CN104120273B - A kind ofly with precious metals containing lead be that raw materials recovery is plumbous, the method for silver and copper - Google Patents
A kind ofly with precious metals containing lead be that raw materials recovery is plumbous, the method for silver and copper Download PDFInfo
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- CN104120273B CN104120273B CN201410361740.8A CN201410361740A CN104120273B CN 104120273 B CN104120273 B CN 104120273B CN 201410361740 A CN201410361740 A CN 201410361740A CN 104120273 B CN104120273 B CN 104120273B
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Abstract
The present invention relates to a kind ofly with precious metals containing lead be that raw materials recovery is plumbous, the method for silver and copper, belong to the technical field that pyrogenic process and wet method combine.First by precious metals containing lead through vacuum distilling separation of lead, antimony, bismuth, copper, plumbous and your silver of output height bismuth; Obtain separating out lead after the plumbous electrolysis of high bismuth by plumbous for the high bismuth obtained, it is slightly silver-colored that your silver obtained carries out converter refining output, and obtain converter pre-slag and converter later stage slag according to the length of converter refining time; The thick galactic longitude silver electrolysis obtained is obtained silver ingot, the converter pre-slag obtained and converter later stage slag are crushed to granularity < 6mm respectively, and then to be finely ground into granularity be that the powder of below 100 orders obtains converter slag fine powder, then converter slag fine powder is added sulphuric acid soln to leach, after having leached, obtain leached mud and copper-bath.The processing technological flow of the method to precious metals containing lead material is improved, and has that technical process refining is succinct, energy-saving and cost-reducing, the effect of optimization production environment.
Description
Technical field
The present invention relates to a kind ofly with precious metals containing lead be that raw materials recovery is plumbous, the method for silver and copper, belong to the technical field that pyrogenic process and wet method combine.
Background technology
At present, the prior art reclaiming copper method from precious metals containing lead byproduct silver converter slag mainly contains: (1) sulfuric acid adds salt or hydrochloric acid carries out leaching recovery, its principle utilizes copper, bismuth metal is dissolved in the feature that in solution, other metal is insoluble, then the copper in solution will be entered, bismuth obtains copper bismuth slag through displacement, carry out recovery copper again, its process is first that converter slag is broken, be finely ground to the following powder of 100 order, again it is dropped into sulfuric acid with in the solution of salt by liquid-solid ratio 5 ~ 6:1, by mechanical stirring, keep extraction temperature 80 ~ 95 DEG C reaction 2 hours, obtain leach liquor caustic soda or soda ash solution and carry out neutralizing hydrolysis except bismuth, after hydrolysis, liquid iron replacement copper obtains copper sponge, displaced liquid send sewage plant process, copper sponge is through reducing molten output blister copper, the major defect of this method has waste water to produce, (2) nitric acid Leaching of Silver converter slag reclaims copper, its principle is all dissolved in salpeter solution by metals all in silver converter slag, then difference recover silver is carried out, plumbous, bismuth, the metals such as copper, its process is first that converter slag is broken, be finely ground to the following powder of 100 order, again it being dropped into concentration of nitric acid by liquid-solid ratio 5 ~ 6:1 is in the salpeter solution of 460 ~ 480g/l, by mechanical stirring, keep extraction temperature 60 ~ 65 DEG C reaction 2 hours, obtain leach liquor and carry out chlorination desilver with adding salt, plumbous, deleading, the rear liquid of silver adds caustic soda again or soda ash solution carries out neutralizing hydrolysis except bismuth, after hydrolysis, liquid iron replacement copper obtains copper sponge, this method defect has that waste water produces, nitric acid is expensive and volatile cost is higher, (3) recovery copper is carried out by the method for ammonia leaching-extraction-electrodeposition from silver converter slag, its process first silver converter is soaked through twice adverse current ammonia, the ammonia leaching solution obtained carries out two-stage extraction, the organic extract liquid obtained carries out one-level back extraction after washing, strip liquor carries out electrodeposition again and obtains electrolytic copper product, the defect of this method is that ammonia is volatile, electrolytic deposition process electrolytic solution steam output large, the higher production cost that causes of power consumption is higher, and flow process is more complicated.
Our company's precious metals containing lead adopts former flow process to be precious metals containing lead is directly dropped into converter to blow oxidation and cause slag and add the slag making of alkali deep oxidation and obtain silver converter slag and thick silver products, but in former flow process the silver converter slag of output exist leaded, bismuth is higher and production cost high shortcoming, need be alloy by the melting of silver converter slag, the step of alloy liquation decoppering could extract further copper in silver converter slag, silver products is obtained after the thick galactic longitude electrolysis obtained, the silver converter slag that former flow process obtains directly drops into reverberatory smelting output height bismuth alloy, high bismuth alloy in kier during liquation decoppering copper enter copper dross slag, obtain after high bismuth alloy electrolysis after refining separating out lead, the byproduct copper dross slag of separating out output in plumbous process enters the manufacture ice method of copper of reverberatory furnace and reclaims copper together with the copper dross slag of lead bullion liquation decoppering output, but reclaim plumbous in above-mentioned traditional process, the defect of silver and copper method is that cost recovery is high, the copper efficiency reclaimed is low, and in matte, argentiferous is high causes incidental losses.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides a kind ofly with precious metals containing lead be that raw materials recovery is plumbous, the method for silver and copper.The processing technological flow of the method to precious metals containing lead material is improved, have that technical process refining is succinct, energy-saving and cost-reducing, the effect of optimization production environment, from precious metals containing lead, the production cost of output silver converter slag process saves about 2037 yuan/ton of precious metals containing lead than former flow process, about 1500 yuan/tCu is saved than former flow process from the production cost of silver converter slag output copper products process, the production cost of silver products has saved 13580 yuan/tAg than former flow process, the production cost of plumbous product has saved 3395 yuan/tPb than former flow process, and the present invention is achieved through the following technical solutions.
Take precious metals containing lead as a method for raw materials recovery lead, silver and copper, its concrete steps are as follows:
Step 1: first precious metals containing lead is placed in vacuum oven, then controls that vacuum tightness is 10 ~ 20Pa, temperature is 940 ~ 960 DEG C, precious metals containing lead charging capacity is vacuum distilling separation of lead, antimony, bismuth, copper under 69 ~ 71g/s condition, plumbous and your silver of output height bismuth;
Step 2: high bismuth step 1 obtained is plumbous to be obtained separating out lead after the plumbous electrolysis of high bismuth, and it is slightly silver-colored that your silver that step 1 obtains carries out converter refining output, and obtain converter pre-slag and converter later stage slag according to the length of converter refining time;
Step 3: thick galactic longitude silver electrolysis step 2 obtained obtains silver ingot, the converter pre-slag that step 2 obtains and converter later stage slag are crushed to granularity < 6mm respectively, and then to be finely ground into granularity be that the powder of below 100 orders obtains converter slag fine powder, then converter slag fine powder is added sulphuric acid soln to leach, leached mud and copper-bath is obtained after leaching completes, leached mud should meet the standard that copper content should be less than 4wt.%, if leached mud closes when copper content is greater than 4wt.% should carry out multistage leaching until conformance with standard, obtain copper-bath and obtain residual solution and copper sulfate crystal after normal temperature cooling, residual solution returns leaching process and recycles.
Described precious metals containing lead comprises following mass percent component: Pb40 ~ 60%, Sb13 ~ 16%, Cu3 ~ 4%, Bi8 ~ 15%, Ag15 ~ 20%; The component of described converter pre-slag comprises following mass percent component: Pb3.8 ~ 30%, Sb5.5 ~ 25%, Cu16 ~ 40%, Bi < 8%, Ag6 ~ 12%; The component of described converter later stage slag comprises following mass percent component: Pb < 1%, Sb2 ~ 6%, Cu7 ~ 13%, Bi < 1.5%, Ag1 ~ 4.5%.
The plumbous electrolytic process of the high bismuth of described step 2 is specially: (1) adds 0.5 ~ 0.8kg/t in electrolytic solution
pbox glue, add 0.02 ~ 0.06kg/t
pb2-Naphthol is combined into new electrolytic solution; (2) in the new electrolytic solution be combined into, current density 183 ~ 190A/m is controlled
2, Pb in electrolytic solution
2+content 55 ~ 80g/l, free silica fluoric acid 90 ~ 120g/l, electrolyte temperature 38 ~ 45 DEG C, produces 72h under circulation of elecrolyte amount 22 ~ 27L/min condition in a cell.
Described step 2 converter refining process is specially: when the temperature in Converter reaches 1100 DEG C, drop into your silver in stove, keeps your silver of temperature 1100 ~ 1200 DEG C fusing, after your silver major part fusing, temperature is reduced to 900 DEG C, takes off slag clean; Keep melt temperature 850 ~ 950 DEG C to insert airduct table again and blow voloxidation slag making removal of impurities, duration of blast is 2 ~ 3 days, and the slag obtained that blows is converter pre-slag; After finishing blowing, liquation Ag grade is 85 ~ 95wt.%, furnace temperature is remained on 1100 ~ 1200 DEG C and carry out later stage slag making deep impurity-removing, add in liquation SODIUMNITRATE fully stir after-frame pipe blowing 2 ~ 3 hours after drain slag, repeat above operation, until sample examination is containing Ag > 98wt.%, during Cu < 1wt.%, thoroughly drain clean slag, obtain converter later stage slag and thick silver products.
The detailed process that in described step 3, the silver-colored electrolysis of thick galactic longitude obtains silver ingot is: thick silver is made positive plate and loads electrolyzer, at current density 200 ~ 250A/m
2, bath voltage 1.5 ~ 2.5V carries out electrolysis, controls Ag80 ~ 120g/l, HNO in electrolytic solution
34 ~ 10g/l, Cu≤40g/l, electrolyte temperature 35 ~ 45 DEG C, circulation of elecrolyte speed 0.8 ~ 1L/min, electrolysing period 96 hours, the silver powder of output argentiferous > 99.99wt.%; Silver powder, after washing and drying, drops into 105 ~ 115 ㎏ silver powder and keeps temperature 1200 DEG C to melt, drag for clean scum silica frost and maintain the temperature at 1200 DEG C and carry out ingot casting, obtain silver ingot product after fusing in plumbago crucible.
When converter slag fine powder in described step 3 is converter pre-slag fine powder, be that to add concentration be that the sulfuric acid of 270 ~ 400g/l leaches 2 ~ 3h at temperature is 80 ~ 90 DEG C to 13 ~ 17:1 by converter slag fine powder according to liquid-solid ratio, obtain a leached mud and copper-bath, one time leached mud carries out multistage leaching until conformance with standard according to identical Parameter Conditions.
When converter slag fine powder in described step 3 is converter later stage slag fine powder, is that to add concentration be that the sulfuric acid of 270 ~ 400g/l leaches 2 ~ 3h at temperature is 80 ~ 90 DEG C to 8 ~ 10:1 by converter slag fine powder according to liquid-solid ratio, obtains leached mud and copper-bath.
The product copper sulfate of final acquisition is containing CuSO
45H
2o is at more than 84=wt.%, and silver converter pre-slag can reach more than 92% through the leaching yield that two sections are leached copper, and the leaching yield of silver converter later stage slag copper can reach more than 95%.
The invention has the beneficial effects as follows: the production cost that (1) precious metals containing lead carries out converter refining separating copper again after vacuum distilling process significantly reduces, and decreases the generation of production process waste gas; (2) with wet processing silver converter slag, improve operation environment, production cost reduces; (3) output leached mud argentiferous is high, can directly return and lead anode slurry melting output precious metals containing lead; (4) whole technical process refining is succinct, production process waste gas few (only having during converter refining has a small amount of waste gas to produce), produces without waste residue, waste water, belongs to environmental protection low-carbon (LC) metallurgical technology, has great promotion potential in industry.
Accompanying drawing explanation
The process flow sheet of Fig. 1 to be precious metals containing lead byproduct of the present invention be silver converter pre-slag;
The process flow sheet of Fig. 2 to be precious metals containing lead byproduct of the present invention be silver converter later stage slag.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
As illustrated in fig. 1 and 2, should be the method for raw materials recovery lead, silver and copper with precious metals containing lead, its concrete steps be as follows:
Step 1: first precious metals containing lead is placed in vacuum oven, then control that vacuum tightness is 10 ~ 20Pa, temperature is 940 ~ 960 DEG C, precious metals containing lead charging capacity is vacuum distilling separation of lead, antimony, bismuth, copper under 70g/s condition, plumbous and your silver of output height bismuth, wherein precious metals containing lead comprises and draws together following mass percent component: Pb40.8%, Sb15.8%, Cu4.0%, Bi14.76%, Ag19.83%;
Step 2: high bismuth step 1 obtained is plumbous to be obtained separating out lead after the plumbous electrolysis of high bismuth, separates out plumbous main process and adds 0.5 ~ 0.6kg/t for (1) in silicofluoric acid electrolytic solution
pbox glue, add 0.02 ~ 0.03kg/t
pb2-Naphthol is combined into new electrolytic solution; (2) in the new electrolytic solution be combined into, current density 183 ~ 185A/m is controlled
2, Pb in electrolytic solution
2+content 55 ~ 60g/l, free silica fluoric acid 90 ~ 100g/l, electrolyte temperature 38 ~ 40 DEG C, produces 72h under circulation of elecrolyte amount 22 ~ 25L/min condition in a cell; It is slightly silver-colored that your silver that step 1 obtains carries out converter refining output, and obtain converter pre-slag and converter later stage slag according to the length of converter refining time, wherein converter refining process is specially: when the temperature in Converter reaches 1100 DEG C, your silver is dropped in stove, keep your silver of temperature 1100 ~ 1200 DEG C fusing, after your silver major part fusing, temperature is reduced to 900 DEG C, takes off slag clean; Keep melt temperature 850 ~ 950 DEG C to insert airduct table again and blow voloxidation slag making removal of impurities, duration of blast is 2 days, and the slag obtained that blows is converter pre-slag; After finishing blowing, liquation Ag grade is 94wt.%, furnace temperature is remained on 1100 ~ 1150 DEG C and carry out later stage slag making deep impurity-removing, each 50kg SODIUMNITRATE that adds in liquation fully stirs the blowing of after-frame pipe and puts clean slag after 2 ~ 3 hours, repeat above operation 10 times, get the chemical examination of liquation sample containing Ag98.66wt.%, Cu0.92wt.%, at this moment thoroughly drains clean slag, obtains thick silver products and converter later stage slag;
Step 3: thick galactic longitude silver electrolysis step 2 obtained obtains silver ingot, and detailed process is: thick silver is made positive plate and loads electrolyzer, at current density 250A/m
2, bath voltage 2.5V carries out electrolysis, controls Ag120g/l, HNO in electrolytic solution
310g/l, Cu40g/l, electrolyte temperature 45 DEG C, circulation of elecrolyte speed 1L/min, electrolysing period 96 hours, output silver powder (Ag99.9946wt.%), silver powder is after washing and drying, in plumbago crucible, drop into 115 ㎏ silver powder keeps temperature 1200 DEG C to melt, drag for clean scum silica frost after fusing to maintain the temperature at 1200 DEG C and carry out ingot casting, obtain silver ingot product (comprising following mass percent: Ag99.9954%, Pb0.0004%, Bi0.0003%, Fe0.0004%, Cu0.0028%, Sb0.0005%, Pd0.00005%, Se0.00005%, Te0.00005%), converter pre-slag step 2 obtained and converter later stage slag are crushed to granularity < 6mm respectively, and then to be finely ground into granularity be that the powder of below 100 orders obtains converter slag fine powder, then converter slag fine powder is added sulphuric acid soln to leach, leached mud and copper-bath is obtained after leaching completes, leached mud should meet the standard that copper content should be less than 4wt.%, if leached mud closes when copper content is greater than 4wt.% should carry out multistage leaching until conformance with standard, obtain copper-bath and obtain residual solution and copper sulfate crystal after normal temperature cooling, residual solution returns leaching process and recycles,
When converter slag fine powder is converter pre-slag (component of converter pre-slag comprises following mass percent component: Pb4.2%, Sb6.2%, Cu37.62%, Bi7.01%, Ag11.24%) fine powder, be that to add concentration be at temperature is 80 DEG C, leach 2h in the sulphuric acid soln of 270g/l to 15:1 by converter slag fine powder according to liquid-solid ratio, obtain a leached mud and copper-bath, a leached mud carries out two sections according to identical Parameter Conditions and leaches until conformance with standard, and one section of leaching terminates rear solution temperature and carry out press filtration with pressure filter more than 70 DEG C; One section of leach liquor (Pb0.03g/l, Sb0.22g/l, Cu45g/l, Bi0.63g/l, Ag0.002g/l) is cooled to normal temperature and separates out copper sulfate crystal, filters after drying and obtains copper sulfate product (CuSO
45H
2o83wt.%); Remaining leach liquor (Cu11.0g/l) returns leaching vat and recycles; Two sections of leach liquors (Cu36g/l) are cooled to normal temperature and separate out copper sulfate crystal, filter after drying and obtain copper sulfate product (CuSO
45H
2o83.3wt.%), remaining leach liquor (Cu12.3g/l) returns leaching vat and recycles, and secondary leached mud (Pb14.25wt.%, Sb11.79wt.%, Cu2.51wt.%, Bi13.65wt.%, Ag29.38wt.%) send lead anode slurry reverberatory furnace to reclaim the valuable metals such as lead, antimony, silver; The leaching yield leaching copper through two sections is 97.22%.
When converter slag fine powder is converter later stage slag (component of converter later stage slag comprises following mass percent component: Pb0.3%, Sb2.75%, Cu12.76%, Bi1.04%, Ag3.84%) fine powder, be that to add concentration be at temperature is 80 DEG C, leach 2h in the sulphuric acid soln of 270g/l to 10:1 by converter slag fine powder according to liquid-solid ratio, obtain leached mud and copper-bath, leaching terminates rear solution temperature and carry out press filtration with pressure filter more than 70 DEG C; Leach liquor (Pb0.013g/l, Sb0.31g/l, Cu35.2g/l, Bi0.01g/l, Ag0.0013g/l) is cooled to normal temperature and separates out copper sulfate crystal, filters after drying and obtains copper sulfate product (CuSO
45H
2o85.32wt.%); Remaining leach liquor (Cu9.6g/l) returns leaching vat and recycles, and leached mud (Pb4.0wt.%, Sb27.78wt.%, Cu0.89wt.%, Bi5.76wt.%, Ag31.56wt.%) send lead anode slurry reverberatory furnace to reclaim the valuable metals such as lead, antimony, silver; Copper leaching rate is 98.23%.
Embodiment 2
As illustrated in fig. 1 and 2, should be the method for raw materials recovery lead, silver and copper with precious metals containing lead, its concrete steps be as follows:
Step 1: first precious metals containing lead is placed in vacuum oven, then control that vacuum tightness is 10 ~ 20Pa, temperature is 940 ~ 960 DEG C, precious metals containing lead charging capacity is vacuum distilling separation of lead, antimony, bismuth, copper under 70g/s condition, plumbous and your silver of output height bismuth, wherein precious metals containing lead comprises and draws together following mass percent component: Pb51%, Sb14.3%, Cu3.47%, Bi12.33%, Ag17.46%;
Step 2: high bismuth step 1 obtained is plumbous to be obtained separating out lead after the plumbous electrolysis of high bismuth, and the plumbous electrolytic process of high bismuth is specially: (1) adds 0.6 ~ 0.7kg/t in silicofluoric acid electrolytic solution
pbox glue, add 0.04 ~ 0.05kg/t
pb2-Naphthol is combined into new electrolytic solution; (2) in the new electrolytic solution be combined into, current density 184 ~ 186A/m is controlled
2, Pb in electrolytic solution
2+content 60 ~ 70g/l, free silica fluoric acid 98 ~ 112g/l, electrolyte temperature 39 ~ 42 DEG C, produces 72h under circulation of elecrolyte amount 23 ~ 24L/min condition in a cell; It is slightly silver-colored that your silver that step 1 obtains carries out converter refining output, and obtain converter pre-slag and converter later stage slag according to the length of converter refining time, wherein converter refining process is specially: when the temperature in Converter reaches 1100 DEG C, your silver is dropped in stove, keep your silver of temperature 1100 ~ 1200 DEG C fusing, after your silver major part fusing, temperature is reduced to 900 DEG C, takes off slag clean; Keep melt temperature 850 ~ 950 DEG C to insert airduct table again and blow voloxidation slag making removal of impurities, duration of blast is 2.5 days, and the slag obtained that blows is converter pre-slag; After finishing blowing, liquation Ag grade is 90wt.%, furnace temperature is remained on 1100 ~ 1180 DEG C and carry out later stage slag making deep impurity-removing, each 50kg SODIUMNITRATE that adds in liquation fully stirs the blowing of after-frame pipe and puts clean slag after 2 ~ 3 hours, repeat above operation 10 times, get the chemical examination of liquation sample containing Ag98.56wt.%, Cu0.94wt.%, at this moment thoroughly drains clean slag, obtains thick silver products and converter later stage slag;
Step 3: thick galactic longitude silver electrolysis step 2 obtained obtains silver ingot, and detailed process is: thick silver is made positive plate and loads electrolyzer, at current density 200A/m
2, bath voltage 1.5V carries out electrolysis, controls Ag80g/l, HNO in electrolytic solution
34g/l, Cu20g/l, electrolyte temperature 35 DEG C, circulation of elecrolyte speed 0.8L/min, electrolysing period 96 hours, output silver powder (Ag99.9932wt.%), silver powder is after washing and drying, in plumbago crucible, drop into 105 ㎏ silver powder keeps temperature 1200 DEG C to melt, drag for clean scum silica frost after fusing to maintain the temperature at 1200 DEG C and carry out ingot casting, obtain silver ingot product (comprising following mass percent component: Ag99.9953%, Pb0.0005%, Bi0.0003%, Fe0.0004%, Cu0.0028%, Sb0.0005%, Pd0.00005%, Se0.00005%, Te0.00005%), the thick galactic longitude silver electrolysis that step 2 obtains obtains silver ingot, the converter pre-slag that step 2 obtains and converter later stage slag are crushed to granularity < 6mm respectively, and then to be finely ground into granularity be that the powder of below 100 orders obtains converter slag fine powder, then converter slag fine powder is added sulphuric acid soln to leach, leached mud and copper-bath is obtained after leaching completes, leached mud should meet the standard that copper content should be less than 4wt.%, if leached mud closes when copper content is greater than 4wt.% should carry out multistage leaching until conformance with standard, obtain copper-bath and obtain residual solution and copper sulfate crystal after normal temperature cooling, residual solution returns leaching process and recycles,
When converter slag fine powder is converter pre-slag (component of converter pre-slag comprises following mass percent component: Pb6.5%, Sb11.2%, Cu30.61%, Bi7.48%, Ag10.84%) fine powder, be that to add concentration be at temperature is 80 DEG C, leach 2h in the sulphuric acid soln of 270g/l to 15:1 by converter slag fine powder according to liquid-solid ratio, obtain a leached mud and copper-bath, a leached mud carries out two sections according to identical Parameter Conditions and leaches until conformance with standard, and one section of leaching terminates rear solution temperature and carry out press filtration with pressure filter more than 70 DEG C; One section of leach liquor (Pb0.03g/l, Sb0.26g/l, Cu44g/l, Bi0.74g/l, Ag0.003g/l) is cooled to normal temperature and separates out copper sulfate crystal, filters after drying and obtains copper sulfate product (CuSO
45H
2o84.2wt.%); Remaining leach liquor (Cu11.4g/l) returns leaching vat and recycles; Two sections of leach liquors (Cu35.2g/l) are cooled to normal temperature and separate out copper sulfate crystal, filter after drying and obtain copper sulfate product (CuSO
45H
2o84.6wt.%), remaining leach liquor (Cu10.6g/l) returns leaching vat and recycles, and secondary leached mud (Pb18.62wt.%, Sb23.3wt.%, Cu1.89wt.%, Bi14.31wt.%, Ag28.65wt.%) send lead anode slurry reverberatory furnace to reclaim the valuable metals such as lead, antimony, silver; The leaching yield leaching copper through two sections is 97.43%.
When converter slag fine powder is converter later stage slag (component of converter later stage slag comprises following mass percent component: Pb0.41%, Sb3.53%, Cu11.0%, Bi1.12%, Ag3.56%) fine powder, be that to add concentration be at temperature is 80 DEG C, leach 2h in the sulphuric acid soln of 270g/l to 8:1 by converter slag fine powder according to liquid-solid ratio, obtain leached mud and copper-bath, leaching terminates rear solution temperature and carry out press filtration with pressure filter more than 70 DEG C; Leach liquor (Pb0.014g/l, Sb0.26g/l, Cu34.62g/l, Bi0.01g/l, Ag0.0015g/l) is cooled to normal temperature and separates out copper sulfate crystal, filters after drying and obtains copper sulfate product (CuSO
45H
2o84.86wt.%); Remaining leach liquor (Cu10.6g/l) returns leaching vat and recycles, and leached mud (Pb4.2wt.%, Sb28.31wt.%, Cu0.92wt.%, Bi5.88wt.%, Ag30.82wt.%) send lead anode slurry reverberatory furnace to reclaim the valuable metals such as lead, antimony, silver; Copper leaching rate is 98.36%.
Embodiment 3
As illustrated in fig. 1 and 2, should be the method for raw materials recovery lead, silver and copper with precious metals containing lead, its concrete steps be as follows:
Step 1: first precious metals containing lead is placed in vacuum oven, then control that vacuum tightness is 10 ~ 20Pa, temperature is 940 ~ 960 DEG C, precious metals containing lead charging capacity is vacuum distilling separation of lead, antimony, bismuth, copper under 69g/s condition, plumbous and your silver of output height bismuth, wherein precious metals containing lead comprises and draws together following mass percent component: Pb58.62%, Sb13.03%, Cu3.66%, Bi8.56%, Ag15.37%;
Step 2: high bismuth step 1 obtained is plumbous to be obtained separating out lead after the plumbous electrolysis of high bismuth, and the plumbous electrolytic process of high bismuth is specially: (1) adds 0.7 ~ 0.8kg/t in electrolytic solution
pbox glue, add 0.05 ~ 0.06kg/t
pb2-Naphthol is combined into new electrolytic solution; (2) in the new electrolytic solution be combined into, current density 188 ~ 190A/m is controlled
2, Pb in electrolytic solution
2+content 76 ~ 80g/l, free silica fluoric acid 110 ~ 120g/l, electrolyte temperature 44 ~ 45 DEG C, produces 72h under circulation of elecrolyte amount 25 ~ 27L/min condition in a cell; It is slightly silver-colored that your silver that step 1 obtains carries out converter refining output, and obtain converter pre-slag and converter later stage slag according to the length of converter refining time, wherein converter refining process is specially: when the temperature in Converter reaches 1100 DEG C, your silver is dropped in stove, keep your silver of temperature 1100 ~ 1200 DEG C fusing, after your silver major part fusing, temperature is reduced to 900 DEG C, takes off slag clean; Keep melt temperature 850 ~ 950 DEG C to insert airduct table again and blow voloxidation slag making removal of impurities, duration of blast is 3 days, and the slag obtained that blows is converter pre-slag; After finishing blowing, liquation Ag grade is 89wt.%, furnace temperature is remained on 1100 ~ 1150 DEG C and carry out later stage slag making deep impurity-removing, each 50kg SODIUMNITRATE that adds in liquation fully stirs the blowing of after-frame pipe and puts clean slag after 2 ~ 3 hours, repeat above operation 10 times, get the chemical examination of liquation sample containing Ag98.58wt.%, Cu0.91wt.%, at this moment thoroughly drains clean slag, obtains thick silver products and converter later stage slag;
Step 3: thick galactic longitude silver electrolysis step 2 obtained obtains silver ingot, and the detailed process that the electrolysis of thick galactic longitude silver obtains silver ingot is: thick silver is made positive plate and loads electrolyzer, at current density 230A/m
2, bath voltage 2.0V carries out electrolysis, controls Ag100g/l, HNO in electrolytic solution
37g/l, Cu30g/l, electrolyte temperature 40 DEG C, circulation of elecrolyte speed 0.9L/min, electrolysing period 96 hours, output silver powder (Ag99.9949wt.%); Silver powder is after washing and drying, in plumbago crucible, drop into 110 ㎏ silver powder keeps temperature 1200 DEG C to melt, drag for clean scum silica frost after fusing to maintain the temperature at 1200 DEG C and carry out ingot casting, obtain silver ingot product (comprising following mass percent component: Ag99.9951%, Pb0.0005%, Bi0.0003%, Fe0.0005%, Cu0.0029%, Sb0.0005%, Pd0.00005%, Se0.00005%, Te0.00005%);
The converter pre-slag that step 2 obtains and converter later stage slag are crushed to granularity < 6mm respectively, and then to be finely ground into granularity be that the powder of below 100 orders obtains converter slag fine powder, then converter slag fine powder is added sulphuric acid soln to leach, leached mud and copper-bath is obtained after leaching completes, leached mud should meet the standard that copper content should be less than 4wt.%, if leached mud closes when copper content is greater than 4wt.% should carry out multistage leaching until conformance with standard, obtain copper-bath and obtain residual solution and copper sulfate crystal after normal temperature cooling, residual solution returns leaching process and recycles,
When converter slag fine powder is converter pre-slag (component of converter pre-slag comprises following mass percent component: Pb29.3%, Sb5.5%, Cu39.7%, Bi2.6%, Ag11.8%) fine powder, be that to add concentration be at temperature is 85 DEG C, leach 3h in the sulphuric acid soln of 400g/l to 17:1 by converter slag fine powder according to liquid-solid ratio, obtain a leached mud and copper-bath, a leached mud carries out two sections according to identical Parameter Conditions and leaches until conformance with standard, and one section of leaching terminates rear solution temperature and carry out press filtration with pressure filter more than 70 DEG C; One section of leach liquor (Pb0.042g/l, Sb0.31g/l, Cu46g/l, Bi0.66g/l, Ag0.002g/l) is cooled to normal temperature and separates out copper sulfate crystal, filters after drying and obtains copper sulfate product (CuSO
45H
2o84.8wt.%); Remaining leach liquor (Cu10.6g/l) returns leaching vat and recycles; Two sections of leach liquors (Cu36.1g/l) are cooled to normal temperature and separate out copper sulfate crystal, filter after drying and obtain copper sulfate product (CuSO
45H
2o85.2wt.%), remaining leach liquor (Cu10.4g/l) returns leaching vat and recycles, and secondary leached mud (Pb20.66wt.%, Sb30.2wt.%, Cu1.31wt.%, Bi10.23wt.%, Ag23.1wt.%) send lead anode slurry reverberatory furnace to reclaim the valuable metals such as lead, antimony, silver; The leaching yield leaching copper through two sections is 96.82%.
When converter slag fine powder is converter later stage slag (component of converter later stage slag comprises following mass percent component: Pb0.92%, Sb5.1%, Cu7.1%, Bi1.1%, Ag4.3%) fine powder, be that to add concentration be at temperature is 90 DEG C, leach 2.5h in the sulphuric acid soln of 400g/l to 9:1 by converter slag fine powder according to liquid-solid ratio, obtain leached mud and copper-bath, leaching terminates rear solution temperature and carry out press filtration with pressure filter more than 70 DEG C; Leach liquor (Pb0.011g/l, Sb0.34g/l, Cu35.33g/l, Bi0.012g/l, Ag0.0013g/l) is cooled to normal temperature and separates out copper sulfate crystal, filters after drying and obtains copper sulfate product (CuSO
45H
2o84.69wt.%); Remaining leach liquor (Cu10.8g/l) returns leaching vat and recycles, and leached mud (Pb4.5wt.%, Sb29.56wt.%, Cu0.88wt.%, Bi5.57wt.%, Ag29.76wt.%) send lead anode slurry reverberatory furnace to reclaim the valuable metals such as lead, antimony, silver; Copper leaching rate is 97.85%.
Embodiment 4
As illustrated in fig. 1 and 2, should be the method for raw materials recovery lead, silver and copper with precious metals containing lead, its concrete steps be as follows:
Step 1: first precious metals containing lead is placed in vacuum oven, then control that vacuum tightness is 10 ~ 20Pa, temperature is 940 ~ 960 DEG C, precious metals containing lead charging capacity is vacuum distilling separation of lead, antimony, bismuth, copper under 71g/s condition, plumbous and your silver of output height bismuth, wherein precious metals containing lead comprises and draws together following mass percent component: Pb59.8%, Sb15.3%, Cu3.0%, Bi8.68%, Ag15.2%;
Step 2: high bismuth step 1 obtained is plumbous to be obtained separating out lead after the plumbous electrolysis of high bismuth, and the plumbous electrolytic process of high bismuth is specially: (1) adds 0.7 ~ 0.78kg/t in silicofluoric acid electrolytic solution
pbox glue, add 0.05 ~ 0.06kg/t
pb2-Naphthol is combined into new electrolytic solution; (2) in the new electrolytic solution be combined into, current density 188 ~ 190A/m is controlled
2, Pb in electrolytic solution
2+content 70 ~ 80g/l, free silica fluoric acid 100 ~ 120g/l, electrolyte temperature 42 ~ 45 DEG C, produces 72h under circulation of elecrolyte amount 26 ~ 27L/min condition in a cell; It is slightly silver-colored that your silver that step 1 obtains carries out converter refining output, and obtain converter pre-slag and converter later stage slag according to the length of converter refining time, wherein converter refining process is specially: when the temperature in Converter reaches 1100 DEG C, your silver is dropped in stove, keep your silver of temperature 1100 ~ 1200 DEG C fusing, after your silver major part fusing, temperature is reduced to 900 DEG C, takes off slag clean; Keep melt temperature 850 ~ 950 DEG C to insert airduct table again and blow voloxidation slag making removal of impurities, duration of blast is 3 days, and the slag obtained that blows is converter pre-slag; After finishing blowing, liquation Ag grade is 85.6%, furnace temperature is remained on 1100 ~ 1180 DEG C and carry out later stage slag making deep impurity-removing, each 50kg SODIUMNITRATE that adds in liquation fully stirs the blowing of after-frame pipe and puts clean slag after 2 ~ 3 hours, repeat above operation 12 times, get the chemical examination of liquation sample containing Ag98.49%, Cu0.88%, at this moment thoroughly drains clean slag, obtains thick silver products and converter later stage slag;
Step 3: thick galactic longitude silver electrolysis step 2 obtained obtains silver ingot, and the detailed process that the electrolysis of thick galactic longitude silver obtains silver ingot is: thick silver is made positive plate and loads electrolyzer, at current density 225A/m
2, bath voltage 1.9V carries out electrolysis, controls Ag100g/l, HNO in electrolytic solution
36g/l, Cu28g/l, electrolyte temperature 41 DEG C, circulation of elecrolyte speed 0.9L/min, electrolysing period 96 hours, output silver powder (Ag99.9938wt.%); Silver powder is after washing and drying, in plumbago crucible, drop into 110 ㎏ silver powder keeps temperature 1200 DEG C to melt, drag for clean scum silica frost after fusing to maintain the temperature at 1200 DEG C and carry out ingot casting, obtain silver ingot product (comprise following mass percent component: Ag99.9946%, Pb0.0005%, Bi0.0004%, Fe0.0004%, Cu0.0034%, Sb0.0005%, Pd0.00005%, Se0.00005%, Te0.00005%);
The converter pre-slag that step 2 obtains and converter later stage slag are crushed to granularity < 6mm respectively, and then to be finely ground into granularity be that the powder of below 100 orders obtains converter slag fine powder, then converter slag fine powder is added sulphuric acid soln to leach, leached mud and copper-bath is obtained after leaching completes, leached mud should meet the standard that copper content should be less than 4%, if leached mud closes when copper content is greater than 4% should carry out multistage leaching until conformance with standard, obtain copper-bath and obtain residual solution and copper sulfate crystal after normal temperature cooling, residual solution returns leaching process and recycles,
When converter slag fine powder is converter pre-slag (component of converter pre-slag comprises following mass percent component: Pb28.6%, Sb25%, Cu16.4%, Bi3.5%, Ag6.2%) fine powder, be that to add concentration be at temperature is 80 DEG C, leach 2h in the sulphuric acid soln of 270g/l to 13:1 by converter slag fine powder according to liquid-solid ratio, obtain a leached mud and copper-bath, a leached mud carries out two sections according to identical Parameter Conditions and leaches until conformance with standard, and one section of leaching terminates rear solution temperature and carry out press filtration with pressure filter more than 70 DEG C; One section of leach liquor (Pb0.05g/l, Sb0.37g/l, Cu45g/l, Bi0.68g/l, Ag0.0022g/l) is cooled to normal temperature and separates out copper sulfate crystal, filters after drying and obtains copper sulfate product (CuSO
45H
2o85wt.%); Remaining leach liquor (Cu10.4g/l) returns leaching vat and recycles; Two sections of leach liquors (Cu36.3g/l) are cooled to normal temperature and separate out copper sulfate crystal, filter after drying and obtain copper sulfate product (CuSO
45H
2o84.8wt.%), remaining leach liquor (Cu11.5g/l) returns leaching vat and recycles, and secondary leached mud (Pb41.3wt.%, Sb38.6wt.%, Cu1.66wt.%, Bi6.8wt.%, Ag12.3wt.%) send lead anode slurry reverberatory furnace to reclaim the valuable metals such as lead, antimony, silver; The leaching yield leaching copper through two sections is 96.5%.
When converter slag fine powder is converter later stage slag (component of converter later stage slag comprises following mass percent component: Pb0.96%, Sb5.8%, Cu7.42%, Bi0.97%, Ag2.2%) fine powder, be that to add concentration be at temperature is 80 DEG C, leach 2h in the sulphuric acid soln of 270g/l to 8:1 by converter slag fine powder according to liquid-solid ratio, obtain leached mud and copper-bath, leaching terminates rear solution temperature and carry out press filtration with pressure filter more than 70 DEG C; Leach liquor (Pb0.015g/l, Sb0.29g/l, Cu35.54g/l, Bi0.011g/l, Ag0.0012g/l) is cooled to normal temperature and separates out copper sulfate crystal, filters after drying and obtains copper sulfate product (CuSO
45H
2o84.52wt.%); Remaining leach liquor (Cu11.4g/l) returns leaching vat and recycles, and leached mud (Pb3.8wt.%, Sb29.2wt.%, Cu1.01wt.%, Bi4.79wt.%, Ag25.1wt.%) send lead anode slurry reverberatory furnace to reclaim the valuable metals such as lead, antimony, silver; Copper leaching rate is 96.9%.
By reference to the accompanying drawings the specific embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (6)
1. be a method for raw materials recovery lead, silver and copper with precious metals containing lead, it is characterized in that concrete steps are as follows:
Step 1: first precious metals containing lead is placed in vacuum oven, then controls that vacuum tightness is 10 ~ 20Pa, temperature is 940 ~ 960 DEG C, precious metals containing lead charging capacity is vacuum distilling separation of lead, antimony, bismuth, copper under 69 ~ 71g/s condition, plumbous and your silver of output height bismuth;
Step 2: high bismuth step 1 obtained is plumbous to be obtained separating out lead after the plumbous electrolysis of high bismuth, and it is slightly silver-colored that your silver that step 1 obtains carries out converter refining output, and obtain converter pre-slag and converter later stage slag according to the length of converter refining time;
Step 3: thick galactic longitude silver electrolysis step 2 obtained obtains silver ingot, the converter pre-slag that step 2 obtains and converter later stage slag are crushed to granularity < 6mm respectively, and then to be finely ground into granularity be that the powder of below 100 orders obtains converter slag fine powder, then converter slag fine powder is added sulphuric acid soln to leach, leached mud and copper-bath is obtained after leaching completes, leached mud should meet the standard that copper content should be less than 4wt.%, if leached mud closes when copper content is greater than 4wt.% should carry out multistage leaching until conformance with standard, obtain copper-bath and obtain residual solution and copper sulfate crystal after normal temperature cooling, residual solution returns leaching process and recycles,
Described precious metals containing lead comprises following mass percent component: Pb40 ~ 60%, Sb13 ~ 16%, Cu3 ~ 4%, Bi8 ~ 15%, Ag15 ~ 20%; The component of described converter pre-slag comprises following mass percent component: Pb3.8 ~ 30%, Sb5.5 ~ 25%, Cu16 ~ 40%, Bi < 8%, Ag6 ~ 12%; The component of described converter later stage slag comprises following mass percent component: Pb < 1%, Sb2 ~ 6%, Cu7 ~ 13%, Bi < 1.5%, Ag1 ~ 4.5%.
2. according to claim 1ly with precious metals containing lead be that raw materials recovery is plumbous, the method for silver and copper, it is characterized in that: the plumbous electrolytic process of the high bismuth of described step 2 is specially: (1) adds 0.5 ~ 0.8kg/t in electrolytic solution
pbox glue, add 0.02 ~ 0.06kg/t
pb2-Naphthol is combined into new electrolytic solution; (2) in the new electrolytic solution be combined into, current density 183 ~ 190A/m is controlled
2, Pb in electrolytic solution
2+content 55 ~ 80g/l, free silica fluoric acid 90 ~ 120g/l, electrolyte temperature 38 ~ 45 DEG C, produces 72h under circulation of elecrolyte amount 22 ~ 27l/min condition in a cell.
3. according to claim 1ly with precious metals containing lead be that raw materials recovery is plumbous, the method for silver and copper, it is characterized in that: described step 2 converter refining process is specially: when the temperature in Converter reaches 1100 DEG C, your silver is dropped in stove, keep your silver of temperature 1100 ~ 1200 DEG C fusing, after your silver major part fusing, temperature is reduced to 900 DEG C, takes off slag clean; Keep melt temperature 850 ~ 950 DEG C to insert airduct table again and blow voloxidation slag making removal of impurities, duration of blast is 2 ~ 3 days, and the slag obtained that blows is converter pre-slag; After finishing blowing, liquation Ag grade is 85 ~ 95wt.%, furnace temperature is remained on 1100 ~ 1200 DEG C and carry out later stage slag making deep impurity-removing, add in liquation SODIUMNITRATE fully stir after-frame pipe blowing 2 ~ 3 hours after drain slag, repeat above operation, until sample examination is containing Ag > 98wt.%, during Cu < 1wt.%, thoroughly drain clean slag, obtain converter later stage slag and thick silver products.
4. according to claim 1ly with precious metals containing lead be that raw materials recovery is plumbous, the method for silver and copper, it is characterized in that: in described step 3, the electrolysis of thick galactic longitude silver obtains the detailed process of silver ingot and is: thick silver makes positive plate loading electrolyzer, at current density 200 ~ 250A/m
2, bath voltage 1.5 ~ 2.5V carries out electrolysis, controls Ag80 ~ 120g/l, HNO in electrolytic solution
34 ~ 10g/l, Cu≤40g/l, electrolyte temperature 35 ~ 45 DEG C, circulation of elecrolyte speed 0.8 ~ 1l/min, electrolysing period 96 hours, the silver powder of output argentiferous > 99.99wt.%; Silver powder, after washing and drying, drops into silver powder and keeps temperature 1200 DEG C to melt, drag for clean scum silica frost and maintain the temperature at 1200 DEG C and carry out ingot casting, obtain silver ingot product after fusing in plumbago crucible.
5. according to claim 1ly with precious metals containing lead be that raw materials recovery is plumbous, the method for silver and copper, it is characterized in that: when the converter slag fine powder in described step 3 is converter pre-slag fine powder, be that to add concentration be that the sulfuric acid of 270 ~ 400g/l leaches 2 ~ 3h at temperature is 80 ~ 90 DEG C to 13 ~ 17:1 by converter slag fine powder according to liquid-solid ratio, obtain a leached mud and copper-bath, one time leached mud carries out multistage leaching until conformance with standard according to identical Parameter Conditions.
6. according to claim 1ly with precious metals containing lead be that raw materials recovery is plumbous, the method for silver and copper, it is characterized in that: when the converter slag fine powder in described step 3 is converter later stage slag fine powder, be that to add concentration be that the sulfuric acid of 270 ~ 400g/l leaches 2 ~ 3h at temperature is 80 ~ 90 DEG C to 8 ~ 10:1 by converter slag fine powder according to liquid-solid ratio, obtain leached mud and copper-bath.
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| CN108456778B (en) * | 2018-03-27 | 2019-12-31 | 广州万仕智投资有限公司 | Method for preparing gold-silver alloy from rich lead |
| CN109055765A (en) * | 2018-09-30 | 2018-12-21 | 蒙自矿冶有限责任公司 | A method of recycling refined bismuth from precious metals containing lead |
| CN110172570B (en) * | 2018-12-27 | 2020-02-14 | 昆明理工大学 | Method for treating noble lead |
| CN110172578B (en) * | 2018-12-27 | 2020-02-11 | 昆明理工大学 | Comprehensive treatment method for precious lead |
| CN111455180B (en) * | 2020-04-17 | 2021-11-23 | 昆明铂锐金属材料有限公司 | Method for enriching platinum and co-producing metal aluminum from spent alumina platinum catalyst |
| CN112063854B (en) * | 2020-09-02 | 2022-08-26 | 河南豫光金铅股份有限公司 | Method for comprehensively recovering bismuth, silver and copper metals by taking precious lead as raw material |
| CN112359209A (en) * | 2020-11-09 | 2021-02-12 | 昆明理工大学 | Method for enriching and recovering noble metal in lead anode slime |
| CN114525413A (en) * | 2022-01-21 | 2022-05-24 | 励福(江门)环保科技股份有限公司 | Method for separating copper and noble metal from copper alloy containing noble metal |
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