CN102586608B - Method for preparing sponge indium with indium-rich slag produced in lead-zinc smelting process - Google Patents
Method for preparing sponge indium with indium-rich slag produced in lead-zinc smelting process Download PDFInfo
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 133
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 72
- 239000002893 slag Substances 0.000 title claims abstract description 45
- 238000003723 Smelting Methods 0.000 title claims abstract description 25
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002386 leaching Methods 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006073 displacement reaction Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000011787 zinc oxide Substances 0.000 claims abstract description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 23
- 239000000706 filtrate Substances 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 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 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052742 iron Chemical group 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000002411 adverse Effects 0.000 claims description 2
- 238000004364 calculation method Methods 0.000 claims description 2
- 230000035800 maturation Effects 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 3
- -1 ferrous metals Chemical class 0.000 abstract 1
- 238000009854 hydrometallurgy Methods 0.000 abstract 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract 1
- 239000011686 zinc sulphate Substances 0.000 abstract 1
- 235000009529 zinc sulphate Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000011133 lead Substances 0.000 description 13
- 239000003500 flue dust Substances 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000635 Spelter Inorganic materials 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002481 rotproofing Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for preparing sponge indium with indium-rich slag produced in a lead-zinc smelting process and belongs to the technical field of hydrometallurgy of non-ferrous metals. The method comprises the processing steps as follows: curing and leaching the indium-rich slag, performing secondary high-temperature acid leaching on filtered slag which is cured again, removing impurities in indium-rich liquid, and displacing the sponge indium; and after the displacement, the liquid is recovered and then is used for producing white vitriol or zinc oxide products. The method has the advantages that the process flow is short, the suitability of the raw material is strong, the recovery rate of indium is high, and the energy consumption, the pollution and the production cost are low.
Description
Technical field
The invention belongs to the non-ferrous metal technical field of wet metallurgy, be specifically related to the method that a kind of indium slag that produces with the lead-zinc smelting process is produced the sponge indium.
Background technology
Indium belongs to rare elements, indium mainly is widely used in: the ITO target, numerous high-tech areas such as special scolder, high performance alloys and the photoelectricity of information material, high temperature superconducting materia, unicircuit, the energy, aviation, nuclear industry, medication chemistry, the added value of product height.Indium content in the earth's crust seldom owing to itself can not independently become the ore deposit, most ofly is present in the sulfide mineral of lead, zinc, tin and copper with association, rare diffusing form, can only reclaim from the lead-zinc smelting byproduct followed or flue dust.Generally contain indium (wt%) 0.36～12.76% in described lead-zinc smelting byproduct or the flue dust; The present invention is called indium slag with lead-zinc smelting byproduct or the flue dust that these contain indium 0.36～12.76%.
At present both at home and abroad the processing method of production indium metal mainly contains: acidleach-extraction process, acidizing fired-extraction process, chloride volatility process, vacuum distillation method.Industrial major part is based on acidleach-extraction common process.As: state's invention patent publication No. CN 101643853A disclosed " from the tin flue dust, extracting the method for indium and recovery valuable metal " in 10 days February in 2010, be to soak-twice leaching of acidleach in adopting, part of impurity elements such as arsenic, cadmium, zinc enter middle immersion liquid in neutral normal temperature or the low temperature leaching elder generation leaching tin flue dust; In soak slag again acidic twice leach, indium and residual part of impurity elements leach again and enter the high temperature leach liquor; Tin, lead are reclaimed in high temperature leached mud washing back.Indium in the high temperature leach liquor adopts the P204 extraction, and hydrochloric acid soln back extraction enrichment with the spelter displacement, gets product sponge indium; The sponge indium obtains thick indium behind the group of pressure, alkali fusion.But there is long flow path in common process, metal recovery rate low (being generally 50-75%), and spent process water contains heavy metal ion, difficult treatment, reagent consumption is big, and environmental pollution is serious, and national environmental protection department supervision simultaneously is strict; Chloride volatility process makes indium exist with oxide compound and muriate form because raw material is controlled pre-treatment, causes indium leaching yield height, leach liquor is reusable edible also, but chlorion corrosive equipment in the process, the operation easier height causes rotproofing, exotic materials facility investment bigger; Vacuum distillation method mainly utilizes the vapour pressure deficit under metal vacuum, the boiling point condition to come progressively enrichment and improves indium grade, be fit to the processing of high pure metal, and the investment of the support equipment of this vacuum operating is big, and the control condition strictness causes process power consumption and cost higher.
Summary of the invention
The objective of the invention is at indium recovery in the existing routine techniques low, problems such as technical process is long, provide a kind of indium slag that produces with the lead-zinc smelting process to produce the method for sponge indium, this method technical process is short, adaptability to raw material is strong, indium recovery height, and advantage such as energy consumption is little, pollution is little, production cost is low.
The technical solution used in the present invention is: a kind of indium slag that produces with the lead-zinc smelting process is produced the method for sponge indium, and concrete processing step is as follows:
(1) the indium slag slaking is leached: be raw material with the indium slag that contains indium 0.36～12.76, after broken processing, mix the industrial vitriol oil that leaches 0.8～3 times of the whole required Theoretical Calculation amount of rich indium material, slaking is 3～8 hours under 70～90 ℃ condition, then the material after the slaking is once leached with diluted acid or water, control extraction temperature at 60～95 ℃, liquid-solid ratio 3～6:1, reaction times 3～6h; Get first-time filtrate after the liquid-solid separation; A filter residue is through carrying out the acidleach of secondary high temperature after the slaking again, extraction time 4～6h, 85～95 ℃ of temperature, liquid-solid ratio 3～5:1; After the liquid-solid separation of reaction ore pulp, secondary filtrate is returned and is once leached the circulated in countercurrent utilization, send comprehensive recovery Pb, Ag behind the secondary residue washing;
(2) rich indium liquid removal of impurities: with first-time filtrate with NaOH neutralize to contain acid 20～50g/l after, add Sodium Sulphide and reductive agent B and carry out removal of impurities and handle, the control temperature is at 30～60 ℃, reaction times 1～3h, the medicament add-on is pressed 0.5～3 times of impurity theoretical amount; Carry out after reaction finishes liquid-solid separate three filtrates; Three filter residues return plumbous the smelting and recycle after washing;
(3) displacement sponge indium: three filtrates after the removal of impurities are adjusted the pH value of solution 0.5～2.5 with NaOH, add 60～120 order zinc contents greater than 90% zinc powder, the zinc powder add-on is by 1.5～15 times of displacement indium theoretical amount, 25～50 ℃ of control temperature of reaction, in 1～4 day reaction times, obtain containing the indium amount and be 60～98% sponge indium; Deionized water wash 2～3 times of sponge indium, the group of pressure back is fusible to cast thick indium; Displaced liquid reclaims the back and produces Zinc Sulphate Heptahydrate or zinc oxide product;
The diluted acid of described (1) step is the H of 50g/L
2SO
4Solution;
Sodium Sulphide in described (2) step is sodium sulphite; Reductive agent B is iron powder or iron filings.
[0006]The chemical ingredients of employing indium slag of the present invention: In:0.36～12.76%, Fe:0.46～1.89%, Zn:1.38～25.46%, Pb:10.75～21.71%, Sb:1.19～27.8%, As:0.26～2.94% contains Sn0.9～0.12%, Cu0.2～0.4%, Ag0.001～0.003% valuable metal in addition.
Above-mentioned steps (1) adopts vitriol oil slaking preprocessing process to indium slag, contains indium for reducing leached mud simultaneously, can according to circumstances also carry out 1～3 time maturation process respectively to leaching filter residue.
Above-mentioned steps (1) can adopt 2～3 sections adverse currents to leach flow process in indium slag slaking leaching process, and namely secondary high temperature leaches filtrate and returns leaching last time as liquid before reacting; The reuse of filter residue wash water is as leaching dosing.
What above-mentioned steps (3) obtained after with zinc dust precipitation sponge indium contains indium less than 50mg/l, and the zinc sulfate liquid that contains zinc 45～60g/l is through purifying, can be used for producing Zinc Sulphate Heptahydrate, zinc oxide Chemicals after the removal of impurities.
The sponge indium that above-mentioned steps (3) obtains zinc dust precipitation (containing indium amount 60～98%) is with deionized water wash 3 times, can carry out alkali fusion refining, removal of impurities after the group of pressure and makes thick indium, and wash water returns the leaching process utilization.
Ultimate principle of the present invention is: contain the indium material after the slaking of vitriol oil temperature control, contained principal element as: indium, iron, zinc, silicon-dioxide etc. form vitriol and insoluble SiO soluble in water
2Form enters respectively in leach liquor and the slag, and major parts such as lead, arsenic, antimony, tin, bismuth enter and be able to enrichment in the slag, and the leaching yield of indium is greater than more than 96%, and the indium total yield is more than 98%.The removal of impurities process is that the sulfide precipitation that utilize to produce is removed other valuable elements of most of dissolving, and replacement process is to utilize the difference in Electrode Potential of indium and zinc and indium is separated out with the sponge reaction.The process principal reaction is as follows:
MeO?+?H
2SO
4?=?MeSO
4?+?H
2O
Me
2+?+?S
2-?=?MeS↓
2In
3+?+3Zn?=?2In?+?3Zn
2+
(annotating: Me---Zn, Pb, In, As, Sb, Fe, Sn, Bi etc.)
The present invention can make indissoluble things such as the zinc ferrite of being combined with indium in the common process, sulfide decompose fully, thereby reduces the indium content in the slag; Utilize solution heat to satisfy process need substantially in the reaction process simultaneously, and do not need outer auxilliary heating installation, there is no low concentration SO
2Advantages such as waste gas generation.Compared with the prior art, the present invention does not need P204 extraction and hydrochloric acid soln back extraction enrichment; Therefore this processing method has adaptability to raw material by force, and Process configuration is reasonable, flow process and simple to operate, and energy consumption and cost are low, and environmental pollution is little, indium leaching yield and rate of recovery height, advantage such as resource comprehensive recycle level is good.
Embodiment
Describe the present invention in detail below in conjunction with embodiment
Embodiment 1
A kind of indium slag that produces with the lead-zinc smelting process is produced the method for sponge indium, and the indium slag of its use is the indium enrichment slag of lead blast furnace flue dust after the fuming volatilization, and its composition (wt%): In 0.76, Zn 25.46, and Pb 15.71, and Fe 1.89, As 2.94, and Sb 1.19, SiO
27.85, Sn0.12, Cu0.2, Ag0.001.
Take by weighing 500g indium slag raw material, add the industrial vitriol oil and (contain H
2SO
4Be 98%) consumption be 1.5 times (398.4mL) of theoretical consumption (265.6mL), (process is noted ventilating and micro-negative pressure operation) stirs in enamel reaction still, then wet feed is put into design temperature 75-85 ℃ baking oven slaking 6 hours, after finishing with the fragmentation of slaking material, granularity is less than the 40-60 order, and with containing H
2SO
450g/L solution (perhaps water) carries out an agitation leach, and liquid-solid volume mass is than 5:1, and temperature of reaction is 75-80 ℃, reaction times 4h, and reaction is carried out liquid-solid separation after finishing; One time filter residue carries out secondary concentrated acid curing and the leaching of secondary high temperature peracid, the secondary leaching condition is controlled to be: liquid contains sour 100-120g/L before the solution, liquid-solid volume mass is than 3:1, and temperature of reaction 85-90 ℃, reaction times 4-6h, liquid-solid separation, the secondary filter residue send the plumbous comprehensive metals such as lead, silver that reclaim of smelting after washing, it is 0.03% that slag contains indium, and the slag rate is 25%, total process indium leaching yield is 96.7%, and filtrate is returned and once leached circulated in countercurrent.Once leach filtrate with NaOH neutralize to contain acid 30～50g/l after, contain according to solution that assorted situation adds Sodium Sulphide and the reductive agent iron powder carries out removal of impurities, purification, the control temperature of reaction is at 60-65 ℃, and the reaction churning time is 1-2h, and the medicament add-on is pressed 1.5 times of impurity theoretical amount; Reaction is carried out liquid-solid separation after finishing, and three times filtrate is sent the indium displacement, returns the plumbous recycling of smelting after three filter residue washings.Rich indium liquid after the removal of impurities is adjusted the pH value about 0.5～1.5 with NaOH, the zinc powder add-on is by 5 times of theoretical amount, 25～50 ℃ of control temperature of reaction, 2 days reaction times, obtain containing the indium amount respectively and be 97.8% and 65% sponge indium, deionized water wash 2-3 time of sponge indium send alkali fusion to refine into thick indium after the group of pressure; Displaced liquid is produced Zinc Sulphate Heptahydrate after professional treatment.This technological process indium total yield is greater than 98.5%.
Embodiment 2
A kind of indium slag that produces with the lead-zinc smelting process is produced the method for sponge indium, and the indium slag of its use is the product of plumbous electrolysis reverberatory furnace scum silica frost behind fuming enrichment indium, and concrete composition (wt%): In 12.76, Zn 5.46, and Pb 21.71, and Fe 0.69, As 1.24, and Sb 2.06, SiO
23.27, Sn0.1, Cu0.4, Ag0.002.
Take by weighing 1000g indium slag raw material, add the industrial vitriol oil and (contain H
2SO
4Be 98%) consumption be 1.5 times (956.7mL) of theoretical consumption (637.8mL), (process is noted ventilating and micro-negative pressure operation) stirs in enamel reaction still, then wet feed is put into design temperature 80-85 ℃ baking oven slaking 5 hours, then with the fragmentation of slaking material, carry out an agitation leach with the aqueous solution, liquid-solid volume mass is than 5:1, and temperature of reaction is 75-80 ℃, reaction times 3h, reaction is carried out liquid-solid separation after finishing; One time filter residue carries out secondary concentrated acid curing and the leaching of secondary high temperature peracid, the secondary leaching condition is: liquid contains sour 80-100g/L before the solution, liquid-solid volume mass compares 3:1, temperature of reaction 85-90 ℃, reaction times 4h send the plumbous comprehensive metals such as lead, silver that reclaim of smelting after the filter residue washing, it is 0.02% that slag contains indium, the slag rate is 30%, and total process indium leaching yield is 97.8%, and filtrate is returned and once leached circulated in countercurrent.Once leach filtrate with NaOH neutralize to contain acid 30～50g/l after, contain according to solution that assorted situation adds Sodium Sulphide and the reductive agent iron filings carry out removal of impurities, purification, the control temperature of reaction is at 60-65 ℃, and the reaction churning time is 1-2h, and the medicament add-on is pressed 1.2 times of impurity theoretical amount; Reaction is carried out liquid-solid separation after finishing, and three times filtrate is sent the indium displacement, and three times filter residue returns the plumbous recycling of smelting after washing.Rich indium liquid after the removal of impurities is adjusted the pH value of solution about 0.5～1.0 with NaOH, the zinc powder add-on is by 3 times of theoretical amount, 25～50 ℃ of control temperature of reaction, 1.5 days reaction times, obtain containing the indium amount respectively and be 98.5% and 70% sponge indium, deionized water wash 2-3 time of sponge indium send alkali fusion to refine into thick indium after the group of pressure, and this technological process indium total yield is greater than 98.3%.Displaced liquid after professional treatment for the production of Zinc Sulphate Heptahydrate.
Embodiment 3
A kind of indium slag that produces with the lead-zinc smelting process is produced the method for sponge indium, and the indium slag of its use is indium enrichment slag after the fuming of stibium blast furnace slag, and its composition (wt%): In 0.36, and Zn 1.38, and Pb 10.75, and Fe 0.46, and As 0.26, and Sb 27.8, SiO
22.63, Sn0.09, Cu0.3, Ag0.003.
Take by weighing 300g indium slag raw material, add the industrial vitriol oil and (contain H
2SO
4Be 98%) consumption be 1.5 times (209.8mL) of theoretical consumption (139.9mL), (process is noted ventilating and micro-negative pressure operation) stirs in enamel reaction still, then compound is put into design temperature 85-90 ℃ baking oven slaking 8 hours, and with the fragmentation of slaking material, with containing H
2SO
480g/L solution carries out an agitation leach, and liquid-solid volume mass is than 6:1, and temperature of reaction is 85 ℃, reaction times 6h, and reaction is carried out liquid-solid separation after finishing; One time filter residue carries out secondary concentrated acid curing and the leaching of secondary high temperature peracid, the secondary leaching condition: liquid contains sour 120g/L before the solution, liquid-solid volume mass compares 3:1,90 ℃ of temperature of reaction, reaction times 6h send the plumbous comprehensive metals such as lead, silver that reclaim of smelting after the filter residue washing, it is 0.015% that slag contains indium, the slag rate is 22%, and total process indium leaching yield is 96.7%, and filtrate is returned and once leached circulated in countercurrent.Once leach filtrate with NaOH neutralize to contain sour 50g/l after, contain according to solution that assorted situation adds Sodium Sulphide and the reductive agent iron filings carry out removal of impurities, purification, the control temperature of reaction is at 60-65 ℃, the reaction churning time is 2h, the medicament add-on is pressed 1.8 times of impurity theoretical amount; Liquid-solid separation rear filtrate send the indium displacement, and three times filter residue returns the plumbous recycling of smelting after washing.Rich indium liquid after the removal of impurities is adjusted the pH value of solution about 0.5 with NaOH, the zinc powder add-on is by 6 times of theoretical amount, 25～50 ℃ of control temperature of reaction, 3 days reaction times, obtain containing the indium amount respectively and be 97.6% and 58% sponge indium, with deionized water wash 3～4 times, can carry out alkali fusion refining, removal of impurities after the group of pressure and make thick indium, wash water returns the leaching process utilization, and this technological process indium recovery is greater than 97.8%.Displaced liquid can be produced Zinc Sulphate Heptahydrate after removal of impurities, concentration.
Claims (5)
1. an indium slag that produces with the lead-zinc smelting process is produced the method for sponge indium, and it is characterized in that: concrete processing step is as follows:
(1) the indium slag slaking is leached: be raw material with the indium slag that contains indium 0.36～12.76%, after broken processing, mix the industrial vitriol oil that leaches 0.8～3 times of volume ratio of the whole required Theoretical Calculation amount of rich indium material, slaking is 3～8 hours under 70～90 ℃ condition, then the material after the slaking is once leached with diluted acid or water, control extraction temperature at 60～95 ℃, liquid-solid ratio 3～6:1, reaction times 3～6h; Get first-time filtrate after the liquid-solid separation; A filter residue is through carrying out the acidleach of secondary high temperature after the slaking again, extraction time 4～6h, 85～95 ℃ of temperature, liquid-solid ratio 3～5:1; After the liquid-solid separation of reaction ore pulp, secondary filtrate is returned and is once leached the circulated in countercurrent utilization, send comprehensive recovery Pb, Ag behind the secondary residue washing;
(2) rich indium liquid removal of impurities: with first-time filtrate with NaOH neutralize to contain acid 20～50g/L after, add Sodium Sulphide and reductive agent B and carry out removal of impurities and handle, the control temperature is at 30～60 ℃, reaction times 1～3h, the medicament add-on is pressed 0.5～3 times of impurity theoretical amount; Carry out after reaction finishes liquid-solid separate three filtrates; Three filter residues return plumbous the smelting and recycle after washing;
(3) displacement sponge indium: three filtrates after the removal of impurities are adjusted the pH value of solution 0.5～2.5 with NaOH, add 60～120 order zinc contents greater than 90% zinc powder, the zinc powder add-on is by 1.5～15 times of displacement indium theoretical amount, 25～50 ℃ of control temperature of reaction, in 1～4 day reaction times, obtain containing the indium amount and be 60～98% sponge indium; Deionized water wash 2～3 times of sponge indium, the back founding of the group of pressure becomes thick indium; Displaced liquid reclaims the back and produces Zinc Sulphate Heptahydrate or zinc oxide product;
The diluted acid of described (1) step is the H of 50g/L
2SO
4Solution;
Sodium Sulphide in described (2) step is sodium sulphite; Reductive agent B is iron powder or iron filings.
2. produce the method for sponge indium according to the described indium slag that produces with the lead-zinc smelting process of claim 1, it is characterized in that: described step (1) adopts vitriol oil slaking preprocessing process to indium slag, carries out maturation process respectively 1～3 time to leaching filter residue.
3. produce the method for sponge indium according to the described indium slag that produces with the lead-zinc smelting process of claim 1, it is characterized in that: described step (1) adopts 2～3 sections adverse currents to leach flow process in indium slag slaking leaching process, and namely secondary high temperature leaches filtrate and returns leaching last time as liquid before reacting; The reuse of filter residue wash water is as leaching dosing.
4. produce the method for sponge indium according to the described indium slag that produces with the lead-zinc smelting process of claim 1, it is characterized in that: what described step (3) obtained after with zinc dust precipitation sponge indium contains indium less than 50mg/L, the zinc sulfate liquid that contains zinc 45～60g/L through purify, after the removal of impurities for the production of Zinc Sulphate Heptahydrate, zinc oxide Chemicals.
5. produce the method for sponge indium according to the described indium slag that produces with the lead-zinc smelting process of claim 1, it is characterized in that: it is 60～98% sponge indium that described step (3) obtains containing the indium amount to zinc dust precipitation, with deionized water wash 3 times, press and to carry out alkali fusion refining, removal of impurities after the group and make thick indium, wash water returns the leaching process utilization.
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| CN102787242B (en) * | 2012-08-27 | 2013-12-11 | 中南大学 | Method for recovering germanium and indium from germanium-containing material generated from lead and zinc smelting process |
| CN103173625B (en) * | 2013-04-19 | 2014-12-10 | 长沙矿冶研究院有限责任公司 | Method for efficiently leaching indium from zinc oxide smoke |
| CN104561563A (en) * | 2014-12-29 | 2015-04-29 | 河南豫光锌业有限公司 | Indium-rich slag reduction presoaking technology and device thereof |
| CN105219970B (en) * | 2015-10-29 | 2017-07-07 | 红河锌联科技发展有限公司 | A kind of method that many metals and calcium chloride are reclaimed in roasting dirt |
| KR102528342B1 (en) | 2017-09-13 | 2023-05-03 | 에스케이이노베이션 주식회사 | Method of Decreasing Carbon Dioxide and Dust Containing Metal |
| CN111270091A (en) * | 2020-02-29 | 2020-06-12 | 河南豫光锌业有限公司 | Method for reducing indium content in indium leaching slag |
| CN115896487A (en) * | 2022-11-25 | 2023-04-04 | 沈阳有色金属研究院有限公司 | Method for enriching and extracting indium from tin smelting smoke dust |
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