CN116425338A - Recycling recycling method of nickel-containing electroplating wastewater - Google Patents
Recycling recycling method of nickel-containing electroplating wastewater Download PDFInfo
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- CN116425338A CN116425338A CN202310329511.7A CN202310329511A CN116425338A CN 116425338 A CN116425338 A CN 116425338A CN 202310329511 A CN202310329511 A CN 202310329511A CN 116425338 A CN116425338 A CN 116425338A
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- nickel
- electroplating wastewater
- containing electroplating
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 84
- 239000002351 wastewater Substances 0.000 title claims abstract description 52
- 238000009713 electroplating Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004064 recycling Methods 0.000 title claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000706 filtrate Substances 0.000 claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 22
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002893 slag Substances 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 20
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 18
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000011084 recovery Methods 0.000 abstract description 30
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 description 20
- 238000001556 precipitation Methods 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 11
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229960004887 ferric hydroxide Drugs 0.000 description 5
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LKCUKVWRIAZXDU-UHFFFAOYSA-L zinc;hydron;phosphate Chemical compound [Zn+2].OP([O-])([O-])=O LKCUKVWRIAZXDU-UHFFFAOYSA-L 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 2
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000004503 fine granule Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic 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
- C02F1/66—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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2001/5218—Crystallization
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The application relates to the field of wastewater treatment, in particular to a recycling method of nickel-containing electroplating wastewater. A recycling method of nickel-containing electroplating wastewater comprises the following steps: adding hydrogen peroxide into the nickel-containing electroplating wastewater, reacting for 50-90min at 55-65 ℃, adding ammonia water to adjust the pH to 3.5-5.0, and obtaining iron slag and primary filtrate;adding sodium thiosulfate into the primary filtrate for reaction, and then adjusting the pH to 1.0-1.5 by sulfuric acid to obtain copper slag and secondary filtrate; adding phosphoric acid into the secondary filtrate for reaction, adding ammonia water to adjust the pH value to 4.5-5.5, and obtaining zinc slag and tertiary filtrate; adding ammonium sulfate into the three filtrates to react, crystallizing to obtain Ni (NH) 4 ) 2 (SO 4 ) 2 ·6H 2 And O crystal. The method has the advantages of high recovery rate, high purity, simple process, low cost and the like of various metals.
Description
Technical Field
The application relates to the field of wastewater treatment, in particular to a recycling method of nickel-containing electroplating wastewater.
Background
Nickel electroplating is an important plating branch in the electroplating industry, and not only realizes the corrosion resistance, the enhanced hardness and the wear resistance of materials, high thermal stability and the like, but also has excellent appearance decoration and excellent electric conductivity, so that the nickel electroplating material is widely applied to the fields of basic manufacturing, electrical element manufacturing, aerospace and the like. The processing amount is second in the electroplating industry, and is second to galvanization. With the increasing demand of the nickel plating industry, a great deal of problems concerning the treatment of nickel plating waste liquid are derived. If the wastewater is improperly treated, nickel ions are polluted, a series of problems such as skin diseases, respiratory organ disorders, cancers and the like can be caused.
The main treatment method of the nickel-containing electroplating wastewater at present comprises the following steps: chemical precipitation, redox, electrochemical, reverse osmosis, ion exchange, and the like. The chemical precipitation method is to add precipitants such as hydroxide into nickel-containing wastewater to change nickel metal into sludge in a precipitation form, and the nickel metal after sludge formation can be recovered through acid-soluble extraction and other ways. However, this treatment method increases the pollution treatment chain, requires recovery of sludge by a qualified recovery mechanism, and has complicated recovery route and risk of secondary pollution. The electrochemical method is favorable for recycling the high-concentration nickel-containing wastewater, but the current efficiency is reduced and the energy consumption is increased along with the reduction of the nickel concentration. The reverse osmosis membrane method has the advantages of high treatment efficiency, short process flow, easy control and the like, but for electroplating wastewater with complex components, not only is a severe pretreatment needed, but also the quality requirement on the membrane is higher. The ion exchange method does not require a severe pretreatment, but during the ion exchange process, a small amount of impurity metals such as copper and zinc may participate in the exchange, affecting the ion exchange efficiency and purity of the recovered nickel resources. Therefore, there is still a need for improvement.
Disclosure of Invention
The application provides a recycling method of nickel-containing electroplating wastewater.
The recycling method for nickel-containing electroplating wastewater provided by the application adopts the following technical scheme:
a recycling method of nickel-containing electroplating wastewater comprises the following steps:
adding hydrogen peroxide into the nickel-containing electroplating wastewater, reacting for 50-90min at 55-65 ℃, adding ammonia water to adjust the pH to 3.5-5.0, and obtaining iron slag and primary filtrate;
adding sodium thiosulfate into the primary filtrate for reaction, and then adjusting the pH to 1.0-1.5 by sulfuric acid to obtain copper slag and secondary filtrate; adding phosphoric acid into the secondary filtrate for reaction, adding ammonia water to adjust the pH value to 4.5-5.5, and obtaining zinc slag and tertiary filtrate;
adding ammonium sulfate into the three filtrates to react, crystallizing to obtain Ni (NH) 4 ) 2 (SO 4 ) 2 ·6H 2 And O crystal.
By adopting the technical scheme, the Fe is oxidized by hydrogen peroxide 2+ Adding ammonia water to regulate pH to obtain Fe (OH) 3 Precipitation to remove iron, adding sodium thiosulfate to generate Cu 2 S precipitation copper removal, adding phosphoric acid to generate ZnHPO 4 After precipitation and dezincification, equivalent NH is added 4 SO 4 Dissolving and crystallizing to obtain Ni (NH) with high recovery value and purity 4 ) 2 (SO 4 ) 2 ·6H 2 And O crystal.
The inventor has unexpectedly found that when the reaction temperature of hydrogen peroxide in nickel-containing wastewater is 55-65 ℃, the hydrogen peroxide can have a relatively high reaction speed with ferrous iron and can not be split too fast, so that the iron can be removed efficiently. In addition, the pH in each step is also critical, and too high or too low can affect the precipitation of the corresponding element.
Adding the specific selected raw materials into the nickel-containing electroplating wastewater according to a specific sequence, gradually separating iron, copper, zinc and nickel in the nickel-containing electroplating wastewater by adopting a fractional precipitation mode, and obtaining iron slag, copper slag and zinc slag which have high purity and recovery rate and single components and are convenient to recover. Meanwhile, the obtained nickel-containing crystal has high purity, less nickel loss and good recovery value. According to the technical scheme, the nickel in the nickel-containing wastewater is removed in a branched manner, so that high-purity nickel recovery is realized. The method has the advantages of simple process, low cost, single precipitation component generated by impurity removal, high copper slag grade, high recovery rate of nickel, direct economic value of the product and the like.
Preferably, when the ammonia water is added dropwise, the dropping speed is controlled to be 10-15mL/min.
Although ammonia is a weak base, if a large amount of ammonia is poured into nickel-containing electroplating wastewater, the region becomes too alkaline in a short time. When the alkalinity of a part of the area is too strong, nickel in the nickel-containing electroplating wastewater is easy to be directly changed into nickel hydroxide sediment, and the subsequent treatment is difficult to be redissolved, so that the recovery rate and purity of the nickel are affected.
By adopting the technical scheme, the inventor searches for the ammonia water dropping speed which is matched with the whole system, so that the pH adjustment can be realized, and the regional alkalinity is not excessively strong.
Preferably, the concentration of the ammonia water is 3-5%.
If the concentration of the ammonia water is too high, local pH is easy to be too high, nickel hydroxide precipitation is generated and can not be dissolved; if the ammonia concentration is too low, the ammonia input is too large, so that the overall nickel ion concentration is reduced.
By adopting the technical scheme, the concentration of the ammonia water is further limited to be in a proper range, and a good reaction foundation is provided for the system.
Preferably, after adding sodium thiosulfate to the primary filtrate, stirring and heating to 85-95 ℃, maintaining for 20-50min, and then adjusting the pH.
The inventors found that Cu can be formed even without heating 2 The S particles are recovered, but such particles tend to be in the form of fine particle powders. When separating copper slag and secondary filtrate, usually adopt the suction filtration mode, this fine granule powder form granule is easy to be blocked up, is unfavorable for subsequent operation, and the quality is also not enough.
By adopting the technical scheme, the Cu is further stirred and heated to a specific temperature and time 2 The S particles precipitate and flocculate into large particles, which is convenient for suction filtration and has better quality.
Preferably, after adding ammonium sulfate to the three filtrates for reaction, stirring and heating until the ammonium sulfate is completely dissolved, and then standing, cooling and crystallizing.
The ammonium sulfate reacts with nickel in the nickel-containing electroplating wastewater, and most of the nickel exists in the form of nickel sulfate at the moment and reacts with the ammonium sulfate to obtain nickel ammonium sulfate. At normal temperature, the nickel ammonium sulfate can be supersaturated and separated out, and most of the product is in powder form and has low purity. However, after the improvement of the inventor, the nickel ammonium sulfate is heated to a just complete state, so that the solubility of the nickel ammonium sulfate is increased, then the nickel ammonium sulfate is cooled and separated out, large-particle crystals are obtained, and the purity and the recovery rate can be effectively improved.
Preferably, the concentration of the hydrogen peroxide is 20-40%; when the iron content is 1-2mL/L, the adding amount of hydrogen peroxide is 10-20mL/L.
By adopting the technical scheme, the dosage relation of hydrogen peroxide and iron is further limited, and ferrous iron is fully oxidized, so that the follow-up precipitation in the form of ferric hydroxide is facilitated.
Preferably, the addition amount of the sodium thiosulfate is 6-8 times of the mass of the copper.
By adopting the technical scheme, the dosage relation between the sodium thiosulfate and the copper is further limited. In this system, sodium thiosulfate reacts with copper ions to produce a precipitate of cuprous sulfide, while sodium thiosulfate does not react with other ions.
Preferably, the concentration of the phosphoric acid is 75-85%; the addition amount of phosphoric acid is 2-3 times of the mass of zinc.
Preferably, the addition amount of the ammonium sulfate is 2-3 times of the mass of the nickel.
Preferably, in the nickel-containing electroplating wastewater, the concentration of nickel is more than or equal to 10g/L, and the concentration of iron, copper and zinc is less than 2g/L.
The technical scheme of the application has the best effect when treating the nickel-containing electroplating wastewater.
In summary, the present application has the following beneficial effects:
1. oxidizing Fe with hydrogen peroxide 2+ Adding ammonia water to regulate pH to obtain Fe (OH) 3 Precipitation to remove iron, adding sodium thiosulfate to generate Cu 2 S precipitation copper removal, adding phosphoric acid to generate ZnHPO 4 After precipitation and dezincification, equivalent NH is added 4 SO 4 Dissolving and crystallizing to obtain Ni (NH) with high recovery value and purity 4 ) 2 (SO 4 ) 2 ·6H 2 And O crystal.
2. According to the technical scheme, the metal impurities in the nickel-containing wastewater are removed in a branched manner, so that high-purity nickel recovery is realized; the method has the advantages of simple process, low cost, single precipitation component generated by impurity removal, high copper slag grade, high recovery rate of nickel, direct economic value of the product and the like.
3. Fe (OH) obtained by the present application 3 、Cu 2 S、ZnHPO 4 、Ni(NH 4 ) 2 (SO 4 ) 2 ·6H 2 O is in large particles, the blockage is not easy to be caused in the suction filtration process, and the purity and the recovery rate are good.
Detailed Description
The present application is described in further detail below with reference to examples.
The raw materials used in the following examples and comparative examples are all commercially available products.
Examples
Example 1
The nickel-containing regulating tank concentrated water of a certain electroplating plant is used as a treatment object, the total nickel content of raw water is 25g/L, the total zinc content is 1.5g/L, the total copper content is 0.8g/L, the total iron content is 1.5g/L, and the pH value is 1.98.
A recycling method of nickel-containing electroplating wastewater comprises the following steps:
step 1): adding hydrogen peroxide into the nickel-containing electroplating wastewater, wherein the adding amount of the hydrogen peroxide is 20mL/L, heating to 60 ℃, and stirring for reaction for 30min.
Then 5 percent (mass fraction) of ammonia water is added while stirring to adjust the pH value to 4.5, and the dropping speed of the ammonia water is 12mL/min.
After the pH was adjusted, the mixture was heated to slight boiling (90 ℃ C.) and kept in the slight boiling state for 30 minutes.
Then standing, cooling and precipitating for 1h, taking out supernatant, and carrying out suction filtration to obtain ferric hydroxide precipitate; the supernatant is primary filtrate, and ferric hydroxide precipitate is iron slag.
Step 2): to the primary filtrate, a sodium thiosulfate solution with a concentration of 20% was added in an amount of 30mL/L.
Adjusting pH to 1.5 with 10% dilute sulfuric acid, stirring, heating to slight boiling (90deg.C), and maintaining slight boiling state for 30min.
And then standing, cooling and precipitating for 1h, and filtering to obtain copper slag (cuprous sulfide precipitate) and clarified secondary filtrate.
Step 3): 75% of concentrated phosphoric acid is added into the secondary filtrate, and the adding amount of the concentrated phosphoric acid is 4mL/L.
Then, the pH was adjusted to 5.5 with 5% aqueous ammonia at a dropping rate of 12mL/min under stirring.
After the pH was adjusted, the mixture was heated to slight boiling (90 ℃ C.) and kept in the slight boiling state for 30 minutes.
And then standing, cooling and precipitating for 1h, taking out supernatant, and carrying out suction filtration to obtain zinc hydrogen phosphate precipitate. The supernatant is the three times of filtrate, and the zinc hydrogen phosphate precipitate is zinc slag.
Step 4): adding ammonium sulfate into the filtrate for three times, wherein the adding amount of the ammonium sulfate is 65g/L, heating until the ammonium sulfate is just completely dissolved, standing and cooling to room temperature, crystallizing at 0 ℃, filtering and washing with a small amount of clear water to obtain the ammonium nickel sulfate crystal.
Dissolving a small amount of ammonium nickel sulfate crystals, and measuring the concentration of each metal, wherein the concentration of nickel is 1220mg/L, the concentration of copper is 0.05mg/L, the concentration of zinc is 0.3mg/L, the concentration of iron is 0.3mg/L, the purity of the ammonium nickel sulfate crystals is more than 99%, 145g of ammonium nickel sulfate crystals are obtained per liter of concentrated water, and the nickel recovery rate is 90%.
Example 2
The resource recycling method of the nickel-containing electroplating wastewater is different from the embodiment 1 in that the dropping speed is 30mL/min when ammonia water is added dropwise in the steps 1) and 3).
Example 3
The difference between the recycling method of the nickel-containing electroplating wastewater and the method of the embodiment 1 is that the concentration of the ammonia water is 10%.
Example 4
The method for recycling nickel-containing electroplating wastewater is different from example 1 in that the operation of heating to micro-boiling (90 ℃) and keeping the micro-boiling state for 30min in the step 2) is omitted.
I.e. after adjusting the pH, directly standing for precipitation.
Example 5
The method for recycling nickel-containing electroplating wastewater is different from the method in the embodiment 1 in that the operation of heating until ammonium sulfate is just completely dissolved, standing and cooling to room temperature in the step 4) is omitted.
I.e. adding ammonium sulfate for reaction, and directly cooling for crystallization.
Example 6
A recycling method of nickel-containing electroplating wastewater is different from that of the embodiment 1 in that,
in step 1):
the addition amount of hydrogen peroxide is 10mL/L;
reacting for 90min at the temperature of 55 ℃,
adding ammonia water to adjust the pH value to 5.0, wherein the dropping speed of the ammonia water is 10mL/min;
heating to slight boiling (85 ℃).
In step 2):
the addition amount of the sodium thiosulfate solution is 8 times of the mass of copper;
the pH is adjusted to 1.0, and the mixture is stirred and heated to slight boiling (85 ℃);
in step 3):
the addition amount of phosphoric acid is 2 times of the mass of zinc;
adjusting the pH value to 4.5, and enabling the dropping speed of the ammonia water to be 10mL/min;
heating to slight boiling (85 ℃).
In step 4):
the addition amount of ammonium sulfate is 2 times of the mass of nickel.
Example 7
A recycling method of nickel-containing electroplating wastewater is different from that of the embodiment 1 in that,
in step 1):
reacting for 50min at the temperature of 65 ℃,
adding ammonia water to adjust the pH value to 3.5, wherein the dropping speed of the ammonia water is 15mL/min;
heating to slight boiling (95 ℃).
In step 2):
the addition amount of the sodium thiosulfate solution is 6 times of the mass of the copper;
the pH is adjusted to 1.0, and the mixture is stirred and heated to slight boiling (95 ℃);
in step 3):
phosphoric acid concentration was 85%;
adjusting the pH value to 4.5, and enabling the dropping speed of the ammonia water to be 15mL/min;
heating to slight boiling (95 ℃).
In step 4):
the addition amount of ammonium sulfate is 3 times of the mass of nickel.
Comparative example
Comparative example 1
A recycling method of nickel-containing electroplating wastewater comprises the following steps:
in the step 1), 20% sodium thiosulfate solution is added into the nickel-containing electroplating wastewater, and the addition amount of the sodium thiosulfate solution is 30mL/L.
Adjusting pH to 1.5 with 10% dilute sulfuric acid, stirring, heating to slight boiling (90deg.C), and maintaining slight boiling state for 30min.
Then standing, cooling and precipitating for 1h, and carrying out suction filtration to obtain a small amount of elemental sulfur and primary filtrate.
Step 2): adding hydrogen peroxide into the primary filtrate, wherein the adding amount of the hydrogen peroxide is 20mL/L, heating to 60 ℃, and stirring for reaction for 30min.
Then 5 percent (mass fraction) of ammonia water is added while stirring to adjust the pH value to 4.5, and the dropping speed of the ammonia water is 12mL/min.
After the pH was adjusted, the mixture was heated to slight boiling (90 ℃ C.) and kept in the slight boiling state for 30 minutes.
Then standing, cooling and precipitating for 1h, taking out supernatant, and carrying out suction filtration to obtain ferric hydroxide precipitate; the supernatant is primary filtrate, and ferric hydroxide precipitate is iron slag.
Step 3): adding concentrated phosphoric acid into the secondary filtrate, wherein the adding amount of the concentrated phosphoric acid is 4mL/L.
Then, the pH was adjusted to 5.5 with 5% aqueous ammonia at a dropping rate of 12mL/min under stirring.
After the pH was adjusted, the mixture was heated to slight boiling (90 ℃ C.) and kept in the slight boiling state for 30 minutes.
And then standing, cooling and precipitating for 1h, taking out supernatant, and carrying out suction filtration to obtain zinc hydrogen phosphate precipitate. The supernatant is the three times of filtrate, and the zinc hydrogen phosphate precipitate is zinc slag.
Step 4): adding ammonium sulfate into the filtrate for three times, wherein the adding amount of the ammonium sulfate is 65g/L, heating until the ammonium sulfate is just completely dissolved, standing and cooling to room temperature, crystallizing at 0 ℃, filtering and washing with a small amount of clear water to obtain the ammonium nickel sulfate crystal.
Comparative example 2
The method for recycling nickel-containing electroplating wastewater is different from the method in the embodiment 1 in that hydrogen peroxide in the step 1) is replaced by potassium chlorate.
Comparative example 3
The method for recycling nickel-containing electroplating wastewater is different from example 1 in that sodium thiosulfate in the step 2) is replaced by sodium sulfide.
Comparative example 4
The method for recycling nickel-containing electroplating wastewater is different from example 1 in that the phosphoric acid in step 3) is replaced with sulfuric acid.
Comparative example 5
The method for recycling nickel-containing electroplating wastewater is different from example 1 in that ammonium sulfate in step 4) is replaced with sodium sulfate.
Comparative example 6
The method for recycling nickel-containing electroplating wastewater is different from example 1 in that the ammonia water in steps 1) and 3) is replaced by sodium hydroxide.
Performance test
The filter residues obtained in examples 1 to 7 and comparative examples 1 to 6 were examined to determine the purity and recovery rate of the corresponding metals. Details are shown in Table 1.
TABLE 1
As is clear from comparison of the detection data of example 1 and comparative example 1 in Table 1, the recovery rates of nickel, copper, zinc and iron obtained in example 1 and the purity of the corresponding substances are very high, and the components are single, so that the recovery value is good. However, after the specific recovery step sequence (comparative example 1) is destroyed, the recovery rate and purity of zinc and iron are greatly reduced, the purity and recovery rate of nickel are obviously reduced, and copper is not recovered even. In addition, since the recovery step is changed, more hydrogen peroxide is needed to be put into the process of oxidizing ferrous iron, and the cost is increased.
As can be seen from comparison of the test data of example 1 and comparative examples 2 to 6 in Table 1, the materials used in each step in example 1 are specific and endless in the system, and the material replacement in any one step has an effect on the purity and recovery rate of the recovered metal.
As can be seen from comparison of the test data of example 1 and examples 2 and 3 in Table 1, example 1 has higher recovery rate in terms of nickel and higher purity in terms of zinc and iron than examples 2 and 3. It was revealed that the operation of increasing the dropping speed of aqueous ammonia (example 2) or increasing the concentration of aqueous ammonia (example 3) easily caused too strong alkalinity in a short time in a partial region of the system, thereby affecting the recovery effect.
According to example 1 and implementation in Table 1Comparison of the test data of example 4 shows that example 1 has better purity and recovery of zinc, iron and copper than example 4. Omitting part of the operation of step 2 will cause Cu to be 2 S particles are changed into fine particle powder, and the purity and the recovery rate are correspondingly affected; and is also unfavorable for subsequent recovery of iron and zinc.
From comparison of the test data of example 1 and example 5 in table 1, it is understood that example 1 has better effect than example 5 in terms of purity and recovery rate of nickel, and the effect of the remaining metals is similar.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. The recycling method of the nickel-containing electroplating wastewater is characterized by comprising the following steps of:
adding hydrogen peroxide into the nickel-containing electroplating wastewater, reacting for 50-90min at 55-65 ℃, adding ammonia water to adjust the pH to 3.5-5.0, and obtaining iron slag and primary filtrate;
adding sodium thiosulfate into the primary filtrate for reaction, and then adjusting the pH to 1.0-1.5 by sulfuric acid to obtain copper slag and secondary filtrate;
adding phosphoric acid into the secondary filtrate for reaction, adding ammonia water to adjust the pH value to 4.5-5.5, and obtaining zinc slag and tertiary filtrate;
adding ammonium sulfate into the three filtrates to react, crystallizing to obtain Ni (NH) 4 ) 2 (SO 4 ) 2 ·6H 2 And O crystal.
2. The recycling method for nickel-containing electroplating wastewater according to claim 1, which is characterized in that: when the ammonia water is added dropwise, the dropping speed is controlled to be 10-15mL/min.
3. The recycling method for nickel-containing electroplating wastewater according to claim 2, which is characterized in that: the concentration of the ammonia water is 3-5%.
4. The recycling method for nickel-containing electroplating wastewater according to claim 1, which is characterized in that: adding sodium thiosulfate into the primary filtrate, stirring and heating to 85-95 ℃, maintaining for 20-50min, and then adjusting the pH.
5. The recycling method for nickel-containing electroplating wastewater according to claim 1, which is characterized in that: and adding ammonium sulfate into the three filtrates for reaction, stirring and heating until the ammonium sulfate is completely dissolved, and then standing, cooling and crystallizing.
6. The recycling method for nickel-containing electroplating wastewater according to claim 1, which is characterized in that: the concentration of the hydrogen peroxide is 20-40%; when the iron content is 1-2mL/L, the adding amount of hydrogen peroxide is 10-20mL/L.
7. The recycling method for nickel-containing electroplating wastewater according to claim 1, which is characterized in that: the addition amount of the sodium thiosulfate is 6-8 times of the mass of the copper.
8. The recycling method for nickel-containing electroplating wastewater according to claim 1, which is characterized in that: the concentration of the phosphoric acid is 75-85%; the addition amount of phosphoric acid is 2-3 times of the mass of zinc.
9. The recycling method for nickel-containing electroplating wastewater according to claim 1, which is characterized in that: the addition amount of the ammonium sulfate is 2-3 times of the mass of the nickel.
10. The recycling method for nickel-containing electroplating wastewater according to claim 1, which is characterized in that: in the nickel-containing electroplating wastewater, the concentration of nickel is more than or equal to 10g/L, and the concentration of iron, copper and zinc is less than 2g/L.
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