cake, (4) adding the nickel-containing heavy metal filter cake into a filter pressing device, filtering and slagging to obtain nickel sulfide slag. The method has the advantages of simple process, low operation temperature, low energy consumption, low operation cost and no secondary pollution; valuable metal resources such as nickel and the like can be recovered by evaporating concentrated water for vulcanization and weight removal, and the scale of wastewater weight removal treatment can be reduced; the whole method achieves the purposes of water saving, emission reduction and wastewater recycling, realizes the resource utilization of heavy metals, and reduces cost and improves efficiency for enterprises.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and relates to a method for treating nickel electrolysis high-salinity wastewater by using flash steam.
Background
In the nickel electrolysis process of a smelting plant, supernatant liquid obtained after nickel ions are precipitated by sodium carbonate is weakly alkaline high-salt wastewater with the salt content of about 120g/L, the salt content of the wastewater mainly exists in the forms of sodium sulfate and sodium carbonate and contains heavy metal ions such as nickel and the like, the high-salt wastewater cannot be used for production water, the recycling rate of the wastewater cannot meet the standard requirement, and if the wastewater is directly discharged, the peripheral soil and water bodies are damaged, so that the ecological environment is seriously threatened.
At present, the treatment technology of high-salinity wastewater mainly comprises the following steps: (1) membrane concentration techniques, separation techniques driven by pressure differences, concentration differences, potential differences, and the like, are achieved by size exclusion, charge repulsion, and physicochemical interactions between solutes, solvents, and membranes. The technology has the advantages that substances are not subjected to phase change in the separation process, separation products are easy to recover, the membrane is easy to be influenced by osmotic pressure, the salt content of concentrated water is limited, the salt content of waste water can be concentrated to 15% by the existing high-pressure reverse osmosis and electrodialysis technology, the waste water reduction effect is not obvious, the TDS content in produced water is about 3000mg/L, and the membrane cannot be directly used for production. In addition, the membrane technology has higher requirement on water quality before entering the membrane, the pretreatment process is longer, the membrane is easy to damage and pollute, and the cleaning and replacing periods are short, which can directly cause the separation effect of the membrane to be poor; (2) the thermal concentration technology adopts a heating method to vaporize and remove part of the solvent in the solution, thereby improving the concentration of the solution and reducing the volume of the waste water. The technology mainly comprises the technologies of multi-stage flash evaporation, multi-effect evaporation, MVR and the like. The thermal concentration technology is mature, safe and reliable, but has the problems of high operation temperature, high energy consumption, easy corrosion and scaling of equipment, incapability of utilizing low-grade heat sources such as exhaust steam and the like when treating high-salinity wastewater.
The problems existing in the technology obviously hinder the popularization and application of the technology, and the short flow, low energy consumption, difficult scaling and low operation cost become important breakthrough points of the technology popularization.
Patent document CN110217933A discloses a method for treating high-salinity wastewater. The method is divided into four working procedures, heavy metals in the high-salinity wastewater can be removed after two-stage neutralization and precipitation treatment, so that the wastewater can reach the discharge standard and the resource recovery of the heavy metals is effectively realized, and then the working procedures of low-temperature evaporation and natural evaporation are carried out. Compared with the prior art, the method has the advantages of short process flow, low energy consumption, low operation cost, high efficiency, no secondary pollution to the environment and the like. The method has the advantages of low operation temperature, difficult corrosion and scaling of equipment, high concentration ratio of high-salinity wastewater and capability of directly recycling produced water for production, but the method needs two stages of precipitation and clarification processes to remove heavy metals, more steps are needed before low-temperature evaporation of the high-salinity wastewater, and the scale of wastewater weight removal treatment is larger.
Disclosure of Invention
The invention aims to provide a method for treating nickel electrolysis high-salinity wastewater by using flash steam, aiming at the problems in the prior art.
Therefore, the invention adopts the following technical scheme:
a method for treating nickel electrolysis high-salinity wastewater by using flash steam is characterized by comprising the following steps:
(1) pressurizing and leaching the electrodeposited nickel to extract ore pulp flash steam, washing the ore pulp flash steam, and introducing the ore pulp flash steam into a low-temperature evaporator to serve as a heat source;
(2) adjusting the pH value of the nickel electrolysis high-salinity wastewater, adding the nickel electrolysis high-salinity wastewater into a low-temperature evaporator, concentrating and reducing to generate concentrated water, and condensing evaporated water vapor to generate fresh water;
(3) adding a vulcanizing agent into the concentrated water, putting the concentrated water into a vulcanization and weight removal device for vulcanization and weight removal reaction, adding a coagulant after the reaction is finished, precipitating and filtering to obtain a nickel-containing heavy metal filter cake and filtered water, and evaporating, crystallizing or recycling the filtered water;
(4) adding the nickel-containing heavy metal filter cake into a filter pressing device for filtering and slagging to obtain nickel sulfide slag and filtrate, and evaporating, crystallizing or recycling the filtrate.
Further, the flash steam temperature of the ore pulp in the step (1) is 60-120 ℃.
Further, in the step (1), the flash steam of the ore pulp is washed in a spraying mode.
Further, the salt content of the high-salt wastewater in the step (2) is more than 100g/L, the nickel ion content is 20-60mg/L, the sodium sulfate concentration is 70-120g/L, the sodium carbonate concentration is 10-30g/L, and the salt content is 90-140 mg/L.
Further, the step (2) is to add sulfuric acid to the high-salinity wastewater to adjust the pH value to be 6-9.
Further, the effect number of the low-temperature evaporator in the step (2) is 4-8, and the temperature difference between the effects is 3-10 ℃.
Further, in the step (3), the vulcanizing agent is sodium sulfide or sodium hydrosulfide, and the coagulant is PAM.
Further, the stirring time of the sulfurization and weight removal reaction in the step (3) is 0.5-2h, and the reaction temperature is 40-80 ℃.
Further, the filtered water in the step (3) and the filtrate in the step (4) are crystallized by adopting a multi-effect evaporation method, an MVR method or a natural airing method.
The invention has the beneficial effects that:
the method utilizes ore pulp flash steam after pressure leaching of electrodeposited nickel in a smelting plant as a heat source, is effectively linked with a low-temperature evaporation technology, nickel electrolysis high-salinity wastewater is concentrated in a low-temperature evaporation device, the evaporated water is recycled as fresh water, the concentrated water enters a vulcanization and weight removal process, sodium sulfide is added into the concentrated water to carry out deep treatment on residual heavy metals such as nickel and the like in the wastewater, and valuable metals are recovered. The method has the advantages of simple process, low operation temperature, low energy consumption, low operation cost and no secondary pollution; valuable metal resources such as nickel and the like can be recovered by evaporating concentrated water for vulcanization and weight removal, and the scale of wastewater weight removal treatment can be reduced; the whole method achieves the purposes of water saving, emission reduction and wastewater recycling, realizes the resource utilization of heavy metals, and reduces cost and improves efficiency for enterprises.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
the high-salinity wastewater generated by the nickel electrolysis production line of the smelting plant has the nickel ion content of 50mg/L, the sodium sulfate concentration of 100g/L, the sodium carbonate concentration of 20g/L and the salt content of 120g/L, and is treated by adopting the following steps:
(1) pressurizing and leaching the electrodeposited nickel to obtain ore pulp flash steam, washing the ore pulp flash steam in a spraying mode, and introducing the flash steam with the temperature of 95 ℃ and the pressure of 0.085MPa into a low-temperature evaporator to serve as a heat source;
(2) adding sulfuric acid into the nickel electrolysis high-salt wastewater to adjust the pH value of the wastewater to 6, then adding the wastewater into a low-temperature evaporator, and performing concentration and decrement operation on the wastewater to generate concentrated water, wherein in the one-step process, the effect number of the low-temperature evaporator is 5 effects, the temperature difference between the effects is 8 ℃, the TDS content in the generated concentrated water can reach 10g/L-450 g/L, 64% volume of water vapor can be evaporated from the wastewater, and fresh water can be obtained after the water vapor is condensed;
(3) adding a vulcanizing agent into concentrated water, wherein the vulcanizing agent can be sodium sulfide or sodium hydrosulfide, adding the sodium sulfide into the concentrated water, adding the concentrated water into a vulcanization weight removal device, stirring for 1h under the reaction condition of 50 ℃ for vulcanization weight removal reaction, adopting a common device in the field for the vulcanization weight removal device, settling and filtering after the reaction is finished, adding PAM (polyacrylamide) as a coagulant before the settlement to obtain a nickel-containing heavy metal filter cake and filtered water, wherein the nickel ion content in the filtered water is less than 0.5mg/L, so that the standard discharge standard is met, the filtered water can be recycled, or the filtered water is crystallized into salt steam by adopting a multi-effect evaporation method, MVR (mechanical vapor recompression) method or natural airing method;
(4) adding the nickel-containing heavy metal filter cake into a filter pressing device for filtering and slagging to obtain nickel sulfide slag and filtrate, wherein the nickel sulfide slag can be continuously recycled, and meanwhile, the filtrate can also be directly recycled.
The whole method realizes the resource utilization of heavy metal while achieving the aims of water saving, emission reduction and wastewater recycling, and reduces cost and improves efficiency for enterprises.
Claims (9)
1. A method for treating nickel electrolysis high-salinity wastewater by using flash steam is characterized by comprising the following steps:
(1) pressurizing and leaching the electrodeposited nickel to extract ore pulp flash steam, washing the ore pulp flash steam, and introducing the ore pulp flash steam into a low-temperature evaporator to serve as a heat source;
(2) adjusting the pH value of the nickel electrolysis high-salinity wastewater, adding the nickel electrolysis high-salinity wastewater into a low-temperature evaporator, concentrating and reducing to generate concentrated water, and condensing evaporated water vapor to obtain fresh water;
(3) adding a vulcanizing agent into the concentrated water, putting the concentrated water into a vulcanization and weight removal device for vulcanization and weight removal reaction, adding a coagulant after the reaction is finished, precipitating and filtering to obtain a nickel-containing heavy metal filter cake and filtered water, and evaporating, crystallizing or recycling the filtered water;
(4) adding the nickel-containing heavy metal filter cake into a filter pressing device for filtering and slagging to obtain nickel sulfide slag and filtrate, and evaporating, crystallizing or recycling the filtrate.
2. The method for treating the nickel electrolysis high-salinity wastewater by using the flash steam as claimed in claim 1, wherein the flash steam temperature of the ore pulp in the step (1) is 60-120 ℃.
3. The method for treating the nickel electrolysis high-salinity wastewater by using the flash steam as claimed in claim 1, characterized in that the flash steam of the ore pulp in the step (1) is washed by spraying.
4. The method for treating nickel electrolysis high-salinity wastewater by using flash steam according to claim 1, characterized in that the salt content of the high-salinity wastewater in the step (2) is more than 100g/L, the nickel ion content is 20-60mg/L, the sodium sulfate concentration is 70-120g/L, the sodium carbonate concentration is 10-30g/L, and the salt content is 90-140 mg/L.
5. The method for treating the nickel electrolysis high-salinity wastewater by using the flash steam as claimed in claim 1, characterized in that the sulfuric acid is added into the high-salinity wastewater in the step (2) to adjust the pH value to the environment of 6-9.
6. The method for treating nickel electrolysis high-salinity wastewater by using flash steam as claimed in claim 1, wherein the effect number of the low-temperature evaporator in the step (2) is 4-8, and the temperature difference between the effects is 3-10 ℃.
7. The method for treating nickel electrolysis high-salinity wastewater by using flash steam according to claim 1, characterized in that in the step (3), the vulcanizing agent is sodium sulfide or sodium hydrosulfide, and the coagulant is PAM.
8. The method for treating the nickel electrolysis high-salinity wastewater by using the flash steam as claimed in claim 1, wherein the stirring time of the sulfurization-de-weighting reaction in the step (3) is 0.5-2h, and the reaction temperature is 40-80 ℃.
9. The method for treating nickel electrolysis high-salinity wastewater by using flash steam according to claim 1, characterized in that the filtered water in the step (3) and the filtrate in the step (4) are crystallized by multi-effect evaporation, MVR or natural air drying.
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| CN113860615A (en) * | 2021-10-29 | 2021-12-31 | 深圳市福田区环境技术研究所有限公司 | Chemical nickel waste liquid treatment process |
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