CN104878211A - Ammonia leaching-based method for recycling copper in lead-copper smelting dross - Google Patents
Ammonia leaching-based method for recycling copper in lead-copper smelting dross Download PDFInfo
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Abstract
The invention provides an ammonia leaching-based method for recycling copper in the lead-copper smelting dross, which comprises the steps of a, immersing copper in the lead-copper smelting dross through the ammonia leaching process to obtain an ammonia leaching solution; b, obtaining a loaded organic phase and an extracted aqueous phase through the extraction and separation process of the ammonia leaching solution; c, obtaining a copper-rich liquid through the reverse extraction of the loaded organic phase; d, obtaining copper through the electrolysis process. The ammonia leaching-based method for recycling copper in the lead-copper smelting dross is simple in process and high in copper recovery rate.
Description
Technical field
The present invention relates to wet processing refining plumbous product copper dross slag technical field, particularly relate to a kind of method adopting ammonia leaching process to reclaim copper in refining lead bronze scum silica frost.
Background technology
Lead is one of the most frequently used non-ferrous metal.Obtain in lead bullion process at the refining of lead bullion, because pyrorefining is for electrorefining, have energy consumption low, take up an area less, the plurality of advantages such as simple, the with short production cycle and the finished product easy control of components of equipment and being generally used, the lead bullion output of current pyrorefining lead bullion accounts for 80% of lead bullion output.Fire refining of crude lead comprises steps for copper removal, and at it except in process for copper, generally adopt and add elemental sulfur copper-removing method, the avidity of the Cu namely utilizing S right is greater than Pb and generates the plumbous little Cu of density ratio
2the principle of S, makes copper form scum silica frost, then obtains copper dross slag by dragging for slag mode.Containing Cu10% ~ 50%, Pb40% ~ 80% in this copper dross slag, Ag100 ~ 10000g/t, in addition, also containing valuable metals such as a small amount of Zn, Sn, As, Sb, Co, Ni, Au.According to the difference of dragging for slag mode and equipment, scum silica frost physical form is also different, and common have loose fine particulate, bulk etc.
Smeltery adopts the valuable metal such as lead, copper, silver in thermal process recovery copper dross slag mostly both at home and abroad at present.Because equipment used is different, it is divided into again Blast Furnace Method, reflection oven process and rotary kiln etc.What treatment process application was more is soda ash-iron chip filter, utilizes soda ash to make the arsenic antimony in copper dross slag generate sodium salt and enters slag, and make sodium copper matte regulus, add iron filings and reduce in matte and slag leaded, improve the copper-lead ratio of matte.Add partial oxidation lead in process, impel As, Sn in scum silica frost to volatilize, thus again can recycle in flue dust.The recovering effect of above-mentioned technique is also different because adopted equipment is different.
Reverberatory furnace soda ash-iron chip filter and soda ash-iron chip filter adopt reverberatory furnace process copper dross slag, and its advantage is that in copper matte regulus, copper-lead ratio can reach 5 ~ 9:1, and lead recovery is high, can reach 97%.Adopt 9.5 ㎡ reverberatory furnace process containing Cu10% ~ 20% in prior art, containing the copper dross slag of Pb60% ~ 70%, output copper matte regulus contains Cu26% ~ 45%, Pb3% ~ 7%; Process is containing Cu10% ~ 15%, and containing the copper dross slag of Pb60%, output copper matte regulus is containing Cu > 40%, Pb < 7%.But it is high that this method exists energy consumption, environmental pollution is serious, and the shortcomings such as converter life is short, have been classified as time limit by country and have eliminated technique;
Adopt blast furnace process copper dross slag generally first to be sintered by copper dross slag before adding blast furnace, its object one is oxidation sweetening, makes Cu
2s becomes CuO, to be reduced, and sulphur is with SO
2form is overflowed, so that relieving haperacidity, two is at high temperature powder sintering is become block, to adapt to blast furnacing requirement.So only utilize lead blast furnace to complete recovery, without the need to building other equipment again, equipment cost is low.But its shortcoming is that in copper matte regulus, copper-lead is than low, and the rate of recovery of copper is low, and a large amount of copper still remains in lead, asunder copper and lead is not thorough, and matte productive rate is low, causes copper, arsenic and precious metal to circulate in plumbous production system process.In prior art, adopt blast furnace process containing Cu20% ~ 30%, during the copper dross slag of Pb50% ~ 70%, containing Cu35% ~ 40% in the copper matte regulus of output, Pb5% ~ 6%.
Adopt the difference on effect of rotary kiln process copper dross slag large, because it adopts refining splicer's skill and different, gained copper dross slag material composition difference is also very large, and output copper matte regulus generally contains Cu30% ~ 40%, Pb10% ~ 15%.USSR (Union of Soviet Socialist Republics) Lenin Knowles Ke Qian factory develops electric furnace process copper dross slag technology, and a Jia Qian factory liquid of USSR (Union of Soviet Socialist Republics) electricity Xin factory and Japan adopts this method.This method exhaust gas volumn is little, and metal loss is few, but cost is higher.Lenin's Knowles Ke Qian factory and office reason is containing Cu20% ~ 30%, and the copper dross slag of Pb50% ~ 70%, output copper matte regulus is containing Cu41.5%, Pb6.2%.Electric furnace process is difficult in the area of power tense realize, and needs to add reductive agent coke, and production cost is high;
Except aforesaid device, utilize the method for electric furnace, rotary kiln process copper dross slag in addition.The method of above-mentioned pyrogenic attack copper dross slag all has weak point in a word, has not yet to see and reclaims the effective hydrometallurgic recovery method of copper.
In sum, the method reclaiming copper in refining lead bronze scum silica frost of the prior art needs to improve further.
Summary of the invention
It is comparatively complicated to there is technique in the method in order to solve copper in existing recovery refining lead bronze scum silica frost of the present invention, the defect that the metallic copper rate of recovery is lower, thus providing a kind of technique simple, the ammonia leaching process that the metallic copper rate of recovery is high, production cost is low reclaims the method for copper in refining lead bronze scum silica frost.
The invention provides a kind of method that ammonia leaching process reclaims copper in refining lead bronze scum silica frost, the method comprises the steps:
A, the copper leaching adopting ammonia leaching process to refine in lead bronze scum silica frost, obtain ammonia leaching solution: soaked by refining lead bronze scum silica frost and soak in a solvent; Described solvent is ammoniacal liquor and ammonium sulfate, NH
3/ SO
4 2+=1.5 ~ 3;
B, ammonia leaching solution is carried out extracting and separating obtain load organic phases and aqueous phase extracted: adopt extraction liquid to extract the ammonia leaching solution obtained in step a, be separated and obtain load organic phases and aqueous phase extracted; Described extraction liquid comprises extraction agent and thinner, and described extraction agent is aldoxime kind of extractants, and described thinner is kerosene, and the volumetric concentration of described extraction agent is 20% ~ 30%, is in a ratio of A/O=1/2 ~ 1/3, and extraction time is 5 ~ 8 minutes; Described load organic phases carries out next step back extraction, and aqueous phase extracted returns step a and carries out ammonia leaching as solvent;
C, the back extraction of load machine phase obtain rich copper liquid: load organic phases mixed with copper spent electrolyte and carry out back extraction, obtain the rich copper liquid of aqueous phase and organic phase; Described copper spent electrolyte is sulfuric acid and copper sulfate mixing solutions; The rich copper liquid of described aqueous phase carries out next step electrolysis, and described organic phase returns step b and extracts as extraction liquid;
D, electrolysis obtain copper: rich for aqueous phase copper liquid is carried out electrolysis production copper, and the copper spent electrolyte that electrolysis produces returns step c and carries out back extraction.
As further restriction of the present invention, in step a, soak time is 4h, and described soaking temperature is 50 DEG C, described total NH
3concentration be 6 ~ 10mol/L.
As further restriction of the present invention, in step b, described aldoxime kind of extractants is Lix84.
As further restriction of the present invention, in step b, the volumetric concentration of described extraction agent is 20% ~ 30%.
As further restriction of the present invention, in step b, the progression of described extraction is 3 ~ 4 grades.
As further restriction of the present invention, in step c, in described copper spent electrolyte, the content of Cu is 30 ~ 40g/L, H
2sO
4content be 140 ~ 160g/L.
As further restriction of the present invention, in step c, the progression of described back extraction is 1 ~ 2 grade.
As further restriction of the present invention, between described step b and described step c, carry out the washing of 1 ~ 2 grade; Described washing compare A/O=1/3 ~ 1/8.
Reaction principle of the present invention is: in ammonia-ammonium salt system, leaching agent and complexing agent is done with the mixture of ammoniacal liquor and ammonium sulfate, copper in refining lead bronze scum silica frost is dissolved out with the form of Copper-ammonia Complex and enters solution, realize the Selectively leaching of valuable metal copper, thus with other component separating, the ammonia leaching solution obtained is extracting and separating copper again, obtain load organic phases and aqueous phase extracted, load organic phases mixes with copper electrolyte carries out back extraction, obtains rich copper liquid, rich copper liquid is carried out electrolysis and gets final product production of copper.
Leaching copper provided by the present invention-extracting and separating copper-back extraction obtains the operational path that the liquid-electrolysis of rich copper obtains copper, achieves the effects such as copper recovery is high, copper grade is high, and cost is low.Particularly, the present invention first adopts ammonia leaching process to reclaim copper in refining lead bronze scum silica frost, and leaching yield can reach more than 90%, ensure that the rate of recovery.In the electrolytic copper that final electrolysis obtains, the content of copper is greater than 99.95%, ensure that the GOOD TASTE of copper, because after back extraction of the present invention, organic phase is regenerated, extraction cycle can be returned and use, electrolysis produces waste electrolyte and also returns stripping steps and use, and achieves making full use of of raw material and the energy.
Copper in refining lead bronze scum silica frost is by after Selectively leaching, mainly leaded, silver and the valuable metal such as zinc in residue, above-mentioned residue can enter conventional plumbous smelting procedure as raw material backflow, reclaim lead wherein, residue enters blast furnace after drying and sintering, and silver is dissolved in lead bullion, is finally enriched in lead anode slurry and is reclaimed, the valuable metals such as zinc then enter zinc oxide fumes with blast furnace slag fuming blowing, are recycled in the subsequent handling of zinc hydrometallurgy.In the present invention, ammonia is utilized to soak selective separation copper and other valuable metals, copper is reclaimed through extraction electrolysis, copper recovery is high, technical process is simple, the precious metals such as copper, arsenic and silver also can be avoided to circulate in lead-zinc production process, simultaneously, the valuable metals such as lead, silver and zinc utilize conventional lead-zinc smelting operation to reclaim, and are conducive to the effect improving synthetical recovery in wet method lead-zinc production.Compared with pyrogenic attack technique, be more conducive to the plumbous zinc technology with wet method and link.
The present invention adopts wet processing copper dross slag, produces without the new three wastes, to equipment without particular requirement, without the need to heat, compared with current thermal process, and environmental friendliness, production safety is reliable, processing ease; Energy consumption is low, and the metallic copper rate of recovery is high simultaneously, reaches more than 90%; Technical process is simple, and cost is low.Method of the present invention can be widely used in the enterprise that process refining lead bronze scum silica frost reclaims copper-lead, also can be widely used in the transformation of non-ferrous metals smelting works' ore deposit business processes copper-lead material technique.
Accompanying drawing explanation
Fig. 1 is technical process of the present invention.
Embodiment
The invention provides a kind of method that ammonia leaching process reclaims copper in refining lead bronze scum silica frost, the method comprises the steps:
A, the copper leaching adopting ammonia leaching process to refine in lead bronze scum silica frost, obtain ammonia leaching solution: soaked by refining lead bronze scum silica frost and soak in a solvent; Described solvent is ammoniacal liquor and ammonium sulfate, NH
3/ SO
4 2+=1.5 ~ 3;
B, ammonia leaching solution is carried out extracting and separating obtain load organic phases and aqueous phase extracted: adopt extraction liquid to extract the ammonia leaching solution obtained in step a, be separated and obtain load organic phases and aqueous phase extracted; Described extraction liquid comprises extraction agent and thinner, and described extraction agent is aldoxime kind of extractants, and described thinner is kerosene, and the volumetric concentration of described extraction agent is 20% ~ 30%, is in a ratio of A/O=1/2 ~ 1/3, and extraction time is 5 ~ 8 minutes; Described load organic phases carries out next step back extraction, and aqueous phase extracted is returned and can be carried out ammonia leaching as solvent by step a;
C, the back extraction of load machine phase obtain rich copper liquid: load organic phases mixed with copper spent electrolyte and carry out back extraction, obtain the rich copper liquid of aqueous phase and organic phase; Described copper spent electrolyte is sulfuric acid and copper sulfate mixing solutions; The rich copper liquid of described aqueous phase carries out next step electrolysis, and described organic phase returns step b and extracts as extraction liquid.
Reclaim the method for copper in refining lead bronze scum silica frost according to ammonia leaching process provided by the present invention, preferably, described soak time is 4h, and described soaking temperature is 50 DEG C, described NH
3concentration be 6 ~ 10mol/L, the leaching yield of copper can be ensured to the full extent.
Reclaim the method for copper in refining lead bronze scum silica frost according to ammonia leaching process provided by the present invention, preferably, described aldoxime kind of extractants is Lix84, can selective extraction copper when pH is 11, and charge capacity reaches 46mg/ml.
Reclaim the method for copper in refining lead bronze scum silica frost according to ammonia leaching process provided by the present invention, preferably, described extraction agent volumetric concentration is 20% ~ 30%, when ensureing percentage extraction, reduces proportion and the viscosity of extraction agent, the flowing being conducive to two-phase be separated.
Reclaim the method for copper in refining lead bronze scum silica frost according to ammonia leaching process provided by the present invention, in order to ensure the effect of back extraction, preferably, in described copper spent electrolyte, the content of Cu is 30 ~ 40g/L, H
2sO
4content be 140 ~ 160g/L.
Reclaim the method for copper in refining lead bronze scum silica frost according to ammonia leaching process provided by the present invention, in order to improve effect of extracting, preferably, the progression of described extraction is 3 ~ 4 grades.
Reclaim the method for copper in refining lead bronze scum silica frost according to ammonia leaching process provided by the present invention, in order to improve back extraction effect, preferably, the progression of described back extraction is 1 ~ 2 grade.
The method of copper in refining lead bronze scum silica frost is reclaimed, in order to wash away the NH carried secretly in organic phase according to ammonia leaching process provided by the present invention
3, preferably, between described step b and described step c, carry out the washing of 1 ~ 2 grade; In order to ensure wash effect control leaching requirement simultaneously, described washing compare A/O=1/3 ~ 1/8.Described washing composition is subacidity water.
As shown in Figure 1, refining lead bronze scum silica frost is ground, then carry out carrying out ammonia leaching in the solution formed at ammoniacal liquor and ammonium sulfate, after solid phase is separated, plumbous for solid phase residue is returned plumbous conventional system process, be oximes extraction agent system by ammonia leaching solution at extraction agent, thinner is extract in the extraction liquid of kerosene, obtain load organic phases and aqueous phase extracted, aqueous phase extracted is returned ammonia leaching step, load organic phases is carried out in copper electrolyte back extraction and obtain the rich copper liquid of aqueous phase and organic phase, described organic phase regeneration returns extraction step, the rich copper liquid of described aqueous phase carries out electrolysis and obtains copper and electrolytic solution, electrolytic solution returns stripping steps.
Leaching copper provided by the present invention-extracting and separating copper-back extraction obtains the operational path that the liquid-electrolysis of rich copper obtains copper, achieves the effects such as copper recovery is high, copper grade is high, and cost is low.Particularly, the present invention first adopts ammonia leaching process to reclaim copper in refining lead bronze scum silica frost, and leaching yield can reach more than 90%, ensure that the rate of recovery.In the electrolytic copper that final electrolysis obtains, the content of copper is greater than 99.95%, ensure that the of high grade of copper, because after back extraction of the present invention, organic phase is regenerated, extraction cycle can be returned use, electrolysis produces waste electrolyte and also returns stripping steps use, achieve making full use of of raw material and the energy, production cost reduces, obvious environment benefit.
Particularly, in the present invention, copper in refining lead bronze scum silica frost by after Selectively leaching, the main valuable metal such as leaded, silver and zinc in residue, above-mentioned residue can enter conventional plumbous smelting procedure as raw material backflow, reclaim lead wherein, residue enters blast furnace after drying and sintering, and silver is dissolved in lead bullion, is finally enriched in lead anode slurry and is reclaimed, the valuable metals such as zinc then enter zinc oxide fumes with blast furnace slag fuming blowing, are recycled in the subsequent handling of zinc hydrometallurgy.In the present invention, ammonia is utilized to soak selective separation copper and other valuable metals, copper is reclaimed through extraction electrolysis, copper recovery is high, technical process is simple, the precious metals such as copper, arsenic and silver also can be avoided to circulate in lead-zinc production process, simultaneously, the valuable metals such as lead, silver and zinc utilize conventional lead-zinc smelting operation to reclaim, and are conducive to the effect improving synthetical recovery in wet method lead-zinc production.Compared with pyrogenic attack technique, be more conducive to the plumbous zinc technology with wet method and link.
The present invention adopts wet processing copper dross slag, produces without the new three wastes, to equipment without particular requirement, without the need to heat, compared with current thermal process, and environmental friendliness, production safety is reliable, processing ease; Energy consumption is low, and the metallic copper rate of recovery is high simultaneously, reaches more than 90%; Technical process is simple, and cost is low.Method of the present invention can be widely used in the enterprise that process refining lead bronze scum silica frost reclaims copper-lead, also can be widely used in the transformation of non-ferrous metals smelting works' ore deposit business processes copper-lead material technique.
Apply specific embodiment to be below described in further detail the present invention.
Embodiment 1
A, get 1000g containing Cu about 10%, containing Pb about 80%, the refining lead that argentiferous is about 3000g/t produces copper dross slag and loads in beaker, and liquid-solid ratio L/S=6, by total ammonia density 6mol/L, NH
3/ SO
4 2+=1.5 add ammoniacal liquor and ammonium sulfate, then agitation leach 4h in temperature 50 C situation, and leach complete suction filtration and washing leaching slag, obtain leach liquor 610ml, it is containing Cu14.9g/L, Cu leaching yield 91.3%.Leach liquor 25% (V/V) Lix 84 extracting copper, measures 100ml leach liquor and 200ml 25%Lix 84 puts into separating funnel, vibration mixing 5min, and leave standstill phase-splitting, percentage extraction reaches 99.90%, and load organic phases adds 200ml and is about 40g/L, H containing Cu
2sO
4the waste solution of copper electrolysis of about 160g/L carries out back extraction, obtains being about 30g/L, H containing Cu
2sO
4the rich copper liquid of about 140g/L, this electrolysis of solutions can output 1# electrolytic copper (Cu > 99.95%).In process, main consumption is chemical reagent and artificial power cost, wherein leaching agent can part reuse, by 30% consumption calculating, extraction agent life cycle is 45 days ~ 60 days, manually, electric power and other costs calculate by 240 yuan/ton of copper dross slags, then consuming cost is about 1.07 yuan, i.e. 1070 yuan/ton of copper dross slags.
B, ammonia leaching residue are after washing, drying and sintering enters lead blast furnace and reclaims plumbous, and silver is dissolved in lead bullion, is finally enriched in lead anode slurry and is reclaimed, the valuable metals such as zinc then enter zinc oxide fumes with blast furnace slag fuming blowing, are recycled in the subsequent handling of zinc hydrometallurgy.
Whole process copper recovery is 91.91%.
Embodiment 2
A, get 1000g containing Cu about 20%, containing Pb about 70%, the refining lead that argentiferous is about 3300g/t produces copper dross slag and loads in beaker, and liquid-solid ratio L/S=8, by total ammonia density 8mol/L, NH
3/ SO
4 2+=3 add ammoniacal liquor and ammonium sulfate, then agitation leach 4h in temperature 50 C situation, and leach complete suction filtration and washing leaching slag, obtain leach liquor 810ml, it is containing Cu22.46g/L, Cu leaching yield 91%.Leach liquor 25% (V/V) Lix 84 extracting copper, measures 100ml leach liquor and 200ml 25%Lix 84 puts into separating funnel, vibration mixing 8min, and leave standstill phase-splitting, percentage extraction reaches 99.90%, and load organic phases adds 200ml and is about 40g/L, H containing Cu
2sO
4the waste solution of copper electrolysis of about 160g/L carries out back extraction, obtains rich copper liquid, and this electrolysis of solutions can output 1# electrolytic copper (Cu > 99.95%).
In process, main consumption is chemical reagent and artificial power cost, wherein leaching agent can part reuse, by 30% consumption calculating, extraction agent life cycle is 45 days ~ 60 days, manually, electric power and other costs calculate by 240 yuan/ton of copper dross slags, then consuming cost is about 1.10 yuan, i.e. 1100 yuan/ton of copper dross slags.
B, ammonia leaching residue are after washing, drying and sintering enters lead blast furnace and reclaims plumbous, and silver is dissolved in lead bullion, is finally enriched in lead anode slurry and is reclaimed, the valuable metals such as zinc then enter zinc oxide fumes with blast furnace slag fuming blowing, are recycled in the subsequent handling of zinc hydrometallurgy.
Whole process copper recovery is 94.7%.
Embodiment 3
A, get 1000g containing Cu about 25%, containing Pb about 65%, the refining lead that argentiferous is about 3300g/t produces copper dross slag and loads in beaker, and liquid-solid ratio L/S=8, by total ammonia density 9mol/L, NH
3/ SO
4 2+=2 add ammoniacal liquor and ammonium sulfate, then agitation leach 4h in temperature 50 C situation, and leach complete suction filtration and washing leaching slag, obtain leach liquor 810ml, it is containing Cu 33..46g/L, Cu leaching yield 90.4%.Leach liquor 25% (V/V) Lix 84 extracting copper, measures 100ml leach liquor and 200ml 30%Lix 84 puts into separating funnel, vibration mixing 6min, and leave standstill phase-splitting, percentage extraction reaches 99.90%, and load organic phases adds 200ml and is about 40g/L, H containing Cu
2sO
4the waste solution of copper electrolysis of about 160g/L carries out back extraction, obtains rich copper liquid, and this electrolysis of solutions can output 1# electrolytic copper (Cu > 99.95%).In process, main consumption is chemical reagent and artificial power cost, wherein leaching agent can part reuse, by 30% consumption calculating, extraction agent life cycle is 45 days ~ 60 days, manually, electric power and other costs calculate by 240 yuan/ton of copper dross slags, then consuming cost is about 1.10 yuan, i.e. 1100 yuan/ton of copper dross slags.
B, ammonia leaching residue are after washing, drying and sintering enters lead blast furnace and reclaims plumbous, and silver is dissolved in lead bullion, is finally enriched in lead anode slurry and is reclaimed, the valuable metals such as zinc then enter zinc oxide fumes with blast furnace slag fuming blowing, are recycled in the subsequent handling of zinc hydrometallurgy.
Whole process copper recovery is 94.45%.
Embodiment 4
A, get 1000g containing Cu about 30%, containing Pb about 60%, the refining lead that argentiferous is about 3500g/t produces copper dross slag and loads in beaker, and liquid-solid ratio L/S=8, by total ammonia density 9mol/L, NH
3/ SO
4 2+=2 add ammoniacal liquor and ammonium sulfate, then agitation leach 4h in temperature 50 C situation, and leach complete suction filtration and washing leaching slag, obtain leach liquor 810ml, it is containing Cu 33..46g/L, Cu leaching yield 91%.Leach liquor 30% (V/V) Lix 84 extracting copper, measures 100ml leach liquor and 200ml 30%Lix 84 puts into separating funnel, vibration mixing 5min, and leave standstill phase-splitting, percentage extraction reaches 99.90%, and load organic phases adds 200ml and is about 40g/L, H containing Cu
2sO
4the waste solution of copper electrolysis of about 150g/L carries out back extraction, obtains rich copper liquid, and this electrolysis of solutions can output 1# electrolytic copper (Cu > 99.95%).In process, main consumption is chemical reagent and artificial power cost, wherein leaching agent can part reuse, by 70% consumption calculating, extraction agent life cycle is 45 days ~ 60 days, manually, electric power and other costs calculate by 240 yuan/ton of copper dross slags, then consuming cost is about 1.13 yuan, i.e. 1130 yuan/ton of copper dross slags.
B, ammonia leaching residue are after washing, drying and sintering enters lead blast furnace and reclaims plumbous, and silver is dissolved in lead bullion, is finally enriched in lead anode slurry and is reclaimed, the valuable metals such as zinc then enter zinc oxide fumes with blast furnace slag fuming blowing, are recycled in the subsequent handling of zinc hydrometallurgy.
Whole process copper recovery is 95.1%.
Embodiment 5
A, get 1000g containing Cu about 35%, containing Pb about 55%, the refining lead that argentiferous is about 3500g/t produces copper dross slag and loads in beaker, and liquid-solid ratio L/S=8, by total ammonia density 9mol/L, NH
3/ SO
4 2+=2 add ammoniacal liquor and ammonium sulfate, then agitation leach 4h in temperature 50 C situation, and leach complete suction filtration and washing leaching slag, obtain leach liquor 810ml, it is containing Cu 33..46g/L, Cu leaching yield 91.4%.Leach liquor 30% (V/V) Lix 84 extracting copper, measures 100ml leach liquor and 200ml 20%Lix 84 puts into separating funnel, vibration mixing 5min, and leave standstill phase-splitting, percentage extraction reaches 99.90%, and load organic phases adds 200ml and is about 40g/L, H containing Cu
2sO
4the waste solution of copper electrolysis of about 160g/L carries out back extraction, obtains rich copper liquid, and this electrolysis of solutions can output 1# electrolytic copper (Cu > 99.95%).In process, main consumption is chemical reagent and artificial power cost, wherein leaching agent can part reuse, by 30% consumption calculating, extraction agent life cycle is 45 days ~ 60 days, manually, electric power and other costs calculate by 240 yuan/ton of copper dross slags, then consuming cost is about 1.13 yuan, i.e. 1130 yuan/ton of copper dross slags.
B, ammonia leaching residue are after washing, drying and sintering enters lead blast furnace and reclaims plumbous, and silver is dissolved in lead bullion, is finally enriched in lead anode slurry and is reclaimed, the valuable metals such as zinc then enter zinc oxide fumes with blast furnace slag fuming blowing, are recycled in the subsequent handling of zinc hydrometallurgy.
Whole process copper recovery is 96.5%.
Embodiment 6
A, get 100g containing Cu about 40%, containing Pb about 50%, the refining lead that argentiferous is about 3500g/t produces copper dross slag and loads in beaker, and liquid-solid ratio L/S=8, by total ammonia density 10mol/L, NH
3/ SO
4 2+=2 add ammoniacal liquor and ammonium sulfate, then agitation leach 4h in temperature 50 C situation, and leach complete suction filtration and washing leaching slag, obtain leach liquor 810ml, it is containing Cu 33..46g/L, Cu leaching yield 90.4%.Leach liquor 35% (V/V) Lix 84 extracting copper, measures 100ml leach liquor and 200ml 25%Lix 84 puts into separating funnel, vibration mixing 5min, and leave standstill phase-splitting, percentage extraction reaches 99.90%, and load organic phases adds 200ml and is about 40g/L, H containing Cu
2sO
4the waste solution of copper electrolysis of about 160g/L carries out back extraction, obtains rich copper liquid, and this electrolysis of solutions can output 1# electrolytic copper (Cu > 99.95%).In process, main consumption is chemical reagent and artificial power cost, wherein leaching agent can part reuse, by 30% consumption calculating, extraction agent life cycle is 45 days ~ 60 days, manually, electric power and other costs calculate by 240 yuan/ton of copper dross slags, then consuming cost is about 1.15 yuan, i.e. 1150 yuan/ton of copper dross slags.
B, ammonia leaching residue are after washing, drying and sintering enters lead blast furnace and reclaims plumbous, and silver is dissolved in lead bullion, is finally enriched in lead anode slurry and is reclaimed, the valuable metals such as zinc then enter zinc oxide fumes with blast furnace slag fuming blowing, are recycled in the subsequent handling of zinc hydrometallurgy.
Whole process copper recovery is 94.7%.
Comparative example 1
Adopt 9.5 ㎡ reverberatory furnace process containing Cu10% ~ 20%, containing the copper dross slag of Pb60% ~ 70%, output lead bullion and copper matte regulus, wherein copper matte regulus is containing Cu26% ~ 45%, Pb3% ~ 7%, and copper matte regulus send converting furnace to blow into blister copper again, blister copper obtains smart copper through electrolysis, wherein copper recovery 80% ~ 85%; Process is containing Cu10% ~ 15%, and containing the copper dross slag of Pb60%, output lead bullion and copper matte regulus, wherein copper matte regulus is 40%, Pb7% containing Cu, and copper matte regulus send converting furnace to blow into blister copper again, and blister copper obtains smart copper through electrolysis, and wherein copper recovery is less than 80%.The consumption of reverberatory furnace processing cost is mainly energy consumption and additive soda ash and iron filings, and the reverberatory furnace energy consumption of coal combustion is lower, is about 890 yuan/ton of copper dross slags, add depletion of additive, body of heater loss, artificial and other, total cost is about 1270 yuan/copper dross slag; The reverberatory furnace energy consumption of gas-firing is higher, is about 1050 yuan/ton of copper dross slags, add depletion of additive, body of heater loss, artificial and other, total cost is about 1400 yuan/ton of copper dross slags.Namely adopt reverberatory furnace process 1 ton of copper dross slag, its cost is about 1270 ~ 1400 yuan.
As can be seen from copper recovery and the cost analysis of embodiment 1-6 and comparative example 1, adopt ammonia leaching process process copper dross slag copper recovery high, the construction of its production line, production cost are all lower than reverberatory furnace facture production line, especially the equipment cost of reverberatory furnace is built far away higher than ammonia leaching apparatus for production line cost provided by the present invention, running cost is also as aforementioned, and cost is obviously too high, and another importance is, there is larger environmental pollution in reverberatory furnace facture simultaneously, belongs to superseded technique.The method technique that ammonia leaching process of the present invention reclaims copper in refining lead bronze scum silica frost is simple, and cost is low, and copper recovery is high, environmental friendliness, produces without the new three wastes.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. ammonia leaching process reclaims a method for copper in refining lead bronze scum silica frost, and it is characterized in that, the method comprises the steps:
A, the copper leaching adopting ammonia leaching process to refine in lead bronze scum silica frost, obtain ammonia leaching solution: soaked by refining lead bronze scum silica frost and leach in a solvent; Described solvent is ammoniacal liquor and ammonium sulfate, NH
3/ SO
4 2+=1.5 ~ 3.0;
B, ammonia leaching solution is carried out extracting and separating obtain load organic phases and aqueous phase extracted: adopt extraction liquid to extract the ammonia leaching solution obtained in step a, be separated after leaving standstill and obtain load organic phases and aqueous phase extracted; Described extraction liquid comprises extraction agent and thinner, and described extraction agent is oximes extraction agent system, and described thinner is kerosene, and the volumetric concentration of described extraction agent is 20% ~ 30%, is in a ratio of A/O=1/2 ~ 1/3, and extraction time is 5 ~ 8 minutes; Described load organic phases carries out next step back extraction, and aqueous phase extracted returns step a and carries out ammonia leaching as solvent;
C, load organic oppositing back-extraction obtain rich copper liquid: load organic phases mixed with copper spent electrolyte and carry out back extraction, obtain the rich copper liquid of aqueous phase and organic phase; Described copper spent electrolyte is sulfuric acid and copper sulfate mixing solutions; The rich copper liquid of described aqueous phase carries out next step electrolysis, and described organic phase returns step b and extracts as extraction liquid;
D, electrolysis obtain copper: rich for aqueous phase copper liquid is carried out electrolysis production copper, and the copper spent electrolyte that electrolysis produces returns step c and carries out back extraction.
2. ammonia leaching process according to claim 1 reclaims the method for copper in refining lead bronze scum silica frost, and it is characterized in that, described soak time is 4h, and described soaking temperature is 50 DEG C, described total NH
3concentration be 6 ~ 10mol/L.
3. ammonia leaching process according to claim 1 reclaims the method for copper in refining lead bronze scum silica frost, and it is characterized in that, described aldoxime kind of extractants is Lix84.
4. ammonia leaching process according to claim 1 reclaims the method for copper in refining lead bronze scum silica frost, and it is characterized in that, the volumetric concentration of described extraction agent is 20% ~ 30%.
5. ammonia leaching process according to claim 1 reclaims the method for copper in refining lead bronze scum silica frost, and it is characterized in that, in described copper spent electrolyte, the content of Cu is 30 ~ 40g/L, H
2sO
4content be 140 ~ 160g/L.
6. ammonia leaching process according to claim 1 reclaims the method for copper in refining lead bronze scum silica frost, and it is characterized in that, the progression of described extraction is 3 ~ 4 grades.
7. ammonia leaching process according to claim 1 reclaims the method for copper in refining lead bronze scum silica frost, and it is characterized in that, the progression of described back extraction is 1 ~ 2 grade.
8. ammonia leaching process according to claim 1 reclaims the method for copper in refining lead bronze scum silica frost, it is characterized in that, carries out the washing of 1 ~ 2 grade between described step b and described step c; Described washing compare A/O=1/3 ~ 1/8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108728665A (en) * | 2018-05-04 | 2018-11-02 | 昆明理工大学 | A method of recycling copper from Water Quenching Slag |
| CN114214522A (en) * | 2021-12-23 | 2022-03-22 | 江西自立环保科技有限公司 | Wet treatment process for refined copper slag |
-
2015
- 2015-04-02 CN CN201510153572.8A patent/CN104878211A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108728665A (en) * | 2018-05-04 | 2018-11-02 | 昆明理工大学 | A method of recycling copper from Water Quenching Slag |
| CN114214522A (en) * | 2021-12-23 | 2022-03-22 | 江西自立环保科技有限公司 | Wet treatment process for refined copper slag |
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Application publication date: 20150902 |