CN113354024A - Method for preparing nickel nitrate by using electroplating wastewater - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 44
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002351 wastewater Substances 0.000 title claims abstract description 38
- 238000009713 electroplating Methods 0.000 title claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 15
- 239000003350 kerosene Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000007127 saponification reaction Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000012071 phase Substances 0.000 abstract description 4
- 239000012074 organic phase Substances 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002699 waste material Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000007865 diluting Methods 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910001453 nickel ion Inorganic materials 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 102000004452 Arginase Human genes 0.000 description 1
- 108700024123 Arginases Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 210000004165 myocardium Anatomy 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- 230000001629 suppression Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- 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
-
- 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
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a method for preparing nickel nitrate by using electroplating wastewater, which belongs to the field of wastewater treatment. And (3) carrying out back extraction by using a loaded organic phase and a nitric acid solution with a certain concentration, wherein the organic phase is a nickel-containing complex, the water phase is converted into nickel nitrate, and finally, the obtained nickel nitrate is reused again. The method has the advantages of relatively simple equipment, easy operation, strong selectivity and high separation efficiency, and can achieve the purposes of reducing cost, discharging wastewater up to the standard and recycling nickel metal resources.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for preparing nickel nitrate by using electroplating wastewater.
Background
With the continuous development of national economy and industrial production, the demand of human beings on metal resources is continuously increased, the exploitation and production scale of the metal resources is continuously enlarged, but the environmental problems of three wastes and the like generated along with the continuous development of the metal resources are the biggest difficult problems for hindering the economic development, wherein the problem of industrial heavy metal wastewater pollution is the most serious. Heavy metals are one of the main components causing water pollution. The treatment of heavy metal wastewater pollution is an important and urgent task, especially the treatment and recovery of complex mixed component heavy metal wastewater. Nickel is a hard and corrosion resistant heavy metal commonly used in the electroplating industry. The electroplating industry produces a large amount of nickel-containing wastewater, which causes serious pollution to the environment. In the nickel plating rinsing wastewater, a large amount of nickel sulfate and nickel chloride are contained, and nickel compounds can stimulate arginase and carboxylase of a human body, cause various inflammations and damage cardiac muscle and liver. Meanwhile, nickel is a carcinogenic substance. Therefore, the exploration of an effective and economic nickel-containing wastewater treatment method has great significance for environmental protection.
The existing treatment method of nickel electroplating wastewater mainly comprises a chemical treatment method, a physical treatment method, a biological treatment method and a comprehensive treatment method. The chemical treatment method causes secondary pollution, reversible reaction exists, and the nickel content of the effluent hardly reaches the standard of Table 3 of GB 21900-2008; the effluent water treated by the biological treatment method contains a large amount of microorganisms which are difficult to directly recycle; the adsorption method is to transfer heavy metals by adsorption, and the adsorption carrier is difficult to handle. Therefore, the development of a high-efficiency and low-cost treatment process is of great significance for solving the problem of environmental pollution of electroplating wastewater. The method for preparing the nickel nitrate mainly comprises a reverse extraction method, an ion exchange method and the like. For example: (Chengyu, Zhang Guo Yong, Shi jin Qiu, etc. a method for preparing nickel nitrate A method for preparing nickel nitrate CN, CN103818973A [ P ] 2014.). The ion exchange method has high investment cost, the design and the operation management of the whole engineering system are also complex, and the ion exchange method is difficult to adapt to common small and medium-sized enterprises.
Disclosure of Invention
The invention aims to solve at least one technical problem in the prior art and provides a method for preparing nickel nitrate by using electroplating wastewater.
The technical solution of the invention is as follows:
a method for preparing nickel nitrate by using electroplating wastewater comprises the steps of firstly extracting the electroplating wastewater containing nickel by using a mixed solution of an extracting agent and isooctanol, then carrying out back extraction by using a back extracting agent, and treating a water phase after the back extraction to prepare a nickel nitrate product; wherein the back-extraction agent adopts nitric acid.
Preferably comprising the steps of:
the method comprises the following steps: mixing di (2-ethylhexyl) phosphate and sulfonated kerosene, and adding sodium hydroxide for saponification reaction to obtain saponified solution;
step two: standing and layering the saponified solution obtained in the step one, and taking supernatant as an extracting agent; when the di (2-ethylhexyl) phosphate and the sulfonated kerosene are directly mixed for use, the di (2-ethylhexyl) phosphate and the sulfonated kerosene belong to one kindThe acidic extractant, during extraction, hydrogen atoms on hydroxyl groups released by di (2-ethylhexyl) phosphate are subjected to displacement reaction with extracted cations, so that metal cations enter an organic phase to react, any reaction is dynamic when chemical equilibrium is reached, the acidity of the solution is increased along with the reaction, the forward progress of the chemical reaction is hindered, and H can be relieved by adding alkali liquor for saponification+The increase causes a problem of suppression of metal extraction.
Step three: adding isooctyl alcohol into the extracting agent in the second step to prepare a mixed solution;
step four: adding nickel-containing electroplating wastewater into the mixed solution in the third step for reaction to prepare an extract;
step five: standing and layering the extract liquor in the fourth step to prepare upper layer liquor and lower layer liquor;
step six: and (4) adding the upper layer solution in the fifth step into a nitric acid solution, stirring for back extraction, standing for layering, taking the lower layer solution, evaporating, cooling, crystallizing, filtering, washing and drying to obtain a nickel nitrate product.
Preferably, in the first step, the saponification reaction is specifically a stirring reaction at 20-30 ℃, and the saponification rate of the di (2-ethylhexyl) phosphate and the sulfonated kerosene is 40-60%.
Preferably, in the third step, the addition amount of the isooctyl alcohol accounts for 10-40% of the mass ratio of the extracting agent.
Preferably, in the fourth step, the reaction temperature is 10-35 ℃ and the reaction time is 5-10 min.
Preferably, the following components: in the fourth step, the adding amount of the nickel-containing electroplating wastewater is controlled according to the volume ratio of the nickel-containing electroplating wastewater to the water phase in the mixed solution being 1: 1-3.
Preferably, the concentration of the nitric acid solution is 0.5-1.5 mol/L.
Preferably, in step six, the evaporation is carried out at 60-80 ℃ until a crystalline film appears and then enters cooling.
Preferably, in the second step and the fifth step, the standing time is 5-10 min.
The invention has at least one of the following beneficial effects:
according to the method for preparing nickel nitrate by using electroplating wastewater, provided by the invention, bis (2-ethylhexyl) phosphate in an extracting agent and isooctanol are adopted to have a synergistic effect, namely P204 generally exists in a dimer form, two monomer molecules are connected by a hydrogen bond, a polar group (-OH) in isooctanol can break the hydrogen bond connecting the dimer, the elimination of the hydrogen bond can shorten the length of a P-O bond connected with the isooctanol, so that the electron density around oxygen is increased, namely, the hydrogen atom on the hydroxyl is subjected to cation exchange with metal ions, and the extraction is more favorably carried out. Therefore, the extraction rate is greatly improved, in addition, the invention directly uses nitric acid as a stripping agent, can directly prepare a high-purity nickel nitrate product, reduces the preparation process of intermediate raw materials compared with the traditional method, saves raw materials and reduces the production cost. In addition, the method can efficiently utilize nickel ions in the nickel plating waste liquid, so that the concentration of the residual nickel ions reaches the emission standard of industrial pollution sources of copper, cobalt and nickel (GB 25467-2010).
Drawings
FIG. 1 is a schematic block diagram of a process for preparing nickel nitrate from electroplating wastewater according to the present invention.
Detailed Description
The method for extracting and recycling nickel resources from electroplating wastewater provided by the invention is described in detail below with reference to examples, but the method should not be construed as limiting the scope of the invention.
The waste liquid in the example is taken from the centralized control area of Shangang electroplating in Xian county, Xingxing city, Jiangxi province, and the concentration of nickel ions is measured to be 3487ppm, and the following example refers to the figure 1.
The water ratios referred to herein are: the water phase volume ratio of the two solutions.
P204 referred to herein is di (2-ethylhexyl) phosphate at ambient temperature of 25 ℃.
Example 1
And 3mL of P204 is taken, 7mL of sulfonated kerosene is added, the mixture is stirred for 10min at normal temperature and then poured into a separating funnel, and the mixture is kept stand for layering, and the upper layer is taken as an extracting agent. And then adding 1mL of isooctanol into the mixture, stirring the mixture for 6min, adding 10mL of waste liquid, continuing stirring the mixture for 10min at normal temperature, pouring the solution into a separating funnel, standing the mixture for layering, taking the layered product out, diluting the layered product, and putting the diluted product into a colorimetric tube. Slowly adding 0.5mol/L nitric acid solution into the upper layer for back extraction, extracting, standing and layering, wherein the solution at the lower layer is clear, green and transparent; evaporating the lower layer solution at the reaction temperature of 60 ℃ until a crystal film appears, and then cooling and crystallizing; then filtering, washing and drying to obtain the high-purity nickel nitrate product.
Example 2
And 6mL of P204 is taken, 14mL of sulfonated kerosene is added, the mixture is stirred for 5min at normal temperature and then poured into a separating funnel, and the mixture is kept stand for layering, and the upper layer is taken as an extracting agent. And then adding 3mL of isooctanol into the mixture, stirring the mixture for 10min, adding 20mL of waste liquid, continuously stirring the mixture for 10min at normal temperature, pouring the solution into a separating funnel, standing the mixture for layering, taking the layered product out, diluting the layered product, and putting the diluted product into a colorimetric tube. Slowly adding 0.8mol/L nitric acid solution into the upper layer for back extraction, extracting, standing and layering, wherein the solution at the lower layer becomes clear, green and transparent; evaporating the lower layer solution at the reaction temperature of 70 ℃ until a crystal film appears, and then cooling and crystallizing; then filtering, washing and drying to obtain the high-purity nickel nitrate product.
Example 3
And adding 12mL of P204 into 28mL of sulfonated kerosene, stirring at normal temperature for 5min, pouring into a separating funnel, standing for layering, and taking the upper layer as an extracting agent. And then adding 8mL of isooctanol into the mixture, stirring the mixture for 10min, adding 40mL of waste liquid, continuing stirring the mixture for 10min at normal temperature, pouring the solution into a separating funnel, standing the mixture for layering, taking the layered product out, diluting the layered product, and putting the diluted product into a colorimetric tube. Slowly adding 1.0mol/L nitric acid solution into the upper layer for back extraction, extracting, standing and layering, wherein the solution at the lower layer is clear, green and transparent; evaporating the lower layer solution at the reaction temperature of 70 ℃ until a crystal film appears, and then cooling and crystallizing; then filtering, washing and drying to obtain the high-purity nickel nitrate product.
Example 4
And taking 25mL of P204, adding 35mL of sulfonated kerosene, stirring for 10min at normal temperature, pouring into a separating funnel, standing for layering, and taking the upper layer as an extracting agent. And then adding 18mL of isooctanol into the mixture, stirring the mixture for 10min, adding 50mL of waste liquid, continuing stirring the mixture for 10min at normal temperature, pouring the solution into a separating funnel, standing the mixture for layering, taking the layered product out, diluting the layered product, and putting the diluted product into a colorimetric tube. Slowly adding 1.2mol/L nitric acid solution into the upper layer for back extraction, extracting, standing and layering, wherein the solution at the lower layer is clear, green and transparent; evaporating the lower layer solution at the reaction temperature of 80 ℃ until a crystal film appears, and then cooling and crystallizing; then filtering, washing and drying to obtain the high-purity nickel nitrate product.
Example 5
And adding 25mL of P204 into 35mL of sulfonated kerosene, stirring at normal temperature for 10min, pouring into a separating funnel, standing for layering, and taking the upper layer as an extracting agent. And then adding 24mL of isooctanol into the mixture, stirring the mixture for 10min, adding 60mL of waste liquid, continuously stirring the mixture for 10min at normal temperature, pouring the solution into a separating funnel, standing the mixture for layering, taking the layered product out, diluting the layered product, and putting the diluted product into a colorimetric tube. Slowly adding 1.5mol/L nitric acid solution into the upper layer for back extraction, extracting, standing and layering, wherein the solution at the lower layer becomes clear, green and transparent; evaporating the lower layer solution at the reaction temperature of 80 ℃ until a crystal film appears, and then cooling and crystallizing; then filtering, washing and drying to obtain the high-purity nickel nitrate product.
Comparative example 1
And adding 25mL of P204 into 35mL of sulfonated kerosene, stirring at normal temperature for 10min, pouring into a separating funnel, standing for layering, and taking the upper layer as an extracting agent. Adding 60mL of waste liquid, continuously stirring at normal temperature for 10min, pouring the solution into a separating funnel, standing for layering, taking the layered layer down, diluting and putting into a colorimetric tube. Slowly adding 1.5mol/L nitric acid solution into the upper layer for back extraction, extracting, standing and layering, wherein the solution at the lower layer becomes clear, green and transparent; evaporating at the reaction temperature of 80 ℃ until a crystal film appears, and then cooling and crystallizing; then filtering, washing and drying to obtain the high-purity nickel nitrate product.
Comparative example 2
The preparation of the nickel nitrate of this comparative example was carried out with reference to the following documents: chenshengwei, Zhangguo, Shijinqiu, etc. a preparation method of nickel nitrate A method for preparing nickel nitrate CN, CN103818973A [ P ] 2014
The wastewater treated in the above examples and comparative example 1 was subjected to concentration analysis using an atomic absorption spectrophotometer (AAS, conttra A700, Analytik Jena), and was able to meet the emission standards of copper, cobalt, and nickel industrial pollution sources (GB 25467-2010). And simultaneously, the samples prepared in the embodiment and the comparative example 2 are subjected to main content and impurity analysis (cation: atomic absorption spectrometer test and anion: ion chromatograph test), so that the requirement of the nickel plating industry on nickel nitrate can be met, and specific numerical values are shown in the following table:
TABLE 1 concentration of nickel ions remaining after treating wastewater as in example and comparative example 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | |
| Residual nickel ion (ppm) | 0.23ppm | 0.19ppm | 0.15ppm | 0.09ppm | 0.29ppm | 0.87ppm |
Table 2 main contents and impurity contents of examples and comparative examples 2 converted into nickel nitrate
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 2 | |
| Main content% | 99.34 | 99.46 | 99.83 | 99.95 | 97.60 | 87.81 |
| Copper (ppm) | 4.8 | 4.2 | 2.8 | 1.7 | 5.2 | 5.1 |
| Zinc (ppm) | 5.9 | 5.4 | 4.9 | 3.7 | 6.2 | 6.0 |
| Iron (ppm) | 3.0 | 5.8 | 2.8 | 1.9 | 3.4 | 3.2 |
| Chromium (ppm) | 2.3 | 1.6 | 1.9 | 1.5 | 2.8 | 2.6 |
| Aluminum (ppm) | 5.1 | 2.5 | 2.1 | 0.9 | 5.7 | 5.3 |
| Chloride (ppm) | 10.8 | 9.6 | 8.6 | 5.7 | 11.6 | 11.2 |
| Water insoluble matter% | 0.003 | 0.002 | 0.001 | 0.001 | 0.002 | 0.002 |
It can be seen from tables 1 and 2 that the wastewater treated by the method of the present invention reaches the discharge standard, the recovery rate of nickel is high, the purity of the converted nickel nitrate is high, the impurity content is low, and the requirement of nickel plating process on nickel source is satisfied, in addition, from table 1, it can be seen that the residual amount of nickel ions in the example is lower than that in comparative example 1, which indicates that the recovery rate of nickel in the method of the present invention is high, the main reason may be the synergistic effect of isooctanol and extractant adopted in the present invention, i.e. P204 generally exists in the form of dimer, two monomer molecules are connected by hydrogen bond, while polar group (-OH) in octanol destroys hydrogen bond connecting dimer, and the disappearance of hydrogen bond shortens the length of P-O bond connected therewith, so that the electron density around oxygen is increased, which is more beneficial for extraction. Therefore, the extraction rate is greatly improved, and the recovery rate of nickel is improved. Meanwhile, as can be seen from table 2, the main content of the nickel nitrate product is higher than that of comparative example 2, mainly because the nickel nitrate solution is obtained by directly and practically back-extracting the nitric acid, the preparation process of the intermediate raw material required by the traditional method for preparing the nickel nitrate is reduced, that is, the possibility of mixing other impurities is reduced, and therefore, the purity of the nickel nitrate product is high.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing nickel nitrate by using electroplating wastewater is characterized by comprising the following steps: firstly, the electroplating wastewater containing nickel is extracted by a mixed solution of an extracting agent and isooctanol, then is back-extracted by a back-extracting agent, and the water phase after back-extraction is treated to prepare a nickel nitrate product.
2. The method for preparing nickel nitrate by using electroplating wastewater according to claim 1, which is characterized in that: the stripping agent adopts nitric acid.
3. The method for preparing nickel nitrate by using electroplating wastewater according to claim 1, which is characterized in that: comprises the following steps:
the method comprises the following steps: mixing di (2-ethylhexyl) phosphate and sulfonated kerosene, and adding sodium hydroxide for saponification reaction to obtain saponified solution;
step two: standing and layering the saponified solution obtained in the step one, and taking supernatant as an extracting agent;
step three: adding isooctyl alcohol into the extracting agent in the second step to prepare a mixed solution;
step four: adding nickel-containing electroplating wastewater into the mixed solution in the third step for reaction to prepare an extract;
step five: standing and layering the extract liquor in the fourth step to prepare upper layer liquor and lower layer liquor;
step six: and (4) adding the upper layer solution in the fifth step into a nitric acid solution, stirring for back extraction, standing for layering, taking the lower layer solution, evaporating, cooling, crystallizing, filtering, washing and drying to obtain a nickel nitrate product.
4. The method for preparing nickel nitrate by using electroplating wastewater according to claim 3, which is characterized in that: in the first step, the saponification reaction is specifically a stirring reaction at 20-30 ℃, and the saponification rate of the di (2-ethylhexyl) phosphate and the sulfonated kerosene is 40-60%.
5. The method for preparing nickel nitrate by using electroplating wastewater according to claim 3, which is characterized in that: in the third step, the addition amount of the isooctyl alcohol accounts for 10-40% of the mass ratio of the extracting agent.
6. The method for preparing nickel nitrate by using electroplating wastewater according to claim 3, which is characterized in that: in the fourth step, the reaction temperature is 10-35 ℃, and the reaction time is 5-10 min.
7. The method for preparing nickel nitrate by using electroplating wastewater according to claim 3, which is characterized in that: in the fourth step, the adding amount of the nickel-containing electroplating wastewater is controlled according to the volume ratio of the nickel-containing electroplating wastewater to the water phase in the mixed solution being 1: 1-3.
8. The method for preparing nickel nitrate by using electroplating wastewater according to claim 3, which is characterized in that: the concentration of the nitric acid solution is 0.5-1.5 mol/L.
9. The method for preparing nickel nitrate by using electroplating wastewater according to claim 3, which is characterized in that: and in the sixth step, the evaporation is carried out at the temperature of 60-80 ℃ until a crystal film appears, and then the crystal film enters for cooling.
10. The method for preparing nickel nitrate by using electroplating wastewater according to claim 3, which is characterized in that: in the second step and the fifth step, the standing time is 5-10 min.
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