CN1301337C - Once process for extracting and separating Ni, Mg and Co from nickel sulfate solution recovered from waste nickel-hydrogen and nickel-cadmium cells - Google Patents
Once process for extracting and separating Ni, Mg and Co from nickel sulfate solution recovered from waste nickel-hydrogen and nickel-cadmium cells Download PDFInfo
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- CN1301337C CN1301337C CNB2005101002096A CN200510100209A CN1301337C CN 1301337 C CN1301337 C CN 1301337C CN B2005101002096 A CNB2005101002096 A CN B2005101002096A CN 200510100209 A CN200510100209 A CN 200510100209A CN 1301337 C CN1301337 C CN 1301337C
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 56
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 29
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 title claims abstract description 21
- 239000002699 waste material Substances 0.000 title claims abstract description 19
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 title claims description 18
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 title claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 12
- 239000001257 hydrogen Substances 0.000 title claims description 12
- 238000005406 washing Methods 0.000 claims abstract description 43
- 239000012074 organic phase Substances 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003350 kerosene Substances 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims description 61
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 50
- 238000000605 extraction Methods 0.000 claims description 41
- 229910017052 cobalt Inorganic materials 0.000 claims description 30
- 239000010941 cobalt Substances 0.000 claims description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001556 precipitation Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 238000005194 fractionation Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005201 scrubbing Methods 0.000 claims 2
- 241000220317 Rosa Species 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- 230000011218 segmentation Effects 0.000 claims 1
- -1 2-ethylhexyl Chemical group 0.000 abstract description 12
- 150000002148 esters Chemical class 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 239000001117 sulphuric acid Substances 0.000 abstract description 5
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract description 2
- 229910003307 Ni-Cd Inorganic materials 0.000 abstract 2
- 229910018502 Ni—H Inorganic materials 0.000 abstract 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 150000002815 nickel Chemical class 0.000 description 8
- 150000003009 phosphonic acids Chemical class 0.000 description 8
- 238000007127 saponification reaction Methods 0.000 description 5
- 229910017709 Ni Co Inorganic materials 0.000 description 4
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical class CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 1
- 229910020634 Co Mg Inorganic materials 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- DQKCIMQPUTUPAP-UHFFFAOYSA-K [OH-].[Na+].[Ni+2].[OH-].[OH-] Chemical compound [OH-].[Na+].[Ni+2].[OH-].[OH-] DQKCIMQPUTUPAP-UHFFFAOYSA-K 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention discloses a method for extracting and separating Ni, Mg and Co from a recovery nickel sulphate solution of waste Ni-H or Ni-Cd cells. The method is characterized by comprising the following steps: the pH value of a sulphuric acid leachate of positive electrode waste material of the edulcorated Ni-H and/or Ni-Cd cells is regulated to 4.5 to 5.0, and then the leachate is fractionally extracted, so that Mg and Co are converted into an organic phase but Ni is reserved in a water phase. By separately washing the Ni and the Mg, Mg wash liquid is led out from another separate outlet, so that Ni, Mg and Co are separated. The organic phase is composed of two-(2-ethylhexyl) phosphonic acid single (2-ethylhexyl) ester as the extractant and kerosene as the diluent. The present invention can separate Mg from the nickel sulphate solution, so that Mg ions in the nickel sulphate solution are reduced to below 50 mg/L so as to remove a demagging step with chemical method. The present invention has the advantages of low cost, high efficiency, simple process, reliability, strong operability, high safety and small equipment investment.
Description
Technical field
The present invention relates to a kind of in solubility single nickel salt, magnesium, cobalt mixture solution the method for separating nickel, cobalt, magnesium, particularly a kind of method that from waste nickel-hydrogen, nickel-cadmium cell reclaim(ed) sulfuric acid nickel solution, adopts a step extracting and separating nickel, cobalt, magnesium.
Background technology
Single nickel salt, xNiSO46H
2OyNiSO
47H
2O, a kind of important material of Chang Zuowei is used for electroplating industry, is used for nickel preplating, nickel plating, ferro-nickel alloy, nickel-cobalt plating, nickel and zinc alloy, also is used for solution such as chemical nickel plating; Also be used to make mordant, metallochrome of catalyzer, the vat dyes of nickel-cadmium cell, nickel metal hydride battery, winterized stearin or paint etc., also be used to produce nickel accelerant and other nickel salts etc.Therefore content≤0.015% of single nickel salt quality requirements (the chemical industry standard HG/T2824-1997 of the industrial sulphuric acid nickel People's Republic of China (PRC)) impurity Mg needs the nickel sulfate solution demagging.About the removal of magnesium in the nickel sulfate solution, method in common is to add Sodium Fluoride at present, makes magnesium and fluorine form the magnesium fluoride precipitation of indissoluble, filters and removes.The shortcoming of this method is: (1) Sodium Fluoride solubleness is little, and long reaction time needs heating, and energy consumption of reaction is big, and the magnesium fluoride sedimentation and filtration poor performance that generates; (2) demagging process is introduced sodium ion and is entered nickel sulfate solution, influences single nickel salt crystalline quality; (3) remaining fluorine has corrosive nature to the enamel concentration kettle in the nickel sulfate solution in follow-up concentration process, influences equipment life; (4) fluorine-containing in the waste water, cause the wastewater treatment difficulty.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of method from waste nickel-hydrogen, A Step Extraction Separation Nickel through Nickel-cadmium Cell Retrieving In Nickelous Sulfate Solution, magnesium, cobalt, this method technology is simple, reliable, facility investment is few, removal effect good and can not cause environmental pollution.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of method from waste nickel-hydrogen, A Step Extraction Separation Nickel through Nickel-cadmium Cell Retrieving In Nickelous Sulfate Solution, magnesium, cobalt, it is characterized in that this method comprises regulates pH value to 4.5-5.0 with the sulphuric leachate of ni-mh after the removal of impurities and/or nickel-cadmium cell anode waste, then leach liquor is carried out fractionation extraction, make magnesium and cobalt change organic phase over to and nickel remaines among the water, again by washing nickel and washing magnesium respectively, the washings of magnesium drawn from an independent outlet reach nickel, magnesium, cobalt and separate; Specifically be that the organic phase of load magnesium is washed with sulfuric acid, washing terminal point pH value is controlled at 5.0 ± 0.1, to isolate the nickel in the organic phase, the organic phase that to wash then behind the nickel is washed with sulfuric acid, washing terminal point pH value is controlled at 4.4 ± 0.1, magnesium is transferred in the magnesium washing outlet liquid, with sodium hydroxide nickel and magnesium precipitate in the washing outlet liquid is reclaimed again; Described organic phase is by constituting as two of extraction agent-(2-ethylhexyl) phosphonic acids list (2-ethylhexyl) ester with as the kerosene of thinner.
For guaranteeing the clearance of magnesium in waste nickel-hydrogen, the nickel-cadmium cell reclaim(ed) sulfuric acid nickel solution, the present invention carries out ten secondary fractionation extractions with leach liquor and organic phase.
Extraction agent two-the concentration of (2-ethylhexyl) phosphonic acids list (2-ethylhexyl) ester (P507) in organic phase that the present invention adopts is preferably 0.3mol/L～1.5mol/L.
Owing to also contain the cobalt of certain content in waste nickel-hydrogen, the nickel-cadmium cell reclaim(ed) sulfuric acid nickel solution, therefore nickel magnesium carried out the isolating separation that also need consider simultaneously cobalt.Experiment showed, that nickel, cobalt, magnesium change along with the change of extraction equilibrium pH value at the separation factor of two-(2-ethylhexyl) phosphonic acids list (2-ethylhexyl) ester (P507) during as extraction agent.
Experiment condition: organic phase is a 20%P507+80% kerosene, and P507 concentration is 0.6mol/L, is in a ratio of O/A=1/1, and organic phase is carried out the homogeneous phase saponification with NaOH earlier, is converted into the nickel saponification again, control PH=6 during the nickel saponification, NiSO
4About concentration 50g/L, nickel saponification degree 30%, organic phase nickel-loaded 5.31g/L after the saponification, promptly the equivalents of organic phase nickel-loaded is 0.18N.Water is that P204 purifies back solution, PH=3.2-3.5, Ni 103g/L, Co 8.5g/L, Mg 2.0g/L.
β under the different extraction equilibrium pH values of table 1
Ni/Co, β
Ni/MgTest-results
| Equilibrated ph value | Water g/L | Load organic phases g/L | β Ni/Mg | β Ni/Co | ||||
| Ni | Co | Mg | Ni | Co | Mg | |||
| 3.5 | 104.7 | 6.87 | 1.96 | 3.57 | 1.62 | 0.05 | 0.75 | 6.92 |
| 3.8 | 105.9 | 5.93 | 1.85 | 2.45 | 2.55 | 0.13 | 3.04 | 18.6 |
| 4.0 | 106.7 | 5.27 | 1.80 | 1.65 | 3.23 | 0.14 | 5.03 | 39.63 |
| 4.5 | 107.7 | 4.67 | 1.67 | 0.63 | 3.83 | 0.20 | 20.5 | 140.2 |
| 5.0 | 108.3 | 4.35 | 1.54 | 0.58 | 4.20 | 0.21 | 25.5 | 180.3 |
By table 1 as seen, the extraction equilibrium pH value is to β
Ni/Co, β
Ni/MgHave a significant impact, pH value is lower than at 4.0 o'clock, β
Ni/Mg＜5; PH value is 4.5～5.0 o'clock, β
Ni/CoReach 140～180, β
Ni/MgReach 20～25.If pH value further improves, then the extracting power to nickel strengthens, and is unfavorable for that nickel, cobalt separate.Desire to make nickel, cobalt separation and magnesium to enter organic phase, need adjust pH value 4.5-5.0 to P204 purification back solution and be advisable,, can make equilibrated ph value remain on 4.5～5.0 owing to used the saponified organic phase.PH value during therefore, by the control extraction can make nickel, cobalt, magnesium be separated preferably.
For guaranteeing the further recovery of nickel, cobalt, the present invention reclaims nickel and cobalt precipitation with sodium hydroxide the rich magniferous washings of washing outlet; With sodium hydroxide the precipitation terminal point pH value that the nickel precipitation in the washing outlet liquid reclaims is preferably 8.5.
The invention has the beneficial effects as follows: (1) the present invention dexterously extraction of nickel, cobalt is separated and demagging combines together, realizing that solvent extraction method carries out nickel, isolating while of cobalt, design one step of method of two sections washings and removed magnesium, make to contain magnesium in nickel sulfate solution and the cobalt sulfate solution and all reach requirement, magnesium is drawn separately from the washing outlet for the magnesium setting; (2) the present invention separates magnesium from nickel sulfate solution, make the magnesium ion in the nickel sulfate solution be reduced to the following level of 50mg/L, thereby make the single nickel salt product meet the chemical industry standard HG/T2824-1997 of the People's Republic of China (PRC), and saved the step of chemical method demagging; (3) cost of the present invention is low, the efficient height; (4) technology of the present invention is simple, reliable, strong operability, and safety, facility investment is little; (5) the present invention has except that the versatility on the magnesium method, promptly can be used for nickel sulfate solution demagging that other any methods produce, the demagging of single nickel salt mother liquor etc.
The present invention is further described below in conjunction with embodiment.
Embodiment
Embodiment 1
The sulphuric leachate of ni-mh after the removal of impurities and/or nickel-cadmium cell anode waste is regulated pH value to 5.0, organic phase is by constituting as two of extraction agent-(2-ethylhexyl) phosphonic acids list (2-ethylhexyl) ester with as the kerosene of thinner, wherein the concentration of two-(2-ethylhexyl) phosphonic acids list (2-ethylhexyl) esters is 0.6mol/L, O/A=1/1,12 grades of contact extractions, make magnesium change organic phase over to and nickel remaines among the water, with dilute sulphuric acid load organic phases is carried out six grades of washings again, washing terminal point pH value is controlled at 5.0, isolate the nickel in the organic phase, then, with dilute sulphuric acid load organic phases is carried out six grades of washings again, washing terminal point pH value is controlled at 4.4, magnesium is transferred in the washing outlet liquid, with 1N sodium hydroxide the nickel precipitation in the washing outlet liquid is reclaimed, precipitation terminal point pH value is 8.5, the results are shown in Table 2 again.
Table 2 extraction system major metal balance
| Element | The source | Whereabouts | ||||
| Title | Quantity g/min (flow L/min * content g/L) | Ratio % | Title | Quantity g/min (flow L/min * content g/L) | Ratio % | |
| Ni | Feed liquid | 10×103 ＝1030 | 86.22 | Raffinate | 10×118.8＝1188 | 99.45 |
| The magnesium washings | 1.0×6.93＝6.93 | 0.58 | ||||
| The organic nickel soap | 31×5.31 ＝164.6 | 13.78 | Load is organic | 31× 0.0025＝0.0775 | 0.006 | |
| ∑％ | 100.0 | |||||
| Co | Feed liquid | 10×8.5＝85 | 100.0 | Raffinate | 10×0.011＝0.11 | 0.13 |
| The magnesium washings | 1×3.842＝3.842 | 4.52 | ||||
| Load is organic | 31×2.614＝84.57 | 95.35 | ||||
| ∑％ | 100.0 | |||||
| Mg | Feed liquid | 10×2.0＝20 | 100.0 | Raffinate | 10×0.068＝0.68 | 3.43 |
| The magnesium washings | 1×18.9＝18.9 | 94.5 | ||||
| Load is organic | 31×0.014＝0.434 | 2.17 | ||||
| ∑％ | 100.0 | |||||
Through above fractionation extraction process, the clearance of magnesium reaches 94.5% in the system, and the direct recovery rate of nickel is 99.45%, and the direct recovery rate of cobalt is 95.35%.
Embodiment 2
The sulphuric leachate of ni-mh after the removal of impurities and/or nickel-cadmium cell anode waste is regulated pH value to 4.8, organic phase is by constituting as two of extraction agent-(2-ethylhexyl) phosphonic acids list (2-ethylhexyl) ester with as the kerosene of thinner, wherein the concentration of two-(2-ethylhexyl) phosphonic acids list (2-ethylhexyl) esters is 1.2mol/L, O/A=1/1,12 grades of contact extractions, make magnesium change organic phase over to and nickel remaines among the water, with dilute sulphuric acid load organic phases is carried out six grades of washings again, washing terminal point pH value is controlled at 5.0, isolate the nickel in the organic phase, then, with dilute sulphuric acid load organic phases is carried out six grades of washings again, washing terminal point pH value is controlled at 4.5, and magnesium is transferred in the washing outlet liquid, with 1N sodium hydroxide the nickel precipitation in the washing outlet liquid is reclaimed again, comprehensive extracting and washing precipitation process, the total recovery of nickel is 99.99%, and the total recovery of cobalt is 99.95%, and the clearance of magnesium is 94.02%.
Embodiment 3
The sulphuric leachate of ni-mh after the removal of impurities and/or nickel-cadmium cell anode waste is regulated pH value to 4.9, organic phase is by constituting as two of extraction agent-(2-ethylhexyl) phosphonic acids list (2-ethylhexyl) ester with as the kerosene of thinner, wherein the concentration of two-(2-ethylhexyl) phosphonic acids list (2-ethylhexyl) esters is 1.5mol/L, adopt the fractionation extraction of 12 grades of extractions and 6 grades of washing nickel, 6 grades of washing magnesium, extraction is carried out in mixer-settler.Extraction mixes stirring velocity 80rpm, the useful volume 600L of clarifying chamber with the mixing section useful volume 200L of mixer-settler.
Need 5 minutes approximately because the magnesium extraction reaches starting time, therefore, feed liquid flow and organic phase flow sum are 40L/min, and the feed liquid flow is got 10L/min, organic phase flow 31L/min, washings flow 1L/min.Extraction conditions: extraction equilibrium pH value=4.5, nickel washing section equilibrated ph value=5.0, magnesium washing section equilibrated ph value=4.4.Make extraction system reach balance through operation in 72 hours, the result is as shown in table 3.
By table 3 as seen, through after the tandem fractionation extraction, Ni, Co in the feed liquid, Mg separating effect are better.Wherein, in the raffinate single nickel salt that reclaims Ni, the Ni/Co ratio reaches 10780 times, Mg
2+Content be reduced to 0.068g/L, can directly carry out condensing crystal, its crystallization can reach the HG/T2824-1997 standard-required.The 24th grade of organic load is through H
2SO
4Back extraction promptly gets CoSO
4Solution is kept reverse-extraction agent acidity, and back extraction capable of circulation is to Co
2+About 90g/L, at this moment, CoSO
4Ni in the solution
2+Be enriched to 0.085g/L, the Co/Ni ratio reaches 1092 times.
Table 3 tandem result
| The 1st grade of raffinate outlet water g/L | The 19th grade of washing outlet water g/L | The 24th grade of organic load g/L of outlet | ||||||
| Ni | Co | Mg | Ni | Co | Mg | Ni | Co | Mg |
| 118.8 | 0.011 | 0.068 | 6.93 | 3.842 | 18.9 | 0.0025 | 2.614 | 0.014 |
Claims (5)
1. one kind from waste nickel-hydrogen, A Step Extraction Separation Nickel through Nickel-cadmium Cell Retrieving In Nickelous Sulfate Solution, cobalt, the method of magnesium, it is characterized in that this method comprises regulates pH value to 4.5-5.0 with the sulphuric leachate of ni-mh after the removal of impurities and/or nickel-cadmium cell anode waste, then leach liquor is carried out multistage fractionation extraction, make magnesium and cobalt change organic phase over to and nickel remaines among the water, the organic phase of load magnesium is carried out the segmentation washing, use sulfuric acid scrubbing nickel for first section, the pH value of control washing terminal point is 5.0 ± 0.1, make magnesium still be retained in organic phase, the washing water mixes with nickel sulfate solution; Organic phase continues to enter second section washing, and with the magnesium in the sulfuric acid scrubbing organic phase, control washing terminal point PH is 4.4 ± 0.1, makes magnesium enter water, and this rich magniferous water is derived through independent outlet; Cobalt is still stayed organic phase, and the sulfuric acid back extraction of process cobalt obtains not nickeliferous and rose vitriol magnesium; Described organic phase is by constituting as two-di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester of extraction agent with as the kerosene of thinner.
2. a kind of method from waste nickel-hydrogen, A Step Extraction Separation Nickel through Nickel-cadmium Cell Retrieving In Nickelous Sulfate Solution, magnesium, cobalt according to claim 1 is characterized in that the rich magniferous washings of washing outlet is reclaimed nickel and cobalt precipitation with sodium hydroxide.
3. a kind of method from waste nickel-hydrogen, A Step Extraction Separation Nickel through Nickel-cadmium Cell Retrieving In Nickelous Sulfate Solution, cobalt, magnesium according to claim 2 is characterized in that be 8.5 with sodium hydroxide to the precipitation terminal point pH value that the nickel in the magnesium washing outlet liquid and cobalt precipitation reclaim.
4. according to claim 1 or 2 or 3 described a kind of methods, it is characterized in that carrying out ten secondary fractionation extractions after the described leach liquor removal of impurities from waste nickel-hydrogen, A Step Extraction Separation Nickel through Nickel-cadmium Cell Retrieving In Nickelous Sulfate Solution, magnesium, cobalt.
5. according to claim 1 or 2 or 3 described a kind of methods from waste nickel-hydrogen, A Step Extraction Separation Nickel through Nickel-cadmium Cell Retrieving In Nickelous Sulfate Solution, magnesium, cobalt, the concentration that it is characterized in that two-di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester is 0.3mol/L～1.5mol/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101002096A CN1301337C (en) | 2005-10-08 | 2005-10-08 | Once process for extracting and separating Ni, Mg and Co from nickel sulfate solution recovered from waste nickel-hydrogen and nickel-cadmium cells |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101002096A CN1301337C (en) | 2005-10-08 | 2005-10-08 | Once process for extracting and separating Ni, Mg and Co from nickel sulfate solution recovered from waste nickel-hydrogen and nickel-cadmium cells |
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| Publication Number | Publication Date |
|---|---|
| CN1752232A CN1752232A (en) | 2006-03-29 |
| CN1301337C true CN1301337C (en) | 2007-02-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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