CN103924094B - A kind of method processing copper scum silica frost - Google Patents
A kind of method processing copper scum silica frost Download PDFInfo
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Abstract
The present invention provides a kind of method processing copper scum silica frost, described method adopts oxygen enriched molten bath side-blown converter for smelting process copper scum silica frost, coal grain is used to do reductive agent and fuel, prepare burden with copper scum silica frost, soda ash, sulfurous iron ore and water slag, stove is entered through belt from oxygen enriched molten bath side-blown converter for smelting feed opening together with coal grain, and blast oxygen-rich air bath smelting, obtain lead bullion, matte, slag and high-temperature flue gas. Method provided by the invention can realize continuous charging, DCS automatic control technology, and labor strength is low, and flushing and casting environment is good, and side-blown stove process bed ability is big, bath smelting efficiency height, and metal recovery rate height smelts energy consumption low.
Description
Technical field
The invention belongs to metallurgical technology field, it relates to a kind of method processing copper scum silica frost.
Background technology
In prior art, copper scum silica frost treatment process has reverberatory furnace method, Blast Furnace Method, converter process, electric furnace process, pickling process, ammonia leaching process etc.
Wherein, reverberatory furnace method technique labor condition is poor, thermo-efficiency is low and furnace lining corrodes block, maintenance frequently, is classified as time limit by country and eliminates technique. Blast Furnace Method process copper scum silica frost, plumbous of high grade in copper matte regulus, copper grade is low, Cu/Pb lower (only having 2��3), and the rate of recovery that is plumbous and copper is low, and a large amount of copper is stayed in lead bullion, and a large amount of lead enters copper matte regulus, causes copper, arsenic and precious metal to circulate during the course. Rotary kiln (also known as rotary furnace) processes copper scum silica frost and there is diesel consumption relatively big (5��6%), the problem that production cost is higher. There is electricity consumption high (electricity consumption 340��380kwh/t, coke 40��50kg/t) in electric furnace process, the shortcomings such as running cost expense height, are difficult in the area of power tense realize. Pickling process, ammonia leaching process, owing to being all the reaction principle utilizing metallic copper in copper scum silica frost and solvent, are applicable to the copper scum silica frost that Treatment of Copper is high, deal with uneconomical for the copper scum silica frost low containing copper, and wet processing cost height.
The patent of invention that the patent No. is ZL200810058951.9 discloses a kind of method that converter processes copper scum silica frost, and the method comprises prepares burden copper scum silica frost, soda ash, iron filings or sulfurous iron ore and cigarette according to certain ratio, adds retailoring in converter. Control temperature 700��800 DEG C, smelts 1.5��2 hours, and the lead of the metal form in copper scum silica frost is separated with copper, thereafter temperature is improved to slag temperature of superheat 1100��1250 DEG C, smelting 2.5��3 hours, make plumbous compound reduction generate metallic lead, copper then enters matte and achieves asunder copper and lead. Scum silica frost on matte and lead bullion is pulled out, obtains matte and lead bullion. The method makees reductive agent with coal, blast air does fuel with diesel oil.
Application number be 201010582745.5 patent of invention disclose the smelting process of a kind of copper scum silica frost, the method comprises copper scum silica frost oxidation blowing output silver Guillaume metal, flue dust and chloride slag; Silver Guillaume metal electrolysis output cathode copper and copper anode mud, copper anode mud leaches, leach liquor first heavy bismuth obtain chlorine oxygen bismuth, chlorine oxygen bismuth is through the thick bismuth of retailoring output, more heavy copper obtains copper hydroxide, leaches slag rotary kiln melting output slightly silver, flue dust and oxidation sludge; Thick silver electrolysis output finished product silver and silver anode slime, reclaim Au, Pt, Pd from silver anode slime; Oxidation sludge and oxidation sludge retailoring of blast furnace obtain lead antimony alloy, flue dust and slag, and lead antimony alloy reverberatory smelting obtains lead bullion and flue dust; Flue dust reverberatory smelting output lead bullion and weisspiessglanz, weisspiessglanz retailoring output needle antimony; Lead bullion and lead bullion electrolysis output be plumbous and lead anode slurry, reclaims gold and silver from lead anode slurry. The technical process that the method is taked is complicated, and output intermediate material is many.
Application number be 201110343390.9 patent of invention disclose and a kind of be separated the plumbous method producing copper and silver in copper scum silica frost of refining, the method comprises produces copper scum silica frost solid materials by refining lead, under being placed in vacuum condition, after repeatedly heating up, being incubated, collect volatile matter, condensation obtains pb-ag alloy, and remaining solid is slough copper alloy that is plumbous and silver; Pb-ag alloy enters conventional plumbous smelting procedure or electrorefining operation again as raw material, and silver is enriched in the anode sludge, is namely recycled silver; Slough plumbous and silver-colored copper alloy directly as raw material, namely it is recycled metallic copper with conventional way. But the hollow furnace apparatus that the method adopts is difficult to maximize at present, cannot realize scale production.
Application number be 201210160123.2 patent of invention disclose the method that lead bullion is produced in the side-blown melting of a kind of copper scum silica frost, the method comprises prepares burden copper scum silica frost, soda ash, sulfurous iron ore according to the ratio of 100:8��10:6��8, uniform feeding 1��2 hour, feed temperature 600��800 DEG C, evenly blasts hard coal with high-pressure blast simultaneously; Finishing material and after 1��2 hour, temperature is increased to 1100��1200 DEG C of melting 2��3 hours again 600��800 DEG C of meltings, metallic lead and chemical combination state lead in copper scum silica frost are all entered lead bullion by melting; Stopping the blasting of hard coal, clarified separation, after 0.5��1 hour, first releases lead bullion and matte by siphon, then opens cinder notch and release slag, high-temperature flue gas through waste heat recovery, gather dust after up to standard emptying. The method adopts is interrupted mode of operation, blasts hard coal with high-pressure air and carries out melting reaction, and production efficiency is low, melting energy consumption height, processing charges height.
Summary of the invention
Therefore, it is an object of the invention to for the deficiencies in the prior art, thering is provided a kind of new copper scum treatment method, method provided by the invention can realize continuous charging, DCS automatic control technology, labor strength is low, flushing and casting environment is good, and side-blown stove process bed ability is big, bath smelting efficiency height, metal recovery rate height, smelts energy consumption low.
The present invention provides a kind of method processing copper scum silica frost, and described method adopts oxygen enriched molten bath side-blown converter for smelting process copper scum silica frost, it may also be useful to coal grain does reductive agent and fuel. Prepare burden with copper scum silica frost, soda ash, sulfurous iron ore and water slag, enter stove through belt from oxygen enriched molten bath side-blown converter for smelting feed opening together with coal grain, and blast oxygen-rich air bath smelting, obtain lead bullion, matte, slag and high-temperature flue gas.
Specifically, the method for process copper scum silica frost provided by the invention comprises the following steps:
1) copper scum silica frost, soda ash, sulfurous iron ore and water slag are prepared burden with the ratio of mass ratio 100:2��4:5��20:5��15, evenly uninterruptedly throw material 10��30t/h, simultaneously from coal 0.8��3t/h oxygen enriched molten bath side-blown converter for smelting feed opening, blast oxygen-rich air 2000��3000m3/ h, oxygen concn is 40��80%; Control melting atmosphere (reducing degree) carries out retailoring;
3) metallic lead in copper scum silica frost and the plumbous melting of chemical combination state enter lead bullion, are discharged by the siphon of siphon road, and copper is discharged by matte mouth with copper matte regulus form, and the slag containing very low lead and copper is discharged by cinder notch, produces high-temperature flue gas simultaneously.
Preferably, the mass ratio of described copper scum silica frost, soda ash, sulfurous iron ore and water slag is 100:2:8:8
Preferably, the specification of described oxygen enriched molten bath side-blown converter for smelting is 4-12m2, it is preferable that it is selected from 4.8m2��6m2��7.2m2��8.4m2��12m2Oxygen enriched molten bath side-blown converter for smelting; Further preferably, the specification of oxygen enriched molten bath side-blown converter for smelting is 6m2;
Preferably, bottom described oxygen enriched molten bath side-blown converter for smelting, it is provided with safe mouth, discharges the end by safety mouth when blowing out situation occurs plumbous.
Preferably, described copper scum silica frost is containing plumbous 40��80wt%, copper scum silica frost containing copper 4��12wt%.
Preferably, described sulfurous iron ore sulphur content is 15��48wt%;
Preferably, the high-temperature flue gas produced in process copper scum silica frost is gathered dust by waste heat boiler recovery waste heat, pulse dust-precipitator, qualified discharge after thionizer desulfurization, and described emission standard is SO2Concentration is less than 220mg/m3��
Preferably, making siphon road keep unobstructed, the lead tolerance according to entering stove batching freely discharges lead bullion.
Preferably, in step 3), the interval phase of the copper that described matte mouth discharges copper matte regulus form is 1��4h;
Preferably, described cinder notch discharges the interval phase of slag is 2��4h.
Preferably, described coal grain consumption is the 8��15% of copper scum silica frost quality, and further preferably, described coal grain consumption is the 8��11% of copper scum silica frost quality; Again further preferably, described coal grain consumption is the 9.3% of copper scum silica frost quality.
The advantage that the present invention has compared with conventional art:
1) smelting that energy consumption is low, processing charges economy, detailed data are in table 1
The common copper scum silica frost process energy consumption index of table 1
As can be seen from Table 1, energy consumption of the present invention is lower than the energy consumption of other several techniques. The present invention uses coal grain as fuel or reductive agent, and with coke, diesel oil or electric energy, hard coal is compared, and coal grain is cheap, and buying is convenient. The present invention adopts oxygen enriched molten bath melting, and exhaust gas volumn is few, and heat utilization efficiency is the highest, and other several techniques all blast air melting, and exhaust gas volumn is big, thermal losses height. Therefore the present invention smelts that energy consumption is low, processing charges economy.
2) the present invention adopts continuous work production, and other several techniques all adopt interruption mode of operation, therefore smelting efficiency height of the present invention, is more suitable for technical scaleization application.
3) pickling process, the reaction process of ammonia leaching process owing to being all metallic copper and solvent, copper content its direct yield more high is more high, is therefore applicable to the high copper scum silica frost of Treatment of Copper, deals with uneconomical for the copper scum silica frost low containing copper.
But the present invention is easy to the copper segregation in the copper scum silica frost low containing copper is obtained the matte of Cu/Pb than high (4��10).
4) application number be 201210160123.2 the patent of invention method of lead bullion " the side-blown melting of a kind of copper scum silica frost produce " output slag in valuable metal height, slag is containing Pb��2.8%, and slag is containing Cu��0.5%, and metal direct yield is low. Slag of the present invention is containing Pb��1.5%, and slag is containing Cu��0.3%, metal direct yield and rate of recovery height.
Accompanying drawing explanation
Hereinafter, come by reference to the accompanying drawings embodiment of the present invention are described in detail, wherein:
Fig. 1 is the schema of one embodiment of the invention.
Fig. 2 is the schema of another embodiment of the invention.
Embodiment
Embodiment 1
As shown in Figure 1, at 6m2Oxygen enriched molten bath side-blown converter for smelting in, by copper scum silica frost (Pb72%, Cu8.1%), soda ash, sulfurous iron ore (S32%), water slag, prepare burden according to the ratio of mass ratio 100:3:6:12, throw material 3h, amount to 60t, simultaneously from coal 6.6t feed opening, blast oxygen-rich air 2300Nm3/ h, oxygen concentration 51%.
Releasing lead bullion by plumbous siphon road, output lead bullion 33.6t(is containing plumbous 97.5%, Cu0.4%), the lead bullion of output needs to go plumbous refining; By matte mouth output matte (containing plumbous 5.4%, Cu43%) 8.4t, the matte of output removes converter smelting; Putting slag (containing plumbous 1.4%, Cu0.28%) 11.7t by slag notch, this slag is for selling outward; High-temperature flue gas passes through waste heat boiler recovery waste heat, after being gathered dust by pulse, through thionizer desulfurization, and qualified discharge (SO2Concentration is less than 220mg/m3), the flue dust obtained in wherein gathering dust with pulse in waste heat boiler carries out plumbous smelting.
Output cigarette ash 5.2t, coal grain consumption is the 13.3% of copper scum silica frost amount, and plumbous direct yield 91.8%, the rate of recovery 99.5%, copper recovery 89.9%, matte Cu/Pb ratio is 7.96.
Embodiment 2:
As shown in Figure 1, at 6m2Side-blown stove in, by copper scum silica frost (Pb72%, Cu8.1%), soda ash, sulfurous iron ore (S32%), water slag, prepare burden according to the ratio of mass ratio 100:3:5:8, throw material 4h, amount to 80t, simultaneously from coal 8.8t feed opening, blast oxygen-rich air 2500Nm3/ h, oxygen concentration 54%.
Lead bullion is released by plumbous siphon road, output lead bullion 47.3t(is containing plumbous 97.5%, Cu0.4%), cigarette ash 8.3t, slag is (containing plumbous 1.3%, Cu0.25%) 12.1t, matte (containing plumbous 5.1%, Cu46%) 11.7t, plumbous direct yield 92.9%, the rate of recovery 99.7%, copper recovery 92.2%, matte Cu/Pb ratio is 9.02.
Embodiment 3:
As shown in Figure 1, at 6m2Side-blown stove in, by copper scum silica frost (Pb57%, Cu10.2%), soda ash, sulfurous iron ore (S32%), water slag, prepare burden according to the ratio of mass ratio 100:2:8:8, throw material 4h, amount to 48t, simultaneously from coal 3.8t feed opening, blast oxygen-rich air 2300Nm3/ h, oxygen concentration 56%.
Releasing lead bullion by plumbous siphon road, output lead bullion 21.6t(is containing plumbous 97.5%, Cu0.4%), cigarette ash 4.9t, slag (containing plumbous 1.2%, Cu0.24%) 13.5t, matte (containing plumbous 5.2%, Cu48%) 7.7t, plumbous direct yield 93.1%, the rate of recovery 99.3%, copper recovery 89.1%, matte Cu/Pb ratio is 9.1.
Embodiment 4:
As shown in Figure 1, at 6m2Side-blown stove in, by copper scum silica frost (Pb57%, Cu10.2%), soda ash, sulfurous iron ore (S32%), water slag, prepare burden according to the ratio of mass ratio 100:4:15:5, throw material 4h, amount to 60t, simultaneously from coal 7.3t feed opening, blast oxygen-rich air 2300Nm3/ h, oxygen concentration 57%.
Lead bullion is released by plumbous siphon road, output lead bullion 24.3t(is containing plumbous 97.5%, Cu0.4%), cigarette ash 4.7t, slag is (containing plumbous 2.5%, Cu0.48%) 23.8t, matte (containing plumbous 8.7%, Cu35%) 10.5t, plumbous direct yield 85.9%, the rate of recovery 97.8%, copper recovery 74.5%, matte Cu/Pb ratio is 4.02.
Claims (13)
1. one kind processes the method for copper scum silica frost, described method adopts oxygen enriched molten bath side-blown converter for smelting process copper scum silica frost, coal grain is used to do reductive agent and fuel, prepare burden with copper scum silica frost, soda ash, sulfurous iron ore and water slag, enter stove from oxygen enriched molten bath side-blown converter for smelting feed opening together with coal grain, and blast oxygen-rich air bath smelting, obtain lead bullion, matte, slag and high-temperature flue gas, wherein, described method comprises the following steps:
1) copper scum silica frost, soda ash, sulfurous iron ore and water slag are prepared burden with the ratio of mass ratio 100:2��4:5��20:5��15, evenly uninterruptedly throw material 10��30t/h, simultaneously from coal grain 0.8��3t/h oxygen enriched molten bath side-blown converter for smelting feed opening, blast oxygen-rich air 2000��3000m3/ h, oxygen concn is 40��80%; Carry out retailoring; Wherein, described coal grain consumption is the 8��15% of copper scum silica frost quality;
2) metallic lead in copper scum silica frost and the plumbous melting of chemical combination state enter lead bullion, are discharged by the siphon of siphon road, and copper is discharged by matte mouth with copper matte regulus form, and the slag containing very low lead and copper is discharged by cinder notch, produces high-temperature flue gas simultaneously.
2. method according to claim 1, wherein, the mass ratio of described copper scum silica frost, soda ash, sulfurous iron ore and water slag is 100:2��4:5��20:5��15.
3. method according to claim 1 and 2, wherein, the specification of described oxygen enriched molten bath side-blown converter for smelting is 4-12m2��
4. method according to claim 1 and 2, wherein, the specification of described oxygen enriched molten bath side-blown converter for smelting is selected from 4.8m2��6m2��7.2m2��8.4m2And 12m2��
5. method according to claim 1 and 2, wherein, the specification of described oxygen enriched molten bath side-blown converter for smelting is 6m2��
6. method according to claim 1 and 2, wherein, is provided with safe mouth bottom described oxygen enriched molten bath side-blown converter for smelting, discharges the end by safety mouth plumbous when there is blowing out situation.
7. method according to claim 1 and 2, wherein, described copper scum silica frost is containing plumbous 40��80wt%, copper scum silica frost containing copper 4��12wt%.
8. method according to claim 1 and 2, wherein, described sulfurous iron ore sulphur content is 15��48wt%.
9. method according to claim 1 and 2, wherein, described high-temperature flue gas is by waste heat boiler recovery waste heat, and pulse dust-precipitator gathers dust, qualified discharge after thionizer desulfurization, and described emission standard is SO2Concentration is less than 220mg/m3��
10. method according to claim 1 and 2, the interval phase of the copper that wherein said matte mouth discharges copper matte regulus form is 1��4h.
11. methods according to claim 1 and 2, it is 2��4h that wherein said cinder notch discharges the interval phase of slag.
12. methods according to claim 1 and 2, wherein, described coal grain consumption is the 8��12% of copper scum silica frost quality.
13. methods according to claim 1 and 2, wherein, described coal grain consumption is the 9.3% of copper scum silica frost quality.
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| CN109439924A (en) * | 2018-12-05 | 2019-03-08 | 湖南锐异资环科技有限公司 | A kind of processing method of secondary lead-containing material |
| CN111719045A (en) * | 2019-03-21 | 2020-09-29 | 个旧市锦星锑业有限公司 | Oxygen-enriched intensified smelting method for horizontal reduction furnace |
| CN110564972B (en) * | 2019-08-02 | 2024-05-10 | 四川正祥环保技术有限公司 | Treatment method and treatment system for copper removal scum of lead electrolysis anode |
| CN110560076B (en) * | 2019-09-25 | 2022-03-25 | 哈尔滨工业大学 | Preparation method and application of nano Cu-Bi alloy catalyst |
| CN113201654A (en) * | 2021-04-29 | 2021-08-03 | 江西金德铅业股份有限公司 | Novel process method for smelting copper dross in reverberatory furnace |
| CN114015875A (en) * | 2021-09-18 | 2022-02-08 | 济源市万洋冶炼(集团)有限公司 | Method for lead-copper co-smelting and dilution treatment of lead-copper mixed material |
| CN116005019A (en) * | 2022-12-15 | 2023-04-25 | 梧州华锡环保科技有限公司 | Method for promoting efficient recovery of antimony-containing hazardous waste materials based on self-heating of pyrite |
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