CN1233857C - Decoppering refining agent in use for fire refining of non-ferrous metal with low melting point and technical procedure - Google Patents
Decoppering refining agent in use for fire refining of non-ferrous metal with low melting point and technical procedure Download PDFInfo
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- CN1233857C CN1233857C CN 200310110830 CN200310110830A CN1233857C CN 1233857 C CN1233857 C CN 1233857C CN 200310110830 CN200310110830 CN 200310110830 CN 200310110830 A CN200310110830 A CN 200310110830A CN 1233857 C CN1233857 C CN 1233857C
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Abstract
The present invention relates to a decoppering refining agent used for the fire refining of non-ferrous metals with low melting points and a process for the decoppering refining agent, which belongs to the technical field of fire refining in non-ferrous metallurgy. The decoppering refining agent of the present invention comprises industrial NaOH and sulphur, wherein the addition of the industrial NaOH is 1.0 to 2.0% of the total amount of crude metals, and the addition of the sulphur is 1.25 times as much as the copper content of crude metals; the decoppering process for the agent comprises the following steps: the industrial NaOH accounting for 1.0 to 2.0% of the total amount of crude metals is added when the temperature is 280 DEG C, the water content of the NaOH is 25 to 30%, the industrial NaOH is stirred, and the sulphur which is 1.25 times as much as the copper content of the crude metals is pressed in when the NaOH is melted and floats on metal surface in a pasty shape; then, the NaOH and the sulphur are stirred for 30 minutes by starting a stirrer when heated to a temperature of 650 to 680 DEG C, and cooled to a temperature of 450 to 500 DEG C by static banked fire; slag is taken out when refined floating slag encrusts and is separated from metal melt. The present invention has the advantages that the present invention can increase decoppering efficiency by more than 5 times, and reduce the content of slag (bismuth, stannum and copper) to 1.7 to 4.5% from 65 to 70%; in addition, the present invention has the advantages of high recovery rate of metals, short decoppering refining time, low consumption of energy and labour, increase in labor productivity and the productivity of unit equipment, etc.
Description
Technical field:
The present invention relates to the copper removal refinery practice in the pyrorefining of a kind of low melting point non-ferrous metal, belong to the pyrorefining technical field in the Non-ferrous Metallurgy.
Background technology:
The traditional method of low melting point non-ferrous metal pyrorefining copper removals such as bismuth, lead, tin is for adding sulphur copper removal method.But this traditional sulphur copper removal purifying method that adds has following shortcoming: when adding sulphur under (1) temperature more than melting point metal, the as easy as rolling off a log fierce burning of Sulfur has not only increased sulfury consumption, and operator's safety is formed threat; (2) copper removal efficient is low, make the copper content of crude metal drop to 0.001～0.0005% from 0.0x%, need carry out adding sulphur and reaching two hours stirring and the cooling that heats up for a long time at every turn repeatedly, and the unit equipment productivity and the labour productivity of copper removal process are very low; (3) copper ashes contains purpose metal height, and the metal recovery rate of copper removal process is low.Pyrorefining with bismuth is an example, and the slag bismuth-containing that adds the sulphur copper removal reaches 55～70%, drags for copper ashes and takes away a large amount of bismuths, and the direct yield of bismuth is descended.
By literature search, do not see with constructed the disclosing of the present invention and report for work.
Summary of the invention:
The objective of the invention is to overcome the deficiency of prior art, and a kind of copper removal efficient height is provided, remove process for copper in the high low melting point non-ferrous metal pyrorefining of the direct yield of purpose metal.
Principle of the present invention is as follows:
The principal reaction of low melting point metal copper removal purified is:
According to the calculating of compound free energy of formation, (280 ℃ ±) at a lower temperature, sulphur, help sulphur and are absorbed by base metal (Bi, Sn, Pb) greater than the avidity to copper the avidity of Bi, Sn, Pb this moment, sulfide (Bi in the middle of generating
2S
3, SnS, PbS), and under comparatively high temps (as 650 ℃ ±), greater than the avidity to purpose metal (Bi, Sn, Pb), this temperature helps reaction (1), (2) to sulphur, carry out to the right (3) to the avidity of copper, and the middle sulfide that low temperature is generated is converted into cupric sulfide and enters the slag phase.And the adding of NaOH has not only reduced the dissolving of the relative purpose metal of slag, has also alleviated the proportion of slag phase, has reduced the fusing point of slag phase, helps Cu
2The S slag more helps purpose metal (bismuth, tin, copper) with the separation of slag with the separation of metal, significantly reduces the mechanical entrapment of the relative purpose metal of slag, has improved the metal direct recovery rate.The adding of NaOH has reduced Cu in addition
2S helps Cu in the activity or the concentration of slag in mutually
2S enters the slag phase, has increased the efficient of copper removal.
Copper removal refinery practice of the present invention comprises fusion in advance, but the different steps of removing process for copper independently add respectively industrial NaOH and last time copper removal drag for slag, and Sulfur at last; Wherein, industrial NaOH and last time copper removal the add-on of dragging for slag at last be 1.0%～2.0% of crude metal total amount, the sulfury add-on is 1.25 times of crude metal copper content.
The process for copper that removes of the present invention is that low temperature adds sulphur alkali, the high temperature copper removal, slag is dragged in cooling, that is: when temperature is 280 ℃, add crude metal total amount 1.0%～2.0% industrial NaOH and last time copper removal drag for slag at last, NaOH and last time copper removal to drag for the moisture that slag contains at last be 25～30%, when stirring is treated NaOH and is dragged for the slag fusing and float over the metallic surface, be pressed into Sulfur for 1.25 times of crude metal copper contents, be warmed up to 650～680 ℃ then, starting stirrer this moment stirred 30 minutes, leave standstill banking fire then and cool to 450～500 ℃, treat refining scum silica frost crust and drag for slag when separating with metal melt.
Described copper removal refinery practice adapts to the copper refining that removes that is used for bismuth, tin and lead, and the number of times of its copper removal is decided with the copper content height of crude metal.
The sulphur that adds of the present invention and routine removes copper refining and compares and have following advantage: (1) copper removal efficiency ratio routine adds the sulphur copper removal and improves 4～5 times; (2) add the sulphur copper removal with routine and compare, the time that copper removal consumed is only for to add 1/4～1/6 of sulphur copper removal, thereby unit equipment productivity and labour productivity increase substantially; (3) slag rate is few, and slag metal-containing is few, thus the direct yield height of purpose metal; (4) energy consumption reduces to 1/4～1/5; (5) security is good, can not produce the fierce oxidizing fire of sulfury; (6) because the adding of NaOH in the copper removal process, also has subsidiary effect of removing impurity such as Fe, As, Sb, reduced time and the consumption of time step refining except that Fe, As, Sb.
Embodiment:
Embodiment 1 (the efficient copper refining that removes of thick bismuth):
Get the thick bismuth of 3T, copper content is 0.034%, in kier after the heat fused, banking fire cools to 280 ℃, add thick bismuth and weigh (45 kilograms of 1.5% industrial NaOH, wherein 10 kilograms for last time copper removal drag for slag at last), after NaOH added, metallic surface temperature descended, and suitably manual the stirring makes temperature even up and down, and adjust slag mutually and the temperature to 280 of metal ℃, the Sulfur (1.3 kilograms) that adds 1.25 times of thick bismuth copper contents, Sulfur with clip be inserted into slag mutually in, covered by the thickness scum silica frost immediately, can prevent its oxidizing fire, for granular or powdered Sulfur.After the adding, stir rapidly, it is coated also mutually by slag can prevent oxidizing fire.After this after manual a little the stirring, flame enrichment is warmed up to 680 ℃, starts stirrer; stirred 30 minutes; shutdown is left standstill and is cooled to 450 ℃, and the bits crust was broken crisp hard skull and can be dragged for slag with strainer this moment; produce 28.6 kilograms of the quantity of slag; the slag bismuth-containing of pulling out earlier focuses on as copper ashes 1.5～3.5% (weighing 18.6 kilograms), after the slag bismuth-containing 4.5～10.6% (about 10 kilograms of weight) pulled out; add once more as the additive that adds NaOH next time, to reclaim too much bismuth in the slag.For the second time the NaOH add-on of refining copper removal is 1%, and promptly 30 kilograms (contain return high bismuth slag 10 kilograms), adding sulfur content is copper bearing 1.25 times of thick bismuth (promptly 0.10 kilogram).Its operation is with the copper removal first time.Add sulphur alkali copper removal through twice, cupric drops to 0.0006% (being lower than the requirement of No. 1 smart bismuth) in the bismuth.
Embodiment 2 (the efficient copper refining that removes of thick bismuth):
Get the thick bismuth of 3T, copper content is 0.806%, and operating procedure and embodiment are with example 1.Difference is: for the first time copper removal adds 1.5% NaOH (45 kilograms wherein 10 kilograms for returning high bismuth slag), and adding sulfur content is 1.25 times (24.2 kilograms) of thick bismuth copper content; Copper removal adds NaOH 1.0% (30 kilograms, wherein 10 kilograms is high bismuth return slag) for the second time, and adding sulfur content is copper bearing 1.25 times of thick bismuth (0.5 kilogram).
Among above-mentioned two embodiment in the bismuth impure copper see Table 1 with the changing conditions of refining process.The technico-economical comparison of bismuth refining copper removal sees Table 2.
Copper bearing variation in the bismuth in the efficient copper removal process of table 1
| Sequence number | Former thick bismuth cupric (%) | Cupric % behind the copper removal for the first time | Cupric % behind the copper removal for the second time |
| Example 1 | 0.0446 | 0.00248 | 0.0006 |
| Example 2 | 0.806 | 0.016 | 0.0010 |
Embodiment 3 (the efficient copper removal of tin refinement):
Get the thick tin of 4T, cupric is 0.64%, the fusing of thick tin dress pot post-heating, adjusting the tin melt temperature is 280 ℃, the industrial NaOH that adds thick tin amount 1.0% measures (40 kilograms, wherein 10 kilograms are the high tin copper ashes amount of returning), adds the Sulfur amount (27 kilograms) of 1.25 times of thick tin copper contents again.Add NaOH earlier, stir a little make NaOH be melt into thick after, be pressed into block Sulfur with clip again, fascinating slightly after Sulfur adds makes Sulfur be covered by the thickness scum silica frost, can prevent oxidizing fire, granular and powdery Sulfur adds rapid stirring the in back and mixes with scum silica frost, also can prevent oxidizing fire, after Sulfur adds, can stir up and down by hand a little, leave standstill flame enrichment then and be warmed up to 650 ℃, start machine mixer, stirred 30 minutes, and left standstill and cool to scum silica frost crust (about 450 ℃), just available strainer drags for slag, the slag stanniferous of pulling out earlier 1.5～3.5%, can concentrate stack pending, after the slag stanniferous pulled out up to 4.5～10%, can return and remove the amount of making NaOH in the copper refining next time and add again.Behind the copper removal, thick tin cupric just can drop to below 0.01% and (reach the standard of No. 1 refined tin), and the thick efficient copper removal purified of tin technico-economical comparison sees Table 2.
Embodiment 4 (the efficient copper removal of fire refining of crude lead):
Get the 4T lead bullion, cupric is 1.6%, after lead bullion melts in kier, press lead bullion amount 2.0% add industrial NaOH (promptly 80 kilograms, wherein 15 kilograms be last time the high lead slag of copper removal return), extraordinarily go into Sulfur (promptly 64 kilograms) by 1.25% of lead bullion copper content, carry out first time lead bullion by the operating process of embodiment 3 and remove copper refining, remove copper refining for the first time after, the lead bullion cupric drops to 0.054%, still do not reach the cupric standard of No. 1 lead bullion, therefore be necessary to carry out the efficient copper removal second time.(promptly 60 kilograms of the industrial NaOH of the lead bullion of copper removal adding for the second time amount 1.5%, wherein 15 kilograms is the high plumbous return slag of purified last time), extraordinarily go into Sulfur (cupric by 1.25% of copper content in the lead by 0.054%, promptly 2.7% kilogram), carry out the refining of lead bullion copper removal operation second time by the operation of embodiment 3 again, after the copper removal of refining was for the second time finished, the lead bullion cupric dropped to below 0.001%, reach the cupric standard of No. 2 lead, the refining copper removal can be finished.The efficient copper removal purified of lead bullion technico-economical comparison sees Table 2.
The technico-economical comparison of thick (bismuth, tin, lead) the efficiency refining high copper removal of table 2
| Metal | Remove process for copper | Copper removal efficient % for the first time | Required copper removal number of times | Copper removal total time (hour) | Total slag rate % | Slag contains purpose metal (%) | Copper removal process direct yield % | Security |
| Bismuth | Add the sulphur copper removal | 5～20％ | 6 | 20--24 | 25 | 67.16 | 83.2％ | Dangerous |
| The embodiment of the invention 1 | ～94.5％ | 2 | 4 (connecting heating and cooling) | 4.5 | 1.6～4.5% average 2.6% | 96.5％ | Safety | |
| The embodiment of the invention 2 | ＞98％ | 2 | 4 | 5.5 | 1.5～4.2% average 2.58% | 98.6％ | Safety | |
| Tin | Add the sulphur copper removal | 10～25％ | 4 | 16～20 | 20～25％ | Average 75% | 85％ | Dangerous |
| The embodiment of the invention 3 | ～98.4％ | 1 | 2.5 | 5.1％ | 1.5～3.5% average 2.5% | 95％± | Safety | |
| Plumbous | Add the sulphur copper removal | 10～25％ | 3--5 | 17--24 | 26～30％ | 95％ | 79.85％ | Dangerous |
| The embodiment of the invention 4 | 96.6％ | 2 | 4.5 | 2.5％ | 1.6～3.7% average 2.7% | 94.1％ | Safety |
Claims (2)
1, the copper removal refinery practice in the pyrorefining of a kind of low melting point non-ferrous metal, it is characterized in that this copper removal refinery practice comprises fusion in advance, but the different steps of removing process for copper independently add respectively industrial NaOH and last time copper removal drag for slag, and Sulfur at last; Wherein, industrial NaOH and last time copper removal the add-on of dragging for slag at last be 1.0%～2.0% of crude metal total amount, the sulfury add-on is 1.25 times of crude metal copper content.
2, the described copper removal refining agent of claim 1 remove process for copper, the different steps that it is characterized in that this technology is that low temperature adds sulphur alkali, the high temperature copper removal, slag is dragged in cooling, that is: when temperature is 280 ℃, add crude metal total amount 1.0%～2.0% industrial NaOH and last time copper removal drag for slag at last, NaOH and last time copper removal to drag for the moisture that slag contains at last be 25～30%, stirring is treated NaOH and is dragged for the slag fusing and float over the metallic surface when being scattered paste shape, be pressed into Sulfur for 1.25 times of crude metal copper contents, be warmed up to 650～680 ℃ then, starting stirrer this moment stirred 30 minutes, leave standstill banking fire then and cool to 450～500 ℃, treat refining scum silica frost crust and drag for slag when separating with metal melt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310110830 CN1233857C (en) | 2003-10-28 | 2003-10-28 | Decoppering refining agent in use for fire refining of non-ferrous metal with low melting point and technical procedure |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310110830 CN1233857C (en) | 2003-10-28 | 2003-10-28 | Decoppering refining agent in use for fire refining of non-ferrous metal with low melting point and technical procedure |
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| Publication Number | Publication Date |
|---|---|
| CN1540007A CN1540007A (en) | 2004-10-27 |
| CN1233857C true CN1233857C (en) | 2005-12-28 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2435717T3 (en) * | 2005-07-26 | 2013-12-23 | Nihon Superior Sha Co., Ltd | Device for precipitation of copper in lead-free solder, for granulation and separation of compounds (CuX) 6Sn5 and for tin recovery |
| CN102978416B (en) * | 2012-12-23 | 2015-01-07 | 河南豫光金铅股份有限公司 | Device and method for continuously removing copper from liquid crude lead |
| CN104357682B (en) * | 2014-12-09 | 2016-04-06 | 山东恒邦冶炼股份有限公司 | The method of the efficient copper removal of a kind of thick bismuth bismuth kettle refining |
| CN107574307B (en) * | 2017-09-07 | 2019-04-23 | 昆明鼎邦科技股份有限公司 | A method of stannous sulfide is recycled and separates copper-tin alloy |
| BE1025769B1 (en) * | 2017-12-14 | 2019-07-08 | Metallo Belgium | Improved pyrometallurgical process |
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