CN102021336A - Method for separating zinc, fluorine and chlorine from fluorine- and chlorine-containing zinc sulfate solution - Google Patents
Method for separating zinc, fluorine and chlorine from fluorine- and chlorine-containing zinc sulfate solution Download PDFInfo
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- CN102021336A CN102021336A CN2010105845523A CN201010584552A CN102021336A CN 102021336 A CN102021336 A CN 102021336A CN 2010105845523 A CN2010105845523 A CN 2010105845523A CN 201010584552 A CN201010584552 A CN 201010584552A CN 102021336 A CN102021336 A CN 102021336A
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- 239000011701 zinc Substances 0.000 title claims abstract description 80
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 73
- 239000011737 fluorine Substances 0.000 title claims abstract description 50
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000460 chlorine Substances 0.000 title claims abstract description 37
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 36
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 title claims abstract description 22
- 229960001763 zinc sulfate Drugs 0.000 title claims abstract description 21
- 229910000368 zinc sulfate Inorganic materials 0.000 title claims abstract description 21
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 title abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract 5
- 238000000605 extraction Methods 0.000 claims abstract description 86
- 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 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000003350 kerosene Substances 0.000 claims abstract description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000292 calcium oxide Substances 0.000 claims abstract description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003085 diluting agent Substances 0.000 claims abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 45
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 28
- 150000002500 ions Chemical class 0.000 claims description 11
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000012071 phase Substances 0.000 abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 238000003723 Smelting Methods 0.000 abstract 1
- 238000011001 backwashing Methods 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 abstract 1
- -1 fluoride ions Chemical class 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052793 cadmium Inorganic materials 0.000 description 8
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 7
- 239000002956 ash Substances 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 238000006298 dechlorination reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001218 Thorium Chemical class 0.000 description 1
- 229910007613 Zn—MnO2 Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
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Classifications
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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
Abstract
The invention relates to a method for separating zinc, fluorine and chlorine from fluorine- and chlorine-containing zinc sulfate solution, in particular to a method for separating zinc, fluorine and chlorine from fluorine- and chlorine-containing secondary zinc resource Sulfuric acid leaching solution. In the method, during solution pretreatment, zinc powder and calcium oxide are added into the fluorine- and chlorine-containing zinc sulfate solution; during extraction, di-(2-ethylhexyl)phosphate is adopted as an extracting agent and kerosene is adopted as a diluent to prepare an organic phase with certain concentration, the organic phase is mixed with the pretreated solution for extraction, zinc in a water phase is transferred into the organic phase, fluoride ions and chloride ions are remained in the water phase, and the separation of the zinc, fluorine and chlorine is realized; and during back extraction, sulfuric acid solution serves as a back washing agent, the zinc-containing loaded organic phase is mixed for back extraction, the zinc in the loaded organic phase is transferred into the water phase again, zinc sulfate solution is obtained and the organic phase is subjected to impurity removal and recycled. The zinc, fluorine and chlorine separation efficiency is over 95 percent, and the obtained zinc sulfate solution has high purity and can be combined into a purification flow of the traditional zinc smelting. The method has the advantages that: the cost is low, the method is easy to operate, the efficiency is high, and the continuous production can be realized.
Description
Technical field
The present invention relates to zinc and fluorine in a kind of fluorine-containing, sulfuric chlorohydrin zinc solution, the isolating method of chlorine, zinc and fluorine, the isolating method of chlorine in particularly a kind of fluorine-containing, chlorine secondary zinc resource sulphuric leachate.
Background technology:
At present, secondary zinc oxide powder (Zn dust), zinc casting type scum silica frost, blast furnace and electric furnace zinc-containing dust, zinc-plated slag, Zn-MnO
2Secondary resources such as used dry batteries have become the important source material of producing zinc and zinc sulfate.But contain detrimental impurity such as a large amount of fluorine, chlorine in this type of resource, when adopting wet method to leach, fluorine, chlorine enter in the solution of zinc sulfate.When the preparation solution of zinc sulfate, cause fluorine chlorine impurity excessive, particularly the fluorion existence causes zinc metal sheet to be difficult to peel off when the zinc electrodeposition, and the chlorion counter electrode produces very big corrosion, reduces electric zinc quality.So the key of utilizing this type of resource to reclaim zinc is separating of zinc and fluorine, chlorine, makes purified solution of zinc sulfate.Research at present or the separation chlorine method that adopts mainly contain: the Sulfuric acid disilver salt precipitator method, copper ashes method, ion exchange method.Sulfuric acid disilver salt and villaumite effect are adopted in the dechlorination of Sulfuric acid disilver salt precipitation, generate the silver nitride precipitation of indissoluble, and this method dechlorination is effective, simple to operate, but the silver salt price is expensive, silver regeneration difficulty.Copper ashes dechlorination method utilizes copper and cupric ion and chlorion to interact, and forms the cuprous chloride precipitation of indissoluble.The dechlorination of this method is effective, but for the solution of zinc sulfate of high concentration cl, exists copper ashes output to reach copper ashes greatly and handle problems such as complexity.The ion exchange resin dechlorination, dechlorination rate is low, to high chlorine material bad adaptability.The method of separate fluorine mainly contains from solution of zinc sulfate: several methods such as calcium hydroxide, aluminium salt, thorium salt, sal epsom, silica gel and ventilation.But this several method defluorination effect is relatively poor, and effect is undesirable.
Document " research of goethite process fluorine and chlorine removal from the zinc oxide fumes leach liquor " discloses a kind of method that adopts goethite process to remove fluorine, chlorine from solution, but fluorine, chlorine remove efficient and be subjected to that iron concentration limits in the solution, and process is difficult to control.Number of patent application is that 200710035354.X " a kind of method that removes chlorine in the solution of zinc sulfate " discloses a kind of chlorion reaction generation cuprous chloride precipitation of utilizing in copper ashes and the solution, remove the method for chlorine, but still have the source of copper ashes and the handling problem of copper ashes.Patent publication No. is that to disclose a kind of be under 5.0 the acidic conditions, to add Al in the solution of zinc sulfate in the pH value to CN1966407A " fluorine-removing process for zinc sulphate solution "
3+And PO
4 3-, produce the method that precipitation is removed fluorine.
Summary of the invention
[goal of the invention]
The object of the present invention is to provide in a kind of fluorine-containing, sulfuric chlorohydrin zinc solution and make zinc and the isolating method of fluorine chlorine.
[technical scheme]
Realize that above-mentioned purpose of the present invention institute adopting process step has comprised solution pre-treatment, extraction and back extraction, is characterised in that:
1.1 when the solution pre-treatment, in fluorine-containing, sulfuric chlorohydrin zinc solution, add zinc powder and calcium oxide, and to make pH value of solution be 2.0～5.2, trivalent Fe ionic concn＜10mg/L in the solution;
1.2 when extraction, adopting two-(2-ethylhexyl) phosphoric acid (trade(brand)name P204) is extraction agent, kerosene is thinner, the two is hybridly prepared into extracted organic phase, this organic phase is mixed with fluorine-containing, sulfuric chlorohydrin zinc solution, and zine ion enters organic phase by cationic exchange, obtains containing the zinc load organic phases, foreign ion such as fluorine, chlorine is not extracted and still stays aqueous phase, realizes the separation of fluorine, chlorine;
1.3 when back extraction, reverse-extraction agent is a sulphuric acid soln, and the zinc load organic phases that contains of sulphuric acid soln and extraction step gained is mixed and carried out back extraction, makes zinc reenter water, obtains solution of zinc sulfate.
Concrete technical scheme of the present invention also comprises:
(1) temperature is 15～80 ℃ during the solution pre-treatment, and the time is 15～20min; (2) in extraction, extraction agent adopts P204, and the extraction agent volume percent is 15～40%, and all the other be sulfonated kerosene diluent, and the extraction volume is in a ratio of organic phase/water and equals 0.5～5: 1, extract churning time 2～5min, settling time: 2～8min; (3) the back extraction volume is in a ratio of organic phase/water and equals 4～10 in back extraction: 1, and back extraction churning time 2～5min, settling time: 2～6min contains zinc below 0.1g/L in the control organic phase after the back extraction.
The present invention also comprises following scheme in addition: 1. extraction process replenishes alkali lye, and keeping the pH value of solution value is 2.0～3.5; 2. extraction process carries out the extraction of 4～6 stage countercurrents, 15～40 ℃ of extraction temperature; 3. the reverse-extraction agent sulfuric acid concentration is 120～220g/L in the back extraction process, 2～5 grades of countercurrent reextraction progression.
Organic phase after the back extraction is carried out recycle; Fluorine concentration fluorine-containing, the sulfuric chlorohydrin zinc solution is that cl concn is greater than 500mg/L greater than 300mg/L.
[advantage of the present invention]
The present invention adopts solvent extraction technology, utilizes the ionic condition difference in the solution to carry out selective extraction, realizes separating of zinc and fluorine, chlorine in fluorine-containing, the sulfuric chlorohydrin zinc solution.In the solution of zinc sulfate, zinc is with Zn
2+Cationic form exists, and fluorine, chlorine, sulphur content is not with F
-, Cl
-, SO
4 2-Anionic form exists, adopt acidic phosphorus extractant (as P204, in the time of P507), the Zn in the solution
2+With the H in the extraction agent
+Exchange Zn
2+Enter organic phase, H
+Enter water.Negatively charged ion does not participate in reaction and still stays aqueous phase, realizes zinc and anionic separation such as fluorine, chlorine, other metallic cation Fe (II), As, Mn, Mg, Pb, Ca, Sb etc. are owing to extract order less than zine ion, and these metallic impurity ions are not extracted, and still stay aqueous phase.The sulfuric acid that the zinc that enters organic phase adopts 120～150g/L back extraction fully gets off, and zinc reenters water.Therefore, the solution of zinc sulfate foreign matter content that back extraction obtains seldom can be used to prepare Zinc Sulphate Heptahydrate or can directly prepare the zinc electric effusion, incorporates existing zinc electrodeposition system into.Effect of the present invention is: adopt the zine ion in the solvent extration extraction solution, realization zinc separates with fluorine, chlorine, and metal ions such as iron, cadmium, lead, calcium, magnesium, arsenic are purified in the solution simultaneously, make purified solution of zinc sulfate.The separation efficiency of zinc and fluorine, chlorine is greater than 95%, and organic phase can recycle in whole process flow, and cost is low, simple to operate, efficient is high, can realize serialization production.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1:
The solution of zinc sulfate that the secondary zinc oxide powder that adopts rotary kiln evaporation to obtain leaches through sulfuric acid, the chemical ingredients of solution is listed in the table below:
Because Fe (III) and Cd ionic concn are higher in the solution, Fe (III) is extracted by P204 than zinc is easier, and is difficult to back extraction, is extracted by P204 but Fe (II) is difficult.Cd partly comes together into organic phase, easily back extraction.Therefore, need add the awkward Fe (II) that is extracted of Fe (III) reduction that zinc powder will easily be extracted, and cadmium is replaced into cadmium metal removes.When Zn powder add-on is 5g/L, reaction times 30min, 20 ℃ of temperature, the reduction ratio of Fe (III) is 97.3%, cadmium displacement decreasing ratio is 98.7%.Adding calcium oxide regulator solution pH is 4.5, carries out the extraction of 6 stage countercurrents, compares (O/A) 3.0: 1, mixing time 2-3min, and settling time 5min, organic phase is formed 40%P204+60% sulfonated kerosene, 25 ℃ of extraction temperature.In the extraction process,, cause aqueous pH values to descend because the H+ in organic enters water in a large number, when pH value of solution less than 2.0 the time, the effect of extracting of zinc is variation, so extraction process need replenish alkali lye, makes the pH value of solution value stabilization between 2.0-3.5.Zinc extraction yield is 86.3%, and load organic phases contains about zinc 26.0g/L.Load organic phases is carried out back extraction, and reverse-extraction agent uses the sulphuric acid soln of 220g/L.Back extraction mixing time 2min compares 5: 1,4 grades of back extraction progression, and strip liquor contains zinc 128.6g/L, zinc back extraction ratio 99.0%, the concentration of P204 is 0.07g/L in the strip liquor.The trend of each element in extracting-back extraction process is as shown in the table with distribution:
During whole process became: the fluorine clearance was 98.4%, and the chlorine clearance is 98.6%, Cu, and Ni, Cd, Fe, bivalent ions clearance such as As is greater than 90%, and the clearance of cobalt, calcium ion is lower, is respectively 78.4% and 69.1%.
Embodiment 2:
The solution of zinc sulfate that adopts the blast furnace zinc-containing dust to leach through sulfuric acid, the chemical ingredients of solution is listed in the table below:
Zn powder add-on is 5g/L, reaction times 30min, and 25 ℃ of temperature, the reduction ratio of Fe (III) is 98.7%, cadmium displacement decreasing ratio is 99.6%.Adding calcium oxide regulator solution pH is 4.0, carry out the extraction of 5 stage countercurrents, compare (O/A) 2: 1, mixing time 2-3min, settling time 5min, organic phase is formed the 30%P204+70% sulfonated kerosene, 25 ℃ of extraction temperature, needing additional alkali lye to keep raffinate pH in extraction process is 2.0-3.5, zinc extraction yield 87.4%, load organic phases contains about zinc 17.7g/L, and fluorine, chlorine are not extracted.Reverse-extraction agent uses the sulphuric acid soln of 180g/L.Back extraction mixing time 2min compares (O/A) 6: 1,3 grades of back extraction progression, and strip liquor contains zinc 105.1g/L, and poor organic phase contains zinc 0.8g/L, zinc back extraction ratio 99.0%.The concentration of P204 is 0.06g/L in the strip liquor.The trend of each element in extracting-back extraction process is as shown in the table with distribution:
The fluorine separation rate is 99.0%, and the chlorine separation rate is 98.4%, Cu, and Ni, Cd, Fe, bivalent ions clearance such as As is greater than 90%, and the removal of cobalt, calcium ion is respectively 86.3% and 702%.
Embodiment 3:
The solution of zinc sulfate that adopts the Zn-MnO2 used dry batteries to leach through sulfuric acid, the chemical ingredients of solution is listed in the table below:
When Zn powder add-on is 3g/L, reaction times 30min, 25 ℃ of temperature, the reduction ratio of Fe (III) is 98.3%, cadmium displacement decreasing ratio is 99.4%.Adding calcium oxide regulator solution pH is 5.0, carry out the extraction of 4 stage countercurrents, compare (O/A) 1: 1, mixing time 2-3min, settling time 5min, organic phase is formed the 25%P204+80% sulfonated kerosene, 25 ℃ of extraction temperature, needing additional alkali lye to keep raffinate pH in the extraction process is 2.0-3.5, zinc extraction yield 88.3%, load organic phases contains about zinc 16.3g/L, and fluorine, chlorine are not extracted.Reverse-extraction agent uses the sulphuric acid soln of 150g/L.Back extraction mixing time 2min, 2 grades of back extraction progression are compared 7: 1, and strip liquor contains zinc 113.2g/L,, back extraction ratio 99.1%.The concentration of P204 is 0.07g/L in the strip liquor.The trend of each element in extracting-back extraction process is as shown in the table with distribution:
The fluorine clearance is 97.9%, and the chlorine clearance is 98.5%, Cu, and Ni, Cd, Fe, bivalent ions clearance such as As is greater than 90%, and the clearance of cobalt, calcium ion is lower, is respectively 86.2% and 72.9%.
Claims (4)
1. zinc and fluorine, the isolating method of chlorine in fluorine-containing, the sulfuric chlorohydrin zinc solution comprise solution pre-treatment, extraction and stripping process step, it is characterized in that:
1.1 when the solution pre-treatment, in fluorine-containing, sulfuric chlorohydrin zinc solution, add zinc powder and calcium oxide, and to make pH value of solution be 2.0～5.2, trivalent Fe ionic concn＜10mg/L in the solution;
1.2 when extraction, adopting two-(2-ethylhexyl) phosphoric acid is extraction agent, kerosene is thinner, the two is hybridly prepared into extracted organic phase, this organic phase is mixed with fluorine-containing, sulfuric chlorohydrin zinc solution, and zine ion enters organic phase by cationic exchange, obtains containing the zinc load organic phases, foreign ion such as fluorine, chlorine is not extracted and still stays aqueous phase, realizes the separation of fluorine, chlorine;
1.3 when back extraction, reverse-extraction agent is a sulphuric acid soln, and the zinc load organic phases that contains of sulphuric acid soln and extraction step gained is mixed and carried out back extraction, makes zinc reenter water, obtains solution of zinc sulfate.
2. zinc and fluorine, the isolating method of chlorine in fluorine-containing, the sulfuric chlorohydrin zinc solution according to claim 1, it is characterized in that: temperature is 15～80 ℃ during (1) solution pre-treatment, the time is 15～20min; (2) extraction agent employing P204 in extraction, and extraction agent volume percent is 15～40%, and all the other are sulfonated kerosene diluent, and the extraction volume is in a ratio of organic phase/water and equals 0.5～5:1, extraction churning time 2～5min, settling time: 2～8min; (3) the back extraction volume is in a ratio of organic phase/water and equals 4～10:1 in back extraction, back extraction churning time 2～5min, and settling time: 2～6min contains zinc below 0.1g/L in the control organic phase after the back extraction.
3. zinc and fluorine, the isolating method of chlorine in fluorine-containing, the sulfuric chlorohydrin zinc solution according to claim 1 is characterized in that: 1. extraction process replenishes alkali lye, and keeping the pH value of solution value is 2.0～3.5; 2. extraction process carries out the extraction of 4～6 stage countercurrents, 15～40 ℃ of extraction temperature; 3. the reverse-extraction agent sulfuric acid concentration is 120～220g/L in the back extraction process, 2～5 grades of countercurrent reextraction progression.
4. according to zinc and fluorine, the isolating method of chlorine in claim 2 or 3 described fluorine-containing, the sulfuric chlorohydrin zinc solutions, it is characterized in that: the organic phase after the back extraction is carried out recycle; Fluorine concentration fluorine-containing, the sulfuric chlorohydrin zinc solution is that cl concn is greater than 500mg/L greater than 300mg/L.
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