CN101654744A - Reverberatory furnace pyrorefining method of crude copper with high arsenic and antimony - Google Patents
Reverberatory furnace pyrorefining method of crude copper with high arsenic and antimony Download PDFInfo
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- CN101654744A CN101654744A CN200910018365A CN200910018365A CN101654744A CN 101654744 A CN101654744 A CN 101654744A CN 200910018365 A CN200910018365 A CN 200910018365A CN 200910018365 A CN200910018365 A CN 200910018365A CN 101654744 A CN101654744 A CN 101654744A
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Abstract
The invention relates to a reverberatory furnace pyrorefining method of crude copper with high arsenic and antimony which is a pyrorefining method combining melting, redox volatilizing and composite alkaline fusing agent slagging together. When refining the crude copper with high content of arsenic, antimony and other impurities in the reverberatory furnace, the process comprises the following steps: firstly performing fusion volatilization and redox volatilization and slagging with composite alkaline fusing agent to realize multiple stage purification. The invention has the advantage of simple process, high production efficiency and the like.
Description
Technical field:
The invention belongs to the nonferrous metallurgy field, relate to a kind of high arsenic, the difficult treatment process of impurity blister copper in the reflection refining furnace of removing of antimony.
Background technology:
Along with continuing to increase of China's non-ferrous metal consumers demand amount, make all kinds of non-ferrous metal concentrate supply wretched insufficiencies, resource has more and more become the restriction bottleneck of Economic development, countries in the world are all when actively seeking new ore source, also, research and develop new technology and handle the complex multi-metal ore deposit that prior art is difficult to adapt to, particularly high arsenic, the low-grade copper mine of antimony all making great efforts to accelerate the non-ferrous metals industry science and technology development, to alleviate the resource anxiety, satisfy the production needs.---melting---five links such as blowing---pyrorefining---electrorefining etc. that the smelting process of copper is from ore dressing substantially.The purpose of blister copper pyrorefining be for electrorefining provide surfacing, thickness evenly, compact structure and chemical ingredients meet the anode copper of processing requirement, to guarantee electrolytic copper quality and electrorefining cheaply.
From bessemerizing the blister copper of output, except that sulfur-bearing and oxygen were very high, the difference of looking the raw ore source also contained some other impurity, as arsenic, antimony, lead, tin, zinc, iron, cobalt, nickel etc., still contains rare elements and precious metals such as selenium, tellurium, gold and silver in addition.The copper ore concentrates that troublesome impurity is lower, the blister copper total impurities of producing generally in 0.7%～2.5% scope, all meet national blister copper standard 1～No. 3.At present, though that the fire refining process of China's prior art has is multiple, mostly be to adopt the above-mentioned blister copper that meets national standard as refinery feedstock, the anode copper of output just can meet the electrorefining requirement.Yet to high arsenic, the difficult impurity blister copper of removing of antimony, but the present method of refining of also not finding comparative maturity and industrialization as yet.
Prior art is relatively poor to the adaptability of raw material, or requires that raw material is of high grade, troublesome impurity is low, otherwise consumes energy big, produce no benefit.The high arsenic of the present invention, antimony copper material pyrorefining removal method a kind ofly exactly can be handled low-grade refractory impurity and are reduced to the electrorefining requirement, can make production cost control to a kind of pyrorefining technology within the profit scope again.
Summary of the invention:
The reverberatory furnace pyrorefining method that the objective of the invention is to avoid the deficiencies in the prior art and high arsenic, antimony blister copper are provided, the refinery practice that utilizes fusing, redox volatilization to combine with compound basic flux slag making, volatilization of troublesome impurities such as the arsenic of high level in the blister copper, antimony or slag making are removed, thereby produce the qualified anode copper that meets the requirement of subsequent processing electrorefining.
The technical solution adopted in the present invention is:
The reverberatory furnace pyrorefining method of high arsenic, antimony blister copper, it mainly is a kind of pyrorefining method that combines with compound basic flux slag making by fusing, redox volatilization, by the blister copper high to foreign matter contents such as arsenic, antimony, in reverberatory furnace during refining, earlier through fusing volatilization and redox volatilization, come the multistage Technology that removes impurity by compound basic flux fluxing effect again, its refining key step is:
1) fusing, negative pressure volatilization: in charging, melting process, keep negative pressure in the stove, pressure is 30-100Pa, treat that furnace charge melts fully after, remove surface scum immediately;
2) desulfurization, redox: after surface scum scratches clean, will melt copper dissolution solution and change normal desulfurization operations over to; After desulfurization finished, to the heating of copper liquid, temperature was 1250-1300 ℃; Successively insert welding airduct 1-3 root and dry, the internal diameter of welding airduct is generally 45mm, until copper liquid sample section three/titanium dioxide purple plague purpura is arranged; Adding diameter is that coke granule 200-500Kg reduces among the 15-25mm, continues to dry, further volatilized arsenic, antimony;
3) compound basic flux slag making: after reduction finishes, scratch clean slag after, continue blowing, keep strong oxidizing atmosphere in the stove, Control for Kiln Temperature when treating that copper liquid sample section all presents the oxidation purple plague purpura, adds compound basic flux and carries out the slag making refining in 1250-1300 ℃;
4) if after the refining of slag making for the first time, the content of As, Sb still is higher than processing requirement in the copper liquid, carry out again for the second time or the slag making refining of more times number, till copper liquid moiety meets the positive plate standard-required.
With the production practice of 75 tons of reflection refining furnaces is example (blister copper composition: copper 93.79%, arsenic 3.07%, antimony 1.22%), and compared with prior art, the effect that the present invention reached mainly shows the following aspects:
1, the extrusion rate height of arsenic, antimony.As is reduced to 0.19% by original 3.07%, and its decreasing ratio is 93.81%; Sb is reduced to 0.13% by original 1.22%, and its decreasing ratio is 89.34%.
2, enlarge the raw material sources channel, obtained certain economic benefits.Because the present invention can effectively handle the high blister coppers of foreign matter content such as arsenic, antimony, therefore alleviated the resource anxiety, satisfy the production demand.Again owing to handle the high blister coppers of foreign matter content such as arsenic, antimony, therefore its procurement unit's cost is calculated from economic benefit than the reduction value of the standard blister copper raw material increased value (unit cost is calculated with the amount of metal of copper) greater than its unit cost production.
3, thoroughly solve difficult arsenic removal, an antimony blister copper pyrogenic process purified Technology difficult problem in reverberatory furnace, and satisfied the processing requirement of electrorefining operation fully.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Describe embodiments of the invention in detail below in conjunction with accompanying drawing.
Embodiment:
At first, the present invention is according to chemical reaction mechanism, and impurity is to the avidity of oxygen, and the oxidation of arsenic, antimony comes after aluminium, silicon, manganese, zinc, tin, iron, the nickel in proper order, and promptly arsenic, the more above-mentioned element of antimony are difficult to oxidation.Therefore, deviate from more completely, must make the Red copper oxide that contains higher concentration in the copper liquid for making arsenic, antimony.Learn according to the principles of chemistry, oxygen level in the copper liquid reaches 1%, promptly be equivalent to contain Red copper oxide 9%, this kind concentration has surpassed the saturation concentration of Red copper oxide in 1150 ℃ the copper melts, carries out so Technology of the present invention melt temperature in operating process must be controlled under the condition that is higher than 1150 ℃.
Secondly, the chemical combination of impurity and dissolving all have certain limit, otherwise, even the melt of copper stands the oxidation of the degree of depth, can not be fully and the flux slag making.So the flux quantity that relates to during the present invention produces changes with blister copper quantity and foreign matter content height thereof, the quantity of blister copper and foreign matter content improve then that the quantity of flux increases thereupon, and the quantity of blister copper and foreign matter content reduce then that the quantity of flux reduces thereupon.Oxidation depth is big, furnace temperature is higher, under the situation of flux reasonable quantity, the removing of arsenic, antimony in high arsenic, the antimony blister copper often only needs 1-2 slag making to finish.Otherwise, if add flux quantity very little, then certainly will will increase the slag making number of times, the prolongation when causing stove is non-remunerative economically on the contrary.
In addition, the operating process of technology of the present invention can not have the existence of reductive agent when adding flux, with impurity such as the arsenic of the oxidized slag making of tetrandra root, antimony, heavily is reduced in the melt of copper.
Step of the present invention mainly contains:
1, fusing, negative pressure volatilization: in batches add reverberatory furnace in charging machine high arsenic, antimony copper material, in charging, melting process, keep negative-pressure operation (30-100Pa) in the stove, guarantee effective volatilization of arsenic, antimony, after treating that furnace charge melts fully, remove surface scum immediately.
2, desulfurization, redox: change normal desulfurization operations after surface scum scratches clean over to, after desulfurization finishes, make the copper hydraulic control in 1250-1300 ℃ temperature range, successively insert the internal diameter that is surrounded by refractory materials and be welding airduct (hereinafter to be referred as airduct) the 1-3 root of 45mm and dry, till copper liquid sample section has three/titanium dioxide purple plague purpura.Add then that coke granule 200-500Kg carries out restoring operation among the 15-25mm so that be oxidized to be difficult to the evaporable pentavalent arsenic, sb oxide is reduced into trivalent, and arsenic, antimony are further volatilized.For make copper liquid contain oxygen not reason add coke and reduce, so blowing should proceed, to reach arsenic, a large amount of evaporable effects of antimony.
3, compound basic flux slag making: after scratching clean slag, change the slag making refining stage over to, continue blowing again, keep under the prerequisite of strong oxidizing atmosphere in the stove, furnace temperature still is controlled in 1250-1300 ℃ the scope, when treating that copper liquid sample section all presents the oxidation purple plague purpura, can add compound basic flux and carry out slag making, after reducing, pass through the disc casting machine again, produce qualified positive plate and send electrorefining.If after the refining of slag making for the first time, the content of As, Sb still is higher than processing requirement in the copper liquid, carry out again for the second time or the slag making refining of more times number, till copper liquid moiety meets the positive plate standard-required.
In process of production, the required air of refining furnace is supplied with by Ventilator Room, and fusing, intensification, the required fuel oil of insulation are supplied with by the oil pump room of oil depot.
Embodiment: the production practice with 75 tons of reflection refining furnaces are example (copper material composition: copper 93.79%, arsenic 3.07%, antimony 1.22%).Carry out refining in the reverberatory furnace of 75 tons of capacity, handle copper material amount is 74 tons at every turn.In charging and melting process,, can insert a branch wind pipe and stir for the fusing of acceleration copper material and effective volatilization of impurity such as arsenic, antimony.After treating that furnace charge melts fully, take surperficial slag off, and under 1250-1300 ℃ furnace temperature, insert two airducts again and dry (wherein one insert from cinder notch), till copper liquid sample section becomes three/titanium dioxide spot.The coke 300Kg that adds granularity this moment immediately and be 15-25mm in the molten bath reduces so that be oxidized to be difficult to the evaporable pentavalent arsenic, sb oxide is reduced into trivalent, further makes arsenic, antimony obtain volatilization.Keeping bath surface to have under the situation of suitable coke layer, should keep two airducts to continue blowing, the oxidation-reduction process is carried out simultaneously, up to blow all present the oxidation spot to copper liquid sample section till.
The volatilization removal of impurities stage scratches clean slag after finishing.If copper liquid style has sulphur to exist, carry out desulfurization operations earlier.After the end to be desulfurization, can add compound basic flux and carry out the refining slag making first time, its flux consists of: lime 2000Kg, fluorite 1000Kg.Flux adds the back and stirs slag making 1.5 hours with two airduct blowings, removes slag then.The content of arsenic, antimony is respectively 0.57%, 0.38% in the sample examination copper liquid after the slag making refining first time.
After slag making for the first time finished, as long as sample section still is whole oxidation spot shapes, copper liquid temperature can add composite fluxing agent refining slag making for the second time within 1250-1300 ℃ scope, and its flux consists of: lime 1500Kg, fluorite 750Kg.Flux adds the back and stirs slag making 1 hour with two airduct blowings, removes slag then.The content of arsenic, antimony is respectively 0.29%, 0.20% in the sample examination copper liquid after the slag making refining second time.
After slag making for the second time finished, as long as sample section still is whole oxidation spot shapes, copper liquid temperature can add the slag making of composite fluxing agent refining for the third time within 1250-1300 ℃ scope, and its flux consists of: lime 1000Kg, fluorite 500Kg.Still keep two airduct blowings to stir slag making 40 minutes after flux adds, remove slag then.The content of arsenic, antimony is respectively 0.19%, 0.13% in the sample examination copper liquid after slag making refining for the third time, has promptly reached the requirement of high arsenic, antimony copper material pyrorefining anode copper composition.
Claims (3)
1, the reverberatory furnace pyrorefining method of high arsenic, antimony blister copper, it mainly is a kind of pyrorefining method that combines with compound basic flux slag making by fusing, redox volatilization, by the blister copper high to foreign matter contents such as arsenic, antimony, in reverberatory furnace during refining, earlier through fusing volatilization and redox volatilization, come the multistage Technology that removes impurity by compound basic flux fluxing effect again, it is characterized in that the refining key step is:
1) fusing, negative pressure volatilization: in charging, melting process, keep negative pressure in the stove, pressure is 30-100Pa, treat that furnace charge melts fully after, remove surface scum immediately;
2) desulfurization, redox: after surface scum scratches clean, will melt copper dissolution solution and change normal desulfurization operations over to; After desulfurization finished, to the heating of copper liquid, temperature was 1250-1300 ℃; Successively insert welding airduct 1-3 root and dry, three/titanium dioxide purple plague purpura is arranged until copper liquid sample section; Adding diameter is that coke granule 200-500Kg reduces among the 15-25mm, further volatilized arsenic, antimony;
3) compound basic flux slag making: after reduction finishes, scratch clean slag after, continue blowing, keep strong oxidizing atmosphere in the stove, Control for Kiln Temperature when treating that copper liquid sample section all presents the oxidation purple plague purpura, adds compound basic flux and carries out the slag making refining in 1250-1300 ℃;
4) if after the refining of slag making for the first time, the content of As, Sb still is higher than processing requirement in the copper liquid, carry out again for the second time or the slag making refining of more times number, till copper liquid moiety meets the positive plate standard-required.
2, the reverberatory furnace pyrorefining method of high arsenic according to claim 1, antimony blister copper is characterized in that the internal diameter that welds airduct is generally 45mm.
3, the reverberatory furnace pyrorefining method of high arsenic according to claim 1, antimony blister copper is characterized in that in step 2) in add coke when carrying out reduction reaction, continue to dry, so that arsenic, antimony volatilization.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602834A (en) * | 2013-11-07 | 2014-02-26 | 昆明理工大学 | Selective oxidation-reduction method for recycling arsenic and antimony from arsenic-antimony smoke |
| CN114350975A (en) * | 2022-01-06 | 2022-04-15 | 高诺(衡阳)新材料有限责任公司 | Reverberatory furnace fire refining method for high-arsenic and high-antimony crude copper |
| CN115109945A (en) * | 2022-06-30 | 2022-09-27 | 金川集团股份有限公司 | Impurity removal method for PS copper converter |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602834A (en) * | 2013-11-07 | 2014-02-26 | 昆明理工大学 | Selective oxidation-reduction method for recycling arsenic and antimony from arsenic-antimony smoke |
| CN114350975A (en) * | 2022-01-06 | 2022-04-15 | 高诺(衡阳)新材料有限责任公司 | Reverberatory furnace fire refining method for high-arsenic and high-antimony crude copper |
| CN115109945A (en) * | 2022-06-30 | 2022-09-27 | 金川集团股份有限公司 | Impurity removal method for PS copper converter |
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Application publication date: 20100224 |