A kind of method extracting Pb, In, Ag from lead smelting gas containing indium
The present invention relates to the method for wet underwater welding metallic compound and in particular to one kind extract from lead smelting gas containing indium Pb,
The method of In, Ag.
Extract the valuable metal such as Zn, In, Pb from the material relatively low containing 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 sepatation such as ferrum, silicon, calcium, have
Valency metal Zn, In, Pb overwhelming majority forms oxide and enters bag collection system, then is removed by neutral leaching-purification of leaching liquor
Carry out electrolytic separation after miscellaneous and extract zinc, so that the indium in slag is enriched with further by neutral leaching, then carry out sulphuric acid leaching again
Go out the In and neutral Zn leaching residual, acid leaching solution is extracted by P204, HCl back extraction separation and Extraction In, acidic leaching residue is
Be containing Pb40～55%, In300～600g/t, Ag150～400g/t lead smelting gas.Due to leaching through H2SO4 twice, therefore
Lead major part in this lead smelting gas is with PbSO4Form exists, and with the presence of a small amount of with PbS form, and the oxide of In substantially can
By H2SO4Leach, but InS can not be by H2SO4Leach, therefore the indium in lead smelting gas is substantially existed with InS form.Why should
Also contain higher indium in lead smelting gas, have part indium to be combined with sulfur during being because rotary kiln calcination and generate the InS being easy to volatilize,
And reducing roasting process needs to add coal as reducing agent, unavoidably also have certain sulfur in coal, add in raw material and also contain
Certain sulfur, therefore, material unavoidably has InS, PbS, ZnS sulfides by rotary kiln reduction roasting and generates, thus
Cause the response rate of indium relatively low, the indium content in lead smelting gas is higher.
Indium belongs to rare metal, has very big economic worth and use value, and global indium resource is deficienter, ore deposit
Produce amount is few, also disperse very much.And in this lead smelting gas, do not contain only Pb and Ag, also contain substantial amounts of indium, therefore, to this lead smelting gas
In indium further fully reclaim extremely be necessary, be also to have very much economic worth.Traditional smelting process of lead smelting gas
For pyrometallurgical smelting, use retailoring of blast furnace lead, silver is also reduced to metallic state and enters formation pb-ag alloy in lead bullion, then leads to
Cross electrorefining lead separation lead and silver, the method can carry lead well, but the response rate of silver is not high, have partly silver-colored and most of
Indium enters in slag and is difficult to reclaim, and causes the waste of rare precious metal resource, and pyrometallurgical smelting of lead is big for environment pollution, energy consumption
Height, precious and rare metals recovery rate is low；Secondly, existing great majority produce and process lead smelting gas elder generation separation and Extraction silver using floatation, then with fiery
Method extracts lead, and the 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 preferably reclaim, and can cause the waste of resource；Also having is exactly to be leached using pressure oxidation, by adding
Pressure Oxidation Leaching can make ZnS the and InS sulfides in material oxidized leach so as in Zn and In fully leached back
Receive, in leached mud, indium content is naturally relatively low, then pass through other methods smelting lead smelting gas again and reclaim lead and silver, the method is ratio
Comparatively ideal recovery method, can make Zn and In disposably fully be extracted, and obtains the higher lead smelting gas of grade, but pressurization
There is equipment investment greatly in Oxidation Leaching, equipment, technical staff are had high demands, the defect such as is difficult to carry out, applies for medium-sized and small enterprises.
For this present inventor, a kind of method extracting Pb, In, Ag from lead smelting gas containing indium is provided by substantial amounts of experiment and research.
Content of the invention
For solving above-mentioned technical problem, the invention provides a kind of method extracting Pb, In, Ag from lead smelting gas containing indium.
The present invention is achieved by the following technical programs：
A kind of method extracting Pb, In, Ag from lead smelting gas containing indium, the method comprises the following steps：
A, Pb extract：Indium lead smelting gas NH will be contained4F solution is washed, and cleaning mixture returns and recycles, molten using NaOH
Liquid carries out alkaline leaching Pb to washed-residue, then leachate is carried out with electrolytic lead processes obtaining lead sponge, lead sponge through briquetting, molten
Casting processes and obtains lead pig, and electrolyte returns secondary NaOH alkaline leaching Pb, and secondary leachate returns once to leach and uses；
B, In extract：By step a neutral and alkali leached mud H2SO4Solution leaches In, and leachate adopts P204 extraction, HCL molten
In is extracted in liquid back extraction, and leaching indium slag is standby；
C, Ag extract：Leaching indium slag thiourea solution in step b is leached Ag, leachate hydrazine hydrate reduction obtains gold
Belong to Ag.
NH in described step a4F solution washs the L/S=6-10 of lead smelting gas containing indium, NH4F addition is 10-20g/L, temperature control
It is made as 70-80 DEG C, the time is 1-2h.
In described step a, alkaline leaching Pb is carried out to washed-residue using NaOH solution, its alkaline leaching liquid L/S=4-
6, NaOH consumptions are 250-300g/L, and temperature is 85-90 DEG C, and the time is 2-3h, secondary alkaline leaching liquid L/S=6-10, NaOH
For 200-250g/L, temperature is 80-90 DEG C, and the time is 3-5h.
In described step a, electrolytic lead is processed is using corrosion resistant plate as electrolytic negative/positive plate, and pole span is 80mm, and tank voltage is
1-1.5V, electric current density is 150-200A/m2, electrolysis temperature be 20-50 DEG C.
Electrolyte in described step a contains Pb10-20g/L.
Described step b neutral and alkali leached mud H2SO4Solution leaches In, its L/S=5-8, H2SO4For 150-100g/L, temperature
Spend for 80-90 DEG C, the time is 3-5h.
In described step c, leaching indium slag leaches its L/S=5-8 of Ag with thiourea solution, and PH is 1-1.5, and the concentration of thiourea is 20-
30g/L carbamide is 3-5g/L, and temperature is 50-60 DEG C, and extraction time is 5-8h.
The beneficial effects of the present invention is：The present invention adopts Whote-wet method to extract Pb, In, Ag in lead smelting gas containing indium, containing indium
Lead smelting gas first use NH4F solution washs, mainly the H in washing lead smelting gas2SO4, with the consumption of NaOH when reducing alkaline leaching Pb,
And in lead smelting gas, also contain 3～10% SiO2, no matter part SiO2 all can be had to be leached shape in acidic leaching or alkaline leaching
Become the silicic acid of colloidal, silicic acid can affect the strainability of leaching slurry, and SiO2 also can wrap up valuable metal make its be difficult to by
Leach, by adding NH4F makes to exist H in solution+And F+, such that it is able to destroy SiO2, so that the valuable metal of parcel is released,
Also leaching slurry strainability, improve production efficiency can be improved, cleaning mixture can also return recycling simultaneously；Through NH4F solution is washed
Lead smelting gas containing indium after washing carry out alkaline leaching Pb with NaOH solution, and leachate carries out being electrolysed lead sponge, and lead sponge is through briquetting, molten
Casting obtains lead pig, and electrolysis Pb residual liquid returns alkaline leaching and uses；Lead smelting gas containing indium are through alkaline leaching twice, not only separation and Extraction
Metallic lead, makes In and Ag staying in slag be enriched with further simultaneously, and the InS composition in slag is anti-with NaOH at high temperature
The alkali formula indium compound being soluble in acid should be generated, contain such that it is able to leaching-extracting stripping method separation and Extraction by conventional acid
In in indium lead smelting gas；In leached mud leaches Ag with thiourea solution again, and leachate extracts metal Ag with hydrazine hydrate reduction, so,
Pb, In, Ag in lead smelting gas containing indium just can get efficiently, fully reclaim, and the present invention will contain indium lead smelting gas and first use NH4F
Solution washs, not only can in eccysis slag residual H2SO4, with the consumption of NaOH when reducing next step alkaline leaching Pb additionally it is possible to
Destroy SiO2, improve the leaching rate of valuable metal Pb, In, Ag, Si can also be made simultaneously to form the H being easy to filter2SiF6, thus reaching
To the strainability improving leaching slurry；Lead smelting gas containing indium after washing first carry out alkaline leaching separation and Extraction Pb, and leached mud is again
Carry out acidic leaching separation and Extraction In, because the In in lead smelting gas is substantially InS, be difficult to leach In by acidic leaching, and
While carrying out alkaline leaching Pb, InS composition can be reacted with NaOH at high temperature and generate the alkali formula indium compound being soluble in acid,
Again extraction indium can be easily separated by acidic leaching；Lead smelting gas containing indium will not be leached thus reaching through During alkaline leaching Pb
To the enrichment of In, and acidic leaching In can make Ag stay in slag is enriched with further, and In content can get more than twice
Enrichment, Ag content can get the enrichment of more than three times, thus can reduce production cost when extracting In and Ag；The present invention will contain indium
Sulphuric acid lead skim passes through to reclaim valuable metal Pb, In, Ag, resource is fully reclaimed, not only has very high economic worth, with
When it also avoid the pollution to environment for the lead smelting gas.
Fig. 1 is present invention process flow chart
Below in conjunction with drawings and Examples, technical scheme is further described, but claimed scope is simultaneously
It is not limited to described.
By a collection of containing zinc 11.28%, Pb3.51%, Fe12.47%, Si15.83%, In652g/t, Ag273g/t former
Material, obtains cloth bag powder, obtain after sulfuric acid leaching separation and Extraction Zn, In twice contains after rotary kiln reduction-oxidation roasting volatilization
Indium lead smelting gas, its chemical composition is：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 is taken to contain indium lead smelting gas, 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；One time leached mud presses L/S=8, leachate again
(=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 no content；Secondary leachate (800mL) content is：Pb14.3g/L、Zn1.04g/L；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.
Carry out being electrolysed Pb using an alkali immersion (1000mL) in embodiment one, electrolytic condition is：Using corrosion resistant plate as
Cathode-anode plate, pole span L=80cm, tank voltage is 1.2V, and electric current density is 150A/m2, 35 DEG C of electrolysis temperature, electrolysis time 8h；
Electrolysis lead sponge 43.2g, residual electrolyte contains Pb16.4g/L.
First carry out NH 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 addition is 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.
First carry out NH using lead smelting gas containing indium in embodiment one4F solution washs, and adds NH with cleaning mixture in example 34F is extremely
20g/L is washed：Liquid-solid ratio L/S=8,80 DEG C of temperature, mixing time 2h；Cleaning mixture 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；One time leached mud presses L/S=6, leachate NaOH (=200g/L, temperature 80 again
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 is：Pb10.64%,
In946g/t, Ag732g/t, Zn 0.85%；Leaching rate (slag meter)：Pb 92.54%
Pressing tank voltage using an alkali immersion in example four is 1.4V, and electric current density is 200A/m2, 45 DEG C of electrolysis temperature,
Remaining condition is carried out being electrolysed Pb by embodiment two；Electrolysis lead sponge 46.3g, containing Pb99.21%, residual electrolyte contains Pb14.2g/L.
Sulfuric acid leaching In is carried out using alkaline leaching slag (50g) secondary in example IV, leaching condition is：Liquid-solid ratio L/S
=5, H2SO4150g/L, 85 DEG C of temperature, mixing time 3h, leachate 0.25L, containing In165mg/L, In leaching rate (liquid meter) is
87.3%；Leached mud 35.65g, containing Ag1035g/t, then is 25g/ with thiourea by liquid-solid ratio L/S=8, PH=1.0, thiourea concentration
L, carbamide 5g/L, temperature are 55 DEG C of leaching Ag, and extraction time is 6h, and leached mud (31.84g), containing Ag118g/t, silver leaching rate
NH is added using cleaning mixture in the example IV of lead smelting gas containing indium in embodiment one4F to 15g/L is washed：Liquid
Gu ratio 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；One time leached mud presses L/S=7, leachate again
(=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, 90 DEG C of acidic leaching In of temperature, mixing time 4h, In leaching rate (liquid meter) is 92.37%；Leached mud
Press liquid-solid ratio L/S=6, PH=1.5 again, thiourea concentration be 30g/L, carbamide 3g/L, temperature be 60 DEG C of leaching Ag, extraction time is
8h, leached mud contains Ag97g/t, silver leaching rate 92.57%.
Carry out NH using lead smelting gas containing indium in embodiment one by embodiment seven conditional respectively successively4The washing of F solution, NaOH
Leach Pb, H2SO4Leach In, thiourea leaches Ag, Pb, In, Ag leaching rate respectively reaches 93.25%, 94.37%, 90.08%.