CN103820643B - A kind of two sections of melting process lead anode slurries produce the method for precious metals containing lead - Google Patents
A kind of two sections of melting process lead anode slurries produce the method for precious metals containing lead Download PDFInfo
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Abstract
The present invention relates to a kind of method that two sections of melting process lead anode slurries produce precious metals containing lead, belong to precious metal pyrometallurgical smelting technology.The method improve the technique that traditional fire reduction metallurgy lead anode slurry produces precious metals containing lead, compared with producing precious metals containing lead technique with existing traditional lead anode slurry, in same converter, technique is low-temperature oxidation and high temperature reduction melting two processes, auxiliary material adds feed way and changes into after the oxidized blowing of lead anode slurry completely, add reductive agent and flux retailoring again, this processing method greatly reduces reductive agent hard coal, the add-on of flux soda ash and fuel consumption, dearsenification antimony efficiency is high, obtain higher-grade precious metals containing lead, the throughput of former converter improves 50%.
Description
Technical field
The present invention relates to a kind of method that two sections of melting process lead anode slurries produce precious metals containing lead, belong to precious metal pyrometallurgy technology, specifically precious metal pyrometallurgical smelting technology.
Background technology
The process of lead anode slurry has two kinds of modes substantially: thermal process and wet processing.Wet production long flow path, the cycle is long, production cost is high, wastewater treatment capacity is large; Traditional thermal process is generally adopted to the process of lead anode slurry both at home and abroad, current known some relatively large pyrogenic attack anode sludge enterprises both at home and abroad, its technological principle is that lead anode slurry, reductive agent, solvent are added smelting furnace retailoring output precious metals containing lead, then precious metals containing lead is carried out the electrum that oxidation refining output purity is greater than 97%.The domestic Study on processing method to lead anode slurry many:
Open in denomination of invention " a kind of lead anode slurry treatment process " lead anode slurry of Ag grade 14 ~ 16% and solvent and fine coal mixing thermal process melting are traditionally obtained precious metals containing lead, precious metals containing lead obtains the precious metals containing lead that grade is 41.22% after antimony is run in 600 ~ 900 DEG C of blowings, then precious metals containing lead powdered and controlling potential are selected logical chlorine leaching in NHCL solution;
The open precious metals containing lead stove adopting bottom to be provided with oxygen entrance in denomination of invention " a kind of smelting process of separating value metals from anode mud by firing process ", end lead is added in stove, nut coke makees reductive agent, nut coke is 0 ~ 10% of anode sludge dry measure, and the anode sludge mixes with nut coke or allocates gold and silver returning charge into, bath temperature 850 ~ 1200 DEG C, continuous smoke, interruption slagging, interruption put lead, precious metals containing lead argentiferous 20 ~ 85%, this precious metals containing lead enters point further refining of silver stove, makes copper bismuth slag, tellurium slag output electrum;
Open weight proportion lead anode slurry, returning charge, nut coke being pressed 100:0 ~ 40:0 ~ 10 in denomination of invention " a kind of method of continuously treating lead anode slime ", continuous and quantitative adds oxygen bottom blowing precious metals containing lead stove and dissolves, pass into oxygen, oxygen pressure 0.4 ~ 1.2MPa, temperature keeps 900 ~ 1000 DEG C, react 10 ~ 30 minutes, the precious metals containing lead of output gold and silver grade mass percent between 25 ~ 50%, primary slag and a cigarette ash;
Openly lead anode slurry, slag former sodium carbonate, the burnt grain of reductive agent are mixed with the ratio of 100:3 ~ 6:5 ~ 10 in denomination of invention " a kind of method of oxygen-enriched side-blowing direct reduction smelting of anode mud ", join in side-blown converter, and oxygen rich gas and coal gas are sprayed in stove from the heating unit of side-blown converter sidepiece, temperature controls at 1000 ~ 1200 DEG C, under the condition of constantly heating, mixture dissolves, slag making and reduction reaction, finally obtain precious metals containing lead, flue dust, reducing slag, precious metals containing lead enters point further refining of silver stove, make copper bismuth slag and tellurium slag, output is slightly silver-colored;
After denomination of invention " lead anode slurry side-blown converter retailoring technology " openly mixes in proportion lead anode slurry, returning charge, nut coke, enter side blowing smelting furnace, produce precious metals containing lead, side-blown slag and arsenic antimony flue gas, precious metals containing lead blows by blowing antimony converter, produce end water precious metals containing lead and As and Sb flue dust, end water precious metals containing lead enters a point silver stove melting, produce pre-slag, later stage slag, thick silver and flue dust, pre-slag and flue dust return side-blown converter and carry out melting, later stage slag enters bismuth smelting system and carries out bismuth smelting, and thick silver enters silver-colored electrowinning process and carries out refining treatment.
Can find out that the process of lead anode slurry is substantially all adopt smelting furnace from above patent of invention, under the hot conditions of 900 ~ 1000 DEG C or 1000 ~ 1200 DEG C or 1200 ~ 1300 DEG C, retailoring obtains precious metals containing lead, there is following defective workmanship: 1) anode sludge and reductive agent mixing add, in fusion process, be reduced enter precious metals containing lead by the arsenic of natural oxidation, antimony, the consumption of reductive agent is large, the precious metals containing lead productive rate produced is high, precious metals containing lead is on the low side containing Ag grade, back segment precious metals containing lead treatment capacity is large, refining cycle is long, and the output quantity of slag is also large, and when slagging tap, the probability of mechanical entrapment silver is high; 2) anode sludge and flux mixing add, in lead anode slurry, As, Sb oxide compound, plumbous oxide and soda ash comparatively early form highly basic slag, cover bath surface, hinder As, Sb volatilization, cause As, Sb evaporation rate low, the consumption of flux soda ash is large simultaneously, and the slag weight produced containing high-arsenic antimony is large, is unfavorable for the recovery of arsenic antimony; 3) Direct Reductive Melting temperature is relatively high, and fuel, reductive agent and flux consumption are large, directly cause production cost high; 4) Direct Reductive Melting technique, the production cycle is relatively long, and the processing power of smelting furnace is on the low side.
In recent years, anode sludge gold and silver grade declines, and anode sludge quantum of output increases relatively, and the processing cost of the anode sludge constantly rises, and in the urgent need to improving traditional anode slime treatment process, to reduce production cost, improves the throughput of converter.
Summary of the invention
The object of this invention is to provide a kind of method that two sections of melting process lead anode slurries produce precious metals containing lead.
The technical scheme that the present invention's two sections of melting process lead anode slurries produce the method for precious metals containing lead is: first lead anode slurry is added the blowing of converter internal oxidition, treat the voloxidation of arsenic antimony, after flue gas volatilization completely, add reductive agent hard coal and flux soda ash again, by gold and silver, the dysoxidizable metallic reducings such as copper, bismuth, tellurium enter precious metals containing lead, and residual arsenic sb oxide is added flux soda ash slag making removing, concrete technology step is:
Lead anode slurry is loaded in precious metals containing lead converter, open medium and small fire slowly to heat up, smelting temperature controls at 600-700 DEG C, per half an hour rotating furnace once, after forming molten bath in stove, pressurized air is blasted to molten bath, carry out oxidation blowing and accelerate arsenic, antimony volatilizees, oxidation blowing 3.5 ~ 4 hours, turn off the blast, by certain proportion scale, add auxiliary material hard coal and flux soda ash, carry out reducing and slag making, air blast is stirred, furnace temperature rises to 900 ~ 1000 DEG C, weld pool surface forms arsenic antimony skimming, after staticly settling 1.5 hours, slagging, precious metals containing lead is released in cooling, 7 ~ 8 hours production cycles.
The main component of described lead anode slurry is Ag4.59 ~ 12%, Au12 ~ 30g/t, Pb8.66 ~ 23.76%, Sb36.49 ~ 47.5%, As8.1 ~ 16.05%, Cu2.2 ~ 4.09%, Bi5.0 ~ 9.0%, moisture 11 ~ 26%, after natural oxidation, anode sludge degree of oxidation > 50%.
Described hard coal consumption is 0.5 ~ 1% of lead anode slurry weight, and soda ash is 2 ~ 3% of lead anode slurry weight.
Advantage compared with known technology and positively effect:
1, improve the volatilization decreasing ratio of As, Sb, arsenic antimony is comparatively concentrated and is evaporate in flue dust, is convenient to the recycling of follow-up arsenic antimony;
2, precious metals containing lead is improved containing Ag grade, and productive rate reduces, and quantum of output drops to 20 ~ 31% by 55 ~ 65% of lead anode slurry amount, thus, decreases the production load of back segment precious metals containing lead refining, has saved production cost;
3, low-temperature oxidation, decrease fuel consumption, simultaneously the mode that separately adds of hard coal, soda ash and lead anode slurry, make hard coal, soda ash add-on also significantly reduces, especially the add-on minimizing of soda ash makes the life cycle of refractory-lined ovens brick extend, and directly reduces production cost.
4, shorten the production cycle, under quantity-produced condition, the lead anode slurry processing power of original converter improves 50% on existing basis, and the fuel consumption range of decrease is obvious, and lead anode slurry processing cost greatly reduces.
embodiment:
Lead anode slurry and auxiliary material reductive agent, flux are mixed the mode simultaneously entering stove and change into by the present invention in advance, first lead anode slurry is added the blowing of converter internal oxidition, treat the voloxidation of arsenic antimony, after flue gas volatilization completely, add reductive agent hard coal and flux soda ash again, by gold and silver, the dysoxidizable metallic reducings such as copper, bismuth, tellurium enter precious metals containing lead, residual arsenic sb oxide are added flux soda ash slag making removing.Improve the technique that precious metals containing lead is produced in the direct high temperature reduction melting of tradition, adopt first low-temperature oxidation blowing in same converter, the processing method of rear interpolation reductive agent and flux retailoring.
The concrete steps realizing technical scheme of the present invention are: loaded by lead anode slurry in precious metals containing lead converter, open medium and small fire slowly to heat up, smelting temperature controls at 600-700 DEG C, per half an hour rotating furnace once, after forming molten bath in stove, pressurized air is blasted to molten bath, carry out oxidation blowing and accelerate arsenic, antimony volatilizees, oxidation blowing 3.5 ~ 4 hours, turn off the blast, by certain proportion scale, add auxiliary material hard coal and flux soda ash, carry out reducing and slag making, air blast is stirred, furnace temperature rises to 900 ~ 1000 DEG C, weld pool surface forms arsenic antimony skimming, after staticly settling 1.5 hours, slagging, precious metals containing lead is released in cooling, 7 ~ 8 hours production cycles.
The main component of lead anode slurry is Ag4.59 ~ 12%, Au12 ~ 30g/t, Pb8.66 ~ 23.76%, Sb36.49 ~ 47.5%, As8.1 ~ 16.05%, Cu2.2 ~ 4.09%, Bi5.0 ~ 9.0%, moisture 11 ~ 26%, after natural oxidation, anode sludge degree of oxidation > 50%.Hard coal consumption is 0.5 ~ 1% of lead anode slurry weight, and soda ash is 2 ~ 3% of lead anode slurry weight.
embodiment 1:be Ag5.12% by material composition, Au13.79g/t, Pb18.7%, Sb36.13%, As10.37%, Bi5.67%, the lead anode slurry 10t of Cu3.48% joins in precious metals containing lead converter, open medium and small fire, slow intensification, smelting temperature controls at 600 ~ 700 DEG C, per half an hour rotating furnace once, accelerate the fusing of material, material 1.5 ~ 2 hours, compress wind is blasted to molten bath, make arsenic, antimony enters flue gas with the form of white arsenic and antimonous oxide, flue gas volatilization is after 3.5 ~ 4 hours, turn off the blast, add auxiliary material 60kg hard coal and 210kg soda ash, air blast is stirred and is made it to melt completely, turn off the blast, furnace temperature is risen to 900 ~ 1000 DEG C, after staticly settling 1 ~ 1.5 hour, slagging, lower the temperature and precious metals containing lead, 8 ~ 9 hours production cycles.
Result display is as table 1 and table 2:
The productive rate of table 1 the inventive method and former technique ratio of adjuvant and precious metals containing lead contrasts
| Title | Hard coal proportioning (%) | Soda ash proportioning (%) | Precious metals containing lead productive rate (%) |
| Former technique | 6 | 9.04 | 55.13 |
| Example 1 | 0.75 | 2.5 | 24.67 |
The comparison of table 2 the inventive method output precious metals containing lead, reducing slag, flue dust composition and former technique
embodiment 2: be Ag10.13% by material composition, Au14.45g/t, Pb10.4%, Sb36.09%, As10.45%, Bi6.55%, the lead anode slurry 10t of Cu3.16% joins in precious metals containing lead converter, open medium and small fire, slow intensification, smelting temperature controls at 600 ~ 700 DEG C, per half an hour rotating furnace once, accelerate the fusing of material, material is after 1.5 ~ 2 hours, compress wind is blasted to molten bath, make arsenic, antimony enters flue gas with the form of white arsenic and antimonous oxide, flue gas volatilization is after 3.5 ~ 4 hours, turn off the blast, add auxiliary material 50kg hard coal and 200kg soda ash, air blast is stirred and is made it to melt completely, turn off the blast, furnace temperature is risen to 900 ~ 1000 DEG C, after staticly settling 1 ~ 1.5 hour, slagging, lower the temperature and precious metals containing lead, 7 ~ 8 hours production cycles.
Result shows as shown in Table 3 and Table 4:
The productive rate of table 3 the inventive method and former explained hereafter cycle, ratio of adjuvant and precious metals containing lead contrasts
| Title | Production cycle | Hard coal proportioning (%) | Soda ash proportioning (%) | Precious metals containing lead productive rate (%) |
| Former technique | 12h | 5 | 8.12 | 53.23 |
| Example 2 | 8h | 0.6 | 2.1 | 26.63 |
The contrast of table 4 the inventive method output precious metals containing lead, reducing slag, flue dust composition and former technique
Claims (3)
1. the method for one kind two sections melting process lead anode slurry product precious metals containing lead, it is characterized in that: first lead anode slurry is added the blowing of converter internal oxidition, treat the voloxidation of arsenic antimony, after flue gas volatilization completely, add reductive agent hard coal and flux soda ash again, by gold and silver, the dysoxidizable metallic reducing of copper, bismuth, tellurium enters precious metals containing lead, residual arsenic sb oxide is added flux soda ash slag making removing, concrete technology step is:
Lead anode slurry is loaded in precious metals containing lead converter, open medium and small fire slowly to heat up, smelting temperature controls at 600-700 DEG C, per half an hour rotating furnace once, after forming molten bath in stove, pressurized air is blasted to molten bath, carry out oxidation blowing and accelerate arsenic, antimony volatilizees, oxidation blowing 3.5 ~ 4 hours, turn off the blast, by certain proportion scale, add auxiliary material reductive agent hard coal and flux soda ash, carry out reducing and slag making, air blast is stirred, furnace temperature rises to 900 ~ 1000 DEG C, weld pool surface forms arsenic antimony skimming, after staticly settling 1.5 hours, slagging, precious metals containing lead is released in cooling, 7 ~ 8 hours production cycles.
2. according to claims 1, a kind of two sections of melting process lead anode slurries produce the method for precious metals containing lead, it is characterized in that: the main component of lead anode slurry is Ag4.59 ~ 12%, Au12 ~ 30g/t, Pb8.66 ~ 23.76%, Sb36.49 ~ 47.5%, As8.1 ~ 16.05%, Cu2.2 ~ 4.09%, Bi5.0 ~ 9.0%, moisture 11 ~ 26%, after natural oxidation, anode sludge degree of oxidation > 50%.
3. according to claims 1, a kind of two sections of melting process lead anode slurries produce the method for precious metals containing lead, and it is characterized in that: hard coal consumption is 0.5 ~ 1% of lead anode slurry weight, soda ash is 2 ~ 3% of lead anode slurry weight.
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| CN104152702B (en) * | 2014-08-28 | 2016-02-17 | 郴州市金贵银业股份有限公司 | A kind of method of smelting lead anode slurry |
| CN104232912B (en) * | 2014-10-16 | 2016-08-17 | 云南驰宏锌锗股份有限公司 | The technique that the bismuth slag pyrogenic process of a kind of sulfate character reclaims bismuth |
| CN105063363B (en) * | 2015-08-31 | 2017-09-15 | 云南驰宏锌锗股份有限公司 | The method and apparatus that a kind of earth of positive pole prepares thick silver alloy |
| CN106282574B (en) * | 2016-08-25 | 2018-07-24 | 安徽华铂再生资源科技有限公司 | Reviver electrolysis anode sludge low smelting heat technique |
| CN108456777B (en) * | 2018-03-27 | 2020-01-14 | 广西万仕智稀贵金属科技有限公司 | Method for preparing rich noble lead from noble antimony |
| CN114438330B (en) * | 2021-12-31 | 2024-01-05 | 成都易态科技有限公司 | Resource grading recovery method for nonferrous metal smelting anode mud |
| CN115627367B (en) * | 2022-10-14 | 2023-10-13 | 北京科技大学 | Method for cooperatively smelting lead and antimony |
| CN115744837A (en) * | 2022-12-11 | 2023-03-07 | 郴州市金贵银业股份有限公司 | Method for enriching and recovering tellurium from high-bismuth precious lead |
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