A kind of method that Pb, In, Ag are extracted from lead smelting gas containing indium
The present invention relates to the methods of wet underwater welding metallic compound, and in particular to a kind of extraction Pb from lead smelting gas containing indium,
The method of In, Ag.
The valuable metals such as Zn, In, Pb are extracted from containing the relatively low material of the grades such as zinc, indium, lead, silver, generally require first to lead to
Cross rotary kiln and carry out reduction-oxidation calcination process, make valuable metal obtain volatilizing and enriching and with the element sepatations such as iron, silicon, calcium, have
Valency metal Zn, In, Pb overwhelming majority form oxide and enter bag collection system, then are removed by neutral leaching-purification of leaching liquor
Electrolytic separation extraction zinc is carried out after miscellaneous, by neutrality leaching the indium in slag is made further to be enriched with, then carries out sulfuric acid leaching again
Go out the In and neutral remaining Zn of leaching, acid leaching solution is extracted by P204, HCl back extraction separation and Extraction In, and acidic leaching residue is
For containing Pb40~55%, In300~600g/t, Ag150~400g/t lead smelting gas.Due to being leached by H2SO4 twice,
Lead in the lead smelting gas is most of with PbSO4Form exists, and with the presence of on a small quantity in the form of PbS, and the oxide of In substantially can
By H2SO4It leaches, but InS cannot be by H2SO4It leaches, therefore the indium in lead smelting gas exists substantially in the form of InS.Why should
It is to have part indium to be combined the InS that generation is easy to volatilization with sulphur in the process because of rotary kiln calcination also containing higher indium in lead smelting gas,
And reducing roasting process needs to add in coal as reducing agent, sulphur unavoidably also certain in coal, in addition also containing in raw material
Certain sulphur, therefore, material unavoidably have InS, PbS, ZnS sulfides by rotary kiln reduction roasting and generate, so as to
The rate of recovery for causing indium is relatively low, and the indium content in lead smelting gas is higher.
Indium belongs to rare metal, has very big economic value and use value, and global indium resource is deficienter, ore deposit
Produce amount is few, also very scattered.And not only containing Pb and Ag in the lead smelting gas, also containing substantial amounts of indium, therefore, to the lead smelting gas
In indium further fully recycling be very it is necessary to and have very much an economic value.Traditional smelting process of lead smelting gas
For pyrometallurgical smelting, with retailoring of blast furnace lead, silver is also reduced to metallic state and enters form pb-ag alloy in lead bullion, then leads to
Electrorefining lead separation lead and silver are crossed, this method can carry lead well, but the rate of recovery of silver is not high, there is part silver and major part
Indium enters in clinker and is difficult to recycle, and causes the waste of rare precious metal resource, and pyrometallurgical smelting of lead causes serious pollution to the environment, energy consumption
Height, precious and rare metals recovery rate are low；Secondly, existing most of productions are using floatation processing lead smelting gas elder generation separation and Extraction silver, then with fiery
Method extracts lead, and this method is all more satisfactory to the extraction of metallic lead and precious metals silver, but is not suitable for containing rare precious metal indium
Lead smelting gas, indium cannot recycle preferably, can cause the waste of resource；Also it is exactly to be leached using pressure oxidation, by adding
Pressure Oxidation Leaching can make ZnS and InS sulfides in material Zn and In therein be made to obtain fully leaching back by Oxidation Leaching
It receives, indium content is naturally relatively low in leached mud, then recycles lead and silver by the method for other smelting lead smelting gas again, and this method is ratio
Comparatively ideal recovery method can be such that Zn and In is disposably fully extracted, and obtain the higher lead smelting gas of grade, but pressurize
Oxidation Leaching is big there are equipment investment, height is required to equipment, technical staff, the defects of being difficult to carry out, apply for medium-sized and small enterprises.
The present inventor provides a kind of method that Pb, In, Ag are extracted from lead smelting gas containing indium by substantial amounts of experiment and research therefore.
The content of the invention
In order to solve the above technical problems, the present invention provides a kind of methods that Pb, In, Ag are extracted from lead smelting gas containing indium.
The present invention is achieved by the following technical programs：
A kind of method that Pb, In, Ag are extracted from lead smelting gas containing indium, this method comprise the following steps：
A, Pb is extracted：Indium lead smelting gas NH will be contained4F solution is washed, and cleaning solution, which returns, to be recycled, molten using NaOH
Liquid carries out washed-residue alkaline leaching Pb, then electrolytic lead is carried out to leachate and handles to obtain lead sponge, lead sponge by briquetting, molten
Casting handles to obtain lead pig, and electrolyte returns to secondary NaOH alkaline leachings Pb, and secondary leachate is returned once to leach and used；
B, In is extracted：By step a neutral and alkali leached muds H2SO4Solution leaches In, and leachate is molten using P204 extractions, HCL
Liquid back extraction extraction In, leaching indium slag are spare；
C, Ag is extracted：Leaching indium slag in step b thiourea solution is leached into Ag, leachate hydrazine hydrate reduction obtains gold
Belong to Ag.
NH in the step a4F solution washing lead smelting gas containing indium L/S=6-10, NH4F additions be 10-20g/L, temperature control
70-80 DEG C is made as, time 1-2h.
Alkaline leaching Pb, an alkaline leaching liquid L/S=4- are carried out to washed-residue using NaOH solution in the step a
6, NaOH dosages are 250-300g/L, and temperature is 85-90 DEG C, time 2-3h, secondary alkaline leaching liquid L/S=6-10, NaOH
For 200-250g/L, temperature is 80-90 DEG C, time 3-5h.
Electrolytic lead processing is the pole span 80mm using stainless steel plate as electrolytic negative/positive plate in the step a, and tank voltage is
1-1.5V, current density 150-200A/m2, electrolysis temperature is 20-50 DEG C.
Electrolyte in the step a contains Pb10-20g/L.
The step b neutral and alkali leached muds H2SO4Solution leaches In, L/S=5-8, H2SO4For 150-100g/L, temperature
It spends for 80-90 DEG C, time 3-5h.
Indium slag is soaked in the step c and leaches its L/S=5-8 of Ag with thiourea solution, PH 1-1.5, the concentration of thiocarbamide is 20-
30g/L urea is 3-5g/L, and temperature is 50-60 DEG C, extraction time 5-8h.
The beneficial effects of the present invention are：The present invention is using Pb, In, Ag in Whote-wet method extraction lead smelting gas containing indium, containing indium
Lead smelting gas first uses NH4F solution washs, and mainly washs the H in lead smelting gas2SO4, the dosage of NaOH during reducing alkaline leaching Pb,
And also contain 3~10% SiO in lead smelting gas2, no matter all there can be part SiO2 to be leached shape in acidic leaching or alkaline leaching
Into the silicic acid of colloidal, silicic acid can influence the strainability of leaching slurry, and SiO2 can also wrap up valuable metal make its be difficult to by
It leaches, by adding in NH4F makes in solution that there are H+And F+, so as to destroy SiO2, the valuable metal of package is released,
Leaching slurry strainability can also be improved simultaneously, improve production efficiency, cleaning solution can also return to recycling；Through NH4F solution is washed
Lead smelting gas containing indium after washing carries out alkaline leaching Pb with NaOH solution, and leachate carries out electrolysis lead sponge, and lead sponge is through briquetting, molten
Casting obtains lead pig, and electrolysis Pb raffinates return to alkaline leaching and use；Lead smelting gas containing indium is through alkaline leaching twice, not only separation and Extraction
Metallic lead, while make to stay in the In in slag and Ag is further enriched with, and the InS ingredients in slag are anti-with NaOH at high temperature
The alkali formula indium compound for being soluble in acid should be generated, is contained so as to leach-extract stripping method separation and Extraction by conventional acid
In in indium lead smelting gas；In leached muds leach Ag with thiourea solution again, and leachate extracts metal Ag with hydrazine hydrate reduction, in this way,
Pb, In, Ag in lead smelting gas containing indium just can obtain efficiently, fully recycle, and the present invention will contain indium lead smelting gas and first use NH4F
Solution washs, and can not only remove remaining H in slag2SO4, the consumption of NaOH during reducing next step alkaline leaching Pb, additionally it is possible to
Destroy SiO2, the leaching rate of valuable metal Pb, In, Ag are improved, while Si formation can also be made to be easy to the H filtered2SiF6, so as to reach
To the strainability for improving leaching slurry；Lead smelting gas containing indium after washing first carries out alkaline leaching separation and Extraction Pb, and leached mud is again
Acidic leaching separation and Extraction In is carried out, since the In in lead smelting gas is substantially InS, is difficult to leach In by acidic leaching, and
InS ingredients can react the alkali formula indium compound that generation is soluble in acid with NaOH at high temperature while alkaline leaching Pb is carried out,
Extraction indium can be easily separated by acidic leaching again；Lead smelting gas containing indium will not be leached to reach through During alkaline leaching Pb
To the enrichment of In, and acidic leaching In can be such that Ag stays in slag is further enriched with, and In contents can obtain more than twice
Enrichment, Ag contents can obtain enrichments more than three times, so as to reduce production cost when extracting In and Ag；The present invention will contain indium
Sulfuric acid lead skim is fully recycled by recycling valuable metal Pb, In, Ag, to resource, not only has very high economic value, together
When also avoid pollution of the lead smelting gas to environment.
Description of the drawings
Fig. 1 is present invention process flow chart
Technical scheme is further described with reference to the accompanying drawings and embodiments, but claimed scope is simultaneously
It is not limited to described.
By original of a batch containing zinc 11.28%, Pb3.51%, Fe12.47%, Si15.83%, In652g/t, Ag273g/t
Material obtains cloth bag powder after rotary kiln reduction-oxidation roasting volatilization, and what is obtained after sulfuric acid leaching separation and Extraction Zn, In twice contains
Indium lead smelting gas, chemical composition are：Pb45.04%, In356g/t, Ag279g/t, Zn 2.15%, Fe 1.14%, Si
4.36%, contain indium lead smelting gas with this and carry out alkaline leaching Pb：200g lead smelting gas containing indium is taken, by liquid-solid ratio L/S=4, leachate
(=250g/L, 85 DEG C of temperature, mixing time 2h carry out primary alkali leaching to NaOH；Leached mud is again by L/S=8, leachate
(=250g/L, 85 DEG C of temperature, mixing time 3h carry out 2 leachings to NaOH.One time leachate (1000mL) content is：
Pb58.7g/L, Zn2.65g/L, In are without content；Secondary leachate (800mL) content is：Pb14.3g/L、Zn1.04g/L；It is secondary
Leached mud (81.5g) content is：Pb17.32%, In847g/t, Ag652g/t, Zn 1.17%；Leaching rate (slag meter)：
Pb84.33%, Zn77.82%；The alkaline leaching rate of filtration is all slow twice.
Electrolysis Pb is carried out using an alkali immersion liquid (1000mL) in embodiment one, electrolytic condition is：Using stainless steel plate as
Cathode-anode plate, pole span L=80cm, tank voltage 1.2V, current density 150A/m2, 35 DEG C of electrolysis temperature, electrolysis time 8h；
Lead sponge 43.2g is electrolysed, residual electrolyte contains Pb16.4g/L.
NH is first carried out using lead smelting gas containing indium in embodiment one4F solution washs, and slag presses the condition alkaline leaching of example 1 again
Pb, NH4F solution wash conditions are：Liquid-solid ratio L/S=6, NH4F additions be 10g/L, temperature 70 C, mixing time 1h, washing
Liquid contains H2SO48.54g/L、Zn1.34g/L、In 9.6mg/L；Secondary alkaline leaching slag (71.4g) content is：Pb12.17%,
In914g/t, Ag703g/t, Zn 1.05%；Leaching rate (slag meter)：Pb90.35%；The alkaline leaching rate of filtration is very fast twice.
NH is first carried out using lead smelting gas containing indium in embodiment one4F solution washs, and NH is added with cleaning solution in example 34F is extremely
20g/L is washed：Liquid-solid ratio L/S=8,80 DEG C of temperature, mixing time 2h；Cleaning solution contains H2SO412.05g/L、Zn2.18g/
L、In 13.7mg/L；Washed-residue carries out alkaline leaching Pb：By liquid-solid ratio L/S=6, leachate NaOH (=300g/L, temperature 90
DEG C, mixing time 3h carry out primary alkali leaching；Leached mud is again by L/S=6, leachate NaOH (=200g/L, temperature 80
DEG C, mixing time 4h carry out secondary leaching.One time leachate (1100mL) content is：Pb62.4g/L, Zn1.92g/L, secondary leaching
Going out liquid (600mL) content is：Pb21.6g/L, Zn1.52g/L, secondary leached mud (63.1g) content are：Pb10.64%,
In946g/t, Ag732g/t, Zn 0.85%；Leaching rate (slag meter)：Pb 92.54%
Use in example four an alkali immersion liquid by tank voltage for 1.4V, current density 200A/m2, 45 DEG C of electrolysis temperature,
Remaining condition carries out electrolysis Pb by embodiment two；Lead sponge 46.3g is electrolysed, containing Pb99.21%, residual electrolyte contains Pb14.2g/L.
Sulfuric acid leaching In is carried out using secondary alkaline leaching slag (50g) in example IV, leaching condition is：Liquid-solid ratio L/S
=5, H2SO4150g/L, 85 DEG C, mixing time 3h, leachate 0.25L of temperature, containing In165mg/L, In leaching rates (liquid meter) are
87.3%；Leached mud 35.65g, containing Ag1035g/t, then with thiocarbamide by liquid-solid ratio L/S=8, PH=1.0, thiourea concentration 25g/
L, urea 5g/L, temperature leach Ag, extraction time 6h, leached mud (31.84g), containing Ag118g/t, silver leaching rate for 55 DEG C
NH is added with cleaning solution in example IV using lead smelting gas containing indium in embodiment one4F to 15g/L is washed：Liquid
Gu than L/S=10,75 DEG C of temperature, mixing time 1.5h；Washed-residue carries out alkaline leaching Pb：By liquid-solid ratio L/S=5, leachate
(=300g/L, 85 DEG C of temperature, mixing time 3h carry out primary alkali leaching to NaOH；Leached mud is again by L/S=7, leachate
(=250g/L, 85 DEG C of temperature, mixing time 5h carry out secondary leaching to NaOH；Secondary leached mud (61.7g) content is：
Pb8.95%, In941g/t, Ag728g/t, Zn 0.85%；Leaching rate (slag meter)：Pb 93.87%；Leached mud presses liquid-solid ratio L/
S=8, H2SO4200g/L, temperature 90 DEG C of acidic leaching In, mixing time 4h, In leaching rate (liquid meter) are 92.37%；Leached mud
It is again 60 DEG C of leaching Ag by liquid-solid ratio L/S=6, PH=1.5, thiourea concentration 30g/L, urea 3g/L, temperature, extraction time is
8h, leached mud contain Ag97g/t, silver leaching rate 92.57%.
NH is carried out using lead smelting gas containing indium in embodiment one successively respectively by seven conditional of embodiment4The washing of F solution, NaOH
Leach Pb, H2SO4In, thiocarbamide leaching Ag are leached, Pb, In, Ag leaching rate respectively reach 93.25%, 94.37%, 90.08%.