CN104232943B - A kind of method that high purity indium prepared by multi-metal complex height indium height stannum material - Google Patents
A kind of method that high purity indium prepared by multi-metal complex height indium height stannum material Download PDFInfo
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Abstract
The invention discloses a kind of method that high purity indium prepared by multi-metal complex height indium height stannum material, comprise the following steps: points three sections carry out room temperature leaching autoxidation, extract and separate Enrichment Indium stannum, the purification of high indium liquid, thick indium are produced and thick indium electrolysis, finally give the high-purity indium of 99.999%.Present invention process is ripe, and indium, stannum leaching rate are high, and operating cost is low, and indium, the comprehensive recovery height of stannum, the indium of output, stannum are of high grade.Extractant wide material sources, use cycle length, low price, can be greatly reduced processing cost.Carry out autoxidation by sunlight irradiation and solve the problem of indium leaching rate, shorten leaching flow process, it is achieved that the Appropriate application of resource.The present invention is environmentally friendly, and in electrolytic process, the utilization rate of electric current is high, is widely applicable to the lead containing indium stannum, ferrum, the process of zinc ore material.
Description
Technical field
The invention belongs to technical field of wet metallurgy, be specifically related to one multi-metal complex high
The method that high-purity indium prepared by indium height stannum material.
Background technology
Indium metal initially application industrially is process industry bearing, owing to its ductility (can
Plasticity) fabulous, steam forces down, and can stick to again on multiple material, the most also by extensively
As the pad in aerological instrument and aerospace equipment or inner liner material.
Many metals association zinc concentrate, after pyrogenic process repeatedly is enriched with, obtains the high indium many impurity of height stannum
Material, in this material, main metal element is indium, stannum, lead, zinc, ferrum, copper, arsenic, cadmium
Deng.For the valuable element in synthetical recovery material, zinc abstraction industry generally uses electro-smelting
Extracting zinc, during extracting zinc, a large amount of Enrichment Indium, stannum are in crude zinc, and crude zinc is through rectification
The rectification of tower obtains 0# zinc, and tower bottom deposits B# zinc and the hard zinc of a large amount of high zinc richness indium stannum, this
The zinc ingot metal of the high indium of part processes output through further volatilization again and contains the relatively low zinc ingot metal of indium, Gao Yin
Lead at the bottom of the indium slag of stannum and high indium.The indium slag of high indium stannum and end lead are after levigate process and carry indium
Raw material.
Known to put forward indium method and mainly have (1) to 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 side-product hard zinc of pyrometallurgy of zinc, indium is extracted.Wherein, from hard zinc, indium is carried
Flow process is: uses vacuum distilling hard zinc to carry out Enrichment Indium, and extracts indium slag from rich indium raw material,
After recovery indium from indium slag again.The concentration effect of the valuable metal such as indium, stannum is the best, impurity content
Height, and carry the composition of indium raw material and mainly exist with metallic state, leach raw material granularity relatively thick, leaching
Go out difficulty bigger；Indium can be wrapped up by lead in a large number, and the leaching rate causing indium stannum is low.This technique produces
Process is more complicated, leaches flow process and need to use high acidic oils, the leaching rate of indium after repeatedly leaching
Still cannot significantly improve, the thick indium grade of output is relatively low, impurity content is higher；The most effective
Impurity-removing method, so that needing through being repeatedly electrolysed the smart indium that ability output is qualified.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that one multi-metal complex
The method that high purity indium prepared by high indium height stannum material, with relatively low cost obtain 99.999% high-purity
Indium, to promote the utilization rate of resource.
The purpose of the present invention is achieved by the following technical programs.
Except as otherwise noted, percent of the present invention is mass percent.
A kind of method that high purity indium prepared by multi-metal complex height indium height stannum material, including following step
Rapid:
(1) room temperature leaches: leaches operation and divides three sections to leach:
One section of leaching: putting into multi-metal complex height indium height stannum material, solvent is hydrochloric acid and water, leaching
Going out volume ratio 6:1, reaction beginning acid 4～6mol/l, eventually acid 0.2～0.5mol/l, during reaction
Between be 4 hours, solid-liquor separation, leachate enter pH1.5 acid adjustment, leached mud carries out two-stage nitration leaching
Go out；
Two-stage nitration leaches: putting into one section of leached mud, leaching solvent is hydrochloric acid and water, liquid-solid volume ratio
For 5:1, acid 4～6mol/l of beginning, acid 3～5mol/l, in 4 hours response time, is carried out eventually
Solid-liquor separation；Leachate returns and puts into one section of leaching, and leached mud enters slag field and carries out autoxidation；
Autoxidation: two-stage nitration leached mud enters slag field, adds appropriate NaOH and NaNO3 mixing
After Jun Yun, oxidation 1～2 months；
Three stages acid leach: put into through the two-stage nitration leached mud of autoxidation, leaching solvent hydrochloric acid and water,
Beginning acid concentration 10mol/l, whole acid concentration 4～6mol/l, liquid-solid volume ratio 4:1, react 4
Hour, solid-liquor separation, leachate returns and does two-stage nitration leaching, and leached mud warehouse-in is deposited；
(2) extract and separate Enrichment Indium stannum:
I. acid adjustment: take one section of leachate, adds sheet alkali by solution acidity regulation to pH 1.5；
Keep pH constant, add the sour water of pH 1.5 by gravity regulation to 1.08g/cm3；
II. extraction:
1# machine extracts: liquid pH 1.2～1.5 before extraction, proportion 1.08～1.09g/cm3, make
4 stage countercurrent extractions are carried out as extractant with two-2 ethylhexyl phosphoric acids (P204)；
The organic facies and aqueous phase flow started shooting is calculated with extraction time, operation 2 of starting shooting according to comparing
In, Sn content of the remaining liquid of sample analysis extraction after hour, further according to the In in the remaining liquid of extraction,
Flow is suitably adjusted by Sn content situation；Concrete computing formula is:
C In is liquid In concentration before extraction, and C Sn is Sn concentration, 1# machine in liquid before extraction
V=120L, t=3 minute, C=16g/l；
2# machine back extraction: a. back extraction indium: back extraction uses the hydrochloric acid of 7～10N to compare
5 grades of back extractions of 10:1, obtain the strip liquor of the low stannum of high indium, and this reversal indium liquid enters the extraction of 3# machine,
Organic facies contains the stannum of 60%, enters stannum strip stages；B. back extraction stannum: back extraction stannum uses 8N
HF solution carry out 3 stage countercurrent back extractions, 20:1 is compared in back extraction, and anti-tin liquor enters stannum and extracts work
Sequence, organic facies is unloaded organic facies, returns 1# machine and extracts；
3# machine: 2# machine back extraction indium liquid uses tributyl phosphate after the regulation of acidity and concentration
(TBP) carrying out extract and separate, before TBP extraction, liquid acidity controls at 0.8N；Extraction phase than and
Flow control methods and 1# machine extraction phase are same, 3# machine mixing chamber volume V=60L, t=4 minute,
TBP saturated capacity is pressed 10g/l and is calculated；Through 4 grades of extractions, stannum enters organic facies, and indium is stayed
In the remaining liquid of extraction, it is achieved that efficiently separating of indium stannum；The remaining liquid of TBP extraction is rich indium liquid, enters
Remove impurity operation processes, and TBP saturated organic phase carries out the back extraction of indium；The back extraction of indium uses 0.6N
Dilute hydrochloric acid solution carry out 3 grades of back extractions, indium is by whole back extractions, and the stannum of 40% is entered by back extraction simultaneously
Enter in reversal indium liquid, return for this reversal indium liquid before preparing TBP extraction after mixing with 2# machine reversal indium liquid
Liquid；Organic facies after back extraction indium possibly together with 60% stannum, then TBP organic facies is carried out 4 grades dilute
HF solution back extraction stannum；Unloaded TBP organic facies returns extraction section, and anti-tin liquor enters the extraction of stannum
Operation；
(3) purification of high indium liquid:
A. iron removal by oxidation: high indium liquid addition sheet adjusting PH with base is to 2.5, and 20min is reacted in stirring, slow
Slowly hydrogen peroxide is added；Treat that solution colour no longer reddens, after stable reaction 10～20min, add alkali
Water adds hydrogen peroxide detection Fe after pH value of solution is adjusted to 2.52+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 filtering residue, need to return leaching
Go out to use；Supernatant carries out remove impurity after then placing 18～20 hours；
B. precipitation of indium removes zinc cadmium: except indium liquid high after ferrum adds alkali regulation pH value to 5.0 hydrolytic precipitations
Indium, solid-liquor separation, isolated low indium liquid is emitted into wastewater trough and processes, and high indium slag adds hydrochloric acid
Dissolving, the pH of molten indium liquid controls 1.5；
C. zinc dust precipitation removes slicker solder: zinc powder is slowly sprinkled in molten indium liquid, treats that it reacts 30min
After, open stirring and react, stirring reaction 10 hours；Solid-liquor separation, filtering residue uses salt
Acid soak dissolves rear Returning process, and filtrate carries out thick indium remove impurity operation；
D. thick indium plate is heated remove impurity: the filtrate after zinc powder remove impurity adds thick indium plate and adds
Temperature displacement remove impurity, heating-up temperature 50 DEG C, 48 hours response time；
Now, in the high indium liquid after repeatedly purification and impurity removal, major impurity Pb, Sn content is equal
<0.03g/l。
(4) thick indium is produced:
Low impurity height indium liquid enters displacement slot and carries out aluminium sheet replacement extraction sponge indium, and reaction temperature is protected
Hold at 60 DEG C, the response time > 10 hours, reaction end solution I n content is less than 10mg/l；
Sponge indium, through the acid rinsing of pH1.5, carries out briquetting, and moisture after briquetting < 5%, weigh
Metering, slowly puts into the molten melting pot having sodium hydroxide, sodium nitrate, sodium sulfide with the mouse cage that feeds intake
Middle melting, smelting temperature 220 DEG C；Melting takes the dish out of the pot after stirring remove impurity reaction 30min after completing,
Twice glycerol, ammonium chloride remove impurity operation is carried out after taking the dish out of the pot；After remove impurity, indium liquid i.e. can be cast；
Thick indium plate prescription 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, i.e. obtain
The high-purity indium of 99.999%.
Relative to prior art, the invention have the advantages that
1, present invention process is ripe, indium, stannum leaching rate are high, and operating cost is low, indium, stannum
Comprehensive recovery is high, and the indium of output, stannum are of high grade, and economic worth is high.
2, the present invention makes resource be fully used, and extractant wide material sources, extractant make
Use the cycle long, low price, processing cost can be greatly reduced, and technique is simple, separation indium and tin
Effective.
3, carry out autoxidation by sunlight irradiation and solve the problem of indium leaching rate, shorten
Leach flow process, it is achieved that the Appropriate application of resource.
4, the present invention is environmentally friendly, and in electrolytic process, the utilization rate of electric current is high, extensively adapts to
In the lead containing indium stannum, ferrum, the process of zinc ore material.
Detailed description of the invention
By the following examples technical scheme is described in further detail, but real
Executing example is not limitation of the invention.
Embodiment 1
1. leach
Note: this example be whole production system properly functioning in creation data, wherein use
Two immersion (In 5.32g/l, Sn 13.52g/l), three immersion (In 2.3g/l, Sn 14.90g/l)
For existing liquid storage；
One section of leaching: one section of leaching tanks adds 3m3Clear water as leach bottom water, be slowly added to
1.6m3Hydrochloric 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, to avoid reaction acutely to emit groove.Feed intake, stirred
The scum 300kg (weight in wet base), In of slag PH2.5 remove impurity in the middle of adding after mixing reaction 1 hour
10.89%, Sn 11.04% moisture 25%；It is then pumped into two-stage nitration leachate In 5.32g/l,
Sn 13.52g/l is 6:1 to volume ratio, after stirring is reacted 1.5 hours, adds middle slag
PH1.5 slag 300kg (weight in wet base), In 2.24%, Sn 31.83%, moisture 23%, add
The osseocolla solution 30L of 4% prepared, stirring reaction adds the flocculation of 0.4% after 0.5 hour
Agent solution stops stirring after there is clarification to solution in groove and starts filter pressing.After filter pressing completes, add
Enter 2m3The acidifying water of PH1.5 wash, be finally passed through compressed air and dry up, wash
Water enters acid adjustment groove, a leaching slag weight in wet base 1150kg In 1.98%, Sn 5.8%, H2O 19.91%,
Entrance two-stage nitration leaches, filtrate 14m3, In 17.20g/l, Sn 18.74g/l, enter acid adjustment groove
Acid adjustment.
Two-stage nitration leaches: add 1.5m in two immersion troughs3Three stages acid leach liquid In 2.3g/l, Sn
14.90g/l, as bottom water, opens stirring, puts into one section of leached mud 1150kg (weight in wet base), slow
Slowly 0.2m is added3Hydrochloric acid, filling into three immersion to volume ratio is 5:1, after stirring is reacted 4 hours
Carry out filter pressing.Two leaching slags are through 1m3The acidifying water of PH1.5 wash after use compression sky
Gas, two leaching slag 1000kg, In 9964.1g/t, Sn 3.4%, H2O 20.5%, it is transported to slag field
Aoxidize.Two immersion volumes are 6m3, In 2.95g/l, Sn 12.05g/l.
The oxidation of two leaching slags: it is thick that two leaching slag 1000kg are paved into 30cm, adds sheet alkali 50kg, 30kg
Sodium nitrate is uniformly mixed, and finds that the phenomenon of hot-spot i.e. sprays a small amount of water during oxidation,
Prevent slag caking serious and aoxidize not exclusively.Oxidization time 2 months, oxidization time and extraneous gas
Temperature is relevant, during aoxidizing, slag is carried out 3 times and stirs, to guarantee fully connecing of slag and oxygen
Touch.Because slag caking carries out primary fragmentation to it, to increase the contact area with oxygen, improve oxygen
Change effect, thus improve leaching rate.Through snperoxiaized slag weightening finish 10%.
Three stages acid leach: add 1.5m3Clear water make bottom water, add 1.2m3Hydrochloric acid.Slowly throw
Enter 1100kg (weight in wet base) and aoxidize two leaching slags, In 9964.1g/t, Sn 3.4%, H2O 6.4%.
After reacting 1 hour, the sour water filling into PH1.5 is 4:1 to volume ratio, is slowly added to 50kg
Reduced iron powder.Filter pressing is carried out after reacting 3 hours.Add 1m3The acidifying water of PH1.5 to plate
Frame washs, and is finally passed through compressed air and dries up, and wash water returns two together with three immersion
Section leaches and uses, and adds up to 5m3, In 1.39g/l, Sn 4.05g/l.Three leaching slag weight in wet bases 553kg,
In 2107.1g/t, Sn 1.3%H2O 16.56%.
2. extraction:
PH1.5 acid adjustment
One immersion 14m3, In 17.20g/l, Sn 18.74g/l.Enter acid adjustment groove acid adjustment,
Being added water by sheet alkali and be slowly added to after dissolving, PH is adjusted to about 1.0, after stirring 10 minutes,
Add precipitation in groove after being diluted by 20kg concentrated sulphuric acid, except lead, to fill into aqueous alkali and be adjusted to by PH
1.5, the sheet alkali number ultimately joined is 100kg.Add appropriate PH1.5 sour water to carry out than readjustment
Joint, the gravity after acid adjustment is 1.08g/cm3, liquor capacity is 21m3, 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%, H2O 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) as extraction
Agent carries out 4 stage countercurrent extractions.
Flow rate calculation formula isC In=
11.23g/l, C Sn 9.02g/l, 1# machine V=120L, t=3 minute, C=16g/l.
First calculate and compare A=(11.23+9.02)/16=1.266.UWater=
(120*0.95*1000)/[3* (1.266+1) * 60]=279.5ml/s, UHave
=1.266*279.5=353.847ml/s.Production selects to measure the flow of 5s, then UWater
=1390ml/5s, UHave=1770ml/5s.Sample analysis after extracting 2 hours, raffinate In
0.010g/l,Sn 0.55g/l。
2# machine back extraction: a. back extraction indium: back extraction uses the hydrochloric acid of 8N to carry out comparing 10:1
5 grades of back extractions, anti-indium salts acid flow 170ml/5s, obtain high indium low stannum reversal indium liquid, this is anti-
Extraction liquid In 89g/l, Sn 28g/l；B. back extraction stannum: containing 60% in organic facies after back extraction indium
Stannum, for this use about 8N HF solution carry out 3 stage countercurrent back extraction stannum, back extraction is compared
20:1, HF liquid inventory is 90ml/5s, anti-tin liquor Sn 42.5g/l.
3# machine: 3# machine extraction stock solution preparation: 2# machine reversal indium liquid mixes with 3# machine reversal indium liquid 1:1
After allocate into again 20% clear water, acidity Control at about 0.8N, In 48g/l, Sn 15g/l,
Fe 16.8g/l, uses tributyl phosphate (TBP) to carry out extract and separate.Extraction phase ratio and stream
Amount control method and 1# machine extraction phase are same, 3# machine mixing chamber volume V=60L, t=4 minute, TBP
Saturated capacity is pressed 10g/l and is calculated.Through 4 grades of extraction of tin, raffinate In 46g/l, Sn 1.8g/l,
Fe 7g/l, this high indium liquid enters remove impurity operation and purifies.
Indium back extraction uses 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, reversal indium liquid returns after mixing with 2# machine reversal indium liquid joins
Liquid before TBP processed extraction；After back extraction indium organic facies possibly together with 60% stannum, then to TBP organic facies
Using dilute HF solution to carry out 4 grades of back extraction stannum, 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: take the remaining liquid 5.1m of TBP extraction3, In 46g/l, Sn 1.8g/l,
Fe2+7g/l, adds 150kg sheet alkali and regulates solution PH to 2.5, stirring reaction 20min
After be slowly added to hydrogen peroxide, hydrogen peroxide addition is 50kg, treats that hydrogen peroxide adds to solution colour
No longer reddening, 50kg sheet alkali is added water furnishing aqueous alkali by stable reaction 10-20min, fills in groove
Add hydrogen peroxide with a small amount of liquid of filter-cloth filtering after solution PH is adjusted to 2.5 and be measured Fe2+,
No longer the redden amount of then hydrogen peroxide of supernatant is enough.Continue solution after stirring reaction 30min
PH no longer changes, and can carry out solid-liquor separation, the scum 50kg, In 3.3% after filtration, Sn
21.55%, H2O 20%, need to return to leaching post and use.Filtrate 5.3m3, In 44g/l, Sn
< 0.1g/l, Pb 0.16g/l is positioned in storage tank and carries out autoprecipitation extremely for 0.099g/l, Fe
Second day.
B. precipitation of indium removes zinc cadmium: except indium liquid high after ferrum is after the autoprecipitation of more than 18h, pump
Entering heavy indium groove, volume is 5.3m3, add 225kg sheet alkali regulation pH value to 5.0, stirring reaction
Solid-liquor separation is carried out after 20min.High indium slag after solid-liquor separation adds appropriate hydrochloric acid and dissolves,
The PH of molten indium liquid controls about 1.0 to ensure suitable displacement reaction acidity.Isolated
Low indium liquid In 0.005g/l then can be emitted into wastewater trough and process.
C. zinc dust precipitation is except slicker solder: molten indium liquid 1.2m3, In 193.55g/l, Sn
0.21g/l,Pb 0.54g/l,Fe 0.12g/l.Slowly it is sprinkled into 8kg zinc powder, treats that it reacts
After 30min, open stirring, 18 hours response time.Solid-liquor separation, filtering residue uses hydrochloric acid
Rear Returning process is dissolved in immersion.Liquid In192.68g/l after zinc powder remove impurity, Sn 0.087g/l, Pb
0.0.097g/l, Fe < 0.1g/l enters thick indium remove impurity operation.
D. thick indium plate is heated remove impurity: after zinc powder remove impurity, liquid enters thick indium deblending slot, and it is qualified to add
Thick indium plate is carried out heating remove impurity, temperature 50 C, 48 hours response time.Liquid after thick indium remove impurity
In 193.2g/l, Sn 0.029g/l, Pb 0.0.089g/l, Fe < 0.1g/l.
(4) thick indium is produced:
1.2m3After thick indium remove impurity, liquid adds 90kg aluminium sheet replacement extraction sponge indium, replaces temperature 60
About DEG C.20 hours response time, reaction end solution I n0.005g/l.The sponge pulled out
Indium is through the acid rinsing Al of PH1.53+After carry out briquetting operation, H after briquetting2O < 5%, sponge
After indium briquetting, weight is 248kg, with the mouse cage that feeds intake slowly put into molten have 65kg sodium hydroxide,
4kg sodium nitrate, 4kg sodium sulfide melting pot in carry out melting, smelting temperature about 220 DEG C.
Melting takes the dish out of the pot after stirring remove impurity reaction 30min after completing, and is first scooped out by upper strata alkali liquor, then
Bottom indium liquid is scooped out the remove impurity operation carrying out glycerol adding, ammonium chloride for the first time, treats that indium liquid is whole
Transfer to fireless cooker carries out second time glycerol adding, the operation of ammonium chloride remove impurity again.After remove impurity
Indium liquid i.e. can be cast, and finally gives 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, wrap up with filter paper, and put 758 filter bags and avoid
The earth of positive pole enters electrolyte.Tankage: each sulculus loads 12 pieces of positive plates, 13 pieces of minus plates.
Electrolyte is In2(SO4)3、H2SO4System, bath composition: In3+ 75g/l,Cl- 66g/l,
Gelatin 0.6g/l, observes precipitation indium during being electrolysed, and separates out indium and a large amount of burrs occurs
Then require supplementation with gelatin；Electrolyte PH 2.0～2.5, current intensity 140A；Electrolyte temperature
25～30 DEG C；Electrolysing period is 7 days.After being electrolysed, yin, yang pole plate is carefully taken out, point
Not being carried out, in cathode titanium plates, output separates out indium in a large number, and this part separates out after indium is peeled off and needs to adopt
Be filtered dry moisture by clean water the most afterwards and can carry out founding, fusion-casting process need add glycerol and
Ammonium chloride carries out twice stirring remove impurity, can carry out ingot casting, indium ingot matter after dragging for the scum silica frost on surface
Amount controls at about 500g, and final smart indium yield 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 is through washing
Remove to re-start after the earth of positive pole and add alkali fusion and be cast as qualified thick indium plate electrolysis and use, the earth of positive pole
Returning process, it is clean that 758 filter bags use dilution heat of sulfuric acid to soak 2 days post rinses after over cleaning,
Use after drying.
Embodiment 2:
1. leach
Note: this example be whole production system properly functioning in creation data, wherein use
Two immersion In 3.92g/l, Sn 12.65g/l, three immersion In 1.69g/l, Sn 7.35g/l
For existing liquid storage；
One section of leaching:
Note: operation is all with example 1, raw material composition difference.
1.5m3Clear water, as leaching bottom water, adds 1.6m3Hydrochloric 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%.The ferrum of slag PH2.5 remove impurity in the middle of adding
Slag 320kg (weight in wet base) In 8.46%, Sn 10.21% moisture 26.3%, adds two immersion In
3.92g/l, Sn 12.65g/l, to volume ratio 6:1, adds 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%, H2O 20.32% carries out two-stage nitration leaching, filtrate
14.5m3, In 18.17g/l, Sn 20.89g/l, enter acid adjustment groove acid adjustment.
Two-stage nitration leaches:
Two immersion troughs add 1.5m3Three stages acid leach liquid In 1.69g/l, Sn 7.35g/l is the end of as
Water, puts into 1136kg (weight in wet base) leaching slag, adds 0.2m3Hydrochloric acid, fills into three immersion extremely
Volume ratio is 5:1, carries out filter pressing after reacting 4 hours.Two immersion 5m3, In 3.90g/l,
Sn 11.03g/l.Two leaching slag weight in wet bases 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
Entering sheet alkali 45kg, 30kg sodium nitrate is uniformly mixed.
Three stages acid leach:
Add 1.5m3Clear water make bottom water, add 1.1m3Hydrochloric acid.Slowly put into 1186.6kg (wet
Weight) oxidation two leaching slag In 7245.6g/t, Sn 3.2%, H2O 7.34%..Volume ratio is 4:1,
Add 50kg reduced iron powder.3 hours response time.Three immersion volume 5m3, In 1.42g/l,
Sn 6.14g/l, returns two-stage nitration and leaches use.Three leaching slag weight in wet bases 522kg, In 1921.8g/t, Sn
1.02%, H2O 15.8% puts in storage and deposits.
2. extraction:
PH1.5 acid adjustment
One immersion 14.5m3, In 18.17g/l, Sn 20.89g/l.Enter acid adjustment groove acid adjustment,
Add sheet alkali 120kg, concentrated sulphuric acid 23kg, acid adjustment liquor ratio weight 1.08g/cm3.Volume 22m3,
In 11.81g/l, Sn 10.49g/l, filtering 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) as extraction
Agent carries out 4 stage countercurrent extractions.Through calculating the flow measuring 5s, then UWater=1325ml/5s,
UHave=1841ml/5s.Extractive reaction is sample analysis after 2 hours, raffinate In 0.008g/l, Sn
0.45g/l。
2# machine back extraction: a. back extraction indium: strip liquor In 85g/l, Sn 30.1g/l；b.
Back extraction stannum: anti-tin liquor Sn 45.3g/l.
3# machine: use tributyl phosphate (TBP) to carry out extract and separate, liquid In before extraction
43.2g/l, Sn 16.5g/l, Fe 15.6g/l.Raffinate In 41.9g/l, Sn 1.95g/l,
Fe 8.2g/l, this high indium liquid enters remove impurity operation and purifies.
Indium back extraction: reversal indium liquid In 3.4g/l, Sn 17.6g/l, back extraction stannum: anti-tin liquor In
0.03g/l, Sn 13g/l.
(3) purification of high indium liquid:
A. iron removal by oxidation: high indium liquid 4.8m3, In 41.9g/l, Sn 1.55g/l, Fe 8.2g/l,
Addition 225kg sheet alkali, hydrogen peroxide 85kg, solid-liquor separation, scum 56kg, In 9.53%,
Sn 16.91%, H2O 22.5%, returns and leaches use.Filtrate 5.1m3, In 38.62g/l,
Sn 0.025g/l, Fe 0.06g/l, Pb 0.14g/l, is positioned in storage tank second day and adds alkali
Heavy indium.
B. precipitation of indium removes zinc cadmium: except indium liquid high after ferrum amasss 5.1m3, add the regulation of 130kg sheet alkali
PH value is to 5.0.Solid-liquor separation, high indium slag adds dissolving with hydrochloric acid, and molten indium enters zinc dust precipitation remove impurity
Groove, isolated low indium liquid In 0.008g/l, it is emitted into wastewater trough and processes.
C. zinc dust precipitation is except slicker solder: molten indium indium liquid 1m3, In 196.961g/l, Sn
0.13g/l,Pb 0.42g/l,Fe 0.10g/l.Addition 8kg zinc powder remove impurity, solid-liquor separation,
Filtering residue soak with hydrochloric acid dissolves rear Returning process.Liquid In 196.52g/l, Sn after zinc powder remove impurity
0.056g/l,Pb 0.0.037g/l,Fe<0.1g/l。
D. thick indium plate is heated remove impurity: after zinc powder remove impurity, liquid enters thick indium deblending slot, adds thick indium
Plate carries out displacement remove impurity of heating, temperature 50 C, 48 hours response time.Liquid after thick indium remove impurity
In 197.55g/l, Sn 0.011g/l, Pb 0.0.045g/l, Fe 0.05g/l.
(4) thick indium is produced:
1.1m3After thick indium remove impurity, liquid adds 105kg aluminium sheet, reaction temperature about 60 DEG C.Reaction
18 hours time, reaction end solution I n0.005g/l.After briquetting, weight is 228kg, throws
Enter to melt in the melting pot having 75kg sodium hydroxide, 5kg sodium nitrate, 5kg sodium sulfide and carry out melting,
Smelting temperature about 220 DEG C.Twice glycerol adding, the operation of ammonium chloride remove impurity 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, current intensity 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. the method preparing high purity indium with multi-metal complex height indium height stannum material, comprises the following steps:
(1) room temperature leaches: divides three sections and leaches:
One section of leaching: putting into multi-metal complex height indium height stannum 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 response time is 4 hours, liquid
Gu separate, leachate enters pH1.5 acid adjustment, and leached mud carries out two-stage nitration leaching；
Two-stage nitration leaches: putting into one section of leached mud, leaching solvent is hydrochloric acid and water, and liquid-solid volume ratio is 5:1,
Beginning acid 4～6mol/l, acid 3～5mol/l, in 4 hours response time, carries out solid-liquor separation eventually；Leach
Liquid returns and puts into one section of leaching, and leached mud enters slag field and carries out autoxidation；
Autoxidation: two-stage nitration leached mud enters slag field, after adding NaOH and NaNO3 mix homogeneously, oxygen
Change 1～2 months；
Three stages acid leach: put into the two-stage nitration leached mud through autoxidation, leaching solvent hydrochloric acid and water, acid of beginning
Concentration 10mol/l, whole acid concentration 4～6mol/l, liquid-solid volume ratio 4:1, react 4 hours, liquid-solid point
From, leachate returns and does two-stage nitration leaching, and leached mud warehouse-in is deposited；
(2) extract and separate Enrichment Indium stannum:
I. acid adjustment: take one section of leachate, adds sheet alkali by solution acidity regulation to pH 1.5；Keep
PH is constant, adds the sour water of pH 1.5 by gravity regulation to 1.08g/cm3；
II. extraction:
1# machine extracts: take step I. acid adjustment gained pH 1.5, proportion 1.08g/cm3Solution, use
Two-2 ethylhexyl phosphates carry out 4 stage countercurrent extractions as extractant；
The organic facies and aqueous phase flow started shooting is calculated with extraction time, after start runs 2 hours according to comparing
In, Sn content of the remaining liquid of sample analysis extraction, further according to In, Sn content situation pair in the remaining liquid of extraction
Flow is adjusted；Concrete computing 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 back extraction: a. back extraction indium: back extraction uses the hydrochloric acid of 7～10N to carry out comparing the 5 of 10:1
Level back extraction, obtains the strip liquor of the low stannum of high indium, and this strip liquor enters the extraction of 3# machine, and organic facies contains 60%
Stannum, enter stannum strip stages；B. back extraction stannum: back extraction stannum use 8N HF solution carry out 3 grades inverse
Flowing back extraction, 20:1 is compared in back extraction, and anti-tin liquor enters stannum abstraction process, and organic facies is unloaded organic facies, returns
Return 1# machine to extract；
3# machine: 2# machine back extraction indium liquid uses tributyl phosphate to extract after the regulation of acidity and concentration
Separating, before TBP extraction, liquid acidity controls at 0.8N；Extraction phase extracts than with flow control methods and 1# machine
Identical, 3# machine mixing chamber volume V=60L, t=4 minute, TBP saturated capacity was pressed 10g/l and is calculated；Pass through
4 grades of extractions, stannum enters organic facies, and indium is stayed in the remaining liquid of extraction, it is achieved that efficiently separating of indium stannum；TBP
The remaining liquid of extraction is rich indium liquid, enters remove impurity operation and processes, and TBP saturated organic phase carries out the back extraction of indium；Indium
Back extraction use the dilute hydrochloric acid solution of 0.6N to carry out 3 grades of back extractions, indium is by whole back extractions, and the stannum of 40% is simultaneously
Entered in reversal indium liquid by back extraction, return for this reversal indium liquid before preparing TBP extraction after mixing with 2# machine reversal indium liquid
Liquid；Organic facies after back extraction indium, possibly together with the stannum of 60%, then carries out 4 grades of dilute HF solution to TBP organic facies
Back extraction stannum；Unloaded TBP organic facies returns extraction section, and anti-tin liquor enters the abstraction process of stannum；
(3) purification of high indium liquid:
A. iron removal by oxidation: high indium liquid addition sheet adjusting PH with base is to 2.5, and 20min is reacted in stirring, is slowly added to
Hydrogen peroxide；Treat that solution colour no longer reddens, add aqueous alkali after stable reaction 10～20min and pH value of solution is adjusted
Hydrogen peroxide detection Fe is added after 2.52+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 filtering residue, need to return leaching and use；Supernatant then places 18～20
Remove impurity is carried out after hour；
B. precipitation of indium removes zinc cadmium: except indium liquid high after ferrum adds alkali regulation pH value to 5.0 hydrolytic precipitation indiums, liquid
Gu separate, isolated low indium liquid is emitted into wastewater trough and processes, and high indium slag adds hydrochloric acid and dissolves, molten
The pH of indium liquid controls 1.5；
C. zinc dust precipitation removes slicker solder: zinc powder is slowly sprinkled in molten indium liquid, after its reaction 30min, opens
Open stirring to react, stirring reaction 10 hours；Solid-liquor separation, after filtering residue uses soak with hydrochloric acid to dissolve
Returning process, filtrate carries out thick indium remove impurity operation；
D. thick indium plate is heated remove impurity: the filtrate after zinc powder remove impurity adds thick indium plate and carries out displacement of heating
Remove impurity, heating-up temperature 50 DEG C, 48 hours response time；
(4) thick indium is produced:
Low impurity height indium liquid enters displacement slot and carries out aluminium sheet replacement extraction sponge indium, and reaction temperature is maintained at 60
DEG C, the response time > 10 hours, reaction end solution I n content is less than 10mg/l；Sponge indium is through pH1.5
Acid rinsing, carry out briquetting, after briquetting, moisture < 5%, Weighing, with feeding intake, slowly throw by mouse cage
Enter to melt melting in the melting pot having sodium hydroxide, sodium nitrate, sodium sulfide, smelting temperature 220 DEG C；Melting
Take the dish out of the pot after stirring remove impurity reaction 30min after completing, after taking the dish out of the pot, carry out twice glycerol, ammonium chloride remove impurity operation；
After remove impurity, indium liquid i.e. can be cast；
(5) thick indium electrolysis: thick indium is cast into thick indium plate, carries out once electrolytic, i.e. obtain 99.999%
High-purity indium.
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| CN105018752B (en) * | 2015-07-27 | 2017-12-22 | 昆明理工大学 | A kind of method of separation and concentration and recovery indium in solution of indium from low-concentration sulfuric acid |
| CN105861813B (en) * | 2016-04-11 | 2017-10-24 | 马关云铜锌业有限公司 | A kind of processing method for making indium slag easily broken |
| CN106757157B (en) * | 2016-12-12 | 2018-09-25 | 贵州宏达环保科技有限公司 | One kind recycling thick indium method from indium purification slag |
| CN110055432A (en) * | 2019-04-06 | 2019-07-26 | 柳州呈奥科技有限公司 | A kind of phosphide material extraction processing oxidative slagging method |
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