CN104232943A - Method for preparing high-purity indium by using multi-metal complex high-indium high-tin material - Google Patents
Method for preparing high-purity indium by using multi-metal complex high-indium high-tin material Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity indium by using a multi-metal complex high-indium high-tin material. The method comprises the following steps of: leaching at normal temperature in three stages, and carrying out natural oxidation; extracting, separating and enriching indium and tin; purifying a high-indium solution; preparing crude indium; electrolyzing crude indium to finally obtain high-purity indium with purity of 99.999%. The method disclosed by the invention has the advantages of maturity in process, high leaching rate of indium and tin, low operating cost, high integrated recovery rate of indium and tin, and high grade of produced indium and tin; the extracting agent is extensive in source, long in usage period and low in price, so that the processing cost can be greatly reduced; the problem of leaching rate of indium is solved by carrying out the natural oxidation through solar radiation, the leaching process is shortened, the reasonable utilization of resources is realized; and the method is environment-friendly, high in current utilization ratio in an electrolytic process and extensively suitable for processing lead, iron and zinc mineral materials which contain indium and tin.
Description
Technical field
The invention belongs to technical field of wet metallurgy, specifically relate to a kind of method that high purity indium prepared by multi-metal complex height indium height tin material.
Background technology
Indium metal initial application is industrially process industry bearing, because its ductility (plasticity-) is fabulous, steam forces down, can stick to again on multiple material, therefore also be widely used as the pad in aerological instrument and aerospace equipment or air retaining wall material.
Many metals association zinc ore concentrate is after fire enrich repeatedly, and obtain the polymictic material of high indium height tin, in this material, main metal element is indium, tin, lead, zinc, iron, copper, arsenic, cadmium etc.In order to the valuable element in synthetical recovery material, zinc abstraction industry adopts electrosmelting to extract zinc usually, in the process extracting zinc, a large amount of Enrichment Indium, tin are in crude zinc, crude zinc obtains 0# zinc through the rectifying of rectifying tower, the B# zinc of the rich indium tin of a large amount of high zinc of tower bottom deposition and hard zinc, the zinc ingot metal of this part high indium is plumbous at the bottom of the indium slag and high indium of the further volatilization process output zinc ingot metal lower containing indium, high indium tin again.The indium slag of high indium tin and end lead are the raw material carrying indium after levigate process.
Known indium method of carrying mainly contains (1) extract indium from the leaching residue of zinc hydrometallurgy; (2) from lead bullion scum silica frost and copper converter dirt, indium is extracted; (3) from solder electrolytic liquid, indium is extracted; (4) from the byproduct-hard zinc of pyrometallurgy of zinc, indium is extracted.Wherein, the flow process carrying indium from hard zinc is: adopt vacuum distilling hard zinc to carry out Enrichment Indium, and extract indium slag from rich indium raw material, finally recovery indium from indium slag again.The concentration effect of the valuable metal such as indium, tin is not good, and foreign matter content is high, and the composition carrying indium raw material mainly exists with metallic state, leaches raw material granularity comparatively thick, leaches difficulty larger; Plumbous to a large amount of parcel of indium meeting, cause the leaching yield of indium tin low.This art production process is more complicated, and leach flow process and need adopt high acidic oils, after repeatedly leaching, the leaching yield of indium still cannot significantly improve, and the thick indium grade of output is lower, foreign matter content is higher; There is no effective impurity-removing method, so that need through the qualified smart indium of repeatedly electrolysis ability output.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of multi-metal complex height indium height tin material to prepare the method for high purity indium, obtain the high purity indium of 99.999% with lower cost, to promote the utilization ratio of resource.
Object of the present invention is achieved by the following technical programs.
Except as otherwise noted, percentage ratio of the present invention is mass percent.
A method for high purity indium prepared by multi-metal complex height indium height tin material, comprises the following steps:
(1) normal temperature leaches: leach operation and divide three sections to leach:
One section of leaching: drop into multi-metal complex height indium height tin material, solvent is hydrochloric acid and water, leaches volume ratio 6:1, reaction beginning acid 4 ~ 6mol/l, eventually acid 0.2 ~ 0.5mol/l, the reaction times is 4 hours, solid-liquor separation, leach liquor enters pH1.5 acid adjustment, and leached mud carries out two sections of leachings;
Two sections of leachings: drop into one section of leached mud, leaching solvent is hydrochloric acid and water, and liquid-solid volume ratio is 5:1, begin acid 4 ~ 6mol/l, and acid 3 ~ 5mol/l, in 4 hours reaction times, carries out solid-liquor separation eventually; Leach liquor returns input one section leaching, and leached mud enters slag field and carries out natural oxidation;
Natural oxidation: two sections of leached muds enter slag field, adds after appropriate NaOH and NaNO3 mix, is oxidized 1 ~ 2 month;
Three stages acid leach: drop into two sections of leached muds through natural oxidation, leaching solvent hydrochloric acid and water, beginning acid concentration 10mol/l, whole acid concentration 4 ~ 6mol/l, liquid-solid volume ratio 4:1, reacts 4 hours, solid-liquor separation, leach liquor returns and does two sections of leachings, and leached mud warehouse-in is deposited;
(2) extracting and separating Enrichment Indium tin:
I. acid adjustment: get one section of leach liquor, adds sheet alkali and solution acidity is adjusted to pH 1.5; Keep pH constant, gravity is adjusted to 1.08g/cm by the sour water adding pH 1.5
3;
II. extraction:
1# machine extracts: liquid pH 1.2 ~ 1.5, proportion 1.08 ~ 1.09 g/cm before extraction
3, use two-2 ethylhexyl phosphoric acids (P204) to carry out 4 stage countercurrent extractions as extraction agent;
According to comparing the organic phase and the aqueous phase flow that calculate start with extraction time, In, Sn content of start operation remaining liquid of sampling analysis extraction after 2 hours, then according to In, Sn content situation in the remaining liquid of extraction, flow is suitably adjusted; Concrete calculation formula is:
C In is liquid In concentration before extraction, and C Sn is Sn concentration in liquid before extraction, 1# machine V=120L, t=3 minute, C=16 g/l;
2# machine is stripped: a. reextraction indium: back extraction adopts the hydrochloric acid of 7 ~ 10N to carry out the 5 grades of back extractions comparing 10:1, obtains the strip liquor of the low tin of high indium, and this reversal indium liquid enters the extraction of 3# machine, and organic phase contains the tin of 60%, enters tin strip stages; B. to strip tin: back extraction tin adopts the HF solution of 8N to carry out 3 stage countercurrent back extractions, and 20:1 is compared in back extraction, and anti-tin liquor enters tin abstraction process, and organic phase is unloaded organic phase, returns 1# machine and extracts;
3# machine: 2# machine back extraction indium liquid uses tributyl phosphate (TBP) to carry out extracting and separating after the adjustment of acidity and concentration, before TBP extraction, liquid acidity controls at 0.8N; Extraction phase than and flow control methods and 1# machine extraction phase with, 3# machine mixing section volume V=60L, t=4 minute, TBP saturated capacity presses 10g/l calculating; Through 4 grades of extractions, tin enters organic phase, and indium is stayed in the remaining liquid of extraction, achieves effective separation of indium tin; The remaining liquid of TBP extraction is rich indium liquid, and enter the process of removal of impurities operation, TBP saturated organic phase carries out the back extraction of indium; The back extraction of indium adopts the dilute hydrochloric acid solution of 0.6N to carry out 3 grades of back extractions, and indium is by whole back extraction, and the tin of 40% is entered in reversal indium liquid by back extraction simultaneously, and reversal indium liquid is prepared TBP and extracted front liquid after returning and mixing with 2# machine reversal indium liquid for this reason; Organic phase after back extraction indium also contains the tin of 60%, then carries out 4 grades of rare HF solution back extraction tin to TBP organic phase; Unloaded TBP organic phase returns extraction section, and anti-tin liquor enters the abstraction process of tin;
(3) purification of high indium liquid:
A. iron removal by oxidation: high indium liquid adds sheet adjusting PH with base to 2.5, and stirring reaction 20min, slowly adds hydrogen peroxide; Treat that solution colour no longer reddens, add after stable reaction 10 ~ 20min after pH value of solution is adjusted to 2.5 by buck and add hydrogen peroxide detection Fe
2+whether eliminate; After reaction 30min, pH value of solution no longer changes and carries out solid-liquor separation, containing a large amount of In, Sn in filter residue, need return and leach use; Supernatant liquor is then placed after 18 ~ 20 hours and is carried out removal of impurities;
B. precipitation of indium dezincification cadmium: after deironing, high indium liquid adds alkali adjust ph to 5.0 hydrolytic precipitation indium, solid-liquor separation, isolated low indium liquid is disposed to wastewater trough process, and high indium slag adds hydrochloric acid and dissolves, and the pH of molten indium liquid controls 1.5;
C. zinc dust precipitation is except slicker solder: zinc powder is slowly sprinkled in molten indium liquid, after its reaction 30min, opens stirring and reacts, stirring reaction 10 hours; Solid-liquor separation, filter residue adopts salt acid soak to dissolve rear Returning process, and filtrate carries out thick indium removal of impurities operation;
D. thick indium plate is heated removal of impurities: the filtrate after zinc powder removal of impurities adds thick indium plate and carries out displacement removal of impurities of heating, Heating temperature 50 DEG C, 48 hours reaction times;
Now, the equal <0.03g/l of major impurity Pb, Sn content in the high indium liquid after repeatedly purification and impurity removal.
(4) thick indium is produced:
Low impurity height indium liquid enters displacement slot and carries out aluminium sheet replacement extraction sponge indium, and temperature of reaction remains on 60 DEG C, reaction times >10 hour, and reaction end solution I n content is less than 10mg/l; Sponge indium, through the acid rinsing of pH1.5, carries out pressure group, moisture content <5% after pressure group, Weighing, and slowly dropping into melt with the mouse cage that feeds intake has melting in the melting pot of sodium hydroxide, SODIUMNITRATE, sodium sulphite, smelting temperature 220 DEG C; Take the dish out of the pot after stirring removal of impurities reaction 30min after melting completes, carry out twice glycerine, ammonium chloride after taking the dish out of the pot and remove miscellaneous operation; After removal of impurities, namely indium liquid can cast;
Thick indium plate specification of quality In>99.1%, Sn<0.1%, Pb<0.1%, Fe<1%.
(5) thick indium electrolysis: thick indium is cast into thick indium plate, carries out once electrolytic, namely obtain the high purity indium of 99.999%.
Relative to prior art, the present invention has the following advantages:
1, present invention process is ripe, and indium, tin leaching yield are high, and running cost is low, and the comprehensive recovery of indium, tin is high, and indium, the tin of output are of high grade, and economic worth is high.
2, the present invention makes resource be fully used, and extraction agent wide material sources, extraction agent life cycle are long, and low price can significantly cut down finished cost, and technique is simple, and separation indium and tin is effective.
3, carry out by solar radiation the problem that natural oxidation solves indium leaching yield, shorten leaching flow process, achieve the Appropriate application of resource.
4, the present invention is environmentally friendly, and in electrolytic process, the utilization ratio of electric current is high, is extensively adapted to the process containing the lead of indium tin, iron, zinc ore material.
Embodiment
By the following examples technical scheme of the present invention is described in further detail, but embodiment is not limitation of the invention.
Embodiment 1
1. leach
Note: this example is the normal operating production data of whole production system, two immersion liquid wherein used (In 5.32g/l, Sn 13.52g/l), three immersion liquid (In 2.3g/l, Sn 14.90g/l) they are existing liquid storage;
One section of leaching: one section of leaching vat adds 3m
3clear water as leaching the end water, slowly add 1.6m
3hydrochloric acid, slowly feeds intake, indium ground-slag 800kg, In 13.61%; Sn 8.92%; Pb 15.25%; Fe 23.93%; Zn 9.64%; Ag 7000.5g/t; Cu 2.84%, alkaline residue powder 400kg, In20.75%; Sn 11.40%; Pb18.53%; Fe12.75%; Zn6.97%; Ag6610.9g/t; Cu2.45%.Charging time 60min, emits groove to avoid reaction violent.Fed intake, stirring reaction adds the scum 300kg (weight in wet base) of middle slag-PH2.5 removal of impurities after 1 hour, In 10.89%, Sn 11.04% moisture 25%; Then two sections of leach liquor In 5.32g/l are pumped into, Sn 13.52g/l is 6:1 to volume ratio, stirring reaction is after 1.5 hours, add middle slag-PH1.5 slag 300kg (weight in wet base), In 2.24%, Sn 31.83%, moisture 23%, add the gelatine solution 30L of prepare 4%, stirring reaction adds 0.4% flocculant solution after 0.5 hour stops stirring and starting press filtration after clarification appears in solution in groove.After press filtration completes, add 2m
3the acidified water of PH1.5 wash, finally pass into pressurized air and dry up, wash water enters acid adjustment groove, leaching slag weight in wet base 1150kg In 1.98%, Sn 5.8% a, H
2o 19.91%, enters two sections of leachings, filtrate 14m
3, In 17.20g/l, Sn 18.74g/l, enters the acid adjustment of acid adjustment groove.
Two sections of leachings: add 1.5m in two immersion troughs
3three stages acid leach liquid In 2.3g/l, Sn 14.90g/l as end water, open stir, drop into one section of leached mud 1150kg (weight in wet base), slowly add 0.2m
3hydrochloric acid, filling into three immersion liquid to volume ratio is 5:1, and stirring reaction carried out press filtration after 4 hours.Two leaching slags are through 1m
3the acidified water of PH1.5 wash after use pressurized air, two leaching slag 1000kg, In9964.1g/t, Sn 3.4%, H2O 20.5%, is transported to slag field and is oxidized.Two immersion liquid volumes are 6m
3, In2.95g/l, Sn 12.05g/l.
The oxidation of two leaching slags: it is thick that two leaching slag 1000kg are paved into 30cm, and add sheet alkali 50kg, 30kg SODIUMNITRATE is uniformly mixed, and finds that namely the phenomenon of local superheating sprays a small amount of water between oxidation period, prevents slag from luming serious and being oxidized not exclusively.Oxidization time 2 months, oxidization time is relevant with outside air temperature, between oxidation period, carry out 3 times stirring to slag, to guarantee fully contacting of slag and oxygen.Because slag caking carries out primary fragmentation to it, to increase the contact area with oxygen, improve oxidation effectiveness, thus improve leaching yield.Through snperoxiaized slag weightening finish 10%.
Three stages acid leach: add 1.5m
3clear water make end water, add 1.2m
3hydrochloric acid.Slow input 1100kg (weight in wet base) is oxidized two leaching slags, In 9964.1g/t, Sn 3.4%, H2O 6.4%.React after 1 hour, sour water to the volume ratio filling into PH1.5 is 4:1, slowly adds 50kg reduced iron powder.React and carry out press filtration after 3 hours.Add 1m
3the acidified water of PH1.5 sheet frame is washed, finally pass into pressurized air and dry up, wash water returns two sections and leaches and use together with three immersion liquid, adds up to 5m
3, In 1.39g/l, Sn 4.05g/l.Three leaching slag weight in wet base 553kg, In 2107.1g/t, Sn 1.3%H2O 16.56%.
2. extract:
PH1.5 acid adjustment
One immersion liquid 14m
3, In 17.20g/l, Sn 18.74 g/l.Enter the acid adjustment of acid adjustment groove, being added water by sheet alkali to dissolve slowly adds afterwards, and PH is adjusted to about 1.0, stirs after 10 minutes, and add in groove after being diluted by the 20kg vitriol oil and precipitate deleading, fill into buck and PH is adjusted to 1.5, the sheet alkali number finally added is 100kg.Adding appropriate PH1.5 sour water carries out than reconditioning, and the gravity after acid adjustment is 1.08g/cm
3, liquor capacity is 21m
3, In11.23g/l, Sn 9.02g/l, this solution enters extraction, and PH1.5 slag weight in wet base is 285kg, In 2.2%, Sn 32.5%, H
2o 21.5%, PH1.5 acid adjustment slag returns one section and leaches use.
1# machine extracts: after acid adjustment, liquid uses two-2 ethylhexyl phosphoric acids (P204) to carry out 4 stage countercurrent extractions as extraction agent.
Flow rate calculation formula is
c In=11.23g/l, C Sn 9.02g/l, 1# machine V=120L, t=3 minute, C=16 g/l.First calculate and compare A=(11.23+9.02)/16=1.266.U
water=(120*0.95*1000)/[3* (1.266+1) * 60]=279.5ml/s, U
have=1.266*279.5=353.847ml/s.The flow measuring 5s is selected, then U in production
water=1390ml/5s, U
have=1770ml/5s.Extract sampling analysis after 2 hours, raffinate In 0.010g/l, Sn 0.55g/l.
2# machine is stripped: a. reextraction indium: back extraction adopts the hydrochloric acid of 8N to carry out the 5 grades of back extractions comparing 10:1, and anti-indium hydrochloric acid flow 170ml/5s, obtains the low tin reversal indium liquid of high indium, this strip liquor In 89g/l, Sn 28g/l; B. to strip tin: the tin containing 60% in organic phase after back extraction indium, adopt the HF solution of about 8N to carry out 3 stage countercurrent reextraction tin, 20:1 is compared in back extraction, and HF solution flow is 90ml/5s, anti-tin liquor Sn 42.5g/l for this reason.
3# machine: 3# machine extraction stoste preparation: 2# machine reversal indium liquid allocates the clear water of 20% again into after mixing with 3# machine reversal indium liquid 1:1, acidity control is at about 0.8N, In 48g/l, Sn 15g/l, Fe 16.8g/l, uses tributyl phosphate (TBP) to carry out extracting and separating.Extraction phase than and flow control methods and 1# machine extraction phase with, 3# machine mixing section volume V=60L, t=4 minute, TBP saturated capacity presses 10g/l calculating.Through 4 grades of extraction of tin, raffinate In 46g/l, Sn 1.8g/l, Fe 7g/l, this high indium liquid enters removal of impurities operation and purifies.
Indium back extraction adopts the dilute hydrochloric acid solution of 0.6N to carry out 3 grades of back extractions, and 5:1 is compared in back extraction, reversal indium liquid In 3.2g/l, Sn 10.5g/l, and reversal indium liquid is prepared TBP and extracted front liquid after returning and mixing with 2# machine reversal indium liquid; After back extraction indium, organic phase also contains the tin of 60%, then adopts rare HF solution to carry out 4 grades of back extraction tin to TBP organic phase, and back extraction is in a ratio of 3:1, anti-tin liquor In 0.03g/l, Sn 15g/l.
(3) purification of high indium liquid:
A. iron removal by oxidation: get the remaining liquid 5.1m of TBP extraction
3, In 46g/l, Sn 1.8g/l, Fe
2+7g/l, add 150kg sheet alkali and solution PH is adjusted to 2.5, slowly hydrogen peroxide is added after stirring reaction 20min, hydrogen peroxide add-on is 50kg, treat that hydrogen peroxide adds to solution colour and no longer reddens, 50kg sheet alkali adds water furnishing buck by stable reaction 10-20min, fills into add hydrogen peroxide with a small amount of liquid of filter-cloth filtering after solution PH being adjusted to 2.5 in groove and carry out mensuration Fe
2+, no longer the redden amount of then hydrogen peroxide of supernatant liquor is enough.After continuing stirring reaction 30min, solution PH no longer changes, and can carry out solid-liquor separation, the scum 50kg after filtration, In 3.3%, Sn 21.55%, H2O 20%, need return and leach post use.Filtrate 5.3m
3, In44g/l, Sn 0.099g/l, Fe<0.1g/l, Pb 0.16g/l, be positioned in storage tank and carry out autoprecipitation to the second day.
B. precipitation of indium dezincification cadmium: after deironing, high indium liquid is after the autoprecipitation of more than 18h, pumps into heavy indium groove, and volume is 5.3m
3, add 225kg sheet alkali and regulate pH value to 5.0, after stirring reaction 20min, carry out solid-liquor separation.High indium slag after solid-liquor separation adds appropriate hydrochloric acid and dissolves, and the PH of molten indium liquid controls about 1.0 to ensure suitable replacement(metathesis)reaction acidity.Isolated low indium liquid In 0.005g/l then can be disposed to wastewater trough process.
C. zinc dust precipitation is except slicker solder: molten indium liquid 1.2m
3, In 193.55g/l, Sn 0.21g/l, Pb0.54g/l, Fe 0.12g/l.Slowly be sprinkled into 8kg zinc powder, after its reaction 30min, open and stir, 18 hours reaction times.Solid-liquor separation, filter residue adopts salt acid soak to dissolve rear Returning process.Liquid In192.68g/l, Sn 0.087g/l after zinc powder removal of impurities, Pb 0.0.097g/l, Fe<0.1g/l enter thick indium except miscellaneous operation.
D. thick indium plate is heated removal of impurities: after zinc powder removal of impurities, liquid enters thick indium deblending slot, adds qualified thick indium plate and carries out heating removal of impurities, temperature 50 C, 48 hours reaction times.Liquid In 193.2g/l after thick indium removal of impurities, Sn 0.029g/l, Pb 0.0.089g/l, Fe<0.1g/l.
(4) thick indium is produced:
1.2m
3after thick indium removal of impurities, liquid adds 90kg aluminium sheet replacement extraction sponge indium, about displacement temperature 60 C.20 hours reaction times, reaction end solution I n0.005g/l.The sponge indium pulled out is through the acid rinsing Al of PH1.5
3+after carry out pressure group operation, pressure group after H
2o<5%, after sponge indium pressure group, weight is 248kg, slowly drops into melt to have in the melting pot of 65kg sodium hydroxide, 4kg SODIUMNITRATE, 4kg sodium sulphite carry out melting, smelting temperature about 220 DEG C with the mouse cage that feeds intake.Take the dish out of the pot after stirring removal of impurities reaction 30min after melting completes, first upper strata alkali lye is scooped out, again bottom indium liquid is scooped out carry out first time glycerol adding, ammonium chloride except miscellaneous operation, treat that indium liquid all transfers in fireless cooker the operation carrying out second time glycerol adding, ammonium chloride removal of impurities again.Namely indium liquid after removal of impurities can cast, and finally obtains thick indium 233kg, 40 blocks of thick indium plates.Thick indium grade In 99.22%, Sn 0.095%, Pb 0.08%, Fe 0.3%.
(5) thick indium electrolysis:
After qualified thick indium plate is cleaned up, with filter paper parcel, and put 758 filter bags and avoid the anode sludge to enter electrolytic solution.Tankage: each sulculus loads 12 pieces of positive plates, 13 pieces of negative plates.Electrolytic solution is In
2(SO
4)
3, H
2sO
4system, bath composition: In
3+75g/l, Cl-66g/l, gelatin 0.6g/l, observes precipitation indium during electrolysis, separates out indium and occurs that a large amount of burr then needs supplementary gelatin; Electrolytic solution PH 2.0 ~ 2.5, strength of current 140A; Electrolyte temperature 25 ~ 30 DEG C; Electrolysing period is 7 days.By the moon after electrolysis completes, positive plate carefully takes out, clean respectively, in cathode titanium plates, output separates out indium in a large number, this part needs to adopt clean water to be repeatedly filtered dry moisture afterwards after separating out indium stripping can carry out founding, fusion-casting process needs to add glycerine and ammonium chloride carries out twice stirring removal of impurities, ingot casting can be carried out after dragging for the scum silica frost on surface, the quality control of indium ingot is at about 500g, final smart indium output is 25.6kg, In99.999%, Sn<0.0005%, Pb<0.0005%, Fe<0.0005%, Cu<0.0005%, Cd<0.0005%, Al<0.0005%, Zn<0.0005%, Tl<0.0005%, As<0.0005%.The residual plate of anode re-starts and adds alkali fusion and be cast as qualified thick indium plate electrolysis and use after the washing removing anode sludge, and anode sludge Returning process, it is clean that 758 filter bags adopt dilution heat of sulfuric acid to soak 2 days post rinsings after cleaning, dries rear use.
Embodiment 2:
1. leach
Note: this example is the normal operating production data of whole production system, the two immersion liquid In 3.92g/l wherein used, Sn 12.65g/l, three immersion liquid In 1.69g/l, Sn 7.35g/l is existing liquid storage;
One section of leaching:
Note: operation is all with example 1, and raw material composition is different.
1.5m
3clear water, as leaching end water, adds 1.6m
3hydrochloric acid, indium ground-slag 800kg, In 16.67%; Sn 10.08%; Pb 18.16%; Fe14.8%; Zn 14.16%; Ag 6030.8g/t; Cu 2.3%. alkaline residue powder 400kg, In 22.48%; Sn 10.65%; Pb 19.00%; Fe 10.05%; Zn 8.21%; Ag 7610.2g/t; Cu 1.95%.Add scum 320kg (weight in wet base) In 8.46% of middle slag-PH2.5 removal of impurities, Sn 10.21% moisture 26.3%, add two immersion liquid In 3.92g/l, Sn 12.65g/l is to volume ratio 6:1, add middle slag-PH1.5 slag 310kg (weight in wet base), In 1.85%, Sn 40.22%, moisture 22.5%.Solid-liquor separation, a leaching slag weight in wet base 1136kg.In 2.1%, Sn 5.9%, H
2o 20.32% carries out two sections of leachings, filtrate 14.5m
3, In 18.17g/l, Sn 20.89g/l, enters the acid adjustment of acid adjustment groove.
Two sections of leachings:
1.5m is added in two immersion troughs
3three stages acid leach liquid In 1.69g/l, Sn 7.35g/l, as end water, drops into 1136kg (weight in wet base) leaching slag, adds 0.2m
3hydrochloric acid, filling into three immersion liquid to volume ratio is 5:1, reacts and carries out press filtration after 4 hours.Two immersion liquid 5m
3, In 3.90g/l, Sn 11.03g/l.Two leaching slag weight in wet base 999.57kg, In 7245.6g/t, Sn 3.2%, H2O 18.5% is transported to the oxidation of slag field.
The oxidation of two leaching slags: two leaching slags are paved into the thick thin layer of 30cm, and 999.57kg bis-soaks slag and adds sheet alkali 45kg, and 30kg SODIUMNITRATE is uniformly mixed.
Three stages acid leach:
Add 1.5m
3clear water make end water, add 1.1m
3hydrochloric acid.Slow input 1186.6kg (weight in wet base) is oxidized two leaching slag In 7245.6g/t, Sn 3.2%, H2O 7.34%.。Volume ratio is 4:1, adds 50kg reduced iron powder.3 hours reaction times.Three immersion liquid volume 5m
3, In 1.42g/l, Sn 6.14g/l, returns two sections and leaches use.Three leaching slag weight in wet base 522kg, In 1921.8g/t, Sn 1.02%, H2O 15.8% puts in storage and deposits.
2. extract:
PH1.5 acid adjustment
One immersion liquid 14.5m
3, In 18.17g/l, Sn 20.89g/l.Enter the acid adjustment of acid adjustment groove, add sheet alkali 120kg, vitriol oil 23kg, the heavy 1.08g/cm of acid adjustment liquor ratio
3.Volume 22m
3, In 11.81g/l, Sn 10.49g/l, filter residue weight in wet base 270kg, In 1.83%, Sn 35.46%, H2O 24.78%.
1# machine extracts: after acid adjustment, liquid uses two-2 ethylhexyl phosphoric acids (P204) to carry out 4 stage countercurrent extractions as extraction agent.Through calculating the flow measuring 5s, then U
water=1325ml/5s, U
have=1841ml/5s.Extractive reaction is sampling analysis after 2 hours, raffinate In 0.008g/l, Sn 0.45g/l.
2# machine is stripped: a. reextraction indium: strip liquor In 85g/l, Sn 30.1g/l; B. to strip tin: anti-tin liquor Sn 45.3g/l.
3# machine: use tributyl phosphate (TBP) to carry out extracting and separating, liquid In 43.2g/l, Sn 16.5g/l, Fe 15.6g/l before extraction.Raffinate In 41.9g/l, Sn 1.95g/l, Fe 8.2g/l, this high indium liquid enters removal of impurities operation and purifies.
Indium back extraction: reversal indium liquid In 3.4g/l, Sn 17.6g/l, back extraction tin: anti-tin liquor In 0.03g/l, Sn 13g/l.
(3) purification of high indium liquid:
A. iron removal by oxidation: high indium liquid 4.8m
3, In 41.9g/l, Sn 1.55g/l, Fe 8.2g/l, add 225kg sheet alkali, hydrogen peroxide 85kg, solid-liquor separation, scum 56kg, In 9.53%, Sn 16.91%, H2O22.5%, returns to leach to use.Filtrate 5.1m
3, In 38.62g/l, Sn 0.025g/l, Fe 0.06g/l, Pb 0.14g/l, be positioned in storage tank second day and add alkali and sink indium.
B. precipitation of indium dezincification cadmium: after deironing, high indium liquid amasss 5.1m
3, add 130kg sheet alkali and regulate pH value to 5.0.Solid-liquor separation, high indium slag adds dissolving with hydrochloric acid, and molten indium enters zinc dust precipitation deblending slot, and isolated low indium liquid In 0.008g/l, is disposed to wastewater trough process.
C. zinc dust precipitation is except slicker solder: molten indium indium liquid 1m
3, In 196.961g/l, Sn 0.13g/l, Pb0.42g/l, Fe 0.10g/l.Add the removal of impurities of 8kg zinc powder, solid-liquor separation, filter hydrochloric acid for dreg soaks and dissolves rear Returning process.Liquid In 196.52g/l after zinc powder removal of impurities, Sn 0.056g/l, Pb0.0.037g/l, Fe<0.1g/l.
D. thick indium plate is heated removal of impurities: after zinc powder removal of impurities, liquid enters thick indium deblending slot, adds thick indium plate and carries out displacement removal of impurities of heating, temperature 50 C, 48 hours reaction times.Liquid In 197.55g/l after thick indium removal of impurities, Sn 0.011g/l, Pb 0.0.045g/l, Fe 0.05g/l.
(4) thick indium is produced:
1.1m
3after thick indium removal of impurities, liquid adds 105kg aluminium sheet, temperature of reaction about 60 DEG C.18 hours reaction times, reaction end solution I n0.005g/l.After pressure group, weight is 228kg, drops into melt to have in the melting pot of 75kg sodium hydroxide, 5kg SODIUMNITRATE, 5kg sodium sulphite and carries out melting, smelting temperature about 220 DEG C.The operation of twice glycerol adding, ammonium chloride removal of impurities is carried out after taking the dish out of the pot.Obtain thick indium 215kg, 38 blocks of thick indium plates.Thick indium grade In 99.15%, Sn 0.021%, Pb 0.033%, Fe 0.25%.
(5) thick indium electrolysis:
By thick indium plate tankage, carry out once electrolytic, strength of current 150A, output essence indium 27.8kg, In99.999%, Sn<0.0005%, Pb<0.0005%, Fe<0.0005%, Cu<0.0005%, Cd<0.0005%, Al<0.0005%, Zn<0.0005%, Tl<0.0005%, As<0.0005%.
Claims (1)
1. prepare a method for high purity indium with multi-metal complex height indium height tin material, comprise the following steps:
(1) normal temperature leaches: divide three sections and leach:
One section of leaching: drop into multi-metal complex height indium height tin material, solvent is hydrochloric acid and water, leaches volume ratio 6:1, reaction beginning acid 4 ~ 6mol/l, eventually acid 0.2 ~ 0.5mol/l, the reaction times is 4 hours, solid-liquor separation, leach liquor enters pH1.5 acid adjustment, and leached mud carries out two sections of leachings;
Two sections of leachings: drop into one section of leached mud, leaching solvent is hydrochloric acid and water, and liquid-solid volume ratio is 5:1, begin acid 4 ~ 6mol/l, and acid 3 ~ 5mol/l, in 4 hours reaction times, carries out solid-liquor separation eventually; Leach liquor returns input one section leaching, and leached mud enters slag field and carries out natural oxidation;
Natural oxidation: two sections of leached muds enter slag field, adds after appropriate NaOH and NaNO3 mix, is oxidized 1 ~ 2 month;
Three stages acid leach: drop into two sections of leached muds through natural oxidation, leaching solvent hydrochloric acid and water, beginning acid concentration 10mol/l, whole acid concentration 4 ~ 6mol/l, liquid-solid volume ratio 4:1, reacts 4 hours, solid-liquor separation, leach liquor returns and does two sections of leachings, and leached mud warehouse-in is deposited;
(2) extracting and separating Enrichment Indium tin:
I. acid adjustment: get one section of leach liquor, adds sheet alkali and solution acidity is adjusted to pH 1.5; Keep pH constant, gravity is adjusted to 1.08g/cm by the sour water adding pH 1.5
3;
II. extraction:
1# machine extracts: liquid pH 1.2 ~ 1.5, proportion 1.08 ~ 1.09 g/cm before extraction
3, use two-2 ethylhexyl phosphoric acids to carry out 4 stage countercurrent extractions as extraction agent;
According to comparing the organic phase and the aqueous phase flow that calculate start with extraction time, In, Sn content of start operation remaining liquid of sampling analysis extraction after 2 hours, then according to In, Sn content situation in the remaining liquid of extraction, flow is suitably adjusted; Concrete calculation formula is:
C In is liquid In concentration before extraction, and C Sn is Sn concentration in liquid before extraction, 1# machine V=120L, t=3 minute, C=16g/l;
2# machine is stripped: a. reextraction indium: back extraction adopts the hydrochloric acid of 7 ~ 10N to carry out the 5 grades of back extractions comparing 10:1, obtains the strip liquor of the low tin of high indium, and this reversal indium liquid enters the extraction of 3# machine, and organic phase contains the tin of 60%, enters tin strip stages; B. to strip tin: back extraction tin adopts the HF solution of 8N to carry out 3 stage countercurrent back extractions, and 20:1 is compared in back extraction, and anti-tin liquor enters tin abstraction process, and organic phase is unloaded organic phase, returns 1# machine and extracts;
3# machine: 2# machine back extraction indium liquid uses tributyl phosphate to carry out extracting and separating after the adjustment of acidity and concentration, before TBP extraction, liquid acidity controls at 0.8N; Extraction phase than and flow control methods and 1# machine extraction phase with, 3# machine mixing section volume V=60L, t=4 minute, TBP saturated capacity presses 10g/l calculating; Through 4 grades of extractions, tin enters organic phase, and indium is stayed in the remaining liquid of extraction, achieves effective separation of indium tin; The remaining liquid of TBP extraction is rich indium liquid, and enter the process of removal of impurities operation, TBP saturated organic phase carries out the back extraction of indium; The back extraction of indium adopts the dilute hydrochloric acid solution of 0.6N to carry out 3 grades of back extractions, and indium is by whole back extraction, and the tin of 40% is entered in reversal indium liquid by back extraction simultaneously, and reversal indium liquid is prepared TBP and extracted front liquid after returning and mixing with 2# machine reversal indium liquid for this reason; Organic phase after back extraction indium also contains the tin of 60%, then carries out 4 grades of rare HF solution back extraction tin to TBP organic phase; Unloaded TBP organic phase returns extraction section, and anti-tin liquor enters the abstraction process of tin;
(3) purification of high indium liquid:
A. iron removal by oxidation: high indium liquid adds sheet adjusting PH with base to 2.5, and stirring reaction 20min, slowly adds hydrogen peroxide; Treat that solution colour no longer reddens, add after stable reaction 10 ~ 20min after pH value of solution is adjusted to 2.5 by buck and add hydrogen peroxide detection Fe
2+whether eliminate; After reaction 30min, pH value of solution no longer changes and carries out solid-liquor separation, containing a large amount of In, Sn in filter residue, need return and leach use; Supernatant liquor is then placed after 18 ~ 20 hours and is carried out removal of impurities;
B. precipitation of indium dezincification cadmium: after deironing, high indium liquid adds alkali adjust ph to 5.0 hydrolytic precipitation indium, solid-liquor separation, isolated low indium liquid is disposed to wastewater trough process, and high indium slag adds hydrochloric acid and dissolves, and the pH of molten indium liquid controls 1.5;
C. zinc dust precipitation is except slicker solder: zinc powder is slowly sprinkled in molten indium liquid, after its reaction 30min, opens stirring and reacts, stirring reaction 10 hours; Solid-liquor separation, filter residue adopts salt acid soak to dissolve rear Returning process, and filtrate carries out thick indium removal of impurities operation;
D. thick indium plate is heated removal of impurities: the filtrate after zinc powder removal of impurities adds thick indium plate and carries out displacement removal of impurities of heating, Heating temperature 50 DEG C, 48 hours reaction times;
(4) thick indium is produced:
Low impurity height indium liquid enters displacement slot and carries out aluminium sheet replacement extraction sponge indium, and temperature of reaction remains on 60 DEG C, reaction times >10 hour, and reaction end solution I n content is less than 10mg/l; Sponge indium, through the acid rinsing of pH1.5, carries out pressure group, moisture content <5% after pressure group, Weighing, and slowly dropping into melt with the mouse cage that feeds intake has melting in the melting pot of sodium hydroxide, SODIUMNITRATE, sodium sulphite, smelting temperature 220 DEG C; Take the dish out of the pot after stirring removal of impurities reaction 30min after melting completes, carry out twice glycerine, ammonium chloride after taking the dish out of the pot and remove miscellaneous operation; After removal of impurities, namely indium liquid can cast;
(5) thick indium electrolysis: thick indium is cast into thick indium plate, carries out once electrolytic, namely obtain the high purity indium of 99.999%.
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